Mineralogical Magazine, October 2012, Vol. 76(5), pp. 1153–1163

Raberite, Tl5Ag4As6SbS15, a new Tl-bearing sulfosalt from
Lengenbach quarry, Binn valley, Switzerland: description
and crystal structure
L. BINDI1,2,*, F. NESTOLA3, A. GUASTONI4, L. PERUZZO5, M. ECKER6 AND R. CARAMPIN5
1Dipartimento di Scienze della Terra, Università degli Studi di Firenze, Via G. La Pira 4, I-50121 Firenze, Italy
CNR  Istituto di Geoscienze e Georisorse, Sezione di Firenze, Via G. La Pira 4, I-50121 Firenze, Italy
3
Dipartimento di Geoscienze, Università degli Studi di Padova, Via Gradenigo 6, I-35131 Padova, Italy
4
Museo di Mineralogia, Università degli Studi di Padova, Palazzo Cavalli, Via Matteotti 30, I-35121, Padova, Italy5
CNR  Istituto di Geoscienze e Georisorse, Sezione di Padova, Via Gradenigo 6, I-35131, Padova, Italy
6
Pfarrbrunnenstrasse 18, D-66578 Schiffweiler, Germany
2[Received 7 June 2012; Accepted 23 July 2012; Associate Editor: Stuart Mills]
ABSTRACT

Raberite, ideally Tl5Ag4As6SbS15, is a new mineral from Lengenbach quarry in the Binn Valley,
Valais, Switzerland. It occurs very rarely as euhedral crystals up to 150 mm across associated withyellow needle-like smithite, realgar, hatchite and probable trechmannite, edenharterite, jentschite andtwo unidentiﬁed sulfosalts. Raberite is opaque with a metallic lustre and has a dark brown–red streak. It
is brittle with a Vickers hardness (VHN10) of 52 kg mm2 (range 50–55) corresponding to a Mohs
hardness of 2–3. In reﬂected light raberite is moderately bireﬂectant and very weakly pleochroic fromlight grey to a slightly greenish grey. It is very weakly anisotropic with greyish to light blue rotation
tints between crossed polars. Internal reﬂections are absent. Reﬂectance percentages for the four COM
wavelengths [listed as Rmin, Rmax, (l)] are 30.6, 31.8 (471.1 nm), 28.1, 29.3 (548.3 nm), 27.1, 28.0
(586.6 nm), and 25.8, 26.9 (652.3 nm).
Raberite is triclinic, space group P1̄, with a = 8.920(1), b = 9.429(1), c = 20.062(3) Å, a = 79.66(1),b = 88.84(1), g = 62.72(1)º, V = 1471.6(4) Å3 and Z = 2. The crystal structure [R1 = 0.0827 for 2110
reﬂections with I > 2s(I)] consists of columns of nine-coordinate Tl atoms forming irregular polyhedra
extending along [001] and forming sheets parallel to (010). The columns are decorated by cornersharing MS3 pyramids (M = As, Sb) and linked by AgS3 triangles. Of the seven M positions, one isdominated by Sb and the others by As; the mean MS bond distances reﬂect As $ Sb substitution atthese sites.
The eight strongest lines in the powder diffraction pattern [dcalc in Å (I) (hkl)] are: 3.580 (100) (11̄3);
3.506 (58) (1̄2̄3); 3.281 (73) (006); 3.017 (54) (1̄23); 3.001 (98) (133); 2.657 (51) (226); 2.636 (46)(300); 2.591 (57) (330). A mean of 9 electron microprobe analyses gave Tl 39.55(13), Ag 18.42(8), Cu
0.06(2), As 17.08(7), Sb 5.61(6), S 19.15(11); total 99.87 wt.%, which corresponds to
Tl4.85Ag4.28Cu0.02As5.72Sb1.16S14.97 with 31 atoms per formula unit. The new mineral has been
approved by the IMA-CNMNC Commission (IMA 2012-017) and is named for Thomas Raber, an
expert on Lengenbach minerals.
K EY WORDS : raberite, new mineral, Tl-sulfosalts, crystal structure, Lengenbach, Switzerland.

* E-mail: luca.bindi@unifi.it
DOI: 10.1180/minmag.2012.076.5.07# 2012 The Mineralogical Society

Introduction
LENGENBACH quarry in the Binn Valley, Canton
Valais, Switzerland is one of the world’s premiere
localities for Tl-bearing sulfosalts. A considerable
number of thallium-bearing minerals have been

L. BINDI ET AL.

hatchite/wallisite in association with yellowish
ﬁbrous smithite (Fig. 1). It does not contain
inclusions or intergrowths of other minerals.
Raberite has a dark brownred streak. It is
opaque in transmitted light with a metallic lustre.
No cleavage was observed and the fracture is
uneven. The density calculated from the empiricalformula (see below) is 5.649 g cm 3 .
Unfortunately, the density could not be measured
because of the small grain size and absence ofsuitable heavy liquids. Micro-indentation measurements carried out with a VHN load of 10 g give amean value of 52 kg mm2 (range: 5055)
corresponding to a Mohs hardness of 23.
In plane-polarized incident light, raberite isdark grey, moderately bireﬂectant and very
weakly pleochroic from light grey to a slightly
greenish grey. It is very weakly anisotropic withgreyish to light-blue rotation tints between
crossed polars. There are no internal reﬂections
and there is no optical evidence of growthzonation.
Reﬂectance measurements were performed in
air using a Zeiss microphotometer (MPM-200)
equipped with a MSP-20 system processor on a
Zeiss Axioplan ore microscope. The ﬁlament
temperature was approximately 3350 K. An
interference ﬁlter was set to the four wavelengths
recommended by the Commission on Ore
Microscopy (COM). Measurements were takenreported from the quarry; it is the type locality for
imhoﬁte, Tl3As7.67S13 (Burry et al., 1965);
erniggliite, SnTl2(AsS3)2 (Graeser et al., 1992);
edenharterite, TlPbAs3S6 (Graeser and Schwander,1992); stalderite, TlCuZn2(AsS3)2 (Graeser et al.,1995); jentschite, TlPbAs2SbS6 (Graeser and
Edenharter, 1997); sicherite, TlAg2As3S6 (Graeser
et al., 2001); gabrielite, Tl2AgCu2As3S7 (Graeser
et al., 2006); and the recently described species
dalnegroite, Tl 5x Pb 2x (As,Sb) 21x S 34 (x~1)(Nestola et al., 2010).
Raberite was visually identiﬁed as a possible
new species in 2008 by one of the authors (ME);investigations in 2009 by scanning electron
microscopy (Thomas Raber, pers. comm.) and
X-ray diffraction (Stefan Graeser, pers. comm.)
provided conﬁrmation. The specimen containing
raberite was collected in 1992 from the realgarrich zone (the so-called zone 1; Graeser et al.,2008) in the quarry. The association of raberitewith yellow ﬁbrous smithite (Fig. 1), has allowed
us to identify the precise position in the Triassic
dolomite where the specimen originated. Yellow
ﬁbrous smithite has only been found in a realgarrich zone that was worked at the very beginningof the ‘New Lengenbach’ quarry (where operations started in 1987). The dolomite in that zone
has a saccharoidal texture and the associatedsulﬁdes and sulfosalts occur in pore spaces. Pyrite
is of variable abundance. Minerals associated withraberite are yellow smithite, realgar, hatchite;probable trechmannite, edenharterite andjentschite, and two unidentiﬁed sulfosalts.
Raberite has been approved as a new mineralby the Commission on New Minerals,
Nomenclature and Classiﬁcation of the IMA(proposal 2012-017). The name honours Dr
Thomas Raber (b. 1966), a well known expert
on Lengenbach minerals for more than 20 years.
He has published many articles about Lengenbachminerals and is currently Vice-President of the
FGL (Forschungsgemeinschaft Lengenbach;
literally: research community Lengenbach).
Holotype material is deposited in the mineralogical collections of the Museum of Mineralogyof the Department of Geosciences at the
University of Padova (Italy), under catalogue
number MMP M11420. To our knowledge,
raberite has no synthetic or natural analogues.
Physical and optical properties
Raberite crystallizes very rarely as euhedralelongated black crystals up to ~0.15 mm long on

FIG. 1. Black euhedral raberite with yellowish ﬁbroussmithite on a dolomite matrix (white). The picture is
1 mm across.

1154

RABERITE, A NEW TL-BEARING SULFOSALT FROM LENGENBACH

from a 0.1 mm diameter spot on the specimen anda standard (SiC) in the same focussing conditions.
Reﬂectance percentages [listed as Rmin, Rmax, (l)]are as follows: 30.6, 31.8 (471.1 nm); 28.1, 29.3
(548.3 nm); 27.1, 28.0 (586.6 nm); and 25.8, 26.9
(652.3 nm).
X-ray crystallography and crystal-structure
determination
A small crystal fragment (65660655 mm) was
selected for study on a STOE-STADI IV CCD
single-crystal diffractometer (Table 1). No
systematic absences were observed in the initial

dataset, leading to a choice of space groups of P1
or P1̄. Statistical tests on the distribution of |E|
values (|E21| = 0.868) indicated the presence ofan inversion centre, suggesting that P1̄ was theappropriate choice. The positions of most of theatoms (Tl, Ag and As/Sb atoms) were determinedby direct methods using SHELXS (Sheldrick,2008). A least-squares reﬁnement on F2 using
these heavy atom positions and isotropic displacement parameters produced an R factor of 0.216.
Three-dimensional difference-Fourier synthesis
yielded the positions of the remaining sulfur
atoms. The program SHELXL (Sheldrick, 2008)
was used to reﬁne the structure. The occupancy of

TABLE 1. Crystallographic data and reﬁnement parameters for raberite.
Crystal data
Ideal formula
Crystal system
Space group
Unit-cell parameters, a, b, c (Å)
Unit-cell angles a, b, g (º)
Unit-cell volume (Å3)
Z
Crystal size (mm)Tl5Ag4As6SbS15
Triclinic
P1̄
8.920(1), 9.429(1), 20.062(3)79.66(1), 88.84(1), 62.72(1)1471.6(4)2
0.06560.06060.055

Data collection
Diffractometer
Temperature (K)Radiation, wavelength (Å)
2y max for data collection (º)
Crystaldetector distance (mm)h, k, l ranges
Axis, frames, width (º), time per frame (s)Total reflections collected
Unique reflections (Rint)
Unique reflections I > 2s(I)Data completeness to ymax (%)
Absorption correction method

STOE-STADI IV CCD
298(3)
MoKa, 0.71073
59.66
50
8 to 12, 12 to 13, 26 to 28
o, 570, 1.00, 40
14,1268174 (0.124)
2110
99.4
X-RED and X-SHAPE

Structure refinement
Refinement method
Data/restraints/parameters
R1 [I > 2s(I)], wR2 [I > 2s(I)]R1 all, wR2 allGoodness-of-fit on F2
Largest diff. peak and hole (e Å3)

Full-matrix least-squares on I
2110/0/286
0.0827, 0.1788
0.1088, 0.2140
0.752
3.05, 7.78

Reﬁnement parameters are as follows:
Rint = (n/n  1)1/2[F2o  Fo (mean)2]/SF2o
R1 = S||Fo|  |Fc||/S|Fo|; wR2 = {S[w(F2o  F2c )2]/S[w(F2o)2]}1/2;
GooF = {S[w(F2o  F2c )2]/(n  p)}1/2
where n is the number of reﬂections and p is the number of reﬁned parameters.

1155

L. BINDI ET AL.

all the sites, except the M sites (see below), wasleft free to vary (Tl vs. vacancy; Ag vs. vacancy; S
vs. vacancy) and then ﬁxed to the resulting value.
The occupancy of the seven M sites (Table 2) was
reﬁned using the curves of As vs. Sb. The reﬁned
values are given in Table 2. Neutral scattering
curves for Tl, Ag, As, Sb and S were taken fromthe International Tables for X-ray Crystallography(Ibers and Hamilton, 1974). At the last stage of thereﬁnement, with anisotropic atomic displacement
parameters for all atoms and no constraints, theresiduals settled at R = 0.0827 for 2110 observed
reﬂections [2s(I) level] and 286 parameters, and at
R = 0.1088 for all 8174 independent reﬂections.
Experimental details and R values are listed inTable 1. Fractional atom coordinates and isotropic

displacement parameters are reported in Table 2(anisotropic ADPs can be found in the accompanying CIF). Bond distances are given in
Table 3. Calculated X-ray powder diffraction
data, computed using the atom coordinates andoccupancies reported in Table 2, are listed inTable 4, with the measured pattern. Structure
factors have been deposited with the Principal
Editor of Mineralogical Magazine and areavailable at http://www. minersoc.org/pages/
e_journals/dep_mat_mm.html.
Chemical composition
A preliminary chemical analysis by energydispersive spectrometry was performed using a

TABLE 2. Atoms, site occupancies, fractional atom coordinates (Å) and isotropic atomic displacement
parameters (Å2) for raberite.*
Site

Site occupancy

x/a

y/b

z/c

Uiso

Tl1
Tl2
Tl3
Tl4
Tl5
Ag1
Ag2
Ag3
Ag4
M1
M2
M3
M4
M5
M6
M7
S1
S2
S3
S4
S5
S6
S7
S8
S9
S10
S11
S12
S13
S14
S15

Tl1.00
Tl1.00
Tl1.00
Tl1.00
Tl1.00Ag1.00Ag1.00Ag1.00Ag1.00As0.73(3)Sb0.27
Sb0.63(3)As0.37
As0.94(3)Sb0.06
As0.90(3)Sb0.10
As0.98(3)Sb0.02
As0.86(3)Sb0.14
As1.00
S1.00
S1.00
S1.00
S1.00
S1.00
S1.00
S1.00
S1.00
S1.00
S1.00
S1.00
S1.00
S1.00
S1.00
S1.00

0.8636(2)0.4966(2)0.1081(2)0.1239(2)0.5026(2)0.4460(4)0.4806(4)0.4636(4)0.3784(4)0.0113(4)0.2022(3)0.0093(4)0.1848(4)0.1041(4)0.6583(4)0.7797(4)0.188(1)0.175(1)0.175(1)0.200(1)0.742(1)0.170(1)0.507(1)0.463(1)0.205(1)0.170(1)0.148(1)0.245(1)0.250(1)0.245(1)0.481(1)0.6454(2)0.6427(2)0.3673(2)0.3643(2)0.3594(2)0.0195(4)0.0479(5)0.0017(4)0.3520(5)0.8450(4)0.8436(4)0.1649(4)0.8342(4)0.1270(5)0.3139(5)0.1143(5)0.269(1)0.671(1)0.659(1)0.741(1)0.003(1)0.314(1)0.259(1)0.755(1)0.292(1)0.334(1)0.312(1)0.019(1)0.610(1)0.952(1)0.782(1)0.40728(8)0.23847(9)0.27428(8)0.07844(9)0.43830(8)0.4081(2)0.0698(2)0.2397(2)0.1620(2)0.2238(2)0.0485(2)0.4491(2)0.3858(2)0.1402(2)0.0989(2)0.3188(2)0.4276(5)0.1534(5)0.3212(4)0.2416(5)0.4225(5)0.3506(5)0.2823(5)0.3954(5)0.0888(5)0.5160(4)0.1735(5)0.2420(5)0.0014(5)0.0967(5)0.0766(5)0.0385(4)0.0467(5)0.0373(4)0.0496(5)0.0382(4)0.054(1)0.078(1)0.068(1)0.069(2)0.028(1)0.037(1)0.027(1)0.026(1)0.031(1)0.038(2)0.0290(9)0.033(2)0.034(2)0.026(2)0.032(2)0.030(2)0.028(2)0.036(2)0.035(2)0.038(3)0.024(2)0.030(2)0.035(2)0.037(2)0.042(3)0.036(3)* All the atoms are in the 2i position.

1156

RABERITE, A NEW TL-BEARING SULFOSALT FROM LENGENBACHTABLE 3. Selected bond distances (Å) for raberite.
Tl1S1
Tl1S1
Tl1S3
Tl1S4
Tl1S5
Tl1S6
Tl1S8
Tl1S10
Tl1S10<Tl1S>

3.36(1)
3.52(1)3.28(1)
3.27(1)
3.11(1)3.64(1)
3.23(1)
3.46(1)
3.26(1)
3.35

Tl2S2
Tl2S3
Tl2S4
Tl2S6
Tl2S7
Tl2S8
Tl2S11
Tl2S12
Tl2S15<Tl2S>3.25(1)
3.24(1)3.25(1)
3.58(1)
3.53(1)
3.46(1)3.70(1)3.22(1)
3.26(1)
3.39

Tl3S1
Tl3S2
Tl3S3Tl3S4
Tl3S6
Tl3S7
Tl3S9Tl3S11
Tl3S12<Tl3S>

3.05(1)
3.66(1)3.36(1)3.28(1)3.07(1)3.22(1)
3.92(1)3.36(1)
3.13(1)
3.34

Tl4S2
Tl4S4Tl4S9Tl4S9Tl4S11
Tl4S13
Tl4S13
Tl4S14
Tl4S15<Tl4S>3.26(1)
3.55(1)3.33(1)
3.20(1)3.40(1)
3.61(1)
3.57(1)
3.61(1)
3.14(1)
3.41

Tl5S1
Tl5S3
Tl5S5Tl5S6
Tl5S7
Tl5S8
Tl5S8
Tl5S10
Tl5S10<Tl5S>3.31(1)3.51(1)
3.12(1)3.28(1)3.42(1)
3.53(1)3.29(1)
3.23(1)3.31(1)
3.33

Ag1S1
Ag1S5
Ag1S8<Ag1S>

2.51(1)2.59(1)2.49(1)
2.53

Ag2S9Ag2S14
Ag2S15<Ag2S>

2.57(1)2.52(1)2.49(1)
2.53

Ag3S4Ag3S7
Ag3S12<Ag3S>2.50(1)2.61(1)2.53(1)
2.55

Ag4S2Ag4S7
Ag4S9<Ag4S>2.68(1)2.52(1)2.46(1)
2.55

M1S2
M1S3
M1S4
<M1S>

2.39(1)2.43(1)2.30(1)
2.37

M2S2
M2S13
M2S15<M2S>

2.50(1)2.40(1)2.33(1)
2.41

M3S1
M3S6
M3S10<M3 S>2.22(1)2.35(1)2.29(1)
2.29

M4S3
M4S8
M4S10<M4 S>2.31(1)2.24(1)2.34(1)
2.30

M5S9
M5S11
M5S12<M5S>

2.23(1)2.31(1)2.23(1)
2.26

M6S11
M6S13
M6S14<M6 S>2.30(1)2.28(1)2.26(1)
2.28

M7S5
M7S6
M7S7
<M7 S>

2.25(1)2.32(1)2.23(1)
2.27

JEOL-5610 LV SEM at the Museum of Natural
History of Milan. The chemical composition was
subsequently determined by wavelength-dispersive spectrometry (WDS) using a CAMECACAMEBAX electron microprobe. The major- andminor-element composition was determined at
20 kV accelerating voltage and 20 nA beam
current with a 1 mm beam size and 15 s counting
times. The following lines and standards wereused in the WDS analyses: TlMa, AgLa, CuKa,
AsLa, SbLa and SKa; with synthetic Tl2Se (Tl),elemental Ag (Ag), elemental Cu (Cu), synthetic
AsGa (As), stibnite (Sb) and sphalerite (S),respectively. The crystal fragment was homogeneous to within analytical error. The averagechemical compositions (9 analyses on different

spots) together with wt.% ranges of elements arereported in Table 5. On the basis of 31 atoms, theempirical formula of raberite is
Tl4.85Ag4.28Cu0.02As5.72Sb1.16S14.97. The simpliﬁed ideal formula is Tl5Ag4As6SbS15, which
requires Tl 40.79, Ag 17.22, As 17.94, Sb 4.86,
S 19.19; total 100.00 wt.%.
Results and discussion

1157

In the crystal structure of raberite (Fig. 2)
columns of nine-coordinate Tl atoms forming
irregular polyhedra extend along [001] and form
sheets parallel to (010). The Tl atoms in thecolumns are interrupted by Ag4 and M6 positions(i.e. every 5 Tl positions there is the couple

L. BINDI ET AL.

TABLE 4. X-ray powder diffraction data for raberite.
— Calculated* —
hkl
dcalc
Icalc
(Å)
(%)
001
110
103
1̄1̄3
210
1̄13
123
020
200
220
015
213
2̄1̄3
11̄3
223
1̄2̄3
2̄03
2̄2̄2
006
016
2̄1̄4
2̄04
116
1̄2̄4
1̄20
130
2̄12
1̄23
133
1̄1̄6
311
01̄6
3̄2̄1
322
017
3̄2̄2
030
3̄1̄3
216
313
226
12̄3
300
2̄06
2̄1̄6
3̄2̄3
1̄3̄3
330
136
1̄2̄6
1̄26
217

19.687
7.772
4.883
4.760
4.458
4.139
4.136
4.112
3.954
3.886
3.850
3.729
3.647
3.580
3.520
3.506
3.498
3.484
3.281
3.271
3.266
3.195
3.151
3.112
3.108
3.066
3.027
3.017
3.001
2.909
2.899
2.865
2.859
2.839
2.832
2.752
2.742
2.690
2.673
2.669
2.657
2.638
2.636
2.618
2.613
2.609
2.598
2.591
2.483
2.481
2.480
2.405

8
19
14
7
12
14
27
8
16
31
7
37
19
100
26
58
32
13
73
33
5
16
11
8
28
21
10
54
98
26
12
21
8
5
16
9
43
13
14
31
51
13
46
28
12
11
13
57
21
6
25
6

– Measured{ –
dobs
Imeas
(Å)
(%)

3.650
3.578

20
100

3.476

75

3.278
3.267

80
30

3.086
3.050

30
20

2.996
2.994
2.880

50
85
30

2.853

15

2.729

25

2.665

75

2.638
2.624

15
40

2.585
2.478

50
25

2.476

20

— Calculated* —
hkl
dcalc
Icalc
(Å)
(%)
2̄2̄6
036
2̄23
140
3̄10
1̄3̄5
336
423
21̄6
4̄2̄3
109
2̄3̄6
040
1̄1̄9
229
306
2̄09
139
1̄29
3̄3̄6
03̄6
2̄33
444
11̄9
253
1̄2̄9
250
4̄1̄6
22̄6
2̄36
446
256
2̄4̄6
4̄10
149
319
1̄39
23̄3
453
1̄4̄6
2̄5̄3
0112
14̄3
41̄3
0212
4̄5̄3
056
526
0312
5̄3̄6
4̄09

1158

2.380
2.336
2.334
2.261
2.229
2.226
2.153
2.126
2.107
2.096
2.071
2.057
2.056
2.047
2.004
1.987
1.974
1.962
1.955
1.931
1.930
1.894
1.880
1.878
1.875
1.857
1.853
1.829
1.790
1.763
1.760
1.756
1.753
1.747
1.747
1.745
1.745
1.735
1.716
1.715
1.704
1.671
1.658
1.647
1.635
1.604
1.598
1.564
1.544
1.529
1.521

6
7
6
8
10
6
9
8
17
10
8
5
13
11
8
17
8
8
8
11
12
9
5
7
11
6
5
6
8
6
8
12
6
6
7
7
8
12
5
5
6
9
6
9
6
7
11
7
5
9
6

– Measured{ –
dobs
Imeas
(Å)
(%)

RABERITE, A NEW TL-BEARING SULFOSALT FROM LENGENBACHTABLE 5. Electron microprobe analyses (means, ranges and standard deviations) and atomic ratios (on the basisof 31 atoms per formula unit) for raberite.
Element

Mean (wt.%)

Range

SD

Atomic ratio

Tl
Ag
Cu
As
Sb
S
Total

39.55
18.42
0.06
17.08
5.61
19.15
99.87

38.4439.76
18.3020.30
0.000.07
16.3417.21
4.715.90
18.4319.20
98.55100.21

0.13
0.08
0.02
0.07
0.06
0.11
31.00

4.85
4.28
0.02
5.72
1.16
14.97

Ag4M6, which is at a distance of 2.68 Å). The
columns are decorated by corner-sharing MS3
pyramids (M = As, Sb) and linked by AgS3
triangles (Ag1, Ag2, and Ag3 positions). The Tl

atoms are in an irregular coordination environment (Fig. 3) and the distances to the surrounding
sulfur atoms are variable (Table 3). If we use
distances <3.40 Å to represent bonds (continuous

FIG. 2. The crystal structure of raberite projected down [100]. The horizontal direction is the c axis; Tl, Ag, As, Sb,
and S atoms are represented by blue, white, red, orange and yellow spheres, respectively. The unit cell is outlined.

Footnotes to Table 4 (facing page)The eight strongest lines are listed in bold.
* The calculated powder pattern with indexing for raberite on the basis of a = 8.920(1) Å, b = 9.429(1), c = 20.062(3) Å,a = 79.66(1), b = 88.84(1), g = 62.72(1), and with the atom coordinates and occupancies reported in Table 2.
{
The measured powder pattern for raberite obtained with a CCD-equipped single crystal diffractometer (CuKaradiation). The reﬁned unit-cell parameters from these data are as follows: a = 8.8670(9) Å, b = 9.3796(8), c =19.989(2) Å, a = 79.690(8), b = 89.226(8), g = 62.853(8), V = 1451.0(2) Å3.

1159

L. BINDI ET AL.

FIG. 3. Coordination environments of Tl atoms. Bond distances longer than 3.40 Å are represented by dashed lines;
Tl and S atoms are blue and yellow spheres, respectively.

FIG. 4. Corner-sharing M atoms. The As, Sb, and S atoms are red, orange and yellow spheres, respectively.

1160

RABERITE, A NEW TL-BEARING SULFOSALT FROM LENGENBACH

FIG. 5. The mean MS bond distance (Å) plotted against reﬁned As content (a.p.f.u.) at the different sites.

bonds in Fig. 3), Tl2 and Tl4 are ﬁve coordinate,
Tl1 and Tl5 are six coordinate and Tl3 is sevencoordinate. The Tl atoms are, however, nine
coordinate if longer distances (up to 4 Å) are
included (dashed bonds in Fig. 3). The mean bonddistances for the Tl-polyhedra are in the range
3.333.41 Å, which is in excellent agreementwith the sum of the ionic radii of VITl+ and S2
(3.34 Å; Shannon, 1976), suggesting that thebonding of thallium is largely ionic in thisstructure. The TlS distances in raberite aresimilar to Tl sites (Tl1 and Tl3) in gabrielite,
Tl2AsCu2As3S7 (3.383.49 Å; Balić-Žunić et al.,2006) and sicherite, TlAg2(As,Sb)3S6 (3.34 Å;Graeser et al., 2001). The AgS distances are in
the range 2.532.55 Å, which is similar to thosereported for different polytypes of pearceite–
polybasite (2.502.56 Å; Bindi et al., 2006,
2007; Evain et al., 2006). The M atoms, forming
corner-sharing rods along the c axis (Fig. 4), arethree coordinate. They occupy the top of apyramid with 3 sulfur atoms forming the base.
Bond distances are similar to those reported forsilver thioantimonates and silver sulﬁdes. Of theseven corner-sharing M positions (Table 2), only
one (M2) contains more Sb than As. The mean
MS bond distances reﬂect the As $ Sb
substitution that occurs at these sites (Fig. 5).
The Ag4M6 short contact (i.e. 2.68 Å) is
worthy of consideration. In general, all the Ag

FIG. 6. Crystal-chemical environment of the couple
Ag4M6. The contact between the two atoms is
depicted using a dashed line. The Ag, As and S atoms
are white, red and yellow spheres, respectively.

1161

L. BINDI ET AL.

TABLE 6. Bond valences (vu) for raberite.*
Site

BV

Site

BV

Tl1
Tl2
Tl3
Tl4
Tl5
Ag1
Ag2
Ag3
Ag4
M1
M2
M3
M4
M5
M6
M7

1.12(2)
1.02(2)1.30(2)0.98(2)
1.13(2)1.00(2)1.00(2)0.95(2)0.96(2)2.74(2)
3.06(2)3.04(2)3.03(2)
3.19(2)
3.23(2)
3.06(2)

S1
S2
S3
S4
S5
S6
S7
S8
S9
S10
S11
S12
S13
S14
S15

2.11(2)2.22(2)2.20(2)
1.96(2)
1.77(2)2.22(2)2.05(2)
1.98(2)2.14(2)2.39(2)2.04(2)
1.83(2)2.23(2)1.75(2)
1.96(2)(Natural History Museum, Milan, Italy) for theuse of the scanning electron microscope.
References* Calculated from the bond valence curves of Brese andO’Keeffe (1991).

atoms are displaced from the centre of the trigonalplane. The direction of the displacement depends
on the environment, whereas its extent usuallydepends on the degree of Ag substitution by alighter element such as Cu. In raberite, the Ag
positions are fully occupied by silver and, in thecase of the Ag4 site, the displacement is toward
the adjacent M6 with a reﬁned population of
As0.86(3)Sb0.14. The lone pair of electrons of thelatter site points toward the Ag4 atom (Fig. 6).
The short AgAs distance for Ag4M6 might beindicative of a situation in which As plays the roleof an anion. This has been hypothesized insynthetic compounds with short TlAs bonddistances (from 2.74 to 2.88 Å) such as
Rb5TaAs4Tl2 (Huang and Corbett, 1998), atransition-metal Zintl phase which contains the
TaAs4Tl5
2 polyanion.
Bond-valence sums calculated from the curvesof Brese and O’Keeffe (1991) are reported inTable 6. They are in excellent agreement with thecation populations assumed in the present study.
Acknowledgements
The manuscript beneﬁted from the revision of S.
Graeser, P. Leverett, D. Topa, and Associate
Editor S. Mills. The research was supported by‘‘progetto d’Ateneo 2006, University of Padova’’to FN. Thanks are due to Dr Federico Pezzotta

Balić-Žunić, T., Makovicky, E., Karanović, L., Poleti,
D. and Graeser, S. (2006) The crystal structure ofgabrielite, Tl2AgCu2As3S7, a new species of thallium
sulfosalt from Lengenbach, Switzerland. The
Canadian Mineralogist, 44, 141158.
Bindi, L., Evain, M. and Menchetti, S. (2006)
Temperature dependence of the silver distribution
in the crystal structure of natural pearceite,(Ag,Cu) 16 (As,Sb) 2 S 11 . Acta Crystallographica,
B62, 212219.
Bindi, L., Evain, M. and Menchetti, S. (2007) Complex
twinning, polytypism and disorder phenomena in the
crystal structures of antimonpearceite and arsenpolybasite. The Canadian Mineralogist, 45, 321333.
Brese, N.E. and O’Keeffe, M. (1991) Bond-valence
parameters for solids. Acta Crystallographica, B47,
192197.
Burry, G., Graeser, S., Marumo, F. and Nowacki, W.
(1965) Imhoﬁt, ein neues Thallium- Arsensulfosalz
aus dem Lengenbach (Binnatal, Kanton Wallis).
Chimia, 19, 499500.
Evain, M., Bindi, L. and Menchetti, S. (2006) Structuralcomplexity in minerals: twinning, polytypism anddisorder in the crystal structure of polybasite,(Ag,Cu) 16 (Sb,As) 2 S 11 . Acta Crystallographica,
B62, 447456.
Graeser, S. and Edenharter, A. (1997) Jentschite(TlPbAs2SbS6)  a new sulfosalt mineral from
Lengenbach, Binntal (Switzerland). Mineralogical
Magazine, 61, 131137.
Graeser, S. and Schwander, H. (1992) Edenharterite(TlPbAs3S6): a new mineral from Lengenbach,
Binntal (Switzerland). European Journal of
Mineralogy, 4, 12651270.
Graeser, S., Schwander, H., Wulf, R. and Edenharter, A.
(1992) Erniggliite (Tl2SnAs2S6), a new mineral from
Lengenbach, Binntal (Switzerland): description andcrystal structure determination based on data fromsynchrotron radiation. Schweizerische mineralogische und petrographische Mitteilungen, 72,
293305.
Graeser, S., Schwander, H., Wulf, R. and Edenharter, A.
(1995) Stalderite TlCu(Zn,Fe,Hg)2As2S6  a newmineral related to routhierite: description and crystal
structure determination. Schweizerische mineralogische und petrographische Mitteilungen, 75,
337345.
Graeser, S., Berlepsch, P., Makovicky, E. and BalićŽunić, T. (2001) Sicherite, TlAg2(As,Sb)3S6, a new
sulfosalt mineral from Lengenbach (Binntal,
Switzerland): description and structure determina-

1162

RABERITE, A NEW TL-BEARING SULFOSALT FROM LENGENBACH

tion. American Mineralogist, 86, 10871093.
Graeser, S., Topa, D., Balić-Zunić, T. and Makovicky,
E. (2006) Gabrielite, Tl2AgCu2As3S7, a new speciesof thallium sulfosalt from Lengenbach, Binntal,
Switzerland. The Canadian Mineralogist, 44,135140.
Graeser, S., Cannon, R., Drechsler, E., Raber, T. andRoth, P. (2008) Faszination Lengenbach AbbauForschung-Mineralien 19582008. Kristallographik
Verlag, Achberg, Germany.
Huang, D.P. and Corbett, J.D. (1998) A5TaAs4Tl2 (A =Rb, K). Transition-metal Zintl phases with a novel
complex ion: synthesis, structure, and bonding.
Inorganic Chemistry, 37, 40064010.

Ibers, J.A. and Hamilton, W.C. (editors) (1974)
International Tables for X-ray Crystallography,
volume. IV. Kynock Press, Birmingham, UK.
Nestola, F., Guastoni, A., Bindi, L. and Secco L. (2010)
Dalnegroite, Tl5xPb2x(As,Sb)21xS34, a new thallium sulphosalt from Lengenbach quarry, Binntal,
Canton Valais, Switzerland. Mineralogical
Magazine, 73, 10271032.
Shannon, R.D. (1976) Revised effective ionic radii andsystematic studies of interatomic distances in halides
and chalcogenides. Acta Crystallographica, A32,
751767.
Sheldrick, G.M. (2008) A short history of SHELX. Acta
Crystallographica, A64, 112122.

1163

data_shelxl_audit_creation_method_chemical_name_systematic;?
;_chemical_name_common_chemical_melting_point_chemical_formula_moiety_chemical_formula_sum'Ag4 As7 Cu0 S15 Sb0 Tl5'
_chemical_formula_weight

SHELXL-97?
?
?
2458.67

loop__atom_type_symbol_atom_type_description_atom_type_scat_dispersion_real_atom_type_scat_dispersion_imag_atom_type_scat_source'Ag' 'Ag' -0.8971
1.1015'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4''As' 'As'
0.04992.0058'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4''S' 'S'
0.12460.1234'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4''Tl' 'Tl' -2.8358
9.6688'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4''Sb' 'Sb' -0.5866
1.5461'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4''Cu' 'Cu'
0.32011.2651'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'_symmetry_cell_setting_symmetry_space_group_name_H-M

?
?

loop_
_symmetry_equiv_pos_as_xyz'x, y, z''-x, -y, -z'_cell_length_a_cell_length_b_cell_length_c_cell_angle_alpha_cell_angle_beta_cell_angle_gamma_cell_volume_cell_formula_units_Z_cell_measurement_temperature_cell_measurement_reflns_used_cell_measurement_theta_min_cell_measurement_theta_max

8.9200(10)9.4290(10)20.062(3)79.660(10)88.840(10)62.720(10)1471.6(3)2293(2)?
?
?

_exptl_crystal_description_exptl_crystal_colour_exptl_crystal_size_max_exptl_crystal_size_mid_exptl_crystal_size_min

?
?
?
?
?

_exptl_crystal_density_meas_exptl_crystal_density_diffrn_exptl_crystal_density_method_exptl_crystal_F_000_exptl_absorpt_coefficient_mu_exptl_absorpt_correction_type_exptl_absorpt_correction_T_min_exptl_absorpt_correction_T_max_exptl_absorpt_process_details?
5.549'not measured'2128
38.741?
?
?
?

_exptl_special_details;?
;_diffrn_ambient_temperature_diffrn_radiation_wavelength_diffrn_radiation_type_diffrn_radiation_source_diffrn_radiation_monochromator_diffrn_measurement_device_type_diffrn_measurement_method_diffrn_detector_area_resol_mean_diffrn_standards_number_diffrn_standards_interval_count_diffrn_standards_interval_time_diffrn_standards_decay_%_diffrn_reflns_number_diffrn_reflns_av_R_equivalents_diffrn_reflns_av_sigmaI/netI_diffrn_reflns_limit_h_min_diffrn_reflns_limit_h_max_diffrn_reflns_limit_k_min_diffrn_reflns_limit_k_max_diffrn_reflns_limit_l_min_diffrn_reflns_limit_l_max_diffrn_reflns_theta_min_diffrn_reflns_theta_max_reflns_number_total_reflns_number_gt_reflns_threshold_expression

293(2)
0.71073
MoK\a'fine-focus sealed tube'
graphite
?
?
?
?
?
?
?
14126
0.12440.3549
-8
12
-12
13
-26
28
2.84
29.83
8174
2110
>2sigma(I)_computing_data_collection_computing_cell_refinement_computing_data_reduction_computing_structure_solution_computing_structure_refinement_computing_molecular_graphics_computing_publication_material?
?
?
?
'SHELXL-97 (Sheldrick, 1997)'?
?

_refine_special_details;
Refinement of F^2^ against ALL reflections. The weighted R-factor wR andgoodness of fit S are based on F^2^, conventional R-factors R are basedon F, with F set to zero for negative F^2^. The threshold expression ofF^2^ > 2sigma(F^2^) is used only for calculating R-factors(gt) etc. and is
not relevant to the choice of reflections for refinement. R-factors basedon F^2^ are statistically about twice as large as those based on F, and Rfactors based on ALL data will be even larger.
;

_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type
full_refine_ls_weighting_scheme
calc_refine_ls_weighting_details'calc w=1/[\s^2^(Fo^2^)+(0.0725P)^2^+0.0000P] where P=(Fo^2^+2Fc^2^)/3'_atom_sites_solution_primary
direct_atom_sites_solution_secondary
difmap_atom_sites_solution_hydrogens
geom_refine_ls_hydrogen_treatment
mixed_refine_ls_extinction_methodnone_refine_ls_extinction_coef?
_refine_ls_number_reflns
8174_refine_ls_number_parameters286_refine_ls_number_restraints0_refine_ls_R_factor_all
0.1088_refine_ls_R_factor_gt
0.0827_refine_ls_wR_factor_ref
0.2140_refine_ls_wR_factor_gt
0.1788_refine_ls_goodness_of_fit_ref
0.752_refine_ls_restrained_S_all0.752_refine_ls_shift/su_max
0.000_refine_ls_shift/su_mean
0.000
loop_
_atom_site_label_atom_site_type_symbol_atom_site_fract_x_atom_site_fract_y_atom_site_fract_z_atom_site_U_iso_or_equiv_atom_site_adp_type_atom_site_occupancy_atom_site_symmetry_multiplicity_atom_site_calc_flag_atom_site_refinement_flags_atom_site_disorder_assembly_atom_site_disorder_groupTl1 Tl 0.86360(18) 0.64536(19) 0.40728(8) 0.0379(4) Uani 1 1 d . . .
Tl2 Tl 0.49665(19) 0.6427(2) 0.23849(9) 0.0462(5) Uani 1 1 d . . .
Tl3 Tl 0.10798(18) 0.36735(19) 0.27427(8) 0.0368(4) Uani 1 1 d . . .
Tl4 Tl 0.1238(2) 0.3643(2) -0.07842(10) 0.0491(5) Uani 1 1 d . . .
Tl5 Tl 0.50259(18) 0.35940(19) 0.43829(8) 0.0377(4) Uani 1 1 d . . .
Ag1 Ag 0.4460(4) 0.0196(4) 0.4081(2) 0.0535(10) Uani 1 1 d . . .
Ag2 Ag 0.4806(4) 0.0479(5) 0.0697(2) 0.0772(14) Uani 1 1 d . . .
Ag3 Ag -0.4635(4) 0.0017(4) 0.2396(2) 0.0669(12) Uani 1 1 d . . .
Ag4 Ag 0.3783(4) 0.3523(5) 0.1620(2) 0.0685(12) Uani 1 1 d . . .
As1 As -0.0113(4) 0.8450(4) 0.22383(16) 0.0282(13) Uani 0.73(3) 1 d P . .
Sb1 Sb -0.0113(4) 0.8450(4) 0.22383(16) 0.0282(13) Uani 0.27(3) 1 d P . .
As2 As 0.2022(3) 0.8436(4) 0.04852(16) 0.0364(12) Uani 0.37(3) 1 d P . .
Sb2 Sb 0.2022(3) 0.8436(4) 0.04852(16) 0.0364(12) Uani 0.63(3) 1 d P . .
As3 As 0.0093(4) 0.1649(4) 0.44915(18) 0.0264(14) Uani 0.94(3) 1 d P . .
Sb3 Sb 0.0093(4) 0.1649(4) 0.44915(18) 0.0264(14) Uani 0.06(3) 1 d P . .
As4 As 0.1847(4) 0.8340(4) 0.38579(18) 0.0262(13) Uani 0.90(3) 1 d P . .
Sb4 Sb 0.1847(4) 0.8340(4) 0.38579(18) 0.0262(13) Uani 0.10(3) 1 d P . .
As5 As 0.1041(4) 0.1271(5) 0.1402(2) 0.0300(14) Uani 0.98(3) 1 d P . .
Sb5 Sb 0.1041(4) 0.1271(5) 0.1402(2) 0.0300(14) Uani 0.02(3) 1 d P . .
As6 As 0.6583(5) 0.3140(5) 0.0990(2) 0.0396(16) Uani 0.86(3) 1 d P . .
Sb6 Sb 0.6583(5) 0.3140(5) 0.0990(2) 0.0396(16) Uani 0.14(3) 1 d P . .
As7 As 0.7797(4) 0.1143(5) 0.31882(19) 0.0284(9) Uani 1 1 d . . .
S1 S 0.1883(10) 0.2685(12) 0.4275(5) 0.033(2) Uani 1 1 d . . .
S2 S 0.1742(11) 0.6708(12) 0.1533(5) 0.034(2) Uani 1 1 d . . .

S3 S 0.1756(11) 0.6589(11) 0.3212(5) 0.025(2) Uani 1 1 d . . .
S4 S -0.1994(11) 0.7412(12) 0.2416(5) 0.032(2) Uani 1 1 d . . .
S5 S 0.7412(11) 0.0032(11) 0.4223(5) 0.029(2) Uani 1 1 d . . .
S6 S -0.1698(11) 0.3145(11) 0.3503(5) 0.027(2) Uani 1 1 d . . .
S7 S 0.5070(11) 0.2586(11) 0.2823(5) 0.035(3) Uani 1 1 d . . .
S8 S 0.4627(11) 0.7549(12) 0.3953(5) 0.034(2) Uani 1 1 d . . .
S9 S 0.2046(12) 0.2917(13) 0.0887(5) 0.038(3) Uani 1 1 d . . .
S10 S -0.1704(10) 0.3335(10) 0.5161(4) 0.024(2) Uani 1 1 d . . .
S11 S -0.1487(11) 0.3120(11) 0.1734(5) 0.029(2) Uani 1 1 d . . .
S12 S 0.2451(11) 0.0191(12) 0.2418(5) 0.034(2) Uani 1 1 d . . .
S13 S 0.2498(12) 0.6106(12) 0.0014(5) 0.036(2) Uani 1 1 d . . .
S14 S 0.2451(12) 0.9518(13) -0.0968(6) 0.041(3) Uani 1 1 d . . .
S15 S 0.4810(11) 0.7818(13) 0.0764(5) 0.036(3) Uani 1 1 d . . .
loop__atom_site_aniso_label_atom_site_aniso_U_11_atom_site_aniso_U_22_atom_site_aniso_U_33_atom_site_aniso_U_23_atom_site_aniso_U_13_atom_site_aniso_U_12
Tl1 0.0292(8) 0.0324(10) 0.0511(11) -0.0157(8) 0.0138(7) -0.0111(7)Tl2 0.0315(9) 0.0493(12) 0.0614(12) -0.0268(9) 0.0187(8) -0.0168(8)Tl3 0.0326(8) 0.0376(10) 0.0406(10) -0.0159(8) 0.0122(7) -0.0140(7)Tl4 0.0313(9) 0.0479(11) 0.0645(13) -0.0168(9) 0.0110(8) -0.0134(8)Tl5 0.0269(8) 0.0356(10) 0.0491(11) -0.0237(8) 0.0141(7) -0.0081(7)Ag1 0.0289(16) 0.044(2) 0.093(3) -0.035(2) 0.0195(17) -0.0143(15)Ag2 0.0328(19) 0.077(3) 0.139(4) -0.068(3) 0.032(2) -0.025(2)Ag3 0.0244(17) 0.044(2) 0.129(4) -0.036(2) 0.006(2) -0.0072(16)Ag4 0.045(2) 0.098(3) 0.070(3) -0.045(2) 0.0248(19) -0.029(2)As1 0.0243(18) 0.037(2) 0.030(2) -0.0196(16) 0.0181(15) -0.0165(16)Sb1 0.0243(18) 0.037(2) 0.030(2) -0.0196(16) 0.0181(15) -0.0165(16)As2 0.0263(17) 0.041(2) 0.046(2) -0.0259(16) 0.0160(14) -0.0129(14)Sb2 0.0263(17) 0.041(2) 0.046(2) -0.0259(16) 0.0160(14) -0.0129(14)As3 0.0204(19) 0.032(2) 0.030(2) -0.0173(17) 0.0153(15) -0.0106(16)Sb3 0.0204(19) 0.032(2) 0.030(2) -0.0173(17) 0.0153(15) -0.0106(16)As4 0.0162(18) 0.031(2) 0.031(2) -0.0183(17) 0.0090(15) -0.0061(15)Sb4 0.0162(18) 0.031(2) 0.031(2) -0.0183(17) 0.0090(15) -0.0061(15)As5 0.027(2) 0.024(2) 0.042(3) -0.0191(19) 0.0169(17) -0.0106(17)Sb5 0.027(2) 0.024(2) 0.042(3) -0.0191(19) 0.0169(17) -0.0106(17)As6 0.032(2) 0.052(3) 0.038(3) -0.010(2) 0.0107(18) -0.023(2)Sb6 0.032(2) 0.052(3) 0.038(3) -0.010(2) 0.0107(18) -0.023(2)As7 0.0216(18) 0.028(2) 0.036(2) -0.0206(18) 0.0119(16) -0.0071(16)S1 0.016(4) 0.036(6) 0.046(6) -0.015(5) 0.009(4) -0.009(4)S2 0.026(5) 0.031(6) 0.043(6) -0.018(5) 0.021(4) -0.010(4)S3 0.030(5) 0.015(5) 0.027(5) -0.009(4) 0.008(4) -0.006(4)S4 0.035(5) 0.029(6) 0.044(6) -0.017(5) 0.016(5) -0.022(5)S5 0.023(4) 0.024(5) 0.037(6) -0.012(4) 0.006(4) -0.006(4)S6 0.034(5) 0.028(5) 0.029(5) -0.014(4) 0.014(4) -0.020(4)S7 0.030(5) 0.017(5) 0.041(6) -0.007(4) 0.004(4) 0.005(4)S8 0.022(5) 0.035(6) 0.047(6) -0.018(5) 0.015(4) -0.011(4)S9 0.034(5) 0.044(7) 0.038(6) -0.014(5) 0.019(5) -0.018(5)S10 0.027(4) 0.011(5) 0.029(5) -0.008(4) 0.015(4) -0.005(4)S11 0.026(5) 0.025(5) 0.038(6) -0.021(5) 0.011(4) -0.008(4)S12 0.030(5) 0.031(6) 0.037(6) -0.011(5) 0.012(4) -0.010(4)S13 0.042(6) 0.031(6) 0.043(6) -0.018(5) 0.023(5) -0.021(5)S14 0.031(5) 0.042(7) 0.053(7) -0.014(5) 0.003(5) -0.018(5)S15 0.015(4) 0.050(7) 0.034(6) 0.003(5) 0.004(4) -0.013(4)_geom_special_details

;All esds (except the esd in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell esds are taken
into account individually in the estimation of esds in distances, angles
and torsion angles; correlations between esds in cell parameters are onlyused when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell esds is used for estimating esds involving l.s. planes.
;
loop__geom_bond_atom_site_label_1_geom_bond_atom_site_label_2_geom_bond_distance_geom_bond_site_symmetry_2_geom_bond_publ_flag
Tl1 S5 3.105(9) 1_565 ?
Tl2 Ag3 3.566(4) 1_665 ?
Tl3 S1 3.047(10) . ?
Tl3 S6 3.069(9) . ?
Tl3 S12 3.123(10) . ?
Tl3 Ag4 3.238(4) . ?
Tl4 S15 3.140(8) 2_665 ?
Tl5 S5 3.118(9) . ?
Ag1 S8 2.491(11) 1_545 ?
Ag1 S1 2.508(9) . ?
Ag1 S5 2.584(9) . ?
Ag2 S15 2.487(12) 1_545 ?
Ag2 S14 2.518(10) 2_665 ?
Ag2 S9 2.565(10) . ?
Ag2 Ag2 3.056(9) 2_655 ?
Ag2 Ag3 3.376(7) 1_655 ?
Ag3 S4 2.500(10) 1_545 ?
Ag3 S12 2.528(10) 1_455 ?
Ag3 S7 2.612(11) 1_455 ?
Ag3 Ag4 3.051(6) 1_455 ?
Ag3 Ag2 3.376(7) 1_455 ?
Ag3 Tl2 3.566(4) 1_445 ?
Ag4 S9 2.468(11) . ?
Ag4 S7 2.518(11) . ?
Ag4 As6 2.679(5) . ?
Ag4 S2 2.679(10) . ?
Ag4 Ag3 3.051(6) 1_655 ?
As1 S4 2.292(10) . ?
As1 S2 2.384(9) . ?
As1 S3 2.428(10) . ?
As2 S15 2.335(9) . ?
As2 S13 2.403(10) . ?
As2 S2 2.502(10) . ?
As3 S1 2.224(10) . ?
As3 S10 2.290(8) . ?
As3 S6 2.352(10) . ?
As4 S8 2.240(9) . ?
As4 S3 2.303(10) . ?
As4 S10 2.334(9) 2_566 ?
As5 S9 2.223(11) . ?
As5 S12 2.227(11) . ?
As5 S11 2.307(8) . ?
As6 S14 2.255(12) 2_665 ?
As6 S13 2.277(10) 2_665 ?
As6 S11 2.293(10) 1_655 ?
As7 S7 2.233(10) . ?

As7 S5 2.246(10) . ?
As7 S6 2.320(10) 1_655 ?
S4 Ag3 2.500(10) 1_565 ?
S5 Tl1 3.105(9) 1_545 ?
S6 As7 2.320(10) 1_455 ?
S7 Ag3 2.612(11) 1_655 ?
S8 Ag1 2.491(11) 1_565 ?
S10 Sb4 2.334(9) 2_566 ?
S10 As4 2.334(9) 2_566 ?
S11 Sb6 2.293(10) 1_455 ?
S11 As6 2.293(10) 1_455 ?
S12 Ag3 2.528(10) 1_655 ?
S13 Sb6 2.277(10) 2_665 ?
S13 As6 2.277(10) 2_665 ?
S14 Sb6 2.255(12) 2_665 ?
S14 As6 2.255(12) 2_665 ?
S14 Ag2 2.518(10) 2_665 ?
S15 Ag2 2.487(12) 1_565 ?
S15 Tl4 3.140(8) 2_665 ?
loop__geom_angle_atom_site_label_1_geom_angle_atom_site_label_2_geom_angle_atom_site_label_3_geom_angle_geom_angle_site_symmetry_1_geom_angle_site_symmetry_3_geom_angle_publ_flag
S1 Tl3 S6 67.3(2) . . ?
S1 Tl3 S12 97.9(3) . . ?
S6 Tl3 S12 88.3(2) . . ?
S1 Tl3 Ag4 125.47(17) . . ?
S6 Tl3 Ag4 160.65(19) . . ?
S12 Tl3 Ag4 76.10(19) . . ?
S8 Ag1 S1 127.2(3) 1_545 . ?
S8 Ag1 S5 112.4(3) 1_545 . ?
S1 Ag1 S5 119.5(3) . . ?
S15 Ag2 S14 118.4(3) 1_545 2_665 ?
S15 Ag2 S9 118.2(3) 1_545 . ?
S14 Ag2 S9 117.9(4) 2_665 . ?
S15 Ag2 Ag2 68.9(3) 1_545 2_655 ?
S14 Ag2 Ag2 104.4(3) 2_665 2_655 ?
S9 Ag2 Ag2 118.0(3) . 2_655 ?
S15 Ag2 Ag3 93.8(3) 1_545 1_655 ?
S14 Ag2 Ag3 71.4(3) 2_665 1_655 ?
S9 Ag2 Ag3 81.4(3) . 1_655 ?
Ag2 Ag2 Ag3 158.2(2) 2_655 1_655 ?
S4 Ag3 S12 123.0(3) 1_545 1_455 ?
S4 Ag3 S7 127.1(3) 1_545 1_455 ?
S12 Ag3 S7 105.7(3) 1_455 1_455 ?
S4 Ag3 Ag4 138.5(3) 1_545 1_455 ?
S12 Ag3 Ag4 88.8(3) 1_455 1_455 ?
S7 Ag3 Ag4 52.1(2) 1_455 1_455 ?
S4 Ag3 Ag2 90.0(3) 1_545 1_455 ?
S12 Ag3 Ag2 85.0(3) 1_455 1_455 ?
S7 Ag3 Ag2 115.1(3) 1_455 1_455 ?
Ag4 Ag3 Ag2 64.80(13) 1_455 1_455 ?
S4 Ag3 Tl2 61.8(2) 1_545 1_445 ?
S12 Ag3 Tl2 61.2(2) 1_455 1_445 ?
S7 Ag3 Tl2 158.2(3) 1_455 1_445 ?
Ag4 Ag3 Tl2 137.77(15) 1_455 1_445 ?

Ag2 Ag3 Tl2 82.48(12) 1_455 1_445 ?
S9 Ag4 S7 138.0(4) . . ?
S9 Ag4 As6 107.7(3) . . ?
S7 Ag4 As6 97.9(3) . . ?
S9 Ag4 S2 98.8(4) . . ?
S7 Ag4 S2 103.8(3) . . ?
As6 Ag4 S2 108.7(3) . . ?
S9 Ag4 Ag3 89.9(3) . 1_655 ?
S7 Ag4 Ag3 54.9(2) . 1_655 ?
As6 Ag4 Ag3 94.05(16) . 1_655 ?
S2 Ag4 Ag3 151.6(3) . 1_655 ?
S9 Ag4 Tl3 85.7(2) . . ?
S7 Ag4 Tl3 66.7(2) . . ?
As6 Ag4 Tl3 164.56(18) . . ?
S2 Ag4 Tl3 75.8(2) . . ?
Ag3 Ag4 Tl3 77.90(13) 1_655 . ?
S4 As1 S2 100.0(3) . . ?
S4 As1 S3 93.0(4) . . ?
S2 As1 S3 88.2(3) . . ?
S15 As2 S13 100.0(4) . . ?
S15 As2 S2 95.5(3) . . ?
S13 As2 S2 81.5(3) . . ?
S1 As3 S10 101.0(3) . . ?
S1 As3 S6 95.5(4) . . ?
S10 As3 S6 92.8(3) . . ?
S8 As4 S3 101.3(3) . . ?
S8 As4 S10 98.1(4) . 2_566 ?
S3 As4 S10 89.9(3) . 2_566 ?
S9 As5 S12 105.4(4) . . ?
S9 As5 S11 100.9(4) . . ?
S12 As5 S11 98.4(3) . . ?
S14 As6 S13 98.8(4) 2_665 2_665 ?
S14 As6 S11 103.0(4) 2_665 1_655 ?
S13 As6 S11 99.9(4) 2_665 1_655 ?
S14 As6 Ag4 96.1(3) 2_665 . ?
S13 As6 Ag4 142.9(3) 2_665 . ?
S11 As6 Ag4 109.5(3) 1_655 . ?
S7 As7 S5 97.0(4) . . ?
S7 As7 S6 100.5(4) . 1_655 ?
S5 As7 S6 98.1(4) . 1_655 ?
As3 S1 Ag1 99.7(4) . . ?
As3 S1 Tl3 96.4(3) . . ?
Ag1 S1 Tl3 88.4(3) . . ?
As1 S2 As2 108.4(4) . . ?
As1 S2 Ag4 137.6(4) . . ?
As2 S2 Ag4 113.6(3) . . ?
As4 S3 As1 102.2(3) . . ?
As1 S4 Ag3 98.5(4) . 1_565 ?
As7 S5 Ag1 103.9(4) . . ?
As7 S5 Tl1 101.5(3) . 1_545 ?
Ag1 S5 Tl1 82.8(3) . 1_545 ?
As7 S5 Tl5 85.7(3) . . ?
Ag1 S5 Tl5 78.1(2) . . ?
Tl1 S5 Tl5 160.7(3) 1_545 . ?
As7 S6 As3 100.0(4) 1_455 . ?
As7 S6 Tl3 114.0(3) 1_455 . ?
As3 S6 Tl3 93.1(3) . . ?
As7 S7 Ag4 128.4(4) . . ?
As7 S7 Ag3 87.1(3) . 1_655 ?
Ag4 S7 Ag3 73.0(3) . 1_655 ?
As4 S8 Ag1 97.9(3) . 1_565 ?

As5 S9 Ag4 115.9(4) . . ?
As5 S9 Ag2 91.0(4) . . ?
Ag4 S9 Ag2 86.7(3) . . ?
As3 S10 Sb4 106.5(3) . 2_566 ?
As3 S10 As4 106.5(3) . 2_566 ?
Sb4 S10 As4 0.00(18) 2_566 2_566 ?
Sb6 S11 As6 0.0(2) 1_455 1_455 ?
Sb6 S11 As5 102.1(3) 1_455 . ?
As6 S11 As5 102.1(3) 1_455 . ?
As5 S12 Ag3 111.8(4) . 1_655 ?
As5 S12 Tl3 89.7(3) . . ?
Ag3 S12 Tl3 88.2(3) 1_655 . ?
Sb6 S13 As6 0.0(3) 2_665 2_665 ?
Sb6 S13 As2 96.8(4) 2_665 . ?
As6 S13 As2 96.8(4) 2_665 . ?
Sb6 S14 As6 0.0(3) 2_665 2_665 ?
Sb6 S14 Ag2 99.8(4) 2_665 2_665 ?
As6 S14 Ag2 99.8(4) 2_665 2_665 ?
As2 S15 Ag2 105.7(4) . 1_565 ?
As2 S15 Tl4 162.2(5) . 2_665 ?
Ag2 S15 Tl4 85.4(3) 1_565 2_665 ?
_diffrn_measured_fraction_theta_max_diffrn_reflns_theta_full_diffrn_measured_fraction_theta_full_refine_diff_density_max
3.053_refine_diff_density_min-7.780_refine_diff_density_rms
0.718

0.994
29.83
0.965