Cs₄Ge₂S₈

The reaction of Cs₂S₃, Ge and S yields single crystals of tetracesium digermanium octa­sulfide, Cs₄Ge₂S₈. The structure contains the novel dinuclear anion [Ge₂S₈]^4-, and is another example of a chalcogenidogermanate(IV) exhibiting S₂ bridging units. Two GeS₄ tetrahedra in the anion are linked via S-S bonds, yielding a six-membered ring which displays a chair conformation and crystallographic C_2h symmetry. The anions are connected via Cs⁺ ions. The compound crystallizes with the Cs₄Ge₂Se₈ structure.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](S-S) = 0.001 Å
• R factor = 0.021
• wR factor = 0.051
• Data-to-parameter ratio = 34.6

checkCIF/PLATON results

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Computing details

Data collection: DIF4 (Stoe & Cie, 1990); cell refinement: DIF4; data reduction: REDU4 (Stoe & Cie, 1990); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP in SHELXTL (Bruker, 1998); software used to prepare material for publication: CIFTAB in SHELXTL.

Tetracaesium digermanium octasulfide

Crystal data

Cs4Ge2S8	F(000) = 824
Mr = 933.42	Dx = 3.450 Mg m^−3
Monoclinic, C2/m	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2y	Cell parameters from 108 reflections
a = 14.721 (2) Å	θ = 14–19°
b = 7.364 (1) Å	µ = 12.23 mm^−1
c = 9.820 (1) Å	T = 293 K
β = 122.43 (1)°	Polyhedron, orange
V = 898.5 (2) Å^3	0.12 × 0.08 × 0.06 mm
Z = 2

Data collection

Phillips PW1100 four-circle diffractometer	1244 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.034
Graphite monochromator	θmax = 30.0°, θmin = 2.5°
ω/θ scans	h = −20→18
Absorption correction: numerical (X-SHAPE; Stoe & Cie, 1998)	k = −10→10
Tmin = 0.322, Tmax = 0.480	l = −13→13
4059 measured reflections	4 standard reflections every 120 min
1417 independent reflections	intensity decay: none

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.021	w = 1/[σ^2(Fo^2) + (0.0206P)^2 + 2.6105P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.051	(Δ/σ)max < 0.001
S = 1.08	Δρmax = 0.92 e Å^−3
1417 reflections	Δρmin = −0.87 e Å^−3
41 parameters	Extinction correction: SHELXL97 (Sheldrick, 1997), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.00151 (12)

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
Cs1	0.16369 (2)	0.0000	0.28823 (4)	0.03154 (9)
Cs2	0.41590 (2)	0.0000	0.15007 (3)	0.03007 (9)
Ge1	0.15583 (4)	0.0000	0.70131 (5)	0.02168 (10)
S1	0.31312 (10)	0.0000	0.73583 (14)	0.0323 (2)
S2	0.12490 (9)	0.0000	0.89111 (13)	0.0283 (2)
S3	0.07944 (6)	0.24278 (10)	0.53104 (9)	0.02617 (15)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cs1	0.03182 (15)	0.03397 (15)	0.03260 (15)	0.000	0.01977 (13)	0.000
Cs2	0.02964 (15)	0.03338 (14)	0.02519 (14)	0.000	0.01336 (11)	0.000
Ge1	0.0223 (2)	0.02382 (19)	0.0194 (2)	0.000	0.01150 (17)	0.000
S1	0.0250 (5)	0.0424 (6)	0.0321 (6)	0.000	0.0170 (5)	0.000
S2	0.0293 (5)	0.0352 (5)	0.0237 (5)	0.000	0.0165 (4)	0.000
S3	0.0263 (4)	0.0251 (3)	0.0265 (3)	−0.0016 (3)	0.0138 (3)	0.0019 (3)

Geometric parameters (Å, º)

Cs1—S2^i	3.6229 (13)	Cs2—Ge1^iv	4.2959 (5)
Cs1—S2^ii	3.6256 (12)	Cs2—Ge1^v	4.2959 (5)
Cs1—S3	3.6866 (8)	Ge1—S2	2.1428 (11)
Cs1—S3^iii	3.6866 (8)	Ge1—S1	2.1528 (12)
Cs1—S1	3.7132 (13)	Ge1—S3^iii	2.2891 (8)
Cs1—S1^iv	3.7170 (5)	Ge1—S3	2.2891 (8)
Cs1—S1^v	3.7170 (5)	Ge1—Cs2^xi	3.9977 (9)
Cs1—S3^iv	3.7200 (9)	Ge1—Cs2^iv	4.2959 (5)
Cs1—S3^vi	3.7200 (9)	Ge1—Cs2^v	4.2959 (5)
Cs1—Ge1	4.1196 (6)	S1—Cs2^xi	3.4979 (13)
Cs1—Cs2	4.5857 (7)	S1—Cs2^viii	3.5177 (13)
Cs1—Cs2^vii	4.8369 (6)	S1—Cs1^iv	3.7170 (5)
Cs2—S1^ii	3.4979 (13)	S1—Cs1^v	3.7170 (5)
Cs2—S1^viii	3.5177 (13)	S2—Cs1^i	3.6229 (13)
Cs2—S2^ii	3.6241 (14)	S2—Cs2^xi	3.6241 (14)
Cs2—S3^iv	3.6289 (8)	S2—Cs1^xi	3.6256 (12)
Cs2—S3^vi	3.6289 (8)	S2—Cs2^v	3.7176 (5)
Cs2—S3^ix	3.7040 (9)	S2—Cs2^iv	3.7176 (5)
Cs2—S3^x	3.7040 (9)	S3—S3^xii	2.0767 (15)
Cs2—S2^v	3.7176 (5)	S3—Cs2^iv	3.6289 (8)
Cs2—S2^iv	3.7176 (5)	S3—Cs2^xiii	3.7040 (9)
Cs2—Ge1^ii	3.9977 (9)	S3—Cs1^iv	3.7200 (9)
S2^i—Cs1—S2^ii	90.56 (3)	S1^viii—Cs2—Ge1^ii	127.10 (2)
S2^i—Cs1—S3	66.48 (2)	S2^ii—Cs2—Ge1^ii	32.183 (19)
S2^ii—Cs1—S3	141.450 (18)	S3^iv—Cs2—Ge1^ii	120.997 (16)
S2^i—Cs1—S3^iii	66.48 (2)	S3^vi—Cs2—Ge1^ii	120.997 (16)
S2^ii—Cs1—S3^iii	141.450 (18)	S3^ix—Cs2—Ge1^ii	146.395 (13)
S3—Cs1—S3^iii	58.02 (2)	S3^x—Cs2—Ge1^ii	146.395 (13)
S2^i—Cs1—S1	111.80 (3)	S2^v—Cs2—Ge1^ii	82.920 (18)
S2^ii—Cs1—S1	157.64 (3)	S2^iv—Cs2—Ge1^ii	82.920 (18)
S3—Cs1—S1	54.95 (2)	S1^ii—Cs2—Ge1^iv	111.300 (11)
S3^iii—Cs1—S1	54.95 (2)	S1^viii—Cs2—Ge1^iv	109.581 (12)
S2^i—Cs1—S1^iv	95.326 (18)	S2^ii—Cs2—Ge1^iv	79.919 (12)
S2^ii—Cs1—S1^iv	84.174 (18)	S3^iv—Cs2—Ge1^iv	32.198 (13)
S3—Cs1—S1^iv	68.59 (2)	S3^vi—Cs2—Ge1^iv	92.783 (16)
S3^iii—Cs1—S1^iv	126.56 (2)	S3^ix—Cs2—Ge1^iv	50.477 (14)
S1—Cs1—S1^iv	93.379 (19)	S3^x—Cs2—Ge1^iv	103.899 (16)
S2^i—Cs1—S1^v	95.326 (18)	S2^v—Cs2—Ge1^iv	146.205 (19)
S2^ii—Cs1—S1^v	84.174 (18)	S2^iv—Cs2—Ge1^iv	29.921 (17)
S3—Cs1—S1^v	126.56 (2)	Ge1^ii—Cs2—Ge1^iv	96.311 (9)
S3^iii—Cs1—S1^v	68.59 (2)	S1^ii—Cs2—Ge1^v	111.300 (11)
S1—Cs1—S1^v	93.379 (19)	S1^viii—Cs2—Ge1^v	109.581 (12)
S1^iv—Cs1—S1^v	164.27 (4)	S2^ii—Cs2—Ge1^v	79.919 (12)
S2^i—Cs1—S3^iv	149.192 (13)	S3^iv—Cs2—Ge1^v	92.783 (16)
S2^ii—Cs1—S3^iv	92.67 (2)	S3^vi—Cs2—Ge1^v	32.198 (13)
S3—Cs1—S3^iv	93.036 (19)	S3^ix—Cs2—Ge1^v	103.899 (16)
S3^iii—Cs1—S3^iv	123.149 (15)	S3^x—Cs2—Ge1^v	50.477 (14)
S1—Cs1—S3^iv	68.28 (2)	S2^v—Cs2—Ge1^v	29.921 (17)
S1^iv—Cs1—S3^iv	54.65 (2)	S2^iv—Cs2—Ge1^v	146.205 (19)
S1^v—Cs1—S3^iv	115.48 (2)	Ge1^ii—Cs2—Ge1^v	96.311 (9)
S2^i—Cs1—S3^vi	149.192 (13)	Ge1^iv—Cs2—Ge1^v	117.983 (14)
S2^ii—Cs1—S3^vi	92.67 (2)	S2—Ge1—S1	125.13 (5)
S3—Cs1—S3^vi	123.149 (15)	S2—Ge1—S3^iii	112.65 (3)
S3^iii—Cs1—S3^vi	93.036 (19)	S1—Ge1—S3^iii	100.40 (3)
S1—Cs1—S3^vi	68.28 (2)	S2—Ge1—S3	112.65 (3)
S1^iv—Cs1—S3^vi	115.48 (2)	S1—Ge1—S3	100.40 (3)
S1^v—Cs1—S3^vi	54.65 (2)	S3^iii—Ge1—S3	102.71 (4)
S3^iv—Cs1—S3^vi	61.22 (3)	S2—Ge1—Cs2^xi	64.26 (4)
S2^i—Cs1—Ge1	80.44 (2)	S1—Ge1—Cs2^xi	60.86 (3)
S2^ii—Cs1—Ge1	171.00 (2)	S3^iii—Ge1—Cs2^xi	127.60 (2)
S3—Cs1—Ge1	33.523 (13)	S3—Ge1—Cs2^xi	127.60 (2)
S3^iii—Cs1—Ge1	33.523 (13)	S2—Ge1—Cs1	171.03 (4)
S1—Cs1—Ge1	31.359 (19)	S1—Ge1—Cs1	63.85 (4)
S1^iv—Cs1—Ge1	96.582 (18)	S3^iii—Ge1—Cs1	62.80 (2)
S1^v—Cs1—Ge1	96.582 (18)	S3—Ge1—Cs1	62.80 (2)
S3^iv—Cs1—Ge1	95.069 (17)	Cs2^xi—Ge1—Cs1	124.710 (15)
S3^vi—Cs1—Ge1	95.069 (17)	S2—Ge1—Cs2^iv	59.926 (8)
S2^i—Cs1—Cs2	141.31 (2)	S1—Ge1—Cs2^iv	112.711 (15)
S2^ii—Cs1—Cs2	50.75 (2)	S3^iii—Ge1—Cs2^iv	143.47 (3)
S3—Cs1—Cs2	142.933 (13)	S3—Ge1—Cs2^iv	57.64 (2)
S3^iii—Cs1—Cs2	142.933 (13)	Cs2^xi—Ge1—Cs2^iv	83.689 (9)
S1—Cs1—Cs2	106.89 (2)	Cs1—Ge1—Cs2^iv	118.446 (7)
S1^iv—Cs1—Cs2	82.222 (18)	S2—Ge1—Cs2^v	59.927 (8)
S1^v—Cs1—Cs2	82.222 (18)	S1—Ge1—Cs2^v	112.711 (15)
S3^iv—Cs1—Cs2	50.508 (14)	S3^iii—Ge1—Cs2^v	57.64 (2)
S3^vi—Cs1—Cs2	50.508 (14)	S3—Ge1—Cs2^v	143.47 (3)
Ge1—Cs1—Cs2	138.250 (13)	Cs2^xi—Ge1—Cs2^v	83.689 (9)
S2^i—Cs1—Cs2^vii	49.631 (7)	Cs1—Ge1—Cs2^v	118.446 (7)
S2^ii—Cs1—Cs2^vii	92.188 (15)	Cs2^iv—Ge1—Cs2^v	117.983 (14)
S3—Cs1—Cs2^vii	94.928 (16)	Ge1—S1—Cs2^xi	86.62 (4)
S3^iii—Cs1—Cs2^vii	49.277 (14)	Ge1—S1—Cs2^viii	172.04 (5)
S1—Cs1—Cs2^vii	102.179 (15)	Cs2^xi—S1—Cs2^viii	85.42 (3)
S1^iv—Cs1—Cs2^vii	144.82 (2)	Ge1—S1—Cs1	84.79 (4)
S1^v—Cs1—Cs2^vii	46.311 (19)	Cs2^xi—S1—Cs1	171.41 (4)
S3^iv—Cs1—Cs2^vii	160.418 (13)	Cs2^viii—S1—Cs1	103.17 (3)
S3^vi—Cs1—Cs2^vii	99.610 (16)	Ge1—S1—Cs1^iv	96.758 (18)
Ge1—Cs1—Cs2^vii	82.011 (10)	Cs2^xi—S1—Cs1^iv	94.400 (19)
Cs2—Cs1—Cs2^vii	121.699 (8)	Cs2^viii—S1—Cs1^iv	83.865 (18)
S1^ii—Cs2—S1^viii	94.58 (3)	Cs1—S1—Cs1^iv	86.621 (19)
S1^ii—Cs2—S2^ii	64.70 (3)	Ge1—S1—Cs1^v	96.758 (18)
S1^viii—Cs2—S2^ii	159.28 (3)	Cs2^xi—S1—Cs1^v	94.400 (19)
S1^ii—Cs2—S3^iv	143.108 (16)	Cs2^viii—S1—Cs1^v	83.865 (18)
S1^viii—Cs2—S3^iv	103.40 (2)	Cs1—S1—Cs1^v	86.621 (19)
S2^ii—Cs2—S3^iv	94.23 (2)	Cs1^iv—S1—Cs1^v	164.27 (4)
S1^ii—Cs2—S3^vi	143.108 (16)	Ge1—S2—Cs1^i	108.54 (4)
S1^viii—Cs2—S3^vi	103.40 (2)	Ge1—S2—Cs2^xi	83.55 (4)
S2^ii—Cs2—S3^vi	94.23 (2)	Cs1^i—S2—Cs2^xi	167.91 (3)
S3^iv—Cs2—S3^vi	62.93 (2)	Ge1—S2—Cs1^xi	162.03 (5)
S1^ii—Cs2—S3^ix	144.695 (16)	Cs1^i—S2—Cs1^xi	89.44 (3)
S1^viii—Cs2—S3^ix	70.52 (2)	Cs2^xi—S2—Cs1^xi	78.47 (3)
S2^ii—Cs2—S3^ix	126.31 (2)	Ge1—S2—Cs2^v	90.153 (18)
S3^iv—Cs2—S3^ix	32.88 (2)	Cs1^i—S2—Cs2^v	82.427 (18)
S3^vi—Cs2—S3^ix	72.19 (2)	Cs2^xi—S2—Cs2^v	97.905 (18)
S1^ii—Cs2—S3^x	144.695 (16)	Cs1^xi—S2—Cs2^v	92.297 (17)
S1^viii—Cs2—S3^x	70.52 (2)	Ge1—S2—Cs2^iv	90.153 (18)
S2^ii—Cs2—S3^x	126.31 (2)	Cs1^i—S2—Cs2^iv	82.427 (18)
S3^iv—Cs2—S3^x	72.19 (2)	Cs2^xi—S2—Cs2^iv	97.905 (18)
S3^vi—Cs2—S3^x	32.88 (2)	Cs1^xi—S2—Cs2^iv	92.297 (17)
S3^ix—Cs2—S3^x	61.51 (3)	Cs2^v—S2—Cs2^iv	164.12 (4)
S1^ii—Cs2—S2^v	85.963 (18)	S3^xii—S3—Ge1	104.43 (3)
S1^viii—Cs2—S2^v	97.128 (18)	S3^xii—S3—Cs2^iv	75.55 (4)
S2^ii—Cs2—S2^v	82.095 (18)	Ge1—S3—Cs2^iv	90.16 (3)
S3^iv—Cs2—S2^v	122.55 (2)	S3^xii—S3—Cs1	121.78 (4)
S3^vi—Cs2—S2^v	60.27 (2)	Ge1—S3—Cs1	83.67 (2)
S3^ix—Cs2—S2^v	126.58 (2)	Cs2^iv—S3—Cs1	162.56 (2)
S3^x—Cs2—S2^v	65.35 (2)	S3^xii—S3—Cs2^xiii	71.57 (4)
S1^ii—Cs2—S2^iv	85.963 (18)	Ge1—S3—Cs2^xiii	159.35 (3)
S1^viii—Cs2—S2^iv	97.128 (18)	Cs2^iv—S3—Cs2^xiii	107.81 (2)
S2^ii—Cs2—S2^iv	82.095 (18)	Cs1—S3—Cs2^xiii	81.758 (18)
S3^iv—Cs2—S2^iv	60.27 (2)	S3^xii—S3—Cs1^iv	146.79 (2)
S3^vi—Cs2—S2^iv	122.55 (2)	Ge1—S3—Cs1^iv	94.23 (3)
S3^ix—Cs2—S2^iv	65.35 (2)	Cs2^iv—S3—Cs1^iv	77.205 (18)
S3^x—Cs2—S2^iv	126.58 (2)	Cs1—S3—Cs1^iv	86.964 (19)
S2^v—Cs2—S2^iv	164.12 (4)	Cs2^xiii—S3—Cs1^iv	99.51 (2)
S1^ii—Cs2—Ge1^ii	32.52 (2)

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