TlBiS₂

The ternary compound thallium bis­muth disulfide crystallizes in the space group Rm and is isotypic with the structures of most of the ABQ₂ chalcogenides (A = monovalent atom, B = trivalent atom and Q = chalcogen), which are members of the α-NaFeO₂ structure type. In the title compound, the Tl and Bi atoms are situated on positions with m symmetry, whereas the S atom sites exhibit 3m symmetry. The metal atoms occupy octa­hedral voids in distinct planes perpendicular to the c axis. The environment around Tl is more distorted than the polyhedron around Bi.

Key indicators

• Single-crystal X-ray study
• T = 295 K
• Mean [sigma](i-S)= 0.005 Å
• R factor = 0.049
• wR factor = 0.130
• Data-to-parameter ratio = 14.1

checkCIF/PLATON results

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Computing details

Data collection: IPDS (Stoe & Cie, 1998); cell refinement: IPDS; data reduction: IPDS; program(s) used to solve structure: coordinates taken from an isotypic compound (Voroshilov et al., 1972); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: DIAMOND (Brandenburg, 1999); software used to prepare material for publication: SHELXL97.

thallium bismuth disulfide

Crystal data

TlBiS2	Dx = 7.455 Mg m^−3
Mr = 477.47	Mo Kα radiation, λ = 0.71073 Å
Trigonal, R3m	Cell parameters from 781 reflections
Hall symbol: -R 3 2"	θ = 2.8–28.0°
a = 4.1041 (5) Å	µ = 79.89 mm^−1
c = 21.872 (4) Å	T = 295 K
V = 319.05 (8) Å^3	Irregular, black
Z = 3	0.12 × 0.10 × 0.08 mm
F(000) = 588

Data collection

Stoe IPDS diffractometer	127 independent reflections
Radiation source: fine-focus sealed tube	108 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.097
ω scans	θmax = 28.0°, θmin = 2.8°
Absorption correction: numerical [X-SHAPE (Stoe & Cie, 1998) and X-RED (Stoe & Cie, 1998)]	h = −5→5
Tmin = 0.003, Tmax = 0.019	k = −5→5
706 measured reflections	l = −28→24

Refinement

Refinement on F^2	Primary atom site location: isomorph
Least-squares matrix: full	w = 1/[σ^2(Fo^2) + (0.0911P)^2] where P = (Fo^2 + 2Fc^2)/3
R[F^2 > 2σ(F^2)] = 0.049	(Δ/σ)max < 0.001
wR(F^2) = 0.130	Δρmax = 3.15 e Å^−3
S = 1.09	Δρmin = −5.55 e Å^−3
127 reflections	Extinction correction: SHELXL97 (Sheldrick, 1997), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
9 parameters	Extinction coefficient: 0.008 (2)
0 restraints

Special details

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Tl	0.0000	0.0000	0.5000	0.0323 (11)
Bi	0.0000	0.0000	0.0000	0.0241 (11)
S1	0.0000	0.0000	0.2624 (4)	0.0265 (19)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Tl	0.0345 (12)	0.0345 (12)	0.0281 (13)	0.0172 (6)	0.000	0.000
Bi	0.0248 (12)	0.0248 (12)	0.0225 (13)	0.0124 (6)	0.000	0.000
S1	0.030 (3)	0.030 (3)	0.020 (3)	0.0149 (13)	0.000	0.000

Geometric parameters (Å, º)

Tl—S1^i	3.162 (6)	Bi—S1^x	2.832 (5)
Tl—S1^ii	3.162 (6)	Bi—S1^xi	2.832 (5)
Tl—S1^iii	3.162 (6)	Bi—S1^xii	2.832 (5)
Tl—S1^iv	3.162 (6)	S1—Bi^ii	2.832 (5)
Tl—S1^v	3.162 (6)	S1—Bi^iv	2.832 (5)
Tl—S1^vi	3.162 (6)	S1—Bi^v	2.832 (5)
Bi—S1^vii	2.832 (5)	S1—Tl^viii	3.162 (6)
Bi—S1^viii	2.832 (5)	S1—Tl^x	3.162 (6)
Bi—S1^ix	2.832 (5)	S1—Tl^xi	3.162 (6)
S1^i—Tl—S1^ii	180.000 (1)	S1^ix—Bi—S1^xi	87.1 (2)
S1^i—Tl—S1^iii	80.92 (18)	S1^x—Bi—S1^xi	92.9 (2)
S1^ii—Tl—S1^iii	99.08 (18)	S1^vii—Bi—S1^xii	92.9 (2)
S1^i—Tl—S1^iv	99.08 (18)	S1^viii—Bi—S1^xii	87.1 (2)
S1^ii—Tl—S1^iv	80.92 (18)	S1^ix—Bi—S1^xii	92.9 (2)
S1^iii—Tl—S1^iv	180.0	S1^x—Bi—S1^xii	87.1 (2)
S1^i—Tl—S1^v	99.08 (18)	S1^xi—Bi—S1^xii	180.0 (3)
S1^ii—Tl—S1^v	80.92 (18)	Bi^ii—S1—Bi^iv	92.9 (2)
S1^iii—Tl—S1^v	99.08 (18)	Bi^ii—S1—Bi^v	92.9 (2)
S1^iv—Tl—S1^v	80.92 (18)	Bi^iv—S1—Bi^v	92.9 (2)
S1^i—Tl—S1^vi	80.92 (18)	Bi^ii—S1—Tl^viii	171.7 (3)
S1^ii—Tl—S1^vi	99.08 (18)	Bi^iv—S1—Tl^viii	92.82 (3)
S1^iii—Tl—S1^vi	80.92 (18)	Bi^v—S1—Tl^viii	92.83 (3)
S1^iv—Tl—S1^vi	99.08 (18)	Bi^ii—S1—Tl^x	92.82 (3)
S1^v—Tl—S1^vi	180.0 (2)	Bi^iv—S1—Tl^x	171.7 (3)
S1^vii—Bi—S1^viii	180.0 (3)	Bi^v—S1—Tl^x	92.83 (3)
S1^vii—Bi—S1^ix	92.9 (2)	Tl^viii—S1—Tl^x	80.92 (18)
S1^viii—Bi—S1^ix	87.1 (2)	Bi^ii—S1—Tl^xi	92.83 (3)
S1^vii—Bi—S1^x	87.1 (2)	Bi^iv—S1—Tl^xi	92.83 (3)
S1^viii—Bi—S1^x	92.9 (2)	Bi^v—S1—Tl^xi	171.7 (3)
S1^ix—Bi—S1^x	180.0 (3)	Tl^viii—S1—Tl^xi	80.92 (18)
S1^vii—Bi—S1^xi	87.1 (2)	Tl^x—S1—Tl^xi	80.92 (18)
S1^viii—Bi—S1^xi	92.9 (2)

Symmetry codes: (i) −x−2/3, −y−1/3, −z+2/3; (ii) x+2/3, y+1/3, z+1/3; (iii) −x+1/3, −y+2/3, −z+2/3; (iv) x−1/3, y−2/3, z+1/3; (v) x−1/3, y+1/3, z+1/3; (vi) −x+1/3, −y−1/3, −z+2/3; (vii) −x+2/3, −y+1/3, −z+1/3; (viii) x−2/3, y−1/3, z−1/3; (ix) −x−1/3, −y−2/3, −z+1/3; (x) x+1/3, y+2/3, z−1/3; (xi) x+1/3, y−1/3, z−1/3; (xii) −x−1/3, −y+1/3, −z+1/3.