Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270102007898/tr1026sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270102007898/tr1026IVsup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270102007898/tr1026Vsup3.hkl |
CCDC references: 188604; 188605
Ph2Sn(CH2I)2 and Sn(CH2I)4 (Burnett et al., 1998), and [NEt4]2[Zn(dmit)2], where dmit is the (C3S5)2- anion (Doidge-Harrison et al., 1996), were prepared by published procedures. The title compounds were obtained from reactions of [NEt4]2[Zn(dmit)2] (0.286 g, 0.4 mmol) with either Ph2Sn(CH2I)2 (0.445 g, 0.8 mmol), for (IV), or Sn(CH2I)4 (0.274 g, 0.4 mmol), for (V), in refluxing Me2CO (20 ml). After refluxing for 1 h, the reaction mixtures were cooled and rotary evaporated. The products were isolated from the residues after several recrystallizations from ethanol as dark-red-brown crystalline solids.
Analysis for (IV): m.p. 393–398 K (decomposition); 1H NMR (250 MHz, CDCl3, δ, p.p.m): 2.89 [s, 4H, J(119,117Sn-1H) = 33 Hz, CH2], 7.40–7.46 (m, 10H, aryl); 13C NMR (63 MHz, CDCl3, δ, p.p.m.): 15.3 [J(119,117Sn-13C) = 345 and 329 Hz, CH2], 128.8, 129.2, 130.0, 136.1, 142.9 (aryl and C═C); 119Sn NMR (93 MHz, CDCl3, δ, p.p.m): -94.8.
Analysis for (V): decomposed on heating above 373 K; 1H NMR (250 MHz, CDCl3, δ, p.p.m.): 2.84; no Sn coupling detected; 119Sn NMR (93 MHz, C6D6, δ, p.p.m.): -30.
In the final stages of refinement, H atoms were placed in calculated positions, with C—H = 0.93 and 0.97 Å for phenyl and methylene H, respectively, and Uiso(H) = 1.2Ueq of the parent atom. Specifically, in (IV), one reflection, 001, showing particularly poor agreement, was omitted and comparatively large displacement parameters were associated with atom S2. Refinement with this atom split over two sites was attempted but proved unsuccessful, and it is therefore presumed that the libration is genuine and the bond lengths and angles associated with S2 correspondingly dubious. The maximum residual electron density for (IV) (1.12 e Å-3) was 0.84 Å from Sn1, while that for (V) (1.31 e Å-3) was 0.8 Å from Sn1.
For both compounds, data collection: SMART (Bruker, 1999); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT. Program(s) used to solve structure: SHELXS86 (Sheldrick, 1990) for (IV); SHELXS97 (Sheldrick, 1990) for (V). For both compounds, program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 1990).
[Sn(C17H14S5)] | F(000) = 492 |
Mr = 497.27 | Dx = 1.727 Mg m−3 |
Monoclinic, P21 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2yb | Cell parameters from 3614 reflections |
a = 8.6706 (5) Å | θ = 2.8–25.0° |
b = 8.5319 (6) Å | µ = 1.88 mm−1 |
c = 13.3143 (9) Å | T = 303 K |
β = 103.840 (1)° | Block, dark red-brown |
V = 956.35 (11) Å3 | 0.38 × 0.28 × 0.22 mm |
Z = 2 |
Bruker SMART 1000 CCD area-detector diffractometer | 3107 independent reflections |
Radiation source: fine-focus sealed tube | 2767 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.038 |
ϕ and ω scans | θmax = 25.8°, θmin = 2.4° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −9→10 |
Tmin = 0.295, Tmax = 0.662 | k = −10→9 |
6046 measured reflections | l = −16→14 |
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)] = 0.042 | H-atom parameters constrained |
wR(F2) = 0.118 | w = 1/[σ2(Fo2) + (0.0677P)2 + 1.2361P] where P = (Fo2 + 2Fc2)/3 |
S = 1.04 | (Δ/σ)max < 0.001 |
3107 reflections | Δρmax = 1.12 e Å−3 |
208 parameters | Δρmin = −0.58 e Å−3 |
1 restraint | Absolute structure: Flack (1983), 1133 Friedel pairs |
Primary atom site location: heavy-atom method | Absolute structure parameter: −0.03 (5) |
[Sn(C17H14S5)] | V = 956.35 (11) Å3 |
Mr = 497.27 | Z = 2 |
Monoclinic, P21 | Mo Kα radiation |
a = 8.6706 (5) Å | µ = 1.88 mm−1 |
b = 8.5319 (6) Å | T = 303 K |
c = 13.3143 (9) Å | 0.38 × 0.28 × 0.22 mm |
β = 103.840 (1)° |
Bruker SMART 1000 CCD area-detector diffractometer | 3107 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 2767 reflections with I > 2σ(I) |
Tmin = 0.295, Tmax = 0.662 | Rint = 0.038 |
6046 measured reflections |
R[F2 > 2σ(F2)] = 0.042 | H-atom parameters constrained |
wR(F2) = 0.118 | Δρmax = 1.12 e Å−3 |
S = 1.04 | Δρmin = −0.58 e Å−3 |
3107 reflections | Absolute structure: Flack (1983), 1133 Friedel pairs |
208 parameters | Absolute structure parameter: −0.03 (5) |
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) - 4.7193 (0.0266) x - 4.3872 (0.0305) y + 10.3024 (0.0339) z = 2.1985 (0.0186) * 0.0068 (0.0060) C6 * -0.0105 (0.0067) C7 * 0.0112 (0.0068) C8 * -0.0082 (0.0069) C9 * 0.0044 (0.0073) C10 * -0.0037 (0.0066) C11 - 0.0928 (0.0130) Sn1 Rms deviation of fitted atoms = 0.0080 - 4.3705 (0.0076) x - 0.9025 (0.0091) y - 9.4759 (0.0098) z = 0.4052 (0.0039) Angle to previous plane (with approximate e.s.d.) = 76.15 (0.17) * -0.0319 (0.0027) S1 * 0.0198 (0.0031) S2 * 0.0145 (0.0061) C3 * 0.0082 (0.0080) C4 * 0.0243 (0.0024) S3 * -0.0348 (0.0031) S4 0.0022 (0.0094) C5 0.0001 (0.0054) S5 - 1.8282 (0.0097) C1 - 1.6295 (0.0094) C2 - 2.8978 (0.0027) Sn1 Rms deviation of fitted atoms = 0.0241 3.8576 (0.0308) x - 2.5853 (0.0305) y + 9.4780 (0.0350) z = 2.4756 (0.0185) Angle to previous plane (with approximate e.s.d.) = 23.85 (0.32) * 0.0018 (0.0060) C12 * -0.0059 (0.0063) C13 * 0.0065 (0.0065) C14 * -0.0031 (0.0074) C15 * -0.0010 (0.0078) C16 * 0.0017 (0.0068) C17 - 0.0165 (0.0128) Sn1 Rms deviation of fitted atoms = 0.0039 - 4.3242 (0.0260) x - 0.7557 (0.0237) y - 9.5582 (0.0299) z = 0.4065 (0.0159) Angle to previous plane (with approximate e.s.d.) = 22.83 (0.41) * -0.0066 (0.0052) C3 * 0.0108 (0.0054) C4 * -0.0016 (0.0038) S3 * -0.0097 (0.0042) S4 * 0.0071 (0.0040) C5 Rms deviation of fitted atoms = 0.0078 - 4.7193 (0.0266) x - 4.3872 (0.0305) y + 10.3024 (0.0339) z = 2.1985 (0.0186) Angle to previous plane (with approximate e.s.d.) = 75.26 (0.23) * 0.0068 (0.0060) C6 * -0.0105 (0.0067) C7 * 0.0112 (0.0068) C8 * -0.0082 (0.0069) C9 * 0.0044 (0.0073) C10 * -0.0037 (0.0066) C11 - 0.0928 (0.0130) Sn1 Rms deviation of fitted atoms = 0.0080 3.8576 (0.0308) x - 2.5853 (0.0305) y + 9.4780 (0.0350) z = 2.4756 (0.0185) Angle to previous plane (with approximate e.s.d.) = 61.82 (0.27) * 0.0018 (0.0060) C12 * -0.0059 (0.0063) C13 * 0.0065 (0.0065) C14 * -0.0031 (0.0074) C15 * -0.0010 (0.0078) C16 * 0.0017 (0.0068) C17 - 0.0165 (0.0128) Sn1 Rms deviation of fitted atoms = 0.0039 |
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 | 0.06357 (5) | 0.00042 (8) | 0.23369 (3) | 0.05324 (16) | |
S1 | −0.2597 (3) | −0.1837 (4) | 0.0979 (2) | 0.0771 (8) | |
S2 | −0.0959 (3) | 0.1169 (6) | −0.0118 (2) | 0.1123 (14) | |
S3 | −0.4590 (2) | 0.0667 (3) | 0.16001 (18) | 0.0617 (5) | |
S4 | −0.3150 (3) | 0.3218 (4) | 0.0755 (3) | 0.0828 (8) | |
S5 | −0.5710 (4) | 0.3915 (4) | 0.1833 (3) | 0.0990 (10) | |
C1 | −0.1013 (10) | −0.1920 (12) | 0.2152 (7) | 0.064 (2) | |
H1A | −0.0431 | −0.2891 | 0.2152 | 0.076* | |
H1B | −0.1484 | −0.1944 | 0.2743 | 0.076* | |
C2 | 0.0819 (10) | 0.0839 (13) | 0.0834 (6) | 0.065 (2) | |
H2A | 0.1411 | 0.1815 | 0.0937 | 0.078* | |
H2B | 0.1448 | 0.0087 | 0.0557 | 0.078* | |
C3 | −0.3105 (8) | 0.0180 (15) | 0.0972 (6) | 0.056 (2) | |
C4 | −0.2437 (10) | 0.1349 (14) | 0.0559 (8) | 0.066 (3) | |
C5 | −0.4549 (10) | 0.2657 (14) | 0.1415 (8) | 0.071 (3) | |
C6 | 0.2948 (9) | −0.0798 (10) | 0.3151 (6) | 0.0496 (16) | |
C7 | 0.3834 (9) | 0.0146 (17) | 0.3942 (6) | 0.059 (2) | |
H7 | 0.3410 | 0.1078 | 0.4120 | 0.071* | |
C8 | 0.5372 (10) | −0.0326 (14) | 0.4467 (7) | 0.070 (3) | |
H8 | 0.5949 | 0.0272 | 0.5012 | 0.084* | |
C9 | 0.6033 (10) | −0.1687 (13) | 0.4171 (7) | 0.066 (2) | |
H9 | 0.7065 | −0.1975 | 0.4500 | 0.079* | |
C10 | 0.5158 (11) | −0.2605 (12) | 0.3392 (8) | 0.071 (2) | |
H10 | 0.5590 | −0.3530 | 0.3209 | 0.085* | |
C11 | 0.3623 (11) | −0.2159 (12) | 0.2871 (7) | 0.063 (2) | |
H11 | 0.3050 | −0.2775 | 0.2334 | 0.075* | |
C12 | −0.0053 (9) | 0.1941 (11) | 0.3165 (6) | 0.0523 (18) | |
C13 | 0.0749 (11) | 0.3365 (12) | 0.3219 (7) | 0.067 (2) | |
H13 | 0.1580 | 0.3467 | 0.2894 | 0.080* | |
C14 | 0.0331 (12) | 0.4633 (12) | 0.3748 (7) | 0.075 (3) | |
H14 | 0.0889 | 0.5571 | 0.3792 | 0.089* | |
C15 | −0.0931 (13) | 0.4482 (15) | 0.4210 (8) | 0.082 (3) | |
H15 | −0.1232 | 0.5332 | 0.4556 | 0.098* | |
C16 | −0.1747 (12) | 0.3090 (15) | 0.4165 (8) | 0.076 (3) | |
H16 | −0.2589 | 0.3001 | 0.4483 | 0.092* | |
C17 | −0.1310 (11) | 0.1823 (13) | 0.3644 (7) | 0.064 (2) | |
H17 | −0.1862 | 0.0883 | 0.3614 | 0.076* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Sn1 | 0.0448 (2) | 0.0626 (3) | 0.0554 (2) | 0.0046 (3) | 0.01793 (17) | 0.0011 (3) |
S1 | 0.0611 (13) | 0.0792 (19) | 0.0864 (18) | 0.0058 (13) | 0.0083 (12) | −0.0222 (15) |
S2 | 0.0563 (13) | 0.215 (4) | 0.0722 (14) | 0.0224 (19) | 0.0284 (12) | 0.055 (2) |
S3 | 0.0446 (9) | 0.0702 (13) | 0.0750 (13) | −0.0011 (9) | 0.0235 (9) | 0.0030 (10) |
S4 | 0.0555 (12) | 0.0813 (18) | 0.108 (2) | 0.0037 (12) | 0.0131 (12) | 0.0347 (16) |
S5 | 0.0788 (17) | 0.093 (2) | 0.120 (2) | 0.0213 (16) | 0.0136 (16) | −0.0299 (19) |
C1 | 0.059 (5) | 0.063 (6) | 0.071 (5) | 0.004 (4) | 0.021 (4) | 0.007 (5) |
C2 | 0.051 (4) | 0.089 (7) | 0.062 (5) | 0.004 (4) | 0.026 (4) | 0.009 (5) |
C3 | 0.043 (3) | 0.063 (6) | 0.063 (4) | 0.003 (4) | 0.016 (3) | −0.005 (5) |
C4 | 0.045 (4) | 0.086 (7) | 0.071 (6) | 0.008 (4) | 0.022 (4) | 0.019 (5) |
C5 | 0.045 (4) | 0.090 (7) | 0.072 (5) | 0.006 (4) | 0.000 (4) | 0.005 (5) |
C6 | 0.047 (4) | 0.051 (4) | 0.053 (4) | 0.007 (3) | 0.016 (3) | 0.002 (3) |
C7 | 0.057 (4) | 0.063 (6) | 0.061 (4) | 0.001 (5) | 0.021 (3) | −0.008 (5) |
C8 | 0.058 (4) | 0.089 (10) | 0.063 (4) | −0.006 (5) | 0.013 (3) | −0.010 (5) |
C9 | 0.046 (4) | 0.075 (6) | 0.074 (5) | 0.006 (4) | 0.007 (4) | 0.012 (5) |
C10 | 0.068 (5) | 0.058 (6) | 0.087 (6) | 0.020 (4) | 0.017 (5) | 0.002 (5) |
C11 | 0.060 (5) | 0.060 (5) | 0.065 (5) | 0.000 (4) | 0.009 (4) | −0.001 (4) |
C12 | 0.047 (4) | 0.060 (5) | 0.050 (4) | 0.006 (3) | 0.010 (3) | 0.002 (4) |
C13 | 0.060 (5) | 0.069 (6) | 0.072 (5) | 0.001 (4) | 0.016 (4) | 0.009 (5) |
C14 | 0.076 (6) | 0.065 (8) | 0.074 (5) | 0.007 (4) | 0.002 (4) | 0.003 (4) |
C15 | 0.078 (6) | 0.085 (9) | 0.079 (6) | 0.029 (5) | 0.012 (5) | −0.012 (5) |
C16 | 0.073 (6) | 0.090 (8) | 0.074 (6) | 0.011 (6) | 0.032 (5) | −0.008 (5) |
C17 | 0.065 (5) | 0.066 (6) | 0.067 (5) | −0.001 (4) | 0.030 (4) | −0.012 (5) |
Sn1—C12 | 2.149 (8) | C7—C8 | 1.408 (12) |
Sn1—C6 | 2.151 (7) | C7—H7 | 0.9300 |
Sn1—C1 | 2.152 (10) | C8—C9 | 1.393 (15) |
Sn1—C2 | 2.165 (8) | C8—H8 | 0.9300 |
S1—C3 | 1.776 (13) | C9—C10 | 1.374 (14) |
S1—C1 | 1.818 (9) | C9—H9 | 0.9300 |
S2—C4 | 1.742 (9) | C10—C11 | 1.398 (13) |
S2—C2 | 1.768 (9) | C10—H10 | 0.9300 |
S3—C5 | 1.716 (12) | C11—H11 | 0.9300 |
S3—C3 | 1.744 (7) | C12—C17 | 1.392 (11) |
S4—C5 | 1.728 (10) | C12—C13 | 1.393 (14) |
S4—C4 | 1.751 (12) | C13—C14 | 1.385 (14) |
S5—C5 | 1.657 (11) | C13—H13 | 0.9300 |
C1—H1A | 0.9700 | C14—C15 | 1.383 (15) |
C1—H1B | 0.9700 | C14—H14 | 0.9300 |
C2—H2A | 0.9700 | C15—C16 | 1.376 (17) |
C2—H2B | 0.9700 | C15—H15 | 0.9300 |
C3—C4 | 1.336 (15) | C16—C17 | 1.385 (14) |
C6—C11 | 1.391 (13) | C16—H16 | 0.9300 |
C6—C7 | 1.400 (13) | C17—H17 | 0.9300 |
C12—Sn1—C6 | 109.0 (3) | C6—C7—C8 | 119.5 (10) |
C12—Sn1—C1 | 112.8 (3) | C6—C7—H7 | 120.3 |
C6—Sn1—C1 | 109.2 (3) | C8—C7—H7 | 120.3 |
C12—Sn1—C2 | 108.2 (4) | C9—C8—C7 | 120.2 (9) |
C6—Sn1—C2 | 107.8 (3) | C9—C8—H8 | 119.9 |
C1—Sn1—C2 | 109.8 (4) | C7—C8—H8 | 119.9 |
C3—S1—C1 | 100.2 (4) | C10—C9—C8 | 119.9 (8) |
C4—S2—C2 | 105.5 (4) | C10—C9—H9 | 120.1 |
C5—S3—C3 | 97.1 (5) | C8—C9—H9 | 120.1 |
C5—S4—C4 | 98.0 (5) | C9—C10—C11 | 120.5 (9) |
S1—C1—Sn1 | 114.4 (5) | C9—C10—H10 | 119.8 |
S1—C1—H1A | 108.7 | C11—C10—H10 | 119.8 |
Sn1—C1—H1A | 108.7 | C6—C11—C10 | 120.4 (9) |
S1—C1—H1B | 108.7 | C6—C11—H11 | 119.8 |
Sn1—C1—H1B | 108.7 | C10—C11—H11 | 119.8 |
H1A—C1—H1B | 107.6 | C17—C12—C13 | 118.4 (8) |
S2—C2—Sn1 | 118.1 (4) | C17—C12—Sn1 | 121.6 (7) |
S2—C2—H2A | 107.8 | C13—C12—Sn1 | 120.0 (6) |
Sn1—C2—H2A | 107.8 | C14—C13—C12 | 121.3 (9) |
S2—C2—H2B | 107.8 | C14—C13—H13 | 119.4 |
Sn1—C2—H2B | 107.8 | C12—C13—H13 | 119.4 |
H2A—C2—H2B | 107.1 | C15—C14—C13 | 118.9 (10) |
C4—C3—S3 | 117.5 (9) | C15—C14—H14 | 120.5 |
C4—C3—S1 | 126.4 (7) | C13—C14—H14 | 120.5 |
S3—C3—S1 | 116.1 (6) | C16—C15—C14 | 121.0 (10) |
C3—C4—S2 | 126.3 (9) | C16—C15—H15 | 119.5 |
C3—C4—S4 | 114.5 (7) | C14—C15—H15 | 119.5 |
S2—C4—S4 | 119.2 (6) | C15—C16—C17 | 119.7 (9) |
S5—C5—S3 | 123.9 (6) | C15—C16—H16 | 120.2 |
S5—C5—S4 | 123.3 (7) | C17—C16—H16 | 120.2 |
S3—C5—S4 | 112.8 (6) | C16—C17—C12 | 120.7 (10) |
C11—C6—C7 | 119.5 (8) | C16—C17—H17 | 119.6 |
C11—C6—Sn1 | 122.1 (6) | C12—C17—H17 | 119.6 |
C7—C6—Sn1 | 118.3 (6) | ||
C3—S1—C1—Sn1 | −43.1 (5) | C2—Sn1—C6—C11 | −70.9 (8) |
C12—Sn1—C1—S1 | 90.4 (5) | C12—Sn1—C6—C7 | −12.5 (7) |
C6—Sn1—C1—S1 | −148.3 (4) | C1—Sn1—C6—C7 | −136.1 (7) |
C2—Sn1—C1—S1 | −30.3 (6) | C2—Sn1—C6—C7 | 104.7 (7) |
C4—S2—C2—Sn1 | 19.8 (8) | C11—C6—C7—C8 | −2.3 (13) |
C12—Sn1—C2—S2 | −76.0 (7) | Sn1—C6—C7—C8 | −178.0 (7) |
C6—Sn1—C2—S2 | 166.3 (6) | C6—C7—C8—C9 | 2.7 (14) |
C1—Sn1—C2—S2 | 47.4 (7) | C7—C8—C9—C10 | −2.5 (15) |
C5—S3—C3—C4 | −0.6 (8) | C8—C9—C10—C11 | 1.9 (15) |
C5—S3—C3—S1 | 177.7 (5) | C7—C6—C11—C10 | 1.7 (13) |
C1—S1—C3—C4 | 87.4 (9) | Sn1—C6—C11—C10 | 177.2 (7) |
C1—S1—C3—S3 | −90.8 (5) | C9—C10—C11—C6 | −1.5 (15) |
S3—C3—C4—S2 | −179.1 (6) | C6—Sn1—C12—C17 | −112.9 (7) |
S1—C3—C4—S2 | 2.7 (13) | C1—Sn1—C12—C17 | 8.6 (8) |
S3—C3—C4—S4 | 1.6 (10) | C2—Sn1—C12—C17 | 130.2 (7) |
S1—C3—C4—S4 | −176.5 (5) | C6—Sn1—C12—C13 | 68.1 (7) |
C2—S2—C4—C3 | −76.5 (10) | C1—Sn1—C12—C13 | −170.5 (6) |
C2—S2—C4—S4 | 102.8 (7) | C2—Sn1—C12—C13 | −48.8 (7) |
C5—S4—C4—C3 | −1.8 (8) | C17—C12—C13—C14 | 1.0 (13) |
C5—S4—C4—S2 | 178.9 (6) | Sn1—C12—C13—C14 | −180.0 (7) |
C3—S3—C5—S5 | −180.0 (6) | C12—C13—C14—C15 | −1.4 (14) |
C3—S3—C5—S4 | −0.6 (6) | C13—C14—C15—C16 | 1.1 (15) |
C4—S4—C5—S5 | −179.3 (6) | C14—C15—C16—C17 | −0.4 (17) |
C4—S4—C5—S3 | 1.3 (6) | C15—C16—C17—C12 | 0.0 (16) |
C12—Sn1—C6—C11 | 171.9 (7) | C13—C12—C17—C16 | −0.2 (14) |
C1—Sn1—C6—C11 | 48.3 (7) | Sn1—C12—C17—C16 | −179.3 (7) |
[Sn(C10H8S10)] | F(000) = 1112 |
Mr = 567.45 | Dx = 2.029 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2yn | Cell parameters from 7784 reflections |
a = 11.3973 (4) Å | θ = 2.3–30.6° |
b = 14.2749 (5) Å | µ = 2.49 mm−1 |
c = 12.5609 (5) Å | T = 297 K |
β = 114.625 (1)° | Rod, dark red-brown |
V = 1857.74 (12) Å3 | 0.60 × 0.25 × 0.10 mm |
Z = 4 |
Bruker SMART 1000 CCD area-detector diffractometer | 5312 independent reflections |
Radiation source: fine-focus sealed tube | 4279 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.033 |
ϕ and ω scans | θmax = 30.8°, θmin = 2.0° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −16→16 |
Tmin = 0.347, Tmax = 0.780 | k = −10→19 |
15205 measured reflections | l = −18→17 |
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)] = 0.033 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.091 | H-atom parameters constrained |
S = 1.01 | w = 1/[σ2(Fo2) + (0.0498P)2 + 1.0773P] where P = (Fo2 + 2Fc2)/3 |
5312 reflections | (Δ/σ)max = 0.001 |
190 parameters | Δρmax = 1.31 e Å−3 |
0 restraints | Δρmin = −0.75 e Å−3 |
[Sn(C10H8S10)] | V = 1857.74 (12) Å3 |
Mr = 567.45 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 11.3973 (4) Å | µ = 2.49 mm−1 |
b = 14.2749 (5) Å | T = 297 K |
c = 12.5609 (5) Å | 0.60 × 0.25 × 0.10 mm |
β = 114.625 (1)° |
Bruker SMART 1000 CCD area-detector diffractometer | 5312 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 4279 reflections with I > 2σ(I) |
Tmin = 0.347, Tmax = 0.780 | Rint = 0.033 |
15205 measured reflections |
R[F2 > 2σ(F2)] = 0.033 | 0 restraints |
wR(F2) = 0.091 | H-atom parameters constrained |
S = 1.01 | Δρmax = 1.31 e Å−3 |
5312 reflections | Δρmin = −0.75 e Å−3 |
190 parameters |
Experimental. Data are 99.5 or 98.5% complete out to 58 or 59° 2θ, respectively - see below. |
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) - 6.6265 (0.0032) x + 7.5668 (0.0039) y - 4.0049 (0.0037) z = 1.5539 (0.0036) * -0.0310 (0.0009) S1 * 0.0218 (0.0009) S2 * 0.0154 (0.0024) C3 * 0.0021 (0.0023) C4 * 0.0245 (0.0009) S3 * -0.0328 (0.0009) S4 - 0.0516 (0.0030) C5 - 0.0949 (0.0016) S5 - 1.8366 (0.0034) C1 - 1.7566 (0.0034) C2 - 2.6539 (0.0011) Sn1 Rms deviation of fitted atoms = 0.0237 - 9.0152 (0.0024) x + 8.5434 (0.0038) y + 5.5902 (0.0042) z = 3.0027 (0.0029) Angle to previous plane (with approximate e.s.d.) = 45.67 (0.03) * 0.0122 (0.0010) S6 * -0.0144 (0.0010) S7 * -0.0065 (0.0025) C8 * 0.0104 (0.0026) C9 * -0.0128 (0.0010) S8 * 0.0111 (0.0010) S9 - 0.0237 (0.0036) C10 - 0.0541 (0.0020) S10 1.7688 (0.0039) C6 1.5990 (0.0040) C7 2.8846 (0.0010) Sn1 Rms deviation of fitted atoms = 0.0115 |
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 | 0.013577 (19) | 0.240768 (14) | 0.707097 (18) | 0.03320 (7) | |
S1 | −0.27731 (7) | 0.31717 (6) | 0.67784 (7) | 0.04065 (18) | |
S2 | −0.07947 (8) | 0.45489 (6) | 0.59749 (7) | 0.03866 (17) | |
S3 | −0.23058 (8) | 0.46297 (6) | 0.86210 (8) | 0.04340 (19) | |
S4 | −0.05854 (8) | 0.57353 (5) | 0.80067 (7) | 0.03910 (17) | |
S5 | −0.10852 (10) | 0.63033 (7) | 1.00619 (8) | 0.0552 (3) | |
S6 | 0.09415 (10) | 0.10155 (7) | 0.53597 (10) | 0.0576 (3) | |
S7 | 0.31270 (10) | 0.14326 (9) | 0.81993 (9) | 0.0620 (3) | |
S8 | 0.21824 (9) | 0.26740 (7) | 0.47814 (8) | 0.0461 (2) | |
S9 | 0.39717 (8) | 0.30331 (8) | 0.71610 (8) | 0.0499 (2) | |
S10 | 0.40256 (12) | 0.42571 (9) | 0.52606 (12) | 0.0708 (3) | |
C1 | −0.1435 (3) | 0.2390 (2) | 0.7596 (3) | 0.0361 (6) | |
H1A | −0.1766 | 0.1755 | 0.7516 | 0.043* | |
H1B | −0.1101 | 0.2555 | 0.8419 | 0.043* | |
C2 | 0.0605 (3) | 0.3806 (2) | 0.6695 (3) | 0.0406 (7) | |
H2A | 0.1177 | 0.4100 | 0.7423 | 0.049* | |
H2B | 0.1068 | 0.3757 | 0.6200 | 0.049* | |
C3 | −0.2033 (3) | 0.4227 (2) | 0.7432 (3) | 0.0344 (6) | |
C4 | −0.1237 (3) | 0.4752 (2) | 0.7140 (2) | 0.0315 (5) | |
C5 | −0.1304 (3) | 0.5588 (2) | 0.8963 (3) | 0.0358 (6) | |
C6 | −0.0393 (4) | 0.1559 (3) | 0.5519 (3) | 0.0564 (10) | |
H6A | −0.0983 | 0.1075 | 0.5532 | 0.068* | |
H6B | −0.0850 | 0.1949 | 0.4838 | 0.068* | |
C7 | 0.1706 (4) | 0.1682 (3) | 0.8413 (4) | 0.0596 (11) | |
H7A | 0.1965 | 0.2046 | 0.9127 | 0.072* | |
H7B | 0.1374 | 0.1091 | 0.8551 | 0.072* | |
C8 | 0.2107 (3) | 0.1910 (2) | 0.5839 (3) | 0.0400 (7) | |
C9 | 0.2940 (3) | 0.2081 (3) | 0.6952 (3) | 0.0421 (7) | |
C10 | 0.3428 (3) | 0.3370 (3) | 0.5707 (3) | 0.0450 (7) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Sn1 | 0.03190 (11) | 0.03361 (12) | 0.03809 (12) | 0.00304 (7) | 0.01855 (8) | −0.00084 (8) |
S1 | 0.0299 (3) | 0.0400 (4) | 0.0529 (4) | −0.0073 (3) | 0.0181 (3) | −0.0106 (3) |
S2 | 0.0458 (4) | 0.0389 (4) | 0.0377 (4) | 0.0054 (3) | 0.0238 (3) | 0.0039 (3) |
S3 | 0.0494 (4) | 0.0418 (4) | 0.0528 (5) | 0.0009 (3) | 0.0350 (4) | −0.0049 (3) |
S4 | 0.0416 (4) | 0.0295 (4) | 0.0484 (4) | −0.0024 (3) | 0.0210 (3) | −0.0040 (3) |
S5 | 0.0644 (6) | 0.0510 (5) | 0.0393 (4) | 0.0180 (4) | 0.0110 (4) | −0.0110 (4) |
S6 | 0.0639 (6) | 0.0452 (5) | 0.0853 (7) | −0.0149 (4) | 0.0524 (6) | −0.0262 (5) |
S7 | 0.0496 (5) | 0.0808 (8) | 0.0632 (6) | 0.0296 (5) | 0.0310 (5) | 0.0358 (5) |
S8 | 0.0481 (5) | 0.0556 (5) | 0.0404 (4) | −0.0050 (4) | 0.0242 (4) | 0.0002 (4) |
S9 | 0.0361 (4) | 0.0607 (6) | 0.0497 (5) | −0.0038 (4) | 0.0147 (4) | −0.0001 (4) |
S10 | 0.0627 (6) | 0.0558 (6) | 0.0968 (8) | −0.0083 (5) | 0.0362 (6) | 0.0207 (6) |
C1 | 0.0332 (14) | 0.0351 (15) | 0.0438 (16) | −0.0064 (11) | 0.0200 (12) | −0.0050 (12) |
C2 | 0.0374 (16) | 0.0373 (16) | 0.0555 (18) | 0.0036 (12) | 0.0274 (14) | 0.0007 (14) |
C3 | 0.0320 (14) | 0.0322 (15) | 0.0414 (15) | 0.0018 (11) | 0.0177 (12) | −0.0044 (11) |
C4 | 0.0313 (13) | 0.0301 (14) | 0.0355 (13) | 0.0029 (11) | 0.0163 (11) | −0.0014 (11) |
C5 | 0.0368 (15) | 0.0311 (14) | 0.0357 (14) | 0.0102 (12) | 0.0115 (12) | −0.0010 (11) |
C6 | 0.0428 (19) | 0.069 (3) | 0.063 (2) | −0.0108 (17) | 0.0275 (17) | −0.0276 (19) |
C7 | 0.054 (2) | 0.079 (3) | 0.058 (2) | 0.025 (2) | 0.0359 (18) | 0.027 (2) |
C8 | 0.0438 (17) | 0.0365 (16) | 0.0511 (17) | 0.0008 (13) | 0.0312 (15) | −0.0015 (13) |
C9 | 0.0348 (15) | 0.0459 (18) | 0.0509 (18) | 0.0089 (13) | 0.0233 (14) | 0.0096 (14) |
C10 | 0.0365 (16) | 0.0436 (19) | 0.0588 (19) | 0.0022 (13) | 0.0236 (15) | 0.0050 (15) |
Sn1—C7 | 2.146 (4) | S7—C9 | 1.755 (3) |
Sn1—C1 | 2.151 (3) | S7—C7 | 1.784 (4) |
Sn1—C6 | 2.157 (3) | S7—S2v | 3.4724 (12) |
Sn1—C2 | 2.168 (3) | S8—C10 | 1.726 (4) |
Sn1—S5i | 3.7788 (9) | S8—C8 | 1.749 (3) |
S1—C3 | 1.754 (3) | S9—C10 | 1.735 (4) |
S1—C1 | 1.822 (3) | S9—C9 | 1.744 (4) |
S1—S5ii | 3.4122 (13) | S10—C10 | 1.643 (4) |
S2—C4 | 1.759 (3) | S10—S10vi | 3.328 (2) |
S2—C2 | 1.813 (3) | C1—H1A | 0.9700 |
S2—S7iii | 3.4724 (12) | C1—H1B | 0.9700 |
S3—C5 | 1.717 (3) | C2—H2A | 0.9700 |
S3—C3 | 1.744 (3) | C2—H2B | 0.9700 |
S4—C5 | 1.726 (3) | C3—C4 | 1.342 (4) |
S4—C4 | 1.741 (3) | C6—H6A | 0.9700 |
S5—C5 | 1.650 (3) | C6—H6B | 0.9700 |
S5—S1iv | 3.4122 (13) | C7—H7A | 0.9700 |
S5—Sn1i | 3.7788 (9) | C7—H7B | 0.9700 |
S6—C8 | 1.758 (3) | C8—C9 | 1.345 (5) |
S6—C6 | 1.791 (4) | ||
C7—Sn1—C1 | 106.37 (13) | S2—C2—H2A | 108.8 |
C7—Sn1—C6 | 105.46 (18) | Sn1—C2—H2A | 108.8 |
C1—Sn1—C6 | 108.40 (13) | S2—C2—H2B | 108.8 |
C7—Sn1—C2 | 114.51 (16) | Sn1—C2—H2B | 108.8 |
C1—Sn1—C2 | 112.98 (12) | H2A—C2—H2B | 107.7 |
C6—Sn1—C2 | 108.73 (16) | C4—C3—S3 | 115.6 (2) |
C7—Sn1—S5i | 70.88 (13) | C4—C3—S1 | 126.9 (2) |
C1—Sn1—S5i | 70.01 (9) | S3—C3—S1 | 117.47 (17) |
C6—Sn1—S5i | 174.96 (13) | C3—C4—S4 | 116.1 (2) |
C2—Sn1—S5i | 76.17 (9) | C3—C4—S2 | 126.6 (2) |
C3—S1—C1 | 97.83 (14) | S4—C4—S2 | 117.28 (17) |
C3—S1—S5ii | 164.05 (11) | S5—C5—S3 | 123.7 (2) |
C1—S1—S5ii | 84.04 (10) | S5—C5—S4 | 123.8 (2) |
C4—S2—C2 | 100.33 (14) | S3—C5—S4 | 112.45 (16) |
C4—S2—S7iii | 142.92 (10) | S6—C6—Sn1 | 114.44 (19) |
C2—S2—S7iii | 97.72 (12) | S6—C6—H6A | 108.7 |
C5—S3—C3 | 98.02 (15) | Sn1—C6—H6A | 108.7 |
C5—S4—C4 | 97.74 (14) | S6—C6—H6B | 108.7 |
C5—S5—S1iv | 92.03 (11) | Sn1—C6—H6B | 108.7 |
C5—S5—Sn1i | 169.07 (11) | H6A—C6—H6B | 107.6 |
S1iv—S5—Sn1i | 98.16 (3) | S7—C7—Sn1 | 119.35 (19) |
C8—S6—C6 | 101.69 (17) | S7—C7—H7A | 107.5 |
C9—S7—C7 | 104.44 (16) | Sn1—C7—H7A | 107.5 |
C9—S7—S2v | 165.91 (13) | S7—C7—H7B | 107.5 |
C7—S7—S2v | 83.85 (12) | Sn1—C7—H7B | 107.5 |
C10—S8—C8 | 97.74 (17) | H7A—C7—H7B | 107.0 |
C10—S9—C9 | 97.75 (17) | C9—C8—S8 | 116.1 (3) |
C10—S10—S10vi | 164.56 (14) | C9—C8—S6 | 126.4 (3) |
S1—C1—Sn1 | 115.34 (16) | S8—C8—S6 | 117.5 (2) |
S1—C1—H1A | 108.4 | C8—C9—S9 | 116.0 (3) |
Sn1—C1—H1A | 108.4 | C8—C9—S7 | 127.1 (3) |
S1—C1—H1B | 108.4 | S9—C9—S7 | 116.9 (2) |
Sn1—C1—H1B | 108.4 | S10—C10—S8 | 123.8 (2) |
H1A—C1—H1B | 107.5 | S10—C10—S9 | 123.8 (2) |
S2—C2—Sn1 | 113.67 (16) | S8—C10—S9 | 112.5 (2) |
C3—S1—C1—Sn1 | −75.49 (17) | C3—S3—C5—S4 | 2.39 (19) |
S5ii—S1—C1—Sn1 | 88.56 (14) | C4—S4—C5—S5 | 179.7 (2) |
C7—Sn1—C1—S1 | 167.32 (19) | C4—S4—C5—S3 | −1.93 (18) |
C6—Sn1—C1—S1 | −79.7 (2) | C8—S6—C6—Sn1 | −39.5 (3) |
C2—Sn1—C1—S1 | 40.9 (2) | C7—Sn1—C6—S6 | −37.0 (3) |
S5i—Sn1—C1—S1 | 105.37 (16) | C1—Sn1—C6—S6 | −150.6 (2) |
C4—S2—C2—Sn1 | 71.67 (19) | C2—Sn1—C6—S6 | 86.3 (3) |
S7iii—S2—C2—Sn1 | −75.80 (15) | C9—S7—C7—Sn1 | 10.6 (3) |
C7—Sn1—C2—S2 | −159.48 (17) | S2v—S7—C7—Sn1 | 179.1 (3) |
C1—Sn1—C2—S2 | −37.5 (2) | C1—Sn1—C7—S7 | 172.6 (3) |
C6—Sn1—C2—S2 | 82.88 (19) | C6—Sn1—C7—S7 | 57.7 (3) |
S5i—Sn1—C2—S2 | −98.36 (16) | C2—Sn1—C7—S7 | −61.8 (3) |
C5—S3—C3—C4 | −2.1 (3) | S5i—Sn1—C7—S7 | −126.0 (3) |
C5—S3—C3—S1 | 175.84 (18) | C10—S8—C8—C9 | 1.0 (3) |
C1—S1—C3—C4 | 83.6 (3) | C10—S8—C8—S6 | 179.76 (19) |
S5ii—S1—C3—C4 | −12.1 (6) | C6—S6—C8—C9 | 86.4 (3) |
C1—S1—C3—S3 | −94.06 (19) | C6—S6—C8—S8 | −92.2 (2) |
S5ii—S1—C3—S3 | 170.2 (2) | S8—C8—C9—S9 | −0.5 (4) |
S3—C3—C4—S4 | 1.1 (3) | S6—C8—C9—S9 | −179.04 (18) |
S1—C3—C4—S4 | −176.67 (17) | S8—C8—C9—S7 | −178.56 (19) |
S3—C3—C4—S2 | −178.72 (17) | S6—C8—C9—S7 | 2.9 (5) |
S1—C3—C4—S2 | 3.5 (4) | C10—S9—C9—C8 | −0.4 (3) |
C5—S4—C4—C3 | 0.5 (3) | C10—S9—C9—S7 | 177.9 (2) |
C5—S4—C4—S2 | −179.66 (17) | C7—S7—C9—C8 | −71.1 (4) |
C2—S2—C4—C3 | −88.9 (3) | S2v—S7—C9—C8 | 164.0 (3) |
S7iii—S2—C4—C3 | 29.0 (4) | C7—S7—C9—S9 | 110.8 (2) |
C2—S2—C4—S4 | 91.33 (19) | S2v—S7—C9—S9 | −14.1 (7) |
S7iii—S2—C4—S4 | −150.78 (10) | S10vi—S10—C10—S8 | −125.4 (5) |
S1iv—S5—C5—S3 | −119.32 (18) | S10vi—S10—C10—S9 | 55.0 (8) |
Sn1i—S5—C5—S3 | 81.8 (7) | C8—S8—C10—S10 | 179.1 (2) |
S1iv—S5—C5—S4 | 58.88 (19) | C8—S8—C10—S9 | −1.2 (2) |
Sn1i—S5—C5—S4 | −99.9 (7) | C9—S9—C10—S10 | −179.3 (2) |
C3—S3—C5—S5 | −179.2 (2) | C9—S9—C10—S8 | 1.0 (2) |
Symmetry codes: (i) −x, −y+1, −z+2; (ii) −x−1/2, y−1/2, −z+3/2; (iii) x−1/2, −y+1/2, z−1/2; (iv) −x−1/2, y+1/2, −z+3/2; (v) x+1/2, −y+1/2, z+1/2; (vi) −x+1, −y+1, −z+1. |
Experimental details
(IV) | (V) | |
Crystal data | ||
Chemical formula | [Sn(C17H14S5)] | [Sn(C10H8S10)] |
Mr | 497.27 | 567.45 |
Crystal system, space group | Monoclinic, P21 | Monoclinic, P21/n |
Temperature (K) | 303 | 297 |
a, b, c (Å) | 8.6706 (5), 8.5319 (6), 13.3143 (9) | 11.3973 (4), 14.2749 (5), 12.5609 (5) |
β (°) | 103.840 (1) | 114.625 (1) |
V (Å3) | 956.35 (11) | 1857.74 (12) |
Z | 2 | 4 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 1.88 | 2.49 |
Crystal size (mm) | 0.38 × 0.28 × 0.22 | 0.60 × 0.25 × 0.10 |
Data collection | ||
Diffractometer | Bruker SMART 1000 CCD area-detector diffractometer | Bruker SMART 1000 CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.295, 0.662 | 0.347, 0.780 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 6046, 3107, 2767 | 15205, 5312, 4279 |
Rint | 0.038 | 0.033 |
(sin θ/λ)max (Å−1) | 0.613 | 0.721 |
Refinement | ||
R[F2 > 2σ(F2)], wR(F2), S | 0.042, 0.118, 1.04 | 0.033, 0.091, 1.01 |
No. of reflections | 3107 | 5312 |
No. of parameters | 208 | 190 |
No. of restraints | 1 | 0 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 1.12, −0.58 | 1.31, −0.75 |
Absolute structure | Flack (1983), 1133 Friedel pairs | ? |
Absolute structure parameter | −0.03 (5) | ? |
Computer programs: SMART (Bruker, 1999), SAINT (Bruker, 1999), SAINT, SHELXS86 (Sheldrick, 1990), SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), ORTEP-3 (Farrugia, 1997), SHELXL97 and PLATON (Spek, 1990).
Sn1—C12 | 2.149 (8) | Sn1—C1 | 2.152 (10) |
Sn1—C6 | 2.151 (7) | Sn1—C2 | 2.165 (8) |
C12—Sn1—C6 | 109.0 (3) | C12—Sn1—C2 | 108.2 (4) |
C12—Sn1—C1 | 112.8 (3) | C6—Sn1—C2 | 107.8 (3) |
C6—Sn1—C1 | 109.2 (3) | C1—Sn1—C2 | 109.8 (4) |
Sn1—C7 | 2.146 (4) | Sn1—C2 | 2.168 (3) |
Sn1—C1 | 2.151 (3) | Sn1—S5i | 3.7788 (9) |
Sn1—C6 | 2.157 (3) | ||
C7—Sn1—C1 | 106.37 (13) | C6—Sn1—C2 | 108.73 (16) |
C7—Sn1—C6 | 105.46 (18) | C7—Sn1—S5i | 70.88 (13) |
C1—Sn1—C6 | 108.40 (13) | C1—Sn1—S5i | 70.01 (9) |
C7—Sn1—C2 | 114.51 (16) | C6—Sn1—S5i | 174.96 (13) |
C1—Sn1—C2 | 112.98 (12) | C2—Sn1—S5i | 76.17 (9) |
Symmetry code: (i) −x, −y+1, −z+2. |
(IV) | (Va) | (Vb)a | |
C1-S1 | 1.818 (9) | 1.822 (3) | 1.791 (4) |
C2-S2 | 1.768 (9) | 1.813 (3) | 1.784 (4) |
S1-C3 | 1.776 (13) | 1.754 (3) | 1.758 (3) |
S2-C4 | 1.742 (9) | 1.759 (3) | 1.755 (3) |
C3-C4 | 1.336 (15) | 1.342 (4) | 1.345 (5) |
C3-S3 | 1.744 (7) | 1.744 (3) | 1.749 (3) |
C4-S4 | 1.751 (12) | 1.741 (3) | 1.744 (4) |
S3-C5 | 1.716 (12) | 1.717 (3) | 1.726 (4) |
S4-C5 | 1.728 (10) | 1.726 (3) | 1.735 (4) |
S5-C5 | 1.657 (11) | 1.650 (3) | 1.643 (4) |
Sn1-C1-S1 | 114.4 (5) | 115.34 (16) | 114.44 (19) |
Sn1-C2-S2 | 118.1 (4) | 113.67 (16) | 119.35 (19) |
C1-S1-C3 | 100.2 (4) | 97.83 (14) | 101.69 (17) |
C2-S2-C4 | 105.5 (4) | 100.33 (14) | 104.44 (16) |
S1-C3-S3 | 116.1 (6) | 117.47 (17) | 117.5 (2) |
S1-C3-C4 | 126.4 (7) | 126.9 (2) | 126.4 (3) |
S3-C3-C4 | 117.5 (9) | 115.6 (2) | 116.1 (3) |
S2-C4-S4 | 119.2 (6) | 117.28 (17) | 116.9 (2) |
S2-C4-C3 | 126.3 (9) | 126.6 (2) | 127.1 (3) |
S4-C4-C3 | 114.5 (7) | 116.1 (2) | 116.0 (3) |
C3-S3-C5 | 97.1 (5) | 98.02 (15) | 97.74 (17) |
C4-S4-C5 | 98.0 (5) | 97.74 (14) | 97.75 (17) |
S3-C5-S4 | 112.8 (6) | 112.45 (16) | 112.5 (2) |
S3-C5-S5 | 123.9 (6) | 123.7 (2) | 123.8 (2) |
S4-C5-S5 | 123.3 (7) | 123.8 (2) | 123.8 (2) |
Sn1-C1-S1-C3 | -43.1 (5) | -75.49 (17) | -39.5 (3) |
Sn1-C2-S2-C4 | 19.8 (8) | 71.67 (19) | 10.6 (3) |
(a) The numerical elements of the atom designations which are directly applicable to (IV) and (Va) to be incremented by 5 for application to (Vb). |
A search of the Cambridge Structural Database (CSD, Version 5.22; Allen & Kennard, 1993) readily demonstrates that the dianion C3S52-, often designated dmit, resulting from deprotonation of the parent 1,3-dithiole-2-thione-4,5-dithiol, (I), is well known as a bidentate ligand which bonds through the exocyclic thiol S to form, usually anionic, chelate complexes with transition metals and main group elements. In the particular case of Sn, used as an example, other ligating species may be present along with dmit, yielding either charged, [R2SnX(dmit)]- (R is Me, Et, Ph, etc. and X is a halide), or neutral species, e.g. [R2Sn(dmit)] (CCDC reference Nos. 154944–154947; Allan et al., 2001 and references therein). The dmit moiety is also found as a fragment in heterocyclic compounds such as the benzyl derivatives, (II) (X and Y are MeO and NO2; Chohan et al., 1999), and 5H,10H-dithiolo[2,3 - b-2,5-benzodithiocine-2-thione, (III) (Chohan et al., 2000). \sch
The interest in 6,6-diphenyl-6,7-dihydro-5H-1,3,4,8-tetrathia-6-stannaazulene-2-thione, (IV) (Fig. 1), and 6,6'-spirobi[6,7-dihydro-5H-1,3,4,8-tetrathia-6-stannaazulene]-2,2'-dithione, (V) (Fig. 2), is primarily in their chemical and structural situation, which falls somewhere between the true chelates such as the [Sn(dmit)3]2- dianion (de Assis et al., 1999) and heterocyclic compounds such as (III).
The bond distances and angles involving Sn in (IV) and (V) are given in Tables 1 and 2, respectively. In (IV), the Sn atom is in a comparatively regular tetrahedral environment unperturbed by intermolecular interactions. In (V), however, with the inclusion of the intermolecular Sn1···S5i contact of 3.7788 (9) Å, the Sn atom is five-coordinate in a highly distorted trigonal-bipyramidal environment, with atoms S5i and C6 axial and C1, C2 and C7 equatorial [symmetry code: (i) -x, 1 - y, 2 - z]. This contact is only ca 0.27 Å less than the sum of the van der Waals radii for Sn and S [4.05 Å (Huheey et al., 1993) or 4.06 Å (PLATON; Spek, 1990)], has comparatively little effect on the C—Sn—C angles [105.46 (18)–114.51 (16)°, still closely grouped around the ideal tetrahedral value] and, although given some credibility by the C6—Sn1—S5i trans axial angle of 174.96 (13)°, close to the ideal for a trigonal-bipyramidal arrangement, is perceived as an extremely weak interaction. If, however, it is regarded as significant, it represents, to our knowledge, the first case of a tetraorganotin compound with a coordination number greater than four as a consequence of an intermolecular interaction with a soft, S, donor. In contrast, while some five- (e.g. Tzschach & Jurkschat, 1986; Das, Mun, Wei, Blunden & Mak, 1987; Jousseaume et al., 1988; Jastrzebski et al., 1991; Doidge-Harrison et al., 1993; Willem et al., 1994; Kayser et al., 1994) and even six-coordinate (Das, Mun, Wei & Mak, 1987) tetraorganotin compounds have been reported, invariably these are intramolecular and involve, almost exclusively, O or N donor groups suitably sited in fairly rigid molecules. It seems that the α-dmit groups in (V) effectively reduce the electron density at the Sn centre, at the same time enhancing the thione S10···S10ii intermolecular interaction noted below.
The remaining bond lengths and angles in (IV) and (V) (Table 3) show few unusual features. In particular, the geometry of the dmit (C3S5) fragment within these compounds is much the same as it is in related chelate and heterocyclic compounds, such as those noted above. One feature, however, is the similarity between the Sn1—C1—S1—C3 and Sn1—C2—S2—C4 torsion angles in (IV) and the corresponding angles of one stannazulene of (V) but not the other, i.e. with (Vb) but not with (Va). Please define (Va) and (Vb).
There is also a degree of interest in the conformation of the molecules. In both compounds, the stannaazulene rings are boat-shaped relative to the basal fragment comprising atoms C1, C2, S1 and S2 [or the equivalent in the second stannaazulene ring of (V)], and thus are perceived as U-shaped when seen side on. This is exactly the same as the situation in the α and β forms of (III), whose molecular conformations were investigated and confirmed as optimum by molecular mechanics calculations (Chohan et al., 2000). For (IV), this results in the overlap of the C12—C17 phenyl ring with the dithiole ring of the dmit fragment, such that the angle between the least-squares planes is 22.8 (4)°, and for (V) it renders the molecule U-shaped overall.
There are no significant intermolecular interactions in the structure of (IV). The situation in (V) is very different. Here, both thione (S5 and S10) and thiol (S1, S2 and S7) S atoms participate in intermolecular Sn···S or S···S interactions with interatomic distances less than the corresponding sums of the van der Waals radii. The Sn1···S5i contacts alluded to above interconnect the molecules to form centrosymmetric dimers, and then S10···S10ii contacts of 3.328 (2) Å interconnect the dimers to form zigzag chains parallel to [101] (Fig. 3) [symmetry code: (ii) 1 - x, 1 - y, 1 - z]. This last (S10···S10ii) is, to our knowledge, the shortest, and presumably strongest, interaction of this specific type so far identified. Additional weaker S···S contacts, such as S2···S7iii [3.4724 (12) Å] and S5···S1iv [3.4122 (13) Å], interconnect the chains and complete the three-dimensional connectivity of the structure [symmetry codes: (iii) x - 1/2, 1/2 - y, z - 1/2; (iv) -x - 1/2, y + 1/2, 3/2 - z].