Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270108037980/fn3007sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270108037980/fn3007Isup2.hkl |
A crystal was selected from a natural specimen from the type locality (i.e. Jas Roux, France) belonging to the Mineralogical Collection of the Natural History Museum of Florence (catalogue No. 45164/G). A preliminary chemical analysis using energy dispersive spectrometry, performed on the crystal fragment used for the structural study, did not indicate the presence of elements (Z > 9) other than S, Cu, Zn, As, Ag, Sb, Hg and Tl, with a very minor amount of Fe. The chemical composition was then determined using wavelength dispersive analysis (WDS) by means of a Jeol JXA-8600 electron microprobe. Major and minor elements were determined at a 20 kV accelerating voltage and a 40 nA beam current, with a counting time of 10 s. For the WDS analyses the following lines were used: S Kα, Fe Kα, Cu Kα, Zn Kα, As Lα, Ag Lα, Sb Lβ, Hg Lα, Tl Mα. The standards employed were pure metals for Cu, Ag, and Tl; pyrite for Fe and S; cinnabar for Hg; synthetic Sb2S3 for Sb; synthetic As2S3 for As; and synthetic ZnS for Zn. The routhierite fragment was found to be homogeneous within analytical error. On the basis of 12 atoms, the chemical formula can be written as Tl(Cu0.65Ag0.35)Σ=1.00(Hg1.70Zn0.30)Σ=2.00(As1.70Sb0.30)Σ=2.00S6.00.
The crystal structure of routhierite was solved and refined starting from the atomic coordinates reported for stalderite by Graeser et al. (1995). Convergence was rapidly obtained for an anisotropic model of the structure. In the final cycles, the structure was refined as a racemic twin.
Data collection: CrysAlis RED (Oxford Diffraction, 2006); cell refinement: CrysAlis RED (Oxford Diffraction, 2006); data reduction: CrysAlis RED (Oxford Diffraction, 2006); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: Xtaldraw (Downs & Hall-Wallace, 2003); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).
Tl(Cu·Ag)(Hg·Zn)2(As·Sb)2S6 | Dx = 5.895 Mg m−3 |
Mr = 1000.29 | Mo Kα radiation, λ = 0.71073 Å |
Tetragonal, I42m | Cell parameters from 40 reflections |
Hall symbol: I -4 2 | θ = 10.4–25.1° |
a = 9.9821 (11) Å | µ = 46.48 mm−1 |
c = 11.3122 (12) Å | T = 298 K |
V = 1127.2 (2) Å3 | Block, violet |
Z = 4 | 0.12 × 0.10 × 0.07 mm |
F(000) = 1715.9 |
Oxford Xcalibur 3 diffractometer | 586 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.029 |
Graphite monochromator | θmax = 35.0°, θmin = 2.5° |
ω scans | h = −16→16 |
Absorption correction: gaussian (ABSPACK; Oxford Diffraction, 2006) | k = −16→16 |
Tmin = 0.006, Tmax = 0.041 | l = −18→18 |
2692 measured reflections | 10 standard reflections every 150 reflections |
673 independent reflections | intensity decay: none |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.011 | w = 1/[σ2(Fo2) + (0.P)2] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.011 | (Δ/σ)max = 0.007 |
S = 0.88 | Δρmax = 0.76 at 0.0000 0.0000 0.1996 (1.66 Å from TL) e Å−3 |
673 reflections | Δρmin = −0.99 at 0.0000 0.0000 0.2500 (1.09 Å from TL) e Å−3 |
37 parameters | Absolute structure: Flack (1983), No. of Friedel pairs? |
0 restraints | Absolute structure parameter: 0.223 (14) |
Tl(Cu·Ag)(Hg·Zn)2(As·Sb)2S6 | Z = 4 |
Mr = 1000.29 | Mo Kα radiation |
Tetragonal, I42m | µ = 46.48 mm−1 |
a = 9.9821 (11) Å | T = 298 K |
c = 11.3122 (12) Å | 0.12 × 0.10 × 0.07 mm |
V = 1127.2 (2) Å3 |
Oxford Xcalibur 3 diffractometer | 586 reflections with I > 2σ(I) |
Absorption correction: gaussian (ABSPACK; Oxford Diffraction, 2006) | Rint = 0.029 |
Tmin = 0.006, Tmax = 0.041 | 10 standard reflections every 150 reflections |
2692 measured reflections | intensity decay: none |
673 independent reflections |
R[F2 > 2σ(F2)] = 0.011 | 0 restraints |
wR(F2) = 0.011 | Δρmax = 0.76 at 0.0000 0.0000 0.1996 (1.66 Å from TL) e Å−3 |
S = 0.88 | Δρmin = −0.99 at 0.0000 0.0000 0.2500 (1.09 Å from TL) e Å−3 |
673 reflections | Absolute structure: Flack (1983), No. of Friedel pairs? |
37 parameters | Absolute structure parameter: 0.223 (14) |
Experimental. The chemical composition was then determined using wavelength dispersive analysis (WDS) by means of a Jeol JXA-8600 electron microprobe. Major and minor elements were determined at a 20 kV accelerating voltage and a 40 nA beam current, with a counting time of 10 s. For the WDS analyses the following lines were used: S Kα, Fe Kα, Cu Kα, Zn Kα, As Lα, Ag Lα, Sb Lβ, Hg Lα, Tl Mα. The standards employed were pure metals for Cu, Ag, and Tl; pyrite for Fe and S; cinnabar for Hg; synthetic Sb2S3 for Sb; synthetic As2S3 for As; and synthetic ZnS for Zn. |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
Tl | 0.0000 | 0.0000 | 0.34659 (2) | 0.04983 (7) | |
Cu | 0.0000 | 0.5000 | 0.2500 | 0.04981 (19) | 0.644 (8) |
Ag | 0.0000 | 0.5000 | 0.2500 | 0.04981 (19) | 0.356 (8) |
Hg | 0.21531 (2) | 0.5000 | 0.5000 | 0.04991 (6) | 0.851 (2) |
Zn | 0.21531 (2) | 0.5000 | 0.5000 | 0.04991 (6) | 0.149 (2) |
As | 0.26274 (5) | 0.26274 (5) | 0.24989 (13) | 0.0499 (2) | 0.848 (7) |
Sb | 0.26274 (5) | 0.26274 (5) | 0.24989 (13) | 0.0499 (2) | 0.152 (7) |
S1 | 0.09444 (9) | 0.33056 (7) | 0.38015 (13) | 0.04969 (18) | |
S2 | 0.12451 (7) | 0.12451 (7) | 0.1359 (2) | 0.0505 (3) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Tl | 0.05002 (7) | 0.05002 (7) | 0.04945 (12) | −0.0003 (4) | 0.000 | 0.000 |
Cu | 0.0503 (2) | 0.0503 (2) | 0.0489 (3) | 0.000 | 0.000 | 0.000 |
Ag | 0.0503 (2) | 0.0503 (2) | 0.0489 (3) | 0.000 | 0.000 | 0.000 |
Hg | 0.04998 (10) | 0.05017 (9) | 0.04957 (10) | 0.000 | 0.000 | −0.0003 (3) |
Zn | 0.04998 (10) | 0.05017 (9) | 0.04957 (10) | 0.000 | 0.000 | −0.0003 (3) |
As | 0.0504 (3) | 0.0504 (3) | 0.0490 (2) | 0.0004 (3) | 0.0007 (6) | 0.0007 (6) |
Sb | 0.0504 (3) | 0.0504 (3) | 0.0490 (2) | 0.0004 (3) | 0.0007 (6) | 0.0007 (6) |
S1 | 0.0499 (3) | 0.0500 (3) | 0.0491 (5) | −0.0005 (2) | 0.0013 (5) | −0.0002 (5) |
S2 | 0.0499 (3) | 0.0499 (3) | 0.0515 (9) | −0.0002 (3) | −0.0005 (4) | −0.0005 (4) |
Tl—S1 | 3.4526 (8) | Hg—S1viii | 2.4808 (11) |
Tl—S2i | 2.961 (2) | Hg—S2ix | 2.5428 (15) |
Tl—S2 | 2.961 (2) | Hg—S2x | 2.5428 (15) |
Tl—Tlii | 3.4707 (6) | As—S1 | 2.3350 (14) |
Tl—Sbiii | 3.5226 (9) | As—S1xi | 2.3350 (14) |
Tl—Sbiv | 3.5226 (9) | As—S2 | 2.3387 (19) |
Cu—S1v | 2.4325 (11) | S2—Znxii | 2.5428 (15) |
Cu—S1vi | 2.4325 (11) | S2—Znxiii | 2.5428 (15) |
Cu—S1 | 2.4325 (11) | S2—Hgxiii | 2.5428 (15) |
Cu—S1vii | 2.4325 (11) | S2—Hgxii | 2.5428 (15) |
Hg—S1 | 2.4808 (11) | ||
S2i—Tl—S2 | 72.83 (6) | S2ix—Hg—S2x | 102.08 (6) |
S2i—Tl—Tlii | 143.59 (3) | S1—As—S1xi | 91.08 (6) |
S2—Tl—Tlii | 143.59 (3) | S1—As—S2 | 95.41 (5) |
S2i—Tl—Sbiii | 75.56 (2) | S1xi—As—S2 | 95.41 (5) |
S2—Tl—Sbiii | 75.56 (2) | As—S1—Cu | 95.65 (5) |
Tlii—Tl—Sbiii | 108.05 (2) | As—S1—Hg | 101.10 (4) |
S2i—Tl—Sbiv | 75.56 (2) | Cu—S1—Hg | 92.59 (3) |
S2—Tl—Sbiv | 75.56 (2) | As—S2—Znxii | 104.52 (3) |
Tlii—Tl—Sbiv | 108.05 (2) | As—S2—Znxiii | 104.52 (3) |
Sbiii—Tl—Sbiv | 143.90 (5) | Znxii—S2—Znxiii | 104.42 (8) |
S1v—Cu—S1vi | 105.50 (6) | As—S2—Hgxiii | 104.52 (3) |
S1v—Cu—S1 | 111.49 (3) | Znxii—S2—Hgxiii | 104.42 (8) |
S1vi—Cu—S1 | 111.49 (3) | As—S2—Hgxii | 104.52 (3) |
S1v—Cu—S1vii | 111.49 (3) | Znxiii—S2—Hgxii | 104.42 (8) |
S1vi—Cu—S1vii | 111.49 (3) | Hgxiii—S2—Hgxii | 104.42 (8) |
S1—Cu—S1vii | 105.50 (6) | As—S2—Tl | 92.97 (9) |
S1—Hg—S1viii | 121.80 (4) | Znxii—S2—Tl | 123.05 (3) |
S1—Hg—S2ix | 107.97 (5) | Znxiii—S2—Tl | 123.05 (3) |
S1viii—Hg—S2ix | 107.64 (4) | Hgxiii—S2—Tl | 123.05 (3) |
S1—Hg—S2x | 107.64 (4) | Hgxii—S2—Tl | 123.05 (3) |
S1viii—Hg—S2x | 107.97 (5) |
Symmetry codes: (i) −x, −y, z; (ii) x, −y, −z+1; (iii) x−1/2, −y+1/2, −z+1/2; (iv) −x+1/2, y−1/2, −z+1/2; (v) y−1/2, −x+1/2, −z+1/2; (vi) −y+1/2, x+1/2, −z+1/2; (vii) −x, −y+1, z; (viii) x, −y+1, −z+1; (ix) −x+1/2, y+1/2, −z+1/2; (x) −x+1/2, −y+1/2, z+1/2; (xi) y, x, z; (xii) −y+1/2, −x+1/2, z−1/2; (xiii) −x+1/2, −y+1/2, z−1/2. |
Experimental details
Crystal data | |
Chemical formula | Tl(Cu·Ag)(Hg·Zn)2(As·Sb)2S6 |
Mr | 1000.29 |
Crystal system, space group | Tetragonal, I42m |
Temperature (K) | 298 |
a, c (Å) | 9.9821 (11), 11.3122 (12) |
V (Å3) | 1127.2 (2) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 46.48 |
Crystal size (mm) | 0.12 × 0.10 × 0.07 |
Data collection | |
Diffractometer | Oxford Xcalibur 3 diffractometer |
Absorption correction | Gaussian (ABSPACK; Oxford Diffraction, 2006) |
Tmin, Tmax | 0.006, 0.041 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 2692, 673, 586 |
Rint | 0.029 |
(sin θ/λ)max (Å−1) | 0.806 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.011, 0.011, 0.88 |
No. of reflections | 673 |
No. of parameters | 37 |
Δρmax, Δρmin (e Å−3) | 0.76 at 0.0000 0.0000 0.1996 (1.66 Å from TL), −0.99 at 0.0000 0.0000 0.2500 (1.09 Å from TL) |
Absolute structure | Flack (1983), No. of Friedel pairs? |
Absolute structure parameter | 0.223 (14) |
Computer programs: CrysAlis RED (Oxford Diffraction, 2006), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), Xtaldraw (Downs & Hall-Wallace, 2003).
Tl—S1 | 3.4526 (8) | Hg—S1 | 2.4808 (11) |
Tl—S2 | 2.961 (2) | Hg—S2iii | 2.5428 (15) |
Tl—Tli | 3.4707 (6) | As—S1 | 2.3350 (14) |
Tl—Sbii | 3.5226 (9) | As—S2 | 2.3387 (19) |
Cu—S1 | 2.4325 (11) | S2—Zniv | 2.5428 (15) |
Symmetry codes: (i) x, −y, −z+1; (ii) x−1/2, −y+1/2, −z+1/2; (iii) −x+1/2, y+1/2, −z+1/2; (iv) −y+1/2, −x+1/2, z−1/2. |
Routhierite, Tl(Cu,Ag)(Hg,Zn)2(As,Sb)2S6, is a rare mineral first described by Johan et al. (1974) to occur with pierrotite, stibnite, smithite, sphalerite, realgar, orpiment, pyrite and barite in Jas Roux (Hautes-Alpes), France. By means of an X-ray single-crystal study (Weissenberg photographs), these authors pointed out that routhierite is tetragonal (possible space groups I4mm, I42m, I4m2 and I4/mmm, with a = 9.977 (4) Å and c 11.290 Å). However, Johan et al. (1974) were not able to proceed to a crystal structure determination of routhierite at that time. More recently, Graeser et al. (1995) during the structural description of the new Tl sulfosalt mineral stalderite, Tl(Cu,Ag)(Zn,Fe,Hg)2(As,Sb)2S6, pointed out close relationships between stalderite and routhierite. They concluded, indeed, that stalderite represents the Zn equivalent of routhierite. Similar conclusions were reached by Moelo et al. (2008) during a review of sulfosalt systematics. These authors considered routhierite as isotypic with stalderite. To help resolve the concerns relating to the structure of routhierite and to invesitgate the similarity in X-ray patterns for routhierite and stalderite, new crystal structure data for routhierite from its type locality, Jas Roux, are presented.
In the crystal structure of routhierite, (Cu,Ag)S4 and (Hg,Zn)S4 tetrahedra share corners to form a framework with channels parallel to [001] (Fig. 1). These channels contain TlS6 and (As,Sb)S3 polyhedra that share corners and edges with the tetrahedra (Fig. 2). In detail, the Tl atom is coordinated by (2 + 4) S atoms in the form of an orthorhombic pyramid with a split apex. The mean Tl—S bond distance (i.e. 3.29 Å) is nearly identical to that observed in stalderite (i.e. 3.32 Å; Graeser et al., 1995). The (Cu,Ag) and (Hg,Zn) atoms are surrounded by four S atoms to form slightly distorted tetrahedra. The mean (Cu,Ag)—S distance of 2.43 Å is greater than that observed in stalderite (i.e. 2.36 Å) because of the presence of minor amounts of silver replacing copper at this position. The mean (Hg,Zn)—S distance of 2.51 Å is in fair agreement with those observed for christite, TlHgAsS3 (i.e. 2.56 Å; Brown & Dickson, 1976), and laffittite, AgHgAsS3 (i.e. 2.59 Å; Nakai & Appleman, 1983). The shortening of the (Hg,Zn)—S distance in routhierite, however, is due to the minor amount of Zn substituting for Hg. In stalderite, where only Zn is present at this position, the mean bond distance is 2.41 Å (Graser or Graeser et al., 1995). Finally, the (As,Sb) atoms form a trigonal pyramid with three S atoms, with (As,Sb) at the apex [mean (As,Sb)—S = 2.34 Å], as is typical for sulfosalts. It is worth noting that a relatively short Tl—Tl distance of 3.47 Å was observed. This value is similar to the Tl—Tl distance found in elemental thallium (3.40 Å; Wells, 1962) and could indicate some Tl—Tl interactions in the structure. The same feature was also observed in stalderite (Graeser et al., 1995).
The structure determination reported here confirms that routhierite and stalderite possess the same crystal structure.