Eur. J. Mineral.
2019, 31, 1079–1097
Published online 16 September 2019

Argentoliveingite, Ag3+xPb362xAs51+xS112 (0  x < 0.5), a new homeotypeof liveingite from Lengenbach, Binntal, Switzerland, and the crystal
chemistry of the liveingite group
Dan TOPA1,*, Uwe KOLITSCH1,2, Stefan GRAESER3, Emil MAKOVICKY4 and Chris STANLEY5
1Naturhistorisches Museum, Burgring 7, 1010 Wien, Austria*Corresponding author, e-mail: dan.topa@nhm-wien.ac.at2
Institut für Mineralogie und Kristallographie, Universität Wien, Althanstraße 14, 1090 Wien, Austria
3
Mineralogisches Institut, Universität Basel, Bernoullistraße 30, 4056 Basel, Switzerland
4
Department of Geoscience and Resource Management, University of Copenhagen,Østervoldgade 10, 1350 Copenhagen K, Denmark
5
Natural History Museum, Cromwell Road, SW7 5BD London, UK

Abstract: Argentoliveingite, ideally Ag3+xPb362xAs51+xS112 (0  x < 0.5), is a new silver-bearing sulphosalt species found in the
Lengenbach deposit, Binntal, Canton Wallis, Switzerland. Associated minerals in the holotype, an old museum specimen, arebaumhauerite and argentobaumhauerite. In other samples, hendekasartorite, liveingite, rathite and dufrénoysite are present.
Argentoliveingite is dark grey and opaque with metallic lustre and a black streak. It is brittle without any discernible cleavage andwith conchoidal fracture. In reﬂected light argentoliveingite is white, pleochroism is not discernible. Red internal reﬂections are seenon thin edges or at grain boundaries. In crossed polarisers, anisotropism is moderate in dark grey – neutral rotation tints. The
reﬂectance data [Rmin, Rmax (%), in air] are: 36.6, 41.5 at 470 nm, 34.4, 39.4 at 546 nm, 32.9, 37.8 at 589 nm and 30.7, 35.2 at
650 nm. Mohs hardness is four, microhardness VHN25 exhibits a range 208–225 kg mm2, with a mean value of 217 kg mm2.
The average result of 22 electron-microprobe spot analyses for the structurally investigated grain is (in wt%): Ag 2.31(4), Tl 0.35(12), Pb 46.65(26), Sb 0.83(10), As 25.36(14), S 24.27(17), total 99.97(20), corresponding to Ag3.17Tl0.40Pb33.31Sb1.01As50.08S112.02(on the basis of 88Me + 112S = 200 atoms per formula unit, apfu). The ideal formula is in accordance with the results of the crystalstructure analysis and may be derived from the double ideal liveingite formula, Pb40As48S112, by minor substitution of Sb for As, andthe independent, heterovalent [(Ag,Tl)+ + (As,Sb)3+] M 2Pb2+ substitution. The density, 5.23 g cm3, was calculated using theempirical formula. Argentoliveingite is triclinic, space group P
1 (no. 2), with a = 7.905(2), b = 8.469(2), c = 137.96(4) Å, a = 89.592(2), b = 88.969(2), c = 89.893(2)°, V = 9235(5) Å3 and Z = 2. The c axis is double the b axis of liveingite and represents the longest
unit-cell parameter for a known natural sulphosalt. The strongest ﬁve lines in the (calculated) powder-diffraction pattern are [d inÅ(I)(h,k,l)]: 3.781(85)(
2,0,10), 3.668(100)(
1,0,33), 3.553(83)(1,0,35), 3.009(91)(
1,2,27) and 2.938(94)(1,
2,29). Argentoliveingite isa homeotype of liveingite and a new member of the sartorite homologous series with N = 3.67, and with a limited extent of theuncoupled substitutions of [Ag+ + As3+] for 2Pb2+ and [Tl+ + As3+] for 2Pb2+. In argentoliveingite the sequence of alternating N = 3
and N = 4 slabs is different from that in liveingite and is further modiﬁed by alternation of three, chemically distinct, types of N = 4
slabs. The length and arrangement of crankshaft chains of short As–S bonds differ between different slabs, and especially between
the N = 4 slabs of liveingite and argentoliveingite. The crystal structures of liveingite and Ag-bearing liveingite (both quantitatively
analysed) have been reﬁned for comparison purposes. The uncertain relationship with the phase “rathite-IV” is discussed.
Key-words: argentoliveingite; liveingite; sulphosalt; new mineral; crystal structure; sartorite homologous series; Lengenbach;
Binntal; Canton Valais; Switzerland.

1. Introduction
The name liveingite was given by Solly (1901) in honour of
G.D. Liveing, Fellow of the Royal Society, Professor ofChemistry at Cambridge University, to a new mineral of
the “series” sartorite – baumhauerite – dufrénoysite – rathitefrom the Lengenbach deposit (Binntal, Canton Wallis,
Switzerland) with a formula 4PbS3As2S3 (Pb4As6S13).
https://doi.org/10.1127/ejm/2019/0031-2890

Solly stated that the new mineral crystallises in “the obliquesystem with a pseudo-rhombic habit and b = 89.45°.” As
was the custom at that time, the mineral was deﬁned on
the basis of morphological crystallography and wet chemical
analyses. Giusßcă (1930) placed the chemistry of liveingite
between those of baumhauerite and rathite and drew attention to the similarity between all of them in polarized light.
Berry (1953) obtained the ﬁrst unit-cell parameters,
0935-1221/19/0031-2890 $ 8.55

Ó 2019 E. Schweizerbart’sche Verlagsbuchhandlung, 70176 Stuttgart, Germany
Downloaded from https://pubs.geoscienceworld.org/eurjmin/article-pdf/31/5-6/1079/4902547/ejm_31_5-6_1079_1097_topa_2890_online.pdf
by University of Arizona user

1080

D. Topa et al.

a = 8.32, b = 70.9, c = 7.91 Å, b = 90°, with a probablespace group P21/m and a composition of 38PbS26As2S3(Pb38As52S116). Le Bihan (1961) reported the main featuresof the crystal structure for space group P21/c and additional
details were reﬁned by Engel & Nowacki (1970) in the polar
space group P21. An electron microprobe (EMP) study of
liveingite by Engel & Nowacki (1970) pointed to theformula Pb18As26S56 (Z = 2). Further EMP analyses by
Laroussi et al. (1989) showed the presence of Ag(0.2–0.6 wt%) and Tl (0.4–1.3 wt%) and gave an empiricalformula Pb36.88Ag0.48Tl0.42As48.36S112 (Z = 1) for an ideal
formula Pb40As48S112. Extensive HR-TEM studies of liveingite by Pring (2001) revealed sharp electron diffraction spots
and a well-ordered nature of the mineral along the b axis(~70 Å) in high-resolution images.
Makovicky (1985) deﬁned a sartorite homologous seriesof Pb–As and Pb–As–Sb sulphosalts with a set of common
structural features and principles, based on the structure
determinations by Nowacki’s group (publications in theyears 1961–1970), Le Bihan (1961, 1962) and Takéuchi
(1970). He described it as a combinatorial series(Makovicky, 1997a and b), in which a given mineral
member is created by combinations of only two unit homologue slabs (N = 3 and N = 4) in different ratios, whereN (the homologue number) is the number of square coordination pyramids in a slab. All presently known members of
the series have one of the following combinations: 33, 34,
434 and 44 with theoretical homologue numbers N = 3,
3.5, 3.67 and 4, respectively. Liveingite is the sole welldeﬁned mineral member of the series containing the 434
sequence (N = 3.67) to date (Engel & Nowacki, 1970;Moëlo et al., 2008). The last important publications concerning As-based sartorite homologues from the Lengenbach deposit are by Berlepsch et al. (2001, 2002, 2003),
Bindi et al. (2014), Makovicky & Topa (2015), Topa &Makovicky (2016), Topa et al. (2017a), Makovicky et al.
(2018) and Topa & Kolitsch (2018).
Nowacki et al. (1963) described a Pb–As–S phase with ana ~ 140 Å period, from Lengenbach, which later was denoted“rathite-IV.” Ozawa & Nowacki (1974) improved thepseudo-orthorhombic unit-cell by single-crystal ﬁlm methods to a = 138.3(4), b = 7.920(5), c = 8.470(5) Å,
b = 90.33(17)° and suggested two possible space groups,
P21 and P21/m. Ozawa & Nowacki (1974) also noted persistent twinning on {100} and mentioned the common presenceof intimately associated liveingite (as an oriented exsolution
or an oriented intergrowth). They tried to explain the reason
for the long a axis, either by means of formation of a cationordered superstructure of liveingite or by twin operations of
Takéuchi (1970). Ozawa & Tachikawa (1996) investigated
the seemingly same type of material by means of high-resolution transmission electron microscopy (HR-TEM). Basedon the study of a unique fragment about 1 lm in size (foundamong crushed grains), they suggested that the mineral is awell-ordered, distinct sartorite homologue, with the structuralsequence . . .434344343434. . . and average homologue
number N = (5  3 + 7  4)/12 = 3.583. Pring (2001)
re-investigated sartorite homologues from Lengenbach by
HR-TEM and summarized the former results on “rathite-IV.”

All these investigations drew attention to this complex
phase, but failed to make “rathite-IV” a well characterisedmineral, and motivated us to start, in 2013, a careful reinvestigation of the sartorite homologues in old and new samples
from the Lengenbach deposit.
The results obtained so far considerably improved thebasic understanding of the sartorite homologous series interms of redeﬁnition of poorly deﬁned minerals. Thus,“baumhauerite-2a” was redeﬁned as argentobaumhauerite(Topa & Makovicky, 2016) and “sartorite” was recognised
to be a family of anion-omission derivatives (Topa et al.,2017a; Makovicky et al., 2018). Furthermore, several new
species belonging to the sartorite homologous series werediscovered at Lengenbach and deﬁned: argentodufrénoysite(Topa et al., 2016a), incomsartorite (Topa et al., 2016b) anddekatriasartorite (Topa et al., 2017b).
The present paper provides the description of a phaseresembling “rathite-IV” as a new mineral species, argentoliveingite, and discusses the crystal chemistry of the liveingite group based on new EMP analyses and structure
reﬁnements of both pure and Ag-bearing liveingite.
The name argentoliveingite reﬂects the chemistry and general structural features of the new mineral expressed by thehomologue slab sequence 433, i.e. N = 3.67 (same as forliveingite), and emphasises the critical role of silver in its
crystal structure. As will be shown, it is the presence ofessential silver and the substitution mechanism 2Pb2+ ?
Ag+ + As3+ that controls the doubling of the c-axis comparedto the b-axis of liveingite and the concurrent changes in thearchitecture of the structure (a fundamentally different
sequence of N = 3 and N = 4 slabs compared to that in liveingite and “rathite-IV”). The mineral and the mineral namewere approved by the IMA-CNMNC (IMA 2016-029). Typematerial is deposited in the reference collection of the Natural
History Museum, Vienna, Austria, with catalogue number
H 1715 (original museum specimen, for details see below)
and N 9868 (polished sections of fragments taken fromH 1715), and in the reference collection of the Natural
History Museum Basel, Switzerland, with catalogue number
S83.

2. Material examined, appearance
and physical properties
Euhedral crystals and massive sulphosalt aggregates(patches in dolomite matrix) of sartorite homologues fromthe Lengenbach deposit were obtained from the collectionof the Natural History Museum, Vienna, Austria, and the
Natural History Museum, Basel, Switzerland, as well asfrom private collections of Horst Geuer (Germany), Frank
Keutsch (Germany), one of us (UK), Thomas Raber(Germany), Phillippe Roth (Switzerland) and Ralph Cannon(Germany).
The new mineral was found in an old specimen of the mineral collection of the Natural History Museum, Vienna, from
Lengenbach, Binntal, Canton Valais, Switzerland. The specimen (~55  20  30 mm) with the collection number H 1715
was acquired in 1903 as “baumhauerite” (Fig. 1a and b).

Downloaded from https://pubs.geoscienceworld.org/eurjmin/article-pdf/31/5-6/1079/4902547/ejm_31_5-6_1079_1097_topa_2890_online.pdf
by University of Arizona user

Argentoliveingite, a new homeotype of liveingite from Lengenbach1081

Fig. 1. (a) The argentoliveingite-bearing specimen H 1715 (collection of the Natural History Museum, Vienna, Austria) with original labels.
(b, c) Details of the specimen surface showing the morphology of the large prismatic crystals. (d) Fragments used for the polished section(specimen N 9868) which provided the chemistry and single-crystal data.

It is an uncommonly large, stand-alone aggregate, which has
been on display for over one century in Hall 1 of the museum(systematic display collection). We were not allowed to use
parts of the sample (Fig. 1c), but only small fragments(Fig. 1d) derived from the main, brittle body. It is worth
noting the differences in morphological features of baumhauerite (described as a new mineral by Solly, 1902) incomparison to those shown in Fig. 1c. The location in thedeposit is unknown.
A few small fragments from a further sample S83(original working name: P2375, originally characterised by
S.G. using powder X-ray diffraction) and two other polishedsections of massive sulphosalts (P01 and P01A) containing
the phase that later turned out to be argentoliveingite weremade available for investigation by one of us (S.G.) andF. Müller, Germany, respectively. Two further samples,designated E60 and E59, from the private collection of
one of us (UK) were used for chemical and structural studiesof liveingite and Ag-bearing liveingite, respectively.
The argentoliveingite-bearing specimen H 1715 forms anelongate, coarsely crystalline, massive aggregate grading
into prismatic, subparallel crystals with complex forms(Fig. 1b and c), without visual indications of twinning. In
the analysed fragments taken from H 1715 (all mounted
in sample N 9868), argentoliveingite is the most common
phase, followed by argentobaumhauerite and baumhauerite(Fig. 2). Other studied samples contain, beside argentoliveingite, members of the sartorite family, liveingite andrathite. Argentoliveingite is dark grey, opaque, with a black

streak and metallic lustre. Mohs hardness was estimated as
four, based on measured microhardness values (VHN25
range 208–225 kg mm2, mean 217 kg mm2 of 10 measurements). Argentoliveingite is brittle, without cleavage
and with conchoidal fracture. The density could not be measured because of possible admixture with baumhauerite andargentobaumhauerite (see below and Fig. 2b). It wascalculated as 5.23 g cm3 using the empirical chemical
formula and the measured single-crystal unit-cell parameters. The a:b:c ratio calculated from the unit-cell parameters
is 0.9334:1:16.290.
In reﬂected light, the colour of argentoliveingite is greyish-white, with moderate bireﬂectance in air (Table 1), nodiscernible pleochroism and moderate anisotropy. Rotation
tints vary between different shades of grey. Red internal
reﬂections were seen on thin edges or at grain boundaries.

3. Chemical data
Up to 20 separate sulphosalt grains, depending on thequantity of available material in a given sample, weremechanically extracted from the dolomite-hosted sulphosalt
aggregates or crystals and subsequently embedded in an
epoxy-mount, polished, studied in reﬂected light and examined by qualitative (backscattered-electron images andenergy-dispersive spectrometry analyses) and quantitative
wavelength-dispersive spectrometry (WDS) EMP analyses.
This procedure was separately applied to all samples.

Downloaded from https://pubs.geoscienceworld.org/eurjmin/article-pdf/31/5-6/1079/4902547/ejm_31_5-6_1079_1097_topa_2890_online.pdf
by University of Arizona user

1082

D. Topa et al.

Fig. 2. (a, b) Backscattered electron (BSE) images and corresponding (a’, b’) reﬂected-light photographs (crossed polars) of(a) homogeneous argentoliveingite grains and an aggregate of argentoliveingite associated with baumhauerite (white) and argentobaumhauerite (dark) in specimen N 9868.

Table 1. Reﬂectance values (%) for argentoliveingite in air (WTiC
standard).
k (nm)Rmin

Rmax

k (nm)

Rmin

Rmax

400
420
440
460
470
480
500
520
540
546

38.4
37.9
37.4
36.8
36.6
36.3
35.7
35.1
34.5
34.4

43.4
42.8
42..2
41.7
41.5
41.2
40.7
40.2
39.6
39.4

560
580
589
600
620
640
650
660
680
700

33.8
33.2
32.9
32.4
31.7
31.0
30.7
30.3
29.8
29.4

38.9
38.1
37.8
37.3
36.4
35.6
35.2
34.8
34.1
33.6

The reference wavelengths required by the IMA Commission on Ore
Mineralogy (COM) are given in bold.

Chemical analyses of argentoliveingite and associatedminerals were carried out using a JEOL “Hyperprobe”
JXA 8530F ﬁeld-emission gun EMP in the Central ResearchLaboratories at the Natural History Museum, Vienna,
employing JEOL and Probe for EMP analysis software(WDS mode, 25 kV, 20 nA, 2 lm beam diameter, counting
time 10 s on peak and 5 s on background positions). The
following emission lines and standards were used: AsLa,
TlLa and SKa (lorándite, TlAsS2), PbMa (galena), AgLa
(Ag metal) and SbLa (stibnite). Other elements such as
Hg, Cu and Fe, were sought but not detected. The range ofAg, Tl and Sb variations in liveingite and liveingite-related

phases (including argentoliveingite) is larger than thosemeasured by Laroussi et al. (1989) for liveingite. We foundthe presence of Ag (0.08–2.52 wt%), Tl (0.08–1.25 wt%)
and Sb (0.2–1.55 wt%).
The formula calculations for the sartorite homologue
order Ncalc, described by Makovicky & Topa (2015) and
Makovicky (2019), are designed to identify the mineralsof the family from the results of EMP investigations, andwere used here to select all point analyses representativeof liveingite and liveingite-related phases with N = 3.67.
More than 2200 point analyses with calculated homologue
number Ncalc ranging between 3.6 and 3.8, and with chargebalance (calculated from at%) ranging between 2 and +2,
in more than 300 samples, were selected and are plotted inthe (As + Sb–Tl)–Ag–(Pb + 2Tl) ternary diagram (Fig. 3), as
grey background. This representation, in which the(Tl+ + As3+)-for-2Pb2+ substitution is removed, expresses
only the (Ag+ + As3+)-for-2Pb2+ substitution.
The representative mean chemical compositions of liveingite with different degree of (Ag+ + As3+)-for-2Pb2+ substitution and argentoliveingite crystals (some used afterward
for structural studies), are presented in Table 2, whereas
individual points of each group are plotted in the ternary
diagram of Fig. 3, with the (Tl+ + As3+)-for-2Pb2+ substitution extracted.
The empirical formulae, based on 100 atoms per formula
unit (apfu), 44Me + 56S for liveingite, and 200 apfu,
88Me + 112S for argentoliveingite, as derived from theresults of the single-crystal studies, are presented in the

Downloaded from https://pubs.geoscienceworld.org/eurjmin/article-pdf/31/5-6/1079/4902547/ejm_31_5-6_1079_1097_topa_2890_online.pdf
by University of Arizona user

Argentoliveingite, a new homeotype of liveingite from Lengenbach1083

Fig. 3. Substitutional variations in argentoliveingite and associated minerals from Lengenbach in the (As + Sb–Tl)–Ag–(Pb + 2Tl) ternary
diagram (at%) with the relevant substitution lines indicated. The composition of dufrénoysite, Ag-bearing dufrénoysite andargentodufrénoysite are also indicated for comparison, but as minerals, they are not associated with the liveingite and baumhauerite
groups. Numbers 1–11 indicate the following ideal chemistries: 1 – baumhauerite: Pb24As16S36, 2 – 3 argentobaumhauerite range:(AgPb22As33S72 – Ag2Pb20As34S72), 4 – liveingite: Pb20As24S56, 5 – Ag-bearing liveingite: Ag0.5Pb19As24.5S56, 6 – phase “IL”:
AgPb18As25S56, 7 – 8 argentoliveingite range: (Ag3Pb34As51S112 – Ag4Pb32As52S112), 9 – dufrénoysite: Pb16As16S40, 10 – Ag-bearing
dufrénoysite: Ag0.5Pb15As16.5S56, 11 – argentodufrénoysite: Ag3Pb26As35S80.

Table 2. Analytical data (wt%) for liveingite, phase “IL” and argentoliveingite.
No. Mineral
d

1
2d
3
4a
5d
6
7
8e
9e

SampleLiveingite
E60
Ag-bearing liveingite
E59
Phase “IL”
P01, P01A
Argentoliveingite
S83(Ag min.)Argentoliveingite
N 9868Argentoliveingite
P01, P01A(Ag max.)
Argentoliveingite
P01, P01A(Tl max.)
Ag3Pb34As51S112–
Ag4Pb32As52S112
–

NAb

Ag

Tl

Pb

As

Sb

S

Total

chc

Ncalc

10
20
10
18

0.08(5) 0.08(6) 53.40(31) 22.78(47) 0.56(57) 22.99(28) 99.90(34) 0.7 3.70
0.95(9) 1.05(13) 49.62(34) 23.67(11) 0.52(14) 23.67(11) 100.01(43) 0.1 3.72
1.58(9) 0.35(13) 48.62(44) 24.34(20) 1.05(14) 23.84(19) 99.78(26) 0.1 3.70
2.11(10) 0.55(10) 46.41(36) 25.28(21) 1.03(9) 24.06(10) 99.44(59) 0.5 3.66

22
13

2.31(4)2.52(2)0.55(12) 46.65(26) 25.36(14) 0.83(10) 24.27(17)0.64(18) 46.34(52) 25.65(25) 0.59(13) 24.22(21)5

2.51(2)

1.25(10) 45.61(51) 25.84(36)

–
–

2.19
2.97

–
–

47.66
45.57

25.85
26.78

a

0.51(6)––99.97(13)99.96(24)24.32(12) 100.03(37)
24.30
24.69

100.00100.000.2 3.70
0.4 3.74
0.0

3.76

0.0
0.0

3.67
3.67

Sample studied by power XRD.
Number of analyses.
cCharge balance (R cation charges – R anion charges) based on at%. Ncalc is deﬁned in the text.
dStudied by single-crystal XRD.
e
Calculated chemistry for the point #7 and #8 in the ternary plot of Fig. 3.
The following empirical formulae are calculated on the basis of the crystal-structure determinations: 100 independent sites, 44Me + 56S forliveingite and Ag-bearing liveingite; 200 independent sites, 88Me + 112S for argentoliveingite (all with Z = 2). The phase “IL” is assumed tohave approximate liveingite metrics. 1) Ag0.06Tl0.03Pb20.06As23.67Sb0.36S55.82; 2) Ag0.67Tl0.39Pb18.15As24.48Sb0.32S55.97; 3) Ag1.11Tl0.13
Pb17.67As24.46Sb0.65S55.98; 4) Ag2.91Tl0.40Pb33.37As50.28Sb1.25S111.79; 5) Ag3.17Tl0.40Pb33.31As50.08Sb1.01S112.02; 6) Ag3.45Tl0.46Pb32.07
As50.62Sb0.72S111.68; 7) Ag3.43Tl0.90Pb32.44As50.83Sb0.72S111.78.
b

Downloaded from https://pubs.geoscienceworld.org/eurjmin/article-pdf/31/5-6/1079/4902547/ejm_31_5-6_1079_1097_topa_2890_online.pdf
by University of Arizona user

1084

D. Topa et al.

Fig. 4. Inhomogeneous grains of argentoliveingite from the specimen S83 previously studied by one of us (S.G.) using power X-ray
diffraction (Table S3). (a, b) BSE images of a ﬁne intergrowth of liveingite (bright) and argentoliveingite (dark). (a’, b’) Reﬂected-light
photographs (crossed polarisers); note the ﬁne twin domains.

footnote of Table 2. The empirical formula of liveingite(point no. 1 in Table 2 and point no. 4 in Fig. 3), only
slightly affected by substitution, is Ag0.07Tl0.03Pb20.06(As23.67Sb0.36)R24.03S58.82, very close to the theoretical oneof Pb20As24S56, whereas the empirical formula of Ag-bearing liveingite (point no. 2 in Table 2 and point no. 5 inFig. 3) is Ag0.67Tl0.39Pb18.15(As24.48Sb0.32)R24.8S55.97. The
empirical formula of argentoliveingite (point no. 5 inTable 2) is Ag3.17Tl0.40Pb33.31(As50.08Sb1.01)R51.09S112.02.
The simpliﬁed formula Ag3+xPb362xAs51+xS112 is derived
from the doubled ideal liveingite formula, Pb40As48S112,
by the substitution 2Pb2+ ? Ag+ + As3+, where the experimental factor x is in the range 0 to ~0.5 (Table 2 and Fig. 3)
and never reaches the theoretical value of four (point no. 8
in Fig. 3). Minor Tl and Sb substitutions are not taken into
account for the sake of simplicity.
Figure 4 and analysis no. 4 (with lowest Ag content,
Table 2) describe the chemical and optical inhomogeneityof the argentoliveingite sample S83, characterised previously by one of us (S.G) using X-ray powder diffraction.
The ﬁne twin lamellae and domains recognisable inFig. 4a’ and b’ are tentatively explained by twinning bypseudo-merohedry due to the pseudo-orthorhombic metricsof the unit cell.

The BSE images of samples P01 and P01A in Fig. 5
show large areas (several mm2) of mixed exsolution
lamellae between Ag-bearing liveingite (bright grey phase)and a possibly new species, still under investigation, here
designated “IL” (medium grey phase) on the one side andbetween phase “IL” and argentoliveingite (dark grey phase)on the other side. The empirical formula of phase “IL”
(point no. 3 in Table 2 and point no. 6 in Fig. 3), with
Ncalc = 3.7, is Ag1.11Tl0.13Pb17.67As24.46Sb0.65S55.98 (basedon 100 apfu) and indicates its membership of the liveingite
group. Note the gaps between the chemical compositions of
Ag-bearing liveingite, phase “IL” and argentoliveingite in
the ternary plot of Fig. 3, when all chemical-analytical data
are considered. The meaning and importance of this observation will be discussed later, in connection with the crystal
structures and crystal chemistry of the liveingite-groupmembers.

4. Crystallography and crystal structures
Single-crystal studies were performed on argentoliveingite
fragments, mechanically extracted after quantitative electron
microprobe analysis, from sample N 9868 (argentoliveingite

Downloaded from https://pubs.geoscienceworld.org/eurjmin/article-pdf/31/5-6/1079/4902547/ejm_31_5-6_1079_1097_topa_2890_online.pdf
by University of Arizona user

Argentoliveingite, a new homeotype of liveingite from Lengenbach1085

Fig. 5. Backscattered electron images of large areas of samples (a) PO1 and (c) PO1A and (b, d) enlarged marked regions, showing
complex three-phase aggregates (bright, Ag-bearing liveingite; medium grey, phase “IL”; dark grey, argentoliveingite). Note thesimultaneous overall (and sometimes mixed) presence of two different exsolution pairs: Ag-bearing liveingite with phase “IL” andargentoliveingite with phase “IL”.

type material, analyses no. 5 in Table 2), on liveingite fromsample E60 (analyses no. 1 in Table 2) and on Ag-bearing
liveingite from sample E59 (analyses no. 2 in Table 2). So
far we were unable to obtain structural information for phase“IL”, but the search for suitable fragments is still ongoing.
Single-crystal X-ray diffraction data were collected on a
Bruker SMART APEX CCD-three-circle-diffractometer at
the University of Salzburg. Intensity data were collectedwith graphite-monochromatised MoKa X-radiation (50 kV,
30 mA) using the SMART software (Bruker AXS,
1998a). The crystal-to-detector distance was set to 80 mm
for liveingite and Ag-bearing liveingite (due to the long70 Å axis) and to 140 mm for argentoliveingite. The detector was positioned at 28° 2h using an x-scan mode strategy at four different / positions (0°, 90°, 180° and 270°).
In total, 630 frames with Dx = 0.3° were acquired for eachrun, with an 80 s/frame and 120 s/frame time of acquisition
for liveingite and Ag-bearing liveingite, and argentoliveingite, respectively. The intensity data were integrated using
the SAINT software (Bruker AXS, 1998b). The semiempirical absorption correction based on pseudo x scans
was done with XPREP software (Bruker AXS, 1997). The

centrosymmetric space group P1 proposed by XPREP waschosen for argentoliveingite and the chiral (absence of asymmetry centre) space group P21 for liveingite andAg-bearing liveingite, in accordance with their systematic
extinctions and intensity statistics.
The structure of argentoliveingite was solved by direct
methods (SHELXS-97; Sheldrick, 2008), which revealed
most of the atom positions. In subsequent cycles of the reﬁnement (SHELXL-2014/6), remaining atom positions werededuced from difference-Fourier syntheses. For liveingite
and Ag-bearing liveingite, the crystal-structure model andatom-site labelling of Engel & Nowacki (1970) were usedas starting points for the reﬁnements using SHELXL-2014/6.
The single-crystal diffraction data of argentoliveingite
indicate that it has a triclinic cell, space group P
1, witha = 7.905(2), b = 8.469(2), c = 137.96(4) Å, a =89.592(2), b = 88.969(2), c = 89.893(2)°, V = 9235(5) Å3,
and Z = 2. The unusual value of the c axis (~138 Å) is thelargest presently known unit-cell parameter for a sulphosalt
mineral. In agreement with previous investigations, liveingite
is monoclinic, space group P21, a = 7.9039(5),b = 70.969(5), c = 8.3640(5) Å, b = 90.147(1)°,

Downloaded from https://pubs.geoscienceworld.org/eurjmin/article-pdf/31/5-6/1079/4902547/ejm_31_5-6_1079_1097_topa_2890_online.pdf
by University of Arizona user

1086

D. Topa et al.

V = 4691.6(5) Å3. Ag-bearing liveingite has a slightly shorterb axis and a lower unit-cell volume: a = 7.9113(4),b = 70.355(4), c = 8.3708(4), b = 90.115(1)°,V = 4659.2(49) Å3.
Occupancies of several mixed and split sites wereassigned based on geometric features and crystal-chemical
considerations. Details on data collection and results of thestructure reﬁnement of argentoliveingite, Ag-bearing liveingite and liveingite are given in Table 3, the fractional atomic
coordinates, anisotropic atomic displacement parameters arecompiled in Tables 4 and 5, while Table S1 in the Supplementary Material (linked to this article and freely available
online on the GSW website of the journal: https://pubs.
geoscienceworld.org/eurjmin) gives selected bond lengths
for argentoliveingite. The full set of data is accessible via
the CIF ﬁles also included in the Supplementary Material.
Unit-cell parameters, space group, atom positions, site
occupancy factors and isotropic displacement factors fromthe crystal-structure determination of argentoliveingite wereused to calculate its theoretic X-ray powder diffraction
pattern (PowderCell 2.3 software, Kraus & Nolze, 1999),
presented in Table S2. Experimental powder diffraction data
for sample S83 (Basel) was indexed with the unit-cellparameters of argentoliveingite and the results are presented
in Table S3 in comparison to the calculated pattern.
4.1. Structure and crystal-chemistry of liveingite
and Ag-bearing liveingite
In agreement with its structure scheme, as a sartorite homologue N1,2,3 = 434 = 3.67, the crystal structure of liveingite
contains 44 cation sites and 56 sulfur sites (Table 4 andFigs. 6 and 7a and b). The liveingite structure model ofEngel & Nowacki (1970) consists of 17 fully occupied Pb
sites, 23 fully occupied As sites, one mixed (Pb,As) position(Pb0.75As0.25), one partially occupied Pb position (Pb0.75),
two partially occupied As positions (each with occupancy
As0.50) and 56 sulfur sites. The resulting structural formulacan be written as Pb18.5As25.25S56 (for Z = 2), is chargeunbalanced (+0.75) and relatively far away from the ideal
theoretical formula Pb20As24S56 (Z = 2) of Makovicky(1985) and Laroussi et al. (1989).
In contrast to the model of Engel & Nowacki (1970),
we found 19 fully occupied Pb sites, 22 fully occupied As
sites and three (As,Pb) mixed sites: As4, As5 and As21,
the latter of which is split (Table 4). The structural formula,
Pb20.12As23.88S56, is only slightly charge-unbalanced(+0.12) and very close to the ideal theoretical formula.
The small amounts of Ag (0.06 apfu), Tl (0.03 apfu) andSb (0.36 apfu) were not localised among the 44 cation sites.
The ﬁnal reﬁnement for liveingite yielded R1 = 0.0492 for
12,457 reﬂections with Fo > 4r(Fo) and 0.0560 for all
13,453 data. Calculated X-ray powder diffraction data
(Tables S4 and S5) and tables listing bond lengths(Tables S6 and S7) for the two liveingite structures arefreely available online as part of the Supplementary
Material.
The details of the liveingite structure will be describedaccording to the slabs deﬁned for sartorite homologues by

Makovicky (1985, 1997a and b). These are slabs of structure
based on a SnS-like archetype, and are of different widths(three and four coordination polyhedra wide), primarily
formed by As-centred coordination polyhedra (CN = 5–7)
with a crankshaft arrangement of the short As–S bonds.
They terminate in a zig-zag layer of Pb tricapped trigonal
coordination prisms (CN = 9) at both their margins. Eachslab consists of double-ribbons (1D fragments of tightlybonded double-layers), the walls of which contain crankshaft chains of (predominantly) As-centred coordination
polyhedra interconnected via common S atoms.
The crystal structure of liveingite (as well as that of
Ag-bearing liveingite) contains one type of N = 3 slab built
from As-centred coordination polyhedra with participationof Pb. It alternates regularly with two slightly different
N = 4 slabs, R1 and R2. The crystal structure of liveingite,
as described by Engel & Nowacki (1970) and Makovicky(1985), consists of an alternation sequence . . .434434. . .
of two types of building ribbons, N = 3 and N = 4(Fig. 7a and b). The last three ribbons in the sequence(434) are related to the ﬁrst three ones by inversion, mirror
and translation operations, e.g. (434)", (434); using Pring’s(2001) notation. The cation conﬁgurations in the asymmetricN = 3 ribbon (Pb5As7S16, charge 1, neglecting long Pb–S
bonds) of the liveingite structure (Fig. 8c) are identical tothose of the N = 3 ribbon in baumhauerite (Fig. 8a) andargentobaumhauerite (Topa & Makovicky, 2016). Thisribbon has two asymmetric conﬁgurations in its surface
layers L31 and L32, formed by an alternation, along the
8.2 Å axis, of cation-centred polyhedra of (Pb13, Pb14) –(As12, As13) – (As11, As10) for L1 and of (Pb10,
Pb11) – (Pb12, As14) – (As15, As16) for L2, respectively(Fig. 8c).
The cation conﬁguration of the two independent,
asymmetric N = 4 ribbons (R1 and R2) of the liveingite structure (Fig. 8c) is similar to that of the N = 4 ribbon in baumhauerite (Fig. 8a). As Engel & Nowacki (1970) and Pring(2001) mentioned, although these ribbons are topologically
identical, their chemistries differ. We found (Table 4 andFig. 8c) the occupancies of the mixed sites As4 and As5
in R1 and As21 in R2 to be different compared to those of
the N = 4 ribbon in baumhauerite (Fig. 8a), and to thoseof Engel & Nowacki (1970). As depicted in Fig. 8b, thesequence of ideal theoretical liveingite (with chargeunbalanced formula Pb19As25S56 compared to Pb20As24S56)
with . . .434. . ., made up of two baumhauerite-type N = 4
ribbons, cannot exist in this form due to positive
overcharging (+1) of the (434) block.
In order to keep the sequence (434) electrostaticallyneutral, the positive charge of each ribbon (Pb7As9S20,
charge +1) is reduced to +0.3 for R1 and +0.6 for R2, by“pumping” small amounts of Pb in the central As sites(As4, As5 and As21) of the ribbons. In other words, thesimpliﬁed liveingite formula, Pb20As24S56, with 44 cationsites, does not mean that 20 Pb and 24 As fully occupied
sites are present. This mechanism produces different (andnot equal) chemistries for the two ribbons, approximately
Pb7.7As8.3S20 and Pb7.4As8.6S20 for R1 and R2, respectively,
perhaps because of partly different structural environments.

Downloaded from https://pubs.geoscienceworld.org/eurjmin/article-pdf/31/5-6/1079/4902547/ejm_31_5-6_1079_1097_topa_2890_online.pdf
by University of Arizona user

Argentoliveingite, a new homeotype of liveingite from Lengenbach

1087

Table 3. Crystal data and summary of parameters describing data collection and reﬁnement for argentoliveingite, Ag-bearing liveingite andliveingite.

Crystal data
Chemical formula
Formula weight
Crystal system
Space group
Dx (g cm3)
No. of reﬂections for cell params.
Unit-cell parameters
a (Å)
b (Å)
c (Å)
a (Å)
b (Å)
c (Å)
V (Å3)Zl (mm1)
Crystal size (mm)Data collection
Tmin, Tmax
No. of measured reﬂections
No. of independent reﬂections
No. of observed reﬂections
Criterion for observed reﬂections
Rint (%), Rsigma (%)
hmax (o)Range of h, k, lReﬁnement
Reﬁnement on F 2o
R[Fo > 4r(Fo)]wR(F 2o )S (GooF)
No. of parameters reﬁned
Weighting scheme(D/r)max
Dqmax (e/Å3)
Dqmin (e/Å3)
Source of atomic scattering factors

Argentoliveingite

Ag-bearing liveingite

Liveingite

Ag3.17Tl0.4Pb33.31As50.08
Sb1.01S112.02
29,096
TriclinicP1 (no. 2)
5.27
6618

Ag0.67Tl0.39Pb18.15As24.48
Sb0.32S55.97
15,162
Monoclinic
P21 (no. 4)
5.40
9819

Ag0.06Tl0.03Pb20.06As23.67
Sb0.36S55.82
15,405
Monoclinic
P21 (no. 4)
5.49
8405

7.905(2)8.469(2)137.96(4)89.592(2)88.969(2)89.892(2)9235(5)2
40.00
0.06  0.06  0.07

7.9113(4)70.355(4)8.3708(4)9090.115(1)904659.2(49)2
43.46
0.05  0.07  0.13

7.9039(5)70.969(5)8.3640(5)9090.147(1)904691.6(5)2
44.90
0.06  0.08  0.09

0.116, 0.521
28,046
16,432
13,0880.111, 0.425
40,032
13,248
11,974
I > 2r(I)11.38, 8.83
23.26
8  h  8, 78  k  78,
9  l  90.075, 0.621
40,654
13,453
12,457

8.86, 9.49
21.61
8  h  8, 8  k  8,
141  l  142

12.87, 9.27
23.30
8  h  8, 78  k  78,
9  l  90.1406
0.06410.04920.16000.0737
0.0560
1.111
1.051
1.050
1192
907
914
a = 0.0144, b = 4790
a = 0.0673, b = 171
a = 0.048, b = 67.1
w = 1/[r2(F 2o ) + (aP)2 + bP],
where P = (F 2o + 2F 2c )/3
0.001
0.001
0.003
3.3 (0.6 Å from As38)
3.8 (0.9 Å from Ag6)
2.7 (0.9 Å from Pb3)
3.4 (0.95 Å from Pb8)
3.1 (0.3 Å from Pb18)
2.9 (1.9 Å from Pb2)
International Tables for X-Ray Crystallography, Vol. C (1992) (Tables 4.2.6.8 and 6.1.1.4)

The ﬁnal reﬁnement for Ag-bearing liveingite yielded
R1 = 0.0641 for 11,974 reﬂections with Fo > 4r(Fo) and
0.0737 for all 13,248 data. The volume of its unit cell,V = 4659.2(49) Å3, is slightly smaller than that of liveingite,
V = 4691.6(5) Å3, mainly due to its shorter b axis (Table 3),
because of the two types of substitutions mentioned above.
The slight difference between the structural formulaAg0.54Pb18.15As24.90Sb0.36S56 (Table 4) and the empiricalformula Ag0.67Tl0.39Pb18.15As24.48Sb0.32S55.97 (Table 2)
reﬂects the difﬁculties in ﬁnding the minor Tl substituent(0.39 among 44 cation sites) in the reﬁned structure model,
as well as the correct amounts and locations of Ag and Sb.
The latter two are clearly located in the R1 ribbon, however.
The ﬁnal compromise results are shown in Table 4, Fig. 7b
and partially in Fig. 8d.

4.2. Structure and crystal chemistryof argentoliveingite
The very large crystal-detector distance (140 mm) and necessary acquisition strategy are responsible for a lower number of unique (independent) reﬂections (16,432) comparedto the theoretical (22,647) ones and restrict the Bragg reﬂections to a minimum resolution value of 0.9 Å. Nonetheless,the integration of intensities resulted in good Rint and Rsigma
values.
The basic structural model revealed 20 Pb and 15 As
sites, representing only 40% of the cation positions and only
18% of all 200 independent sites. The positions of remaining cations and anions were deduced from differenceFourier syntheses by selecting from among the strongest

Downloaded from https://pubs.geoscienceworld.org/eurjmin/article-pdf/31/5-6/1079/4902547/ejm_31_5-6_1079_1097_topa_2890_online.pdf
by University of Arizona userDownloaded from https://pubs.geoscienceworld.org/eurjmin/article-pdf/31/5-6/1079/4902547/ejm_31_5-6_1079_1097_topa_2890_online.pdf
by University of Arizona user

a

As
As

As
As

Pb

Pb
As

x

y

z

Liveingite (Engel & Nowacki, 1970)
Site Atom

sof

x

y

z

Liveingite (this study)
Site

Atom

sof

x

y

z

Ag-bearing liveingite (this study)

0.21267(39) 0.99870(4) 0.13554(32) Pb1
Pb
0.2313(2) 0.99925(3) 0.13830(20) Pb1
Pb
0.2094(3) 0.99882(4) 0.1351(3)0.20697(30) 0.99939(3) 0.63182(25) Pb2
Pb
0.2162(2) 0.00039(2) 0.63545(18) Pb2
Pb
0.2042(3) 0.99972(3) 0.6322(3)0.71726(38) 0.96622(4) 0.11552(33) Pb3
Pb0.7348(2) 0.96605(3) 0.11260(19) Pb3
Pb
0.7134(4) 0.96674(4) 0.1165(3)0.70593(29) 0.96560(3) 0.62092(26) Pb4
Pb
0.7153(2) 0.96461(2) 0.61841(18) Pb4
Pb
0.7023(3) 0.96582(4) 0.6209(3)0.86370(39) 0.04605(3) 0.14054(30) Pb5
Pb0.8738(2) 0.04696(2) 0.14333(18) Pb5 Pb,Sba 0.70,0.30(2) 0.8638(4) 0.04610(4) 0.1405(3)0.75 0.34847(37) 0.06132(4) 0.90667(33) Pb6
Pb
0.3516(2) 0.06019(3) 0.91222(19) Me6 Ag,Pba 0.54,0.46(2) 0.3451(3) 0.06122(5) 0.9074(3)0.25 0.3069(28) 0.0539(3) 0.9431(27)0.00506(27) 0.10004(2) 0.39434(23) Pb7
Pb
0.0033(2) 0.10020(2) 0.39460(17) Pb7
Pb
0.0047(3) 0.09987(3) 0.3942(2)0.68004(34) 0.14791(3) 0.36401(29) Pb8
Pb0.6769(2) 0.14810(3) 0.36900(20) Pb8
Pb
0.6798(3) 0.14810(3) 0.3623(3)0.65736(27) 0.14731(3) 0.87004(24) Pb9
Pb0.6553(2) 0.14772(2) 0.87463(18) Pb9
Pb0.6587(3) 0.14742(3) 0.8684(2)0.16632(35) 0.18083(3) 0.37090(27) Pb10 Pb
0.1634(2) 0.18126(3) 0.37526(19) Pb10
Pb
0.1676(3) 0.18079(4) 0.3687(3)0.16593(28) 0.18065(3) 0.86535(24) Pb11 Pb
0.1631(2) 0.18152(2) 0.86949(18) Pb11
Pb
0.1672(3) 0.18073(3) 0.8640(2)0.51024(25) 0.22623(2) 0.34883(23) Pb12 Pb
0.5079(2) 0.22632(2) 0.35402(17) Pb12
Pb0.5102(3) 0.22638(3) 0.3487(2)0.35043(34) 0.28494(3) 0.10298(29) Pb13 Pb
0.3518(2) 0.28513(3) 0.10670(20) Pb13
Pb
0.3481(3) 0.28517(4) 0.1026(3)0.32799(32) 0.28325(3) 0.61251(26) Pb14 Pb
0.3274(2) 0.28288(2) 0.61606(19) Pb14
Pb
0.3290(3) 0.28359(3) 0.6121(3)0.83312(30) 0.31385(3) 0.11268(25) Pb15 Pb
0.8326(2) 0.31401(2) 0.11671(18) Pb15
Pb0.8336(3) 0.31424(3) 0.1117(3)0.84751(27) 0.31639(3) 0.61231(24) Pb16 Pb
0.8483(2) 0.31636(2) 0.61653(17) Pb16
Pb
0.8471(3) 0.31660(3) 0.6114(2)0.50129(26) 0.36505(3) 0.14801(23) Pb17 Pb
0.5004(2) 0.36527(2) 0.14844(17) Pb17
Pb0.5014(3) 0.36538(3) 0.1467(2)0.75 0.15803(31) 0.40321(3) 0.65297(28) Pb18 Pb
0.1525(2) 0.40386(3) 0.65977(19) Pb18
Pb
0.1595(3) 0.40390(4) 0.6522(3)0.63697(33) 0.41937(3) 0.89127(28) Pb19 Pb
0.6288(2) 0.41907(2) 0.89467(18) Pb19 Pb,As 0.70,0.30(2) 0.6378(3) 0.41961(4) 0.8903(3)0.64064(69) 0.01897(8) 0.43689(66) As1 As
0.6513(4) 0.01783(5) 0.4378(4)As1As
0.6367(6) 0.01844(8) 0.4363(6)0.62114(76) 0.01523(8) 0.88474(63) As2 As
0.6395(5) 0.01399(5) 0.8857(4)As2As
0.6176(7) 0.01472(8) 0.8849(6)0.30960(86) 0.05150(8) 0.37518(73) As3 As
0.3236(5) 0.05007(6) 0.3737(4)As3As
0.3044(7) 0.05072(8) 0.3750(7)0.9394(11) 0.05002(9) 0.67066(91) As4 As,Pb 0.72,0.28(1) 0.9274(5) 0.04932(5) 0.6673(4)As4 As,Pb 0.81,0.19(2) 0.9334(8) 0.04914(9) 0.6678(8)0.5 0.9754(19) 0.0917(2) 0.8925(18) As5 As,Pb 0.58,0.42(1) 0.9725(4) 0.09509(4) 0.9038(3)As5 As,Pb 0.84,0.16(2) 0.9545(10) 0.09318(11) 0.9105(9)0.5 0.9420(16) 0.0960(2) 0.9212(15)0.57092(73) 0.09101(9) 0.20349(65) As6 As
0.5676(5) 0.09119(6) 0.2078(4)As6As
0.5697(6) 0.09010(8) 0.2013(6)0.57672(70) 0.09647(7) 0.61732(57) As7 As
0.5700(4) 0.09645(5) 0.6224(4)As7As
0.5776(6) 0.09564(7) 0.6169(6)0.25499(67) 0.13208(7) 0.12863(59) As8 As
0.2481(5) 0.13205(5) 0.1322(4)As8As
0.2555(7) 0.13100(7) 0.1287(6)0.22977(68) 0.12836(7) 0.68850(59) As9 As
0.2260(4) 0.12858(5) 0.6921(4)As9As
0.2305(6) 0.12750(7) 0.6871(6)0.73235(68) 0.19920(7) 0.06493(61) As10 As
0.7303(5) 0.19858(5) 0.0690(4)As10 As
0.7343(6) 0.19852(7) 0.0658(6)0.74424(70) 0.19563(7) 0.61748(58) As11 As
0.7416(5) 0.19501(5) 0.6213(4)As11 As
0.7460(6) 0.19479(7) 0.6163(6)0.07062(65) 0.23082(6) 0.13223(58) As12 As
0.0677(4) 0.23007(5) 0.1363(4)As12 As
0.0703(6) 0.23009(7) 0.1311(6)0.08231(83) 0.23550(8) 0.56491(80) As13 As
0.0789(5) 0.23486(6) 0.5700(5)As13 As
0.0815(7) 0.23471(8) 0.5662(8)0.44308(70) 0.23633(7) 0.86587(61) As14 As
0.4421(5) 0.23559(6) 0.8709(4)As14 As
0.4413(7) 0.23569(8) 0.8633(6)0.7724(7) 0.27047(7) 0.36026(59) As15 As
0.7719(5) 0.26961(6) 0.3642(4)As15 As
0.7701(7) 0.26963(7) 0.3586(6)0.77879(75) 0.26679(8) 0.83431(84) As16 As
0.7793(5) 0.26573(6) 0.8434(5)As16 As
0.7784(7) 0.26593(8) 0.8363(8)0.27868(65) 0.33839(7) 0.43324(56) As17 As
0.2788(4) 0.33692(5) 0.4377(4)As17 As
0.2768(6) 0.33777(7) 0.4323(6)0.25038(69) 0.33443(7) 0.87208(59) As18 As
0.2519(5) 0.33314(5) 0.8764(4)As18 As
0.2501(6) 0.33368(7) 0.8720(6)0.92834(69) 0.37000(7) 0.36487(61) As19 As
0.9319(5) 0.36901(5) 0.3679(4)As19 As
0.9286(6) 0.36953(8) 0.3633(6)0.93289(73) 0.37709(9) 0.95422(69) As20 As
0.9331(5) 0.37564(6) 0.9580(4)As20 As
0.9333(6) 0.37637(8) 0.9516(6)0.55690(78) 0.37151(9) 0.66858(74) As21 As
0.58(1) 0.554(3) 0.3731(3) 0.681(3)As21 As
0.5573(7) 0.37086(9) 0.6665(7)0.5 0.5657(15) 0.4146(2) 0.4390(14)Pb
0.42(1) 0.534(2) 0.3684(1) 0.649(1)0.5 0.5403(15) 0.4170(2) 0.4112(14) As22 As
0.5553(5) 0.41471(6) 0.4281(5)As22 As
0.5580(8) 0.41522(9) 0.4249(8)0.18893(78) 0.41578(8) 0.12134(65) As23 As
0.1803(5) 0.41545(5) 0.1200(4)As23 As
0.1922(7) 0.41490(8) 0.1202(6)0.86002(67) 0.44799(7) 0.18338(62) As24 As
0.8490(4) 0.44719(5) 0.1860(4)As24 As
0.8624(6) 0.44722(7) 0.1818(6)0.87804(74) 0.45197(7) 0.62938(62) As25 As
0.8624(5) 0.45094(5) 0.6316(4)As25 As
0.8808(7) 0.45101(8) 0.6298(6)Atom sof

Tentative assignment.

Pb1
Pb2
Pb3
Pb4
Pb5
Pb6
As4
Pb7
Pb8
Pb9
Pb10
Pb11
Pb12
Pb13
Pb14
Pb15
Pb16
Pb17
Pb18
Pb19
As1
As2
As3
As5
As6a
As6b
As7
As8
As9
As10
As11
As12
As13
As14
As15
As16
As17
As18
As19
As20
As21
As22
As23a
As23b
As24
As25
As26

Site

Table 4. Comparison of atom fractional coordinates and site occupancy factors (sof) in liveingite of Engel & Nowacki (1970) and present study (main differences in bold).

1088
D. Topa et al.

Argentoliveingite, a new homeotype of liveingite from Lengenbach

1089

Table 5. Coordinates, occupancy factors and displacement parameters (Å2) of atoms in argentoliveingite.
Site

Atom

sof

a

b

c

Ueq

Atom

a

Pb1
Pb2a
Pb3
Pb4
Pb5
Pb6
Pb7
Pb8
Pb9
Pb10
Pb11
Pb12
Pb13
Pb14
Pb15
Pb16
Pb17
Pb18
Pb19
Pb20
Pb21
Pb22
Pb23
Pb24
Pb25
Pb26
Pb27
Pb28
Pb29
Pb30a
Pb31
Pb32
Ag1
Ag2
Ag3
Ag4b
As1
As2
As3
As4
As5
As6
As7
As8c
As9
As10
As11
As12
As13
As14
As15
As16
As17
As18
As19
As20
As21
As22
As23
As24
As25
As26

Pb
Pb
Pb
Pb
Pb
Pb
Pb
Pb
Pb
Pb
Pb
Pb
Pb
Pb
Pb
Pb
Pb
Pb
Pb
Pb
Pb
Pb
Pb
Pb,As
Pb
Pb
Pb,As
Pb
Pb
Pb
Pb
Pb
Ag,Pb
Ag
Ag,As
Ag
As,Pb
As,Pb
As,Pb
As,Pb
As
As
As
As
As
As
As
As
As
As
As
As
As
As
As
As
As
As
As
As
As
As

1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
0.65(4),0.35
1
10.65(4),0.35
1
1
1
1
1
0.86(5),0.14
10.8(3),0.2
0.69(7)0.87(5),0.13
0.78(5),0.22
0.67(5),0.33
0.75(5),0.25
1
1
1
0.97(10)
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1

0.0878(3)0.2675(8)0.3790(3)0.4325(3)0.2594(3)0.2589(4)0.2910(3)0.2049(3)0.1457(3)0.2343(4)0.1919(4)0.4760(4)0.2953(4)0.0422(4)0.4823(4)0.0206(5)0.0205(4)0.3536(4)0.4798(5)0.0171(5)0.2100(5)0.4576(5)0.2940(5)0.1216(5)0.3080(6)0.0664(7)0.4151(6)0.2077(6)0.2387(7)0.2364(9)0.2636(7)0.2361(3)0.3258(8)0.1732(8)0.0451(18)0.006(2)0.2316(13)0.4442(11)0.0214(10)0.4935(9)0.3166(15)0.3686(16)0.1820(15)0.478(2)0.1120(12)0.3369(7)0.3234(7)0.3701(7)0.1806(8)0.2816(8)0.1163(7)0.2865(9)0.4028(9)0.1079(10)0.0561(10)0.4065(9)0.2128(11)0.2189(10)0.3990(11)0.1285(10)0.0923(11)0.1231(10)0.6328(3)0.3667(7)0.8951(3)0.3684(3)0.8676(3)0.3700(3)0.6029(3)0.3988(3)0.0858(3)0.6354(3)0.8906(4)0.3420(3)0.1013(4)0.6561(3)0.8514(4)0.1732(4)0.6517(4)0.9103(4)0.8328(5)0.1431(4)0.3933(5)0.3490(4)0.6061(5)0.1063(5)0.1117(5)0.6287(5)0.3678(6)0.8930(6)0.1320(6)0.6315(7)0.8686(6)0.1333(3)0.1461(7)0.8517(6)0.6224(14)0.149(2)0.3820(12)0.3796(11)0.1157(10)0.8503(9)0.0934(16)0.5736(18)0.6733(15)0.8890(17)0.6454(11)0.6069(7)0.3281(7)0.7908(7)0.9047(9)0.1352(7)0.1438(7)0.7145(9)0.0977(7)0.8444(11)0.1057(9)0.5786(8)0.2915(11)0.8694(10)0.1603(11)0.2014(10)0.4179(14)0.3951(9)0.01286(2)0.44594(5)0.10242(2)0.92349(2)0.96346(2)0.96382(2)0.87384(2)0.14258(2)0.83392(2)0.05333(2)0.14271(2)0.78864(2)0.87419(2)0.19540(2)0.78997(2)0.19510(2)0.71333(2)0.66774(3)0.30290(3)0.71195(2)0.62766(3)0.30270(2)0.35579(3)0.39634(3)0.35557(3)0.57766(4)0.48690(5)0.62725(4)0.53719(4)0.53675(5)0.44634(4)0.05285(2)0.73732(4)0.76457(4)0.3976(1)0.5786(2)0.76240(9)0.1008(1)0.01161(8)0.92227(8)0.59878(9)0.4175(1)0.4732(1)0.4882(2)0.65199(6)0.98912(4)0.02648(4)0.84788(4)0.90261(5)0.16805(4)0.11778(4)0.17048(4)0.81187(4)0.22368(5)0.25906(5)0.81380(5)0.32796(6)0.33016(6)0.27440(6)0.65361(6)0.68800(6)0.22152(5)0.0179(6)0.1018(18)0.0200(6)0.0193(6)0.0172(6)0.0352(8)0.0214(6)0.0250(7)0.0190(6)0.0341(8)0.0394(8)0.0334(7)0.0400(9)0.0348(8)0.0337(7)0.0427(8)0.0442(8)0.0479(9)0.0599(10)0.0472(9)0.0577(10)0.0467(9)0.0558(10)0.045(3)0.0691(12)0.0801(13)0.066(3)0.0823(14)0.0889(15)0.1072(19)0.0862(14)0.0176(6)0.048(4)0.0348(15)0.121(9)0.111(12)0.087(7)0.094(7)0.091(6)0.079(6)0.078(3)0.089(4)0.076(3)0.136(14)0.048(2)0.0097(13)0.0079(13)0.0124(14)0.0241(16)0.0139(14)0.0084(13)0.0237(16)0.0201(16)0.039(2)0.0303(18)0.0266(16)0.044(2)0.0377(19)0.044(2)0.039(2)0.058(3)0.0284(17)

S1
S2
S3
S4
S5
S6
S7
S8
S9
S10
S11
S12
S13
S14
S15
S16
S17
S18
S19
S20
S21
S22
S23
S24
S25
S26
S27
S28
S29
S30
S31
S32
S33
S34
S35
S36
S37
S38
S39
S40
S41
S42
S43
S44
S45
S46
S47
S48
S49
S50
S51
S52
S53
S54
S55
S56
S57
S58
S59
S60
S61
S62

0.409(2)0.488(2)0.188(2)0.371(2)0.129(2)0.287(2)0.075(2)0.288(2)0.342(2)0.490(2)0.165(2)0.218(2)0.043(2)0.035(2)0.049(2)0.201(2)0.317(2)0.162(2)0.441(2)0.338(2)0.432(2)0.011(2)0.066(2)0.491(2)0.410(3)0.480(2)0.261(2)0.459(2)0.464(2)0.239(3)0.156(2)0.217(2)0.350(2)0.237(2)0.211(2)0.294(2)0.291(3)0.255(3)0.019(3)0.398(3)0.356(2)0.002(2)0.166(2)0.322(2)0.012(2)0.241(2)0.249(2)0.017(2)0.255(2)0.053(2)0.288(2)0.114(2)0.110(2)0.144(3)0.318(4)0.054(2)0.292(5)0.416(2)0.270(3)0.055(2)0.077(3)0.247(2)Downloaded from https://pubs.geoscienceworld.org/eurjmin/article-pdf/31/5-6/1079/4902547/ejm_31_5-6_1079_1097_topa_2890_online.pdf
by University of Arizona user

b

c

Uiso

0.346(2)0.8893(1) 0.012(3)0.890(2)0.0420(1) 0.013(3)0.327(2)0.0014(1) 0.013(3)0.871(2)0.8906(1) 0.015(3)0.608(2)0.9785(1) 0.006(3)0.361(2)0.1211(1) 0.017(4)0.131(2)0.1569(1) 0.017(4)0.589(2)0.0906(1) 0.015(3)0.836(2)0.9423(1) 0.011(3)0.406(2)0.9831(1) 0.007(3)0.097(2)0.0317(1) 0.007(3)0.566(2)0.8528(1) 0.006(3)0.852(2)0.8688(1) 0.003(3)0.100(2)0.9509(1) 0.004(3)0.139(2)0.8941(1) 0.021(4)0.921(2)0.0023(1) 0.018(4)0.653(2)0.9125(1) 0.015(3)0.690(2)0.0325(1) 0.011(3)0.931(2)0.1622(1) 0.021(4)0.066(2)0.9122(1) 0.015(3)0.343(2)0.1612(1) 0.017(3)0.323(2)0.9274(1) 0.017(4)0.324(2)0.3060(1) 0.020(4)0.816(2)0.9822(1) 0.006(3)0.638(2)0.7705(1) 0.036(5)0.164(2)0.1388(1) 0.005(3)0.406(2)0.2074(1) 0.024(4)0.640(2)0.1367(1) 0.015(3)0.364(2)0.0401(1) 0.008(3)0.398(3)0.7019(2) 0.042(5)0.422(2)0.1815(1) 0.021(4)0.160(2)0.8542(1) 0.005(3)0.423(2)0.9432(1) 0.003(3)0.100(2)0.7989(1) 0.024(4)0.800(2)0.8213(1) 0.017(4)0.949(2)0.1222(1) 0.006(3)0.197(3)0.6798(2) 0.042(5)0.903(2)0.7035(1) 0.036(5)0.846(3)0.3594(2) 0.059(6)0.338(3)0.3399(2) 0.042(5)0.874(2)0.0681(1) 0.003(3)0.919(2)0.9286(1) 0.016(3)0.132(2)0.9795(1) 0.008(3)0.396(2)0.0691(1) 0.008(3)0.620(2)0.9528(1) 0.010(3)0.395(2)0.8222(1) 0.016(3)0.890(2)0.2097(1) 0.019(4)0.369(2)0.8709(1) 0.012(3)0.122(2)0.2883(1) 0.030(4)0.552(2)0.8930(1) 0.008(3)0.694(2)0.2325(1) 0.029(4)0.871(2)0.1796(1) 0.011(3)0.663(2)0.1584(1) 0.016(3)0.916(3) 0.2708(2) 0.042(5)0.676(4)0.4980(2) 0.071(7)0.799(2)0.7822(1) 0.032(4)0.087(5)0.4983(3) 0.102(1)0.098(8)0.1914(1) 0.020(4)0.102(3)0.2349(2) 0.051(6)0.386(2)0.7805(1) 0.022(4)0.654(3)0.6122(2) 0.061(6)0.912(2)0.2628(1) 0.033(4)(Continued on next page)1090

D. Topa et al.

Table 5. (Continued).
Site

Atom

sof

a

b

c

Ueq

Atom

a

b

c

Uiso

As27
As28
As29
As30
As31
As32
As33
As34
As35
As36
As37
As38
As39
As40
As41
As42
As43
As44
As45
As46
As47
As48
As49
As50
As51
As52

As
As
As
As
As
As
As
As
As
As
As
As
As
As
As
As
As
As
As
As
As
As
As
As
As
As

1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1

0.4073(11)0.3410(7)0.1952(7)0.3887(7)0.1704(7)0.1368(7)0.0999(10)0.1324(9)0.1401(7)0.1906(7)0.0644(9)0.3466(8)0.4346(10)0.3638(12)0.3844(11)0.0975(12)0.4453(9)0.3144(14)0.3267(15)0.3583(15)0.3042(14)0.1600(15)0.1494(17)0.3791(10)0.2722(14)0.1577(17)0.3289(10)0.8808(7)0.3444(6)0.3538(7)0.6174(6)0.5876(7)0.8983(10)0.4227(8)0.8736(6)0.0647(7)0.5945(8)0.1656(8)0.3984(9)0.4147(13)0.8569(11)0.6771(12)0.8976(9)0.9323(15)0.3826(13)0.1320(13)0.6555(12)0.1161(14)0.8423(19)0.6070(9)0.6098(11)0.3924(13)0.24232(5)0.02840(4)0.89993(4)0.84979(4)0.93925(4)0.11588(4)0.68987(5)0.08145(5)0.07852(4)0.93724(4)0.82908(4)0.99211(5)0.67258(6)0.38257(7)0.38072(7)0.25572(6)0.23906(5)0.56377(9)0.56186(9)0.42035(9)0.60139(8)0.4711(1)0.5081(1)0.27649(5)0.73972(9)0.5108(1)0.039(2)0.0066(12)0.0060(12)0.0076(13)0.0052(12)0.0114(13)0.0352(19)0.0251(16)0.0059(12)0.0126(14)0.0208(15)0.0215(15)0.0359(19)0.057(3)0.050(2)0.049(2)0.0281(17)0.072(3)0.069(3)0.068(3)0.062(3)0.076(3)0.096(4)0.0315(18)0.068(3)0.076(3)

S63
S64
S65
S66
S67
S68
S69
S70
S71
S72
S73
S74
S75
S76
S77
S78
S79
S80
S81
S82
S83
S84
S85
S86
S87
S88
S89
S90
S91
S92
S93
S94
S95
S96
S97
S98
S99
S100
S101
S102
S103
S104
S105
S106
S107
S108
S109
S110
S111
S112

0.451(3)0.209(3)0.358(3)0.440(3)0.466(3)0.147(3)0.277(2)0.485(3)0.057(3)0.235(3)0.442(2)0.282(3)0.068(2)0.418(3)0.274(3)0.389(3)0.093(2)0.253(2)0.460(3)0.068(3)0.456(3)0.426(3)0.059(3)0.287(3)0.212(3)0.058(3)0.186(4)0.050(3)0.122(4)0.209(2)0.440(2)0.481(4)0.356(2)0.243(3)0.005(3)0.491(3)0.375(4)0.340(4)0.461(4)0.140(4)0.217(4)0.021(4)0.159(4)0.161(3)0.334(4)0.159(4)0.326(4)0.035(4)0.486(4)0.022(4)0.419(3)0.045(3)0.585(2)0.597(2)0.856(3)0.938(3)0.181(2)0.630(3)0.073(2)0.815(3)0.682(2)0.421(3)0.175(2)0.822(3)0.585(3)0.131(3)0.359(2)0.594(2)0.439(3)0.898(2)0.145(3)0.872(3)0.656(2)0.835(3)0.642(3)0.573(3)0.604(4)0.358(3)0.131(3)0.303(2)0.196(2)0.667(3)0.078(2)0.607(3)0.121(3)0.081(3)0.384(4)0.316(3)0.892(4)0.128(4)0.407(4)0.412(4)0.342(4)0.169(3)0.861(4)0.578(4)0.901(4)0.627(4)0.379(4)0.181(4)0.7468(2)0.3771(2)0.3165(1)0.7215(2)0.6075(2)0.5890(2)0.0910(1)0.6309(2)0.3362(2)0.4073(2)0.1917(1)0.6490(2)0.7530(1)0.7484(2)0.6794(2)0.3187(2)0.7314(1)0.8000(1)0.6085(2)0.3072(1)0.6331(2)0.3416(2)0.3375(2)0.6475(2)0.3778(2)0.7546(2)0.4301(2)0.3619(2)0.6108(2)0.2656(1)0.7200(1)0.5729(2)0.7729(2)0.2912(2)0.4576(2)0.5724(2)0.5219(2)0.4677(2)0.5501(2)0.4315(2)0.4080(2)0.4833(2)0.5889(2)0.5589(2)0.5201(2)0.5579(2)0.4689(2)0.4596(2)0.5479(2)0.5180(2)0.050(6)0.056(6)0.036(5)0.038(5)0.050(6)0.058(6)0.027(4)0.049(5)0.039(5)0.062(7)0.025(4)0.047(5)0.029(4)0.044(5)0.045(5)0.044(5)0.032(4)0.013(3)0.059(6)0.036(5)0.053(6)0.050(6)0.038(5)0.050(6)0.056(6)0.044(5)0.071(7)0.060(6)0.067(7)0.031(4)0.031(4)0.064(7)0.032(4)0.044(5)0.060(6)0.059(6)0.073(8)0.065(7)0.079(8)0.078(8)0.073(8)0.083(9)0.072(7)0.057(6)0.072(7)0.081(8)0.074(8)0.070(7)0.081(8)0.079(8)aPb2 (and possibly Pb30) might contain some Tl, considering the comparatively high Ueq value and the comparatively long Pb2–S bonds(Table S1).
b
Ag4 shows anomalous behaviour (see text): comparatively high Ueq value, occupancy of ~0.67 and long Ag4–S bonds (Table S1).
Reﬁnement as a mixed (Ag,As) site was impossible; the reﬁnement “blew up.”c
As8 shows anomalous behaviour (see text): comparatively high Ueq value, occupancy of ~0.97 and long As8–S bonds (Table S1).

electron-density maxima at appropriate distance values. All
cation atoms were reﬁned at the beginning with anisotropic
displacement parameters. The atomic displacement parameters of all S atoms had to be kept isotropic because theanisotropic treatment of some of them resulted in a “nonpositive deﬁnite” character during the reﬁnement.
The asymmetric unit of argentoliveingite contains 32 Pb
sites, four Ag sites, 52 As sites and 112 sulfur sites, all in

Downloaded from https://pubs.geoscienceworld.org/eurjmin/article-pdf/31/5-6/1079/4902547/ejm_31_5-6_1079_1097_topa_2890_online.pdf
by University of Arizona user

Argentoliveingite, a new homeotype of liveingite from Lengenbach

1091

Fig. 6. Atom labelling in the crystal structure of liveingite. Blue spheres – Pb, cyan spheres – As, bright blue spheres – (As,Pb) mixed sites
and white spheres – S.

general positions (Table 5 and Fig. 9). During the reﬁnement
process, the atomic displacement parameters and bondlengths (Table 5 and Table S1) for all cation sites were
examined in detail. Lead in the Pb27–Pb31 sites shows
larger anisotropic displacement parameters, but with normalbond lengths, when compared to all other Pb sites, except
Pb24 and Pb27 where some As is supposed to be present.
Arsenic in the As1–As4 and As8 sites has longer bondlengths and higher anisotropic displacement parameters than
the remaining As sites. When freely reﬁned, the originally
reﬁned As occupancies in the As1–As4 sites range between
1.2 and 1.5 and is 0.8 for As8, without signiﬁcant improvement of the residual index R1. Substitution by Pb isconsidered to be responsible for the relatively large electron-density values in the sites As1–As4, whereas therelatively low value for site As8 is considered an artefact.
The silver site Ag2 appears well deﬁned, in contrast to theAg1, Ag3 and Ag4 sites, where some As could be locatedon the As3 and Ag4 sites and some Pb on the Ag1 site.
Another site possibly affected by substitutions is the Pb2 sitewhere some Tl may be located. We decided to keep low thenumber of reﬁned parameters (1192) in accordance with therelatively low number of observed reﬂections (13,088 for
Fo > 4rFo) and the large R1 (14%) by leaving all cation sites
un-split and anion sites isotropically reﬁned. The clearly
mixed sites are (Ag,Pb)1, (Ag,As)3, (As,Pb)1 to 4, (Pb,
As)24 and (Pb,As)27 (Table 5). The quality of the data does
not allow a more detailed investigation of the mixed sites
and the calculation of reliable bond-valence values.
Thallium (0.4 apfu) and antimony (1.01 apfu) were not
localised among the 88 cation sites. The ﬁnal reﬁnement
for argentoliveingite yielded R1 = 0.1401 for 13,088 reﬂections with Fo > 4r(Fo) and 0.1600 for all 16,432 data. The
structure formula is Ag3.35Pb32.28As51.74S112, with goodcharge balance (0.87).
Based on bond lengths shorter than the shortest cation–
cation distances (Table S1), it is possible to distinguishbetween Pb atoms located on sites with coordination numbers seven and nine (Fig. 8g). Silver sites are surroundedby six and As sites by ﬁve S positions (three short, two longand two very long bonds, exceeding cation–cation distances,which are neglected in Table S1). Thus, the crystal structureof argentoliveingite can be described, at polyhedral level, bymeans of 88 cation polyhedra, of which 24 are tricapped
trigonal coordination prisms (CN = 9) of pure Pb, eight
are monocapped trigonal coordination prisms (CN = 7) ofPb, four are irregular coordination bipyramids (CN = 6)
centred by Ag and 52 are trapezoidal coordination pyramids(CN = 5) of As.
Using the general modular description of Makovicky(1985, 1997a and b) and the modular description of theliveingite structure in particular, the argentoliveingite structure can be understood by means of six unique (three andfour polyhedra wide) SnS-like slabs, each with its tightly
bonded double-layer ribbons, which are formed by meansof short As–S bonds and are separated by broader spaces
which accommodate the lone-electron pairs of the As3+
cations. There are two N = 3 and four N = 4 ribbons in
the asymmetric unit (Fig. 9). Lead (CN = 7) in eight sites(Pb1, Pb3, Pb4, Pb9, Pb18, Pb24, Pb26 and Pb27) is locatedin the central part of the ribbons (Fig. 9) and the remaining
24 Pb (CN = 9) sites are situated in terminal positions of theribbons. The four Ag sites (Ag1–Ag4) are located in thecentral part of the N = 4 ribbons. Out of the 52 As sites,
24 also belong to the central part, while 28 are found in
the apical sites of the ribbons.
The detailed description of the N = 3 and N = 4 ribbons of
the argentoliveingite structure, as presented in the argentobaumhauerite structure paper (Topa & Makovicky, 2016),
will be not repeated here. Instead, the crankshaft chains of
the tightly bonded double-layer ribbons (Figs. 10 and 11)
and the corresponding ribbon chemistries will be analysed
in detail and compared with those of liveingite. To achieve
that, (3  8.4) Å fragments of individual ribbons wereoriented with Pb-dominated layers on the left side and sliced
along their median plane in order to separate their surface
layers (L31, L32 and L41, L42 for N = 3 and N = 4 ribbons,respectively). These were 90° clockwise rotated and placedon the left and right sides of each ribbon. The short As–S
bonds are shown in orange colour while the As–S bonds
longer than 2.57 Å are indicated by broken lines, indicatingan As site which apparently assumes two partially occupied
sites (“ﬂips”) inside its coordination polyhedron. For each
ribbon the length and direction of the crankshaft chains isindicated, for N = 3 ribbons in Fig. 10 and for N = 4 ribbons
in Fig. 11. One can distinguish parallel and almost

Downloaded from https://pubs.geoscienceworld.org/eurjmin/article-pdf/31/5-6/1079/4902547/ejm_31_5-6_1079_1097_topa_2890_online.pdf
by University of Arizona user

1092

D. Topa et al.

Fig. 7. The crystal structures of (a) liveingite, (b) Ag-bearing liveingite, (c) argentoliveingite, (d) phase “IL” and (e) argentobaumhauerite ina projection along the 8.4 Å axis, and the comparison of their fundamental slabs (N = 3 and N = 4). The N = 3 and N = 4 slabs are built of
double SnS-like layer ribbons of different lengths. The N = 3 ribbons (of Pb5As7S16 composition) are shown in dark grey colour in all
structures, whereas the four chemically different types of N = 4 ribbons are coloured according to their idealised composition: R1, R2
light grey (4) – ~Pb7–8As9–8S20; R1s, R1as, R1cs pale blue (4) – Pb6As10S20; R3 pale green (4) – Ag2Pb4As6S20; and R2 dark green(4) – Ag2Pb6As8S20. Note the different arrangements of N = 3 and N = 4 slabs, along the long axes, in the crystal structures of liveingite andAg-bearing liveingite (. . .434434. . .), argentoliveingite (. . .444343444343. . .), phase “IL” (hypothetical sequence . . .444343. . .) andargentobaumhauerite (. . .4343. . .). The charge balances of the slabs were calculated and added in red near each slab, except for Ag-bearing
liveingite. The hypothetical crystal structure of the phase “IL” is derived by mixing a 343 sequence (as in argentoliveingite) with a modiﬁed
444 sequence based on the R2 ribbon in liveingite.

Downloaded from https://pubs.geoscienceworld.org/eurjmin/article-pdf/31/5-6/1079/4902547/ejm_31_5-6_1079_1097_topa_2890_online.pdf
by University of Arizona user

Argentoliveingite, a new homeotype of liveingite from Lengenbach1093

Fig. 8. Details concerning chemistry, topology and charge balanceof the N = 3 and N = 4 double-layer ribbons (all oriented along the
8.4 Å axis for each structure; ribbon colours as explained in Fig. 7)
in the crystal structure of: (a) baumhauerite, (b) “ideal (434 based on
baumhauerite N = 4 ribbons) liveingite,” (c) liveingite, (d) Agbearing liveingite, (e) argentoliveingite and (f) dufrénoysite. Generalview (g) of a N = 4 double-layer ribbon with tricapped trigonal
coordination prisms (CN = 9) of Pb near its ends, monocapped
trigonal coordination prisms (CN = 7) of remaining Pb atoms andtrapezoidal coordination pyramids (CN = 5) of As. Only the central
part of the ribbon (marked in red), containing three polyhedra of As
and three polyhedra of Pb, is affected by the (Ag+ + As3+)-for-2Pb2+
substitution.

perpendicular directions of the chain directions, between theleft and right sides of the layers in each ribbon and between
ribbons themselves.
The chemistry of the two N = 3 ribbons of argentoliveingite (Fig. 10b and c) and the N = 3 ribbon of liveingite(Fig. 10a) is equal to Pb5As7S16. The asymmetric conﬁguration of this ribbon of liveingite consists primarily of two
SnS-like surface layers. On the Pb-rich side (L32), the lengthof the crankshaft chain corresponds to a three-member
polyhedral chain (As15, As16 and As14). On the low-Pb side(L31) the crankshaft chain also corresponds to a threemember chain (As11, As10 and As13), but is followed by
a ﬂipping As12 site. The direction of the crankshaft chainsis almost perpendicular to each other. In contrast, thetwo asymmetric ribbons in argentoliveingite (labelled 3

Fig. 9. Atom labelling in the crystal structure of argentoliveingite.
Blue spheres – Pb, cyan spheres – As, green spheres – Ag sites andwhite spheres – S. The length of the asymmetric unit cell, thedenomination and chemistry (colour) of ribbons, as well as thegeneral orientation of the crankshaft chains of the ribbons areshown.

Downloaded from https://pubs.geoscienceworld.org/eurjmin/article-pdf/31/5-6/1079/4902547/ejm_31_5-6_1079_1097_topa_2890_online.pdf
by University of Arizona user

1094

D. Topa et al.

Fig. 10. Comparison of the N = 3 asymmetric double-layer ribbons (three unit cells along the 8.4 Å axis) with SnS-like layers (L31 and L32)
in the crystal structures of (a) liveingite and (b, c) argentoliveingite. The building polyhedra, the short As–S bonds, the directions and lengthsof the crankshaft chains are indicated by straight black lines. The symbol ┴ indicates the almost perpendicular directions of the crankshaft
chains for L31 and L32 in each ribbon. Note the difference between (b) ribbon 3 and (c) ribbon 3: topologically they are identical, but thedirections of the crankshaft chains are opposite. There is a close resemblance between (a) liveingite and (c) argentoliveingite ribbons.

and 3 in Figs. 9 and 10b and c), with almost perpendicularorientations of crankshaft chains, have a four-member chain(As10, As26, As23 and As22 for 3 and As32, As13, As15
and As17 for 3) in the low-Pb SnS-like layers and a broken
two-member chain (As41 and As35 in 3 and As18 and 39 in3) due to ﬂipping of As27 and As21. The directions of
crankshaft chains for ribbons 3 and 3 are anti-parallel.
The chemistries of the N = 4 ribbons in argentoliveingite
display different degrees of substitution of the “central”
cations, As and Pb by Ag and As, respectively, comparedwith the N = 4 ribbons (R1 and R2) in liveingite (Figs. 8cand e, 9 and 11). They are labelled R1, R2 and R3 according
to their idealised compositions of Pb6As10S20, Ag2Pb6
As8S20 and Ag2Pb4As10S20, respectively. The asymmetricR1 and R2 ribbons of liveingite display a slightly different
chemistry (due to mixed sites As4, As5 and As21), an
almost perpendicular direction of the crankshaft chains
between L42 and L41 and same-length three-member chainsin L42 and four-member chains in L41 (Fig. 11a1 and a2).
For the centrosymmetric, Ag-free R1-type ribbon in argentoliveingite (Figs. 9 and 11b1,2,3) one can distinguish three“versions” (i.e., R1s, R1as and R1cs) with slightly different
chemistries and charge balances, when the mixed occupancies of the As2, As3, As4 and Pb27 sites are taken inaccount. The halves of the ribbons R1s and R1cs are locatedat the beginning and the end of the asymmetric unit cell andpossess a local inversion centre. Topologically the ribbon
R1as is centrosymmetric, but the cation sites for the SnS-likelayers (L41 and L42) are not equivalent. The same situation
is valid for the Ag-rich ribbons R2 and R3 (Fig. 11c and d).

The directions of the crankshaft chains between L41 and L42
for all N = 4 ribbons in argentoliveingite (i.e., R1s, R1as,
R1cs, R2 and R3) are parallel to each other in contrast to
the above speciﬁed case in liveingite (Fig. 11a1 and a2).
The length of the crankshaft chains varies from the ﬁvemember polyhedral chain in R3 to the broken three-member
polyhedral chain followed by one or two ﬂipping As site(s)in the remaining ones. It is useful to note the regular alternation of the directions of crankshaft chains in the R1s,
R1as, R3, R2 and R1cs ribbon sequence along the c axis
(Figs. 9 and 11).
Considering the symmetrical ribbons R1s and R1cs, which
are almost identical (difference only in chemistry, Fig. 11),the content of the asymmetric unit of argentoliveingite, of
two N = 3 ribbons and four N = 4 ribbons, shows the uniqueslab sequence of . . .444343. . . For the whole unit cell ofargentoliveingite the sequence is . . .444343444343. . .. The
description of the sequence (Figs. 7 and 9) can be speciﬁed
in more detail as . . .444343444343. . ., by taking into
account the differences in chemistry and the directions of
the crankshaft chains based on the short As–S bonds.
Comparing these results with the main features reported
in the literature for “rathite-IV” (Ozawa & Tachikawa,
1996; Pring, 2001), it is clear that unit-cell parameters,chemistry and number of ribbons (12) are common, but
the repeat sequence and number of N = 3 and N = 4 ribbons
within the sequence clearly differ. However, the repeat
sequence in “rathite-IV” was based only on visual interpretation of HR-TEM images and not on a crystal-structure
determination.

Downloaded from https://pubs.geoscienceworld.org/eurjmin/article-pdf/31/5-6/1079/4902547/ejm_31_5-6_1079_1097_topa_2890_online.pdf
by University of Arizona user

Argentoliveingite, a new homeotype of liveingite from Lengenbach

1095

Fig. 12. Comparison of the asymmetric unit of (a) argentoliveingite
and (b) asymmetric unit of unsubstituted argentoliveingite (corresponding to the full unit cell of liveingite) in terms of main sites
implied in the 2Pb2+ ? Ag+ + As3+ substitution mechanism.

Fig. 11. Comparison of the asymmetric and centrosymmetric N = 4
double-layer ribbons (three unit cells along the 8.4 Å axis) with SnSlike layers (L41 and L42) in the crystal structures of liveingite (a1, a2)
and argentoliveingite (b1, b2, b3, c, d), respectively. The building
polyhedra, the short As–S bonds, the directions and lengths of the
crankshaft chains are indicated by straight black lines. The symbols┴ and ║ indicate the almost perpendicular and parallel directionsof the crankshaft chains for L41 and L42. The asymmetric ribbons R1
and R2 of liveingite are topologically identical, but the directions of
the crankshaft chains are opposite.

4.3. Substitution mechanisms
The empirical formula of argentoliveingite is Ag3.17Tl0.40
Pb33.31(As,Sb)51.09S112.02, which can be rewritten as Ag3.17

Pb34.11(As,Sb)50.69S112.02 after “extraction” of Tl substitution, and as Pb40.45(As,Sb)47.52S112.02 after “extraction” ofAg substitution. It is then relatively close to an ideal unsubstituted formula Pb40As48S112. The Ag and As substitution
for 2Pb, from chemistry, can be written as: 6.34Pb2+ ?
3.17Ag+ + 3.17As3+, which implies six to seven Pb sites
to be replaced by 3–3.5 Ag sites and 3–3.5 As sites.
A closer look at the ribbons and the sites (Figs. 8g and 12)
affected by the substitution mechanism 2Pb2+ ? Ag+ + As3+
shows a more complicated picture. The substitutions takeplace only in the six octahedra with CN = 5–7 in the central
part of the N = 4 ribbons (red in Fig. 8g). There are six
Pb sites in the unsubstituted asymmetric unit, completely
replaced by two Ag and four As sites and two As sites
replaced by two Ag (Fig. 12). Together, that means
6Pb2+ ? 4Ag+ + 2As3+ with an unbalanced charge (+2),
corrected by two Pb sites (Pb24, Pb27) being partly replaced
by As and four As sites (As1–As4) being partly replaced by
Pb. The partial occupancies of the Ag1, Ag3 and Ag4 sites,
derived from the structure reﬁnement and correlating withthe degree of Ag substitution from the EPMA data, explain
the measured range of Ag substitution (~3 to ~3.5).

Downloaded from https://pubs.geoscienceworld.org/eurjmin/article-pdf/31/5-6/1079/4902547/ejm_31_5-6_1079_1097_topa_2890_online.pdf
by University of Arizona user

1096

D. Topa et al.

Table 6. Comparison of crystal and other data for argentoliveingite, phase “IL”, Ag-bearing liveingite and liveingite (all sartorite
homologues with N = 3.67). Ideal formula for liveingite is Pb20As24S56 (Z = 2).
MineralArgentoliveingite

Ag3.17Tl0.4Pb33.3
As50.1SbS112
Structural formulaAg3.35Pb32.28
As51.74S112
Crystal system
Triclinic
Space groupP1
Unit-cell parameters (Å,°)
a7.905(2)b8.469(2)c137.96(4)a89.592(2)b88.969(2)c89.893(2)
R1
0.141
V
9235(5)
Z
2
Ref.
1

Chemical formula

Phase “IL”

Ag-bearing liveingite

Liveingite

Liveingite

Ag1.08Tl0.13Pb17.74
As24.48Sb0.65S56–

Ag0.06Tl0.03Pb20.06
As23.67Sb0.36S56
Pb20.12As23.88S56

Pb18As26S56
Pb18.5As25.25S56

Monoclinic/triclinic (?)
P2/P
1 (?)

Ag0.67Tl0.39Pb18.15
As24.48Sb0.32S56
Ag0.54Pb18.15As24.95
Sb0.36S56
Monoclinic
P21

Monoclinic
P21

Monoclinic
P21

~7.9
~8.5
~68.9
~89.6
~95.0
~89.9
–
?
2
1

7.9113(4)70.355(4)8.3708(4)9090.115(1)90
0.064
4659.2(4)2
17.9039(5)70.969(5)8.3640(5)9090.147(1)90
0.049
4691.6(5)218.371(5)70.49(5)7.914(5)9090.13(3)90
0.071
4669.82
2

1: this study; 2: Engel & Nowacki (1970).

The theoretical upper limit of substitution (point 8 in Fig. 3),
which would yield an ideal formula Ag4Pb32As52S112 basedon the 8Pb2+ ? 4Ag+ + 4As3+ substitution mechanism, is
not observed in the experimental chemical dataset.
As mentioned above, two other, minor substitutions (Tl+for Pb2+ and Sb3+ for As3+) also operate in argentoliveingite,
but the very low Tl and Sb contents and the quality of thesingle-crystal diffraction data do not allow a statement on
which Pb and As sites are involved in these substitutions.
4.4. Phase “IL”
The phase “IL” forms exsolution lamellae (with variable
thickness, medium grey in BSE images of Fig. 5) with
Ag-bearing liveingite (dark grey) and with argentoliveingite(bright grey). This phenomenon is well documented forlarge areas, in two separate samples. The presence of threekinds of lamellae implies three distinct phases with different
chemistries and structures. The exsolved intergrowths may
have formed during cooling of a previously stable, homogeneous higher-temperature Ag–Pb–As–S phase. It is worth
noting that at least two stages of exsolution process exist.
The chemical composition of phase “IL” lies between
those of Ag-bearing liveingite and argentoliveingite (Table 2
and Fig. 3), and in special places (where the thinness of thelamellae was large enough) an accurate determination of thecomposition and its range was possible. As more samples
were measured during the course of our study, the compositional gaps between Ag-bearing liveingite, phase “IL” andargentoliveingite were ﬁlled (Fig. 3) with values representing mixtures between two phases and showing a continuous
increase of the (Ag + As)-for-2Pb substitution. The calculated homologue order Ncalc is 3.7 for “IL”, indicating theexistence of a periodicity based on a . . .443. . . sequence(as in liveingite).
For the moment, a hypothetical crystal structure for phase“IL” is presented in Fig. 7d, based on its known simpliﬁed

chemistry, AgPb18As25S56 (Z = 2), and modular arrangements based on a mixture of features characteristic forliveingite (. . .44. . .) and argentoliveingite (. . .343. . .) structures combined by “scissors crystallography.” The structure
could have a similar metric as liveingite (Table 6), butshould have a lower symmetry (possibly monoclinic P2 ortriclinic P1) in order to produce one asymmetric N = 4
ribbon, similar to R2 in the liveingite structure and one
symmetric N = 4 ribbon enriched in Ag and Pb-depleted
as in argentoliveingite (R3). The resulting sequence. . .444343. . . would be topologically compatible withliveingite metrics.
To prove that, a crystal-structure determination is necessary and would necessitate either careful electron diffraction
studies and/or simultaneous reﬁnement of two phases in thesame crystal fragment, or ﬁnding a homogeneous grain of
the “IL” phase, suitable for single-crystal studies.

5. Conclusions
The new mineral species argentoliveingite is one of the mostcomplex natural sulphosalts studied so far. Our studies show
once again that a systematic investigation of Lengenbachsulphosalt samples, both in museum as well as othercollections, makes the complexity of this unique deposit
even more attractive to be studied, unravelled and better
understood.
There are fascinating structural aspects of this novel structure: (a) diversiﬁcation into two modules which are (or atleast one of which is) again diversiﬁed in their/its composition and other crystal-chemical aspects. Already heralded byargentobaumhauerite, the second diversiﬁcation becomeseven more pronounced and variable in argentoliveingite;(b) a wave-like long-range chemical modulation of thestructure, probably ruled by strains and stresses producedby (especially) Ag substitutions on exsolution and/or on

Downloaded from https://pubs.geoscienceworld.org/eurjmin/article-pdf/31/5-6/1079/4902547/ejm_31_5-6_1079_1097_topa_2890_online.pdf
by University of Arizona user

Argentoliveingite, a new homeotype of liveingite from Lengenbach

primary crystallisation of argentoliveingite; and (3) displacements, exchanges, and transﬁgurations of the two ribbon
types which must take place during exsolution of argentoliveingite and phase “IL” from a precursor phase.
The relationship between argentoliveingite and “rathiteIV” is difﬁcult to deﬁne based on the current knowledge.
We can neither prove that they are identical nor disprove it.
Acknowledgements: The authors express their gratitude to
all the above listed donors, which contributed material tothis study. We thank Goran Batic for his technical assistance. The paper was handled by Editor-in-Chief Sergey
Krivovichev and the comments of two anonymous reviewers helped to improve it.

References
Berlepsch, P., Makovicky, E., Balić-Žunić, T. (2001): Crystal
chemistry of sartorite homologues and related sulfosalts. N. Jb.
Mineral. Abh., 176, 45–66.
Berlepsch, P., Armbruster, T., Topa, D. (2002): Structural andchemical variations in rathite, Pb8Pb4-x(Tl2As2)x(Ag2As2)
As16S40: modulations of a parent structure. Z. Kristallogr.,
217, 1–10.
Berlepsch, P., Armbruster, T., Makovicky, E., Topa, D. (2003):
Another step toward understanding the true nature of sartorite:
determination and reﬁnement of a nine-fold superstructure. Am.
Mineral., 88, 450–461.
Berry, L.G. (1953): New data on lead sulpharsenites from Binnental,
Switzerland. Am. Mineral., 38, 330.
Bindi, L., Nestola, F., Makovicky, E., Guastoni, A., de Battisti, L.
(2014): Tl-bearing sulfosalt from the Lengenbach quarry, Binn
valley, Switzerland: Philrothite, TlAs3S5. Mineral. Mag., 78, 1–9.
Bruker AXS (1997): SHELXTL, version 5.1. Bruker AXS, Inc.,
Madison, WI, USA.
— (1998a): SMART, version 5.0. Bruker AXS, Inc., Madison, WI,
USA.
— (1998b): SAINT, version 5.0. Bruker AXS, Inc., Madison, WI,
USA.
Engel, P. & Nowacki, W. (1970): Die Kristallstruktur von Rathit-II[As25S56|Pb6.5VIIPb12IX]. Z. Kristallogr., 131, 356–375.
Giusßcă, D. (1930): Die Erze der Lagerstätte vom Lengenbach im
Binnental (Wallis). Schweiz. Mineral. Petrogr. Mitt., 10, 152–177.
Kraus, W. & Nolze, G. (1999): PowderCell 2.3. Federal Institute forMaterials Research and Testing, Berlin, Germany.
Laroussi, A., Moëlo, Y., Ohnenstetter, D., Ginderow, D. (1989):
Argent et thallium dans les sulfosels de la série de la sartorite(Gisement de Lengenbach, vallée de Binn, Suisse). C. R. Acad.
Sci., Sér. II, 308, 927–933.
Le Bihan, M.-Th. (1961): Structure de la rathite II. Comparaison
entre les différentes structures connues de sulfures d’arsenic etde plomb. Acta Crystallogr., 14, 1211–1212.
— (1962): Etude structurale de quelques sulfures de plomb etd’arsenic naturels du gisement de Binn. Bull. Soc. fr. Minéral.
Cristallogr., 85, 15–47.
Makovicky, E. (1985): The building principles and classiﬁcation of
sulfosalts based on the SnS archetype. Fortschr. Mineral., 63,
45–89.
— (1997a): Modular crystal chemistry of sulfosalts and othercomplex sulphides. in “Modular aspects of minerals”, S. Merlino,ed., European Mineralogical Union, Notes in Mineralogy, 1,
237–271. Eötvös University Press, Budapest, Hungary.

1097— (1997b): Modularity – different types and approaches. in “Modular
aspects of minerals”, S. Merlino, ed., European Mineralogical
Union, Notes in Mineralogy, 1, 315–343. Eötvös University
Press, Budapest, Hungary.
— (2019): Algorithms for calculations of homologue order N in thehomologous series of sulfosalts. Eur. J. Mineral., 31, 83–97.
Makovicky, E. & Topa, D. (2015): Crystal chemical formula forsartorite homologues. Mineral. Mag., 79, 25–31.
Makovicky, E., Topa, D., Stoeger, B. (2018): The crystal structuresof heptasartorite, Tl7Pb22As55S108, and enneasartorite,
Tl6Pb32As70S140, two members of an anion-omission series ofcomplex sulfosalts from Lengenbach, the Swiss Alps, andcomparison with the structures of As–Sb sartorite homologues.
Eur. J. Mineral., 30, 149–164.
Moëlo, Y., Makovicky, E., Mozgova, N.N., Jambor, J.L., Cook, N.,
Pring, A., Paar, W., Nickel, E.H., Graeser, S., Karup-Møller, S.,
Balić-Žunić, T., Mumme, W.G., Vurro, F., Topa, D., Bindi, L.,
Bente, K., Shimizu, M. (2008): Sulfosalt systematics: a review.
Report of the sulfosalt sub-committee of the IMA commission
on ore mineralogy. Eur. J. Mineral., 20, 7–46.
Nowacki, W., Marumo, F., Takeuchi, Y. (1963): Investigations on
sulﬁdes from Binntal (Canton Valais, Switzerland). Schweiz.
Mineral. Petrogr. Mitt., 44, 5–9.
Ozawa, T. & Nowacki, W. (1974): Note on the mineral rathite-IV.
N. Jb. Mineral. Mh., 1974, 530–531.
Ozawa, T. & Tachikawa, O. (1996): A transmission electron
microscope observation of a 138 Å period in Pb–As–S
sulfosalts. Mineral. J., 18, 97–101.
Pring, A. (2001): The crystal chemistry of the sartorite groupminerals from Lengenbach, Binntal, Switzerland – a HRTEM
study. Schweiz. Mineral. Petrogr. Mitt., 81, 69–87.
Sheldrick, G.M. (2008): A short history of SHELX. Acta Crystallogr. A, 64, 112–122.
Solly, R.H. (1901): Liveingite, a new mineral from the Binnenthal.
Proc. Camb. Philos. Soc., 11, 239–240.
— (1902): Sulpharsenites of lead from the Binnenthal. Part III.
Baumhauerite, a new mineral; and dufrenoysite. Mineral. Mag.
13, 151–171.
Takéuchi, Y. (1970): On the crystal chemistry of sulphides andsulfosalts. in “Volcanism and ore genesis”, T. Tatsumi, ed.
Univ. of Tokyo Press, Tokyo, Japan, 395–420.
Topa, D. & Kolitsch, U. (2018): The crystal chemistry of rathitebased on new electron-microprobe data and single-crystal
structure reﬁnements: the role of thallium. Minerals, 8, 466.
Topa, D. & Makovicky, E. (2016): Argentobaumhauerite: name,chemistry, crystal structure, comparison with baumhauerite, andposition in the Lengenbach mineralization sequence. Mineral.
Mag., 80, 819–840.
Topa, D., Makovicky, E., Stanley, C., Cannon, R. (2016a):
Argentodufrénoysite, IMA 2016–046. CNMNC newsletter no.
33, October 2016, page 1138. Mineral. Mag., 80, 1135–1144.
Topa, D., Stoeger, B., Makovicky, E., Stanley, C. (2016b):
Incomsartorite, IMA 2016–035. CNMNC newsletter no. 33,
October 2016, page 1136. Mineral. Mag., 80, 1135–1144.
Topa, D., Makovicky, E., Stoeger, B., Stanley, C.J. (2017a):
Heptasartorite, Tl7Pb22As55S108, enneasartorite, Tl6Pb32As70S140,
and hendekasartorite, Tl2Pb48As82S172, three members of theanion-omission series of “sartorites” from the Lengenbach quarry
at Binntal, Wallis, Switzerland. Eur. J. Mineral., 27, 701–712.
—, —, —. — (2017b): Dekatriasartorite, IMA 2017–071. CNMNC
newsletter no. 40, December 2017, page 1084. Eur. J. Mineral.,29, 1083–1087.
Received 5 April 2019
Modiﬁed version received 4 June 2019
Accepted 12 June 2019

Downloaded from https://pubs.geoscienceworld.org/eurjmin/article-pdf/31/5-6/1079/4902547/ejm_31_5-6_1079_1097_topa_2890_online.pdf
by University of Arizona user