Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270199014560/bm1382sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270199014560/bm13821csup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270199014560/bm13821msup3.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270199014560/bm13822msup4.hkl |
CCDC references: 142773; 142774; 142775
All hydrogen atoms were refined using a riding model. For compound (1 m) very few single crystals were available, and these could not be cut because they deformed: the crystal size is therefore greter than would normally be acceptable. For (2 m), which diffracted more weakly, 307 similarity restraints were applied to the Uij components of carbon atoms.
For all compounds, data collection: XSCANS (Siemens, 1991); cell refinement: XSCANS; data reduction: XSCANS; program(s) used to solve structure: SHELXS86 (Sheldrick, 1990); program(s) used to refine structure: SHELXL93 (Sheldrick, 1993); molecular graphics: XP5 (Siemens, 1994); software used to prepare material for publication: SHELXL93.
C33H32 | F(000) = 920 |
Mr = 428.59 | Dx = 1.260 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
a = 24.928 (3) Å | Cell parameters from 64 reflections |
b = 7.8409 (6) Å | θ = 4.8–12.5° |
c = 11.5716 (12) Å | µ = 0.07 mm−1 |
β = 92.256 (8)° | T = 173 K |
V = 2260.0 (4) Å3 | Hexagonal tablet, colourless |
Z = 4 | 0.76 × 0.46 × 0.22 mm |
Siemens P4 diffractometer | Rint = 0.025 |
Radiation source: fine-focus sealed tube | θmax = 27.5°, θmin = 3.2° |
Graphite monochromator | h = 0→32 |
ω–scans | k = −10→2 |
3066 measured reflections | l = −15→15 |
2589 independent reflections | 3 standard reflections every 247 reflections |
1912 reflections with I > 2σ(I) | intensity decay: none |
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)] = 0.045 | H-atom parameters constrained |
wR(F2) = 0.131 | Calculated w = 1/[σ2(Fo2) + (0.0763P)2 + 0.4887P] where P = (Fo2 + 2Fc2)/3 |
S = 1.02 | (Δ/σ)max < 0.001 |
2587 reflections | Δρmax = 0.27 e Å−3 |
151 parameters | Δρmin = −0.21 e Å−3 |
0 restraints | Extinction correction: SHELXL93 (Sheldrick, 1993), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0080 (12) |
C33H32 | V = 2260.0 (4) Å3 |
Mr = 428.59 | Z = 4 |
Monoclinic, C2/c | Mo Kα radiation |
a = 24.928 (3) Å | µ = 0.07 mm−1 |
b = 7.8409 (6) Å | T = 173 K |
c = 11.5716 (12) Å | 0.76 × 0.46 × 0.22 mm |
β = 92.256 (8)° |
Siemens P4 diffractometer | Rint = 0.025 |
3066 measured reflections | 3 standard reflections every 247 reflections |
2589 independent reflections | intensity decay: none |
1912 reflections with I > 2σ(I) |
R[F2 > 2σ(F2)] = 0.045 | 0 restraints |
wR(F2) = 0.131 | H-atom parameters constrained |
S = 1.02 | Δρmax = 0.27 e Å−3 |
2587 reflections | Δρmin = −0.21 e Å−3 |
151 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. torsion angles 4.61 (0.03) C9 - C2 - C1 - C10 − 113.80 (0.12) C4 - C17 - C4_$1 - C5_$1 intramolecular distances 2.7919 (0.0018) C3 - C14 2.7795 (0.0018) C6 - C11 3.1350 (0.0018) C4 - C15 3.1009 (0.0018) C5 - C16 3.0931 (0.0019) C7 - C12 3.0839 (0.0019) C8 - C13 Least-squares planes (x,y,z in crystal coordinates) and deviations from them (* indicates atom used to define plane) 13.4395 (0.0163) x − 5.5890 (0.0031) y − 5.4327 (0.0087) z = 0.7251 (0.0120) * 0.0107 (0.0006) C4 * −0.0108 (0.0006) C5 * 0.0108 (0.0006) C7 * −0.0108 (0.0006) C8 − 0.1716 (0.0019) C3 − 0.1552 (0.0019) C6 Rms deviation of fitted atoms = 0.0108 − 13.7193 (0.0176) x + 5.5243 (0.0032) y + 5.4310 (0.0088) z = 2.2540 (0.0126) Angle to previous plane (with approximate e.s.d.) = 0.80 (0.11) * 0.0000 (0.0006) C12 * 0.0000 (0.0006) C13 * 0.0000 (0.0006) C15 * 0.0000 (0.0006) C16 − 0.1555 (0.0020) C11 − 0.1531 (0.0020) C14 Rms deviation of fitted atoms = 0.0000 |
Refinement. Refinement on F2 for ALL reflections except for 2 with very negative F2 or flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The observed criterion of F2 > σ(F2) is used only for calculating _R_factor_obs 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 | ||
C1 | 0.43287 (6) | 0.3431 (2) | 1.02048 (13) | 0.0327 (4) | |
H1A | 0.42529 | 0.3286 | 1.10324 | 0.039* | |
H1B | 0.45867 | 0.4384 | 1.01436 | 0.039* | |
C2 | 0.45959 (5) | 0.1738 (2) | 0.97480 (11) | 0.0260 (3) | |
H2A | 0.49890 (5) | 0.1907 | 0.97259 | 0.031* | |
H2B | 0.45298 (5) | 0.0799 | 1.02962 | 0.031* | |
C3 | 0.43813 (5) | 0.1229 (2) | 0.85551 (11) | 0.0211 (3) | |
C4 | 0.44971 (5) | 0.2154 (2) | 0.75542 (11) | 0.0187 (3) | |
C5 | 0.41162 (5) | 0.2169 (2) | 0.66368 (11) | 0.0211 (3) | |
H5 | 0.41848 (5) | 0.2828 | 0.59696 | 0.025* | |
C6 | 0.36378 (5) | 0.1247 (2) | 0.66675 (11) | 0.0232 (3) | |
C7 | 0.36015 (5) | 0.0024 (2) | 0.75298 (12) | 0.0267 (3) | |
H7 | 0.33269 (5) | −0.0816 | 0.74796 | 0.032* | |
C8 | 0.39680 (5) | 0.0034 (2) | 0.84660 (12) | 0.0259 (3) | |
H8 | 0.39360 (5) | −0.0793 | 0.90592 | 0.031* | |
C9 | 0.31484 (6) | 0.1811 (2) | 0.59501 (13) | 0.0304 (3) | |
H9A | 0.29319 | 0.0794 | 0.57320 | 0.036* | |
H9B | 0.32675 | 0.2345 | 0.52287 | 0.036* | |
C10 | 0.27823 (6) | 0.3117 (2) | 0.65983 (14) | 0.0353 (4) | |
H10A | 0.27066 | 0.4108 | 0.60874 | 0.042* | |
H10B | 0.24357 | 0.2563 | 0.67529 | 0.042* | |
C11 | 0.30363 (5) | 0.3742 (2) | 0.77273 (12) | 0.0262 (3) | |
C12 | 0.29664 (6) | 0.2846 (2) | 0.87486 (12) | 0.0283 (3) | |
H12 | 0.26521 | 0.2179 | 0.88308 | 0.034* | |
C13 | 0.33508 (6) | 0.2916 (2) | 0.96484 (12) | 0.0274 (3) | |
H13 | 0.32978 | 0.2295 | 1.03396 | 0.033* | |
C14 | 0.38138 (5) | 0.3890 (2) | 0.95453 (11) | 0.0254 (3) | |
C15 | 0.38177 (5) | 0.5063 (2) | 0.86446 (12) | 0.0266 (3) | |
H15 | 0.40865 (5) | 0.5922 | 0.86445 | 0.032* | |
C16 | 0.34327 (6) | 0.4992 (2) | 0.77442 (12) | 0.0273 (3) | |
H16 | 0.34403 | 0.5803 | 0.71352 | 0.033* | |
C17 | 0.5000 | 0.3238 (2) | 0.7500 | 0.0204 (4) | |
H17 | 0.5028 | 0.3981 | 0.8192 | 0.024* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0300 (8) | 0.0421 (9) | 0.0259 (7) | 0.0032 (7) | −0.0014 (6) | −0.0096 (6) |
C2 | 0.0239 (7) | 0.0328 (8) | 0.0214 (6) | 0.0032 (6) | 0.0020 (5) | 0.0043 (6) |
C3 | 0.0185 (6) | 0.0215 (6) | 0.0235 (7) | 0.0039 (5) | 0.0035 (5) | 0.0000 (5) |
C4 | 0.0171 (6) | 0.0178 (6) | 0.0214 (6) | 0.0028 (5) | 0.0032 (5) | −0.0024 (5) |
C5 | 0.0185 (6) | 0.0235 (6) | 0.0216 (6) | 0.0015 (5) | 0.0044 (5) | −0.0024 (5) |
C6 | 0.0186 (6) | 0.0276 (7) | 0.0236 (7) | 0.0011 (5) | 0.0018 (5) | −0.0082 (5) |
C7 | 0.0208 (6) | 0.0239 (7) | 0.0357 (8) | −0.0041 (5) | 0.0065 (6) | −0.0058 (6) |
C8 | 0.0258 (7) | 0.0231 (7) | 0.0296 (7) | −0.0002 (5) | 0.0084 (6) | 0.0021 (6) |
C9 | 0.0193 (6) | 0.0425 (9) | 0.0291 (7) | 0.0008 (6) | −0.0022 (5) | −0.0079 (6) |
C10 | 0.0245 (7) | 0.0442 (9) | 0.0367 (8) | 0.0091 (7) | −0.0047 (6) | −0.0073 (7) |
C11 | 0.0209 (6) | 0.0286 (7) | 0.0292 (7) | 0.0082 (5) | 0.0014 (5) | −0.0034 (6) |
C12 | 0.0222 (7) | 0.0284 (7) | 0.0348 (8) | 0.0001 (6) | 0.0090 (6) | −0.0037 (6) |
C13 | 0.0296 (7) | 0.0281 (7) | 0.0251 (7) | 0.0028 (6) | 0.0090 (6) | −0.0004 (6) |
C14 | 0.0262 (7) | 0.0277 (7) | 0.0225 (7) | 0.0035 (6) | 0.0033 (5) | −0.0073 (5) |
C15 | 0.0250 (7) | 0.0215 (7) | 0.0337 (7) | 0.0004 (5) | 0.0073 (6) | −0.0055 (6) |
C16 | 0.0287 (7) | 0.0241 (7) | 0.0295 (7) | 0.0075 (5) | 0.0065 (6) | 0.0025 (6) |
C17 | 0.0178 (8) | 0.0208 (9) | 0.0226 (9) | 0.000 | 0.0010 (7) | 0.000 |
C1—C14 | 1.511 (2) | C7—C8 | 1.389 (2) |
C1—C2 | 1.585 (2) | C9—C10 | 1.581 (2) |
C2—C3 | 1.514 (2) | C10—C11 | 1.511 (2) |
C3—C8 | 1.393 (2) | C11—C16 | 1.391 (2) |
C3—C4 | 1.406 (2) | C11—C12 | 1.392 (2) |
C4—C5 | 1.396 (2) | C12—C13 | 1.388 (2) |
C4—C17 | 1.518 (2) | C13—C14 | 1.393 (2) |
C5—C6 | 1.396 (2) | C14—C15 | 1.390 (2) |
C6—C7 | 1.389 (2) | C15—C16 | 1.390 (2) |
C6—C9 | 1.514 (2) | C17—C4i | 1.518 (2) |
C14—C1—C2 | 113.02 (11) | C6—C9—C10 | 113.38 (11) |
C3—C2—C1 | 112.75 (11) | C11—C10—C9 | 112.98 (11) |
C8—C3—C4 | 117.46 (12) | C16—C11—C12 | 117.15 (13) |
C8—C3—C2 | 118.59 (12) | C16—C11—C10 | 120.92 (13) |
C4—C3—C2 | 122.56 (12) | C12—C11—C10 | 120.55 (14) |
C5—C4—C3 | 118.36 (11) | C13—C12—C11 | 120.75 (13) |
C5—C4—C17 | 120.14 (10) | C12—C13—C14 | 120.47 (13) |
C3—C4—C17 | 121.30 (10) | C15—C14—C13 | 117.20 (13) |
C4—C5—C6 | 122.17 (12) | C15—C14—C1 | 120.37 (13) |
C7—C6—C5 | 117.09 (12) | C13—C14—C1 | 121.08 (13) |
C7—C6—C9 | 121.42 (12) | C14—C15—C16 | 120.71 (13) |
C5—C6—C9 | 120.35 (13) | C15—C16—C11 | 120.53 (13) |
C6—C7—C8 | 119.78 (12) | C4—C17—C4i | 111.91 (15) |
C7—C8—C3 | 121.54 (13) | ||
C14—C1—C2—C3 | 17.0 (2) | C6—C9—C10—C11 | 8.7 (2) |
C1—C2—C3—C8 | −95.9 (2) | C9—C10—C11—C16 | 78.3 (2) |
C1—C2—C3—C4 | 70.2 (2) | C9—C10—C11—C12 | −87.9 (2) |
C8—C3—C4—C5 | 16.5 (2) | C16—C11—C12—C13 | −14.5 (2) |
C2—C3—C4—C5 | −149.75 (12) | C10—C11—C12—C13 | 152.25 (13) |
C8—C3—C4—C17 | −168.63 (12) | C11—C12—C13—C14 | 0.2 (2) |
C2—C3—C4—C17 | 25.1 (2) | C12—C13—C14—C15 | 14.2 (2) |
C3—C4—C5—C6 | −2.5 (2) | C12—C13—C14—C1 | −152.61 (13) |
C17—C4—C5—C6 | −177.38 (12) | C2—C1—C14—C15 | −96.5 (2) |
C4—C5—C6—C7 | −13.5 (2) | C2—C1—C14—C13 | 69.8 (2) |
C4—C5—C6—C9 | 154.48 (12) | C13—C14—C15—C16 | −14.2 (2) |
C5—C6—C7—C8 | 15.3 (2) | C1—C14—C15—C16 | 152.66 (13) |
C9—C6—C7—C8 | −152.61 (13) | C14—C15—C16—C11 | −0.1 (2) |
C6—C7—C8—C3 | −1.2 (2) | C12—C11—C16—C15 | 14.4 (2) |
C4—C3—C8—C7 | −15.0 (2) | C10—C11—C16—C15 | −152.24 (13) |
C2—C3—C8—C7 | 151.85 (13) | C5—C4—C17—C4i | −113.80 (12) |
C7—C6—C9—C10 | 78.5 (2) | C3—C4—C17—C4i | 71.47 (11) |
C5—C6—C9—C10 | −89.0 (2) |
Symmetry code: (i) −x+1, y, −z+3/2. |
C33H32 | F(000) = 1840 |
Mr = 428.59 | Dx = 1.220 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
a = 25.969 (3) Å | Cell parameters from 64 reflections |
b = 7.720 (1) Å | θ = 5.3–12.5° |
c = 23.329 (3) Å | µ = 0.07 mm−1 |
β = 94.044 (6)° | T = 173 K |
V = 4665.3 (10) Å3 | Tablet, colourless |
Z = 8 | 1.20 × 0.64 × 0.34 mm |
Siemens P4 diffractometer | Rint = 0.011 |
Radiation source: fine-focus sealed tube | θmax = 25.0°, θmin = 3.2° |
Graphite monochromator | h = −30→30 |
ω–scans | k = −9→1 |
4268 measured reflections | l = −27→0 |
4095 independent reflections | 3 standard reflections every 247 reflections |
3240 reflections with I > 2σ(I) | intensity decay: none |
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)] = 0.042 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.116 | H-atom parameters constrained |
S = 1.04 | Calculated w = 1/[σ2(Fo2) + (0.0671P)2 + 1.794P] where P = (Fo2 + 2Fc2)/3 |
4094 reflections | (Δ/σ)max < 0.001 |
298 parameters | Δρmax = 0.18 e Å−3 |
0 restraints | Δρmin = −0.23 e Å−3 |
C33H32 | V = 4665.3 (10) Å3 |
Mr = 428.59 | Z = 8 |
Monoclinic, C2/c | Mo Kα radiation |
a = 25.969 (3) Å | µ = 0.07 mm−1 |
b = 7.720 (1) Å | T = 173 K |
c = 23.329 (3) Å | 1.20 × 0.64 × 0.34 mm |
β = 94.044 (6)° |
Siemens P4 diffractometer | Rint = 0.011 |
4268 measured reflections | 3 standard reflections every 247 reflections |
4095 independent reflections | intensity decay: none |
3240 reflections with I > 2σ(I) |
R[F2 > 2σ(F2)] = 0.042 | 0 restraints |
wR(F2) = 0.116 | H-atom parameters constrained |
S = 1.04 | Δρmax = 0.18 e Å−3 |
4094 reflections | Δρmin = −0.23 e Å−3 |
298 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. torsion angles −1.26 (0.04) C9 - C2 - C1 - C10 2.00 (0.04) C9' - C2' - C1' - C10' intramolecular distances 2.7672 (0.0021) C3 - C14 2.7707 (0.0022) C6 - C11 3.0627 (0.0020) C4 - C15 3.0581 (0.0022) C5 - C16 3.0767 (0.0022) C7 - C12 3.0817 (0.0021) C8 - C13 2.7744 (0.0020) C3' - C14' 2.7726 (0.0020) C6' - C11' 3.1280 (0.0020) C4' - C15' 3.0994 (0.0020) C5' - C16' 3.0515 (0.0020) C7' - C12' 3.0412 (0.0021) C8' - C13' Least-squares planes (x,y,z in crystal coordinates) and deviations from them (* indicates atom used to define plane) − 1.4006 (0.0233) x + 3.3012 (0.0057) y + 21.0869 (0.0086) z = 11.4080 (0.0087) * −0.0023 (0.0007) C4 * 0.0023 (0.0007) C5 * −0.0023 (0.0007) C7 * 0.0023 (0.0007) C8 − 0.1503 (0.0021) C3 − 0.1460 (0.0023) C6 Rms deviation of fitted atoms = 0.0023 − 1.5982 (0.0246) x + 3.3280 (0.0060) y + 21.0497 (0.0091) z = 8.2787 (0.0092) Angle to previous plane (with approximate e.s.d.) = 0.49 (0.09) * −0.0020 (0.0008) C12 * 0.0021 (0.0008) C13 * −0.0021 (0.0008) C15 * 0.0021 (0.0008) C16 0.1485 (0.0023) C11 0.1564 (0.0023) C14 Rms deviation of fitted atoms = 0.0021 24.7457 (0.0057) x − 1.6588 (0.0068) y + 3.4134 (0.0158) z = 9.8645 (0.0116) Angle to previous plane (with approximate e.s.d.) = 87.63 (0.07) * −0.0061 (0.0007) C4' * 0.0061 (0.0007) C5' * −0.0061 (0.0007) C7' * 0.0061 (0.0007) C8' 0.1598 (0.0021) C3' 0.1481 (0.0021) C6' Rms deviation of fitted atoms = 0.0061 24.5234 (0.0062) x − 1.7290 (0.0072) y + 4.0538 (0.0175) z = 13.2107 (0.0127) Angle to previous plane (with approximate e.s.d.) = 1.70 (0.06) * 0.0040 (0.0007) C12' * −0.0040 (0.0007) C13' * 0.0040 (0.0007) C15' * −0.0039 (0.0007) C16' −0.1500 (0.0022) C11' −0.1575 (0.0022) C14' Rms deviation of fitted atoms = 0.0040 |
Refinement. Refinement on F2 for ALL reflections except for 1 flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The observed criterion of F2 > σ(F2) is used only for calculating _R_factor_obs 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 | ||
C1 | 0.25939 (7) | 0.5062 (2) | 0.36923 (8) | 0.0481 (5) | |
H1A | 0.26576 (7) | 0.3806 (2) | 0.37444 (8) | 0.058* | |
H1B | 0.22473 (7) | 0.5204 (2) | 0.34925 (8) | 0.058* | |
C2 | 0.25972 (6) | 0.5949 (2) | 0.43025 (8) | 0.0413 (4) | |
H2A | 0.22594 (6) | 0.6515 (2) | 0.43416 (8) | 0.050* | |
H2B | 0.26416 (6) | 0.5045 (2) | 0.46029 (8) | 0.050* | |
C3 | 0.30194 (6) | 0.7277 (2) | 0.44000 (6) | 0.0289 (3) | |
C4 | 0.35295 (6) | 0.6819 (2) | 0.45757 (6) | 0.0265 (3) | |
C5 | 0.39265 (6) | 0.7900 (2) | 0.44350 (6) | 0.0302 (3) | |
H5 | 0.42716 (6) | 0.7597 (2) | 0.45565 (6) | 0.036* | |
C6 | 0.38366 (6) | 0.9420 (2) | 0.41208 (7) | 0.0332 (4) | |
C7 | 0.33305 (6) | 1.0014 (2) | 0.40624 (7) | 0.0339 (4) | |
H7 | 0.32603 (6) | 1.1153 (2) | 0.39247 (7) | 0.041* | |
C8 | 0.29286 (6) | 0.8959 (2) | 0.42031 (6) | 0.0318 (4) | |
H8 | 0.25850 (6) | 0.9388 (2) | 0.41648 (6) | 0.038* | |
C9 | 0.42438 (7) | 1.0126 (2) | 0.37517 (9) | 0.0491 (5) | |
H9A | 0.45895 (7) | 0.9868 (2) | 0.39385 (9) | 0.059* | |
H9B | 0.42077 (7) | 1.1401 (2) | 0.37261 (9) | 0.059* | |
C10 | 0.42059 (7) | 0.9340 (3) | 0.31237 (8) | 0.0567 (6) | |
H10A | 0.41258 (7) | 1.0285 (3) | 0.28445 (8) | 0.068* | |
H10B | 0.45459 (7) | 0.8852 (3) | 0.30433 (8) | 0.068* | |
C11 | 0.38035 (6) | 0.7951 (3) | 0.30351 (6) | 0.0392 (4) | |
C12 | 0.32927 (6) | 0.8363 (2) | 0.28597 (6) | 0.0375 (4) | |
H12 | 0.32201 (6) | 0.9385 (2) | 0.26420 (6) | 0.045* | |
C13 | 0.28921 (6) | 0.7302 (2) | 0.29990 (7) | 0.0366 (4) | |
H13 | 0.25466 (6) | 0.7599 (2) | 0.28770 (7) | 0.044* | |
C14 | 0.29923 (6) | 0.5797 (2) | 0.33179 (7) | 0.0369 (4) | |
C15 | 0.34991 (7) | 0.5219 (2) | 0.33725 (7) | 0.0376 (4) | |
H15 | 0.35710 (7) | 0.4075 (2) | 0.35052 (7) | 0.045* | |
C16 | 0.38997 (7) | 0.6279 (3) | 0.32373 (6) | 0.0404 (4) | |
H16 | 0.42446 (7) | 0.5864 (3) | 0.32825 (6) | 0.049* | |
C17 | 0.36547 (6) | 0.5087 (2) | 0.48558 (6) | 0.0304 (4) | |
H17A | 0.40214 (6) | 0.4811 (2) | 0.48080 (6) | 0.037* | |
H17B | 0.34419 (6) | 0.4183 (2) | 0.46527 (6) | 0.037* | |
C1' | 0.42562 (7) | 0.1488 (2) | 0.55630 (7) | 0.0395 (4) | |
H1'1 | 0.43425 (7) | 0.0305 (2) | 0.57025 (7) | 0.047* | |
H1'2 | 0.43797 (7) | 0.1605 (2) | 0.51730 (7) | 0.047* | |
C2' | 0.36508 (6) | 0.1727 (2) | 0.55273 (7) | 0.0345 (4) | |
H2'1 | 0.35165 (6) | 0.1644 (2) | 0.51204 (7) | 0.041* | |
H2'2 | 0.34958 (6) | 0.0772 (2) | 0.57403 (7) | 0.041* | |
C3' | 0.34851 (5) | 0.3432 (2) | 0.57694 (6) | 0.0265 (3) | |
C4' | 0.35626 (5) | 0.5017 (2) | 0.54920 (6) | 0.0239 (3) | |
C5' | 0.36212 (5) | 0.6504 (2) | 0.58257 (6) | 0.0246 (3) | |
H5' | 0.36813 (5) | 0.7576 (2) | 0.56420 (6) | 0.029* | |
C6' | 0.35949 (5) | 0.6480 (2) | 0.64205 (6) | 0.0251 (3) | |
C7' | 0.33998 (5) | 0.4994 (2) | 0.66614 (6) | 0.0281 (3) | |
H7' | 0.33019 (5) | 0.5008 (2) | 0.70462 (6) | 0.034* | |
C8' | 0.33489 (5) | 0.3495 (2) | 0.63377 (6) | 0.0295 (3) | |
H8' | 0.32177 (5) | 0.2481 (2) | 0.65064 (6) | 0.035* | |
C9' | 0.38728 (6) | 0.7831 (2) | 0.67935 (7) | 0.0340 (4) | |
H9'1 | 0.37168 (6) | 0.7876 (2) | 0.71684 (7) | 0.041* | |
H9'2 | 0.38231 (6) | 0.8978 (2) | 0.66084 (7) | 0.041* | |
C10' | 0.44693 (7) | 0.7468 (2) | 0.69008 (9) | 0.0495 (5) | |
H10C | 0.46624 (7) | 0.8455 (2) | 0.67507 (9) | 0.059* | |
H10D | 0.45577 (7) | 0.7397 (2) | 0.73199 (9) | 0.059* | |
C11' | 0.46415 (6) | 0.5821 (2) | 0.66221 (7) | 0.0328 (4) | |
C12' | 0.45500 (6) | 0.4229 (2) | 0.68766 (7) | 0.0323 (4) | |
H12' | 0.45243 (6) | 0.4165 (2) | 0.72803 (7) | 0.039* | |
C13' | 0.44961 (6) | 0.2743 (2) | 0.65493 (7) | 0.0316 (4) | |
H13' | 0.44317 (6) | 0.1671 (2) | 0.67304 (7) | 0.038* | |
C14' | 0.45348 (5) | 0.2794 (2) | 0.59582 (6) | 0.0295 (3) | |
C15' | 0.47424 (6) | 0.4289 (2) | 0.57379 (7) | 0.0319 (4) | |
H15' | 0.48528 (6) | 0.4283 (2) | 0.53583 (7) | 0.038* | |
C16' | 0.47912 (6) | 0.5789 (2) | 0.60628 (7) | 0.0349 (4) | |
H16' | 0.49284 (6) | 0.6804 (2) | 0.59014 (7) | 0.042* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0393 (10) | 0.0420 (10) | 0.0622 (12) | −0.0127 (8) | −0.0024 (8) | 0.0024 (9) |
C2 | 0.0272 (8) | 0.0495 (11) | 0.0482 (10) | 0.0007 (7) | 0.0093 (7) | 0.0145 (8) |
C3 | 0.0284 (8) | 0.0388 (9) | 0.0202 (7) | 0.0052 (7) | 0.0066 (6) | 0.0034 (6) |
C4 | 0.0310 (8) | 0.0324 (8) | 0.0162 (6) | 0.0060 (6) | 0.0012 (6) | −0.0015 (6) |
C5 | 0.0277 (8) | 0.0344 (8) | 0.0272 (7) | 0.0029 (7) | −0.0061 (6) | −0.0045 (7) |
C6 | 0.0363 (9) | 0.0278 (8) | 0.0347 (8) | −0.0042 (7) | −0.0036 (7) | −0.0038 (7) |
C7 | 0.0437 (9) | 0.0262 (8) | 0.0311 (8) | 0.0058 (7) | −0.0032 (7) | −0.0022 (7) |
C8 | 0.0310 (8) | 0.0401 (9) | 0.0243 (7) | 0.0115 (7) | 0.0030 (6) | −0.0007 (7) |
C9 | 0.0391 (10) | 0.0364 (10) | 0.0715 (13) | −0.0105 (8) | 0.0012 (9) | 0.0109 (9) |
C10 | 0.0392 (10) | 0.084 (2) | 0.0471 (11) | −0.0105 (10) | 0.0044 (8) | 0.0317 (11) |
C11 | 0.0337 (9) | 0.0649 (12) | 0.0197 (7) | 0.0016 (8) | 0.0071 (6) | 0.0065 (8) |
C12 | 0.0403 (9) | 0.0507 (11) | 0.0213 (7) | 0.0057 (8) | 0.0000 (6) | 0.0033 (7) |
C13 | 0.0306 (8) | 0.0483 (10) | 0.0299 (8) | 0.0028 (7) | −0.0054 (6) | −0.0080 (7) |
C14 | 0.0399 (9) | 0.0384 (9) | 0.0314 (8) | −0.0035 (7) | −0.0039 (7) | −0.0114 (7) |
C15 | 0.0485 (10) | 0.0387 (9) | 0.0255 (8) | 0.0095 (8) | 0.0016 (7) | −0.0081 (7) |
C16 | 0.0372 (9) | 0.0641 (12) | 0.0206 (7) | 0.0157 (8) | 0.0062 (6) | 0.0018 (8) |
C17 | 0.0367 (8) | 0.0323 (8) | 0.0221 (7) | 0.0078 (7) | 0.0012 (6) | 0.0007 (6) |
C1' | 0.0465 (10) | 0.0322 (9) | 0.0397 (9) | 0.0051 (8) | 0.0029 (7) | −0.0069 (8) |
C2' | 0.0447 (9) | 0.0257 (8) | 0.0319 (8) | −0.0036 (7) | −0.0063 (7) | −0.0021 (7) |
C3' | 0.0238 (7) | 0.0277 (8) | 0.0272 (7) | −0.0031 (6) | −0.0055 (6) | 0.0006 (6) |
C4' | 0.0205 (7) | 0.0286 (8) | 0.0222 (7) | 0.0029 (6) | −0.0019 (5) | 0.0009 (6) |
C5' | 0.0224 (7) | 0.0245 (7) | 0.0264 (7) | 0.0035 (6) | −0.0007 (6) | 0.0032 (6) |
C6' | 0.0218 (7) | 0.0286 (8) | 0.0243 (7) | 0.0058 (6) | −0.0011 (5) | −0.0018 (6) |
C7' | 0.0223 (7) | 0.0411 (9) | 0.0208 (7) | 0.0016 (6) | 0.0013 (5) | 0.0016 (6) |
C8' | 0.0259 (8) | 0.0337 (9) | 0.0285 (8) | −0.0074 (6) | −0.0007 (6) | 0.0064 (7) |
C9' | 0.0383 (9) | 0.0328 (9) | 0.0301 (8) | 0.0039 (7) | −0.0024 (7) | −0.0076 (7) |
C10' | 0.0391 (10) | 0.0426 (10) | 0.0644 (12) | 0.0021 (8) | −0.0138 (8) | −0.0231 (9) |
C11' | 0.0208 (7) | 0.0344 (9) | 0.0418 (9) | −0.0014 (6) | −0.0072 (6) | −0.0060 (7) |
C12' | 0.0251 (8) | 0.0448 (10) | 0.0264 (7) | 0.0025 (7) | −0.0026 (6) | 0.0003 (7) |
C13' | 0.0302 (8) | 0.0300 (8) | 0.0345 (8) | 0.0029 (6) | 0.0011 (6) | 0.0077 (7) |
C14' | 0.0254 (8) | 0.0297 (8) | 0.0334 (8) | 0.0070 (6) | 0.0020 (6) | −0.0002 (7) |
C15' | 0.0234 (7) | 0.0407 (9) | 0.0322 (8) | 0.0032 (7) | 0.0061 (6) | 0.0040 (7) |
C16' | 0.0223 (7) | 0.0342 (9) | 0.0479 (10) | −0.0054 (7) | 0.0004 (7) | 0.0088 (8) |
C1—C14 | 1.511 (2) | C17—C4' | 1.521 (2) |
C1—C2 | 1.579 (3) | C1'—C14' | 1.515 (2) |
C2—C3 | 1.507 (2) | C1'—C2' | 1.579 (2) |
C3—C8 | 1.392 (2) | C2'—C3' | 1.507 (2) |
C3—C4 | 1.404 (2) | C3'—C8' | 1.397 (2) |
C4—C5 | 1.384 (2) | C3'—C4' | 1.405 (2) |
C4—C17 | 1.513 (2) | C4'—C5' | 1.389 (2) |
C5—C6 | 1.394 (2) | C5'—C6' | 1.394 (2) |
C6—C7 | 1.390 (2) | C6'—C7' | 1.388 (2) |
C6—C9 | 1.512 (2) | C6'—C9' | 1.509 (2) |
C7—C8 | 1.382 (2) | C7'—C8' | 1.383 (2) |
C9—C10 | 1.582 (3) | C9'—C10' | 1.577 (2) |
C10—C11 | 1.501 (3) | C10'—C11' | 1.510 (2) |
C11—C16 | 1.391 (3) | C11'—C16' | 1.388 (2) |
C11—C12 | 1.397 (2) | C11'—C12' | 1.393 (2) |
C12—C13 | 1.381 (2) | C12'—C13' | 1.379 (2) |
C13—C14 | 1.394 (2) | C13'—C14' | 1.390 (2) |
C14—C15 | 1.387 (2) | C14'—C15' | 1.388 (2) |
C15—C16 | 1.377 (3) | C15'—C16' | 1.385 (2) |
C14—C1—C2 | 113.45 (14) | C14'—C1'—C2' | 112.65 (13) |
C3—C2—C1 | 112.88 (13) | C3'—C2'—C1' | 113.07 (12) |
C8—C3—C4 | 117.75 (14) | C8'—C3'—C4' | 117.43 (13) |
C8—C3—C2 | 118.72 (14) | C8'—C3'—C2' | 118.97 (13) |
C4—C3—C2 | 122.29 (14) | C4'—C3'—C2' | 122.28 (13) |
C5—C4—C3 | 118.83 (14) | C5'—C4'—C3' | 118.36 (12) |
C5—C4—C17 | 119.63 (13) | C5'—C4'—C17 | 119.93 (13) |
C3—C4—C17 | 121.20 (14) | C3'—C4'—C17 | 121.19 (13) |
C4—C5—C6 | 122.16 (14) | C4'—C5'—C6' | 122.39 (13) |
C7—C6—C5 | 116.82 (15) | C7'—C6'—C5' | 117.31 (13) |
C7—C6—C9 | 121.33 (15) | C7'—C6'—C9' | 120.71 (13) |
C5—C6—C9 | 120.33 (15) | C5'—C6'—C9' | 120.64 (13) |
C8—C7—C6 | 120.49 (15) | C8'—C7'—C6' | 119.58 (13) |
C7—C8—C3 | 121.00 (14) | C7'—C8'—C3' | 121.77 (14) |
C6—C9—C10 | 112.88 (14) | C6'—C9'—C10' | 113.15 (12) |
C11—C10—C9 | 113.49 (14) | C11'—C10'—C9' | 113.51 (13) |
C16—C11—C12 | 117.0 (2) | C16'—C11'—C12' | 116.90 (15) |
C16—C11—C10 | 120.6 (2) | C16'—C11'—C10' | 122.1 (2) |
C12—C11—C10 | 121.0 (2) | C12'—C11'—C10' | 119.7 (2) |
C13—C12—C11 | 120.8 (2) | C13'—C12'—C11' | 120.76 (14) |
C12—C13—C14 | 120.29 (15) | C12'—C13'—C14' | 120.95 (14) |
C15—C14—C13 | 117.2 (2) | C15'—C14'—C13' | 116.58 (14) |
C15—C14—C1 | 120.7 (2) | C15'—C14'—C1' | 120.63 (14) |
C13—C14—C1 | 120.8 (2) | C13'—C14'—C1' | 121.35 (14) |
C16—C15—C14 | 121.0 (2) | C16'—C15'—C14' | 121.04 (14) |
C15—C16—C11 | 120.6 (2) | C15'—C16'—C11' | 120.58 (15) |
C4—C17—C4' | 114.14 (12) | ||
C14—C1—C2—C3 | −3.4 (2) | C14'—C1'—C2'—C3' | 14.1 (2) |
C1—C2—C3—C8 | 85.0 (2) | C1'—C2'—C3'—C8' | −95.9 (2) |
C1—C2—C3—C4 | −82.0 (2) | C1'—C2'—C3'—C4' | 70.7 (2) |
C8—C3—C4—C5 | −13.5 (2) | C8'—C3'—C4'—C5' | 15.0 (2) |
C2—C3—C4—C5 | 153.61 (14) | C2'—C3'—C4'—C5' | −151.71 (13) |
C8—C3—C4—C17 | 173.23 (13) | C8'—C3'—C4'—C17 | −173.33 (13) |
C2—C3—C4—C17 | −19.6 (2) | C2'—C3'—C4'—C17 | 20.0 (2) |
C3—C4—C5—C6 | −0.5 (2) | C4—C17—C4'—C5' | −30.6 (2) |
C17—C4—C5—C6 | 172.82 (13) | C4—C17—C4'—C3' | 157.82 (13) |
C4—C5—C6—C7 | 13.9 (2) | C3'—C4'—C5'—C6' | −1.4 (2) |
C4—C5—C6—C9 | −152.2 (2) | C17—C4'—C5'—C6' | −173.15 (13) |
C5—C6—C7—C8 | −13.2 (2) | C4'—C5'—C6'—C7' | −13.4 (2) |
C9—C6—C7—C8 | 152.8 (2) | C4'—C5'—C6'—C9' | 153.50 (14) |
C6—C7—C8—C3 | −0.7 (2) | C5'—C6'—C7'—C8' | 14.2 (2) |
C4—C3—C8—C7 | 14.3 (2) | C9'—C6'—C7'—C8' | −152.70 (14) |
C2—C3—C8—C7 | −153.33 (15) | C6'—C7'—C8'—C3' | −0.5 (2) |
C7—C6—C9—C10 | −78.0 (2) | C4'—C3'—C8'—C7' | −14.3 (2) |
C5—C6—C9—C10 | 87.5 (2) | C2'—C3'—C8'—C7' | 152.81 (14) |
C6—C9—C10—C11 | −4.7 (2) | C7'—C6'—C9'—C10' | 87.9 (2) |
C9—C10—C11—C16 | −78.4 (2) | C5'—C6'—C9'—C10' | −78.6 (2) |
C9—C10—C11—C12 | 88.1 (2) | C6'—C9'—C10'—C11' | −1.4 (2) |
C16—C11—C12—C13 | 13.9 (2) | C9'—C10'—C11'—C16' | 88.5 (2) |
C10—C11—C12—C13 | −153.0 (2) | C9'—C10'—C11'—C12' | −77.8 (2) |
C11—C12—C13—C14 | 0.0 (2) | C16'—C11'—C12'—C13' | −14.3 (2) |
C12—C13—C14—C15 | −14.3 (2) | C10'—C11'—C12'—C13' | 152.72 (15) |
C12—C13—C14—C1 | 152.6 (2) | C11'—C12'—C13'—C14' | 0.4 (2) |
C2—C1—C14—C15 | 83.4 (2) | C12'—C13'—C14'—C15' | 14.2 (2) |
C2—C1—C14—C13 | −83.1 (2) | C12'—C13'—C14'—C1' | −152.20 (15) |
C13—C14—C15—C16 | 14.8 (2) | C2'—C1'—C14'—C15' | −97.1 (2) |
C1—C14—C15—C16 | −152.1 (2) | C2'—C1'—C14'—C13' | 68.7 (2) |
C14—C15—C16—C11 | −0.8 (2) | C13'—C14'—C15'—C16' | −15.0 (2) |
C12—C11—C16—C15 | −13.5 (2) | C1'—C14'—C15'—C16' | 151.52 (15) |
C10—C11—C16—C15 | 153.5 (2) | C14'—C15'—C16'—C11' | 1.2 (2) |
C5—C4—C17—C4' | 106.2 (2) | C12'—C11'—C16'—C15' | 13.5 (2) |
C3—C4—C17—C4' | −80.6 (2) | C10'—C11'—C16'—C15' | −153.18 (15) |
C32H30S | Z = 2 |
Mr = 446.62 | F(000) = 476 |
Triclinic, P1 | Dx = 1.264 Mg m−3 |
a = 8.1084 (12) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 12.334 (2) Å | Cell parameters from 55 reflections |
c = 12.826 (2) Å | θ = 5.5–12.5° |
α = 94.525 (12)° | µ = 0.16 mm−1 |
β = 105.516 (12)° | T = 173 K |
γ = 105.779 (8)° | Tablet, colourless |
V = 1173.3 (3) Å3 | 0.60 × 0.30 × 0.08 mm |
Siemens P4 diffractometer | Rint = 0.019 |
Radiation source: fine-focus sealed tube | θmax = 25.0°, θmin = 3.3° |
Graphite monochromator | h = −9→5 |
ω–scans | k = −14→14 |
5091 measured reflections | l = −14→15 |
4117 independent reflections | 3 standard reflections every 247 reflections |
2443 reflections with I > 2σ(I) | intensity decay: 3% |
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) = 0.090 | H-atom parameters constrained |
S = 0.82 | Calculated w = 1/[σ2(Fo2) + (0.0439P)2] where P = (Fo2 + 2Fc2)/3 |
4115 reflections | (Δ/σ)max = 0.001 |
298 parameters | Δρmax = 0.27 e Å−3 |
307 restraints | Δρmin = −0.18 e Å−3 |
C32H30S | γ = 105.779 (8)° |
Mr = 446.62 | V = 1173.3 (3) Å3 |
Triclinic, P1 | Z = 2 |
a = 8.1084 (12) Å | Mo Kα radiation |
b = 12.334 (2) Å | µ = 0.16 mm−1 |
c = 12.826 (2) Å | T = 173 K |
α = 94.525 (12)° | 0.60 × 0.30 × 0.08 mm |
β = 105.516 (12)° |
Siemens P4 diffractometer | Rint = 0.019 |
5091 measured reflections | 3 standard reflections every 247 reflections |
4117 independent reflections | intensity decay: 3% |
2443 reflections with I > 2σ(I) |
R[F2 > 2σ(F2)] = 0.040 | 307 restraints |
wR(F2) = 0.090 | H-atom parameters constrained |
S = 0.82 | Δρmax = 0.27 e Å−3 |
4115 reflections | Δρmin = −0.18 e Å−3 |
298 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. torsion angles 4.64 (0.05) C9 - C2 - C1 - C10 − 0.90 (0.05) C9' - C2' - C1' - C10' intramolecular distances 2.7733 (0.0028) C3 - C14 2.7767 (0.0030) C6 - C11 3.0722 (0.0027) C4 - C15 3.0742 (0.0028) C5 - C16 3.0820 (0.0029) C7 - C12 3.0902 (0.0028) C8 - C13 2.7627 (0.0028) C3' - C14' 2.7715 (0.0027) C6' - C11' 3.0984 (0.0027) C4' - C15' 3.0699 (0.0027) C5' - C16' 3.0599 (0.0028) C7' - C12' 3.0524 (0.0028) C8' - C13' Least-squares planes (x,y,z in crystal coordinates) and deviations from them (* indicates atom used to define plane) 5.5191 (0.0081) x + 5.5733 (0.0147) y − 7.5008 (0.0084) z = 2.0450 (0.0100) * −0.0012 (0.0010) C4 * 0.0012 (0.0010) C5 * −0.0012 (0.0010) C7 * 0.0012 (0.0010) C8 0.1606 (0.0028) C3 0.1519 (0.0030) C6 Rms deviation of fitted atoms = 0.0012 5.5002 (0.0086) x + 5.5823 (0.0161) y − 7.5515 (0.0088) z = 5.0673 (0.0108) Angle to previous plane (with approximate e.s.d.) = 0.31 (0.22) * −0.0037 (0.0010) C12 * 0.0037 (0.0010) C13 * −0.0037 (0.0010) C15 * 0.0037 (0.0010) C16 − 0.1479 (0.0032) C11 − 0.1493 (0.0030) C14 Rms deviation of fitted atoms = 0.0037 4.9226 (0.0085) x − 1.7289 (0.0099) y + 7.5476 (0.0136) z = 8.3222 (0.0059) Angle to previous plane (with approximate e.s.d.) = 79.88 (0.08) * 0.0094 (0.0009) C4' * −0.0094 (0.0010) C5' * 0.0094 (0.0010) C7' * −0.0094 (0.0010) C8' −0.1670 (0.0028) C3' −0.1399 (0.0028) C6' Rms deviation of fitted atoms = 0.0094 4.9622 (0.0091) x − 1.5981 (0.0105) y + 7.4538 (0.0147) z = 5.2436 (0.0062) Angle to previous plane (with approximate e.s.d.) = 0.80 (0.23) * 0.0005 (0.0010) C12' * −0.0005 (0.0010) C13' * 0.0005 (0.0010) C15' * −0.0005 (0.0010) C16' 0.1487 (0.0030) C11' 0.1524 (0.0030) C14' Rms deviation of fitted atoms = 0.0005 |
Refinement. Refinement on F2 for ALL reflections except for 2 with very negative F2 or flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The observed criterion of F2 > σ(F2) is used only for calculating _R_factor_obs 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 | ||
S | 0.81745 (8) | 0.47511 (5) | 0.67668 (4) | 0.0437 (2) | |
C1 | 1.2905 (3) | 0.6149 (2) | 0.8248 (2) | 0.0554 (7) | |
H1A | 1.4171 (3) | 0.6276 (2) | 0.8681 (2) | 0.066* | |
H1B | 1.2688 (3) | 0.5689 (2) | 0.7529 (2) | 0.066* | |
C2 | 1.1631 (3) | 0.5454 (2) | 0.8867 (2) | 0.0464 (6) | |
H2A | 1.1148 (3) | 0.4644 (2) | 0.8508 (2) | 0.056* | |
H2B | 1.2342 (3) | 0.5483 (2) | 0.9633 (2) | 0.056* | |
C3 | 1.0086 (3) | 0.5910 (2) | 0.8872 (2) | 0.0320 (5) | |
C4 | 0.8639 (3) | 0.5791 (2) | 0.7934 (2) | 0.0322 (5) | |
C5 | 0.7714 (3) | 0.6586 (2) | 0.7841 (2) | 0.0364 (5) | |
H5 | 0.6743 (3) | 0.6497 (2) | 0.7199 (2) | 0.044* | |
C6 | 0.8173 (3) | 0.7513 (2) | 0.8667 (2) | 0.0388 (5) | |
C7 | 0.9311 (3) | 0.7467 (2) | 0.9675 (2) | 0.0389 (5) | |
H7 | 0.9449 (3) | 0.7984 (2) | 1.0304 (2) | 0.047* | |
C8 | 1.0246 (3) | 0.6679 (2) | 0.9774 (2) | 0.0373 (5) | |
H8 | 1.1014 (3) | 0.6662 (2) | 1.0472 (2) | 0.045* | |
C9 | 0.7798 (3) | 0.8605 (2) | 0.8389 (2) | 0.0560 (7) | |
H9A | 0.7547 (3) | 0.8981 (2) | 0.9014 (2) | 0.067* | |
H9B | 0.6710 (3) | 0.8418 (2) | 0.7747 (2) | 0.067* | |
C10 | 0.9407 (4) | 0.9462 (2) | 0.8122 (2) | 0.0671 (8) | |
H10A | 0.8932 (4) | 0.9733 (2) | 0.7431 (2) | 0.081* | |
H10B | 0.9949 (4) | 1.0133 (2) | 0.8714 (2) | 0.081* | |
C11 | 1.0852 (3) | 0.8951 (2) | 0.8006 (2) | 0.0445 (6) | |
C12 | 1.2301 (3) | 0.9002 (2) | 0.8909 (2) | 0.0457 (6) | |
H12 | 1.2689 (3) | 0.9605 (2) | 0.9513 (2) | 0.055* | |
C13 | 1.3175 (3) | 0.8183 (2) | 0.8930 (2) | 0.0422 (6) | |
H13 | 1.4171 (3) | 0.8235 (2) | 0.9546 (2) | 0.051* | |
C14 | 1.2624 (3) | 0.7286 (2) | 0.8068 (2) | 0.0400 (5) | |
C15 | 1.1449 (3) | 0.7391 (2) | 0.7098 (2) | 0.0419 (6) | |
H15 | 1.1239 (3) | 0.6887 (2) | 0.6444 (2) | 0.050* | |
C16 | 1.0586 (3) | 0.8212 (2) | 0.7066 (2) | 0.0446 (6) | |
H16 | 0.9799 (3) | 0.8272 (2) | 0.6390 (2) | 0.054* | |
C1' | 0.5861 (3) | 0.2264 (2) | 0.4611 (2) | 0.0564 (7) | |
H1'1 | 0.6171 (3) | 0.2955 (2) | 0.4271 (2) | 0.068* | |
H1'2 | 0.5622 (3) | 0.1591 (2) | 0.4055 (2) | 0.068* | |
C2' | 0.7516 (3) | 0.2308 (2) | 0.5616 (2) | 0.0407 (6) | |
H2'1 | 0.7847 (3) | 0.1599 (2) | 0.5518 (2) | 0.049* | |
H2'2 | 0.8555 (3) | 0.2959 (2) | 0.5625 (2) | 0.049* | |
C3' | 0.7142 (3) | 0.2433 (2) | 0.6705 (2) | 0.0324 (5) | |
C4' | 0.7110 (3) | 0.3479 (2) | 0.71985 (15) | 0.0307 (5) | |
C5' | 0.6036 (3) | 0.3494 (2) | 0.78776 (15) | 0.0310 (5) | |
H5' | 0.5976 (3) | 0.4204 (2) | 0.81821 (15) | 0.037* | |
C6' | 0.5046 (3) | 0.2488 (2) | 0.81202 (15) | 0.0316 (5) | |
C7' | 0.5428 (3) | 0.1497 (2) | 0.7841 (2) | 0.0361 (5) | |
H7' | 0.4984 (3) | 0.0831 (2) | 0.8131 (2) | 0.043* | |
C8' | 0.6456 (3) | 0.1476 (2) | 0.7141 (2) | 0.0370 (5) | |
H8' | 0.6700 (3) | 0.0788 (2) | 0.6953 (2) | 0.044* | |
C9' | 0.3370 (3) | 0.2458 (2) | 0.8434 (2) | 0.0423 (6) | |
H9'1 | 0.3609 (3) | 0.3168 (2) | 0.8943 (2) | 0.051* | |
H9'2 | 0.3087 (3) | 0.1808 (2) | 0.8830 (2) | 0.051* | |
C10' | 0.1690 (3) | 0.2339 (2) | 0.7424 (2) | 0.0516 (6) | |
H10C | 0.0706 (3) | 0.1656 (2) | 0.7424 (2) | 0.062* | |
H10D | 0.1272 (3) | 0.3015 (2) | 0.7507 (2) | 0.062* | |
C11' | 0.2071 (3) | 0.2234 (2) | 0.6335 (2) | 0.0354 (5) | |
C12' | 0.2148 (3) | 0.1206 (2) | 0.5864 (2) | 0.0408 (6) | |
H12' | 0.1483 (3) | 0.0509 (2) | 0.6021 (2) | 0.049* | |
C13' | 0.3185 (3) | 0.1186 (2) | 0.5168 (2) | 0.0415 (6) | |
H13' | 0.3220 (3) | 0.0475 (2) | 0.4849 (2) | 0.050* | |
C14' | 0.4178 (3) | 0.2196 (2) | 0.4929 (2) | 0.0386 (5) | |
C15' | 0.3769 (3) | 0.3181 (2) | 0.5208 (2) | 0.0367 (5) | |
H15' | 0.4207 (3) | 0.3850 (2) | 0.4920 (2) | 0.044* | |
C16' | 0.2729 (3) | 0.3196 (2) | 0.5903 (2) | 0.0378 (5) | |
H16' | 0.2461 (3) | 0.3877 (2) | 0.6086 (2) | 0.045* |
U11 | U22 | U33 | U12 | U13 | U23 | |
S | 0.0491 (4) | 0.0388 (3) | 0.0325 (3) | −0.0064 (3) | 0.0173 (3) | −0.0012 (2) |
C1 | 0.046 (2) | 0.063 (2) | 0.067 (2) | 0.0242 (13) | 0.0248 (14) | 0.0098 (14) |
C2 | 0.050 (2) | 0.0414 (13) | 0.0481 (14) | 0.0172 (12) | 0.0116 (12) | 0.0100 (11) |
C3 | 0.0333 (12) | 0.0290 (11) | 0.0326 (11) | 0.0026 (10) | 0.0134 (10) | 0.0102 (9) |
C4 | 0.0300 (12) | 0.0319 (11) | 0.0285 (11) | −0.0030 (10) | 0.0117 (10) | 0.0040 (9) |
C5 | 0.0238 (12) | 0.0482 (13) | 0.0326 (12) | 0.0033 (11) | 0.0092 (10) | 0.0060 (10) |
C6 | 0.0293 (13) | 0.0458 (13) | 0.0431 (13) | 0.0098 (11) | 0.0158 (11) | 0.0057 (11) |
C7 | 0.0406 (14) | 0.0421 (13) | 0.0326 (12) | 0.0059 (11) | 0.0180 (11) | −0.0017 (10) |
C8 | 0.0364 (13) | 0.0415 (13) | 0.0276 (11) | 0.0019 (11) | 0.0090 (10) | 0.0082 (10) |
C9 | 0.050 (2) | 0.059 (2) | 0.062 (2) | 0.0264 (14) | 0.0143 (14) | 0.0037 (13) |
C10 | 0.063 (2) | 0.0394 (15) | 0.094 (2) | 0.0190 (14) | 0.012 (2) | 0.0104 (14) |
C11 | 0.0401 (14) | 0.0314 (12) | 0.0555 (15) | 0.0016 (11) | 0.0106 (12) | 0.0178 (11) |
C12 | 0.0436 (15) | 0.0365 (13) | 0.0447 (13) | −0.0040 (12) | 0.0100 (12) | 0.0046 (10) |
C13 | 0.0262 (13) | 0.0547 (15) | 0.0377 (13) | 0.0014 (12) | 0.0066 (11) | 0.0117 (11) |
C14 | 0.0305 (13) | 0.0504 (14) | 0.0434 (13) | 0.0088 (11) | 0.0205 (11) | 0.0120 (11) |
C15 | 0.0363 (14) | 0.0513 (14) | 0.0345 (12) | −0.0018 (12) | 0.0198 (11) | 0.0084 (11) |
C16 | 0.0366 (14) | 0.0471 (14) | 0.0404 (13) | −0.0018 (12) | 0.0068 (11) | 0.0206 (11) |
C1' | 0.0419 (15) | 0.097 (2) | 0.0335 (13) | 0.0242 (14) | 0.0143 (12) | 0.0046 (13) |
C2' | 0.0305 (13) | 0.0498 (14) | 0.0422 (13) | 0.0129 (11) | 0.0138 (11) | −0.0020 (11) |
C3' | 0.0186 (11) | 0.0420 (13) | 0.0349 (11) | 0.0114 (10) | 0.0041 (10) | 0.0027 (10) |
C4' | 0.0227 (11) | 0.0365 (12) | 0.0256 (11) | 0.0020 (9) | 0.0033 (9) | 0.0021 (9) |
C5' | 0.0285 (12) | 0.0355 (12) | 0.0242 (10) | 0.0060 (10) | 0.0053 (9) | 0.0006 (9) |
C6' | 0.0257 (12) | 0.0413 (13) | 0.0246 (10) | 0.0064 (10) | 0.0056 (9) | 0.0077 (9) |
C7' | 0.0311 (13) | 0.0369 (12) | 0.0362 (12) | 0.0074 (10) | 0.0043 (10) | 0.0135 (10) |
C8' | 0.0282 (12) | 0.0380 (13) | 0.0435 (13) | 0.0163 (10) | 0.0023 (11) | 0.0065 (10) |
C9' | 0.0363 (13) | 0.0544 (15) | 0.0362 (12) | 0.0088 (11) | 0.0158 (11) | 0.0086 (11) |
C10' | 0.0336 (14) | 0.078 (2) | 0.0482 (14) | 0.0213 (13) | 0.0166 (12) | 0.0109 (13) |
C11' | 0.0202 (11) | 0.0481 (13) | 0.0362 (12) | 0.0108 (10) | 0.0053 (10) | 0.0057 (10) |
C12' | 0.0278 (12) | 0.0433 (13) | 0.0395 (13) | 0.0003 (11) | 0.0020 (11) | 0.0061 (10) |
C13' | 0.0386 (14) | 0.0399 (13) | 0.0372 (12) | 0.0139 (11) | −0.0013 (11) | −0.0071 (10) |
C14' | 0.0292 (13) | 0.0567 (15) | 0.0250 (11) | 0.0119 (11) | 0.0035 (10) | −0.0005 (10) |
C15' | 0.0307 (12) | 0.0415 (13) | 0.0293 (11) | 0.0055 (11) | 0.0000 (10) | 0.0087 (10) |
C16' | 0.0319 (13) | 0.0400 (13) | 0.0414 (13) | 0.0194 (11) | 0.0028 (11) | 0.0043 (10) |
S—C4 | 1.778 (2) | C15—C16 | 1.376 (3) |
S—C4' | 1.780 (2) | C1'—C14' | 1.509 (3) |
C1—C14 | 1.507 (3) | C1'—C2' | 1.577 (3) |
C1—C2 | 1.580 (3) | C2'—C3' | 1.512 (3) |
C2—C3 | 1.507 (3) | C3'—C8' | 1.389 (3) |
C3—C8 | 1.391 (3) | C3'—C4' | 1.402 (3) |
C3—C4 | 1.403 (3) | C4'—C5' | 1.389 (3) |
C4—C5 | 1.382 (3) | C5'—C6' | 1.391 (3) |
C5—C6 | 1.391 (3) | C6'—C7' | 1.384 (3) |
C6—C7 | 1.389 (3) | C6'—C9' | 1.509 (3) |
C6—C9 | 1.508 (3) | C7'—C8' | 1.382 (3) |
C7—C8 | 1.379 (3) | C9'—C10' | 1.572 (3) |
C9—C10 | 1.576 (3) | C10'—C11' | 1.513 (3) |
C10—C11 | 1.507 (3) | C11'—C16' | 1.384 (3) |
C11—C16 | 1.383 (3) | C11'—C12' | 1.385 (3) |
C11—C12 | 1.394 (3) | C12'—C13' | 1.383 (3) |
C12—C13 | 1.382 (3) | C13'—C14' | 1.393 (3) |
C13—C14 | 1.386 (3) | C14'—C15' | 1.389 (3) |
C14—C15 | 1.389 (3) | C15'—C16' | 1.383 (3) |
C4—S—C4' | 101.41 (9) | C14'—C1'—C2' | 113.0 (2) |
C14—C1—C2 | 112.9 (2) | C3'—C2'—C1' | 113.0 (2) |
C3—C2—C1 | 112.6 (2) | C8'—C3'—C4' | 116.4 (2) |
C8—C3—C4 | 116.4 (2) | C8'—C3'—C2' | 120.7 (2) |
C8—C3—C2 | 119.1 (2) | C4'—C3'—C2' | 121.6 (2) |
C4—C3—C2 | 123.3 (2) | C5'—C4'—C3' | 119.8 (2) |
C5—C4—C3 | 120.2 (2) | C5'—C4'—S | 121.1 (2) |
C5—C4—S | 118.3 (2) | C3'—C4'—S | 118.4 (2) |
C3—C4—S | 120.8 (2) | C4'—C5'—C6' | 121.3 (2) |
C4—C5—C6 | 121.5 (2) | C7'—C6'—C5' | 117.4 (2) |
C7—C6—C5 | 116.6 (2) | C7'—C6'—C9' | 121.6 (2) |
C7—C6—C9 | 121.9 (2) | C5'—C6'—C9' | 119.5 (2) |
C5—C6—C9 | 120.0 (2) | C8'—C7'—C6' | 120.1 (2) |
C8—C7—C6 | 120.8 (2) | C7'—C8'—C3' | 121.8 (2) |
C7—C8—C3 | 121.4 (2) | C6'—C9'—C10' | 113.5 (2) |
C6—C9—C10 | 112.8 (2) | C11'—C10'—C9' | 113.3 (2) |
C11—C10—C9 | 113.7 (2) | C16'—C11'—C12' | 117.2 (2) |
C16—C11—C12 | 117.1 (2) | C16'—C11'—C10' | 120.9 (2) |
C16—C11—C10 | 120.3 (2) | C12'—C11'—C10' | 120.4 (2) |
C12—C11—C10 | 121.2 (2) | C13'—C12'—C11' | 120.5 (2) |
C13—C12—C11 | 120.4 (2) | C12'—C13'—C14' | 120.9 (2) |
C12—C13—C14 | 121.1 (2) | C15'—C14'—C13' | 116.8 (2) |
C13—C14—C15 | 116.5 (2) | C15'—C14'—C1' | 120.8 (2) |
C13—C14—C1 | 121.3 (2) | C13'—C14'—C1' | 121.2 (2) |
C15—C14—C1 | 120.5 (2) | C16'—C15'—C14' | 120.5 (2) |
C16—C15—C14 | 121.3 (2) | C15'—C16'—C11' | 121.0 (2) |
C15—C16—C11 | 120.7 (2) | ||
C14—C1—C2—C3 | 15.6 (3) | C14'—C1'—C2'—C3' | −7.7 (3) |
C1—C2—C3—C8 | −95.4 (2) | C1'—C2'—C3'—C8' | 90.7 (2) |
C1—C2—C3—C4 | 71.1 (3) | C1'—C2'—C3'—C4' | −75.9 (3) |
C8—C3—C4—C5 | 14.7 (3) | C8'—C3'—C4'—C5' | −16.1 (3) |
C2—C3—C4—C5 | −152.1 (2) | C2'—C3'—C4'—C5' | 151.1 (2) |
C8—C3—C4—S | −174.76 (14) | C8'—C3'—C4'—S | 173.75 (14) |
C2—C3—C4—S | 18.4 (3) | C2'—C3'—C4'—S | −19.1 (3) |
C4'—S—C4—C5 | −111.9 (2) | C4—S—C4'—C5' | 33.8 (2) |
C4'—S—C4—C3 | 77.5 (2) | C4—S—C4'—C3' | −156.2 (2) |
C3—C4—C5—C6 | −0.5 (3) | C3'—C4'—C5'—C6' | 3.0 (3) |
S—C4—C5—C6 | −171.2 (2) | S—C4'—C5'—C6' | 172.89 (14) |
C4—C5—C6—C7 | −14.0 (3) | C4'—C5'—C6'—C7' | 12.2 (3) |
C4—C5—C6—C9 | 152.3 (2) | C4'—C5'—C6'—C9' | −154.5 (2) |
C5—C6—C7—C8 | 14.1 (3) | C5'—C6'—C7'—C8' | −13.9 (3) |
C9—C6—C7—C8 | −151.8 (2) | C9'—C6'—C7'—C8' | 152.5 (2) |
C6—C7—C8—C3 | 0.2 (3) | C6'—C7'—C8'—C3' | 0.4 (3) |
C4—C3—C8—C7 | −14.7 (3) | C4'—C3'—C8'—C7' | 14.6 (3) |
C2—C3—C8—C7 | 152.8 (2) | C2'—C3'—C8'—C7' | −152.7 (2) |
C7—C6—C9—C10 | 75.4 (3) | C7'—C6'—C9'—C10' | −87.2 (2) |
C5—C6—C9—C10 | −90.1 (3) | C5'—C6'—C9'—C10' | 78.9 (2) |
C6—C9—C10—C11 | 9.9 (3) | C6'—C9'—C10'—C11' | 2.1 (3) |
C9—C10—C11—C16 | 76.2 (3) | C9'—C10'—C11'—C16' | −87.8 (3) |
C9—C10—C11—C12 | −89.9 (3) | C9'—C10'—C11'—C12' | 78.1 (3) |
C16—C11—C12—C13 | −13.3 (3) | C16'—C11'—C12'—C13' | 13.8 (3) |
C10—C11—C12—C13 | 153.1 (2) | C10'—C11'—C12'—C13' | −152.6 (2) |
C11—C12—C13—C14 | −0.9 (3) | C11'—C12'—C13'—C14' | 0.3 (3) |
C12—C13—C14—C15 | 14.2 (3) | C12'—C13'—C14'—C15' | −14.2 (3) |
C12—C13—C14—C1 | −151.3 (2) | C12'—C13'—C14'—C1' | 153.1 (2) |
C2—C1—C14—C13 | 71.7 (3) | C2'—C1'—C14'—C15' | 91.9 (3) |
C2—C1—C14—C15 | −93.3 (2) | C2'—C1'—C14'—C13' | −74.9 (3) |
C13—C14—C15—C16 | −13.5 (3) | C13'—C14'—C15'—C16' | 14.0 (3) |
C1—C14—C15—C16 | 152.2 (2) | C1'—C14'—C15'—C16' | −153.4 (2) |
C14—C15—C16—C11 | −0.7 (3) | C14'—C15'—C16'—C11' | 0.0 (3) |
C12—C11—C16—C15 | 14.1 (3) | C12'—C11'—C16'—C15' | −14.0 (3) |
C10—C11—C16—C15 | −152.5 (2) | C10'—C11'—C16'—C15' | 152.3 (2) |
Experimental details
(1c) | (1m) | (2m) | |
Crystal data | |||
Chemical formula | C33H32 | C33H32 | C32H30S |
Mr | 428.59 | 428.59 | 446.62 |
Crystal system, space group | Monoclinic, C2/c | Monoclinic, C2/c | Triclinic, P1 |
Temperature (K) | 173 | 173 | 173 |
a, b, c (Å) | 24.928 (3), 7.8409 (6), 11.5716 (12) | 25.969 (3), 7.720 (1), 23.329 (3) | 8.1084 (12), 12.334 (2), 12.826 (2) |
α, β, γ (°) | 90, 92.256 (8), 90 | 90, 94.044 (6), 90 | 94.525 (12), 105.516 (12), 105.779 (8) |
V (Å3) | 2260.0 (4) | 4665.3 (10) | 1173.3 (3) |
Z | 4 | 8 | 2 |
Radiation type | Mo Kα | Mo Kα | Mo Kα |
µ (mm−1) | 0.07 | 0.07 | 0.16 |
Crystal size (mm) | 0.76 × 0.46 × 0.22 | 1.20 × 0.64 × 0.34 | 0.60 × 0.30 × 0.08 |
Data collection | |||
Diffractometer | Siemens P4 diffractometer | Siemens P4 diffractometer | Siemens P4 diffractometer |
Absorption correction | – | – | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3066, 2589, 1912 | 4268, 4095, 3240 | 5091, 4117, 2443 |
Rint | 0.025 | 0.011 | 0.019 |
(sin θ/λ)max (Å−1) | 0.649 | 0.594 | 0.595 |
Refinement | |||
R[F2 > 2σ(F2)], wR(F2), S | 0.045, 0.131, 1.02 | 0.042, 0.116, 1.04 | 0.040, 0.090, 0.82 |
No. of reflections | 2587 | 4094 | 4115 |
No. of parameters | 151 | 298 | 298 |
No. of restraints | 0 | 0 | 307 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.27, −0.21 | 0.18, −0.23 | 0.27, −0.18 |
Computer programs: XSCANS (Siemens, 1991), XSCANS, SHELXS86 (Sheldrick, 1990), SHELXL93 (Sheldrick, 1993), XP5 (Siemens, 1994), SHELXL93.
C4—C17 | 1.518 (2) | C17—C4i | 1.518 (2) |
C5—C4—C17—C4i | −113.80 (12) |
Symmetry code: (i) −x+1, y, −z+3/2. |
C4—C17 | 1.513 (2) | C17—C4' | 1.521 (2) |
C5—C4—C17—C4' | 106.2 (2) | C4—C17—C4'—C5' | −30.6 (2) |
S—C4 | 1.778 (2) | S—C4' | 1.780 (2) |
C4'—S—C4—C5 | −111.9 (2) | C4—S—C4'—C5' | 33.8 (2) |
Because of the (planar) chirality of monosubstituted [2.2]paracyclophanes (Q), compounds ZQ2 composed of a central atom or group (Z) carrying two Q ligands can occur as meso and chiral diastereomers. Some time ago we reported the X-ray structures of the first pair of such diastereomers, in which Z was Si(CH3)2 (Jones et al., 1997), and recently the structure of meso-bis[2.2]paracyclophan-4-yl (Z = nil) has been determined (Jones & Kuś, 1998). The configurations of the title compounds (1 m) and (1c) as determined by NMR data, where the chemical equivalence or non-equivalence of the H atoms of the central methylene group indicate the chiral or meso-configuration, respectively, were confirmed by the X-ray structures; (1c) crystallizes as a racemate with imposed twofold symmetry. The X-ray diffraction study of the sulfide (2 m) was necessary because NMR data gave no indication of its configuration.
The paracyclophanyl groups in the title compounds show the characteristic structural features of substituted [2.2]paracyclophanes, similar to the diastereomeric pair of dimethyl-bis[2.2]paracyclophan-4-yl)silanes C34H36Si, (3) (Jones et al., 1997). The aromatic rings are distorted into boat shapes and the carbon atoms bearing the ethylene bridges are displaced out of the plane of the four other atoms. The mean aromatic planes are slightly inclined with respect to one another; the angles within paracyclophanyl groups vary from 0.3 (2)° in (2 m) to 1.7 (1)° in (1 m), cf. 1.6 (4) to 4.5 (4)° in (3).
The para carbon atoms are displaced out of the planes by amounts similar to those in the parent compound (4), [2.2]paracyclophane, (0.156 Å and 0.157 Å; Stalke, 1996). The values vary from 0.153 (2) to 0.172 (2) Å in (1c), 0.146 (2) to 0.160 (2) Å in (1 m) and 0.140 (3) Å to 0.167 (3) Å in (2 m). In contrast to the diastereomeric pair (3), no differences in the displacements between the substituted and non-substituted rings can be recognized.
The non-bonded distances of the corresponding bridgehead carbon atoms, which eclipse one another transannularly, are less than 2.8 Å [2.780 (2) Å and 2.792 (2) Å in (1c), 2.767 (2) to 2.774 (2) Å in (1 m) and 2.763 (3) Å to 2.777 (3) Å in (2 m)]. The intramolecular separation of the planes results in values of 3.084 (2) to 3.135 (2) Å in (1c), 3.041 (2) Å to 3.128 (2) Å in (1 m) and 3.052 (3) Å to 3.098 (3) Å in (2 m). The deviations from the geometry of the parent compound (4) [2.779 Å and 3.093 Å (Stalke, 1996)] are less pronounced than in the diastereomeric pair of (3) with their bulkier central Si(CH3)2 moieties.
The torsion angle C9···C2—C1···C10 indicates a mutual twist of the aromatic rings. Individual values are 4.61 (3)° (C9···C2—C1···C10) in (1c), −1.26 (4)° (C9···C2—C1···C10) and 2.00 (4)° (C9'···C2'—C1'···C10') in (1 m). The sulfur-bridged compound (2 m) displays values of 4.64 (5)° (C9···C2—C1···C10) and −0.90 (5)° (C9'···C2'—C1'···C10').
As usual, the Csp3—Csp3 bonds of the ethylene bridges are characteristically elongated to values of 1.581 (2) and 1.585 (2) Å in (1c), 1.577 (2) to 1.582 (3) Å in (1 m) and 1.572 (3) to 1.580 (3) Å, similar to the parent compound (4) (1.571 Å; Stalke, 1996).
The carbon-carbon bonds in (1c) and (1 m) and the sulfur-carbon bonds in (2 m) between the two halves of the molecules lie in the range of the mean standard bond length of 1.513 Å for a Csp3—Car (Allen et al., 1987) and 1.768 Å for a Car—S bond length (Allen et al., 1987): 1.518 (2) Å in (1c), 1.513 (2) and 1.521 (2) Å in (1 m) and 1.778 (2) and 1.780 (2) Å in (2 m).
The torsion angles C5—C4—Z—C4' and C4—Z—C4'—C5' indicate the orientation of the paracyclophane groups with respect to each other. The central bond C4—Z in all cases shows torsion angles close to 120° and thus an ac conformation: −113.80 (12)° [C5—C4—C17—C4i; symmetry code: (i) 1 − x, y, 3/2 − z] in (1c), 106.24 (15)° (C5—C4—C17–C4') in (1 m) and −111.86 (16)° (C5—C4—S—C4') in (2 m). In constrast, the bond Z—C4' has a flattened sc conformation: −30.64 (19)° (C4—C17—C4'—C5') in (1 m) and 33.75 (18)° (C4—S—C4'—C5') in (2 m).