metal-organic compounds
(Dimethyl sulfoxide-κO)diphenyl(3-thioxo-3H-1,2-dithiole-4,5-dithiolato-κ2S4,S5)tin(IV)
aDepartamento de Química Inorgânica, Instituto de Química, Universidade, Federal do Rio de Janeiro, CP 68563, 21941-909 Rio de Janeiro, RJ, Brazil, bDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia, cCentro de Desenvolvimento Tecnológico em Saúde (CDTS), Fundação Oswaldo Cruz (FIOCRUZ), Casa Amarela, Campus de Manguinhos, Av. Brasil 4365, 21040-900, Rio de Janeiro, RJ, Brazil, and dCHEMSOL, 1 Harcourt Road, Aberdeen AB15 5NY, Scotland
*Correspondence e-mail: edward.tiekink@gmail.com
The Sn atom in the title compound, [Sn(C6H5)2(C3S5)(C2H6OS)], exists within a distorted trigonal-bipyramidal geometry defined by two S atoms of the 1,2-dithiole-3-thione-4,5-dithiolate dianion, two ipso-C atoms from the phenyl groups, and the O atom of the dimethyl sulfoxide molecule. In this description, one of the S atoms and the O occupy axial positions. In the crystal, centrosymmetrically related molecules associate via pairs of C—H⋯S contacts, forming dimeric aggregates.
Related literature
For background to the synthesis of dmt compounds, see: Steimecke et al. (1982). For related crystal structures, see: Aupers et al. (1998); Khan et al. (1998); Chohan et al. (1999); Bordinhão et al. (2006, 2008); Comerlato et al. (2008). For additional analysis of geometry, see: Addison et al. (1984).
Experimental
Crystal data
|
Refinement
|
|
Data collection: COLLECT (Hooft, 1998); cell 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
10.1107/S1600536809047904/hb5220sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536809047904/hb5220Isup2.hkl
To a stirred suspension of 4,5-bis(benzoylthio)-1,2-dithiole-3-thione (Steimecke et al., 1982) (410 mg, 1 mmol) in methanol (10 ml), under argon, was added a sodium methoxide solution prepared from sodium (150 mg, 6.75 mmol) and methanol (10 ml). To the resulting purple solution of Na2dmt was added with stirring a methanolic solution of Ph2SnCl2 (345 mg, 1 mmol). The reaction mixture was stirred for 1 h, rotary evaporated and the residue washed well with water. The solid residue (535 mg) was dissolved in a mixture of DMSO and MeOH (ca v:v 3:1) and left to slowly recrystallize to give (I); m.pt. 428–431 K (dec.) IR (KBr, cm-1): 1061 (ν C—S), 950, 941 (ν S—O), 910, 827, 720 (ν C=S).
All H atoms were geometrically placed (C–H = 0.95–0.98 Å) and refined as riding with Uiso(H) = 1.2–1.5Ueq(C). The maximum and minimum residual electron density peaks of 0.85 and 1.26 e Å-3, respectively, were located 1.81 Å and 0.82 Å from the S1 and Sn atoms, respectively.
Data collection: COLLECT (Hooft, 1998); cell
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).[Sn(C6H5)2(C3S5)(C2H6OS)] | F(000) = 1088 |
Mr = 547.35 | Dx = 1.747 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71069 Å |
Hall symbol: -P 2yn | Cell parameters from 44319 reflections |
a = 11.1420 (5) Å | θ = 2.9–27.5° |
b = 15.7237 (6) Å | µ = 1.83 mm−1 |
c = 11.9646 (6) Å | T = 120 K |
β = 96.892 (2)° | Block, yellow |
V = 2080.97 (16) Å3 | 0.24 × 0.16 × 0.10 mm |
Z = 4 |
Bruker–Nonius 95mm CCD camera on κ-goniostat diffractometer | 4770 independent reflections |
Radiation source: Bruker-Nonius FR591 rotating anode | 3906 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.057 |
Detector resolution: 9.091 pixels mm-1 | θmax = 27.5°, θmin = 3.1° |
ϕ and ω scans | h = −14→14 |
Absorption correction: multi-scan (SADABS; Sheldrick, 2007) | k = −20→19 |
Tmin = 0.536, Tmax = 0.746 | l = −15→15 |
22729 measured reflections |
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)] = 0.037 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.088 | H-atom parameters constrained |
S = 1.06 | w = 1/[σ2(Fo2) + (0.0404P)2 + 1.7706P] where P = (Fo2 + 2Fc2)/3 |
4770 reflections | (Δ/σ)max < 0.001 |
228 parameters | Δρmax = 0.85 e Å−3 |
0 restraints | Δρmin = −1.26 e Å−3 |
[Sn(C6H5)2(C3S5)(C2H6OS)] | V = 2080.97 (16) Å3 |
Mr = 547.35 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 11.1420 (5) Å | µ = 1.83 mm−1 |
b = 15.7237 (6) Å | T = 120 K |
c = 11.9646 (6) Å | 0.24 × 0.16 × 0.10 mm |
β = 96.892 (2)° |
Bruker–Nonius 95mm CCD camera on κ-goniostat diffractometer | 4770 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2007) | 3906 reflections with I > 2σ(I) |
Tmin = 0.536, Tmax = 0.746 | Rint = 0.057 |
22729 measured reflections |
R[F2 > 2σ(F2)] = 0.037 | 0 restraints |
wR(F2) = 0.088 | H-atom parameters constrained |
S = 1.06 | Δρmax = 0.85 e Å−3 |
4770 reflections | Δρmin = −1.26 e Å−3 |
228 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
Sn | 0.823308 (19) | 0.079364 (13) | 0.201486 (19) | 0.01886 (9) | |
S1 | 0.64254 (8) | 0.07006 (5) | 0.29688 (7) | 0.02196 (18) | |
S2 | 0.68225 (8) | 0.10256 (6) | 0.01905 (8) | 0.0263 (2) | |
S3 | 0.42347 (8) | 0.12813 (5) | −0.02069 (8) | 0.0266 (2) | |
S4 | 0.30214 (8) | 0.12492 (6) | 0.09713 (8) | 0.0302 (2) | |
S5 | 0.35612 (8) | 0.08574 (6) | 0.33685 (9) | 0.0301 (2) | |
S6 | 0.89763 (8) | 0.13614 (5) | 0.46902 (8) | 0.0264 (2) | |
O1 | 0.9096 (2) | 0.06287 (13) | 0.38570 (19) | 0.0218 (5) | |
C1 | 0.5279 (3) | 0.09377 (19) | 0.1865 (3) | 0.0210 (7) | |
C2 | 0.5481 (3) | 0.1063 (2) | 0.0763 (3) | 0.0226 (7) | |
C3 | 0.4068 (3) | 0.0995 (2) | 0.2126 (3) | 0.0249 (7) | |
C4 | 0.8953 (3) | −0.0427 (2) | 0.1706 (3) | 0.0199 (7) | |
C5 | 1.0061 (3) | −0.0547 (2) | 0.1308 (3) | 0.0291 (8) | |
H5 | 1.0562 | −0.0073 | 0.1200 | 0.035* | |
C6 | 1.0440 (3) | −0.1366 (2) | 0.1067 (3) | 0.0349 (9) | |
H6 | 1.1200 | −0.1448 | 0.0798 | 0.042* | |
C7 | 0.9712 (3) | −0.2061 (2) | 0.1217 (3) | 0.0327 (9) | |
H7 | 0.9965 | −0.2616 | 0.1037 | 0.039* | |
C8 | 0.8622 (3) | −0.1945 (2) | 0.1626 (3) | 0.0277 (8) | |
H8 | 0.8126 | −0.2423 | 0.1735 | 0.033* | |
C9 | 0.8241 (3) | −0.1133 (2) | 0.1883 (3) | 0.0216 (7) | |
H9 | 0.7495 | −0.1059 | 0.2179 | 0.026* | |
C10 | 0.9274 (3) | 0.1927 (2) | 0.1953 (3) | 0.0212 (7) | |
C11 | 1.0477 (3) | 0.1947 (2) | 0.2438 (3) | 0.0260 (7) | |
H11 | 1.0842 | 0.1443 | 0.2758 | 0.031* | |
C12 | 1.1145 (3) | 0.2691 (2) | 0.2459 (3) | 0.0331 (9) | |
H12 | 1.1963 | 0.2698 | 0.2792 | 0.040* | |
C13 | 1.0608 (4) | 0.3427 (2) | 0.1990 (4) | 0.0376 (10) | |
H13 | 1.1055 | 0.3943 | 0.2023 | 0.045* | |
C14 | 0.9438 (4) | 0.3415 (2) | 0.1480 (3) | 0.0350 (9) | |
H14 | 0.9085 | 0.3919 | 0.1147 | 0.042* | |
C15 | 0.8763 (3) | 0.2666 (2) | 0.1450 (3) | 0.0270 (8) | |
H15 | 0.7956 | 0.2658 | 0.1087 | 0.032* | |
C16 | 1.0469 (3) | 0.1532 (2) | 0.5361 (3) | 0.0351 (9) | |
H16A | 1.0823 | 0.0987 | 0.5628 | 0.053* | |
H16B | 1.0443 | 0.1917 | 0.6002 | 0.053* | |
H16C | 1.0962 | 0.1785 | 0.4824 | 0.053* | |
C17 | 0.8353 (4) | 0.0869 (3) | 0.5831 (4) | 0.0423 (10) | |
H17A | 0.7533 | 0.0670 | 0.5574 | 0.064* | |
H17B | 0.8326 | 0.1281 | 0.6441 | 0.064* | |
H17C | 0.8858 | 0.0384 | 0.6105 | 0.064* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Sn | 0.01908 (13) | 0.01369 (12) | 0.02314 (14) | 0.00039 (8) | −0.00013 (9) | 0.00187 (8) |
S1 | 0.0222 (4) | 0.0193 (4) | 0.0241 (5) | 0.0009 (3) | 0.0015 (3) | 0.0028 (3) |
S2 | 0.0210 (4) | 0.0330 (5) | 0.0243 (5) | 0.0008 (3) | 0.0000 (4) | 0.0059 (4) |
S3 | 0.0213 (4) | 0.0276 (4) | 0.0293 (5) | 0.0011 (3) | −0.0039 (4) | 0.0000 (4) |
S4 | 0.0194 (4) | 0.0347 (5) | 0.0356 (5) | 0.0019 (4) | −0.0007 (4) | −0.0036 (4) |
S5 | 0.0259 (5) | 0.0298 (5) | 0.0360 (6) | −0.0008 (3) | 0.0096 (4) | −0.0007 (4) |
S6 | 0.0326 (5) | 0.0183 (4) | 0.0263 (5) | 0.0038 (3) | −0.0041 (4) | −0.0022 (3) |
O1 | 0.0270 (13) | 0.0153 (11) | 0.0224 (13) | 0.0015 (9) | 0.0004 (10) | −0.0005 (9) |
C1 | 0.0199 (16) | 0.0128 (15) | 0.0292 (19) | 0.0002 (12) | −0.0021 (14) | −0.0015 (13) |
C2 | 0.0222 (17) | 0.0168 (15) | 0.0276 (19) | 0.0021 (13) | −0.0011 (14) | −0.0005 (13) |
C3 | 0.0210 (17) | 0.0190 (16) | 0.034 (2) | −0.0001 (13) | −0.0012 (15) | −0.0006 (14) |
C4 | 0.0210 (16) | 0.0172 (15) | 0.0203 (17) | 0.0019 (13) | −0.0024 (13) | 0.0010 (13) |
C5 | 0.0271 (19) | 0.0246 (17) | 0.036 (2) | 0.0000 (14) | 0.0059 (16) | 0.0053 (16) |
C6 | 0.031 (2) | 0.041 (2) | 0.035 (2) | 0.0111 (17) | 0.0121 (17) | 0.0045 (17) |
C7 | 0.044 (2) | 0.0218 (17) | 0.032 (2) | 0.0098 (16) | 0.0041 (17) | −0.0024 (15) |
C8 | 0.039 (2) | 0.0174 (16) | 0.0254 (19) | −0.0013 (14) | 0.0002 (16) | 0.0044 (14) |
C9 | 0.0221 (17) | 0.0195 (16) | 0.0222 (18) | −0.0016 (13) | −0.0013 (14) | 0.0008 (13) |
C10 | 0.0257 (17) | 0.0170 (15) | 0.0216 (18) | −0.0003 (13) | 0.0063 (14) | −0.0002 (13) |
C11 | 0.0243 (17) | 0.0233 (17) | 0.030 (2) | −0.0018 (14) | 0.0027 (15) | −0.0018 (14) |
C12 | 0.029 (2) | 0.034 (2) | 0.038 (2) | −0.0086 (16) | 0.0099 (17) | −0.0065 (17) |
C13 | 0.049 (3) | 0.0236 (18) | 0.045 (2) | −0.0145 (17) | 0.026 (2) | −0.0081 (17) |
C14 | 0.050 (2) | 0.0178 (17) | 0.041 (2) | 0.0041 (16) | 0.021 (2) | 0.0026 (16) |
C15 | 0.0300 (19) | 0.0197 (16) | 0.032 (2) | 0.0039 (14) | 0.0051 (15) | 0.0014 (14) |
C16 | 0.035 (2) | 0.033 (2) | 0.034 (2) | −0.0047 (16) | −0.0112 (17) | 0.0022 (17) |
C17 | 0.049 (3) | 0.049 (3) | 0.031 (2) | −0.0049 (19) | 0.012 (2) | −0.0018 (18) |
Sn—C4 | 2.130 (3) | C7—C8 | 1.375 (5) |
Sn—C10 | 2.133 (3) | C7—H7 | 0.9500 |
Sn—O1 | 2.311 (2) | C8—C9 | 1.392 (5) |
Sn—S1 | 2.4357 (9) | C8—H8 | 0.9500 |
Sn—S2 | 2.5582 (9) | C9—H9 | 0.9500 |
S1—C1 | 1.764 (3) | C10—C11 | 1.396 (5) |
S2—C2 | 1.718 (3) | C10—C15 | 1.398 (5) |
S3—C2 | 1.734 (3) | C11—C12 | 1.386 (5) |
S3—S4 | 2.0674 (13) | C11—H11 | 0.9500 |
S4—C3 | 1.744 (4) | C12—C13 | 1.390 (6) |
S5—C3 | 1.667 (4) | C12—H12 | 0.9500 |
S6—O1 | 1.540 (2) | C13—C14 | 1.372 (6) |
S6—C16 | 1.778 (4) | C13—H13 | 0.9500 |
S6—C17 | 1.781 (4) | C14—C15 | 1.395 (5) |
C1—C2 | 1.379 (5) | C14—H14 | 0.9500 |
C1—C3 | 1.423 (5) | C15—H15 | 0.9500 |
C4—C5 | 1.388 (5) | C16—H16A | 0.9800 |
C4—C9 | 1.395 (5) | C16—H16B | 0.9800 |
C5—C6 | 1.396 (5) | C16—H16C | 0.9800 |
C5—H5 | 0.9500 | C17—H17A | 0.9800 |
C6—C7 | 1.384 (5) | C17—H17B | 0.9800 |
C6—H6 | 0.9500 | C17—H17C | 0.9800 |
C4—Sn—C10 | 121.97 (12) | C6—C7—H7 | 120.0 |
C4—Sn—O1 | 86.68 (10) | C7—C8—C9 | 120.3 (3) |
C10—Sn—O1 | 87.79 (10) | C7—C8—H8 | 119.8 |
C4—Sn—S1 | 112.16 (9) | C9—C8—H8 | 119.8 |
C10—Sn—S1 | 123.38 (9) | C8—C9—C4 | 120.2 (3) |
O1—Sn—S1 | 79.58 (6) | C8—C9—H9 | 119.9 |
C4—Sn—S2 | 100.73 (9) | C4—C9—H9 | 119.9 |
C10—Sn—S2 | 97.58 (9) | C11—C10—C15 | 118.8 (3) |
O1—Sn—S2 | 166.52 (6) | C11—C10—Sn | 120.2 (2) |
S1—Sn—S2 | 87.16 (3) | C15—C10—Sn | 121.0 (2) |
C1—S1—Sn | 101.66 (12) | C12—C11—C10 | 120.9 (3) |
C2—S2—Sn | 98.03 (12) | C12—C11—H11 | 119.6 |
C2—S3—S4 | 94.35 (12) | C10—C11—H11 | 119.6 |
C3—S4—S3 | 96.65 (12) | C11—C12—C13 | 119.5 (4) |
O1—S6—C16 | 104.84 (17) | C11—C12—H12 | 120.3 |
O1—S6—C17 | 104.05 (17) | C13—C12—H12 | 120.3 |
C16—S6—C17 | 98.6 (2) | C14—C13—C12 | 120.5 (3) |
S6—O1—Sn | 118.36 (12) | C14—C13—H13 | 119.7 |
C2—C1—C3 | 117.9 (3) | C12—C13—H13 | 119.7 |
C2—C1—S1 | 124.0 (3) | C13—C14—C15 | 120.3 (3) |
C3—C1—S1 | 118.0 (3) | C13—C14—H14 | 119.9 |
C1—C2—S2 | 128.8 (3) | C15—C14—H14 | 119.9 |
C1—C2—S3 | 117.3 (3) | C14—C15—C10 | 120.0 (3) |
S2—C2—S3 | 113.9 (2) | C14—C15—H15 | 120.0 |
C1—C3—S5 | 128.2 (3) | C10—C15—H15 | 120.0 |
C1—C3—S4 | 113.7 (3) | S6—C16—H16A | 109.5 |
S5—C3—S4 | 118.1 (2) | S6—C16—H16B | 109.5 |
C5—C4—C9 | 119.3 (3) | H16A—C16—H16B | 109.5 |
C5—C4—Sn | 123.5 (2) | S6—C16—H16C | 109.5 |
C9—C4—Sn | 117.2 (2) | H16A—C16—H16C | 109.5 |
C4—C5—C6 | 120.0 (3) | H16B—C16—H16C | 109.5 |
C4—C5—H5 | 120.0 | S6—C17—H17A | 109.5 |
C6—C5—H5 | 120.0 | S6—C17—H17B | 109.5 |
C7—C6—C5 | 120.3 (3) | H17A—C17—H17B | 109.5 |
C7—C6—H6 | 119.9 | S6—C17—H17C | 109.5 |
C5—C6—H6 | 119.9 | H17A—C17—H17C | 109.5 |
C8—C7—C6 | 119.9 (3) | H17B—C17—H17C | 109.5 |
C8—C7—H7 | 120.0 | ||
C4—Sn—S1—C1 | −105.26 (14) | O1—Sn—C4—C5 | −94.0 (3) |
C10—Sn—S1—C1 | 92.39 (15) | S1—Sn—C4—C5 | −171.4 (3) |
O1—Sn—S1—C1 | 172.71 (12) | S2—Sn—C4—C5 | 97.3 (3) |
S2—Sn—S1—C1 | −4.83 (10) | C10—Sn—C4—C9 | 173.5 (2) |
C4—Sn—S2—C2 | 116.74 (14) | O1—Sn—C4—C9 | 88.2 (3) |
C10—Sn—S2—C2 | −118.59 (14) | S1—Sn—C4—C9 | 10.8 (3) |
O1—Sn—S2—C2 | −5.7 (3) | S2—Sn—C4—C9 | −80.5 (2) |
S1—Sn—S2—C2 | 4.72 (11) | C9—C4—C5—C6 | 1.4 (5) |
C2—S3—S4—C3 | −1.58 (16) | Sn—C4—C5—C6 | −176.4 (3) |
C16—S6—O1—Sn | −130.43 (17) | C4—C5—C6—C7 | 0.3 (6) |
C17—S6—O1—Sn | 126.56 (19) | C5—C6—C7—C8 | −1.3 (6) |
C4—Sn—O1—S6 | 177.97 (16) | C6—C7—C8—C9 | 0.5 (6) |
C10—Sn—O1—S6 | 55.76 (16) | C7—C8—C9—C4 | 1.2 (5) |
S1—Sn—O1—S6 | −68.78 (13) | C5—C4—C9—C8 | −2.2 (5) |
S2—Sn—O1—S6 | −58.2 (3) | Sn—C4—C9—C8 | 175.8 (3) |
Sn—S1—C1—C2 | 4.4 (3) | C4—Sn—C10—C11 | −42.9 (3) |
Sn—S1—C1—C3 | −176.2 (2) | O1—Sn—C10—C11 | 41.8 (3) |
C3—C1—C2—S2 | −179.4 (3) | S1—Sn—C10—C11 | 117.8 (2) |
S1—C1—C2—S2 | 0.0 (5) | S2—Sn—C10—C11 | −150.6 (3) |
C3—C1—C2—S3 | 0.1 (4) | C4—Sn—C10—C15 | 138.4 (3) |
S1—C1—C2—S3 | 179.45 (17) | O1—Sn—C10—C15 | −136.9 (3) |
Sn—S2—C2—C1 | −4.1 (3) | S1—Sn—C10—C15 | −60.9 (3) |
Sn—S2—C2—S3 | 176.36 (15) | S2—Sn—C10—C15 | 30.7 (3) |
S4—S3—C2—C1 | 1.1 (3) | C15—C10—C11—C12 | 2.3 (5) |
S4—S3—C2—S2 | −179.35 (16) | Sn—C10—C11—C12 | −176.4 (3) |
C2—C1—C3—S5 | 178.8 (3) | C10—C11—C12—C13 | −0.1 (6) |
S1—C1—C3—S5 | −0.6 (4) | C11—C12—C13—C14 | −1.8 (6) |
C2—C1—C3—S4 | −1.6 (4) | C12—C13—C14—C15 | 1.4 (6) |
S1—C1—C3—S4 | 179.03 (17) | C13—C14—C15—C10 | 0.9 (5) |
S3—S4—C3—C1 | 2.0 (2) | C11—C10—C15—C14 | −2.7 (5) |
S3—S4—C3—S5 | −178.38 (18) | Sn—C10—C15—C14 | 176.0 (3) |
C10—Sn—C4—C5 | −8.7 (4) |
D—H···A | D—H | H···A | D···A | D—H···A |
C6—H6···S2i | 0.95 | 2.71 | 3.599 (4) | 157 |
Symmetry code: (i) −x+2, −y, −z. |
Experimental details
Crystal data | |
Chemical formula | [Sn(C6H5)2(C3S5)(C2H6OS)] |
Mr | 547.35 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 120 |
a, b, c (Å) | 11.1420 (5), 15.7237 (6), 11.9646 (6) |
β (°) | 96.892 (2) |
V (Å3) | 2080.97 (16) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.83 |
Crystal size (mm) | 0.24 × 0.16 × 0.10 |
Data collection | |
Diffractometer | Bruker–Nonius 95mm CCD camera on κ-goniostat diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2007) |
Tmin, Tmax | 0.536, 0.746 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 22729, 4770, 3906 |
Rint | 0.057 |
(sin θ/λ)max (Å−1) | 0.650 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.037, 0.088, 1.06 |
No. of reflections | 4770 |
No. of parameters | 228 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.85, −1.26 |
Computer programs: , DENZO (Otwinowski & Minor, 1997) and COLLECT (Hooft, 1998), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg, 2006), publCIF (Westrip, 2009).
Sn—C4 | 2.130 (3) | Sn—S1 | 2.4357 (9) |
Sn—C10 | 2.133 (3) | Sn—S2 | 2.5582 (9) |
Sn—O1 | 2.311 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
C6—H6···S2i | 0.95 | 2.71 | 3.599 (4) | 157 |
Symmetry code: (i) −x+2, −y, −z. |
Footnotes
‡Additional correspondence author: 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 CAPES (Brazil).
References
Addison, A. W., Rao, T. N., Reedijk, J., van Rijn, J. & Verschoor, G. C. (1984). J. Chem. Soc. Dalton Trans. pp. 1349–1356. CSD CrossRef Web of Science Google Scholar
Aupers, J. H., Chohan, Z. H., Cox, P. J., Doidge-Harrison, S. M. S. V., Howie, R. A., Khan, A., Spencer, G. M. & Wardell, J. L. (1998). Polyhedron, 17, 4475–4486. Web of Science CSD CrossRef CAS Google Scholar
Bordinhão, J., Comerlato, N. M., de Castro Cortás, L., Ferreira, G. B., Howie, R. A. & Wardell, J. L. (2008). J. Organomet. Chem. 693, 763–768. Google Scholar
Bordinhão, J., Comerlato, N. M., Ferreira, G. B., Howie, R. A., da Silva, C. X. A. & Wardell, J. L. (2006). J. Organomet. Chem. 691, 1598–1605. Google Scholar
Brandenburg, K. (2006). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Chohan, Z. H., Howie, R. A. & Wardell, J. L. (1999). J. Organomet. Chem. 577, 140–149. Web of Science CSD CrossRef CAS Google Scholar
Comerlato, N. M., Ferreira, G. B., Howie, R. A., Silva, C. X. A. & Wardell, J. L. (2008). J. Organomet. Chem. 693, 2424–2430. Web of Science CSD CrossRef CAS Google Scholar
Hooft, R. W. W. (1998). COLLECT. Nonius BV, Delft, The Netherlands. Google Scholar
Khan, A., Low, J. N., Wardell, J. L. & Ferguson, G. (1998). Acta Cryst. C54, 1399–1401. Web of Science CSD CrossRef IUCr Journals Google Scholar
Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, Macromolecular Crystallography, Part A, edited by C. W. Carter Jr & R. M. Sweet, pp. 307–326. New York: Academic Press. Google Scholar
Sheldrick, G. M. (2007). SADABS. Version 2007/2. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Steimecke, G., Sieler, H.-J., Kirmse, R., Dietzch, W. & Hoyer, E. (1982). Phosphorus Sulfur, 12, 237–247. CrossRef CAS Web of Science Google Scholar
Westrip, S. P. (2009). publCIF. In preparation. Google Scholar
This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.
While several structures of (1,3-dithiole-2-thione-4,5-dithiolato)tin, [Sn-dmit], and (1,3-dithiole-2-one-4,5-dithiolato)tin [Sn-dmio] complexes have been reported (e.g., Comerlato et al., 2008), similar (1,2-dithiole-3-thione-4,5-dithiolato)tin complexes have been essentially neglected, with only one systematic study known (Bordinhão et al., 2006; Bordinhão et al., 2008); see Fig. 1 for chemical structures of dmit, dmio and dmt. The poor solubility of 1,2-dithiole-3-thione-4,5-dithiolato (dmt) complexes has been put forward as a major cause for the limited number of their reported crystal structures. Attempts to obtain good crystals of Ph2Sn(dmt), prepared from reaction of Na2(dmt) and Ph2SnCl2 in MeOH solution, failed as only amorphous material was obtained. However, crystallization of Ph2Sn(dmt) from a DMSO/MeOH solution produced crystals of the DMSO solvate, (I), suitable for the X-Ray study reported herein.
As compounds, R2Sn(dmit) and R2Sn(dmio), having non-functionalized alkyl or aryl R groups (e.g., R = Me, Et, Bu or Ph), are aggregated in both the solid–state and in non-coordinating solvents as a consequence of intermolecular Sn···S interactions., it is assumed that the R2Sn(dmt) analogues are similarly aggregated. The formation of adducts such as [Ph2Sn(dmt)(dmso)] will generally provide coordinatively saturated tin centres and hence result in appreciably more soluble species having essentially non-interacting cations and anions. Structures of ionic species, [Q][R2Sn(dmit)X] and [Q][R2Sn(dmio)X] [Q+ = onium cation, X = halide or pseudohalide], with 5-coordinate tin have also been determined (Chohan et al., 1999; Khan et al., 1998; Aupers et al., 1998).
The Sn atom in (1) is five-coordinate, existing within a C2OS2 donor set defined by a chelating dmt ligand, two ipso-C atoms and the O atom derived from the DMSO molecule, Fig. 2. The coordination geometry is based on a trigonal bipyramid with the S2–Sn–O1 axial angle being 166.52 (6) °. As expected, the Sn–S1equatorial distance of 2.4357 (9) Å is shorter than the Sn–S2axial distance of 2.5582 (9) Å. The coordination geometry is distorted towards trigonal bipyramidal (TP). This is quantified by the value of τ = 0.72, which compares with the ideal values of 1.0 and 0.0 for TP and square pyramidal, respectively (Addison et al., 1984).
The most prominent intermolecular interaction connecting molecules is of the type C–H···S and these occur between centrosymmetric pairs to form loosely associated dimers, Table 1 and Fig. 3.