Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270103024272/dn1033sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270103024272/dn1033Isup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270103024272/dn1033IIsup3.hkl |
CCDC references: 229074; 229075
Compound (I) was obtained by reaction of [PhC(Me)2CH2]Ph3Sn, (V), with HgCl2 in acetone. Recrystallization from ethanol provided crystals suitable for analysis (m.p. 328–330 K). IR (nujol mull, cm−1) ν: 344 s br, Sn—Cl. 1H NMR (200 MHz, Me2CO-d6): δ: 1.53 [s, 6H, J(119,117Sn-1H) = 10.7 Hz, Me], 2.67 [s, 2H, J(119,117Sn-1H) = 78.4, 75.3 Hz, CH2Sn], 7.3–7.7 [m, 10H, Ph]. 13C NMR (50 MHz, Me2CO-d6): δ: 32.7 [J(119,117Sn-13C) = 67.2, 64.2 Hz, Me], 39.1 [J(119,117Sn-13C) = 22 Hz, CMe2], 49.1 [J(119,117Sn-13C) = 548, 524 Hz, CH2], 126.1 [Cm, Phneo], 127.5 [Cp, Phneo], 129.7 [J(119,117Sn-13C) = 22 Hz, Co, Phneo], 129.8 [J(119,117Sn-13C) = 82.2, 78.4 Hz, Cm, PhSn], 131.6 [J(119,117Sn-13C) = 16.7 Hz, Cp, PhSn], 135.4 [J(119,117Sn-13C) = 65.0, 62.3 Hz, Co, PhSn], 142.9 [J(119,117Sn-13C) nd, Cipso, PhSn], 150.5 [J(119,117Sn-13C) = 55.5, 52.5 Hz, Cipso, Phneo]. 119Sn NMR (75 MHz, Me2CO-d6): δ: −32.3 Compound (II) was obtained by reaction of (V) with Br2 in acetone solution [the molar ratio of (V)/Br2 was 1:2] and recrystallized from heptane (m.p. 318–320 K). IR (polythene film, cm−1) ν: 252 br, Sn—Br. 1H NMR (200 MHz, CDCl3): δ: 1.58 [s, 6H, J(119,117Sn-1H) = 10.4 Hz, Me], 2.84 [s, 2H, J(119,117Sn-1H) = 73.6, 70.8 Hz, CH2Sn], 7.3–7.7 [m, 10H, Ph]. 13C NMR (50 MHz, CDCl3): δ: 32.4 [J(119,117Sn-13C) = 69.4, 66.5 Hz, Me], 38.8 [J(119,117Sn-13C) = 19.9 Hz, CMe2], 49.4 [J(119,117Sn-13C) = 475.7, 455.2 Hz, CH2], 125.1 [Cm, Phneo], 127.0 [Cp, Phneo], 129.0 [J(119,117Sn-13C) = 22.2 Hz, Co, Phneo], 129.1 [J(119,117Sn-13C) = 78.7, 75.6 Hz, Cm, PhSn], 130.8 [J(119,117Sn-13C) = 16.4 Hz, Cp, PhSn], 134.2 [J(119,117Sn-13C) = 65.0, 62.3 Hz, Co, PhSn], 139.4 [J(119,117Sn-13C) 637, 604 Hz, Cipso, PhSn], 148.5 [J(119,117Sn-13C) = 38 Hz, Cipso, Phneo].
In the final stages of the refinement of (I), H atoms were introduced in calculated positions and treated with a riding model, with C—H distances of 0.95, 0.99 and 0.98 Å and Uiso(H) values of 1.2, 1.2 and 1.5 times Ueq of the parent C atom for, respectively, phenyl, methylene and methyl H atoms. The rotational orientation of the rigid-body methyl groups was also refined. Subsequent to the initial independent solution and refinement of the structure of (II), the structure was re-refined in an identical manner with the coordinates found for (I) as starting parameters, but with Br substituted for Cl. The number of Friedel pairs used to refine the absolute structure were 1373 and 1725 for (I) and (II), respectively.
Data collection: DENZO (Otwinowski and Minor, 1997) and COLLECT (Hooft, 1998) for (I); DENZO (Otwinowski & Minor, 1997) and COLLECT (Hooft, 1998) for (II). For both compounds, cell refinement: DENZO and COLLECT; data reduction: DENZO and COLLECT; program(s) used to solve structure: SHELXS86 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2003).
[SnCl2(C6H5)(C10H13)] | F(000) = 396 |
Mr = 399.89 | Dx = 1.618 Mg m−3 |
Monoclinic, P21 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2yb | Cell parameters from 4852 reflections |
a = 9.1673 (3) Å | θ = 2.9–27.5° |
b = 9.0698 (2) Å | µ = 1.87 mm−1 |
c = 9.8939 (3) Å | T = 120 K |
β = 93.8823 (17)° | Block, colourless |
V = 820.75 (4) Å3 | 0.24 × 0.22 × 0.14 mm |
Z = 2 |
Enraf–Nonius KappaCCD area-detector diffractometer | 3375 independent reflections |
Radiation source: Enraf–Nonius FR591 rotating anode | 3239 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.030 |
Detector resolution: 9.091 pixels mm-1 | θmax = 27.5°, θmin = 2.9° |
ϕ and ω scans to fill the Ewald sphere | h = −11→10 |
Absorption correction: multi-scan (SORTAV; Blessing, 1995, 1997) | k = −10→11 |
Tmin = 0.668, Tmax = 0.692 | l = −11→12 |
6614 measured reflections |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.026 | H-atom parameters constrained |
wR(F2) = 0.063 | w = 1/[σ2(Fo2) + (0.0183P)2 + 0.81P] where P = (Fo2 + 2Fc2)/3 |
S = 1.05 | (Δ/σ)max < 0.001 |
3375 reflections | Δρmax = 0.78 e Å−3 |
174 parameters | Δρmin = −0.72 e Å−3 |
1 restraint | Absolute structure: Flack (1983); 1386 Friedel pairs |
Primary atom site location: heavy-atom method | Absolute structure parameter: 0.07 (3) |
[SnCl2(C6H5)(C10H13)] | V = 820.75 (4) Å3 |
Mr = 399.89 | Z = 2 |
Monoclinic, P21 | Mo Kα radiation |
a = 9.1673 (3) Å | µ = 1.87 mm−1 |
b = 9.0698 (2) Å | T = 120 K |
c = 9.8939 (3) Å | 0.24 × 0.22 × 0.14 mm |
β = 93.8823 (17)° |
Enraf–Nonius KappaCCD area-detector diffractometer | 3375 independent reflections |
Absorption correction: multi-scan (SORTAV; Blessing, 1995, 1997) | 3239 reflections with I > 2σ(I) |
Tmin = 0.668, Tmax = 0.692 | Rint = 0.030 |
6614 measured reflections |
R[F2 > 2σ(F2)] = 0.026 | H-atom parameters constrained |
wR(F2) = 0.063 | Δρmax = 0.78 e Å−3 |
S = 1.05 | Δρmin = −0.72 e Å−3 |
3375 reflections | Absolute structure: Flack (1983); 1386 Friedel pairs |
174 parameters | Absolute structure parameter: 0.07 (3) |
1 restraint |
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. Least-squares planes (x,y,z in crystal coordinates) and deviations from them (* indicates atom used to define plane) − 0.2580 (0.0164) x − 6.1990 (0.0124) y + 7.2191 (0.0126) z = 2.5049 (0.0092) * −0.0055 (0.0028) C5 * 0.0056 (0.0031) C6 * −0.0014 (0.0034) C7 * −0.0028 (0.0036) C8 * 0.0027 (0.0035) C9 * 0.0014 (0.0031) C10 − 3.1444 (0.0044) Sn1 − 1.3791 (0.0076) C1 − 0.0839 (0.0065) C2 1.0850 (0.0080) C3 − 0.0356 (0.0083) C4 Rms deviation of fitted atoms = 0.0037 1.3243 (0.0158) x − 4.9228 (0.0137) y + 8.0703 (0.0104) z = 0.2309 (0.0109) A ngle to previous plane (with approximate e.s.d.) = 13.97 (0.23) * −0.0108 (0.0027) C11 * 0.0039 (0.0029) C12 * 0.0044 (0.0031) C13 * −0.0057 (0.0031) C14 * −0.0012 (0.0032) C15 * 0.0094 (0.0030) C16 − 0.0399 (0.0061) Sn1 Rms deviation of fitted atoms = 0.0068 |
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 | 0.23213 (2) | 0.26489 (3) | 0.14716 (2) | 0.02167 (7) | |
Cl1 | 0.12186 (9) | 0.28363 (15) | −0.07630 (8) | 0.0270 (2) | |
Cl2 | 0.14501 (14) | 0.48258 (13) | 0.24754 (13) | 0.0291 (3) | |
C1 | 0.1273 (5) | 0.0748 (5) | 0.2248 (5) | 0.0241 (11) | |
H1A | 0.0213 | 0.0952 | 0.2256 | 0.029* | |
H1B | 0.1396 | −0.0086 | 0.1620 | 0.029* | |
C2 | 0.1835 (4) | 0.0279 (4) | 0.3659 (4) | 0.0254 (8) | |
C3 | 0.1132 (5) | −0.1180 (5) | 0.4000 (5) | 0.0400 (11) | |
H3A | 0.1473 | −0.1479 | 0.4920 | 0.060* | |
H3B | 0.1404 | −0.1935 | 0.3354 | 0.060* | |
H3C | 0.0067 | −0.1068 | 0.3945 | 0.060* | |
C4 | 0.1358 (6) | 0.1413 (6) | 0.4682 (5) | 0.0468 (13) | |
H4A | 0.0290 | 0.1402 | 0.4694 | 0.070* | |
H4B | 0.1682 | 0.2396 | 0.4423 | 0.070* | |
H4C | 0.1794 | 0.1167 | 0.5585 | 0.070* | |
C5 | 0.3506 (4) | 0.0110 (4) | 0.3682 (4) | 0.0223 (8) | |
C6 | 0.4077 (5) | −0.0931 (5) | 0.2823 (4) | 0.0312 (9) | |
H6 | 0.3433 | −0.1550 | 0.2287 | 0.037* | |
C7 | 0.5576 (6) | −0.1073 (6) | 0.2746 (6) | 0.0455 (13) | |
H7 | 0.5952 | −0.1777 | 0.2149 | 0.055* | |
C8 | 0.6512 (5) | −0.0201 (8) | 0.3526 (6) | 0.0604 (18) | |
H8 | 0.7538 | −0.0300 | 0.3471 | 0.072* | |
C9 | 0.5979 (6) | 0.0812 (7) | 0.4384 (6) | 0.0576 (17) | |
H9 | 0.6634 | 0.1411 | 0.4929 | 0.069* | |
C10 | 0.4462 (6) | 0.0970 (5) | 0.4464 (4) | 0.0383 (11) | |
H10 | 0.4096 | 0.1677 | 0.5064 | 0.046* | |
C11 | 0.4596 (4) | 0.3004 (4) | 0.1351 (4) | 0.0230 (9) | |
C12 | 0.5415 (5) | 0.2033 (5) | 0.0643 (4) | 0.0324 (10) | |
H12 | 0.4959 | 0.1196 | 0.0219 | 0.039* | |
C13 | 0.6890 (5) | 0.2268 (5) | 0.0544 (5) | 0.0390 (13) | |
H13 | 0.7446 | 0.1595 | 0.0052 | 0.047* | |
C14 | 0.7559 (5) | 0.3480 (6) | 0.1161 (5) | 0.0388 (11) | |
H14 | 0.8573 | 0.3648 | 0.1085 | 0.047* | |
C15 | 0.6760 (5) | 0.4438 (5) | 0.1883 (5) | 0.0388 (11) | |
H15 | 0.7223 | 0.5270 | 0.2309 | 0.047* | |
C16 | 0.5270 (5) | 0.4204 (5) | 0.1997 (4) | 0.0325 (10) | |
H16 | 0.4722 | 0.4860 | 0.2514 | 0.039* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Sn1 | 0.01552 (11) | 0.02109 (12) | 0.02812 (12) | 0.00006 (13) | −0.00064 (8) | 0.00215 (15) |
Cl1 | 0.0185 (4) | 0.0364 (7) | 0.0254 (3) | 0.0037 (5) | −0.0030 (3) | 0.0044 (5) |
Cl2 | 0.0270 (6) | 0.0207 (5) | 0.0397 (6) | 0.0026 (4) | 0.0040 (5) | −0.0038 (5) |
C1 | 0.013 (2) | 0.021 (2) | 0.039 (3) | −0.0024 (16) | 0.0008 (18) | 0.0026 (19) |
C2 | 0.021 (2) | 0.019 (2) | 0.037 (2) | 0.0014 (15) | 0.0075 (17) | 0.0040 (17) |
C3 | 0.022 (2) | 0.034 (2) | 0.065 (3) | −0.0011 (18) | 0.006 (2) | 0.019 (2) |
C4 | 0.058 (3) | 0.040 (3) | 0.044 (3) | 0.018 (2) | 0.023 (2) | 0.009 (2) |
C5 | 0.0217 (19) | 0.022 (2) | 0.0235 (17) | −0.0015 (15) | 0.0011 (15) | 0.0025 (15) |
C6 | 0.026 (2) | 0.030 (2) | 0.039 (2) | 0.0070 (18) | 0.0038 (18) | 0.0043 (19) |
C7 | 0.034 (3) | 0.049 (3) | 0.056 (3) | 0.020 (2) | 0.019 (2) | 0.017 (3) |
C8 | 0.018 (2) | 0.091 (5) | 0.072 (4) | 0.004 (3) | −0.002 (3) | 0.044 (4) |
C9 | 0.041 (3) | 0.075 (4) | 0.053 (3) | −0.031 (3) | −0.027 (3) | 0.031 (3) |
C10 | 0.046 (3) | 0.040 (3) | 0.027 (2) | −0.010 (2) | −0.009 (2) | 0.0062 (19) |
C11 | 0.0175 (17) | 0.027 (3) | 0.0240 (16) | −0.0031 (14) | 0.0005 (14) | 0.0071 (14) |
C12 | 0.023 (2) | 0.040 (2) | 0.034 (2) | −0.0003 (17) | 0.0008 (18) | −0.0017 (18) |
C13 | 0.025 (2) | 0.052 (4) | 0.041 (2) | 0.0100 (19) | 0.0057 (19) | 0.000 (2) |
C14 | 0.016 (2) | 0.059 (3) | 0.041 (2) | −0.002 (2) | −0.0014 (19) | 0.015 (2) |
C15 | 0.029 (2) | 0.044 (3) | 0.041 (2) | −0.014 (2) | −0.010 (2) | 0.005 (2) |
C16 | 0.028 (2) | 0.034 (2) | 0.034 (2) | −0.0059 (19) | −0.0021 (19) | 0.0016 (19) |
Sn1—C11 | 2.121 (4) | C6—H6 | 0.9500 |
Sn1—C1 | 2.141 (5) | C7—C8 | 1.368 (9) |
Sn1—Cl2 | 2.3727 (12) | C7—H7 | 0.9500 |
Sn1—Cl1 | 2.3740 (8) | C8—C9 | 1.363 (8) |
C1—C2 | 1.516 (6) | C8—H8 | 0.9500 |
C1—H1A | 0.9900 | C9—C10 | 1.406 (8) |
C1—H1B | 0.9900 | C9—H9 | 0.9500 |
C2—C3 | 1.520 (6) | C10—H10 | 0.9500 |
C2—C4 | 1.527 (6) | C11—C12 | 1.379 (6) |
C2—C5 | 1.538 (6) | C11—C16 | 1.386 (5) |
C3—H3A | 0.9800 | C12—C13 | 1.379 (6) |
C3—H3B | 0.9800 | C12—H12 | 0.9500 |
C3—H3C | 0.9800 | C13—C14 | 1.381 (7) |
C4—H4A | 0.9800 | C13—H13 | 0.9500 |
C4—H4B | 0.9800 | C14—C15 | 1.368 (7) |
C4—H4C | 0.9800 | C14—H14 | 0.9500 |
C5—C10 | 1.372 (6) | C15—C16 | 1.394 (6) |
C5—C6 | 1.396 (6) | C15—H15 | 0.9500 |
C6—C7 | 1.387 (6) | C16—H16 | 0.9500 |
C11—Sn1—C1 | 127.53 (16) | C7—C6—C5 | 120.7 (4) |
C11—Sn1—Cl2 | 104.91 (10) | C7—C6—H6 | 119.7 |
C1—Sn1—Cl2 | 110.36 (13) | C5—C6—H6 | 119.7 |
C11—Sn1—Cl1 | 107.15 (10) | C8—C7—C6 | 120.1 (5) |
C1—Sn1—Cl1 | 102.62 (14) | C8—C7—H7 | 120.0 |
Cl2—Sn1—Cl1 | 101.31 (5) | C6—C7—H7 | 120.0 |
C2—C1—Sn1 | 115.0 (3) | C9—C8—C7 | 120.3 (5) |
C2—C1—H1A | 108.5 | C9—C8—H8 | 119.9 |
Sn1—C1—H1A | 108.5 | C7—C8—H8 | 119.9 |
C2—C1—H1B | 108.5 | C8—C9—C10 | 120.1 (5) |
Sn1—C1—H1B | 108.5 | C8—C9—H9 | 120.0 |
H1A—C1—H1B | 107.5 | C10—C9—H9 | 120.0 |
C1—C2—C3 | 109.0 (4) | C5—C10—C9 | 120.4 (5) |
C1—C2—C4 | 109.1 (4) | C5—C10—H10 | 119.8 |
C3—C2—C4 | 107.1 (4) | C9—C10—H10 | 119.8 |
C1—C2—C5 | 108.5 (3) | C12—C11—C16 | 119.7 (4) |
C3—C2—C5 | 110.3 (3) | C12—C11—Sn1 | 120.2 (3) |
C4—C2—C5 | 112.8 (4) | C16—C11—Sn1 | 120.1 (3) |
C2—C3—H3A | 109.5 | C11—C12—C13 | 120.5 (4) |
C2—C3—H3B | 109.5 | C11—C12—H12 | 119.7 |
H3A—C3—H3B | 109.5 | C13—C12—H12 | 119.7 |
C2—C3—H3C | 109.5 | C12—C13—C14 | 120.0 (4) |
H3A—C3—H3C | 109.5 | C12—C13—H13 | 120.0 |
H3B—C3—H3C | 109.5 | C14—C13—H13 | 120.0 |
C2—C4—H4A | 109.5 | C15—C14—C13 | 120.0 (4) |
C2—C4—H4B | 109.5 | C15—C14—H14 | 120.0 |
H4A—C4—H4B | 109.5 | C13—C14—H14 | 120.0 |
C2—C4—H4C | 109.5 | C14—C15—C16 | 120.5 (4) |
H4A—C4—H4C | 109.5 | C14—C15—H15 | 119.8 |
H4B—C4—H4C | 109.5 | C16—C15—H15 | 119.8 |
C10—C5—C6 | 118.4 (4) | C11—C16—C15 | 119.4 (4) |
C10—C5—C2 | 123.3 (4) | C11—C16—H16 | 120.3 |
C6—C5—C2 | 118.2 (3) | C15—C16—H16 | 120.3 |
C11—Sn1—C1—C2 | 52.5 (4) | C6—C5—C10—C9 | 0.8 (6) |
Cl2—Sn1—C1—C2 | −76.7 (3) | C2—C5—C10—C9 | −176.6 (4) |
Cl1—Sn1—C1—C2 | 176.1 (3) | C8—C9—C10—C5 | 0.0 (7) |
Sn1—C1—C2—C3 | −172.9 (3) | C1—Sn1—C11—C12 | 57.8 (4) |
Sn1—C1—C2—C4 | 70.4 (4) | Cl2—Sn1—C11—C12 | −171.0 (3) |
Sn1—C1—C2—C5 | −52.8 (4) | Cl1—Sn1—C11—C12 | −63.9 (3) |
C1—C2—C5—C10 | 116.2 (4) | C1—Sn1—C11—C16 | −121.4 (3) |
C3—C2—C5—C10 | −124.5 (4) | Cl2—Sn1—C11—C16 | 9.8 (3) |
C4—C2—C5—C10 | −4.8 (5) | Cl1—Sn1—C11—C16 | 116.9 (3) |
C1—C2—C5—C6 | −61.2 (4) | C16—C11—C12—C13 | −1.7 (6) |
C3—C2—C5—C6 | 58.2 (5) | Sn1—C11—C12—C13 | 179.1 (3) |
C4—C2—C5—C6 | 177.9 (4) | C11—C12—C13—C14 | 0.2 (7) |
C10—C5—C6—C7 | −1.2 (6) | C12—C13—C14—C15 | 0.7 (7) |
C2—C5—C6—C7 | 176.3 (4) | C13—C14—C15—C16 | −0.2 (7) |
C5—C6—C7—C8 | 0.8 (7) | C12—C11—C16—C15 | 2.2 (6) |
C6—C7—C8—C9 | 0.0 (8) | Sn1—C11—C16—C15 | −178.6 (3) |
C7—C8—C9—C10 | −0.4 (8) | C14—C15—C16—C11 | −1.2 (7) |
[SnBr2(C6H5)(C10H13)] | F(000) = 468 |
Mr = 488.81 | Dx = 1.925 Mg m−3 |
Monoclinic, P21 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2yb | Cell parameters from 7897 reflections |
a = 9.2966 (3) Å | θ = 2.9–27.5° |
b = 9.3763 (3) Å | µ = 6.24 mm−1 |
c = 9.6898 (3) Å | T = 120 K |
β = 93.010 (2)° | Slab, colourless |
V = 843.47 (5) Å3 | 0.30 × 0.18 × 0.08 mm |
Z = 2 |
Enraf Nonius KappaCCD area detector diffractometer | 3772 independent reflections |
Radiation source: Enraf Nonius FR591 rotating anode | 3618 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.034 |
Detector resolution: 9.091 pixels mm-1 | θmax = 27.5°, θmin = 3.0° |
ϕ and ω scans to fill the Ewald sphere | h = −12→10 |
Absorption correction: multi-scan (SORTAV; Blessing, 1995, 1997) | k = −12→11 |
Tmin = 0.528, Tmax = 0.861 | l = −12→12 |
9872 measured reflections |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.026 | H-atom parameters constrained |
wR(F2) = 0.061 | w = 1/[σ2(Fo2) + (0.0343P)2] where P = (Fo2 + 2Fc2)/3 |
S = 1.08 | (Δ/σ)max = 0.001 |
3772 reflections | Δρmax = 0.37 e Å−3 |
174 parameters | Δρmin = −1.27 e Å−3 |
1 restraint | Absolute structure: (Flack, 1983; 1735 Friedel pairs) |
Primary atom site location: heavy-atom method | Absolute structure parameter: 0.006 (7) |
[SnBr2(C6H5)(C10H13)] | V = 843.47 (5) Å3 |
Mr = 488.81 | Z = 2 |
Monoclinic, P21 | Mo Kα radiation |
a = 9.2966 (3) Å | µ = 6.24 mm−1 |
b = 9.3763 (3) Å | T = 120 K |
c = 9.6898 (3) Å | 0.30 × 0.18 × 0.08 mm |
β = 93.010 (2)° |
Enraf Nonius KappaCCD area detector diffractometer | 3772 independent reflections |
Absorption correction: multi-scan (SORTAV; Blessing, 1995, 1997) | 3618 reflections with I > 2σ(I) |
Tmin = 0.528, Tmax = 0.861 | Rint = 0.034 |
9872 measured reflections |
R[F2 > 2σ(F2)] = 0.026 | H-atom parameters constrained |
wR(F2) = 0.061 | Δρmax = 0.37 e Å−3 |
S = 1.08 | Δρmin = −1.27 e Å−3 |
3772 reflections | Absolute structure: (Flack, 1983; 1735 Friedel pairs) |
174 parameters | Absolute structure parameter: 0.006 (7) |
1 restraint |
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. Least-squares planes (x,y,z in crystal coordinates) and deviations from them (* indicates atom used to define plane) 0.1145 (0.0159) x + 6.2483 (0.0126) y − 7.2201 (0.0117) z = 1.6849 (0.0210) * −0.0068 (0.0027) C5 * 0.0083 (0.0029) C6 * −0.0020 (0.0033) C7 * −0.0058 (0.0033) C8 * 0.0070 (0.0030) C9 * −0.0008 (0.0028) C10 − 3.1534 (0.0043) Sn1 − 1.3928 (0.0068) C1 − 0.0784 (0.0061) C2 1.0786 (0.0073) C3 − 0.0073 (0.0078) C4 Rms deviation of fitted atoms = 0.0058 1.3529 (0.0154) x − 5.3677 (0.0143) y + 7.7339 (0.0110) z = 3.6651 (0.0194) A ngle to previous plane (with approximate e.s.d.) = 11.11 (0.24) * 0.0115 (0.0028) C11 * −0.0010 (0.0030) C12 * −0.0077 (0.0032) C13 * 0.0059 (0.0032) C14 * 0.0047 (0.0032) C15 * −0.0133 (0.0029) C16 0.0183 (0.0058) Sn1 Rms deviation of fitted atoms = 0.0084 |
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 | 0.76993 (2) | 0.735210 (18) | 0.85186 (2) | 0.02404 (7) | |
Br1 | 0.88162 (4) | 0.72228 (5) | 1.09150 (3) | 0.03338 (10) | |
Br2 | 0.86195 (4) | 0.51400 (4) | 0.74505 (4) | 0.03449 (10) | |
C1 | 0.8730 (4) | 0.9194 (4) | 0.7690 (4) | 0.0278 (8) | |
H1A | 0.8614 | 1.0006 | 0.8328 | 0.033* | |
H1B | 0.9774 | 0.8997 | 0.7658 | 0.033* | |
C2 | 0.8149 (4) | 0.9634 (4) | 0.6242 (4) | 0.0275 (7) | |
C3 | 0.8846 (5) | 1.1056 (4) | 0.5881 (5) | 0.0368 (9) | |
H3A | 0.8442 | 1.1389 | 0.4983 | 0.055* | |
H3B | 0.9888 | 1.0926 | 0.5835 | 0.055* | |
H3C | 0.8653 | 1.1763 | 0.6592 | 0.055* | |
C4 | 0.8641 (5) | 0.8535 (4) | 0.5199 (4) | 0.0410 (10) | |
H4A | 0.9696 | 0.8500 | 0.5234 | 0.062* | |
H4B | 0.8281 | 0.8806 | 0.4268 | 0.062* | |
H4C | 0.8263 | 0.7594 | 0.5429 | 0.062* | |
C5 | 0.6525 (4) | 0.9782 (4) | 0.6244 (3) | 0.0263 (7) | |
C6 | 0.5919 (5) | 1.0792 (4) | 0.7088 (4) | 0.0346 (9) | |
H6 | 0.6536 | 1.1418 | 0.7614 | 0.042* | |
C7 | 0.4448 (5) | 1.0914 (6) | 0.7185 (5) | 0.0522 (13) | |
H7 | 0.4064 | 1.1604 | 0.7782 | 0.063* | |
C8 | 0.3544 (5) | 1.0033 (7) | 0.6413 (5) | 0.0577 (14) | |
H8 | 0.2532 | 1.0112 | 0.6481 | 0.069* | |
C9 | 0.4094 (5) | 0.9037 (6) | 0.5542 (5) | 0.0513 (13) | |
H9 | 0.3462 | 0.8442 | 0.4997 | 0.062* | |
C10 | 0.5585 (5) | 0.8903 (5) | 0.5461 (4) | 0.0389 (9) | |
H10 | 0.5963 | 0.8207 | 0.4866 | 0.047* | |
C11 | 0.5455 (4) | 0.7022 (4) | 0.8673 (4) | 0.0277 (8) | |
C12 | 0.4675 (4) | 0.7963 (5) | 0.9446 (4) | 0.0366 (9) | |
H12 | 0.5140 | 0.8746 | 0.9904 | 0.044* | |
C13 | 0.3199 (4) | 0.7747 (6) | 0.9547 (5) | 0.0456 (12) | |
H13 | 0.2659 | 0.8392 | 1.0070 | 0.055* | |
C14 | 0.2526 (5) | 0.6624 (5) | 0.8902 (5) | 0.0431 (10) | |
H14 | 0.1523 | 0.6482 | 0.8992 | 0.052* | |
C15 | 0.3294 (5) | 0.5684 (5) | 0.8114 (5) | 0.0421 (10) | |
H15 | 0.2824 | 0.4899 | 0.7666 | 0.051* | |
C16 | 0.4765 (4) | 0.5907 (4) | 0.7988 (4) | 0.0347 (9) | |
H16 | 0.5293 | 0.5287 | 0.7427 | 0.042* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Sn1 | 0.01824 (12) | 0.02568 (11) | 0.02818 (11) | −0.00088 (10) | 0.00118 (8) | 0.00219 (10) |
Br1 | 0.02490 (18) | 0.0442 (2) | 0.03059 (17) | 0.00090 (18) | −0.00303 (13) | 0.00279 (18) |
Br2 | 0.0331 (2) | 0.02855 (18) | 0.0423 (2) | 0.00375 (16) | 0.00686 (16) | −0.00133 (17) |
C1 | 0.0193 (18) | 0.0272 (18) | 0.036 (2) | −0.0013 (14) | −0.0026 (15) | −0.0014 (15) |
C2 | 0.0249 (19) | 0.0249 (16) | 0.0331 (18) | 0.0012 (14) | 0.0044 (14) | 0.0024 (15) |
C3 | 0.029 (2) | 0.033 (2) | 0.049 (2) | −0.0028 (16) | 0.0046 (18) | 0.0111 (19) |
C4 | 0.053 (3) | 0.034 (2) | 0.038 (2) | 0.0122 (19) | 0.017 (2) | 0.0054 (18) |
C5 | 0.0248 (18) | 0.0249 (17) | 0.0292 (17) | −0.0035 (13) | 0.0008 (14) | 0.0032 (14) |
C6 | 0.027 (2) | 0.040 (2) | 0.037 (2) | 0.0033 (16) | 0.0030 (16) | 0.0006 (17) |
C7 | 0.031 (3) | 0.068 (3) | 0.060 (3) | 0.017 (2) | 0.017 (2) | 0.016 (3) |
C8 | 0.027 (2) | 0.082 (4) | 0.064 (3) | 0.005 (2) | 0.003 (2) | 0.035 (3) |
C9 | 0.035 (3) | 0.063 (3) | 0.053 (3) | −0.020 (2) | −0.019 (2) | 0.023 (2) |
C10 | 0.041 (2) | 0.041 (2) | 0.034 (2) | −0.0105 (19) | −0.0079 (17) | 0.0080 (18) |
C11 | 0.0190 (17) | 0.036 (2) | 0.0285 (16) | 0.0023 (13) | 0.0017 (13) | 0.0042 (14) |
C12 | 0.025 (2) | 0.046 (2) | 0.038 (2) | 0.0004 (17) | 0.0010 (16) | −0.0067 (18) |
C13 | 0.025 (2) | 0.065 (3) | 0.048 (2) | 0.0081 (18) | 0.0088 (18) | 0.001 (2) |
C14 | 0.019 (2) | 0.066 (3) | 0.044 (2) | −0.0019 (19) | −0.0018 (17) | 0.014 (2) |
C15 | 0.031 (2) | 0.048 (2) | 0.046 (2) | −0.0130 (19) | −0.0065 (18) | 0.003 (2) |
C16 | 0.024 (2) | 0.038 (2) | 0.042 (2) | −0.0044 (16) | 0.0003 (16) | −0.0021 (17) |
Sn1—C11 | 2.122 (3) | C6—H6 | 0.9500 |
Sn1—C1 | 2.151 (4) | C7—C8 | 1.371 (8) |
Sn1—Br2 | 2.4895 (4) | C7—H7 | 0.9500 |
Sn1—Br1 | 2.4963 (4) | C8—C9 | 1.375 (8) |
C1—C2 | 1.534 (5) | C8—H8 | 0.9500 |
C1—H1A | 0.9900 | C9—C10 | 1.399 (7) |
C1—H1B | 0.9900 | C9—H9 | 0.9500 |
C2—C5 | 1.517 (5) | C10—H10 | 0.9500 |
C2—C4 | 1.530 (5) | C11—C16 | 1.379 (5) |
C2—C3 | 1.531 (5) | C11—C12 | 1.386 (5) |
C3—H3A | 0.9800 | C12—C13 | 1.395 (6) |
C3—H3B | 0.9800 | C12—H12 | 0.9500 |
C3—H3C | 0.9800 | C13—C14 | 1.360 (7) |
C4—H4A | 0.9800 | C13—H13 | 0.9500 |
C4—H4B | 0.9800 | C14—C15 | 1.388 (7) |
C4—H4C | 0.9800 | C14—H14 | 0.9500 |
C5—C6 | 1.389 (5) | C15—C16 | 1.394 (6) |
C5—C10 | 1.396 (5) | C15—H15 | 0.9500 |
C6—C7 | 1.381 (6) | C16—H16 | 0.9500 |
C11—Sn1—C1 | 127.04 (14) | C7—C6—C5 | 122.0 (4) |
C11—Sn1—Br2 | 105.57 (10) | C7—C6—H6 | 119.0 |
C1—Sn1—Br2 | 110.13 (10) | C5—C6—H6 | 119.0 |
C11—Sn1—Br1 | 106.84 (9) | C8—C7—C6 | 119.6 (5) |
C1—Sn1—Br1 | 102.38 (10) | C8—C7—H7 | 120.2 |
Br2—Sn1—Br1 | 102.183 (15) | C6—C7—H7 | 120.2 |
C2—C1—Sn1 | 114.5 (3) | C7—C8—C9 | 120.5 (4) |
C2—C1—H1A | 108.6 | C7—C8—H8 | 119.8 |
Sn1—C1—H1A | 108.6 | C9—C8—H8 | 119.8 |
C2—C1—H1B | 108.6 | C8—C9—C10 | 119.8 (5) |
Sn1—C1—H1B | 108.6 | C8—C9—H9 | 120.1 |
H1A—C1—H1B | 107.6 | C10—C9—H9 | 120.1 |
C5—C2—C4 | 113.3 (3) | C5—C10—C9 | 120.7 (4) |
C5—C2—C3 | 110.7 (3) | C5—C10—H10 | 119.6 |
C4—C2—C3 | 106.9 (3) | C9—C10—H10 | 119.6 |
C5—C2—C1 | 109.0 (3) | C16—C11—C12 | 119.9 (4) |
C4—C2—C1 | 108.6 (3) | C16—C11—Sn1 | 120.7 (3) |
C3—C2—C1 | 108.1 (3) | C12—C11—Sn1 | 119.3 (3) |
C2—C3—H3A | 109.5 | C11—C12—C13 | 119.4 (4) |
C2—C3—H3B | 109.5 | C11—C12—H12 | 120.3 |
H3A—C3—H3B | 109.5 | C13—C12—H12 | 120.3 |
C2—C3—H3C | 109.5 | C14—C13—C12 | 120.7 (4) |
H3A—C3—H3C | 109.5 | C14—C13—H13 | 119.6 |
H3B—C3—H3C | 109.5 | C12—C13—H13 | 119.6 |
C2—C4—H4A | 109.5 | C13—C14—C15 | 120.4 (4) |
C2—C4—H4B | 109.5 | C13—C14—H14 | 119.8 |
H4A—C4—H4B | 109.5 | C15—C14—H14 | 119.8 |
C2—C4—H4C | 109.5 | C14—C15—C16 | 119.2 (4) |
H4A—C4—H4C | 109.5 | C14—C15—H15 | 120.4 |
H4B—C4—H4C | 109.5 | C16—C15—H15 | 120.4 |
C6—C5—C10 | 117.4 (4) | C11—C16—C15 | 120.3 (4) |
C6—C5—C2 | 119.9 (3) | C11—C16—H16 | 119.8 |
C10—C5—C2 | 122.7 (3) | C15—C16—H16 | 119.8 |
C11—Sn1—C1—C2 | −52.1 (3) | C6—C5—C10—C9 | −0.6 (6) |
Br2—Sn1—C1—C2 | 77.3 (3) | C2—C5—C10—C9 | 177.2 (4) |
Br1—Sn1—C1—C2 | −174.6 (2) | C8—C9—C10—C5 | −0.7 (6) |
Sn1—C1—C2—C5 | 52.3 (3) | C1—Sn1—C11—C16 | 118.4 (3) |
Sn1—C1—C2—C4 | −71.5 (4) | Br2—Sn1—C11—C16 | −12.7 (3) |
Sn1—C1—C2—C3 | 172.8 (2) | Br1—Sn1—C11—C16 | −121.0 (3) |
C4—C2—C5—C6 | −176.8 (3) | C1—Sn1—C11—C12 | −60.0 (4) |
C3—C2—C5—C6 | −56.6 (4) | Br2—Sn1—C11—C12 | 168.9 (3) |
C1—C2—C5—C6 | 62.2 (4) | Br1—Sn1—C11—C12 | 60.6 (3) |
C4—C2—C5—C10 | 5.5 (5) | C16—C11—C12—C13 | 1.5 (6) |
C3—C2—C5—C10 | 125.6 (4) | Sn1—C11—C12—C13 | 179.9 (3) |
C1—C2—C5—C10 | −115.6 (4) | C11—C12—C13—C14 | 0.4 (7) |
C10—C5—C6—C7 | 1.5 (6) | C12—C13—C14—C15 | −1.1 (7) |
C2—C5—C6—C7 | −176.3 (4) | C13—C14—C15—C16 | −0.1 (7) |
C5—C6—C7—C8 | −1.1 (7) | C12—C11—C16—C15 | −2.6 (6) |
C6—C7—C8—C9 | −0.3 (7) | Sn1—C11—C16—C15 | 178.9 (3) |
C7—C8—C9—C10 | 1.2 (7) | C14—C15—C16—C11 | 2.0 (7) |
Experimental details
(I) | (II) | |
Crystal data | ||
Chemical formula | [SnCl2(C6H5)(C10H13)] | [SnBr2(C6H5)(C10H13)] |
Mr | 399.89 | 488.81 |
Crystal system, space group | Monoclinic, P21 | Monoclinic, P21 |
Temperature (K) | 120 | 120 |
a, b, c (Å) | 9.1673 (3), 9.0698 (2), 9.8939 (3) | 9.2966 (3), 9.3763 (3), 9.6898 (3) |
α, β, γ (°) | 90, 93.8823 (17), 90 | 90, 93.010 (2), 90 |
V (Å3) | 820.75 (4) | 843.47 (5) |
Z | 2 | 2 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 1.87 | 6.24 |
Crystal size (mm) | 0.24 × 0.22 × 0.14 | 0.30 × 0.18 × 0.08 |
Data collection | ||
Diffractometer | Enraf–Nonius KappaCCD area-detector diffractometer | Enraf Nonius KappaCCD area detector diffractometer |
Absorption correction | Multi-scan (SORTAV; Blessing, 1995, 1997) | Multi-scan (SORTAV; Blessing, 1995, 1997) |
Tmin, Tmax | 0.668, 0.692 | 0.528, 0.861 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 6614, 3375, 3239 | 9872, 3772, 3618 |
Rint | 0.030 | 0.034 |
(sin θ/λ)max (Å−1) | 0.649 | 0.649 |
Refinement | ||
R[F2 > 2σ(F2)], wR(F2), S | 0.026, 0.063, 1.05 | 0.026, 0.061, 1.08 |
No. of reflections | 3375 | 3772 |
No. of parameters | 174 | 174 |
No. of restraints | 1 | 1 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.78, −0.72 | 0.37, −1.27 |
Absolute structure | Flack (1983); 1386 Friedel pairs | (Flack, 1983; 1735 Friedel pairs) |
Absolute structure parameter | 0.07 (3) | 0.006 (7) |
Computer programs: DENZO (Otwinowski and Minor, 1997) and COLLECT (Hooft, 1998), DENZO (Otwinowski & Minor, 1997) and COLLECT (Hooft, 1998), DENZO and COLLECT, SHELXS86 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), ORTEP-3 for Windows (Farrugia, 1997), SHELXL97 and PLATON (Spek, 2003).
I | II | |
X = Cl | X = Br | |
Sn1—C11 | 2.121 (4) | 2.122 (3) |
Sn1—C1 | 2.141 (5) | 2.151 (4) |
Sn1—X2 | 2.3727 (12) | 2.4895 (4) |
Sn1—X1 | 2.3740 (8) | 2.4963 (4) |
C1—C2 | 1.516 (6) | 1.534 (5) |
C2—C3 | 1.520 (6) | 1.531 (5) |
C2—C4 | 1.527 (6) | 1.530 (5) |
C2—C5 | 1.538 (6) | 1.517 (5) |
C11—Sn1—C1 | 127.53 (16) | 127.04 (14) |
C11—Sn1—X2 | 104.91 (10) | 105.57 (10) |
C1—Sn1—X2 | 110.36 (13) | 110.13 (10) |
C11—Sn1—X1 | 107.15 (10) | 106.84 (9) |
C1—Sn1—X1 | 102.62 (14) | 102.38 (10) |
X2—Sn1—X1 | 101.31 (5) | 102.183 (13) |
C2—C1—Sn1 | 115.0 (3) | 114.5 (3) |
C1—C2—C3 | 109.0 (4) | 108.1 (3) |
C1—C2—C4 | 109.1 (4) | 108.6 (3) |
C3—C2—C4 | 107.1 (4) | 106.9 (3) |
C1—C2—C5 | 108.5 (3) | 109.0 (3) |
C3—C2—C5 | 110.3 (3) | 110.7 (3) |
C4—C2—C5 | 112.8 (4) | 113.3 (3) |
C11-Sn1-C1-C2 | 52.5 (4) | -52.1 (3) |
X2-Sn1-C1-C2 | -76.7 (3) | 77.3 (3) |
X1-Sn1-C1-C2 | 176.1 (3) | -174.6 (2) |
Sn1-C1-C2-C3 | -172.9 (3) | 172.8 (2) |
Sn1-C1-C2-C4 | 70.4 (4) | -71.5 (4) |
Sn1-C1-C2-C5 | -52.8 (4) | 52.3 (3) |
C1-C2-C5-C10 | 116.2 (4) | -115.6 (4) |
C3-C2-C5-C10 | -124.5 (4) | 125.6 (4) |
C4-C2-C5-C10 | -4.8 (5) | 5.5 (5) |
C1-C2-C5-C6 | -61.2 (4) | 62.2 (4) |
C3-C2-C5-C6 | 58.2 (5) | -56.6 (4) |
C4-C2-C5-C6 | 177.9 (4) | -176.8 (3) |
Cpd | C—H | H.·Cg | Hperpa | X-H.·Cg | X.·Cg | |
C10-H10.·Cg1i | I | 0.95 | 3.32 | 2.97 | 140 | 4.096 |
II | 0.95 | 3.41 | 2.91 | 137 | 4.149 | |
C12-H12.·Cg2ii | I | 0.95 | 3.17 | 2.79 | 171 | 4.115 |
II | 0.95 | 3.24 | 2.79 | 166 | 4.121 |
Note: (a) Hperp is the perpendicular distance of the H atom from the plane of the benzene ring. Symmetry codes (i) 1 − x, 1/2 + y, 1 − z; (ii) 1 − x, y − 1/2, −z. |
Numerous entries in the Cambridge Structural Database (CSD; Allen, 2002) reveal that simple non-functionalized diorganodihalotins, RR'SnX2, exist in the solid state as molecular compounds sometimes exhibiting various types of intermolecular interaction. Regardless of the involvement of the tin centre in these intermolecular interactions, such as that noted for a series of compounds (with X = Cl) by Amini et al. (1987), they are generally weak. The interactions and conformations of the title compounds, (I) and (II), have been investigated. Fig. 1 shows the molecule of (I); this figure, with Br substituted for Cl, is equally appropriate for the molecule of (II). Selected bond lengths and angles for (I) and (II) are given in Table 1. The C—C distances and internal angles in the benzene rings of (I) and (II) (not given in Table 1) are in the ranges 1.346 (12)–1.406 (8) Å and 117.3 (10)122.6 (11)°, respectively, and are not discussed further. The Sn—C bond lengths and the angles at the Sn atom are similar for the two molecules. More significant, however, is the similarity of the intramolecular Sn—X [X = Cl for (I) and Br for (II)] bond lengths; as discussed in greater detail later, such a similiarity is not observed in other formally similar compounds. The torsion angles in Table 1 clearly demonstrate that, while (I) and (II) are isostructural, the sample crystals are, by chance, enantiomeric, i.e. of opposite polarity.
Totally unexpected, however, is the overall `U' shape of the molecules of (I) and (II), which brings the two benzene rings in the molecule face to face. The intramolecular interaction between the rings [designated as ring 1, with centroid Cg1, forming part of the 2-methyl-2-phenylpropyl (also known as neophyl) ligand, and ring 2, with centroid Cg2, bonded directly to the Sn atom] is characterized as follows [values for (II) are given in parentheses]. The distance between the ring centroids, Cg1—Cg2, vector A, is 3.940 (3.898) Å. The perpendicular distances from Cg1 to the plane of ring 2 (vector B), and from Cg2 to the plane of ring 1 (vector C), are 3.368 (3.416) and 3.757 (3.713) Å, respectively. The dihedral angle between the planes, the angle between vectors A and B at Cg1, and the angle between vectors A and C at Cg2 are, respectively, 14.0 (2) [11.1 (2)], 17.5 (17.7) and 31.3 (28.8)°. The intramolecular separation between these planes, the only face-to-face separation between them of any significance, is roughly comparable to that normally associated with π..π stacking (ca 3.4 Å; Pauling, 1960). For both (I) and (II), this conformation has the effect of bringing about the C—H..π interactions given in Table 2. These connect the molecules to form layers parallel to (100) (Fig. 2) and related to one another by cell translation. Of some interest in Fig. 2 and Table 2 is the fact that each C—H..π interaction is confined to a single ring type, which provides both the donated H atom and the benzene-ring acceptor. Ring 1 is employed in connecting molecules related to one another by the operation of a crystallographic twofold screw axis with equation 1/2,y,1/2, in which the ?donor-to-acceptor polarity in (I) is in the +b direction?. For ring 2, the equation of the twofold screw axis is 1/2,y,0, and the polarity of the interaction in (I) is now in the −b direction. Thus, in each case, the C—H..π interaction can be considered to connect chains of molecules propagated in the b direction, but the participation of the molecules in both chains connects them and completes the connectivity of the layer. Clearly, it is the orientation of the molecules and the resulting polarity of the C—H..π interactions that determine the polarity of the structure as a whole, which is compatible with the non-centrosymmetric space group P21. The layer surfaces are populated primarily by methyl groups, the edges of the phenyl groups and Cl atoms. There is, however, no evidence of C—H.·Cl or any other form of intermolecular interaction other than van der Waals interactions across the interlayer boundary. Indeed, the shortest intermolecular Sn..halide distances in (I) and (II) are of the order of 5.4 and 5.6 Å, respectively. The situation in (I) is in striking contrast to that found in the formally analogous compounds dichloro(diphenyl)tin, Ph2SnCl2 (III) (CSD, version 5.24, refcode DCDPSN; Greene & Bryan, 1971), and methylphenyltin(IV) dichloride, (IV) (CSD refcode GIJYAZ; Amini et al., 1987). Bokii et al. (1972) in re-evaluating the published results of Greene & Bryan (1971) showed that intermolecular Sn···Cl contacts [lengths now computed as being in the range 3.7697 (18)–3.8724 (19) Å] are present, inducing significant distortion of the Sn coordination and, in particular, accounting for the comparatively wide range [2.336 (2)–2.357 (2) Å] in the primary Sn—Cl bond lengths in (III). Likewise, for (IV), Amini et al. (1987) report primary Sn—Cl bonds in the range 2.36 (1)–2.39 (1) Å associated with intermolecular Sn···Cl contacts now computed to be in the range 3.422 (9)–3.806 (11) Å. Similar weak intermolecular Sn.·I bonds have been invoked by Howie & Wardell (1996) in explanation of features of the coordination of the Sn atom in diphenyltin diiodide (CSD refcode HIHCUW). Also present in (III), with no equivalent in the structures of (I) and (II), are aryl C—H···Cl hydrogen bonds; ?for C—H distances of 1.08 Å, the H···Cl and C···Cl distances fall in the ranges 2.80–2.81 and 3.449 (6)–3.825 (7) Å, respectively, and the C—H.·Cl angles range from 118 to 156°. Pairwise π···π and C—H..π contacts are present in all three structures, but in (III), the former are in the form of intermolecular contacts between centrosymmetrically related pairs of only one of the two molecules present in the asymmetric unit, as distinct from the intramolecular contact of this type present in (I) and (II). The presence of intermolecular Sn···Cl bonds in (III) and (IV) is clearly consistant with the differences in the lengths of the primary Sn—Cl bonds in these structures and their absence with the equivalence of the bonds in (I)?. The fact that the Sn—Cl bonds are longer in (I) than in (III) or (IV) is, however, surprising.