Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807049185/at2421sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807049185/at2421Isup2.hkl |
CCDC reference: 667187
A solution of aqueous HCl (38%) was added at ambient temperature to a solution PhSnCl3 (50 mg) in 0.5 ml C6D6. Colourless crystals of the title compound were grown by storing this solution at ambient temperature for several days.
H atoms bonded to C and those of the solvent water molecule were refined with fixed individual displacement parameters [Uiso(H) = 1.2 Ueq(C,O)] using a riding model with C—H = 0.93Å and O—H = 0.88 Å. The H atoms of the hydroxyl O atoms and water O atoms bonded to Sn could not be located and were omitted from refinement.
Recently we have reported the synthesis and structure of the SnCl4 complex with dimethylsulfide (Ruth et al., 2005) and of the adduct of Me3SnCl with Me3SnOH and H2O (Lerner et al., 2005) (Me = CH3). The structure of Me3SnCl.Me3SnOH.H2O features an array of Me3Sn units connected alternately by bridging Cl and OH ligands (Lerner et al., 2005) whereas the structure of the dimethylsulfide complex with tin tetrachloride consists of discrete [(SnCl4).(SMe2)2] molecules (Ruth et al., 2005). It is interesting to note that Me3SnCl.Me3SnOH.H2O represents an intermediate in Me3SnCl hydrolysis. Herein we report the X-ray crystal structure analysis of the HOSnCl3 complex with water which features a dimer in solid state. The synthesis of [HOSnCl3.H2O]2 was achieved by treatment of PhSnCl3 with an aqueous HCl solution as indicated in the equation below.
The asymmetric unit of the title compound contains one bis(µ-Hydroxo)-bis(aqua-trichloro-tin(iv)) molecule, a water molecule and half a benzene molecule. The latter is located on a centre of inversion. The Sn atoms are in an octahedral environment each coordinated by three Cl and one water and two briding hydroxyl ligands. Two Cl atom and the hydroxyl groups are in the equatorial plane, whereas the third Cl atom and the water molecules are located in the axial positions.
For related literature, see: Lerner et al. (2005); Ruth et al. (2005).
Data collection: X-AREA (Stoe & Cie, 2001); cell refinement: X-AREA (Stoe & Cie, 2001); data reduction: X-AREA (Stoe & Cie, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP in SHELXTL-Plus (Sheldrick, 1991); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).
[Sn2Cl6(OH)2(H2O)2]·0.5C6H6·H2O | Z = 2 |
Mr = 577.20 | F(000) = 542 |
Triclinic, P1 | Dx = 2.491 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 6.3682 (7) Å | Cell parameters from 10632 reflections |
b = 10.8299 (12) Å | θ = 3.1–25.7° |
c = 11.8619 (13) Å | µ = 4.29 mm−1 |
α = 74.180 (9)° | T = 173 K |
β = 78.048 (9)° | Block, colourless |
γ = 88.588 (9)° | 0.22 × 0.21 × 0.19 mm |
V = 769.59 (15) Å3 |
Stoe IPDSII two-circle diffractometer | 2887 independent reflections |
Radiation source: fine-focus sealed tube | 2382 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.079 |
ω scans | θmax = 25.6°, θmin = 3.0° |
Absorption correction: multi-scan (MULABS; Spek, 2003; Blessing, 1995) | h = −7→7 |
Tmin = 0.452, Tmax = 0.497 | k = −13→13 |
11598 measured reflections | l = −14→14 |
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)] = 0.040 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.107 | H-atom parameters constrained |
S = 1.04 | w = 1/[σ2(Fo2) + (0.0647P)2 + 0.5227P] where P = (Fo2 + 2Fc2)/3 |
2887 reflections | (Δ/σ)max < 0.001 |
145 parameters | Δρmax = 1.07 e Å−3 |
0 restraints | Δρmin = −1.56 e Å−3 |
[Sn2Cl6(OH)2(H2O)2]·0.5C6H6·H2O | γ = 88.588 (9)° |
Mr = 577.20 | V = 769.59 (15) Å3 |
Triclinic, P1 | Z = 2 |
a = 6.3682 (7) Å | Mo Kα radiation |
b = 10.8299 (12) Å | µ = 4.29 mm−1 |
c = 11.8619 (13) Å | T = 173 K |
α = 74.180 (9)° | 0.22 × 0.21 × 0.19 mm |
β = 78.048 (9)° |
Stoe IPDSII two-circle diffractometer | 2887 independent reflections |
Absorption correction: multi-scan (MULABS; Spek, 2003; Blessing, 1995) | 2382 reflections with I > 2σ(I) |
Tmin = 0.452, Tmax = 0.497 | Rint = 0.079 |
11598 measured reflections |
R[F2 > 2σ(F2)] = 0.040 | 0 restraints |
wR(F2) = 0.107 | H-atom parameters constrained |
S = 1.04 | Δρmax = 1.07 e Å−3 |
2887 reflections | Δρmin = −1.56 e Å−3 |
145 parameters |
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 | ||
Sn1 | 0.18222 (6) | 0.78127 (4) | 0.63209 (3) | 0.01735 (15) | |
Sn2 | 0.01184 (6) | 0.47034 (4) | 0.75109 (3) | 0.01833 (15) | |
Cl1 | 0.0470 (3) | 0.96136 (15) | 0.69735 (14) | 0.0272 (4) | |
Cl2 | 0.3898 (3) | 0.87397 (17) | 0.44209 (14) | 0.0298 (4) | |
Cl3 | 0.4706 (2) | 0.75927 (16) | 0.73589 (14) | 0.0248 (3) | |
Cl4 | 0.1403 (3) | 0.28184 (17) | 0.70417 (16) | 0.0337 (4) | |
Cl5 | −0.2737 (3) | 0.48558 (17) | 0.64389 (14) | 0.0270 (4) | |
Cl6 | −0.2008 (3) | 0.38714 (17) | 0.94412 (14) | 0.0302 (4) | |
O1 | −0.0872 (7) | 0.7947 (5) | 0.5432 (4) | 0.0260 (10) | |
O2 | 0.2802 (7) | 0.4640 (5) | 0.8379 (4) | 0.0257 (10) | |
O3 | 0.2191 (7) | 0.5961 (4) | 0.6082 (4) | 0.0208 (9) | |
O4 | −0.0274 (7) | 0.6559 (4) | 0.7707 (4) | 0.0190 (9) | |
O5 | 0.2830 (8) | 0.2681 (5) | 1.0377 (4) | 0.0278 (11) | |
H5A | 0.2825 | 0.3284 | 0.9758 | 0.033* | |
H5B | 0.2068 | 0.2905 | 1.0950 | 0.033* | |
C1 | 0.6070 (17) | 0.0702 (8) | 0.8914 (8) | 0.053 (3) | |
H1 | 0.6824 | 0.1211 | 0.8159 | 0.063* | |
C2 | 0.4107 (18) | 0.0216 (8) | 0.9002 (9) | 0.050 (2) | |
H2 | 0.3496 | 0.0348 | 0.8315 | 0.061* | |
C3 | 0.2988 (14) | −0.0484 (9) | 1.0120 (11) | 0.054 (3) | |
H3 | 0.1573 | −0.0809 | 1.0210 | 0.065* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Sn1 | 0.0166 (2) | 0.0156 (2) | 0.0180 (2) | 0.00007 (16) | −0.00268 (16) | −0.00222 (17) |
Sn2 | 0.0197 (2) | 0.0152 (2) | 0.0189 (2) | −0.00060 (16) | −0.00191 (17) | −0.00422 (17) |
Cl1 | 0.0309 (8) | 0.0194 (8) | 0.0307 (8) | 0.0043 (6) | −0.0049 (7) | −0.0075 (6) |
Cl2 | 0.0268 (8) | 0.0334 (9) | 0.0215 (7) | −0.0035 (7) | 0.0020 (6) | 0.0001 (7) |
Cl3 | 0.0207 (8) | 0.0288 (8) | 0.0256 (7) | 0.0002 (6) | −0.0085 (6) | −0.0061 (6) |
Cl4 | 0.0428 (10) | 0.0222 (9) | 0.0397 (9) | 0.0073 (7) | −0.0092 (8) | −0.0145 (7) |
Cl5 | 0.0219 (8) | 0.0339 (9) | 0.0287 (8) | 0.0006 (6) | −0.0057 (6) | −0.0139 (7) |
Cl6 | 0.0320 (9) | 0.0292 (9) | 0.0229 (7) | −0.0082 (7) | 0.0043 (6) | −0.0033 (7) |
O1 | 0.024 (2) | 0.031 (3) | 0.024 (2) | 0.0016 (19) | −0.0092 (19) | −0.005 (2) |
O2 | 0.024 (2) | 0.028 (3) | 0.025 (2) | 0.0018 (19) | −0.0066 (19) | −0.006 (2) |
O3 | 0.022 (2) | 0.019 (2) | 0.021 (2) | −0.0006 (17) | 0.0006 (17) | −0.0085 (17) |
O4 | 0.019 (2) | 0.016 (2) | 0.021 (2) | 0.0000 (17) | −0.0017 (17) | −0.0039 (17) |
O5 | 0.034 (3) | 0.029 (3) | 0.017 (2) | 0.007 (2) | −0.0055 (19) | −0.0013 (19) |
C1 | 0.074 (7) | 0.029 (4) | 0.041 (5) | 0.000 (4) | 0.021 (5) | −0.011 (4) |
C2 | 0.080 (7) | 0.031 (5) | 0.056 (5) | 0.018 (4) | −0.045 (5) | −0.016 (4) |
C3 | 0.030 (4) | 0.039 (5) | 0.100 (8) | 0.004 (4) | −0.021 (5) | −0.025 (5) |
Sn1—O4 | 2.072 (4) | Sn2—Cl5 | 2.4038 (17) |
Sn1—O3 | 2.102 (4) | O5—H5A | 0.8398 |
Sn1—O1 | 2.175 (5) | O5—H5B | 0.8391 |
Sn1—Cl2 | 2.3307 (16) | C1—C2 | 1.341 (14) |
Sn1—Cl1 | 2.3685 (16) | C1—C3i | 1.364 (15) |
Sn1—Cl3 | 2.3876 (16) | C1—H1 | 0.9500 |
Sn2—O4 | 2.088 (4) | C2—C3 | 1.388 (15) |
Sn2—O3 | 2.091 (4) | C2—H2 | 0.9500 |
Sn2—O2 | 2.161 (5) | C3—C1i | 1.364 (15) |
Sn2—Cl4 | 2.3441 (17) | C3—H3 | 0.9500 |
Sn2—Cl6 | 2.3537 (16) | ||
O4—Sn1—O3 | 71.71 (16) | O4—Sn2—Cl6 | 89.85 (12) |
O4—Sn1—O1 | 82.67 (17) | O3—Sn2—Cl6 | 159.25 (13) |
O3—Sn1—O1 | 86.18 (18) | O2—Sn2—Cl6 | 86.68 (13) |
O4—Sn1—Cl2 | 160.56 (13) | Cl4—Sn2—Cl6 | 101.36 (7) |
O3—Sn1—Cl2 | 91.84 (12) | O4—Sn2—Cl5 | 93.53 (13) |
O1—Sn1—Cl2 | 86.04 (13) | O3—Sn2—Cl5 | 93.81 (13) |
O4—Sn1—Cl1 | 92.10 (12) | O2—Sn2—Cl5 | 176.57 (13) |
O3—Sn1—Cl1 | 163.20 (12) | Cl4—Sn2—Cl5 | 93.52 (6) |
O1—Sn1—Cl1 | 87.29 (14) | Cl6—Sn2—Cl5 | 96.63 (6) |
Cl2—Sn1—Cl1 | 103.15 (6) | Sn2—O3—Sn1 | 107.71 (18) |
O4—Sn1—Cl3 | 95.04 (13) | Sn1—O4—Sn2 | 108.94 (18) |
O3—Sn1—Cl3 | 92.68 (13) | H5A—O5—H5B | 106.6 |
O1—Sn1—Cl3 | 177.66 (13) | C2—C1—C3i | 121.6 (9) |
Cl2—Sn1—Cl3 | 96.05 (6) | C2—C1—H1 | 119.2 |
Cl1—Sn1—Cl3 | 93.25 (6) | C3i—C1—H1 | 119.2 |
O4—Sn2—O3 | 71.60 (16) | C1—C2—C3 | 118.6 (8) |
O4—Sn2—O2 | 85.57 (18) | C1—C2—H2 | 120.7 |
O3—Sn2—O2 | 82.77 (18) | C3—C2—H2 | 120.7 |
O4—Sn2—Cl4 | 165.97 (13) | C1i—C3—C2 | 119.7 (8) |
O3—Sn2—Cl4 | 95.83 (13) | C1i—C3—H3 | 120.2 |
O2—Sn2—Cl4 | 86.68 (14) | C2—C3—H3 | 120.2 |
O4—Sn2—O3—Sn1 | 1.34 (18) | O1—Sn1—O4—Sn2 | 89.7 (2) |
O2—Sn2—O3—Sn1 | −86.4 (2) | Cl2—Sn1—O4—Sn2 | 34.8 (5) |
Cl4—Sn2—O3—Sn1 | −172.27 (16) | Cl1—Sn1—O4—Sn2 | 176.74 (17) |
Cl6—Sn2—O3—Sn1 | −26.3 (5) | Cl3—Sn1—O4—Sn2 | −89.80 (17) |
Cl5—Sn2—O3—Sn1 | 93.79 (17) | O3—Sn2—O4—Sn1 | −1.36 (18) |
O4—Sn1—O3—Sn2 | −1.35 (18) | O2—Sn2—O4—Sn1 | 82.5 (2) |
O1—Sn1—O3—Sn2 | −84.9 (2) | Cl4—Sn2—O4—Sn1 | 25.8 (7) |
Cl2—Sn1—O3—Sn2 | −170.78 (17) | Cl6—Sn2—O4—Sn1 | 169.16 (17) |
Cl1—Sn1—O3—Sn2 | −17.5 (6) | Cl5—Sn2—O4—Sn1 | −94.21 (17) |
Cl3—Sn1—O3—Sn2 | 93.08 (18) | C3i—C1—C2—C3 | 2.5 (15) |
O3—Sn1—O4—Sn2 | 1.36 (18) | C1—C2—C3—C1i | −2.5 (15) |
Symmetry code: (i) −x+1, −y, −z+2. |
D—H···A | D—H | H···A | D···A | D—H···A |
O5—H5A···O2 | 0.84 | 1.88 | 2.719 (6) | 180 |
O5—H5B···O4ii | 0.84 | 1.97 | 2.813 (6) | 180 |
Symmetry code: (ii) −x, −y+1, −z+2. |
Experimental details
Crystal data | |
Chemical formula | [Sn2Cl6(OH)2(H2O)2]·0.5C6H6·H2O |
Mr | 577.20 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 173 |
a, b, c (Å) | 6.3682 (7), 10.8299 (12), 11.8619 (13) |
α, β, γ (°) | 74.180 (9), 78.048 (9), 88.588 (9) |
V (Å3) | 769.59 (15) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 4.29 |
Crystal size (mm) | 0.22 × 0.21 × 0.19 |
Data collection | |
Diffractometer | Stoe IPDSII two-circle |
Absorption correction | Multi-scan (MULABS; Spek, 2003; Blessing, 1995) |
Tmin, Tmax | 0.452, 0.497 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 11598, 2887, 2382 |
Rint | 0.079 |
(sin θ/λ)max (Å−1) | 0.608 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.040, 0.107, 1.04 |
No. of reflections | 2887 |
No. of parameters | 145 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 1.07, −1.56 |
Computer programs: X-AREA (Stoe & Cie, 2001), SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), XP in SHELXTL-Plus (Sheldrick, 1991).
D—H···A | D—H | H···A | D···A | D—H···A |
O5—H5A···O2 | 0.84 | 1.88 | 2.719 (6) | 179.6 |
O5—H5B···O4i | 0.84 | 1.97 | 2.813 (6) | 179.7 |
Symmetry code: (i) −x, −y+1, −z+2. |
Recently we have reported the synthesis and structure of the SnCl4 complex with dimethylsulfide (Ruth et al., 2005) and of the adduct of Me3SnCl with Me3SnOH and H2O (Lerner et al., 2005) (Me = CH3). The structure of Me3SnCl.Me3SnOH.H2O features an array of Me3Sn units connected alternately by bridging Cl and OH ligands (Lerner et al., 2005) whereas the structure of the dimethylsulfide complex with tin tetrachloride consists of discrete [(SnCl4).(SMe2)2] molecules (Ruth et al., 2005). It is interesting to note that Me3SnCl.Me3SnOH.H2O represents an intermediate in Me3SnCl hydrolysis. Herein we report the X-ray crystal structure analysis of the HOSnCl3 complex with water which features a dimer in solid state. The synthesis of [HOSnCl3.H2O]2 was achieved by treatment of PhSnCl3 with an aqueous HCl solution as indicated in the equation below.
The asymmetric unit of the title compound contains one bis(µ-Hydroxo)-bis(aqua-trichloro-tin(iv)) molecule, a water molecule and half a benzene molecule. The latter is located on a centre of inversion. The Sn atoms are in an octahedral environment each coordinated by three Cl and one water and two briding hydroxyl ligands. Two Cl atom and the hydroxyl groups are in the equatorial plane, whereas the third Cl atom and the water molecules are located in the axial positions.