supplementary materials
Di-![[mu]](/logos/entities/mu_rmgif.gif)
-hydroxido-bis[aquatrichloridotin(IV)] diethyl ether disolvate
The title compound, [Sn2Cl6(OH)2(H2O)2]·2C4H10O, consists of a centrosymmetric molecule and two additional solvent molecules and has an infinite two-dimensional network extending parallel to (101). The Sn atom is six-coordinate with a distorted octahedral geometry. Additional O-H
O hydrogen bonding leads to stabilization of the crystal structure.
The reaction was carried out under nitrogen atmosphere. 3-Thiophenemalonic acid
(1 mmol) and sodium ethoxide (2.2 mmol) were added to the solution of benzene
(30 ml) in a Schlenk flask and stirred for 0.5 h. Phenyltin trichloride (1 mmol) was then added to the reactor and the mixture was stirred for 12 h at
338 K.The resulting clear solution was evaporated under vacuum. The product
was crystallized from a mixture of diethylether/petroleum ether
(1:1).Unexpectedly,a dimeric complex, was isolated from the filtrate. (yield
52%; m.p. 446 K). Analysis calculated (%) for C4H13Cl3O3Sn (Mr =
334.18): C,46.72; H, 4.49; O, 9.57. found: C, 46.52; H, 4.55; O, 9.62.
H atoms were positioned geometrically, with O—H = 0.85 and 0.93 Å and C—H
= 0.96 and 0.97 Å for aromatic, methyl and methylene H atoms, respectively,
and constrained to ride on their parent atoms, with Uiso(H) =
xUeq(C,O) where x = 1.5 for methyl H and x = 1.2
for all other H atoms.
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).
Di-µ-hydroxido-bis[aquatrichloridotin(IV)] diethyl ether disolvate
top
Crystal data top
| [Sn2Cl6(OH)2(H2O)2]·2C4H10O | F(000) = 648 |
| Mr = 668.36 | Dx = 1.999 Mg m−3 |
| Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
| a = 10.1171 (15) Å | Cell parameters from 4261 reflections |
| b = 10.0212 (15) Å | θ = 2.4–28.2° |
| c = 11.2641 (18) Å | µ = 2.99 mm−1 |
| β = 103.536 (1)° | T = 298 K |
| V = 1110.3 (3) Å3 | Block, colorless |
| Z = 2 | 0.46 × 0.32 × 0.30 mm |
Data collection top
Siemens SMART CCD area-detector
diffractometer | 1909 independent reflections |
| Radiation source: fine-focus sealed tube | 1685 reflections with I > 2σ(I) |
| graphite | Rint = 0.027 |
| φ and ω scans | θmax = 25.0°, θmin = 2.4° |
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996) | h = −11→12 |
| Tmin = 0.340, Tmax = 0.468 | k = −11→11 |
| 5168 measured reflections | l = −7→13 |
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)] = 0.023 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.063 | H-atom parameters constrained |
| S = 0.84 | w = 1/[σ2(Fo2) + (0.0489P)2 + 0.9726P]
where P = (Fo2 + 2Fc2)/3 |
| 1909 reflections | (Δ/σ)max = 0.001 |
| 102 parameters | Δρmax = 1.05 e Å−3 |
| 0 restraints | Δρmin = −0.68 e Å−3 |
Crystal data top
| [Sn2Cl6(OH)2(H2O)2]·2C4H10O | V = 1110.3 (3) Å3 |
| Mr = 668.36 | Z = 2 |
| Monoclinic, P21/n | Mo Kα radiation |
| a = 10.1171 (15) Å | µ = 2.99 mm−1 |
| b = 10.0212 (15) Å | T = 298 K |
| c = 11.2641 (18) Å | 0.46 × 0.32 × 0.30 mm |
| β = 103.536 (1)° | |
Data collection top
Siemens SMART CCD area-detector
diffractometer | 1909 independent reflections |
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996) | 1685 reflections with I > 2σ(I) |
| Tmin = 0.340, Tmax = 0.468 | Rint = 0.027 |
| 5168 measured reflections | θmax = 25.0° |
Refinement top
| R[F2 > 2σ(F2)] = 0.023 | H-atom parameters constrained |
| wR(F2) = 0.063 | Δρmax = 1.05 e Å−3 |
| S = 0.84 | Δρmin = −0.68 e Å−3 |
| 1909 reflections | Absolute structure: ? |
| 102 parameters | Flack parameter: ? |
| 0 restraints | Rogers parameter: ? |
Special details top
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 (Å2) top| | x | y | z | Uiso*/Ueq | |
| Sn1 | 0.53184 (2) | 0.46950 (2) | 0.361848 (19) | 0.02338 (10) | |
| Cl1 | 0.66543 (10) | 0.58991 (10) | 0.25532 (9) | 0.0421 (2) | |
| Cl2 | 0.70089 (10) | 0.30829 (10) | 0.44565 (9) | 0.0434 (2) | |
| Cl3 | 0.41097 (10) | 0.33403 (10) | 0.20324 (9) | 0.0470 (2) | |
| O1 | 0.4121 (2) | 0.4148 (2) | 0.48000 (19) | 0.0261 (5) | |
| H1 | 0.3447 | 0.3497 | 0.4651 | 0.031* | |
| O2 | 0.3762 (3) | 0.6222 (3) | 0.3036 (2) | 0.0402 (6) | |
| H2D | 0.3543 | 0.6636 | 0.2360 | 0.048* | |
| H2E | 0.3425 | 0.6644 | 0.3549 | 0.048* | |
| O3 | 0.8141 (2) | 0.7541 (2) | 0.5809 (2) | 0.0367 (6) | |
| C1 | 0.7894 (5) | 0.8615 (4) | 0.4926 (4) | 0.0518 (11) | |
| H1A | 0.7798 | 0.8260 | 0.4109 | 0.062* | |
| H1B | 0.8653 | 0.9233 | 0.5091 | 0.062* | |
| C2 | 0.6621 (6) | 0.9321 (5) | 0.5016 (5) | 0.0660 (14) | |
| H2A | 0.5884 | 0.8694 | 0.4895 | 0.099* | |
| H2B | 0.6415 | 1.0003 | 0.4402 | 0.099* | |
| H2C | 0.6746 | 0.9720 | 0.5810 | 0.099* | |
| C3 | 0.9279 (4) | 0.6715 (5) | 0.5690 (4) | 0.0537 (12) | |
| H3A | 1.0075 | 0.7267 | 0.5730 | 0.064* | |
| H3B | 0.9066 | 0.6263 | 0.4907 | 0.064* | |
| C4 | 0.9561 (5) | 0.5717 (6) | 0.6692 (5) | 0.0720 (15) | |
| H4A | 0.9715 | 0.6168 | 0.7464 | 0.108* | |
| H4B | 1.0355 | 0.5210 | 0.6650 | 0.108* | |
| H4C | 0.8797 | 0.5128 | 0.6610 | 0.108* | |
Atomic displacement parameters (Å2) top| | U11 | U22 | U33 | U12 | U13 | U23 |
| Sn1 | 0.02419 (15) | 0.02519 (15) | 0.02104 (15) | 0.00006 (8) | 0.00583 (10) | −0.00080 (8) |
| Cl1 | 0.0446 (5) | 0.0476 (5) | 0.0398 (5) | −0.0069 (4) | 0.0216 (4) | 0.0052 (4) |
| Cl2 | 0.0438 (5) | 0.0454 (5) | 0.0423 (5) | 0.0216 (4) | 0.0127 (4) | 0.0053 (4) |
| Cl3 | 0.0515 (6) | 0.0523 (6) | 0.0348 (5) | −0.0129 (5) | 0.0053 (4) | −0.0163 (4) |
| O1 | 0.0273 (12) | 0.0281 (12) | 0.0234 (12) | −0.0074 (10) | 0.0069 (9) | −0.0028 (9) |
| O2 | 0.0460 (15) | 0.0483 (15) | 0.0274 (13) | 0.0203 (12) | 0.0108 (11) | 0.0104 (11) |
| O3 | 0.0334 (13) | 0.0435 (14) | 0.0355 (14) | −0.0047 (11) | 0.0125 (11) | −0.0029 (11) |
| C1 | 0.071 (3) | 0.047 (2) | 0.037 (2) | −0.023 (2) | 0.013 (2) | −0.0013 (19) |
| C2 | 0.076 (4) | 0.048 (2) | 0.063 (3) | 0.002 (2) | −0.008 (3) | 0.011 (2) |
| C3 | 0.034 (2) | 0.074 (3) | 0.056 (3) | −0.002 (2) | 0.015 (2) | −0.025 (2) |
| C4 | 0.056 (3) | 0.064 (3) | 0.088 (4) | 0.020 (3) | 0.003 (3) | −0.012 (3) |
Geometric parameters (Å, °) top
| Sn1—O1 | 2.072 (2) | C1—C2 | 1.493 (7) |
| Sn1—O1i | 2.090 (2) | C1—H1A | 0.9700 |
| Sn1—O2 | 2.183 (2) | C1—H1B | 0.9700 |
| Sn1—Cl1 | 2.3413 (9) | C2—H2A | 0.9600 |
| Sn1—Cl3 | 2.3469 (9) | C2—H2B | 0.9600 |
| Sn1—Cl2 | 2.3813 (9) | C2—H2C | 0.9600 |
| O1—Sn1i | 2.090 (2) | C3—C4 | 1.485 (7) |
| O1—H1 | 0.9300 | C3—H3A | 0.9700 |
| O2—H2D | 0.8500 | C3—H3B | 0.9700 |
| O2—H2E | 0.8500 | C4—H4A | 0.9600 |
| O3—C1 | 1.447 (5) | C4—H4B | 0.9600 |
| O3—C3 | 1.449 (5) | C4—H4C | 0.9600 |
| | | |
| O1—Sn1—O1i | 71.48 (9) | O3—C1—H1A | 110.0 |
| O1—Sn1—O2 | 83.66 (9) | C2—C1—H1A | 110.0 |
| O1i—Sn1—O2 | 84.28 (9) | O3—C1—H1B | 110.0 |
| O1—Sn1—Cl1 | 163.72 (7) | C2—C1—H1B | 110.0 |
| O1i—Sn1—Cl1 | 94.40 (6) | H1A—C1—H1B | 108.4 |
| O2—Sn1—Cl1 | 86.96 (7) | C1—C2—H2A | 109.5 |
| O1—Sn1—Cl3 | 93.27 (6) | C1—C2—H2B | 109.5 |
| O1i—Sn1—Cl3 | 163.56 (6) | H2A—C2—H2B | 109.5 |
| O2—Sn1—Cl3 | 88.04 (8) | C1—C2—H2C | 109.5 |
| Cl1—Sn1—Cl3 | 99.69 (4) | H2A—C2—H2C | 109.5 |
| O1—Sn1—Cl2 | 92.27 (7) | H2B—C2—H2C | 109.5 |
| O1i—Sn1—Cl2 | 90.68 (7) | O3—C3—C4 | 109.3 (4) |
| O2—Sn1—Cl2 | 174.32 (7) | O3—C3—H3A | 109.8 |
| Cl1—Sn1—Cl2 | 96.06 (4) | C4—C3—H3A | 109.8 |
| Cl3—Sn1—Cl2 | 96.16 (4) | O3—C3—H3B | 109.8 |
| Sn1—O1—Sn1i | 108.52 (9) | C4—C3—H3B | 109.8 |
| Sn1—O1—H1 | 125.7 | H3A—C3—H3B | 108.3 |
| Sn1i—O1—H1 | 125.7 | C3—C4—H4A | 109.5 |
| Sn1—O2—H2D | 129.1 | C3—C4—H4B | 109.5 |
| Sn1—O2—H2E | 121.4 | H4A—C4—H4B | 109.5 |
| H2D—O2—H2E | 107.7 | C3—C4—H4C | 109.5 |
| C1—O3—C3 | 112.0 (3) | H4A—C4—H4C | 109.5 |
| O3—C1—C2 | 108.6 (3) | H4B—C4—H4C | 109.5 |
| Symmetry codes: (i) −x+1, −y+1, −z+1. |
Hydrogen-bond geometry (Å, °) top
| D—H···A | D—H | H···A | D···A | D—H···A |
| O1—H1···O3i | 0.93 | 1.88 | 2.799 (3) | 169. |
| O2—H2D···O3ii | 0.85 | 1.89 | 2.736 (3) | 176. |
| O2—H2E···Cl2i | 0.85 | 2.40 | 3.179 (3) | 152. |
| Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) x−1/2, −y+3/2, z−1/2. |
Table 1
Hydrogen-bond geometry (Å, °) top
| D—H···A | D—H | H···A | D···A | D—H···A |
| O1—H1···O3i | 0.93 | 1.88 | 2.799 (3) | 169. |
| O2—H2D···O3ii | 0.85 | 1.89 | 2.736 (3) | 176. |
| O2—H2E···Cl2i | 0.85 | 2.40 | 3.179 (3) | 152. |
| Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) x−1/2, −y+3/2, z−1/2. |
We thank the National Natural Science Foundation of China (20771053) for
financial support.
Janas, Z., Sobota, P. & Lis, T. (1991). J. Chem. Soc. Dalton Trans. pp. 2429–2434.
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.
![[Figure 1]](./sg2266fig1thm.gif)
![[Figure 2]](./sg2266fig2thm.gif)
We have synthesized the title compound unexpectedly, (I), and present its crystal structure here. The title compound consist of a centrosymmetric dimer (Fig. 1) in which the tin atoms have a distorted octahedral arrangement formed by three chlorine atoms, two hydroxy oxygen bridges and one water molecule. A further two water molecules are hydrogen-bonded to the hydroxyl oxygen atoms of the µ-OH bridges. The Sn—O distances in (I) (Table 1), are similar to those in related organotin carboxylates. The Sn—Cl bond lengths and the interbond angles lie within the ranges observed for other related complexes. The Sn1—O1 (2.072 (2) Å) and Sn1—O2 distance (2.183 (2) Å), (Table 1), are close to those reported for organotin carboxylates (Janas et al., 1991).