Kermesite, Sb2S2O: crystal structure revision and order–disorder interpretation

Hybler, J.; Ďurovič, S.

doi:10.1107/S2052519213024238

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Kermesite, Sb₂S₂O: crystal structure revision and order–disorder interpretation

J. Hybler and S. Ďurovič

Kermesite, Sb₂S₂O, is a desymmetrized order–disorder (OD) structure of layers. Two data sets were recorded using twinned crystals from Pezinok, Slovakia (named as Pz21, Pz24). The primitive unit cell is triclinic, $P\bar 1$ , Z = 4, cell parameters are a = 8.1416 (3), b = 10.6968 (3), c = 5.7835 (2) Å, α = 102.758 (3), β = 110.657 (3), γ = 101.020 (3)°, R_obs = 0.0243 (Pz21), and a = 8.1372 (2), b = 10.6969 (2), c = 5.7840 (1) Å, α = 102.787 (2), β = 110.606 (2), γ = 100.983 (2)°, R_obs = 0.0321 (Pz24). The structure can also be described in the non-standard pseudo-monoclinic octuple (Z = 32), F-centered (Kupčík) cell with extra points in ${1\over 4},{1\over 4},0$ ; ${1\over 4},{3\over 4},{1\over 2}$ ; ${3\over 4},{1\over 4},{1\over 2}$ ; ${3\over 4},{3\over 4},0$ , with parameters a = 21.6466 (9), b = 8.1416 (3), c = 20.3824 (9) Å, α = 90.079 (4), β = 101.985 (5), γ = 89.948 (4)° (Pz21), and a = 21.6558 (5), b = 8.1372 (2), c = 20.3859 (8) Å, α = 90.028 (3), β = 101.994 (3), γ = 89.986 (2)° (Pz24). The structure is built of layers parallel to the bc plane, stacked along the a vector of the octuple cell, composed of ribbons parallel to the b vector: (i) ribbon of two strips of SbO₅ flattened quadrangular pyramids, sharing apical edges; (ii) ribbon of edge-sharing corrugated lozenges SbO₃S. Basal S atoms of pyramids share corners of lozenges. Sb atoms are displaced out of coordination polyhedra into the inter-layer space. The OD layer comprises adjacent halves of the structure building layers. The layer group is A(1)2/m1, the protocell is defined by b, c, (a/4)sin β. The MDO1 (4A) polytype is generated by repetition of the ${\bf t}_{(1,\, {1\over 4},\,0)}$ [or alternatively ${\bf t}_{(1,\,-{1\over 4}, \, 0)}$ ] translation. The co-existence of two kinds of domains give rise to the twinning. The twin operation is 2_[010], twin index 2. The total continuation of [. a₂ .] generates the MDO2 (2M) polytype, space group A12/a1. Simulated and real diffraction patterns are presented. The important values (edges, angles) and displacements of atoms due to the desymmetrization were evaluated. The comparison with structures of stibnite, bismuthinite and aikinite is added.

Keywords: order–disorder; polytypes; twinning; desymmetrization.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S2052519213024238/wf5108sup1.cif Contains datablocks global, I, II, III, IV
	Structure factor file (CIF format) https://doi.org/10.1107/S2052519213024238/wf5108Isup2.hkl Contains datablock I
	Structure factor file (CIF format) https://doi.org/10.1107/S2052519213024238/wf5108IIsup3.hkl Contains datablock II
	Structure factor file (CIF format) https://doi.org/10.1107/S2052519213024238/wf5108IIIsup4.hkl Contains datablock III
	Structure factor file (CIF format) https://doi.org/10.1107/S2052519213024238/wf5108IVsup5.hkl Contains datablock IV
	Portable Document Format (PDF) file https://doi.org/10.1107/S2052519213024238/wf5108sup6.pdf Commented responses of the CheckCIF/PLATON report of CIFs corresponding to the data sets of two twinned crystals with various ratio of domains refined in two axial settings

Experimental top

Refinement top

Crystal data, data collection and structure refinement details are summarized in Table 1.

Results and discussion top

Computing details top

Data collection: CrysAlis CCD, Oxford Diffraction Ltd., Version 1.171.33.55 (release 05-01-2010 CrysAlis171 .NET) (compiled Jan 5 2010,16:28:46) for (I). Cell refinement: CrysAlis RED, Oxford Diffraction Ltd., Version 1.171.33.55 (release 05-01-2010 CrysAlis171 .NET) (compiled Jan 5 2010,16:28:46) for (I). Data reduction: CrysAlis RED, Oxford Diffraction Ltd., Version 1.171.33.55 (release 05-01-2010 CrysAlis171 .NET) (compiled Jan 5 2010,16:28:46) for (I).

Figures top

(I) top

Crystal data top

OS₂Sb₂	Z = 4
M_r = 323.6	F(000) = 568
Triclinic, P1	D_x = 4.892 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.7107 Å
a = 8.1416 (3) Å	Cell parameters from 6328 reflections
b = 10.6968 (3) Å	θ = 2.9–32.6°
c = 5.7835 (2) Å	µ = 13.06 mm⁻¹
α = 102.758 (3)°	T = 293 K
β = 110.657 (3)°	Acicular, red
γ = 101.020 (3)°	0.65 × 0.05 × 0.03 mm
V = 439.23 (3) Å³

Data collection top

Xcalibur, Atlas, Gemini ultra diffractometer	4465 independent reflections
Radiation source: Enhance (Mo) X-ray Source	2604 reflections with I > 3σ(I)
Graphite monochromator	R_int = 0.050
Detector resolution: 10.3784 pixels mm^-1	θ_max = 32.7°, θ_min = 2.9°
ω scans	h = −11→12
Absorption correction: gaussian Jana2006 (Petricek, Dusek & Palatinus, 2000)	k = −16→16
T_min = 0.109, T_max = 0.667	l = −8→8
12651 measured reflections

Refinement top

Refinement on F	0 restraints
R[F² > 2σ(F²)] = 0.024	0 constraints
wR(F²) = 0.027	Weighting scheme based on measured s.u.'s w = 1/(σ²(F) + 0.0001F²)
S = 1.12	(Δ/σ)_max = 0.020
4465 reflections	Δρ_max = 1.15 e Å⁻³
92 parameters	Δρ_min = −1.34 e Å⁻³

Crystal data top

OS₂Sb₂	γ = 101.020 (3)°
M_r = 323.6	V = 439.23 (3) Å³
Triclinic, P1	Z = 4
a = 8.1416 (3) Å	Mo Kα radiation
b = 10.6968 (3) Å	µ = 13.06 mm⁻¹
c = 5.7835 (2) Å	T = 293 K
α = 102.758 (3)°	0.65 × 0.05 × 0.03 mm
β = 110.657 (3)°

Data collection top

Xcalibur, Atlas, Gemini ultra diffractometer	4465 independent reflections
Absorption correction: gaussian Jana2006 (Petricek, Dusek & Palatinus, 2000)	2604 reflections with I > 3σ(I)
T_min = 0.109, T_max = 0.667	R_int = 0.050
12651 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.024	92 parameters
wR(F²) = 0.027	0 restraints
S = 1.12	Δρ_max = 1.15 e Å⁻³
4465 reflections	Δρ_min = −1.34 e Å⁻³

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Sb1	0.16840 (3)	0.63146 (2)	0.03891 (5)	0.01099 (8)
Sb2	0.66034 (3)	0.62984 (2)	0.01365 (5)	0.01159 (9)
Sb3	0.12564 (4)	0.85374 (3)	0.63183 (5)	0.01335 (9)
Sb4	0.65245 (4)	0.91530 (3)	0.67939 (5)	0.01500 (9)
S1	0.81008 (13)	0.70292 (9)	0.49744 (18)	0.0144 (3)
S2	0.28992 (13)	0.69210 (9)	0.51780 (18)	0.0144 (3)
S3	0.04760 (13)	0.90934 (9)	0.22597 (18)	0.0131 (3)
S4	0.51998 (13)	0.91063 (9)	0.22786 (18)	0.0134 (3)
O1	0.8979 (4)	0.5681 (2)	0.0301 (5)	0.0133 (10)
O2	0.4149 (3)	0.5711 (2)	0.0761 (5)	0.0139 (10)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Sb1	0.01034 (11)	0.00907 (10)	0.01308 (11)	0.00190 (9)	0.00565 (9)	0.00207 (8)
Sb2	0.00983 (11)	0.00940 (11)	0.01518 (12)	0.00219 (9)	0.00562 (9)	0.00297 (8)
Sb3	0.01271 (12)	0.01414 (12)	0.01179 (11)	0.00299 (9)	0.00518 (9)	0.00210 (8)
Sb4	0.01470 (12)	0.01523 (12)	0.01497 (12)	0.00354 (10)	0.00588 (10)	0.00568 (9)
S1	0.0125 (4)	0.0144 (4)	0.0147 (4)	0.0010 (3)	0.0068 (4)	0.0019 (3)
S2	0.0149 (4)	0.0153 (4)	0.0128 (4)	0.0063 (4)	0.0051 (4)	0.0031 (3)
S3	0.0115 (4)	0.0122 (4)	0.0137 (4)	0.0018 (3)	0.0044 (3)	0.0034 (3)
S4	0.0135 (4)	0.0131 (4)	0.0124 (4)	0.0033 (3)	0.0053 (3)	0.0021 (3)
O1	0.0116 (12)	0.0058 (11)	0.0226 (14)	0.0032 (9)	0.0088 (11)	0.0010 (9)
O2	0.0092 (12)	0.0064 (11)	0.0259 (15)	0.0018 (9)	0.0093 (11)	0.0015 (10)

Geometric parameters (Å, º) top

Sb1—S2	2.4695 (10)	Sb3—S2	2.4932 (12)
Sb1—O1ⁱ	2.155 (3)	Sb3—S3	2.4446 (11)
Sb1—O1ⁱⁱ	2.010 (3)	Sb3—S3ⁱⁱⁱ	3.2176 (11)
Sb1—O2	2.178 (3)	Sb3—S4^iv	3.1624 (10)
Sb2—S1	2.4878 (10)	Sb4—S1	2.9878 (12)
Sb2—O1	2.138 (3)	Sb4—S2	3.1080 (10)
Sb2—O2	2.156 (3)	Sb4—S3^iv	2.5757 (10)
Sb2—O2ⁱⁱ	2.011 (2)	Sb4—S4	2.4330 (10)
Sb3—S1ⁱ	2.5021 (10)	Sb4—S4^iv	2.6106 (12)

S2—Sb1—O1ⁱ	87.49 (8)	S2—Sb3—S3	95.10 (4)
S2—Sb1—O1ⁱⁱ	96.06 (9)	S2—Sb3—S3ⁱⁱⁱ	172.74 (3)
S2—Sb1—O2	86.12 (8)	S2—Sb3—S4^iv	88.26 (3)
O1ⁱ—Sb1—O1ⁱⁱ	72.76 (11)	S3—Sb3—S3ⁱⁱⁱ	81.50 (3)
O1ⁱ—Sb1—O2	143.57 (11)	S3—Sb3—S4^iv	78.73 (3)
O1ⁱⁱ—Sb1—O2	72.33 (11)	S3ⁱⁱⁱ—Sb3—S4^iv	84.80 (3)
S1—Sb2—O1	85.53 (8)	S1—Sb4—S2	88.60 (3)
S1—Sb2—O2	82.81 (7)	S1—Sb4—S3^iv	88.02 (3)
S1—Sb2—O2ⁱⁱ	102.01 (9)	S1—Sb4—S4	86.20 (3)
O1—Sb2—O2	140.35 (11)	S1—Sb4—S4^iv	172.04 (3)
O1—Sb2—O2ⁱⁱ	73.16 (11)	S2—Sb4—S3^iv	174.97 (3)
O2—Sb2—O2ⁱⁱ	72.49 (12)	S2—Sb4—S4	84.22 (3)
S1ⁱ—Sb3—S2	102.34 (3)	S2—Sb4—S4^iv	87.39 (3)
S1ⁱ—Sb3—S3	94.15 (3)	S3^iv—Sb4—S4	91.84 (3)
S1ⁱ—Sb3—S3ⁱⁱⁱ	84.35 (3)	S3^iv—Sb4—S4^iv	95.51 (3)
S1ⁱ—Sb3—S4^iv	167.80 (3)	S4—Sb4—S4^iv	86.56 (4)

Symmetry codes: (i) x−1, y, z; (ii) −x+1, −y+1, −z; (iii) −x, −y+2, −z+1; (iv) −x+1, −y+2, −z+1.

(II) top

Crystal data top

OS₂Sb₂	Z = 32
M_r = 323.6	F(000) = 568
Triclinic, X1	D_x = 4.892 Mg m⁻³
Hall symbol: -X	Mo Kα radiation, λ = 0.7107 Å
a = 21.6466 (9) Å	Cell parameters from 6328 reflections
b = 8.1416 (3) Å	θ = 2.9–32.6°
c = 20.3824 (9) Å	µ = 13.06 mm⁻¹
α = 90.079 (4)°	T = 293 K
β = 101.985 (5)°	Acicular, red
γ = 89.948 (4)°	0.65 × 0.05 × 0.03 mm
V = 3513.8 (3) Å³

Data collection top

Oxford Diffraction CCD diffractometer	4465 independent reflections
Radiation source: X-ray tube	2604 reflections with I > 3σ(I)
Graphite monochromator	R_int = 0.050
Detector resolution: 10.3784 pixels mm^-1	θ_max = 32.7°, θ_min = 2.9°
ω scans	h = −31→31
Absorption correction: gaussian Jana2006 (Petricek, Dusek & Palatinus, 2000)	k = −12→11
T_min = 0.109, T_max = 0.667	l = −30→30
12651 measured reflections

Refinement top

Refinement on F	0 restraints
R[F² > 2σ(F²)] = 0.024	0 constraints
wR(F²) = 0.027	Weighting scheme based on measured s.u.'s w = 1/(σ²(F) + 0.0001F²)
S = 1.11	(Δ/σ)_max = 0.028
4465 reflections	Δρ_max = 1.14 e Å⁻³
92 parameters	Δρ_min = −1.36 e Å⁻³

Crystal data top

OS₂Sb₂	γ = 89.948 (4)°
M_r = 323.6	V = 3513.8 (3) Å³
Triclinic, X1	Z = 32
a = 21.6466 (9) Å	Mo Kα radiation
b = 8.1416 (3) Å	µ = 13.06 mm⁻¹
c = 20.3824 (9) Å	T = 293 K
α = 90.079 (4)°	0.65 × 0.05 × 0.03 mm
β = 101.985 (5)°

Data collection top

Oxford Diffraction CCD diffractometer	4465 independent reflections
Absorption correction: gaussian Jana2006 (Petricek, Dusek & Palatinus, 2000)	2604 reflections with I > 3σ(I)
T_min = 0.109, T_max = 0.667	R_int = 0.050
12651 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.024	92 parameters
wR(F²) = 0.027	0 restraints
S = 1.11	Δρ_max = 1.14 e Å⁻³
4465 reflections	Δρ_min = −1.36 e Å⁻³

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Sb1	0.101846 (13)	0.74919 (3)	0.184271 (11)	0.01093 (7)
Sb2	0.095969 (13)	0.25053 (3)	0.185079 (12)	0.01153 (7)
Sb3	0.194521 (13)	−0.00426 (3)	0.073117 (13)	0.01342 (7)
Sb4	0.191022 (13)	0.49623 (3)	0.042365 (13)	0.01508 (8)
S1	0.19864 (5)	0.24005 (12)	0.14855 (5)	0.0144 (3)
S2	0.20641 (5)	0.76251 (12)	0.15394 (5)	0.0144 (3)
S3	0.07915 (5)	−0.01372 (12)	0.04532 (5)	0.0131 (3)
S4	0.07931 (5)	0.51459 (12)	0.04468 (5)	0.0134 (3)
O1	0.11552 (13)	0.0016 (3)	0.21593 (12)	0.0132 (8)
O2	0.12622 (14)	0.4969 (3)	0.21445 (12)	0.0139 (8)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Sb1	0.01415 (12)	0.00977 (11)	0.00899 (11)	−0.00102 (9)	0.00265 (8)	−0.00054 (8)
Sb2	0.01548 (13)	0.00951 (11)	0.00931 (11)	0.00001 (10)	0.00190 (8)	−0.00064 (8)
Sb3	0.01422 (12)	0.01274 (12)	0.01434 (13)	−0.00091 (10)	0.00537 (9)	−0.00037 (9)
Sb4	0.01398 (13)	0.01547 (13)	0.01544 (13)	−0.00021 (10)	0.00226 (9)	−0.00140 (9)
S1	0.0176 (5)	0.0124 (4)	0.0144 (4)	−0.0028 (4)	0.0057 (3)	−0.0026 (3)
S2	0.0145 (5)	0.0144 (4)	0.0153 (4)	0.0015 (4)	0.0049 (3)	0.0027 (3)
S3	0.0143 (4)	0.0129 (4)	0.0122 (4)	0.0002 (4)	0.0030 (3)	−0.0018 (3)
S4	0.0144 (4)	0.0136 (4)	0.0131 (4)	−0.0005 (4)	0.0047 (3)	0.0001 (3)
O1	0.0244 (15)	0.0091 (12)	0.0057 (11)	0.0003 (11)	0.0021 (10)	0.0020 (9)
O2	0.0276 (16)	0.0069 (11)	0.0064 (11)	0.0003 (12)	0.0017 (10)	0.0002 (9)

Geometric parameters (Å, º) top

Sb1—S2	2.4696 (11)	Sb3—S2ⁱⁱⁱ	2.4935 (10)
Sb1—O1ⁱ	2.155 (3)	Sb3—S3	2.4446 (10)
Sb1—O1ⁱⁱ	2.010 (2)	Sb3—S3^iv	3.2171 (10)
Sb1—O2	2.178 (3)	Sb3—S4^iv	3.1618 (10)
Sb2—S1	2.4876 (11)	Sb4—S1	2.9874 (10)
Sb2—O1	2.139 (3)	Sb4—S2	3.1073 (10)
Sb2—O2	2.156 (3)	Sb4—S3^iv	2.5762 (10)
Sb2—O2ⁱⁱ	2.011 (2)	Sb4—S4	2.4330 (11)
Sb3—S1	2.5026 (10)	Sb4—S4^v	2.6111 (10)

S2—Sb1—O1ⁱ	87.48 (8)	S2ⁱⁱⁱ—Sb3—S3	95.10 (3)
S2—Sb1—O1ⁱⁱ	96.07 (9)	S2ⁱⁱⁱ—Sb3—S3^iv	172.74 (3)
S2—Sb1—O2	86.12 (8)	S2ⁱⁱⁱ—Sb3—S4^iv	88.25 (3)
O1ⁱ—Sb1—O1ⁱⁱ	72.75 (10)	S3—Sb3—S3^iv	81.49 (3)
O1ⁱ—Sb1—O2	143.56 (9)	S3—Sb3—S4^iv	78.75 (3)
O1ⁱⁱ—Sb1—O2	72.33 (10)	S3^iv—Sb3—S4^iv	84.80 (2)
S1—Sb2—O1	85.53 (8)	S1—Sb4—S2	88.60 (3)
S1—Sb2—O2	82.83 (8)	S1—Sb4—S3^iv	88.02 (3)
S1—Sb2—O2ⁱⁱ	102.00 (9)	S1—Sb4—S4	86.20 (3)
O1—Sb2—O2	140.36 (9)	S1—Sb4—S4^v	172.05 (3)
O1—Sb2—O2ⁱⁱ	73.16 (10)	S2—Sb4—S3^iv	174.97 (3)
O2—Sb2—O2ⁱⁱ	72.49 (10)	S2—Sb4—S4	84.23 (3)
S1—Sb3—S2ⁱⁱⁱ	102.35 (3)	S2—Sb4—S4^v	87.39 (3)
S1—Sb3—S3	94.14 (3)	S3^iv—Sb4—S4	91.83 (3)
S1—Sb3—S3^iv	84.35 (3)	S3^iv—Sb4—S4^v	95.52 (3)
S1—Sb3—S4^iv	167.81 (3)	S4—Sb4—S4^v	86.57 (3)

Symmetry codes: (i) x, y+1, z; (ii) −x+1/4, −y+3/4, −z+1/2; (iii) x, y−1, z; (iv) −x+1/4, −y+1/4, −z; (v) −x+1/4, −y+5/4, −z.

(III) top

Crystal data top

OS₂Sb₂	Z = 4
M_r = 323.6	F(000) = 568
Triclinic, P1	D_x = 4.892 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.7107 Å
a = 8.1372 (2) Å	Cell parameters from 12220 reflections
b = 10.6969 (3) Å	θ = 3.8–32.7°
c = 5.7840 (1) Å	µ = 13.06 mm⁻¹
α = 102.787 (2)°	T = 293 K
β = 110.6063 (19)°	Acicular, red
γ = 100.9833 (19)°	0.95 × 0.07 × 0.01 mm
V = 439.24 (2) Å³

Data collection top

Oxford Diffraction CCD diffractometer	4591 independent reflections
Radiation source: X-ray tube	3769 reflections with I > 3σ(I)
Graphite monochromator	R_int = 0.079
Detector resolution: 10.3784 pixels mm^-1	θ_max = 32.7°, θ_min = 3.8°
ω scans	h = −11→12
Absorption correction: gaussian Jana2006 (Petricek, Dusek & Palatinus, 2000)	k = −16→16
T_min = 0.048, T_max = 0.779	l = −8→8
24475 measured reflections

Refinement top

Refinement on F	0 restraints
R[F² > 2σ(F²)] = 0.032	0 constraints
wR(F²) = 0.038	Weighting scheme based on measured s.u.'s w = 1/(σ²(F) + 0.0001F²)
S = 2.19	(Δ/σ)_max = 0.017
4591 reflections	Δρ_max = 2.33 e Å⁻³
92 parameters	Δρ_min = −2.62 e Å⁻³

Crystal data top

OS₂Sb₂	γ = 100.9833 (19)°
M_r = 323.6	V = 439.24 (2) Å³
Triclinic, P1	Z = 4
a = 8.1372 (2) Å	Mo Kα radiation
b = 10.6969 (3) Å	µ = 13.06 mm⁻¹
c = 5.7840 (1) Å	T = 293 K
α = 102.787 (2)°	0.95 × 0.07 × 0.01 mm
β = 110.6063 (19)°

Data collection top

Oxford Diffraction CCD diffractometer	4591 independent reflections
Absorption correction: gaussian Jana2006 (Petricek, Dusek & Palatinus, 2000)	3769 reflections with I > 3σ(I)
T_min = 0.048, T_max = 0.779	R_int = 0.079
24475 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.032	92 parameters
wR(F²) = 0.038	0 restraints
S = 2.19	Δρ_max = 2.33 e Å⁻³
4591 reflections	Δρ_min = −2.62 e Å⁻³

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Sb1	0.16830 (7)	0.63147 (3)	0.03899 (5)	0.01036 (13)
Sb2	0.66029 (7)	0.62981 (3)	0.01367 (5)	0.01097 (13)
Sb3	0.12564 (5)	0.85373 (3)	0.63172 (5)	0.01265 (11)
Sb4	0.65275 (5)	0.91541 (3)	0.67960 (6)	0.01425 (12)
S1	0.8098 (3)	0.70294 (12)	0.4978 (2)	0.0139 (4)
S2	0.2896 (3)	0.69203 (13)	0.5174 (2)	0.0139 (4)
S3	0.0478 (2)	0.90942 (12)	0.2258 (2)	0.0123 (4)
S4	0.5202 (2)	0.91063 (13)	0.2286 (2)	0.0128 (4)
O1	0.8989 (9)	0.5687 (3)	0.0304 (6)	0.0140 (13)
O2	0.4155 (8)	0.5712 (3)	0.0745 (6)	0.0136 (13)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Sb1	0.0092 (2)	0.01020 (13)	0.01315 (12)	0.0048 (2)	0.00585 (18)	0.00260 (9)
Sb2	0.0088 (2)	0.01046 (14)	0.01513 (13)	0.0051 (2)	0.00574 (18)	0.00345 (10)
Sb3	0.01101 (15)	0.01518 (15)	0.01180 (12)	0.00504 (16)	0.00517 (12)	0.00248 (10)
Sb4	0.01211 (16)	0.01672 (16)	0.01490 (13)	0.00506 (16)	0.00553 (13)	0.00613 (11)
S1	0.0108 (6)	0.0153 (5)	0.0149 (5)	0.0022 (6)	0.0068 (6)	0.0023 (4)
S2	0.0135 (7)	0.0158 (5)	0.0139 (5)	0.0077 (6)	0.0062 (5)	0.0034 (4)
S3	0.0099 (6)	0.0130 (5)	0.0137 (4)	0.0031 (5)	0.0045 (5)	0.0041 (4)
S4	0.0126 (7)	0.0138 (5)	0.0123 (4)	0.0054 (5)	0.0055 (5)	0.0024 (4)
O1	0.0088 (19)	0.0107 (15)	0.0225 (16)	0.0025 (19)	0.0087 (19)	0.0017 (12)
O2	0.0083 (19)	0.0098 (15)	0.0228 (15)	0.0025 (19)	0.0092 (18)	0.0009 (12)

Geometric parameters (Å, º) top

Sb1—S2	2.4683 (12)	Sb3—S2	2.491 (2)
Sb1—O1ⁱ	2.146 (7)	Sb3—S3	2.4463 (14)
Sb1—O1ⁱⁱ	2.016 (3)	Sb3—S3ⁱⁱⁱ	3.2168 (18)
Sb1—O2	2.184 (7)	Sb3—S4^iv	3.1626 (16)
Sb2—S1	2.4904 (11)	Sb4—S1	2.9834 (19)
Sb2—O1	2.141 (7)	Sb4—S2	3.1125 (17)
Sb2—O2	2.144 (7)	Sb4—S3^iv	2.5721 (17)
Sb2—O2ⁱⁱ	2.013 (3)	Sb4—S4	2.4312 (12)
Sb3—S1ⁱ	2.5044 (18)	Sb4—S4^iv	2.6101 (19)

S2—Sb1—O1ⁱ	87.49 (10)	S2—Sb3—S3	95.09 (5)
S2—Sb1—O1ⁱⁱ	96.08 (10)	S2—Sb3—S3ⁱⁱⁱ	172.81 (5)
S2—Sb1—O2	86.34 (10)	S2—Sb3—S4^iv	88.34 (5)
O1ⁱ—Sb1—O1ⁱⁱ	72.7 (2)	S3—Sb3—S3ⁱⁱⁱ	81.52 (5)
O1ⁱ—Sb1—O2	143.82 (15)	S3—Sb3—S4^iv	78.66 (4)
O1ⁱⁱ—Sb1—O2	72.6 (2)	S3ⁱⁱⁱ—Sb3—S4^iv	84.78 (4)
S1—Sb2—O1	85.50 (10)	S1—Sb4—S2	88.50 (5)
S1—Sb2—O2	82.98 (10)	S1—Sb4—S3^iv	88.16 (5)
S1—Sb2—O2ⁱⁱ	101.77 (10)	S1—Sb4—S4	86.23 (5)
O1—Sb2—O2	140.58 (16)	S1—Sb4—S4^iv	171.89 (3)
O1—Sb2—O2ⁱⁱ	73.6 (2)	S2—Sb4—S3^iv	174.97 (4)
O2—Sb2—O2ⁱⁱ	72.1 (2)	S2—Sb4—S4	84.11 (5)
S1ⁱ—Sb3—S2	102.31 (5)	S2—Sb4—S4^iv	87.35 (5)
S1ⁱ—Sb3—S3	94.21 (5)	S3^iv—Sb4—S4	91.91 (5)
S1ⁱ—Sb3—S3ⁱⁱⁱ	84.32 (5)	S3^iv—Sb4—S4^iv	95.50 (5)
S1ⁱ—Sb3—S4^iv	167.75 (5)	S4—Sb4—S4^iv	86.43 (5)

Symmetry codes: (i) x−1, y, z; (ii) −x+1, −y+1, −z; (iii) −x, −y+2, −z+1; (iv) −x+1, −y+2, −z+1.

(IV) top

Crystal data top

OS₂Sb₂	Z = 32
M_r = 323.6	F(000) = 4544
Triclinic, X1	D_x = 4.892 Mg m⁻³
Hall symbol: -X	Mo Kα radiation, λ = 0.7107 Å
a = 21.6558 (5) Å	Cell parameters from 12220 reflections
b = 8.1372 (2) Å	θ = 3.8–32.7°
c = 20.3859 (8) Å	µ = 13.06 mm⁻¹
α = 90.028 (3)°	T = 293 K
β = 101.994 (3)°	Acicular, red
γ = 89.986 (2)°	0.95 × 0.07 × 0.01 mm
V = 3513.92 (19) Å³

Data collection top

Oxford Diffraction CCD diffractometer	4591 independent reflections
Radiation source: X-ray tube	3769 reflections with I > 3σ(I)
Graphite monochromator	R_int = 0.079
Detector resolution: 10.3784 pixels mm^-1	θ_max = 32.7°, θ_min = 3.8°
ω scans	h = −32→32
Absorption correction: gaussian Jana2006 (Petricek, Dusek & Palatinus, 2000)	k = −12→11
T_min = 0.048, T_max = 0.779	l = −30→30
24475 measured reflections

Refinement top

Refinement on F	0 restraints
R[F² > 2σ(F²)] = 0.032	0 constraints
wR(F²) = 0.038	Weighting scheme based on measured s.u.'s w = 1/(σ²(F) + 0.0001F²)
S = 2.19	(Δ/σ)_max = 0.033
4591 reflections	Δρ_max = 2.34 e Å⁻³
93 parameters	Δρ_min = −2.58 e Å⁻³

Crystal data top

OS₂Sb₂	γ = 89.986 (2)°
M_r = 323.6	V = 3513.92 (19) Å³
Triclinic, X1	Z = 32
a = 21.6558 (5) Å	Mo Kα radiation
b = 8.1372 (2) Å	µ = 13.06 mm⁻¹
c = 20.3859 (8) Å	T = 293 K
α = 90.028 (3)°	0.95 × 0.07 × 0.01 mm
β = 101.994 (3)°

Data collection top

Oxford Diffraction CCD diffractometer	4591 independent reflections
Absorption correction: gaussian Jana2006 (Petricek, Dusek & Palatinus, 2000)	3769 reflections with I > 3σ(I)
T_min = 0.048, T_max = 0.779	R_int = 0.079
24475 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.032	93 parameters
wR(F²) = 0.038	0 restraints
S = 2.19	Δρ_max = 2.34 e Å⁻³
4591 reflections	Δρ_min = −2.58 e Å⁻³

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Sb1	0.101874 (14)	0.74931 (7)	0.184267 (14)	0.01034 (8)
Sb2	0.095971 (14)	0.25058 (7)	0.185095 (14)	0.01094 (8)
Sb3	0.194498 (14)	−0.00428 (5)	0.073132 (16)	0.01268 (8)
Sb4	0.191048 (14)	0.49601 (5)	0.042299 (17)	0.01427 (9)
S1	0.19871 (6)	0.2404 (3)	0.14853 (6)	0.0139 (3)
S2	0.20635 (6)	0.7627 (2)	0.15398 (6)	0.0139 (3)
S3	0.07910 (5)	−0.0140 (2)	0.04529 (6)	0.0123 (3)
S4	0.07948 (6)	0.5145 (2)	0.04468 (6)	0.0128 (3)
O1	0.11543 (16)	0.0008 (8)	0.21564 (16)	0.0140 (9)
O2	0.12582 (16)	0.4959 (8)	0.21441 (16)	0.0136 (9)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Sb1	0.01397 (13)	0.00697 (13)	0.01016 (14)	0.00034 (19)	0.00273 (10)	0.0022 (2)
Sb2	0.01522 (13)	0.00689 (13)	0.01042 (14)	0.00146 (19)	0.00199 (10)	0.0022 (2)
Sb3	0.01408 (13)	0.00977 (13)	0.01525 (15)	0.00021 (12)	0.00551 (10)	0.00157 (16)
Sb4	0.01381 (13)	0.01195 (14)	0.01679 (16)	0.00090 (13)	0.00256 (11)	−0.00019 (17)
S1	0.0177 (5)	0.0098 (6)	0.0153 (5)	−0.0021 (6)	0.0058 (4)	−0.0015 (6)
S2	0.0155 (5)	0.0112 (6)	0.0158 (5)	0.0014 (5)	0.0049 (4)	0.0040 (6)
S3	0.0137 (5)	0.0103 (6)	0.0129 (5)	0.0008 (6)	0.0027 (4)	−0.0008 (6)
S4	0.0142 (5)	0.0114 (7)	0.0137 (5)	0.0003 (6)	0.0048 (4)	0.0022 (6)
O1	0.0250 (17)	0.0064 (14)	0.0106 (15)	0.000 (2)	0.0039 (13)	0.000 (2)
O2	0.0259 (17)	0.0052 (14)	0.0098 (15)	−0.0009 (19)	0.0042 (13)	0.000 (2)

Geometric parameters (Å, º) top

Sb1—S2	2.4683 (13)	Sb3—S2ⁱⁱⁱ	2.4907 (18)
Sb1—O1ⁱ	2.146 (7)	Sb3—S3	2.4463 (12)
Sb1—O1ⁱⁱ	2.016 (3)	Sb3—S3^iv	3.2166 (16)
Sb1—O2	2.184 (6)	Sb3—S4^iv	3.1623 (16)
Sb2—S1	2.4903 (14)	Sb4—S1	2.9833 (17)
Sb2—O1	2.142 (7)	Sb4—S2	3.1122 (17)
Sb2—O2	2.144 (6)	Sb4—S3^iv	2.5722 (17)
Sb2—O2ⁱⁱ	2.013 (3)	Sb4—S4	2.4312 (13)
Sb3—S1	2.5045 (18)	Sb4—S4^v	2.6103 (17)

S2—Sb1—O1ⁱ	87.49 (11)	S2ⁱⁱⁱ—Sb3—S3	95.09 (5)
S2—Sb1—O1ⁱⁱ	96.08 (10)	S2ⁱⁱⁱ—Sb3—S3^iv	172.81 (5)
S2—Sb1—O2	86.34 (11)	S2ⁱⁱⁱ—Sb3—S4^iv	88.33 (5)
O1ⁱ—Sb1—O1ⁱⁱ	72.7 (2)	S3—Sb3—S3^iv	81.52 (4)
O1ⁱ—Sb1—O2	143.82 (13)	S3—Sb3—S4^iv	78.67 (4)
O1ⁱⁱ—Sb1—O2	72.6 (2)	S3^iv—Sb3—S4^iv	84.78 (4)
S1—Sb2—O1	85.50 (11)	S1—Sb4—S2	88.50 (5)
S1—Sb2—O2	82.98 (11)	S1—Sb4—S3^iv	88.16 (5)
S1—Sb2—O2ⁱⁱ	101.77 (10)	S1—Sb4—S4	86.23 (5)
O1—Sb2—O2	140.58 (14)	S1—Sb4—S4^v	171.90 (4)
O1—Sb2—O2ⁱⁱ	73.6 (2)	S2—Sb4—S3^iv	174.97 (4)
O2—Sb2—O2ⁱⁱ	72.1 (2)	S2—Sb4—S4	84.12 (5)
S1—Sb3—S2ⁱⁱⁱ	102.32 (5)	S2—Sb4—S4^v	87.34 (5)
S1—Sb3—S3	94.20 (5)	S3^iv—Sb4—S4	91.91 (5)
S1—Sb3—S3^iv	84.32 (5)	S3^iv—Sb4—S4^v	95.51 (5)
S1—Sb3—S4^iv	167.75 (4)	S4—Sb4—S4^v	86.43 (5)

Symmetry codes: (i) x, y+1, z; (ii) −x+1/4, −y+3/4, −z+1/2; (iii) x, y−1, z; (iv) −x+1/4, −y+1/4, −z; (v) −x+1/4, −y+5/4, −z.

Experimental details

	(I)	(II)	(III)	(IV)
Crystal data
Chemical formula	OS₂Sb₂	OS₂Sb₂	OS₂Sb₂	OS₂Sb₂
M_r	323.6	323.6	323.6	323.6
Crystal system, space group	Triclinic, P1	Triclinic, X1	Triclinic, P1	Triclinic, X1
Temperature (K)	293	293	293	293
a, b, c (Å)	8.1416 (3), 10.6968 (3), 5.7835 (2)	21.6466 (9), 8.1416 (3), 20.3824 (9)	8.1372 (2), 10.6969 (3), 5.7840 (1)	21.6558 (5), 8.1372 (2), 20.3859 (8)
α, β, γ (°)	102.758 (3), 110.657 (3), 101.020 (3)	90.079 (4), 101.985 (5), 89.948 (4)	102.787 (2), 110.6063 (19), 100.9833 (19)	90.028 (3), 101.994 (3), 89.986 (2)
V (Å³)	439.23 (3)	3513.8 (3)	439.24 (2)	3513.92 (19)
Z	4	32	4	32
Radiation type	Mo Kα	Mo Kα	Mo Kα	Mo Kα
µ (mm⁻¹)	13.06	13.06	13.06	13.06
Crystal size (mm)	0.65 × 0.05 × 0.03	0.65 × 0.05 × 0.03	0.95 × 0.07 × 0.01	0.95 × 0.07 × 0.01

Data collection
Diffractometer	Xcalibur, Atlas, Gemini ultra diffractometer	Oxford Diffraction CCD diffractometer	Oxford Diffraction CCD diffractometer	Oxford Diffraction CCD diffractometer
Absorption correction	Gaussian Jana2006 (Petricek, Dusek & Palatinus, 2000)	Gaussian Jana2006 (Petricek, Dusek & Palatinus, 2000)	Gaussian Jana2006 (Petricek, Dusek & Palatinus, 2000)	Gaussian Jana2006 (Petricek, Dusek & Palatinus, 2000)
T_min, T_max	0.109, 0.667	0.109, 0.667	0.048, 0.779	0.048, 0.779
No. of measured, independent and observed [I > 3σ(I)] reflections	12651, 4465, 2604	12651, 4465, 2604	24475, 4591, 3769	24475, 4591, 3769
R_int	0.050	0.050	0.079	0.079
(sin θ/λ)_max (Å⁻¹)	0.760	0.760	0.760	0.760

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.024, 0.027, 1.12	0.024, 0.027, 1.11	0.032, 0.038, 2.19	0.032, 0.038, 2.19
No. of reflections	4465	4465	4591	4591
No. of parameters	92	92	92	93
Δρ_max, Δρ_min (e Å⁻³)	1.15, −1.34	1.14, −1.36	2.33, −2.62	2.34, −2.58

Computer programs: CrysAlis CCD, Oxford Diffraction Ltd., Version 1.171.33.55 (release 05-01-2010 CrysAlis171 .NET) (compiled Jan 5 2010,16:28:46), CrysAlis RED, Oxford Diffraction Ltd., Version 1.171.33.55 (release 05-01-2010 CrysAlis171 .NET) (compiled Jan 5 2010,16:28:46).

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