Bis(2-ethoxy­carbonyl­ethyl-κ2C1,O)(2-thioxo-1,3-dithiole-4,5-dithiol­ato-κ2S4,S5)tin(IV)

Lima, G.M. de; Wardell, S.M.S.V.; Wardell, J.L.; Tiekink, E.R.T.

doi:10.1107/S1600536809048971

metal-organic compounds

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ISSN: 2056-9890

Volume 65| Part 12| December 2009| Pages m1635-m1636

doi:10.1107/S1600536809048971

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Bis(2-ethoxycarbonylethyl-κ²C¹,O)(2-thioxo-1,3-dithiole-4,5-dithiolato-κ²S⁴,S⁵)tin(IV)

Geraldo M. de Lima,^a Solange M. S. V. Wardell,^b James L. Wardell ^a ‡ and Edward R. T. Tiekink ^c ^*

^aDepartamento de Quimica, ICEx, Universidade Federal de Minas Gerais, 31270-901 Belo Horizonte, MG, Brazil, ^bCHEMSOL, 1 Harcourt Road, Aberdeen AB15 5NY, Scotland, and ^cDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
^*Correspondence e-mail: edward.tiekink@gmail.com

(Received 11 November 2009; accepted 17 November 2009; online 21 November 2009)

In the title compound, [Sn(C₅H₉O₂)₂(C₃S₅)], the immediate environment around the Sn centre is defined by two S and two C atoms that define an approximately tetrahedral geometry. The close approach of the pendant carbonyl O atoms [Sn—O = 2.577 (3) and 2.573 (3) Å] increases the coordination number to six. Supramolecular chains are formed along the a axis in the crystal structure owing to the presence of C—H⋯O contacts.

Related literature

For original industrial interest in functionally substituted-alkyl-tin compounds, see: Lanigen & Weinberg (1976 ). For studies concerning the coordination chemistry of functionally substituted-alkyl-tin compounds, see: Harrison et al. (1979 ); Balasubramanian et al. (1997 ); Milne et al. (2005 ); Tian et al. (2005 ); de Lima et al. (2009 ). For related structures of functionally substituted-alkyl-tin compounds, see: Buchanan et al. (1996 ); Howie & Wardell, (2001 ). For the synthesis, see: Hutton & Oakes (1976 ); Valade et al. (1985 ).

Experimental

Crystal data

[Sn(C₅H₉O₂)₂(C₃S₅)]
M_r = 517.26
Orthorhombic, P n a 2₁
a = 12.1224 (2) Å
b = 13.3825 (2) Å
c = 11.9228 (2) Å
V = 1934.21 (5) Å³
Z = 4
Mo Kα radiation
μ = 1.87 mm⁻¹
T = 120 K
0.25 × 0.10 × 0.08 mm

Data collection

Bruker–Nonius 95mm CCD camera on κ-goniostat diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2003 ) T_min = 0.025, T_max = 0.052
14014 measured reflections
3895 independent reflections
3457 reflections with I > 2σ(I)
R_int = 0.056

Refinement

R[F² > 2σ(F²)] = 0.029
wR(F²) = 0.064
S = 1.04
3895 reflections
211 parameters
15 restraints
H-atom parameters constrained
Δρ_max = 0.64 e Å⁻³
Δρ_min = −0.48 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C12—H12a⋯O1ⁱ	0.99	2.38	3.338 (6)	164
C7—H7a⋯O3ⁱⁱ	0.99	2.46	3.450 (7)	178
Symmetry codes: (i) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, z]$ ; (ii) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z]$ .

Data collection: COLLECT (Hooft, 1998 ); cell refinement: DENZO (Otwinowski & Minor, 1997 ) and COLLECT; data reduction: DENZO and COLLECT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2006 ); software used to prepare material for publication: publCIF (Westrip, 2009 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809048971/im2162sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809048971/im2162Isup2.hkl

checkCIF report

Comment top

Functionally substituted-alkyl-tin compounds, X₃SnCR₂CH₂CO₂R' and X₂Sn(CR₂CH₂CO₂R')₂ (X = halide, R = H or alkyl; R' = alkyl or aryl), are readily available from reactions first reported in the 1970's (Hutton & Oakes, 1976), starting from R₂CCHCOY (Y = R' or OR'), HX and SnX₂ (for X₃SnCR₂CH₂COY compounds) or HX and tin (for X₂Sn(CR₂CH₂COY)₂ substrates). Original interest with these compounds was primarily concerned with their industrial potential as precursors of PVC stabilizers (Lanigen & Weinberg, 1976) but also with regard to their coordination chemistry. Although the potential for use in PVC stabilization has not been realised commercially, the interest in the coordination chemistry, generally of compounds containing SnCR₂CH₂COY moieties, has been maintained over the succeeding decades. Particular interest has been paid to coordination modes of the CR₂CH₂COY ligands (de Lima et al. 2009; Tian et al., 2005; Milne et al., 2005; Harrison et al., 1979). Diester-tin compounds, (MeO₂CCH₂CH₂)₂SnX₂ (X = halide or thiocyanate) (Balasubramanian et al., 1997; Harrison et al., 1979) and (MeO₂CCH₂CH₂)₂Sn(dmit) (dmit = 1,3-dithiole-2-thione-4,5-dithiolato; Buchanan et al., 1996) have been shown to be molecular species with hexa-coordinate tin centres both in the solid-state and in non-coordinating solutions, as a consequence of the (C,O)-chelating ligands. Compounds (MeCOCH₂CMe₂)SnX₂ also contain contain hexa-co-ordinate tin centres (X = Cl or dmit; Howie & Wardell, 2001).

The molecular structure of (I) features a chelating dmit ligand as well as two C-bound CH₂CH₂CO₂Et ligands, each of which coordinates via the α carbon atom. The Sn atom exists within a distorted tetrahedral C₂S₂ donor set, Fig. 1. Significant distortions from the ideal geometry arise from the close approach of two carbonyl-O atoms [Sn—O = 2.577 (3) and 2.573 (3) Å] thereby increasing the coordination number to six. The expanded geometry is therefore based on a highly distorted octahedron. The dmit ligand forms nearly equivalent Sn–S bond distances of 2.4805 (11) and 2.4958 (9) Å. In many respects, the molecular structure of (I) resembles that of the previously reported methyl ester analogue (Buchanan et al. (1996). The former has crystallographic twofold symmetry which is absent in (I) owing to a misalignment of the ethyl substituents.

In the crystal structure, molecules are connected into a supramolecular chain along the a axis via C–H···O interactions, with each molecule forming two donor and two acceptor contacts, Table 1 and Fig. 2.

Related literature top

For original industrial interest in functionally substituted-alkyl-tin compounds, see: Lanigen & Weinberg (1976). For studies concerning the coordination chemistry of functionally substituted-alkyl-tin compounds, see: Harrison et al. (1979); Balasubramanian et al. (1997); Milne et al. (2005); Tian et al. (2005); de Lima et al. (2009). For related structures of functionally substituted-alkyl-tin compounds, see: Buchanan et al. (1996); Howie & Wardell, (2001). For the synthesis, see: Hutton & Oakes (1976); Valade et al. (1985).

Experimental top

Solutions of Cl₂Sn(CH₂CH₂CO₂Et)₂ (0.75 g, 2 mmol) (Hutton & Oakes, 1976) in acetone (20 ml) and [NEt₄]₂[Zn(dmit)₂] (0.70 g, 1 mmol) (Valade et al., 1985) in acetone (20 ml) were mixed and the reaction mixture was maintained at room temperature. After 1 h, the reaction mixture was filtered and the filtrate evaporated to leave a solid residue, which after washing with water, was crystallized from acetone to give the title compound as a red-coloured crystalline solid, m.pt. 394–396 K. ¹H NMR (CDCl₃) δ: 1.25 [t, 3H, J(1H-1H) = 7.2 Hz, Me), 1.93 (t, 2H, J(¹H-¹H) = 7.2 Hz, J(¹¹⁹Sn-¹H) = 84.2 Hz), CH₂Sn), 2.96 (t, 2H, J(¹H-¹H) = 7.2 Hz, J(¹¹⁹Sn-¹H) = 137.6 Hz, CH₂CH₂Sn), 4.20 (q, 2H, J(¹H-¹H) = 7.2 Hz, OCH₂) p.p.m. ¹³C NMR (CDCl₃, 62.9 MHz) δ: 13.9 (CH₃), 22.8 [J(¹¹⁹Sn-¹³C) = 580 Hz, CH₂Sn], 28.5 [J(¹¹⁹Sn-¹³C) = 46 Hz, CH₂CH₂Sn), 63.6 (OCH₂), 129.8 (CC), 181.3 (CO), 210.6 (C S) p.p.m. ¹¹⁹Sn (CD₂Cl₂, 93.3 MHz) δ: 84.2 p.p.m. IR (KBr): 1680 (νCO), 1437 (νCC), 1031 (νCS), 890 (νC-S), 465 (νC-S) cm^-1.

Computing details top

Data collection: COLLECT (Hooft, 1998); cell refinement: DENZO (Otwinowski & Minor, 1997) and COLLECT (Hooft, 1998); data reduction: DENZO (Otwinowski & Minor, 1997) and COLLECT (Hooft, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2006); software used to prepare material for publication: publCIF (Westrip, 2009).

Figures top

	Fig. 1. Molecular structure of (I) showing atom-labelling scheme and displacement ellipsoids at the 50% probability level.
	Fig. 2. Supramolecular chain formation along the a axis in (I) mediated by C–H···O contacts (orange dashed lines).

Bis(2-ethoxycarbonylethyl-κ²C¹,O)(2-thioxo-1,3-dithiole- 4,5-dithiolato-κ²S⁴,S⁵)tin(IV) top

Crystal data top

[Sn(C₅H₉O₂)₂(C₃S₅)]	F(000) = 1032
M_r = 517.26	D_x = 1.776 Mg m⁻³
Orthorhombic, Pna2₁	Mo Kα radiation, λ = 0.71069 Å
Hall symbol: P 2c -2n	Cell parameters from 16139 reflections
a = 12.1224 (2) Å	θ = 2.9–27.5°
b = 13.3825 (2) Å	µ = 1.87 mm⁻¹
c = 11.9228 (2) Å	T = 120 K
V = 1934.21 (5) Å³	Block, orange
Z = 4	0.25 × 0.10 × 0.08 mm

Data collection top

Bruker–Nonius 95mm CCD camera on κ-goniostat diffractometer	3895 independent reflections
Radiation source: Bruker-Nonius FR591 rotating anode	3457 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.056
Detector resolution: 9.091 pixels mm^-1	θ_max = 27.5°, θ_min = 3.0°
ϕ and ω scans	h = −15→14
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	k = −17→17
T_min = 0.025, T_max = 0.052	l = −13→15
14014 measured reflections

Refinement top

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)] = 0.029	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.064	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.0188P)² + 0.7375P] where P = (F_o² + 2F_c²)/3
3895 reflections	(Δ/σ)_max = 0.002
211 parameters	Δρ_max = 0.64 e Å⁻³
15 restraints	Δρ_min = −0.48 e Å⁻³

Crystal data top

[Sn(C₅H₉O₂)₂(C₃S₅)]	V = 1934.21 (5) Å³
M_r = 517.26	Z = 4
Orthorhombic, Pna2₁	Mo Kα radiation
a = 12.1224 (2) Å	µ = 1.87 mm⁻¹
b = 13.3825 (2) Å	T = 120 K
c = 11.9228 (2) Å	0.25 × 0.10 × 0.08 mm

Data collection top

Bruker–Nonius 95mm CCD camera on κ-goniostat diffractometer	3895 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	3457 reflections with I > 2σ(I)
T_min = 0.025, T_max = 0.052	R_int = 0.056
14014 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.029	15 restraints
wR(F²) = 0.064	H-atom parameters constrained
S = 1.04	Δρ_max = 0.64 e Å⁻³
3895 reflections	Δρ_min = −0.48 e Å⁻³
211 parameters

Special details top

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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 (Å²) top

	x	y	z	U_iso*/U_eq
Sn	0.529829 (17)	0.337064 (17)	0.45100 (3)	0.02754 (8)
S1	0.53453 (8)	0.51943 (8)	0.41409 (10)	0.0335 (3)
S2	0.73501 (8)	0.33979 (7)	0.46792 (12)	0.0345 (3)
S3	0.88592 (8)	0.51390 (8)	0.48204 (9)	0.0346 (3)
S4	0.72095 (7)	0.66289 (7)	0.43844 (12)	0.0321 (2)
S5	0.94961 (10)	0.72872 (9)	0.49178 (10)	0.0453 (3)
O1	0.5826 (3)	0.1584 (2)	0.5112 (3)	0.0379 (7)
O2	0.6277 (3)	0.0814 (3)	0.6703 (3)	0.0573 (10)
O3	0.3343 (2)	0.3912 (2)	0.3931 (2)	0.0309 (6)
O4	0.2446 (2)	0.4120 (2)	0.2305 (2)	0.0360 (7)
C1	0.6756 (3)	0.5390 (3)	0.4401 (4)	0.0295 (9)
C2	0.7527 (3)	0.4689 (3)	0.4608 (5)	0.0307 (8)
C3	0.8572 (3)	0.6406 (3)	0.4716 (4)	0.0313 (10)
C4	0.4687 (4)	0.3126 (4)	0.6175 (4)	0.0356 (11)
H4A	0.4635	0.3773	0.6572	0.043*
H4B	0.3938	0.2834	0.6134	0.043*
C5	0.5442 (4)	0.2423 (4)	0.6830 (4)	0.0417 (11)
H5A	0.6080	0.2807	0.7119	0.050*
H5B	0.5033	0.2154	0.7483	0.050*
C6	0.5855 (4)	0.1571 (3)	0.6132 (4)	0.0412 (11)
C7	0.6762 (6)	0.0013 (4)	0.6013 (5)	0.0691 (19)
H7A	0.7202	0.0313	0.5399	0.083*
H7B	0.6164	−0.0389	0.5671	0.083*
C8	0.7474 (5)	−0.0643 (6)	0.6694 (5)	0.086 (2)
H8A	0.8081	−0.0250	0.7012	0.129*
H8B	0.7776	−0.1175	0.6220	0.129*
H8C	0.7040	−0.0939	0.7302	0.129*
C9	0.4905 (3)	0.2620 (3)	0.2973 (3)	0.0314 (10)
H9A	0.5593	0.2486	0.2552	0.038*
H9B	0.4553	0.1970	0.3145	0.038*
C10	0.4131 (4)	0.3238 (3)	0.2247 (4)	0.0367 (10)
H10A	0.4569	0.3730	0.1817	0.044*
H10B	0.3758	0.2792	0.1704	0.044*
C11	0.3272 (3)	0.3782 (3)	0.2923 (4)	0.0301 (9)
C12	0.1619 (4)	0.4726 (4)	0.2870 (4)	0.0392 (11)
H12A	0.1468	0.4441	0.3621	0.047*
H12B	0.0924	0.4710	0.2434	0.047*
C13	0.1992 (4)	0.5781 (3)	0.2994 (4)	0.0445 (11)
H13A	0.2706	0.5796	0.3379	0.067*
H13B	0.1448	0.6156	0.3433	0.067*
H13C	0.2068	0.6086	0.2250	0.067*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Sn	0.02877 (12)	0.02691 (13)	0.02694 (13)	−0.00144 (10)	0.00049 (14)	−0.00137 (15)
S1	0.0284 (5)	0.0272 (5)	0.0451 (7)	0.0013 (4)	−0.0039 (4)	0.0017 (4)
S2	0.0292 (4)	0.0272 (5)	0.0472 (9)	0.0016 (4)	−0.0027 (5)	0.0020 (6)
S3	0.0289 (4)	0.0381 (5)	0.0368 (7)	−0.0026 (4)	−0.0014 (4)	−0.0022 (5)
S4	0.0363 (4)	0.0271 (4)	0.0330 (7)	−0.0037 (4)	0.0001 (5)	−0.0019 (5)
S5	0.0491 (6)	0.0502 (7)	0.0367 (6)	−0.0208 (6)	0.0015 (5)	−0.0058 (6)
O1	0.0438 (18)	0.0333 (16)	0.0365 (19)	0.0018 (13)	−0.0047 (14)	−0.0023 (13)
O2	0.075 (3)	0.049 (2)	0.048 (2)	0.0012 (18)	−0.0188 (18)	0.0071 (18)
O3	0.0315 (13)	0.0359 (16)	0.0254 (16)	0.0003 (13)	−0.0035 (12)	−0.0002 (13)
O4	0.0329 (15)	0.0445 (19)	0.0306 (18)	0.0062 (14)	−0.0022 (13)	−0.0018 (15)
C1	0.0323 (17)	0.0266 (17)	0.030 (2)	−0.0050 (15)	−0.003 (2)	0.001 (2)
C2	0.0297 (16)	0.0280 (18)	0.034 (2)	−0.0046 (14)	−0.002 (2)	−0.009 (2)
C3	0.0352 (18)	0.038 (2)	0.021 (3)	−0.0066 (16)	0.0031 (17)	0.0026 (19)
C4	0.039 (3)	0.035 (3)	0.032 (3)	−0.0048 (19)	0.0015 (18)	−0.004 (2)
C5	0.051 (3)	0.047 (3)	0.027 (2)	−0.010 (2)	−0.001 (2)	0.004 (2)
C6	0.042 (3)	0.039 (3)	0.043 (3)	−0.014 (2)	−0.005 (2)	0.008 (2)
C7	0.092 (5)	0.051 (4)	0.065 (4)	0.018 (3)	−0.031 (4)	−0.016 (3)
C8	0.069 (4)	0.121 (7)	0.069 (5)	0.021 (4)	−0.012 (3)	−0.022 (4)
C9	0.034 (2)	0.031 (2)	0.029 (2)	0.0001 (19)	0.0013 (18)	−0.002 (2)
C10	0.036 (2)	0.046 (3)	0.028 (2)	0.006 (2)	−0.003 (2)	−0.003 (2)
C11	0.031 (2)	0.027 (2)	0.032 (3)	0.0007 (18)	−0.0012 (18)	0.0004 (18)
C12	0.032 (2)	0.048 (3)	0.038 (3)	0.007 (2)	0.0047 (19)	−0.002 (2)
C13	0.044 (3)	0.038 (3)	0.051 (3)	0.005 (2)	0.001 (2)	0.006 (2)

Geometric parameters (Å, º) top

Sn—C4	2.144 (5)	C4—H4B	0.9900
Sn—C9	2.144 (4)	C5—C6	1.498 (7)
Sn—S1	2.4805 (11)	C5—H5A	0.9900
Sn—S2	2.4958 (9)	C5—H5B	0.9900
Sn—O3	2.573 (3)	C7—C8	1.475 (4)
Sn—O1	2.577 (3)	C7—H7A	0.9900
S1—C1	1.758 (4)	C7—H7B	0.9900
S2—C2	1.743 (4)	C8—H8A	0.9800
S3—C3	1.735 (4)	C8—H8B	0.9800
S3—C2	1.742 (3)	C8—H8C	0.9800
S4—C3	1.724 (4)	C9—C10	1.520 (6)
S4—C1	1.746 (4)	C9—H9A	0.9900
S5—C3	1.644 (4)	C9—H9B	0.9900
O1—C6	1.217 (5)	C10—C11	1.505 (6)
O2—C6	1.324 (6)	C10—H10A	0.9900
O2—C7	1.474 (4)	C10—H10B	0.9900
O3—C11	1.217 (5)	C12—C13	1.490 (6)
O4—C11	1.323 (5)	C12—H12A	0.9900
O4—C12	1.454 (5)	C12—H12B	0.9900
C1—C2	1.348 (5)	C13—H13A	0.9800
C4—C5	1.527 (6)	C13—H13B	0.9800
C4—H4A	0.9900	C13—H13C	0.9800

C4—Sn—C9	130.01 (17)	H5A—C5—H5B	107.8
C4—Sn—S1	108.82 (14)	O1—C6—O2	122.4 (5)
C9—Sn—S1	108.33 (12)	O1—C6—C5	122.3 (4)
C4—Sn—S2	105.78 (12)	O2—C6—C5	115.2 (4)
C9—Sn—S2	107.32 (11)	O2—C7—C8	111.0 (5)
S1—Sn—S2	88.68 (3)	O2—C7—H7A	109.4
C4—Sn—O3	88.46 (13)	C8—C7—H7A	109.4
C9—Sn—O3	72.38 (13)	O2—C7—H7B	109.4
S1—Sn—O3	72.34 (7)	C8—C7—H7B	109.4
S2—Sn—O3	159.35 (7)	H7A—C7—H7B	108.0
C4—Sn—O1	71.72 (15)	C7—C8—H8A	109.5
C9—Sn—O1	81.87 (14)	C7—C8—H8B	109.5
S1—Sn—O1	163.04 (7)	H8A—C8—H8B	109.5
S2—Sn—O1	75.14 (7)	C7—C8—H8C	109.5
O3—Sn—O1	124.38 (9)	H8A—C8—H8C	109.5
C1—S1—Sn	97.92 (13)	H8B—C8—H8C	109.5
C2—S2—Sn	97.66 (11)	C10—C9—Sn	111.7 (3)
C3—S3—C2	98.14 (18)	C10—C9—H9A	109.3
C3—S4—C1	97.73 (18)	Sn—C9—H9A	109.3
C6—O1—Sn	107.4 (3)	C10—C9—H9B	109.3
C6—O2—C7	115.0 (4)	Sn—C9—H9B	109.3
C11—O3—Sn	106.9 (2)	H9A—C9—H9B	108.0
C11—O4—C12	117.1 (3)	C11—C10—C9	112.7 (4)
C2—C1—S4	116.4 (3)	C11—C10—H10A	109.1
C2—C1—S1	127.1 (3)	C9—C10—H10A	109.1
S4—C1—S1	116.5 (2)	C11—C10—H10B	109.1
C1—C2—S3	115.4 (3)	C9—C10—H10B	109.1
C1—C2—S2	127.9 (3)	H10A—C10—H10B	107.8
S3—C2—S2	116.7 (2)	O3—C11—O4	123.7 (4)
S5—C3—S4	124.2 (2)	O3—C11—C10	123.2 (4)
S5—C3—S3	123.6 (2)	O4—C11—C10	113.1 (4)
S4—C3—S3	112.2 (2)	O4—C12—C13	111.4 (4)
C5—C4—Sn	111.2 (3)	O4—C12—H12A	109.3
C5—C4—H4A	109.4	C13—C12—H12A	109.3
Sn—C4—H4A	109.4	O4—C12—H12B	109.3
C5—C4—H4B	109.4	C13—C12—H12B	109.3
Sn—C4—H4B	109.4	H12A—C12—H12B	108.0
H4A—C4—H4B	108.0	C12—C13—H13A	109.5
C6—C5—C4	112.6 (4)	C12—C13—H13B	109.5
C6—C5—H5A	109.1	H13A—C13—H13B	109.5
C4—C5—H5A	109.1	C12—C13—H13C	109.5
C6—C5—H5B	109.1	H13A—C13—H13C	109.5
C4—C5—H5B	109.1	H13B—C13—H13C	109.5

C4—Sn—S1—C1	99.3 (2)	Sn—S2—C2—S3	174.2 (3)
C9—Sn—S1—C1	−114.8 (2)	C1—S4—C3—S5	−176.2 (3)
S2—Sn—S1—C1	−6.96 (17)	C1—S4—C3—S3	3.4 (3)
O3—Sn—S1—C1	−178.67 (18)	C2—S3—C3—S5	176.1 (3)
O1—Sn—S1—C1	10.3 (3)	C2—S3—C3—S4	−3.5 (3)
C4—Sn—S2—C2	−102.3 (2)	C9—Sn—C4—C5	94.0 (3)
C9—Sn—S2—C2	115.7 (2)	S1—Sn—C4—C5	−129.9 (3)
S1—Sn—S2—C2	6.90 (19)	S2—Sn—C4—C5	−35.8 (3)
O3—Sn—S2—C2	29.8 (3)	O3—Sn—C4—C5	159.3 (3)
O1—Sn—S2—C2	−168.0 (2)	O1—Sn—C4—C5	32.2 (3)
C4—Sn—O1—C6	−24.6 (3)	Sn—C4—C5—C6	−40.7 (5)
C9—Sn—O1—C6	−161.6 (3)	Sn—O1—C6—O2	−168.4 (4)
S1—Sn—O1—C6	70.1 (4)	Sn—O1—C6—C5	9.8 (5)
S2—Sn—O1—C6	88.0 (3)	C7—O2—C6—O1	3.0 (7)
O3—Sn—O1—C6	−99.5 (3)	C7—O2—C6—C5	−175.4 (5)
C4—Sn—O3—C11	−156.3 (3)	C4—C5—C6—O1	17.7 (6)
C9—Sn—O3—C11	−23.1 (3)	C4—C5—C6—O2	−163.9 (4)
S1—Sn—O3—C11	93.4 (3)	C6—O2—C7—C8	164.1 (5)
S2—Sn—O3—C11	69.3 (4)	C4—Sn—C9—C10	102.9 (4)
O1—Sn—O3—C11	−89.7 (3)	S1—Sn—C9—C10	−33.2 (3)
C3—S4—C1—C2	−2.0 (4)	S2—Sn—C9—C10	−127.7 (3)
C3—S4—C1—S1	178.3 (3)	O3—Sn—C9—C10	30.6 (3)
Sn—S1—C1—C2	6.4 (5)	O1—Sn—C9—C10	160.7 (3)
Sn—S1—C1—S4	−173.9 (2)	Sn—C9—C10—C11	−38.3 (4)
S4—C1—C2—S3	−0.2 (5)	Sn—O3—C11—O4	−169.2 (3)
S1—C1—C2—S3	179.5 (3)	Sn—O3—C11—C10	9.5 (5)
S4—C1—C2—S2	−179.9 (3)	C12—O4—C11—O3	3.7 (6)
S1—C1—C2—S2	−0.2 (7)	C12—O4—C11—C10	−175.2 (4)
C3—S3—C2—C1	2.3 (4)	C9—C10—C11—O3	16.6 (6)
C3—S3—C2—S2	−178.0 (3)	C9—C10—C11—O4	−164.6 (4)
Sn—S2—C2—C1	−6.1 (5)	C11—O4—C12—C13	81.2 (5)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C12—H12a···O1ⁱ	0.99	2.38	3.338 (6)	164
C7—H7a···O3ⁱⁱ	0.99	2.46	3.450 (7)	178

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

Experimental details

Crystal data
Chemical formula	[Sn(C₅H₉O₂)₂(C₃S₅)]
M_r	517.26
Crystal system, space group	Orthorhombic, Pna2₁
Temperature (K)	120
a, b, c (Å)	12.1224 (2), 13.3825 (2), 11.9228 (2)
V (Å³)	1934.21 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	1.87
Crystal size (mm)	0.25 × 0.10 × 0.08

Data collection
Diffractometer	Bruker–Nonius 95mm CCD camera on κ-goniostat diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 2003)
T_min, T_max	0.025, 0.052
No. of measured, independent and observed [I > 2σ(I)] reflections	14014, 3895, 3457
R_int	0.056
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.029, 0.064, 1.04
No. of reflections	3895
No. of parameters	211
No. of restraints	15
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.64, −0.48

Computer programs: , DENZO (Otwinowski & Minor, 1997) and COLLECT (Hooft, 1998), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg, 2006), publCIF (Westrip, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C12—H12a···O1ⁱ	0.99	2.38	3.338 (6)	164
C7—H7a···O3ⁱⁱ	0.99	2.46	3.450 (7)	178

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

Footnotes

‡Additional correspondence author, e-mail: j.wardell@abdn.ac.uk.

Acknowledgements

The use of the EPSRC X-ray crystallographic service at the University of Southampton, England, and the valuable assistance of the staff there is gratefully acknowledged. JLW acknowledges support from FAPEMIG (Brazil).

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