Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536802013557/wn6108sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536802013557/wn6108Isup2.hkl |
CCDC reference: 197449
The title adduct was synthesized from the reaction of equimolar quantities of dimethylphenyltin chloride (0.20 g, 0.75 mmol) and 18-crown-6 (0.20 g, 0.75 mmol) in chloroform. The reagents were dissolved in the solvent and crystals of the 2:1 complex (m.p. 344–349 K) separated when the solvent was allowed to evaporate. IR: 3440 (H2O), 2880 (C—H), 1099 (C—O—C), 550 (Sn—C, asymmetric), 520 (Sn—C, symmetric) cm−1. 1H NMR in CDCl3: 0.90 (CH3, 12H), 2.45 (H2O, 4H), 3.65 (CH2, 24H), 7.46–7.60 (C6H5, 10H) p.p.m. 2J|119–1H| = 83 Hz. Dimethylphenyltin chloride was synthesizd by the cleavage of dimethyldiphenyltin with hydrogen chloride in a methanol–carbon tetrachloride mixture at 283 K, and was purified by distillation at 363 K/1 Torr (Simmones, 1977).
The minor disorder in the 18-crown-6 ring was treated by constraining the C—O distances to be approximated equal by a SADI 0.01 instruction in SHELXL97; the C—C distances were also constrained by another SADI 0.01 instruction. The phenyl ring was refined as a rigid hexagon. The carbon-bound H atoms were positioned geometrically, and were allowed to ride on the parent C atoms, with U(H) = 1.2Ueq(C). The water H atoms were located and their positions refined, subject to O—H = 0.85±0.01, H···H = 1.39±0.01 Å, and Uiso(H) = 1.2Ueq(O). The final difference map had a large peak/hole at about 1 Å from atom Sn1.
Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: SHELXL97.
Fig. 1. ORTEPII (Johnson, 1976) plot of the title dinuclear complex, with displacement ellipsoids drawn at the 50% probability level. H atoms are drawn as spheres of arbitrary radii. |
[SnCl(CH3)2(C6H5)(H2O)]2·C12H24O8 | F(000) = 832 |
Mr = 822.96 | Dx = 1.541 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
a = 9.6395 (6) Å | Cell parameters from 4938 reflections |
b = 19.472 (1) Å | θ = 2.4–26.5° |
c = 10.5110 (7) Å | µ = 1.60 mm−1 |
β = 116.015 (1)° | T = 168 K |
V = 1773.0 (2) Å3 | Block, colorless |
Z = 2 | 0.50 × 0.48 × 0.37 mm |
Siemens CCD area-detector diffractometer | 3392 independent reflections |
Radiation source: fine-focus sealed tube | 2495 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.104 |
ω scans | θmax = 26.5°, θmin = 2.4° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −10→11 |
Tmin = 0.502, Tmax = 0.589 | k = −24→24 |
9926 measured reflections | l = −10→13 |
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)] = 0.060 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.107 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.95 | w = 1/[σ2(Fo2) + (0.0348P)2] where P = (Fo2 + 2Fc2)/3 |
3392 reflections | (Δ/σ)max = 0.001 |
177 parameters | Δρmax = 2.62 e Å−3 |
21 restraints | Δρmin = −1.76 e Å−3 |
[SnCl(CH3)2(C6H5)(H2O)]2·C12H24O8 | V = 1773.0 (2) Å3 |
Mr = 822.96 | Z = 2 |
Monoclinic, P21/n | Mo Kα radiation |
a = 9.6395 (6) Å | µ = 1.60 mm−1 |
b = 19.472 (1) Å | T = 168 K |
c = 10.5110 (7) Å | 0.50 × 0.48 × 0.37 mm |
β = 116.015 (1)° |
Siemens CCD area-detector diffractometer | 3392 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 2495 reflections with I > 2σ(I) |
Tmin = 0.502, Tmax = 0.589 | Rint = 0.104 |
9926 measured reflections |
R[F2 > 2σ(F2)] = 0.060 | 21 restraints |
wR(F2) = 0.107 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.95 | Δρmax = 2.62 e Å−3 |
3392 reflections | Δρmin = −1.76 e Å−3 |
177 parameters |
x | y | z | Uiso*/Ueq | ||
Sn1 | 0.36801 (5) | 0.11313 (2) | 0.25316 (5) | 0.0261 (2) | |
Cl1 | 0.6100 (2) | 0.18146 (8) | 0.3566 (2) | 0.0379 (4) | |
O1 | 0.1800 (5) | −0.1056 (2) | 0.1746 (4) | 0.035 (1) | |
O2 | −0.0522 (5) | −0.0498 (2) | 0.2397 (4) | 0.038 (1) | |
O3 | −0.1683 (5) | 0.0761 (2) | 0.0958 (5) | 0.036 (1) | |
O1w | 0.1378 (5) | 0.0411 (2) | 0.1432 (5) | 0.036 (1) | |
C1 | 0.2951 (8) | 0.1546 (3) | 0.0483 (7) | 0.045 (2) | |
C2 | 0.4793 (7) | 0.0165 (3) | 0.3101 (7) | 0.034 (2) | |
C3 | 0.2772 (5) | 0.1511 (2) | 0.3949 (4) | 0.028 (2) | |
C4 | 0.1233 (4) | 0.1702 (2) | 0.3452 (4) | 0.032 (2) | |
C5 | 0.0676 (4) | 0.1933 (2) | 0.4392 (5) | 0.043 (2) | |
C6 | 0.1659 (6) | 0.1973 (2) | 0.5830 (5) | 0.048 (2) | |
C7 | 0.3198 (6) | 0.1783 (2) | 0.6327 (3) | 0.050 (2) | |
C8 | 0.3755 (4) | 0.1552 (2) | 0.5387 (4) | 0.041 (2) | |
C9 | 0.1272 (8) | −0.1370 (3) | 0.2686 (7) | 0.044 (2) | |
C10 | 0.0834 (8) | −0.0817 (3) | 0.3427 (7) | 0.044 (2) | |
C11 | −0.1049 (8) | 0.0044 (3) | 0.2975 (7) | 0.044 (2) | |
C12 | −0.2286 (8) | 0.0426 (3) | 0.1818 (7) | 0.050 (2) | |
C13 | −0.2773 (8) | 0.1215 (3) | −0.0037 (7) | 0.048 (2) | |
C14 | −0.2066 (9) | 0.1554 (3) | −0.0883 (7) | 0.047 (2) | |
H1w1 | 0.148 (6) | −0.001 (1) | 0.125 (7) | 0.043* | |
H1w2 | 0.047 (3) | 0.048 (2) | 0.133 (7) | 0.043* | |
H1a | 0.3803 | 0.1525 | 0.0213 | 0.067* | |
H1b | 0.2639 | 0.2025 | 0.0479 | 0.067* | |
H1c | 0.2075 | 0.1280 | −0.0193 | 0.067* | |
H2a | 0.4103 | −0.0166 | 0.3235 | 0.051* | |
H2b | 0.5741 | 0.0210 | 0.3985 | 0.051* | |
H2c | 0.5051 | 0.0003 | 0.2348 | 0.051* | |
H4 | 0.0561 | 0.1674 | 0.2469 | 0.039* | |
H5 | −0.0376 | 0.2063 | 0.4052 | 0.052* | |
H6 | 0.1279 | 0.2131 | 0.6472 | 0.058* | |
H7 | 0.3870 | 0.1811 | 0.7310 | 0.060* | |
H8 | 0.4807 | 0.1421 | 0.5727 | 0.049* | |
H9a | 0.2101 | −0.1658 | 0.3387 | 0.052* | |
H9b | 0.0370 | −0.1666 | 0.2145 | 0.052* | |
H10a | 0.0631 | −0.1016 | 0.4196 | 0.053* | |
H10b | 0.1678 | −0.0477 | 0.3844 | 0.053* | |
H11a | −0.0183 | 0.0358 | 0.3522 | 0.052* | |
H11b | −0.1448 | −0.0145 | 0.3625 | 0.052* | |
H12a | −0.3117 | 0.0105 | 0.1230 | 0.060* | |
H12b | −0.2734 | 0.0772 | 0.2221 | 0.060* | |
H13a | −0.3088 | 0.1567 | 0.0465 | 0.057* | |
H13b | −0.3704 | 0.0956 | −0.0673 | 0.057* | |
H14a | −0.2765 | 0.1916 | −0.1488 | 0.057* | |
H14b | −0.1077 | 0.1772 | −0.0240 | 0.057* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Sn1 | 0.0353 (3) | 0.0215 (2) | 0.0182 (2) | −0.0007 (2) | 0.0086 (2) | −0.0004 (2) |
Cl1 | 0.041 (1) | 0.0354 (9) | 0.0283 (10) | −0.0104 (7) | 0.0071 (9) | −0.0027 (7) |
O1 | 0.047 (3) | 0.020 (2) | 0.032 (3) | −0.001 (2) | 0.011 (3) | 0.002 (2) |
O2 | 0.048 (3) | 0.041 (3) | 0.018 (3) | −0.005 (2) | 0.010 (3) | −0.003 (2) |
O3 | 0.032 (3) | 0.040 (3) | 0.031 (3) | −0.002 (2) | 0.010 (3) | −0.008 (2) |
O1w | 0.042 (3) | 0.026 (2) | 0.043 (3) | −0.003 (2) | 0.020 (3) | −0.006 (2) |
C1 | 0.049 (5) | 0.042 (4) | 0.020 (4) | −0.011 (3) | −0.007 (4) | 0.006 (3) |
C2 | 0.032 (4) | 0.028 (3) | 0.029 (4) | 0.002 (3) | 0.003 (4) | 0.004 (3) |
C3 | 0.037 (4) | 0.019 (3) | 0.026 (4) | −0.002 (3) | 0.011 (4) | −0.002 (3) |
C4 | 0.037 (4) | 0.025 (3) | 0.024 (4) | −0.008 (3) | 0.005 (4) | −0.003 (3) |
C5 | 0.049 (5) | 0.023 (3) | 0.071 (6) | −0.005 (3) | 0.039 (5) | −0.006 (3) |
C6 | 0.080 (6) | 0.031 (4) | 0.047 (5) | −0.007 (4) | 0.040 (5) | −0.007 (3) |
C7 | 0.068 (6) | 0.047 (4) | 0.032 (4) | −0.004 (4) | 0.019 (5) | −0.006 (4) |
C8 | 0.049 (5) | 0.039 (4) | 0.030 (4) | 0.001 (3) | 0.013 (4) | −0.005 (3) |
C9 | 0.050 (5) | 0.034 (3) | 0.027 (4) | −0.009 (3) | −0.001 (4) | 0.011 (3) |
C10 | 0.058 (5) | 0.046 (4) | 0.021 (4) | −0.017 (4) | 0.010 (4) | 0.001 (3) |
C11 | 0.057 (5) | 0.057 (5) | 0.019 (4) | −0.008 (4) | 0.019 (4) | −0.004 (3) |
C12 | 0.058 (5) | 0.053 (5) | 0.061 (6) | −0.010 (4) | 0.045 (5) | −0.019 (4) |
C13 | 0.048 (5) | 0.039 (4) | 0.056 (5) | 0.007 (4) | 0.023 (5) | −0.015 (4) |
C14 | 0.058 (5) | 0.025 (4) | 0.043 (5) | 0.010 (3) | 0.007 (4) | −0.002 (3) |
Sn1—C1 | 2.111 (6) | C1—H1b | 0.9800 |
Sn1—C2 | 2.119 (5) | C1—H1c | 0.9800 |
Sn1—C3 | 2.163 (3) | C2—H2a | 0.9800 |
Sn1—O1w | 2.445 (4) | C2—H2b | 0.9800 |
Sn1—Cl1 | 2.484 (2) | C2—H2c | 0.9800 |
O1—C14i | 1.426 (6) | C4—H4 | 0.9500 |
O1—C9 | 1.431 (6) | C5—H5 | 0.9500 |
O2—C11 | 1.419 (6) | C6—H6 | 0.9500 |
O2—C10 | 1.423 (6) | C7—H7 | 0.9500 |
O3—C13 | 1.419 (6) | C8—H8 | 0.9500 |
O3—C12 | 1.429 (6) | C9—H9a | 0.9900 |
C3—C4 | 1.3900 | C9—H9b | 0.9900 |
C3—C8 | 1.3900 | C10—H10a | 0.9900 |
C4—C5 | 1.3900 | C10—H10b | 0.9900 |
C5—C6 | 1.3900 | C11—H11a | 0.9900 |
C6—C7 | 1.3900 | C11—H11b | 0.9900 |
C7—C8 | 1.3900 | C12—H12a | 0.9900 |
C9—C10 | 1.494 (7) | C12—H12b | 0.9900 |
C11—C12 | 1.477 (7) | C13—H13a | 0.9900 |
C13—C14 | 1.491 (7) | C13—H13b | 0.9900 |
O1w—H1w1 | 0.85 (1) | C14—H14a | 0.9900 |
O1w—H1w2 | 0.85 (1) | C14—H14b | 0.9900 |
C1—H1a | 0.9800 | ||
C1—Sn1—C2 | 121.9 (3) | H2b—C2—H2c | 109.5 |
C1—Sn1—C3 | 121.2 (2) | C5—C4—H4 | 120.0 |
C1—Sn1—O1w | 84.9 (2) | C3—C4—H4 | 120.0 |
C1—Sn1—Cl1 | 94.0 (2) | C4—C5—H5 | 120.0 |
C2—Sn1—C3 | 114.6 (2) | C6—C5—H5 | 120.0 |
C2—Sn1—O1w | 82.3 (2) | C7—C6—H6 | 120.0 |
C2—Sn1—Cl1 | 95.2 (2) | C5—C6—H6 | 120.0 |
C3—Sn1—O1w | 88.0 (2) | C6—C7—H7 | 120.0 |
C3—Sn1—Cl1 | 95.8 (1) | C8—C7—H7 | 120.0 |
O1w—Sn1—Cl1 | 176.1 (1) | C7—C8—H8 | 120.0 |
C14i—O1—C9 | 111.5 (5) | C3—C8—H8 | 120.0 |
C11—O2—C10 | 112.4 (5) | O1—C9—H9a | 110.0 |
C13—O3—C12 | 112.0 (5) | C10—C9—H9a | 110.0 |
C4—C3—C8 | 120.0 | O1—C9—H9b | 110.0 |
C4—C3—Sn1 | 121.3 (2) | C10—C9—H9b | 110.0 |
C8—C3—Sn1 | 118.7 (2) | H9a—C9—H9b | 108.3 |
C5—C4—C3 | 120.0 | O2—C10—H10a | 110.3 |
C4—C5—C6 | 120.0 | C9—C10—H10a | 110.3 |
C7—C6—C5 | 120.0 | O2—C10—H10b | 110.3 |
C6—C7—C8 | 120.0 | C9—C10—H10b | 110.3 |
C7—C8—C3 | 120.0 | H10a—C10—H10b | 108.6 |
O1—C9—C10 | 108.6 (5) | O2—C11—H11a | 109.8 |
O2—C10—C9 | 107.0 (5) | C12—C11—H11a | 109.8 |
O2—C11—C12 | 109.5 (5) | O2—C11—H11b | 109.8 |
O3—C12—C11 | 110.2 (5) | C12—C11—H11b | 109.8 |
O3—C13—C14 | 109.3 (5) | H11a—C11—H11b | 108.2 |
O1i—C14—C13 | 109.6 (5) | O3—C12—H12a | 109.6 |
Sn1—O1w—H1w1 | 119 (3) | C11—C12—H12a | 109.6 |
Sn1—O1w—H1w2 | 130 (3) | O3—C12—H12b | 109.6 |
H1w1—O1w—H1w2 | 110 (2) | C11—C12—H12b | 109.6 |
Sn1—C1—H1a | 109.5 | H12a—C12—H12b | 108.1 |
Sn1—C1—H1b | 109.5 | O3—C13—H13a | 109.8 |
H1a—C1—H1b | 109.5 | C14—C13—H13a | 109.8 |
Sn1—C1—H1c | 109.5 | O3—C13—H13b | 109.8 |
H1a—C1—H1c | 109.5 | C14—C13—H13b | 109.8 |
H1b—C1—H1c | 109.5 | H13a—C13—H13b | 108.3 |
Sn1—C2—H2a | 109.5 | O1i—C14—H14a | 109.7 |
Sn1—C2—H2b | 109.5 | C13—C14—H14a | 109.7 |
H2a—C2—H2b | 109.5 | O1i—C14—H14b | 109.7 |
Sn1—C2—H2c | 109.5 | C13—C14—H14b | 109.7 |
H2a—C2—H2c | 109.5 | H14a—C14—H14b | 108.2 |
C1—Sn1—C3—C4 | 37.7 (3) | C5—C6—C7—C8 | 0.0 |
C2—Sn1—C3—C4 | −125.6 (3) | C6—C7—C8—C3 | 0.0 |
O1w—Sn1—C3—C4 | −45.0 (2) | C4—C3—C8—C7 | 0.0 |
Cl1—Sn1—C3—C4 | 136.0 (2) | Sn1—C3—C8—C7 | −178.9 (3) |
C1—Sn1—C3—C8 | −143.4 (3) | C14i—O1—C9—C10 | −173.2 (5) |
C2—Sn1—C3—C8 | 53.3 (3) | C11—O2—C10—C9 | −179.5 (5) |
O1w—Sn1—C3—C8 | 133.9 (2) | O1—C9—C10—O2 | 69.4 (7) |
Cl1—Sn1—C3—C8 | −45.1 (2) | C10—O2—C11—C12 | 170.4 (5) |
C8—C3—C4—C5 | 0.0 | C13—O3—C12—C11 | −171.3 (5) |
Sn1—C3—C4—C5 | 178.9 (3) | O2—C11—C12—O3 | −65.5 (7) |
C3—C4—C5—C6 | 0.0 | C12—O3—C13—C14 | 179.2 (5) |
C4—C5—C6—C7 | 0.0 | O3—C13—C14—O1i | 67.0 (7) |
Symmetry code: (i) −x, −y, −z. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1w—H1w1···O1 | 0.85 (1) | 2.10 (3) | 2.884 (5) | 153 (6) |
O1w—H1w2···O3 | 0.85 (1) | 2.01 (1) | 2.851 (6) | 172 (6) |
Experimental details
Crystal data | |
Chemical formula | [SnCl(CH3)2(C6H5)(H2O)]2·C12H24O8 |
Mr | 822.96 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 168 |
a, b, c (Å) | 9.6395 (6), 19.472 (1), 10.5110 (7) |
β (°) | 116.015 (1) |
V (Å3) | 1773.0 (2) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 1.60 |
Crystal size (mm) | 0.50 × 0.48 × 0.37 |
Data collection | |
Diffractometer | Siemens CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.502, 0.589 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 9926, 3392, 2495 |
Rint | 0.104 |
(sin θ/λ)max (Å−1) | 0.628 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.060, 0.107, 0.95 |
No. of reflections | 3392 |
No. of parameters | 177 |
No. of restraints | 21 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 2.62, −1.76 |
Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEPII (Johnson, 1976), SHELXL97.
Sn1—C1 | 2.111 (6) | Sn1—O1w | 2.445 (4) |
Sn1—C2 | 2.119 (5) | Sn1—Cl1 | 2.484 (2) |
Sn1—C3 | 2.163 (3) | ||
C1—Sn1—C2 | 121.9 (3) | C2—Sn1—O1w | 82.3 (2) |
C1—Sn1—C3 | 121.2 (2) | C2—Sn1—Cl1 | 95.2 (2) |
C1—Sn1—O1w | 84.9 (2) | C3—Sn1—O1w | 88.0 (2) |
C1—Sn1—Cl1 | 94.0 (2) | C3—Sn1—Cl1 | 95.8 (1) |
C2—Sn1—C3 | 114.6 (2) | O1w—Sn1—Cl1 | 176.1 (1) |
The coordination status of the Sn atom in mixed triorganotin compounds featuring one methyl group can be investigated from the magnitude of the tin–methyl coupling constants in the NMR. Unfortunately, the synthesis of the mixed triorganotin entity presents difficulties, and only a few such compounds have been synthesized. Earlier, we reported the 2:1 methyldiphenyltin trifluoroacetate complex of 18-crown-6; this exists as a dihydrate in which the coordinated water molecules interact with the centrosymmetric cyclic polyether through hydrogen bonds [Sn—Owater = 2.483 (5) Å; Owater···O18-crown-6 = 2.901 (8) and 2.983 (7) Å; Amini et al., 2002]. In this compound, the trifluoroacetate anion serves to increase the Lewis acidity of the Sn atom through its electron-withdrawing ability.
In the title compound, (I), the dimethylphenyltin chloride moiety is also coordinated by a water molecule [Sn—O = 2.445 (4) Å], and the water molecule similarly interacts with the cyclic polyether [Owater···O18-crown-6 = 2.851 (6) and 2.884 (5) Å]. The two-bond coupling constant of the adduct in solution (83 Hz) is significantly larger than that of the parent Lewis acid (59 Hz), so that the water molecule probably remains attached to the Sn atom even in solution.