295
The Canadian Mineralogist
Vol. 50, pp. 295-312 (2012)
DOI : 10.3749/canmin.50.2.295

CUPROMAKOPAVONITE, Cu8Ag3Pb4Bi19S38, A NEW MINERAL SPECIES,ITS CRYSTAL STRUCTURE AND THE CUPROPAVONITE HOMOLOGOUS SERIESDan TOPA§
Department of Materials Research and Physics, Paris–Lodron University of Salzburg, Hellbrunnerstrasse 34,
A–5020, Salzburg, Austria

Emil MAKOVICKY
Department of Geography and Geology, University of Copenhagen, Østervoldgade 10, DK–1350, Copenhagen K, Denmark

Gheorghe ILINCA
Department of Mineralogy, University of Bucharest, Bd. N. Bălcescu, 1, RO–010041, Bucharest, Romania

Herbert DITTRICH
Department of Materials Research and Physics, Paris–Lodron University of Salzburg, Hellbrunnerstrasse 34,
A–5020, Salzburg, Austria

Abstract
Cupromakopavonite, ideally Cu8Ag3Pb4Bi19S38, is a new mineral species found in quartz veins at the scheelite deposit
Felbertal, Salzburg Province, Austria. It is associated with makovickyite, oversubstituted krupkaite (bd55), hodrušite, andkupčikite. The mineral is opaque and grey with a metallic luster; it is brittle without any discernible cleavage. In reflected light,
it is greyish white, the bireflectance is weak, and the anisotropy is moderate in air and strong in oil. Internal reflections areabsent. The reflectance data (%, air) are: 42.9, 46.6 at 470 nm, 42.1, 46.5 at 546 nm, 41.3, 45.8 at 589 nm and 40.2, 45.1 at 650
nm. The average results of 15 electron-microprobe analyses are: Cu 7.29(6), Ag 5.48(4), Pb 8.84(14), Cd 0.39(6), Bi 59.9(2),S 17.90(6), total 99.80(23) wt.%, corresponding to Cu7.82Ag3.46Pb2.91Cd0.24Bi19.53S38.05 (on the basis of Me + S = 72 apfu). The
simplified formula, Cu8Ag3Pb4Bi19S38, is in accordance with the results of our crystal-structure analysis. The density, 6.85 g/cm3,
was calculated using the ideal (structural) formula. Cupromakopavonite has a monoclinic cell with a 13.380(2), b 4.0007(6), c
31.083(4) Å, b 93.064(2)°, V 1661.5(4) Å3, space group C2/m, and Z = 1. The strongest eight lines in the (calculated) powderdiffraction pattern [d in Å(I)hkl] are: 3.607(57)(207), 3.457(99)(114), 3.436(37)(208), 3.340(34)(401), 2.953(28)(311), 2.874(33)(2010), 2.834(100)(313) and 2.256(29)(1111). The crystal structure was refined to R = 4.53% and wR = 6.0% for 1834 reflections[Fo > 4s(Fo)]. Our crystal-structure determination reveals that the unusually high value of the c parameter results from: (1)regular alternation of pavonite-like N = 4 and N = 5 layers in the structure, (2) regularly oriented distribution of the pairs ofBi pyramids and pairs of Pb–Bi prisms in the thin slabs of the structure, and (3) the appearance of a new three-coordinated Cusite instead of the octahedrally coordinated Ag site in the thin slabs. Cupromakopavonite is the N = 4.5 member of the newly
defined cupropavonite homologous series, and its name underscores its close structural relationships to its two neighboring
members, cupromakovickyite (N = 4) and cupropavonite (N = 5). We define the structural and chemical properties of this series,
with the general, ideal formula, Cu8Ag2N– 6Pb4Bi2N+10S4N+20 for Z = 1, where N is the order of the homologue. It includes N = 7(“cuproplumbian benjaminite”) and N = 8 (“cuproplumbian mummeite”).
Keywords: cupromakopavonite, sulfosalt, new mineral species, crystal structure, pavonite homologous series, cupropavonite
homologous series, Felbertal deposit, Austria.

§

E-mail address: dan.topa@sbg.ac.at296

the canadian mineralogist

Introduction and History
Among sulfosalts, there are very few families thatexhibit spectacular intergrowths produced by exsolution from an originally homogeneous high-temperaturephase: the bismuthinite–aikinite solid-solution series(Topa et al. 2002), stannite–kësterite and other phases
related to chalcopyrite (Moh 1975), and the phases ofa broadly defined pavonite homologous series. Several
natural occurrences of the members of the latter series,
defined by Makovicky et al. (1977), exhibit lamellarintergrowths of Cu (and Pb)-poor and Cu (and Pb)-richphases. The first detailed X-ray-diffraction study ofsuch a pavonite-like material with a lamellar structure
revealed the presence of two chemically and structurally
different phases. Both phases have almost identical a andb parameters (13.4 and 4 Å, respectively), whereas the caxis is doubled for the Cu (and Pb)-rich phase, named
cupropavonite for its Cu-rich content (Karup-Møller &Makovicky 1979, Nuffield 1980). Analogous exsolution phenomena were observed for homologue N = 4,
makovickyite (Žák et al. 1994, Mumme 1990), and forhomologue N = 8, mummeite (Karup-Møller & Mako­
vicky 1992). These cases also were interpreted as theresult of decomposition of a homogeneous high-temperature phase. Such exsolution-related pairs represent two
mineral species, separated by a definite miscibility-gap.
Consequently, the Cu (and Pb)-rich varieties (for N = 4
and 8) received a working modifier, “cuproplumbian”(Karup-Møller & Makovicky 1992, Žák et al. 1994).
During a systematic study of mineral specimens fromBăiţa Bihor, in the Apuseni Mountains of Romania, andfrom the Felbertal deposits, Mittelsill, Austria, we foundlamellar intergrowths of makovickyite and “cuproplumbian” makovickyite, as well as homogeneous
grains of “cuproplumbian” makovickyite. This led tothe description of the 29.9 Å variety as a new mineral,cupromakovickyite, and the first determination of acrystal structure of the copper-rich component (Topa& Paar 2008, Topa et al. 2008). Although no crystal of(relatively) pure cupropavonite has yet been found, andits crystal structure is still unknown, we provide in thepresent contribution a formal mineralogical descriptionof a new mineral species, cupromakopavonite, a Cuand Pb-rich phase structurally positioned between the
N = 4 and N = 5 homologues, together with a complete
determination of its crystal structure. The current levelof structural and chemical knowledge on the Cu–Pb-richphases based on the generalized principle of pavonite
allows us to propose a definition of a new homologous
series, crystal-chemically distinct from the “classical”
pavonite series, and named after its first known member,cupropavonite.

in quartz veins of the K8 orebody, whereas orebodies
K1, K3 and K5 contain Cu-free makovickyite (N = 4)
and pavonite (N = 5) (Topa 2001, Topa et al. 2003b,
Topa & Paar 2008). The minerals associated withcupromakopavonite are bismuthinite derivatives in
the range aikinite (bd92)– krupkaite (bd56), Cu-bearing
makovickyite, hodrušite, cuprobismutite, kupčikite,
traces of wittichenite, native bismuth, chalcopyrite andpyrrhotite in a matrix of quartz. This mineralization
formed by the recrystallization of sulfide and sulfosalt
material in quartz veins hosted within felsic gneisses
and amphibolites. Recrystallization occurred during
the retrograde stage of Alpine metamorphism (Topaet al. 2002).
Cupromakopavonite was found only as inclusions
in a matrix of oversubstituded krupkaite (bd56). It canappear either as homogeneous grains or as a component
in lamellar intergrowths with Cu-bearing makovickyite(Fig. 1). The cupromakopavonite – makovickyite
grains represent remnants of larger aggregates withwell-defined exsolution lamellae of the two minerals,
intensely but selectively replaced by krupkaite (Fig. 1).
The extractable homogeneous grains of each phasereach a size of 0.1 mm. The marked places in Figure 1
were investigated by back-scattered electron imaging
and quantitative chemical analyses, and used for themechanical extraction of cupromakopavonite crystals
for structural studies.

Physical Properties and Optical Data
Cupromakopavonite is opaque with a metallic luster;it has a grey color and a grey streak. The mineral isbrittle, the fracture is uneven, and cleavages or parting
were not observed. The density and microhardness
could not be measured because no suitable free grains
were available. The calculated density based on theideal formula is 6.78 g/cm3.
In polarized light, cupromakopavonite is greyish
white, without internal reflections. Bireflectance isperceptible in air and moderate in oil, and pleochroism
is absent. Anisotropy is moderate in air and strong inoil. The rotation tints between crossed polars are dark
bluish grey to yellowish brown for the most strongly
anisotropic grains. Reflectance data were obtained in
air using a Leitz MPV–SP microscope photometer anda WTiC standard. The observed Rmin and Rmax values
are summarized in Table 1. Both the Rmin curve and theRmax curve are flat, with a weak maximum at 470–500
nm for the R max curve. This maximum is slightly
displaced toward longer wavelengths compared to thatobserved for cupromakovickyite from Felbertal (Topa& Paar 2008).

Research Material

Chemical Data

Cupromakopavonite has been detected at thescheelite deposit of Felbertal, Hohe Tauern, Austria,

Cupromakopavonite and the associated sulfosalt
minerals were analyzed using an JEOL Superprobethe crystal structure of cupromakopavonite

297

F ig . 1. Back-scattered electron images of exsolution intergrowths of Cu-bearing makovickyite (lighter, mak) andcupromakopavonite (darker, cmp) heavily replaced by oversubstituted krupkaite, accompanied by subhedral kupčíkite(ku) and hodrušite (ho). Length of bars is 100 mm in both photographs. The image on the right side makes use of the same
conventions as the one with lettering. The grains extracted for the structure studies are marked (*).

JXA–8600 electron microprobe, controlled by Probefor Windows system of programs, and operated at

25 kV and 35 nA, with a beam diameter of 5 mm.
Wavelength-dispersion data were collected using thefollowing standards (all synthetic except galena) andemission lines: Bi2S3 (BiLa, SKa), galena (PbLa),
chalcopyrite (CuKa, FeKa), Ag metal (AgLa), CdTe
(CdLb, TeLa), and Bi2Se3 (SeLa). The raw data werecorrected with the on-line ZAF–4 procedure. The resultsof the electron-microprobe analyses are compiled inTable 2. The absence of iron, antimony, tellurium, andselenium, and the systematic presence of cadmium (upto 0.5 wt.% in makovickyite, and 0.4 wt.% in cupromakopavonite), have been noted. The empirical formulae

TABLE 1. REFLECTANCE DATA (IN AIR) FOR CUPROMAKOPAVONITE
FROM FELBERTAL, SALZBURG PROVINCE, AUSTRIA____________________________________________________________I (nm)
Rm in %
Rm ax %I (nm)
Rm in %
Rm ax %____________________________________________________________
400
43.45
45.82
560
42.22
46.06
420
43.28
45.77
580
41.86
45.69
440
43.22
45.29
589
41.34
45.78
460
43.13
46.55
600
41.57
45.71
470
42.91
46.56
620
41.01
45.25
480
42.86
47.15
640
40.83
44.64
500
42.74
46.94
650
40.24
45.13
520
42.58
46.64
660
40.73
45.28
540
42.39
46.40
680
40.64
44.43
546
42.1
46.46
700
39.72
44.61
__________________________________________________________of cupromakopavonite and associated makovickyite inTable 2 were calculated on the basis of 18 S apfu formakovickyite, in which previous investigations reveal
a non-integral and variable number of cations pfu, and72 (Me + S) apfu for cupromakopavonite, for whicha structure investigation (below) suggests an integral
number of cations pfu. Chemical data for the Cu-bearing
makovickyite and cupromakopavonite in Table 2 areplotted in the triangular diagram Bi – Ag – (Pb + Cu)
in Figure 2. The chemical composition of associatedkupčíkite, hodrušite and cuprobismutite is presented
and discussed in detail in Topa et al. (2003a, 2003b),whereas bismuthinite derivatives are treated in Topaet al. (2002).
In order to illustrate the associations and the crystal
chemistry of the phases involved, we adopted theempirical Bi – Ag – (Pb + Cu) diagram (Karup-Møller
& Makovicky 1979), used for pavonite homologues(Fig. 2), to present the combined data for the Felbertal
occurrence of cupromakopavonite, makovickyite andpavonite and for those from the Băiţa Bihor occurrenceof makovickyite and cupromakovickyite described byTopa & Paar (2008). From the left-hand side of the
diagram, the copper-free homologues, makovickyite (N= 4) and pavonite (N = 5) (Topa & Paar 2008) [indicated by empty symbols in Fig. 2] follow the lines of
the Ag + Bi $ 2Pb substitution (Topa & Paar 2008),
parallel to those known from lillianite homologues andfrom the matildite–galena solid solution. At the end of
the N = 4 line, the averaged composition, Cu2.21Ag1.83

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the canadian mineralogist

Fig. 2. Positions of selected pavonite homologues, cupromakovickyite and cupromakopavonite in the Ag – Bi – (Pb+ Cu) diagram. Red lines indicate the Ag + Bi $ 2Pb substitution trends for the N = 4 and 5 pavonite homologues,
respectively. Empirical compositions are shown for selected Cu-free makovickyite (N = 4) and pavonite (N = 5) samples,Cu-bearing (homogeneous) makovickyite from Felbertal, and of the makovickyite – cupromakovickyite and makovickyite– cupromakopavonite exsolution pairs from Băiţa Bihor (BB) and Felbertal (K8 and other orebodies, respectively).
Abbreviations: hom: homogeneous, mak: makovickyite, cupromak: cupromakovickyite, exsol: exsolved lamellae, b: bright,
d: dark.

Pb0.48Cd0.15Bi10.21S18, for makovickyite in exsolution
pair with cupromakopavonite, suggests that 1.17 Cu
apfu in makovickyite can be considered substitutional,
compensating for the lack of silver with respect to theideal formula Ag3Bi11S18; in addition, 1.04 Cu apfu isinterstitial to the fundamental cation sites of the N =4 homologue. The large cations amount to 10.85 apfu,
which practically corresponds to the Bi sites of the ideal
formula. The presence of 1.17 atoms Cu pfu substituting
for Ag distorts the substitution trend in the empirical
diagram in the direction of the horizontal Cu $ Ag
substitution line. The presence of interstitial copper,
however, exerts the opposite effect, decreasing theamount of Bi present in favor of more Pb in the formula.
The resulting position of the phase in the diagram isindicated by filled circles in Figure 2.
Another trend is followed by the copper-containing
homogeneous makovickyite from the K8 deposit ofFelbertal (Topa & Paar 2008). In comparison to thephase examined above (and quoted in Table 2), thisphase has less Ag, less Pb, more Bi and about the same
Cu contents. Correspondingly, less interstitial copper ispresent, and at about 20 at.% (Pb + Cu) of the cation
sum, the above-mentioned simple substitution line isabandoned, and a trend toward progressively lower
apparent values of N and the Cu $ Ag substitution
begins (light grey lozenges in Fig. 2). The exsolution
pair makovickyite–cupromakovickyite from Băiţa Bihor(Topa et al. 2008) continues this latter trend. It displays
the makovickyite–cupromakovickyite tie-line with thesame general orientation as observed by Karup-Møller
& Makovicky (1979) for a pavonite–cupropavonite pair.

X-Ray-Diffraction Data
For our single-crystal investigation, irregular,
blade-like fragments were extracted from the polishedspecimen (Fig. 1). Intensity data were collected onthe crystal structure of cupromakopavonite

a Bruker AXS P3 diffractometer operated at 50 kV
and 35 mA, equipped with a CCD area detector usinggraphite-monochromated MoKa radiation. Experimental data are listed in Table 3. The SMART (Bruker
AXS 1998a) system of programs was used for unit-celldetermination and data collection, SAINT+ (Bruker
AXS 1998b) for the reduction of the intensity data, and
XPREP (Bruker AXS 1997) for space-group determination and empirical absorption-correction based on
pseudo C-scans. The centrosymmetric space-groupC2/m, proposed by the XPREP program, was chosen.
It is consistent with the monoclinic symmetry of thelattice and intensity statistics (mean |E * E – 1| = 1.019[expected values: 0.968 for the centrosymmetric caseand 0.736 for the non-centrosymmetric case]). The
structure of cupromakopavonite was solved by direct
methods (program SHELXS, Sheldrick 1997a), which
revealed most of the atom-positions. In subsequent
cycles of the refinement (program SHELXL, Sheldrick
1997b), remaining atom-positions were deduced fromdifference-Fourier syntheses by selecting from among
the strongest maxima at appropriate distances. Dataon X-ray diffraction and the structure refinement aresummarized in Table 3. Positional and displacement
parameters refined are given in Table 4, selected interatomic distances, in Table 5, and coordination-polyhedron characteristics calculated with IVTON program(Balić-Žunić & Vicković 1996), in Table 6. Tables
listing the observed and calculated structure-factors may
be obtained from the Depository of Unpublished Dataon the Mineralogical Association of Canada website

299[document Cupromakopavonite CM50_295]. The sitelabeling and the crystal structure of cupromakopavonite
are illustrated in Figures 3 and 4, respectively.
Cupromakopavonite is monoclinic, space groupC2/m, with a 13.380(2), b 4.0007(6), c 31.083(4) Å, b
93.064(2)°, V 1661.5(4) Å3, and Z = 1, for a structural
formula Cu8Ag3Pb4Bi19S38. Its theoretical powderdiffraction pattern (Table 7) was calculated using
PowderCell 2.3 software (Kraus & Nolze 1999) fora Debye–Scherrer configuration. We used CuKa radiation (l = 1.540598 Å), a fixed slit, no correction for
anomalous dispersion, and unit-cell parameters, spacegroup, atom positions, site occupancy and anisotropic
displacement factors from the refined structure.

Description of the Structure
In the structure of cupromakopavonite, there are five
Bi sites, one Ag site, one Pb site, two Cu sites and ten
S sites. The site-occupancy factors for the two Cu sites
refine to the scattering power of a Cu atom and were
subsequently fixed. The site-occupancy factors of two
Bi sites (Bi4, Bi5) are significantly lower (indicating
the presence of a lighter element) compared with thesite-occupancy factors of the remaining ones (Bi1, Bi2
and Bi3), refined as pure Bi sites.
The structure (Fig. 4) is composed of three types oflayer. The A layers, N = 4, are composed of coordination octahedra, four octahedra thick if counted along the(100)PbS plane diagonal to the layers themselves. The B
layers are thinner and asymmetric; they accommodate

TABLE 2. AVERAGE RESULTS OF ELECTRON-MICROPROBE ANALYSES OF CUPROMAKOPAVONITE
FROM FELBERTAL, AUSTRIA, AND OF OTHER HOMOLOGUES QUOTED______________________________________________________________________________________________________________
No.
mineral
NA
Cu
Ag
Pb
Cd
Bi
S
total
NP NP1 NP2 NP3 ÓMe chev______________________________________________________________________________________________________________
1

cupromakopavonite

17

7.29 5.48 8.84 0.39 59.90 17.90 99.80 4.5 3.50 5.45 4.48 33.91 0.08 0.08
0.06 0.04 0.14 0.06
0.20
0.06
0.23
2
makovickyite
26 4.44 6.23 3.12 0.52 67.24 18.19 99.77
4 3.05 4.11 3.58 14.88 -0.08 -0.21
0.23 0.13 0.50 0.07
0.71
0.06
0.31
3
cupropavonite
9 6.87 5.90 13.09 0.02 56.71 17.60 100.35
5 4.19 6.18 5.18 36.12 0.46 0.44
0.16 0.09 0.16 0.02
0.30
0.07
0.28
4
pavonite
8 2.66 9.32 6.23 0.05 64.17 17.65 100.29
5 4.69 5.45 5.07 16.80 0.57 0.53
0.12 0.18 0.23 0.02
0.31
0.08
0.09
5
cuproplumbian mummeite
3 5.14 12.80 7.80 57.35 17.43 100.68
8 8.06 10.14 9.11 48.43 0.82 0.80
0.01 0.10 0.10
0.05
0.03
0.31
6
mummeite
3 0.91 13.50 10.15 58.13 17.08 99.95
8 8.82 9.20 9.01 22.63 0.39 0.37
0.01 0.02 0.06
0.32
0.04
0.37
______________________________________________________________________________________________________________
1) Cu7.82 Ag3.46 (Pb2.91 Cd0.24 )Ó3.15 Bi19.53 S38.05
4) Cu1.52 Ag3.05Pb1.09Cd0.02Bi11.12Sb0.01Se0.02Te0.07S39.80
2) Cu2.21 Ag1.83 (Pb0.48 Cd0.15 )Ó0.63 Bi10.21 S18
5) Cu7.66 Ag11.23 Pb3.56Bi25.98Te0.12S51.45
3) Cu7.84 Ag3.97 Pb4.59 Cd0.01 Bi19.68 Sb0.03 Se0.02 Te0.07 S39.80
6) Cu0.70 Ag6.00 Pb2.39 Bi13.54 Te0.07 S25.93______________________________________________________________________________________________________________
The compositions are expressed in wt.%. NA: number of analyses. The standard deviation is shown on the second line. The chemical
homologue numbers NP1 , NP2 and NP3 were calculated after Karup-Møller & Makovicky (1979). Empirical formulae were calculated on thebasis of Me + S = 72 apfu for cupromakopavonite, S = 18 apfu for makovickyite, Me + S = 76 apfu for cupropavonite, S = 20 apfu forpavonite and Me + S = 100 apfu for cuproplumbian mummeite, S = 26 apfu for mummeite.

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the canadian mineralogist

Cu, Pb and Bi. The C layers of octahedra, N = 5, arefive octahedra thick if counted along the (100)PbS plane,
with Ag in the central octahedron (Fig. 4). It differs fromall members of the series with known crystal-structures,in which only one value of N is valid for all layers ofoctahedra, even if the details of their occupancy may
differ, e.g., in cupromakovickyite (Topa et al. 2008).
In the A layers, both the marginal coordination octahedra Bi4 and the central ones Bi5 are partly replaced
by Ag (Table 4). In the broader layers (C), silver isconcentrated in the central Ag octahedron, whereas
both the marginal Bi2 octahedra and the central Bi1
octahedra (Fig. 4) were refined as pure Bi. The asymmetric distribution of bond lengths and the eccentricity

TABLE 3. CUPROMAKOPAVONITE: EXPERIMENTAL DETAILS ABOUTTHE STRUCTURE REFINEMENT, AND CRYSTAL DATA___________________________________________________________
Crystal data
Chemical formula
Chemical formula weight
Crystal system
Space group
Cell parametersa, b, c (Å)â ()V (Å3)Z
Dx (mg m–3 )No. of reflections for cell parametersì (mm–1 )Crystal morphology
Crystal size (mm)Crystal color

Cu7.82 Pb2.91 Cd0.24 Ag3.46 Bi19.53 S38.05
6849.6
Monoclinic
C2/m
13.3801(19), 4.0007(6), 31.083(4)93.064(2)1661.5(4)
1
6.85
3105
64.7
irregular
0.02 × 0.04 × 0.08
black

Data collection
Tm in , Tm ax
No. of measured reflections
No. of independent reflections
No. of observed reflections
Criterion for observed reflections
Rint, Rsigm a (%)èm ax ()Range of h, k, l

0.108, 0.545
7811
2215
1834 for which Fo > 4ó(Fo )I > 2ó(I)9.78, 7.54
28.29
-17  h  17, -5  k  5,-40  l  41Refinement
Refinement on Fo
R1 [Fo > 4ó(Fo )] (%)
wR(Fo 2 )S (GooF)
No. of reflections used
No. of parameters refined
2

4.53
6.00
1.018
2215
115

Weighting scheme w = 1/[ó2 (Fo 2 ) + (0.0335P)2 + 0.0P],
where P = (Fo 2 + 2Fc 2 )/3(Ä/ó)m ax
0.014
Äñm ax (e/Å3 )3.98 [1.07 Å from Bi3]
3
Äñ m in (e/Å )-3.98 [1.24 Å from Bi3]
Extinction coefficient
0.000000(17)Source of scattering factors of atoms: International Tables for
Crystallography, (1992, Vol. C, Tables 4.2.6.8 and 6.1.1.4)
Computer programs
Structure solution
SHELXS97 (Sheldrick 1997a)
Structure refinement
SHELXL97 (Sheldrick 1997b)___________________________________________________________of these two bismuth positions are consistent with
their position at the margins of the layer (Tables 5, 6).
Characteristics for the Bi4 and Bi5 sites (Tables 5, 6)
are closest to those of the marginal Bi2 site.
The B layers separate the A and C layers. They
contain columns with a configuration of flat octahedra,in which only one wall of octahedra is occupied byapproximately trigonal–planar Cu2 with a very long
additional distance to S4 (Table 5, Fig. 4). A tetrahedral
space between adjacent octahedra in the [010] column
of foreshortened octahedra is occupied by tetrahedrally coordinated Cu1, situated on the same level as
S5 and S6 (Fig. 4). Both Cu positions were refined as
being fully occupied, unlike those in such columns in
Cu-containing pavonite homologues. The octahedra
themselves can be considered vacant. These columnsof octahedra are interspersed along [100] by [010]
columns of an oriented pair of large cations: a columnof square-coordination pyramids of Bi joined sideways
with a column of capped trigonal coordination prismsof Pb. The former is typical of members of a pavonite
homologous series, but the latter is much closer to thebicapped coordination prisms of Pb in lillianite homologues. Polyhedron characteristics of the Pb position(the shortest bond-distances and smallest bond-valencesum, Table 6) suggest that this position contains an
admixture of Bi.
The Pb polyhedra from two adjacent B layers face
one and the same A layer with N = 4; the Bi polyhedra
from adjacent B layers face the next, crystallographically distinct C layer with N = 5. Both Cu1 and Cu2 in
the B layer are strictly oriented toward their respectivesides of the B layer, in agreement with the Pb–Bi separation and order in this layer. Atom Cu1 is situated on
the Bi-populated side of the thin B layer, whereas Cu2
is on the Pb-populated side of this layer. The observed
scheme of Cu bonding is found also in cupromako­
vickyite (Topa et al. 2008), Cu4Bi4S9 (Takéuchi &Ozawa 1974, Bente & Kupčík 1984) and Cu4Bi4Se9(Makovicky et al. 2002). It is an ordered and much
simplified version of the statistically disordered distribution of Cu in the columns of octahedra in B-typelayers in synthetic pavonite homologues N = 3 and N =4 (Tomeoka et al. 1980) and in makovickyite (Mumme
1990, Žák et al. 1994, Topa et al. 2008), in which the B
layer contains only double columns of Bi coordination
pyramids, i.e., both its surfaces have the same Bi-based
configuration.
Cupromakopavonite is the first natural phase foundto combine a 1:1 ratio of two intergrown layers ofa different thickness of a type found in the pavonite
homologous series. The other case of such a 1:1 intergrowth is the unpublished mention of a regular intergrowth of the third and fourth member of the pavonite
homologous series found among synthetic Pb-substituted copper–bismuth sulfosalts by K. Mariolacos (oralcommun.). More complicated intergrowths of diverse

301

the crystal structure of cupromakopavonite

TABLE 4. POSITIONAL AND DISPLACEMENT PARAMETERS OF ATOMS IN CUPROMAKOPAVONITE______________________________________________________________________________________________________________
ATOM
x
z
sof
Ueq
U11
U22
U33
U13
______________________________________________________________________________________________________________
Ag
000.937(12)0.034(1)0.030(1)0.041(2)0.031(2)-0.002(1)Bi
000.063(12)0.034(1)0.030(2)0.041(2)0.031(2)-0.002(1)Bi10.27808(5)0.05767(2)10.0138(2)0.0159(4)0.0118(3)0.0137(4)0.0013(3)Bi20.44173(5)0.88385(2)10.0133(2)0.0158(4)0.0117(3)0.0126(4)0.0022(3)Bi30.18026(5)0.78873(2)10.0181(2)0.0195(4)0.0210(4)0.0133(41)-0.0031(3)Bi40.42586(6)0.58778(3)0.803(8)0.0207(3)0.0246(5)0.0204(5)0.0170(5)0.0019(3)Ag40.42586(6)0.58778(3)0.197(8)0.0207(3)0.0246(5)0.0204(5)0.0170(5)0.0019(3)Bi50.14238(6)0.53161(3)0.855(9)0.0202(3)0.0208(5)0.0179(5)0.0218(5)-0.0003(3)Ag50.14238(6)0.53161(3)0.145(9)0.0202(3)0.0208(5)0.0179(5)0.0218(5)-0.0003(3)Pb
0.28681(6)0.33522(3)10.0299(2)0.0349(5)0.0179(4)0.0376(5)0.0080(4)Cu1
0.0566(2)0.2257(1)10.0295(6)0.023(1)0.029(1)0.035(21)-0.009(1)Cu2
0.4885(2)0.7134(1)10.0294(6)0.030(1)0.016(1)0.041(2)-0.010(1)S10.3537(3)0.9712(2)10.016(1)0.017(2)0.017(2)0.015(3)0.004(2)S20.0742(4)0.9215(2)10.023(1)0.019(2)0.014(2)0.034(3)-0.004(2)S30.1977(3)0.1365(2)10.0122(9)0.015(2)0.015(2)0.007(2)0.000(2)S40.4906(3)0.1940(2)10.0142(9)0.019(2)0.015(2)0.010(2)0.004(2)S5
0.2194(3)0.2482(2)10.0137(9)0.012(2)0.014(2)0.015(2)-0.001(2)S60.0745(3)0.7170(2)10.0122(9)0.014(2)0.011(2)0.012(2)-0.001(2)S70.3553(3)0.6653(2)10.0166(9)0.017(2)0.013(2)0.020(3)0.002(2)S8
0.0611(3)10.0170(9)0.018(2)0.016(2)0.016(3)-0.001(2)0.6065(2)S90.2245(4)0.4403(2)10.023(1)0.019(2)0.015(2)0.036(3)-0.004(2)
S10
0.5
0.5
1
0.020(1)0.022(3)0.019(3)0.020(4)0.000(3)______________________________________________________________________________________________________________All y = 0, U12 = 0 and U23 = 0 by symmetry.

TABLE 5. SELECTED CATION–ANION BOND DISTANCES (Å) IN CUPROMAKOPAVONITE__________________________________________________________________________________
AgS2
S1

2.684(6) × 2
2.906(3) × 4

Cu1S5
S4
S6

2.252(5)2.379(3) × 2
2.567(5)

Bi1S3
S1
S2
S1

2.728(4)2.783(3) × 2
2.862(4) × 2
2.922(5)

Bi4S7
S8
S9
S10

2.633(5)2.739(3) × 2
2.936(4) × 2
2.953(1)

Bi2S4
S3
S2
S1

2.627(4)2.785(3) × 2
2.879(4) × 2
3.017(5)

Bi5S8
S9
S10
S9

2.622(5)2.788(4) × 2
2.898(1) × 2
3.098(6)

Bi3S6
S5
S4
S3

2.577(4)2.699(3) × 2
3.106(3) × 2
3.415(3) × 2

PbS7
2.759(3) × 2
Cu2S5
2.805(5)S7
2.264(5)S6
3.225(3) × 2
S6
2.307(2) × 2
S8
3.321(4) × 2
S4
2.879(5)S9
3.413(6)__________________________________________________________________________________

N1,2 = 2,3 combinations were synthesized among Cd–Bi
homologues of pavonite (Choe et al. 1997).

Mineral Definition, Name and Type Material
Cupromakopavonite is related to cupromakovickyite
and to cupropavonite and can be described as a 1:1 intergrowth of slabs from these two phases. According tothe orientation of the Pb–Bi pairs, both of those phases
contain two types of layers with the same N value, one
enclosed between the Pb polyhedra on both its sides, theother surrounded by Bi polyhedra on both its surfaces.
In cupromakopavonite, the Pb polyhedra surround thethinner N = 4 layer, whereas the Bi polyhedra surroundthe thicker N = 5 layer. Thus, cupromakopavonite
is a specific combination of selected slabs from theadjacent phases in the system. Its strict structural regularity makes it an independent compound and mineral.
Another interpretation of cupromakopavonite is a 1:1
intergrowth of N = 5 pavonite with N = 4 lillianite. A
boundary goes through the coordination prisms of Pb,
and the columns of octahedra belong to the pavonite
layers. It also is the first case where exsolution produces
two homologues with different N values, suggestingthat the high-temperature phase perhaps contained adisordered mixture of different thicknesses of slab. Boththe mineral and its name were approved by the Commission on new Minerals and Names (IMA 2005–036).

302

the canadian mineralogist

Fig. 3.

Site labeling for the crystal structure of cupromakopavonite.

Fig. 4. The crystal structure of cupromakopavonite in projection on (010), with atoms at y = 0 (white) and at 0.5 (grey shading),
respectively (b ~ 4 Å). In the order of decreasing size, circles represent S, Pb (blue), Ag (green), Bi (white) and Cu (red). The
two types of thicker layers of octahedra, with N = 4 and N = 5, are shaded in dark and light grey tones, respectively. The A,
B and C notation of slabs is explained in the text.

the crystal structure of cupromakopavonite

303

Fig. 5. Selected examples of thinner structural slabs from the crystal structures of pavonite (a, b, and c) and cupropavonite
homologues (d1 and d2). a) Synthetic pavonite AgBi3S5 (Makovicky et al. 1977); the octahedral Ag site (green) is fully
occupied. b) Makovickyite (Topa et al. 2008) and c) Cu-bearing benjaminite (D. Topa, unpubl. data); Ag site (green) and Cusites (blue and red) are partially occupied. d) Two adjacent thin layers d1 and d2 in cupromakovickyite and cupromakopavonite(Topa et al. 2008, this study); the Pb site (dark blue) and Cu sites (red) with opposite orientations are fully occupied.

Holotype material is deposited under catalog no. 14955
in the reference collection (museum) of the Division of
Mineralogy, University of Salzburg, Austria.

The Cupropavonite Homologous Series
In 1977, Makovicky et al. defined the pavonite
homologous series, with pavonite, ideally AgBi3S5,
benjaminite, ideally Ag3Bi7S12, two synthetic Cu–Bi
sulfosalts, and PbBi4S7 as homologues with N between
2 and 7. All these phases, with space-group symmetry
C2/m, have a structure composed of two kinds of regularly alternating (001) layers. The layers composedof arrays of slightly distorted coordination octahedra
of Bi, Ag and Pb are the (311) slabs of PbS structuralarchetype of different thickness, which defines the order
N of the homologue. The other set of (001) layers hasconstant topology, composed of [010] columns of coordination octahedra interspersed with double columnsof coordination pyramids of bismuth. The columns ofoctahedra are occupied by octahedrally coordinated Ag(Pb in PbBi4S7) or variously coordinated partially occupied copper sites. Since then, the pavonite homologous
series has undergone considerable expansion in numberof homologues and number of elemental combinations

that adopt this structure type (Makovicky 1981, 1989,
1997, 2006, Makovicky & Mumme 1979, Mumme &Watts1980, Herbert & Mumme 1981, Mumme 1990,
Ilinca & Makovicky 1999, Ferraris et al. 2004, Chaplygin et al. 2005, Balić-Žunić & Makovicky 2007,
Makovicky et al. 2010). Although there were several
tabulations of the pavonite homologues in these contributions, a comprehensive graphic review of the thicker
and thinner layers in these structures, with their individual configurations, has been missing. Figure 5 illustrates important types of thinner layers, with details of
their occupancy by Cu and Ag, and Figure 6 shows theconfiguration of thicker layers for homologues 1 to 8.
Within two years after its definition, a complicationof the scheme was found (Karup-Møller & Makovicky1979) when copper-rich samples of pavonite (N = 5
member of the series) from the Alaska mine, Colorado,were found to display intimate exsolution-induced
lamellae having a unit cell with the same space-groupbut with the c parameter of the monoclinic cell doubled
compared to that of the associated pavonite: 33.1 Åinstead of ~16.4 Å. It was named cupropavonite. In spiteof its exsolved nature, Weissenberg data on an exsolved
single-crystal aggregate showed good structural orderof both components. Similar exsolution-induced

304

the canadian mineralogist
TABLE 6. POLYHEDRON CHARACTERISTICS IN THE CRYSTAL STRUCTURE
OF CUPROMAKOPAVONITE___________________________________________________________________________________
1
2
3
4
5
6
7
8
9
__________________________________________________________________________________
Ag
6
2.832
0.00350.00000.878495.17330.189
0.991
Bi1
6
2.821
0.00200.11270.995494.08329.887
2.910
Bi2
6
2.821
0.00250.20090.997794.07429.870
2.977
Bi3
7
3.045
0.16080.4824
0.9739 118.278
37.562
2.905
Bi4
6
2.822
0.00210.21260.978194.10029.891
3.040
Bi5
6
2.853
0.00630.23920.995297.27930.771
2.883
Pb
8
3.102
0.0356
0.34880.8918 125.010
52.260
2.307
Cu1
4
2.376
0.03820.22611.000056.181
6.620
0.986
Cu2
4
2.447
0.15670.50140.999661.3476.338
0.997___________________________________________________________________________________The polyhedron characteristics used were defined in Baliæ-Žuniæ & Makovicky (1996) and Makovicky &Baliæ-Žuniæ (1998): 1) atom label, 2) coordination number, 3) radius rs of a circumscribed sphere, leastsquares-fitted to the coordination polyhedron, 4) “volume-based” distortion õ = [V(ideal polyhedron) –V(real polyhedron)] / V(ideal polyhedron). The ideal polyhedron has the same number of ligands. 5)“Volume-based” eccentricity ECCV = 1 – [(rs – Ä)/rs]3 ; Ä is the distance between the center of the sphereand the central atom in the polyhedron, 6) “volume-based” sphericity SPHV = 1 – 3órrs ; ór is a standard
deviation of the radius rs . 7) Volume of the circumscribed sphere, 8) volume of coordination polyhedron,9) bond-valence sum.

TABLE 7. CALCULATED X-RAY POWDER-DIFFRACTION DATAFOR CUPROMAKOPAVONITE___________________________________________________________h k l
dÅI rel.
h k l
dÅI rel.
____________________________________________________________
0 0 2
15.52
7
3̄ 1 102.1876
5
2 0 3
5.48
14
5̄ 1 5
2.1223
17
0 0 6
5.17
3
6 0 4
2.110710
2̄ 0 54.67
3
0 0 152.0692
6
0 0 7
4.43
4
1̄ 1 132.0406
7
2 0 5
4.43
5
6̄ 0 72.0341
3
2̄ 0 64.20
8
5̄ 1 72.0229
19
1 1 0
3.833
3
1 1 132.0127
11
2 0 7
3.607
57
5 1 6
2.0096
6
1 1 3
3.576
3
2̄ 0 15
2.0071
2
1̄ 1 4
3.457
99
6 0 6
2.0068
12
0 0 9
3.449
8
0 2 0
2.000428
2̄ 0 83.436
37
3̄ 1 121.98788
4̄ 0 1
3.340
34
5 1 7
1.9522
3
4 0 1
3.302
3
3 1 12
1.9187
4
1 1 5
3.239
8
5̄ 1 91.90696
4̄ 0 3
3.230
12
5 1 8
1.892310
1̄ 1 63.102
6
0 0 171.82582
3 1 0
2.97625
1 1 151.8092
3
3̄ 1 12.97275
3̄ 1 141.80926
3 1 1
2.952628
4 0 141.80335
3̄ 1 22.9425
4
6̄ 0 111.79534
1 1 7
2.877811
5 1 101.77004
2̄ 0 102.874233
2 2 7
1.749313
3 1 3
2.8335100
3 1 14
1.7483
6
0 0 112.82174
2̄ 2 81.72879
3̄ 1 42.81269
7 1 0
1.72274
3̄ 1 62.62056
4̄ 2 1
1.7161
9
4̄ 0 82.601057 1 2
1.7032
6
4̄ 0 102.33692
4̄ 2 31.7006
4
1̄ 1 112.2891
7
8̄ 0 41.65107
1 1 112.255829
2̄ 2 101.641910
4 0 102.2155
4
4 0 16
1.63992
5̄ 1 3
2.19278
4̄ 2 81.58572____________________________________________________________

aggregates were later found for mummeite, the N =8 member of the series (Karup-Møller & Makovicky1992), although doubling of the slightly larger unit-

cell of the exsolved component could not be detected.
Afterward, Žák et al. (1994) found corresponding
evidence of lamellar exsolution in Cu-rich varietiesof makovickyite, the N = 4 member of the pavonite
homologous series. No superstructure could be determined in this case. Finally, Makovicky et al. (2010)
described the lamellar exsolution-induced textures in
Cu-rich benjaminite as well. Further, chemically lesswell-defined cases of lamellar exsolution were quoted
by Karup-Møller & Makovicky (1979).
The structural explanation for the doubled unit cellof the exsolved “cuproplumbian”component had to wait
for a suitable material in which the “cuproplumbian”
phase was preponderant. [The history of the unusual
term “cuproplumbian” and the involvement of the
IMA Commission in it is described in Karup-Møller &Makovicky (1979)]. This was supplied by material fromthe skarn deposit at Băiţa Bihor and from the scheelite
deposit at Felbertal, the same deposit that yielded
cupromakopavonite. From these deposits, Topa & Paar
(2008) defined cupromakovickyite Cu8Pb4Ag2Bi18S36,
and Topa et al. (2008) described its crystal structure.
The structural investigation revealed several unusual
features. There were two types of N = 4 layers ofoctahedra present, with partial substitutions by Agin most Bi octahedra. Lead is concentrated into a Pb
polyhedron that, together with the adjacent Bi coordination pyramid, replaces the double column of Bi
coordination pyramids seen in pavonite homologues(the latter phases concentrated lead as a substitutional
element on the layers of octahedra). Copper does notfollow the usual pattern of symmetrically disposed
partially occupied tetrahedral and triangular positions,but is concentrated into only two asymmetrically situated sites, entirely analogous to those described here
for cupromakopavonite. All these features contributethe crystal structure of cupromakopavonite

to the doubled periodicity along the [001] direction.
They were all found in cupromakopavonite, with the
exception of a more differentiated Ag–Bi distribution
in the N = 5 slab. Comparison of the thin slab configurations of selected examples from among the pavonite
homologues with the configuration in cupropavonite
homologues is provided in Figure 5. For the thicker
slabs, the configurations depicted in Figure 6 apply.
The constancy of these features, present in cupromakovickyite and cupromakopavonite (N = 4 and N= 4.5, respectively), and their pronounced difference
from the crystal-chemical features of those substitutedpavonite homologues without doubled unit-cells,suggest to us that the “cuproplumbian” varieties forma homologous series of their own. In order to verify
this assumption, we undertook, as a working approach,the crystal-structure determination of cupropavonite ina pavonite–cupropavonite intergrowth from the Alaska
mine, Colorado, U.S.A. The resulting R value is 0.13.
Although it yields an overlap of the two structures, it
reveals a clear cupropavonite-like topology with the two
Cu sites as described above, located in the region of thecolumn of octahera which, in addition, is populated by305

octahedrally coordinated Ag. We ascribe the Ag sites
to the pavonite component of the mixture because it isgeometrically incompatible with the above-mentioned
Cu sites. Furthermore, the distribution Pb versus Bi
and its correlation with Cu distribution are exactly thesame as in the above-mentioned pure “cuproplumbian”
phases. The Pb site of cupropavonite overlaps partlywith the Bi site from the pavonite component, resulting
in a “site” with an elongate displacement ellipsoid andsomewhat modified Me–S distances. The calculated
positional parameters for the model of cupropavonite
are given in Table 8. The site labeling for proposed
cupropavonite structure and its crystal structure arepresented in Figure 7 and Figure 8, respectively.
Powder-diffraction data were calculated from a“purified” model of the cupropavonite structure obtainedby doubling the c unit-cell parameter of a pavonite
crystal structure from Felbertal and by arranging thethinner layers to match the ones in cupromakovickyite(Topa & Paar 2008, Topa et al. 2008) and in thepartially determined cupropavonite structure mentioned
above. The unit-cell parameters used for calculation
were determined from the graphical construction as a

Fig. 6. Configuration of thicker layers of octahedra in the pavonite homologues. Large circles: S, smaller circles: cations. The
order of the homologue Np is determined by the number of octahedra along a diagonal of the layer. The known examples
from the cupropavonite homologous series follow the same pattern.

306

the canadian mineralogist

13.254, b 4.038, c 32.050 Å, b 93.716°. Comparisonof calculated data for cupropavonite with the measured
powder pattern of cupropavonite from the Alaska mine,
Colorado (Karup-Møller & Makovicky 1979) (Table 9)
reveals a good agreement, especially for larger and more
relevant d values. Most of the strongest matching reflections are generated by the thicker layers of octahedra
in both the measured and the calculated structures,
namely by a set of I-centered subcells (e.g., Bi4–Bi5–
Ag2–Bi4–Bi5 in Fig. 7) and subordinately, by a set of

TABLE 8. CALCULATED POSITIONAL PARAMETERS
FOR CUPROPAVONITE____________________________________________________________
ATOM
x
y
z
___________________________________________________________
Ag1
0.000
0.0
0.000
Ag2
0.000
0.0
0.500
Bi1
0.234
0.5
0.056
Bi2
0.468
0.0
0.104
Bi3
0.216
0.0
0.185
Bi4
0.033
0.5
0.391
Bi5
0.265
0.0
0.444
Pb
0.284
0.5
0.305
Cu1
0.070
0.5
0.770
Cu2
0.002
0.0
0.720
S1
0.364
0.0
0.028
S2
0.098
0.0
0.076
S3
0.336
0.5
0.128
S4
0.075
0.5
0.182
S5
0.351
0.5
0.233
S6
0.149
0.0
0.267
S7
0.425
0.0
0.318
S8
0.164
0.0
0.370
S9
0.402
0.5
0.429
S10
0.136
0.5
0.472
____________________________________________________________

Fig. 7.

C-centered monoclinic subcells (e.g., S10–Bi5–S8–S8–S8–Bi5–S10–S10 in Fig. 7) (Ilinca & Makovicky 1999).
A third set of columns in Table 9 shows the calculated
powder-pattern of a “cupropavonite” structure withthe unit-cell parameters as above, but from which all
thinner layers were eliminated. Only a small number ofreflections from the “integral” calculated powder pattern
are lost, as a result. Similar I- and C-centered subcells
are present in all pavonite homologues and, therefore,such comparisons of powder data might be less relevant
unless indexed patterns and large 00l reflections withthe lowest l values are taken into account.
Textural evidence of the constancy of structuraland crystal-chemical principles in the entire series(Table 10) from N = 4 to N = 8 indicates the samemechanism of exsolution observed for all these valuesof N (Fig. 9). The two systems of straight exsolutioninduced lamellae occur as patches that are mutually
exclusive, except for some intersections on theirboundaries. From single-crystal diffraction data, KarupMøller & Makovicky (1979) deduced that the coherent
composition-planes of these intergrowths are the (hkl)
planes with close-packed sulfur atoms in the thicker
slabs. For pavonite–cupropavonite, this means planes
close to (1.±1.3) of pavonite, i.e., (1.±1.6) of cupropavonite. Because of small differences in the metricsof the two phases, there is a misalignment of the twolattices on the composition plane, resulting in a small
displacement of one component after each lamella of theother component. It is these displacements that make thetwo, (113) and (1.1.3) systems of exsolution lamellae
mutually exclusive. These findings apparently hold

Site labeling for the proposed structure of cupropavonite.

307

the crystal structure of cupromakopavonite

Fig. 8. The hypothetical structure of cupropavonite projected along b (~ 4 Å). In order of increasing size, circles represent
Cu (red), Bi (white), Ag (green), Pb (blue) and S (white) positions. Void and shaded circles represent atoms at two y levels,
2 Å apart. Two types of 5P thicker layers (grey shading) are separated by asymmetric thin cupromakovickyite-like layers(unshaded).

TABLE 9. COMPARISON BETWEEN (1) THE MEASURED X-RAY POWDER PATTERNOF CUPROPAVONITE FROM THE ALASKA MINE* AND (2) THE CALCULATEDPOWDER PATTERN FOR CUPROPAVONITE DERIVED GRAPHICALLY FROMA PAVONITE CELL DOUBLED ALONG [001] AND WITH THINNER LAYERCONFIGURATION, AS IN CUPROMAKOVICKYITE. SET (3) SHOWS THE SAMESIMULATION BUT WITH ALL ATOMS IN THE THINNER LAYER OMITTED_______________________________________________________________________________
1_____________________

2_____________________

3_____________________

h k l
d (Å)
Icalc
h k l
d (Å)
I rel.
h k ld (Å)
I rel.
______________________________________________________________________________
0 0 2

16.4992 0 0
2 0 1̄

6.71
6.655

w

2 0 4̄

5.368

m/s

2 0 6̄

4.387

m

0 0 8
1 1 0

(4.125)3.854

w

2 0 8̄

(3.614)

s

1 1 4
3 1 8

3.468
3.376

m

4 0 3̄

3.265

m

0 0 2

16.2158

7.14

2 0 0

6.6129

4.7

2̄
2̄
0
2̄

0
0
0
0

2
3
6
4

6.2700 1.94
5.8113 1.88
5.4053 4.61
5.2954 14.18

2
0
1
1
2̄
1̄
1

0
0
1
1
0
1
1

6
8
0
2
8
4
4

4.0582 14.2
4.05398.4
3.8621 4.42
3.7411 1.78
3.5606 53.42
3.5126 3.78
3.4614 89.82

2 0 8
4 0 0
4̄ 0 23.3605 27.54
3.3065 26.02
3.2817 2.41

0 0 2
0 0 4

16.2158
8.1079

100
2.89

0
2̄
2
2̄

6
4
4
6

5.40535.29544.96934.3247

3.49
1.27
1.78
1.03

1 1 0

3.86211.74

2̄ 0 83.5606

4.53

1 1 4

3.4614

7.56

2 0 8
4 0 0

3.36053.3065

3.09
2.87

0
0
0
0

308

0 0 8
1 1 0

(4.125)3.854

2 0 8̄

(3.614)

1 1 4
3 1 8

3.468
3.376

4 0 3̄

3.265

4 0 2̄
1 1 6̄
1 1 6

3.249
3.182
3.130

4 0 5̄

3.067

2 0 6
4.0582 14.2
0 0 8
4.05398.4
1 1 0
3.8621 4.42
1 1 2
3.7411 1.78s the 2̄canadian
0 8
3.560653.42
mineralogist1̄ 1 43.5126 3.78
1 1 4
3.4614 89.82m
2 0 8
3.3605 27.54
4 0 0
3.3065 26.02
4̄ 0 23.2817 2.41m
0 0 103.2432 4.76s
4 0 2
3.1995 14.05
1̄ 1 6
3.1709 5.13
s
1 1 6
3.1146 6.67
1̄ 1 72.9946 2.21
w

3 1 0
3 1 1
3 1 2̄

2.991
2.968
2.965

m
m
s

3 1 0

2.97783̄ 1 21 1 7

2.9518 22.49
2.9393 1.21

4
2
3
1

0 6̄
0 10
1 3
1 8̄

2.945
2.892
(2.857)
2.841

m
vs
w/m
m

4̄ 0 62 0 102.9057 1.27
2.8400 29.36

3 1 5̄

2.767

m

3̄ 1 41̄ 1 82.83572.8231

100
5.96

0
3
4
1

0 12
1 5
0 8̄
1 9̄

2.750
2.684
2.684
2.680

s/m
m/w
w
w

3 1 4
0 0 123 1 52.75642.70262.6624

8.26
1.47
1.05

3 1 6
3 1 7̄

2.584(2.574)

s/m
w

3 1 6

2.5612

1.51

2̄
1̄
4
2
4̄
0
1̄
2̄

0 12
1 10
0 8
0 12
0 10
0 14
1 12
0 14

2.5606 1.93
2.5071 1.81
2.48466.7
2.4469 1.54
2.3942 1.77
2.3166 1.78
2.2343 23.86
2.2319 2.26

1
5
6̄
4̄

1 12
1 2
0 4
0 12

2.1949 10.83
2.1766 13.39
2.1629 1.89
2.1623 3.73

3
5
6̄
1
3̄
0

1 10
1 4
0 6
1 13
1 12
0 16

2.1471 9.03
2.1058 14.17
2.0900 9.22
2.0777 2.09
2.0463 3.42
2.0270 3.84

w

1 1 1̄2̄

2.257

ws

0 0 15(2.200)

m/w

5 1 2

2.198

s

4
6
2
5

0 1̄2̄
0 4̄
0 14
1 -5

2.193
2.193
2.183
(2.148)

ws
m/s
m
vw

6 0 6̄
6 0 5

2.118
2.080

vs
w/m

0 0 16
12 0 15

2.062(2.054)

s
w

8.63

1 1 0

3.86211.74

2̄ 0 83.5606

4.53

1 1 4

3.4614

7.56

2 0 8
4 0 0

3.36053.3065

3.09
2.87

4 0 2

3.1995

3.13

1 1 6

3.1146

5

2̄ 0 102.9894

1.82

3̄ 1 22.9518

5.84

3 1 2

2.90631.53

2 0 102.8400

6.39

3̄ 1 42.8357 12.97

3̄ 1 62.65782.29

2 0 122.44691.21

1̄ 1 122.23432.62

5 1 4
6̄ 0 62.10582.0900

1.22
1.37

0 2 0
2.0191 29.22
0 2 02.0191 2.48
5 1 6
2.0099 22.05
5 1 6
2.0099 4.76
1̄ 1 142.0034 11.78
1̄ 1 142.0034 4.47
6 0 6
1.9964 4.52
6 0 8̄
2.019
vs6̄ 0 81.9915 12.74
6̄ 0 81.9915 2.22______________________________________________________________________________* Karup-Møller & Makovicky (1979). Thecell parameters for all sets are given in the text.

for all homologues (Fig. 9); only the (hkl) values for
close-packed planes of sulfur in the structure will differ.
The diffraction evidence of a doubled unit-cell witha strongly expressed subcell, which corresponds to theunit cell of pavonite homologues, is well documented
for N = 4, N = 4.5, and partially for N = 5. Lamellar
exsolution-induced aggregates in copper-containing
benjaminite have not yet been subjected to detailed

the crystal structure of cupromakopavonite

X-ray-diffraction studies. Single-crystal diffraction data
for the mummeite – “cuproplumbian mummeite” pair(“cupromummeite” is not a recognized mineral species)
did not yield evidence of a doubled unit-cell and show
continuous [001]* streaks underlying the pavonite-likereciprocal lattice rows parallel to [001]*. The regularalternation of two types of thicker (001) structurallayers, known for N = 4 and for N = 5, thus may have309

broken down, or a consistent orientation of rows of Pb
and Bi polyhedra on the surfaces of the thin layers may
have been lost. The reciprocal lattice of a still higher
homologue than mummeite, observed by Karup-Møller
& Makovicky (1992), shows indications of still thicker
slabs of octahedra, but its periodicity dissolves indisorder streaks. Whether the lack of a superperiod for
N = 8 results from the loss of periodicity due to exces-

Fig. 9. BSE photographs of exsolution aggregates involving members of the pavonite and cupropavonite homologous series. (a)Makovickyite – cupromakovickyite aggregate from Băiţa Bihor, Romania; (b) pavonite – cupropavonite aggregate from the
Alaska mine, Colorado, U.S.A.; (c) benjaminite – cuproplumbian benjaminite aggregate from Erzwies, Austria (Makovicky
et al. 2010); (d) mummeite – cuproplumbian mummeite aggregate from the Alaska mine, Colorado. In each image, thedifferences in the thickness of exsolution lamellae are primarily caused by their orientation. The length of the bars is 100 mm.

310

the canadian mineralogist

Fig. 10. Compositional scheme for pavonite homologues (void symbols) and cupropavonite homologues (solid symbols) in the
Ag – Bi – (Cu + Pb) diagram. Lines for pavonite homologues of the order Np are indicated by points at 0, 25, 50, 75 and 100
at.% of imaginary (Ag+Bi)-for-2Pb substitution by Pb in the octahedral cation sites, for Cu-free cases. Points indicating Np
values for the homologues of cupropavonite are situated on the ideal composition line for this series. Electron-microprobe
data for the exsolution pairs are plotted into the scheme: makovickyite – cupromakovickyite from Băiţa Bihor, makovickyite– cupromakopavonite from Felbertal, pavonite – cupropavonite from the Alaska mine, Colorado, [1: Karup-Møller &Makovicky (1979) and 2: this work], benjaminite – cuproplumbian benjaminite from Erzwies (Makovicky et al. 2010), andmummeite – cuproplumbian mummeite from the Alaska mine (this work). Abbreviations: Np: pavonite homologue with ordervalue N, cupro-Np: cupropavonite homologue with order value N, lam: lamellae, hg: homogeneous.

sive thickness of layers of octahedra or from a hasty
exsolution or recrystallization of the minerals studied,is unknown at present. Interestingly, both cupropavonite
and cuproplumbian mummeite come from the same
locality, but from different museum samples.
On the chemical level, the cupropavonite homologous series and the substitutions in the pavonite homologous series may be modeled using the facts obtained
from crystal-structure determinations (Table 10). Fromthe ideal topology, occupancy and valence balance,
the general formula of the cupropavonite homologous

series is Cu8Ag2N– 6Pb4Bi2N+10S4N+20 for Z = 1, where
N is the average of the N1 and N2 values in cases likecupromakopavonite. This ideal composition line isplotted in Figure 10 as a row of symbols for N = 4 to 9
(full symbols), together with the ideal compositions ofrespective pavonite homologues, in which Pb occupies
0, 25, 50, 75 and 100 percent of cation sites in the layerof octahedra (void symbols). The latter scheme works
ideally for Cu-free homologues. Pavonite homologues
that form exsolution pairs with the cuproplumbian
ones are shown in Figure 10, as well. In general, theythe crystal structure of cupromakopavonite

show substitution percentages of about 75% or below;
they all contain Cu in addition to Pb. Besides limitations imposed by stoichiometry of the thicker slabs, apotential misfit between the thicker and thinner slabs
will limit the amount of Pb that can enter the octahedral
positions of the thicker slabs.
Slight deviations of the members of the cupropavonite series from the ideal compositions may haveexperimental reasons (all data, except for those forhomogeneous cupromakovickyite, come from exsolution lamellae alternating with a pavonite homologue)
or may express a certain admixture of Bi in the Pb
position of the thinner layers. The consistent trend ofanalytical results, closely parallel to the ideal composition line, confirms the constancy of structural andchemical principles involved; these are valid for boththe strictly ordered, partly disordered and structurally
not yet investigated members.

Conclusions
The rare Cu–Ag–Pb–Bi sulfosalt cupromakopavo­nite, a new mineral species, is closely related to cupromakovickyite and cupropavonite. It is a member N1,2
= 4,5 (or N = 4.5) of the newly defined cupropavonite
homologous series Cu8Ag2N– 6Pb4Bi2N+10S4N+20 for Z =1, where N is the homologue order. Members with theorder N from 4 to 8 are known. Although the topologyof these structures resembles that of pavonite homologues, the homologues of cupropavonite have specificconfigurations of Pb and Cu that are distinct from thosein the pavonite homologues. In the Ag–Bi–(Pb + Cu)
diagram, the cupropavonite series assumes a compositional trend that is distinct from the homologues ofpavonite. So far, cupromakopavonite is the only known
member of the series, with two different values of N in
the same structure.

Acknowledgements
There has been a crucial intersection between mymineralogical preoccupations and meeting and getting
to know Emil Makovicky. As one of his Ph.D. students,
I benefitted greatly from his insight and advice on thematter of sulfosalts, on how to approach the analyticalside, and on how to get the most from the results. Ever
since, Emil has been the most reliable scientific support
for me, thus leading my research to numerous positive
outcomes.
We gratefully acknowledge the financial supportof the Christian Doppler Foundation (Austria) and
the Research Council for the Nature and Universe,
Denmark (grant no. 272–08–0227). The manuscript
benefitted from comments of Prof. Giovanni Ferrarisand Dr. Luca Bindi and from the editorial care of Prof.
Robert F. Martin.

311

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data_cupromakopavonite_audit_creation_method_chemical_name_systematic;?
;_chemical_name_common_chemical_melting_point_chemical_formula_moiety_chemical_formula_sum'Ag3 Bi19 Cu8 Pb4 S38'
_chemical_formula_weight

SHELXL-97?
?
?
6849.59

loop__atom_type_symbol_atom_type_description_atom_type_scat_dispersion_real_atom_type_scat_dispersion_imag_atom_type_scat_source'S' 'S'
0.12460.1234'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''Ag' 'Ag' -0.8971
1.1015'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4''Pb' 'Pb' -3.3944 10.1111'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4''Bi' 'Bi' -4.1077 10.2566'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'_symmetry_cell_setting_symmetry_space_group_name_H-M'Monoclinic''C2/m '

loop_
_symmetry_equiv_pos_as_xyz'x, y, z''-x, y, -z''x+1/2, y+1/2, z''-x+1/2, y+1/2, -z''-x, -y, -z''x, -y, z''-x+1/2, -y+1/2, -z''x+1/2, -y+1/2, 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

13.3801(19)4.0007(6)31.083(4)90.00
93.064(2)90.00
1661.5(4)1
297(2)

_cell_measurement_reflns_used_cell_measurement_theta_min_cell_measurement_theta_max?
?
?

_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

?
?
?
?
?
?
6.846
'not measured'
2886
64.746?
?
?
?

_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_expression297(2)
0.71073
MoK\a'fine-focus sealed tube'
graphite
?
?
?
?
?
?
?
7811
0.09780.0754
-17
17
-5
5
-40
41
1.97
28.29
2215
1834
>2sigma(I)_computing_data_collection_computing_cell_refinement_computing_data_reduction_computing_structure_solution?
?
?
'SHELXS-97 (Sheldrick, 1990)'

_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^)+(0.0335P)^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_method
SHELXL_refine_ls_extinction_coef
0.000000(17)_refine_ls_extinction_expression'Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^'_refine_ls_number_reflns
2215_refine_ls_number_parameters
115_refine_ls_number_restraints0_refine_ls_R_factor_all
0.0600_refine_ls_R_factor_gt
0.0453_refine_ls_wR_factor_ref
0.0952_refine_ls_wR_factor_gt
0.0899_refine_ls_goodness_of_fit_ref
1.018_refine_ls_restrained_S_all
1.018_refine_ls_shift/su_max
1.644_refine_ls_shift/su_mean
0.014
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_group
Ag Ag 0.0000 0.0000 0.0000 0.0340(9) Uani 0.937(12) 4 d SP . .

Bi Bi 0.0000 0.0000 0.0000 0.0340(9) Uani 0.063(12) 4 d SP . .
Bi1 Bi 0.27808(5) 0.0000 0.05767(2) 0.01379(18) Uani 1 2 d S . .
Bi2 Bi 0.44173(5) 0.0000 0.88385(2) 0.01332(18) Uani 1 2 d S . .
Bi3 Bi 0.18026(5) 0.0000 0.78873(2) 0.0181(2) Uani 1 2 d S . .
Pb Pb 0.28681(6) 0.0000 0.33522(3) 0.0299(2) Uani 1 2 d S . .
Bi4 Bi 0.42586(6) 0.0000 0.58778(3) 0.0206(3) Uani 0.803(8) 2 d SP . .
Ag4 Ag 0.42586(6) 0.0000 0.58778(3) 0.0206(3) Uani 0.197(8) 2 d SP . .
Bi5 Bi 0.14238(6) 0.0000 0.53161(3) 0.0202(3) Uani 0.855(9) 2 d SP . .
Ag5 Ag 0.14238(6) 0.0000 0.53161(3) 0.0202(3) Uani 0.145(9) 2 d SP . .
Cu1 Cu 0.05663(18) 0.0000 0.22566(9) 0.0295(6) Uani 1 2 d S . .
Cu2 Cu 0.48852(19) 0.0000 0.71336(9) 0.0294(6) Uani 1 2 d S . .
S1 S 0.3537(3) 0.0000 0.97120(15) 0.0162(10) Uani 1 2 d S . .
S2 S 0.0742(4) 0.0000 0.92146(18) 0.0226(11) Uani 1 2 d S . .
S3 S 0.1977(3) 0.0000 0.13651(14) 0.0122(9) Uani 1 2 d S . .
S4 S 0.4906(3) 0.0000 0.19396(14) 0.0142(9) Uani 1 2 d S . .
S5 S 0.2194(3) 0.0000 0.24820(15) 0.0137(9) Uani 1 2 d S . .
S6 S 0.0745(3) 0.0000 0.71698(14) 0.0122(9) Uani 1 2 d S . .
S7 S 0.3553(3) 0.0000 0.66526(16) 0.0166(9) Uani 1 2 d S . .
S8 S 0.0611(3) 0.0000 0.60653(16) 0.0170(10) Uani 1 2 d S . .
S9 S 0.2245(4) 0.0000 0.44028(18) 0.0231(11) Uani 1 2 d S . .
S10 S 0.5000 0.0000 0.5000 0.0199(14) Uani 1 4 d S . .
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
Ag 0.0299(15) 0.0406(15) 0.0310(16) 0.000 -0.0015(10) 0.000
Bi 0.0299(15) 0.0406(15) 0.0310(16) 0.000 -0.0015(10) 0.000
Bi1 0.0159(4) 0.0118(3) 0.0137(4) 0.000 0.0013(3) 0.000
Bi2 0.0158(4) 0.0117(3) 0.0126(4) 0.000 0.0022(3) 0.000
Bi3 0.0195(4) 0.0210(4) 0.0133(4) 0.000 -0.0031(3) 0.000
Pb 0.0349(5) 0.0179(4) 0.0376(5) 0.000 0.0080(4) 0.000
Bi4 0.0246(5) 0.0204(5) 0.0170(5) 0.000 0.0019(3) 0.000
Ag4 0.0246(5) 0.0204(5) 0.0170(5) 0.000 0.0019(3) 0.000
Bi5 0.0208(5) 0.0179(5) 0.0218(5) 0.000 -0.0003(3) 0.000
Ag5 0.0208(5) 0.0179(5) 0.0218(5) 0.000 -0.0003(3) 0.000
Cu1 0.0230(13) 0.0294(14) 0.0350(17) 0.000 -0.0085(12) 0.000
Cu2 0.0294(14) 0.0163(12) 0.0411(17) 0.000 -0.0094(12) 0.000
S1 0.017(2) 0.017(2) 0.015(2) 0.000 0.0036(19) 0.000
S2 0.019(2) 0.014(2) 0.034(3) 0.000 -0.004(2) 0.000
S3 0.015(2) 0.015(2) 0.007(2) 0.000 0.0002(17) 0.000
S4 0.019(2) 0.014(2) 0.010(2) 0.000 0.0043(18) 0.000
S5 0.012(2) 0.014(2) 0.015(2) 0.000 -0.0006(17) 0.000
S6 0.014(2) 0.0108(19) 0.012(2) 0.000 -0.0005(17) 0.000
S7 0.017(2) 0.013(2) 0.020(3) 0.000 0.0018(19) 0.000
S8 0.018(2) 0.016(2) 0.016(2) 0.000 -0.0004(19) 0.000
S9 0.019(2) 0.013(2) 0.036(3) 0.000 -0.004(2) 0.000
S10 0.022(3) 0.018(3) 0.020(4) 0.000 0.000(3) 0.000_geom_special_details;