Ba₂Sb₄GeS₁₀

The title quaternary compound, dibarium tetra­anti­mony germanium deca­sulfide, Ba₂Sb₄GeS₁₀, crystallizes in a novel three-dimensional _∞³[Sb₄GeS₁₀]⁴⁻ network structure, which is composed of triangular pyramidal SbS₃ (site symmetry m..), distorted SbS₅ (m..) polyhedra and regular GeS₄ (-4..) tetra­hedra. The SbS₃ and SbS₅ units are connected with each other through corner- and edge-sharing, forming a Sb₄S₁₀ layer in the ab plane. The GeS₄ tetra­hedra further bridge two neighbouring Sb₄S₁₀ layers, forming a three-dimensional _∞³[Sb₄GeS₁₀]⁴⁻ network. The Ba²⁺ cation (..2) is located between two Sb₄S₁₀ layers and is coordinated by ten S atoms with Ba—S bond lengths in the range 3.2505 (9)–3.4121 (2) Å.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](Sb-S) = 0.001 Å
• R factor = 0.018
• wR factor = 0.042
• Data-to-parameter ratio = 23.2

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT127_ALERT_1_C Implicit Hall Symbol  Inconsistent with Explicit    -P 4ac 2ab
PLAT733_ALERT_1_C Torsion Calc   -84.79(3), Rep   -84.79(1) ......       4.29 su-Ra
              S2  -GE1 -S2  -SB2   11.556   1.555   1.555  15.666      21

Alert level G
PLAT004_ALERT_5_G Info: Polymeric Structure Found with Dimension .          1
PLAT005_ALERT_5_G No _iucr_refine_instructions_details  in the CIF          ?
PLAT042_ALERT_1_G Calc. and Reported MoietyFormula Strings  Differ          ?
PLAT152_ALERT_1_G The Supplied and Calc. Volume s.1. Differ by ...          3 Units
PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_G Check the Reported   _diffrn_ambient_temperature        293 K
PLAT961_ALERT_5_G Dataset Contains no Negative Intensities .......          !

   0 ALERT level A = Most likely a serious problem - resolve or explain
   0 ALERT level B = A potentially serious problem, consider carefully
   2 ALERT level C = Check. Ensure it is not caused by an omission or oversight
   7 ALERT level G = General information/check it is not something unexpected

   6 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   0 ALERT type 2 Indicator that the structure model may be wrong or deficient
   0 ALERT type 3 Indicator that the structure quality may be low
   0 ALERT type 4 Improvement, methodology, query or suggestion
   3 ALERT type 5 Informative message, check

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S1. Comment

Sb-based chalcogenides have attracted a lot of attention in recent years due to their rich structures and interesting physical properties, such as nonlinear optics and ion-exchange properties. The stereochemically active 5 s² lone-pair electrons possess a large electric dipole moment and can influence structures that contain Sb³⁺ (Choi et al. 2000; Babo et al. 2012). SbS₃, SbS₄ or SbS₅ units in a crystal structure are prone to form one-dimensional Sb—S chains through a corner- or edge-sharing manner (Dorrscheidt et al. 1981; Cordier et al. 1984). GeS₄ tetrahedron can be utilized as the second structural unit and introduced into crystal structure to connect Sb—S chains into a two-dimensional layer or three-dimensional framework structure (Feng et al. 2008). In this paper, a new title quaternary sulfide in the Sb—Ge—S system is dexcribed. Ba₂Sb₄GeS₁₀ represents the first example of a structure synthesized and structurally characterized by single-crystal X-ray diffraction in the quaternary Ba—Sb—Ge—S system (Fig. 1). It crystallizes with one Ge atom on 4b and three S atoms on 8h, 16i and 16i, respectively, in terms of the Wyckoff notation. There are two types of coordination polyhedron of SbS groups, i.e. triangle-pyramidal SbS₃ and distorted SbS₅ polyhedra. SbS₃ and SbS₅ polyhedra are connected with each other through corner- and edge-sharing conformations to form Sb₄S₁₀ zigzag chains, which are further arranged side by side into the Sb₄S₁₀ layer in the ab-plane (Fig. 2). The GeS₄ tetrahedra further bridge two neighbouring Sb₄S₁₀ layers, forming athree-dimensional ∞³[Sb₄GeS₁₀]^-4 network (Fig. 3). The Ba atom is located between two Sb₄S₁₀ layers and coordinates with ten S atoms with Ba—S bonding lengths in the range of 3.2505 (9)–3.4121 (2) Å, which are typical values for sulfides (Dorrscheidt et al. 1981; Cordier et al. 1984).

Related literature

The stereochemically active 5s² lone-pair electrons possess a large electric dipole moment and can influence structures that contain Sb³⁺, see: Choi & Kanatzidis (2000); Babo & Albrecht-Schmitt (2012). SbS₃, SbS₄ or SbS₅ units in a crystal structure are prone to form Sb—S chains through corner- or edge-sharing, see: Dorrscheidt & Schafer (1981); Cordier et al. (1984). GeS₄ tetrahedra can be utilized as the second structural unit and introduced into crystal structures to connect Sb—S chains into a two-dimensional layer or three-dimensional framework structure (Feng et al. 2008). For related lieterature [on what subject(s)?], see: Deng et al. (2005); Kim et al. (2008); Ribes et al. (1973); Teske (1979); Lekse et al. (2009).

S2. Experimental

The title compound, Ba₂Sb₄GeS₁₀, was synthesized through a high temperature solid-state reaction in an evacuated and sealed silica tube. A mixture of BaS (0.5 mmol, 0.0847 g), Sb (1 mmol, 0.1218 g), Ge (0.25 mmol, 0.0182 g),S (2 mmol, 0.0641 g) was loaded in a silica ampoule, sealed under 10 ^-2 Pa, heated gradually to 1173 K (holding for 10 h) in 60 h, and then cooled to room temperature in 300 h. Rod-shaped crystals of Ba₂Sb₄GeS₁₀ with a dark red color were obtained. The crystals were stable under air and moisture conditions.

S3. Refinement

All atoms in Ba₂Sb₄GeS₁₀ crystal structure were refined anisotropically without disorder. The highest residual peak (0.66 e×Å^-3) in the difference electron density map was located at (0.1992, 0.3008, 1/4), 1.09 Å from atom Ba1. The deepest hole (- 0.73 e×Å^-3) was located at (0.1670, 0.7496, 0.2499), 0.77 Å from atom Ba1.

Computing details

Data collection: CrystalClear (Rigaku, 2007); cell refinement: CrystalClear (Rigaku, 2007); data reduction: CrystalClear (Rigaku, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2005); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures

	Fig. 1. Crystal structure of Ba2Sb4GeS10 in GeS4 polyhedral representation viewed along [001]. Green tetrahedra represent the GeS4 unit with yellow sulfur atoms at the corners of each tetrahedron.
	Fig. 2. SbS3 and SbS5 polyhedra are connected with each other through corner- and edge-sharing conformations to form the Sb4S10 zigzag chains, which are further arranged side by side into the Sb4S10 layer in the ab-plane.
	Fig. 3. The novel three-dimensional ∞^3[Sb4GeS10]^-4 network viewed along [100] direction. GeS4 tetrahedra act as bridging units for two neighbouring Sb4S10 layers.

Dibarium tetraantimony(III) germanium(IV) decasulfide

Crystal data

Ba2Sb4GeS10	Dx = 4.395 Mg m^−3
Mr = 1154.87	Mo Kα radiation, λ = 0.71073 Å
Tetragonal, P42/mbc	Cell parameters from 1877 reflections
Hall symbol: -P 4ac 2ab	θ = 2.3–27.5°
a = 11.3119 (4) Å	µ = 13.40 mm^−1
c = 13.6384 (9) Å	T = 293 K
V = 1745.16 (14) Å^3	Rod, dark-red
Z = 4	0.22 × 0.07 × 0.07 mm
F(000) = 2032

Data collection

Rigaku SCXMini CCD diffractometer	1046 independent reflections
Radiation source: fine-focus sealed tube	1032 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.030
CCD_Profile_fitting scans	θmax = 27.5°, θmin = 2.6°
Absorption correction: multi-scan (CrystalClear; Rigaku, 2007)	h = −14→14
Tmin = 0.530, Tmax = 1.000	k = −14→11
12411 measured reflections	l = −16→17

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)] = 0.018	w = 1/[σ^2(Fo^2) + (0.0214P)^2 + 3.2912P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.042	(Δ/σ)max < 0.001
S = 1.15	Δρmax = 0.66 e Å^−3
1046 reflections	Δρmin = −0.74 e Å^−3
45 parameters	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.00225 (8)

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
Ba1	0.232424 (19)	0.732424 (19)	0.2500	0.01704 (10)
Sb1	0.13578 (3)	0.41567 (3)	0.0000	0.01543 (10)
Sb2	0.46488 (3)	0.34169 (3)	0.0000	0.01796 (10)
Ge1	0.0000	0.0000	0.2500	0.01175 (15)
S1	0.27060 (10)	0.24355 (10)	0.0000	0.0136 (2)
S2	0.01781 (8)	0.15428 (7)	0.34843 (6)	0.01631 (18)
S3	0.02261 (7)	0.32137 (8)	0.13186 (6)	0.01777 (19)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ba1	0.01715 (12)	0.01715 (12)	0.01683 (15)	0.00214 (11)	−0.00097 (7)	0.00097 (7)
Sb1	0.01518 (17)	0.01341 (17)	0.01771 (17)	0.00143 (11)	0.000	0.000
Sb2	0.01151 (17)	0.02030 (18)	0.02206 (18)	−0.00225 (12)	0.000	0.000
Ge1	0.0126 (2)	0.0126 (2)	0.0101 (3)	0.000	0.000	0.000
S1	0.0101 (5)	0.0121 (5)	0.0184 (6)	−0.0006 (4)	0.000	0.000
S2	0.0201 (4)	0.0142 (4)	0.0146 (4)	−0.0020 (3)	−0.0009 (3)	−0.0026 (3)
S3	0.0131 (4)	0.0254 (4)	0.0147 (4)	−0.0025 (3)	0.0024 (3)	−0.0028 (3)

Geometric parameters (Å, º)

Ba1—S2^i	3.2505 (9)	Sb2—S3^viii	2.6576 (9)
Ba1—S2^ii	3.2505 (9)	Sb2—S2^iv	2.9352 (9)
Ba1—S3^ii	3.3596 (9)	Sb2—S2^ix	2.9352 (9)
Ba1—S3^i	3.3596 (9)	Ge1—S2	2.2110 (8)
Ba1—S3^iii	3.3599 (8)	Ge1—S2^x	2.2110 (8)
Ba1—S3^iv	3.3599 (8)	Ge1—S2^xi	2.2110 (8)
Ba1—S2^iv	3.3849 (9)	Ge1—S2^xii	2.2110 (8)
Ba1—S2^iii	3.3849 (9)	S1—Ba1^xiii	3.4121 (2)
Ba1—S1^ii	3.4121 (2)	S1—Ba1^xiv	3.4121 (2)
Ba1—S1^v	3.4121 (2)	S2—Sb2^xv	2.9352 (9)
Sb1—S3^vi	2.4517 (9)	S2—Ba1^xiv	3.2505 (9)
Sb1—S3	2.4517 (9)	S2—Ba1^iii	3.3849 (9)
Sb1—S1	2.4732 (12)	S3—Sb2^xvi	2.6576 (9)
Sb2—S1	2.4621 (12)	S3—Ba1^xiv	3.3596 (9)
Sb2—S3^vii	2.6576 (9)	S3—Ba1^iii	3.3599 (8)
S2^i—Ba1—S2^ii	130.04 (3)	S3^iv—Ba1—S1^v	120.60 (3)
S2^i—Ba1—S3^ii	76.46 (2)	S2^iv—Ba1—S1^v	68.80 (2)
S2^ii—Ba1—S3^ii	64.06 (2)	S2^iii—Ba1—S1^v	111.96 (2)
S2^i—Ba1—S3^i	64.06 (2)	S1^ii—Ba1—S1^v	177.82 (4)
S2^ii—Ba1—S3^i	76.46 (2)	S3^vi—Sb1—S3	94.37 (4)
S3^ii—Ba1—S3^i	74.69 (3)	S3^vi—Sb1—S1	88.82 (3)
S2^i—Ba1—S3^iii	153.52 (2)	S3—Sb1—S1	88.82 (3)
S2^ii—Ba1—S3^iii	74.09 (2)	S1—Sb2—S3^vii	84.63 (3)
S3^ii—Ba1—S3^iii	129.53 (3)	S1—Sb2—S3^viii	84.63 (3)
S3^i—Ba1—S3^iii	122.17 (3)	S3^vii—Sb2—S3^viii	85.17 (4)
S2^i—Ba1—S3^iv	74.09 (2)	S1—Sb2—S2^iv	80.46 (3)
S2^ii—Ba1—S3^iv	153.52 (2)	S3^vii—Sb2—S2^iv	164.84 (3)
S3^ii—Ba1—S3^iv	122.17 (3)	S3^viii—Sb2—S2^iv	90.69 (3)
S3^i—Ba1—S3^iv	129.53 (3)	S1—Sb2—S2^ix	80.46 (3)
S3^iii—Ba1—S3^iv	85.35 (3)	S3^vii—Sb2—S2^ix	90.69 (3)
S2^i—Ba1—S2^iv	66.88 (3)	S3^viii—Sb2—S2^ix	164.84 (3)
S2^ii—Ba1—S2^iv	131.76 (3)	S2^iv—Sb2—S2^ix	89.54 (3)
S3^ii—Ba1—S2^iv	140.05 (2)	S2—Ge1—S2^x	111.63 (2)
S3^i—Ba1—S2^iv	75.40 (2)	S2—Ge1—S2^xi	105.23 (4)
S3^iii—Ba1—S2^iv	89.05 (2)	S2^x—Ge1—S2^xi	111.63 (2)
S3^iv—Ba1—S2^iv	62.66 (2)	S2—Ge1—S2^xii	111.63 (2)
S2^i—Ba1—S2^iii	131.76 (3)	S2^x—Ge1—S2^xii	105.23 (4)
S2^ii—Ba1—S2^iii	66.88 (3)	S2^xi—Ge1—S2^xii	111.63 (2)
S3^ii—Ba1—S2^iii	75.40 (2)	Sb2—S1—Sb1	101.27 (4)
S3^i—Ba1—S2^iii	140.05 (2)	Sb2—S1—Ba1^xiii	91.466 (19)
S3^iii—Ba1—S2^iii	62.66 (2)	Sb1—S1—Ba1^xiii	91.31 (2)
S3^iv—Ba1—S2^iii	89.05 (2)	Sb2—S1—Ba1^xiv	91.466 (19)
S2^iv—Ba1—S2^iii	142.24 (3)	Sb1—S1—Ba1^xiv	91.31 (2)
S2^i—Ba1—S1^ii	63.42 (2)	Ba1^xiii—S1—Ba1^xiv	175.62 (4)
S2^ii—Ba1—S1^ii	115.56 (2)	Ge1—S2—Sb2^xv	96.58 (3)
S3^ii—Ba1—S1^ii	61.18 (2)	Ge1—S2—Ba1^xiv	92.47 (3)
S3^i—Ba1—S1^ii	116.86 (3)	Sb2^xv—S2—Ba1^xiv	86.85 (2)
S3^iii—Ba1—S1^ii	120.60 (3)	Ge1—S2—Ba1^iii	88.96 (3)
S3^iv—Ba1—S1^ii	61.24 (2)	Sb2^xv—S2—Ba1^iii	154.96 (3)
S2^iv—Ba1—S1^ii	111.96 (2)	Ba1^xiv—S2—Ba1^iii	117.39 (2)
S2^iii—Ba1—S1^ii	68.80 (2)	Sb1—S3—Sb2^xvi	86.21 (3)
S2^i—Ba1—S1^v	115.56 (2)	Sb1—S3—Ba1^xiv	92.95 (3)
S2^ii—Ba1—S1^v	63.42 (2)	Sb2^xvi—S3—Ba1^xiv	108.63 (3)
S3^ii—Ba1—S1^v	116.86 (3)	Sb1—S3—Ba1^iii	151.51 (4)
S3^i—Ba1—S1^v	61.18 (2)	Sb2^xvi—S3—Ba1^iii	89.30 (2)
S3^iii—Ba1—S1^v	61.24 (2)	Ba1^xiv—S3—Ba1^iii	115.09 (3)
S3^vii—Sb2—S1—Sb1	−137.18 (2)	S3—Sb1—S1—Ba1^xiv	−41.05 (3)
S3^viii—Sb2—S1—Sb1	137.18 (2)	S2^x—Ge1—S2—Sb2^xv	157.74 (2)
S2^iv—Sb2—S1—Sb1	45.572 (18)	S2^xi—Ge1—S2—Sb2^xv	36.474 (13)
S2^ix—Sb2—S1—Sb1	−45.572 (18)	S2^xii—Ge1—S2—Sb2^xv	−84.791 (7)
S3^vii—Sb2—S1—Ba1^xiii	−45.55 (3)	S2^x—Ge1—S2—Ba1^xiv	−115.15 (4)
S3^viii—Sb2—S1—Ba1^xiii	−131.19 (3)	S2^xi—Ge1—S2—Ba1^xiv	123.59 (3)
S2^iv—Sb2—S1—Ba1^xiii	137.20 (3)	S2^xii—Ge1—S2—Ba1^xiv	2.32 (3)
S2^ix—Sb2—S1—Ba1^xiii	46.06 (2)	S2^x—Ge1—S2—Ba1^iii	2.23 (2)
S3^vii—Sb2—S1—Ba1^xiv	131.19 (3)	S2^xi—Ge1—S2—Ba1^iii	−119.04 (3)
S3^viii—Sb2—S1—Ba1^xiv	45.55 (3)	S2^xii—Ge1—S2—Ba1^iii	119.70 (3)
S2^iv—Sb2—S1—Ba1^xiv	−46.06 (2)	S3^vi—Sb1—S3—Sb2^xvi	22.13 (4)
S2^ix—Sb2—S1—Ba1^xiv	−137.20 (3)	S1—Sb1—S3—Sb2^xvi	−66.60 (3)
S3^vi—Sb1—S1—Sb2	132.80 (2)	S3^vi—Sb1—S3—Ba1^xiv	130.615 (18)
S3—Sb1—S1—Sb2	−132.80 (2)	S1—Sb1—S3—Ba1^xiv	41.89 (3)
S3^vi—Sb1—S1—Ba1^xiii	41.05 (3)	S3^vi—Sb1—S3—Ba1^iii	−59.38 (9)
S3—Sb1—S1—Ba1^xiii	135.44 (3)	S1—Sb1—S3—Ba1^iii	−148.11 (7)
S3^vi—Sb1—S1—Ba1^xiv	−135.44 (3)

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