Acta Cryst. (2009). E65, m722 [ doi:10.1107/S1600536809020273 ]
Molecules of the title compound, [Sn2(C6H5)6(C6H2O4S)], lie on inversion centres with the central thiophene ring disordered equally over two orientations. The carboxylate groups are approximately coplanar with the thiophene ring [dihedral angle = 4.0 (1)°] and the Sn-O bond distance of 2.058 (4) Å is comparable to that in related organotin carboxylates.
The reaction was carried out under a nitrogen atmosphere. Thiophene-2,5-dicarboxylic acid (10 mmol) and sodium ethoxide (20 mmol) were added to a stirred solution of benzene (50 ml) in a three-necked flask and stirred for 0.5 h. Triphenyltin chloride (20 mmol) was then added and the reaction mixture was stirred for 6 h at room temperature. The resulting clear solution was evaporated under vacuum. The product was crystallized from dichloromethane to yield colourless blocks of the title compound. Elemental analysis: calculated C 57.97, H 3.71 %; found: C 57.68, H 3.55 %.
H atoms were placed in geometrically idealized positions (C—H = 0.93 Å) and treated as riding on their parent atoms, with Uiso(H) = 1.2 Ueq(C).
Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT (Siemens, 1996); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).
![[Figure 1]](./bi2371fig1thm.gif)
| Fig. 1. Molecular structure showing 30% probability displacement ellipsoids, with H atoms are omitted. Unlabelled atoms are related to labelled atoms by the symmetry code: 2-x, -y, 1-z. The symmetry-generated component of the disordered thiophene ring is not shown. |
| [Sn2(C6H5)6(C6H2O4S)] | F(000) = 864 |
| Mr = 870.12 | Dx = 1.550 Mg m−3 |
| Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
| Hall symbol: -P 2ybc | Cell parameters from 3030 reflections |
| a = 10.1302 (10) Å | θ = 2.4–25.2° |
| b = 18.699 (2) Å | µ = 1.44 mm−1 |
| c = 10.3584 (11) Å | T = 298 K |
| β = 108.213 (2)° | Needle, colorless |
| V = 1863.8 (3) Å3 | 0.21 × 0.11 × 0.06 mm |
| Z = 2 |
| Bruker SMART APEX CCD diffractometer | 3281 independent reflections |
| Radiation source: fine-focus sealed tube | 2342 reflections with I > 2σ(I) |
| graphite | Rint = 0.040 |
| φ and ω scans | θmax = 25.0°, θmin = 2.1° |
| Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −12→6 |
| Tmin = 0.752, Tmax = 0.919 | k = −22→20 |
| 9058 measured reflections | l = −11→12 |
| 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)] = 0.052 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.110 | H-atom parameters constrained |
| S = 1.02 | w = 1/[σ2(Fo2) + (0.0214P)2 + 10.153P] where P = (Fo2 + 2Fc2)/3 |
| 3281 reflections | (Δ/σ)max = 0.001 |
| 244 parameters | Δρmax = 0.77 e Å−3 |
| 0 restraints | Δρmin = −0.63 e Å−3 |
| [Sn2(C6H5)6(C6H2O4S)] | V = 1863.8 (3) Å3 |
| Mr = 870.12 | Z = 2 |
| Monoclinic, P21/c | Mo Kα radiation |
| a = 10.1302 (10) Å | µ = 1.44 mm−1 |
| b = 18.699 (2) Å | T = 298 K |
| c = 10.3584 (11) Å | 0.21 × 0.11 × 0.06 mm |
| β = 108.213 (2)° |
| Bruker SMART APEX CCD diffractometer | 3281 independent reflections |
| Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 2342 reflections with I > 2σ(I) |
| Tmin = 0.752, Tmax = 0.919 | Rint = 0.040 |
| 9058 measured reflections | θmax = 25.0° |
| R[F2 > 2σ(F2)] = 0.052 | w = 1/[σ2(Fo2) + (0.0214P)2 + 10.153P] where P = (Fo2 + 2Fc2)/3 |
| wR(F2) = 0.110 | Δρmax = 0.77 e Å−3 |
| S = 1.02 | Δρmin = −0.63 e Å−3 |
| 3281 reflections | Absolute structure: ? |
| 244 parameters | Flack parameter: ? |
| 0 restraints | Rogers parameter: ? |
| H-atom parameters constrained |
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. |
| x | y | z | Uiso*/Ueq | Occ. (<1) | |
| Sn1 | 0.66000 (5) | 0.07183 (3) | 0.78299 (5) | 0.04647 (17) | |
| S1 | 0.9299 (4) | 0.0123 (2) | 0.4533 (4) | 0.0479 (9) | 0.50 |
| O1 | 0.7511 (5) | 0.0595 (3) | 0.6325 (5) | 0.0547 (13) | |
| O2 | 0.9220 (7) | 0.0178 (4) | 0.7991 (8) | 0.110 (3) | |
| C1 | 0.8710 (9) | 0.0308 (4) | 0.6808 (10) | 0.061 (2) | |
| C2 | 0.9687 (17) | −0.0005 (9) | 0.6205 (18) | 0.053 (4) | 0.50 |
| C3 | 1.0869 (15) | −0.0332 (8) | 0.6787 (16) | 0.056 (4) | 0.50 |
| H3 | 1.1227 | −0.0425 | 0.7713 | 0.067* | 0.50 |
| C4 | 1.1513 (16) | −0.0519 (8) | 0.5836 (15) | 0.057 (4) | 0.50 |
| H4 | 1.2341 | −0.0775 | 0.6067 | 0.068* | 0.50 |
| C5 | 1.0826 (16) | −0.0293 (8) | 0.4493 (19) | 0.048 (4) | 0.50 |
| C6 | 0.4678 (8) | 0.1119 (5) | 0.6546 (9) | 0.074 (3) | |
| C7 | 0.4344 (10) | 0.1137 (5) | 0.5168 (10) | 0.089 (3) | |
| H7 | 0.4985 | 0.0981 | 0.4752 | 0.107* | |
| C8 | 0.3042 (12) | 0.1388 (6) | 0.4372 (12) | 0.107 (4) | |
| H8 | 0.2812 | 0.1401 | 0.3430 | 0.129* | |
| C9 | 0.2123 (12) | 0.1611 (6) | 0.4998 (14) | 0.113 (4) | |
| H9 | 0.1275 | 0.1798 | 0.4471 | 0.136* | |
| C10 | 0.2392 (11) | 0.1573 (7) | 0.6336 (14) | 0.123 (5) | |
| H10 | 0.1723 | 0.1709 | 0.6731 | 0.147* | |
| C11 | 0.3691 (9) | 0.1327 (6) | 0.7143 (12) | 0.107 (4) | |
| H11 | 0.3894 | 0.1304 | 0.8082 | 0.128* | |
| C12 | 0.7680 (8) | 0.1508 (4) | 0.9236 (7) | 0.0532 (19) | |
| C13 | 0.7151 (11) | 0.2181 (5) | 0.9169 (11) | 0.100 (3) | |
| H13 | 0.6362 | 0.2302 | 0.8457 | 0.120* | |
| C14 | 0.7770 (12) | 0.2686 (6) | 1.0144 (12) | 0.109 (4) | |
| H14 | 0.7375 | 0.3138 | 1.0089 | 0.131* | |
| C15 | 0.8898 (11) | 0.2541 (6) | 1.1140 (11) | 0.091 (3) | |
| H15 | 0.9309 | 0.2884 | 1.1793 | 0.109* | |
| C16 | 0.9439 (12) | 0.1896 (7) | 1.1196 (12) | 0.121 (4) | |
| H16 | 1.0244 | 0.1788 | 1.1899 | 0.145* | |
| C17 | 0.8848 (11) | 0.1373 (5) | 1.0241 (10) | 0.102 (4) | |
| H17 | 0.9267 | 0.0927 | 1.0301 | 0.123* | |
| C18 | 0.6293 (11) | −0.0309 (5) | 0.8534 (9) | 0.072 (3) | |
| C19 | 0.4946 (13) | −0.0581 (6) | 0.8128 (10) | 0.101 (3) | |
| H19 | 0.4219 | −0.0301 | 0.7600 | 0.121* | |
| C20 | 0.4668 (15) | −0.1284 (7) | 0.8514 (12) | 0.115 (4) | |
| H20 | 0.3770 | −0.1465 | 0.8293 | 0.138* | |
| C21 | 0.5790 (17) | −0.1672 (7) | 0.9219 (13) | 0.127 (5) | |
| H21 | 0.5634 | −0.2144 | 0.9418 | 0.152* | |
| C22 | 0.7120 (16) | −0.1434 (7) | 0.9663 (12) | 0.130 (5) | |
| H22 | 0.7840 | −0.1725 | 1.0172 | 0.156* | |
| C23 | 0.7362 (14) | −0.0732 (6) | 0.9321 (10) | 0.110 (4) | |
| H23 | 0.8258 | −0.0547 | 0.9629 | 0.132* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Sn1 | 0.0405 (3) | 0.0537 (3) | 0.0483 (3) | 0.0019 (3) | 0.0182 (2) | −0.0062 (3) |
| S1 | 0.040 (2) | 0.052 (2) | 0.054 (3) | 0.0089 (19) | 0.0192 (19) | 0.0058 (19) |
| O1 | 0.050 (3) | 0.062 (3) | 0.060 (3) | 0.008 (3) | 0.028 (3) | 0.005 (3) |
| O2 | 0.092 (5) | 0.082 (5) | 0.118 (6) | 0.012 (4) | −0.023 (5) | 0.006 (4) |
| C1 | 0.048 (5) | 0.061 (5) | 0.080 (6) | −0.002 (4) | 0.026 (5) | −0.017 (5) |
| C2 | 0.042 (10) | 0.055 (10) | 0.062 (11) | 0.012 (8) | 0.018 (9) | 0.000 (8) |
| C3 | 0.049 (9) | 0.065 (10) | 0.057 (10) | 0.017 (8) | 0.020 (8) | 0.002 (8) |
| C4 | 0.046 (9) | 0.064 (10) | 0.059 (10) | 0.015 (8) | 0.015 (8) | −0.002 (8) |
| C5 | 0.040 (9) | 0.047 (10) | 0.064 (12) | 0.010 (8) | 0.025 (9) | −0.005 (9) |
| C6 | 0.053 (5) | 0.082 (6) | 0.079 (6) | 0.014 (5) | 0.010 (5) | −0.042 (5) |
| C7 | 0.069 (6) | 0.092 (7) | 0.090 (7) | 0.017 (5) | 0.003 (6) | −0.041 (6) |
| C8 | 0.087 (8) | 0.110 (9) | 0.099 (8) | 0.020 (7) | −0.008 (7) | −0.038 (7) |
| C9 | 0.080 (8) | 0.111 (9) | 0.121 (10) | 0.026 (7) | −0.010 (8) | −0.038 (8) |
| C10 | 0.074 (7) | 0.142 (11) | 0.134 (11) | 0.040 (7) | 0.006 (8) | −0.056 (9) |
| C11 | 0.060 (6) | 0.134 (9) | 0.111 (8) | 0.032 (6) | 0.007 (6) | −0.055 (7) |
| C12 | 0.050 (4) | 0.061 (5) | 0.055 (5) | −0.002 (4) | 0.025 (4) | −0.011 (4) |
| C13 | 0.090 (7) | 0.081 (7) | 0.104 (8) | 0.019 (6) | −0.004 (6) | −0.039 (6) |
| C14 | 0.098 (8) | 0.086 (7) | 0.119 (9) | 0.012 (7) | −0.001 (8) | −0.043 (7) |
| C15 | 0.082 (7) | 0.092 (8) | 0.092 (8) | −0.016 (6) | 0.019 (6) | −0.046 (6) |
| C16 | 0.099 (9) | 0.110 (9) | 0.111 (9) | 0.002 (8) | −0.031 (7) | −0.031 (8) |
| C17 | 0.089 (7) | 0.081 (7) | 0.096 (8) | 0.015 (6) | −0.030 (6) | −0.024 (6) |
| C18 | 0.090 (7) | 0.079 (6) | 0.053 (5) | −0.033 (6) | 0.033 (5) | −0.012 (5) |
| C19 | 0.121 (9) | 0.104 (8) | 0.080 (7) | −0.043 (7) | 0.035 (7) | −0.015 (6) |
| C20 | 0.130 (11) | 0.116 (10) | 0.096 (9) | −0.064 (9) | 0.033 (8) | −0.014 (7) |
| C21 | 0.149 (13) | 0.119 (11) | 0.102 (10) | −0.045 (10) | 0.023 (10) | 0.019 (8) |
| C22 | 0.151 (13) | 0.113 (10) | 0.103 (9) | −0.036 (9) | 0.006 (9) | 0.020 (8) |
| C23 | 0.146 (11) | 0.092 (8) | 0.072 (7) | −0.044 (8) | 0.006 (7) | 0.019 (6) |
| Sn1—O1 | 2.058 (4) | C10—H10 | 0.930 |
| Sn1—C18 | 2.112 (9) | C11—H11 | 0.930 |
| Sn1—C6 | 2.121 (9) | C12—C17 | 1.333 (11) |
| Sn1—C12 | 2.122 (7) | C12—C13 | 1.359 (11) |
| S1—C2 | 1.669 (18) | C13—C14 | 1.382 (12) |
| S1—C5 | 1.744 (15) | C13—H13 | 0.930 |
| O1—C1 | 1.279 (9) | C14—C15 | 1.307 (13) |
| O2—C1 | 1.197 (10) | C14—H14 | 0.930 |
| C1—C2 | 1.449 (17) | C15—C16 | 1.320 (14) |
| C2—C3 | 1.31 (2) | C15—H15 | 0.930 |
| C3—C4 | 1.385 (19) | C16—C17 | 1.386 (13) |
| C3—H3 | 0.930 | C16—H16 | 0.930 |
| C4—C5 | 1.41 (2) | C17—H17 | 0.930 |
| C4—H4 | 0.930 | C18—C23 | 1.382 (14) |
| C5—C1i | 1.560 (19) | C18—C19 | 1.392 (13) |
| C6—C7 | 1.361 (12) | C19—C20 | 1.428 (14) |
| C6—C11 | 1.386 (12) | C19—H19 | 0.930 |
| C7—C8 | 1.400 (13) | C20—C21 | 1.354 (16) |
| C7—H7 | 0.930 | C20—H20 | 0.930 |
| C8—C9 | 1.356 (15) | C21—C22 | 1.355 (16) |
| C8—H8 | 0.930 | C21—H21 | 0.930 |
| C9—C10 | 1.328 (15) | C22—C23 | 1.402 (14) |
| C9—H9 | 0.930 | C22—H22 | 0.930 |
| C10—C11 | 1.399 (13) | C23—H23 | 0.930 |
| O1—Sn1—C18 | 108.0 (3) | C6—C11—H11 | 120.0 |
| O1—Sn1—C6 | 96.1 (3) | C10—C11—H11 | 120.0 |
| C18—Sn1—C6 | 109.4 (4) | C17—C12—C13 | 117.1 (8) |
| O1—Sn1—C12 | 109.9 (2) | C17—C12—Sn1 | 123.0 (6) |
| C18—Sn1—C12 | 119.7 (3) | C13—C12—Sn1 | 119.9 (6) |
| C6—Sn1—C12 | 111.1 (3) | C12—C13—C14 | 120.9 (9) |
| C2—S1—C5 | 92.1 (7) | C12—C13—H13 | 119.6 |
| C1—O1—Sn1 | 110.3 (5) | C14—C13—H13 | 119.6 |
| O2—C1—O1 | 122.7 (8) | C15—C14—C13 | 121.4 (10) |
| O2—C1—C2 | 103.0 (11) | C15—C14—H14 | 119.3 |
| O1—C1—C2 | 134.0 (11) | C13—C14—H14 | 119.3 |
| C3—C2—C1 | 129.7 (16) | C14—C15—C16 | 118.2 (10) |
| C3—C2—S1 | 115.5 (12) | C14—C15—H15 | 120.9 |
| C1—C2—S1 | 114.7 (12) | C16—C15—H15 | 120.9 |
| C2—C3—C4 | 110.8 (15) | C15—C16—C17 | 122.2 (10) |
| C2—C3—H3 | 124.6 | C15—C16—H16 | 118.9 |
| C4—C3—H3 | 124.6 | C17—C16—H16 | 118.9 |
| C3—C4—C5 | 115.4 (15) | C12—C17—C16 | 120.2 (10) |
| C3—C4—H4 | 122.3 | C12—C17—H17 | 119.9 |
| C5—C4—H4 | 122.3 | C16—C17—H17 | 119.9 |
| C4—C5—S1 | 106.1 (13) | C23—C18—C19 | 118.9 (9) |
| C1i—C5—S1 | 122.5 (12) | C23—C18—Sn1 | 123.4 (7) |
| C7—C6—C11 | 118.9 (9) | C19—C18—Sn1 | 117.6 (8) |
| C7—C6—Sn1 | 123.0 (6) | C18—C19—C20 | 120.8 (12) |
| C11—C6—Sn1 | 117.9 (7) | C18—C19—H19 | 119.6 |
| C6—C7—C8 | 120.4 (10) | C20—C19—H19 | 119.6 |
| C6—C7—H7 | 119.8 | C21—C20—C19 | 116.0 (12) |
| C8—C7—H7 | 119.8 | C21—C20—H20 | 122.0 |
| C9—C8—C7 | 118.9 (11) | C19—C20—H20 | 122.0 |
| C9—C8—H8 | 120.6 | C20—C21—C22 | 125.8 (13) |
| C7—C8—H8 | 120.6 | C20—C21—H21 | 117.1 |
| C10—C9—C8 | 122.3 (11) | C22—C21—H21 | 117.1 |
| C10—C9—H9 | 118.8 | C21—C22—C23 | 117.1 (13) |
| C8—C9—H9 | 118.8 | C21—C22—H22 | 121.5 |
| C9—C10—C11 | 119.3 (12) | C23—C22—H22 | 121.5 |
| C9—C10—H10 | 120.4 | C18—C23—C22 | 121.2 (12) |
| C11—C10—H10 | 120.4 | C18—C23—H23 | 119.4 |
| C6—C11—C10 | 120.1 (11) | C22—C23—H23 | 119.4 |
| Symmetry codes: (i) −x+2, −y, −z+1. |
This project was supported by the Foundation of the Affiliated Ruikang Hospital of Guangxi Traditional Chinese Medical College (grant No. LG0901).
Holmes, R. R. (1989). Acc. Chem. Res. 22, 190–197.
Pellei, M., Alidori, S., Benetollo, F., Lobbia, G. G., Mancini, M., Lobbia, G. G. & Santini, C. (2008). J. Organomet. Chem. 693, 996–1004.
Prabusankar, G. & Murugavel, R. (2004). Organometallics, 23, 5644–5647.
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.
Siemens (1996). SMART and SAINT. Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA.
The structural diversity of organotin carboxylates is well recognized and a wide variety of coordination geometries have been reported (Holmes, 1989). It is generally believed that a combination of steric and electronic factors determine the specific structure adapted by a particular organotin carboxylate (Prabusankar & Murugavel, 2004). This is supported through the observation of monomeric, dimeric, tetrameric, oligomeric ladder, cyclic, and drum structures. Furthermore, it has been reported that the size of the carboxylic acids used and the stoichiometry of the reactants play an important role in the formation of solid-state frameworks.