Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801013277/ci6033sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536801013277/ci6033Isup2.hkl |
CCDC reference: 172213
Colourless single crystals of the title compound were obtained as transparent needles by slow evaporation of a benzene solution at room temperature.
The H atoms were placed at calculated positions and were allowed to ride on their respective parent atoms with HFIX instructions using SHELXL97 (Sheldrick, 1997) defaults.
Data collection: CAD-4 Software (Enraf-Nonius, 1989); cell refinement: CAD-4 Software; data reduction: CAD-4 Software; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP (Siemens, 1990); software used to prepare material for publication: SHELXL97.
C32H24Cl4N2O | F(000) = 1224 |
Mr = 594.33 | Dx = 1.425 Mg m−3 |
Monoclinic, P21/c | Cu Kα radiation, λ = 1.54180 Å |
a = 6.818 (3) Å | Cell parameters from 25 reflections |
b = 13.288 (4) Å | θ = 10–25° |
c = 30.670 (14) Å | µ = 4.12 mm−1 |
β = 94.47 (3)° | T = 293 K |
V = 2770 (2) Å3 | Needles, colourless |
Z = 4 | 0.34 × 0.22 × 0.18 mm |
Enraf-Nonius CAD-4 diffractometer | 3549 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.036 |
Graphite monochromator | θmax = 70.1°, θmin = 2.9° |
/w–2/q scans | h = 0→8 |
Absorption correction: ψ scan (North et al., 1968) | k = 0→16 |
Tmin = 0.42, Tmax = 0.48 | l = −37→37 |
5739 measured reflections | 2 standard reflections every 200 reflections |
5268 independent reflections | intensity decay: 2% |
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)] = 0.061 | H-atom parameters constrained |
wR(F2) = 0.149 | Calculated w = 1/[σ2(Fo2) + 8.0771P] where P = (Fo2 + 2Fc2)/3 |
S = 1.16 | (Δ/σ)max < 0.001 |
5268 reflections | Δρmax = 0.37 e Å−3 |
353 parameters | Δρmin = −0.40 e Å−3 |
0 restraints | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.00100 (5) |
C32H24Cl4N2O | V = 2770 (2) Å3 |
Mr = 594.33 | Z = 4 |
Monoclinic, P21/c | Cu Kα radiation |
a = 6.818 (3) Å | µ = 4.12 mm−1 |
b = 13.288 (4) Å | T = 293 K |
c = 30.670 (14) Å | 0.34 × 0.22 × 0.18 mm |
β = 94.47 (3)° |
Enraf-Nonius CAD-4 diffractometer | 3549 reflections with I > 2σ(I) |
Absorption correction: ψ scan (North et al., 1968) | Rint = 0.036 |
Tmin = 0.42, Tmax = 0.48 | 2 standard reflections every 200 reflections |
5739 measured reflections | intensity decay: 2% |
5268 independent reflections |
R[F2 > 2σ(F2)] = 0.061 | 0 restraints |
wR(F2) = 0.149 | H-atom parameters constrained |
S = 1.16 | Δρmax = 0.37 e Å−3 |
5268 reflections | Δρmin = −0.40 e Å−3 |
353 parameters |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | ||
N1 | 0.2913 (5) | 0.7303 (3) | 0.58381 (11) | 0.0366 (8) | |
O11 | −0.1514 (4) | 0.6354 (3) | 0.64983 (11) | 0.0537 (9) | |
C2 | 0.4423 (6) | 0.7662 (3) | 0.61705 (13) | 0.0371 (10) | |
H2A | 0.4675 | 0.8368 | 0.6117 | 0.045* | |
H2B | 0.5634 | 0.7297 | 0.6137 | 0.045* | |
N3 | 0.3890 (5) | 0.7546 (3) | 0.66238 (11) | 0.0365 (8) | |
C4 | 0.2101 (6) | 0.8164 (3) | 0.66696 (13) | 0.0360 (9) | |
H4 | 0.2430 | 0.8849 | 0.6582 | 0.043* | |
C41 | 0.1532 (6) | 0.8238 (3) | 0.71392 (14) | 0.0401 (10) | |
C42 | −0.0375 (7) | 0.8098 (4) | 0.72520 (16) | 0.0479 (12) | |
H42 | −0.1371 | 0.7977 | 0.7033 | 0.057* | |
C43 | −0.0832 (7) | 0.8133 (4) | 0.76859 (16) | 0.0517 (12) | |
H43 | −0.2115 | 0.8028 | 0.7759 | 0.062* | |
C44 | 0.0651 (8) | 0.8326 (4) | 0.80042 (16) | 0.0522 (13) | |
C45 | 0.2534 (8) | 0.8519 (4) | 0.79013 (16) | 0.0584 (14) | |
H45 | 0.3512 | 0.8674 | 0.8119 | 0.070* | |
C46 | 0.2954 (7) | 0.8478 (4) | 0.74690 (16) | 0.0508 (12) | |
H46 | 0.4227 | 0.8616 | 0.7397 | 0.061* | |
Cl47 | 0.0100 (2) | 0.82985 (13) | 0.85482 (4) | 0.0755 (5) | |
C5 | 0.0418 (6) | 0.7804 (4) | 0.63387 (14) | 0.0414 (11) | |
H5 | −0.0782 | 0.8196 | 0.6368 | 0.050* | |
C6 | 0.1101 (6) | 0.7893 (3) | 0.58664 (14) | 0.0403 (10) | |
H6 | 0.0083 | 0.7574 | 0.5669 | 0.048* | |
C61 | 0.1382 (6) | 0.8948 (4) | 0.56972 (15) | 0.0427 (11) | |
C62 | 0.0758 (7) | 0.9813 (4) | 0.58954 (16) | 0.0524 (13) | |
H62 | 0.0093 | 0.9759 | 0.6148 | 0.063* | |
C63 | 0.1099 (8) | 1.0758 (4) | 0.57272 (18) | 0.0604 (14) | |
H63 | 0.0678 | 1.1334 | 0.5865 | 0.073* | |
C64 | 0.2068 (7) | 1.0826 (4) | 0.53553 (18) | 0.0542 (13) | |
C65 | 0.2617 (7) | 0.9987 (4) | 0.51338 (17) | 0.0535 (13) | |
H65 | 0.3200 | 1.0049 | 0.4871 | 0.064* | |
C66 | 0.2287 (7) | 0.9048 (4) | 0.53099 (16) | 0.0507 (12) | |
H66 | 0.2679 | 0.8475 | 0.5166 | 0.061* | |
Cl67 | 0.2628 (2) | 1.20020 (11) | 0.51462 (6) | 0.0817 (5) | |
C7 | 0.2472 (6) | 0.6241 (3) | 0.59039 (14) | 0.0393 (10) | |
H7 | 0.1318 | 0.6076 | 0.5706 | 0.047* | |
C71 | 0.4142 (6) | 0.5568 (3) | 0.57784 (14) | 0.0394 (10) | |
C72 | 0.5537 (7) | 0.5921 (4) | 0.55083 (14) | 0.0435 (11) | |
H72 | 0.5487 | 0.6589 | 0.5418 | 0.052* | |
C73 | 0.6987 (7) | 0.5307 (4) | 0.53709 (15) | 0.0477 (12) | |
H73 | 0.7910 | 0.5557 | 0.5191 | 0.057* | |
C74 | 0.7059 (7) | 0.4317 (4) | 0.55018 (15) | 0.0470 (11) | |
C75 | 0.5678 (7) | 0.3935 (4) | 0.57610 (16) | 0.0541 (13) | |
H75 | 0.5714 | 0.3260 | 0.5842 | 0.065* | |
C76 | 0.4244 (7) | 0.4560 (4) | 0.58989 (16) | 0.0477 (12) | |
H76 | 0.3320 | 0.4302 | 0.6077 | 0.057* | |
Cl77 | 0.8883 (2) | 0.35305 (12) | 0.53312 (5) | 0.0693 (4) | |
C8 | 0.1875 (6) | 0.6072 (3) | 0.63831 (13) | 0.0368 (10) | |
H8 | 0.1605 | 0.5360 | 0.6436 | 0.044* | |
C9 | 0.3605 (6) | 0.6450 (3) | 0.66923 (13) | 0.0353 (9) | |
H9 | 0.4777 | 0.6127 | 0.6590 | 0.042* | |
C91 | 0.3596 (6) | 0.6161 (3) | 0.71697 (14) | 0.0385 (10) | |
C92 | 0.1952 (7) | 0.5834 (4) | 0.73677 (16) | 0.0472 (11) | |
H92 | 0.0764 | 0.5753 | 0.7201 | 0.057* | |
C93 | 0.2061 (8) | 0.5625 (4) | 0.78117 (16) | 0.0544 (13) | |
H93 | 0.0951 | 0.5402 | 0.7942 | 0.065* | |
C94 | 0.3804 (8) | 0.5746 (4) | 0.80584 (16) | 0.0541 (13) | |
C95 | 0.5459 (7) | 0.6029 (4) | 0.78700 (17) | 0.0574 (14) | |
H95 | 0.6652 | 0.6083 | 0.8037 | 0.069* | |
C96 | 0.5349 (7) | 0.6236 (4) | 0.74250 (15) | 0.0485 (12) | |
H96 | 0.6481 | 0.6429 | 0.7296 | 0.058* | |
Cl97 | 0.3921 (3) | 0.55127 (16) | 0.86172 (5) | 0.0923 (6) | |
C10 | 0.0069 (6) | 0.6700 (3) | 0.64207 (13) | 0.0373 (10) |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.0326 (18) | 0.039 (2) | 0.0379 (19) | 0.0042 (16) | 0.0006 (15) | 0.0019 (16) |
O11 | 0.0305 (16) | 0.065 (2) | 0.066 (2) | −0.0058 (16) | 0.0064 (15) | 0.0058 (18) |
C2 | 0.033 (2) | 0.040 (2) | 0.038 (2) | 0.0004 (19) | 0.0055 (18) | 0.0039 (19) |
N3 | 0.0328 (18) | 0.038 (2) | 0.0385 (19) | 0.0022 (15) | 0.0040 (15) | 0.0036 (16) |
C4 | 0.036 (2) | 0.033 (2) | 0.040 (2) | 0.0033 (18) | 0.0052 (18) | 0.0026 (18) |
C41 | 0.044 (3) | 0.036 (2) | 0.041 (2) | 0.004 (2) | 0.006 (2) | 0.0011 (19) |
C42 | 0.045 (3) | 0.052 (3) | 0.048 (3) | 0.005 (2) | 0.009 (2) | −0.003 (2) |
C43 | 0.050 (3) | 0.053 (3) | 0.054 (3) | 0.005 (2) | 0.016 (2) | 0.001 (2) |
C44 | 0.066 (3) | 0.050 (3) | 0.042 (3) | 0.013 (3) | 0.013 (2) | −0.003 (2) |
C45 | 0.061 (3) | 0.070 (4) | 0.043 (3) | −0.001 (3) | 0.000 (2) | −0.009 (3) |
C46 | 0.047 (3) | 0.053 (3) | 0.053 (3) | −0.007 (2) | 0.004 (2) | −0.007 (2) |
Cl47 | 0.0914 (11) | 0.0922 (11) | 0.0449 (7) | 0.0117 (9) | 0.0180 (7) | −0.0045 (7) |
C5 | 0.035 (2) | 0.049 (3) | 0.041 (2) | 0.008 (2) | 0.0059 (19) | 0.005 (2) |
C6 | 0.039 (2) | 0.043 (3) | 0.038 (2) | 0.007 (2) | 0.0002 (19) | 0.001 (2) |
C61 | 0.038 (2) | 0.044 (3) | 0.045 (3) | 0.010 (2) | −0.003 (2) | 0.002 (2) |
C62 | 0.054 (3) | 0.058 (3) | 0.046 (3) | 0.018 (3) | 0.008 (2) | 0.007 (2) |
C63 | 0.073 (4) | 0.044 (3) | 0.064 (3) | 0.017 (3) | 0.006 (3) | 0.004 (3) |
C64 | 0.049 (3) | 0.048 (3) | 0.065 (3) | 0.006 (2) | −0.003 (3) | 0.016 (3) |
C65 | 0.041 (3) | 0.062 (3) | 0.058 (3) | 0.005 (2) | 0.007 (2) | 0.014 (3) |
C66 | 0.048 (3) | 0.054 (3) | 0.051 (3) | 0.012 (2) | 0.010 (2) | 0.006 (2) |
Cl67 | 0.0757 (10) | 0.0542 (9) | 0.1157 (14) | 0.0005 (7) | 0.0107 (9) | 0.0261 (9) |
C7 | 0.037 (2) | 0.040 (2) | 0.041 (2) | −0.0010 (19) | 0.0019 (19) | −0.004 (2) |
C71 | 0.039 (2) | 0.041 (2) | 0.039 (2) | 0.002 (2) | 0.0012 (19) | −0.002 (2) |
C72 | 0.054 (3) | 0.040 (3) | 0.038 (2) | 0.002 (2) | 0.011 (2) | 0.000 (2) |
C73 | 0.049 (3) | 0.058 (3) | 0.037 (2) | 0.004 (2) | 0.011 (2) | −0.003 (2) |
C74 | 0.046 (3) | 0.056 (3) | 0.039 (2) | 0.011 (2) | 0.004 (2) | −0.005 (2) |
C75 | 0.063 (3) | 0.044 (3) | 0.057 (3) | 0.009 (2) | 0.013 (3) | 0.002 (2) |
C76 | 0.048 (3) | 0.044 (3) | 0.053 (3) | 0.002 (2) | 0.015 (2) | 0.007 (2) |
Cl77 | 0.0754 (9) | 0.0760 (10) | 0.0588 (8) | 0.0304 (8) | 0.0194 (7) | −0.0013 (7) |
C8 | 0.035 (2) | 0.039 (2) | 0.036 (2) | −0.0010 (19) | 0.0033 (18) | 0.0031 (19) |
C9 | 0.031 (2) | 0.037 (2) | 0.039 (2) | 0.0016 (18) | 0.0055 (17) | 0.0044 (19) |
C91 | 0.039 (2) | 0.034 (2) | 0.043 (2) | 0.0019 (19) | 0.0033 (19) | 0.0072 (19) |
C92 | 0.037 (2) | 0.048 (3) | 0.058 (3) | 0.000 (2) | 0.006 (2) | 0.009 (2) |
C93 | 0.052 (3) | 0.059 (3) | 0.054 (3) | −0.005 (3) | 0.016 (2) | 0.017 (3) |
C94 | 0.060 (3) | 0.056 (3) | 0.047 (3) | 0.005 (3) | 0.008 (2) | 0.015 (2) |
C95 | 0.047 (3) | 0.072 (4) | 0.052 (3) | 0.001 (3) | −0.003 (2) | 0.015 (3) |
C96 | 0.039 (3) | 0.059 (3) | 0.048 (3) | −0.004 (2) | 0.002 (2) | 0.012 (2) |
Cl97 | 0.0928 (12) | 0.1329 (16) | 0.0516 (8) | 0.0040 (11) | 0.0078 (8) | 0.0351 (9) |
C10 | 0.030 (2) | 0.048 (3) | 0.034 (2) | 0.0002 (19) | −0.0010 (17) | −0.0024 (19) |
N1—C7 | 1.460 (5) | C64—Cl67 | 1.743 (5) |
N1—C2 | 1.471 (5) | C65—C66 | 1.386 (7) |
N1—C6 | 1.471 (5) | C65—H65 | 0.9300 |
O11—C10 | 1.213 (5) | C66—H66 | 0.9300 |
C2—N3 | 1.472 (5) | C7—C71 | 1.520 (6) |
C2—H2A | 0.9700 | C7—C8 | 1.571 (6) |
C2—H2B | 0.9700 | C7—H7 | 0.9800 |
N3—C4 | 1.486 (5) | C71—C76 | 1.390 (6) |
N3—C9 | 1.487 (5) | C71—C72 | 1.390 (6) |
C4—C41 | 1.524 (6) | C72—C73 | 1.373 (6) |
C4—C5 | 1.547 (6) | C72—H72 | 0.9300 |
C4—H4 | 0.9800 | C73—C74 | 1.375 (7) |
C41—C46 | 1.383 (6) | C73—H73 | 0.9300 |
C41—C42 | 1.384 (6) | C74—C75 | 1.376 (7) |
C42—C43 | 1.391 (6) | C74—Cl77 | 1.736 (5) |
C42—H42 | 0.9300 | C75—C76 | 1.375 (6) |
C43—C44 | 1.374 (7) | C75—H75 | 0.9300 |
C43—H43 | 0.9300 | C76—H76 | 0.9300 |
C44—C45 | 1.370 (7) | C8—C10 | 1.499 (6) |
C44—Cl47 | 1.739 (5) | C8—C9 | 1.539 (6) |
C45—C46 | 1.379 (7) | C8—H8 | 0.9800 |
C45—H45 | 0.9300 | C9—C91 | 1.514 (6) |
C46—H46 | 0.9300 | C9—H9 | 0.9800 |
C5—C10 | 1.511 (6) | C91—C96 | 1.381 (6) |
C5—C6 | 1.560 (6) | C91—C92 | 1.386 (6) |
C5—H5 | 0.9800 | C92—C93 | 1.386 (6) |
C6—C61 | 1.513 (6) | C92—H92 | 0.9300 |
C6—H6 | 0.9800 | C93—C94 | 1.368 (7) |
C61—C62 | 1.383 (6) | C93—H93 | 0.9300 |
C61—C66 | 1.387 (6) | C94—C95 | 1.360 (7) |
C62—C63 | 1.384 (7) | C94—Cl97 | 1.737 (5) |
C62—H62 | 0.9300 | C95—C96 | 1.388 (6) |
C63—C64 | 1.365 (7) | C95—H95 | 0.9300 |
C63—H63 | 0.9300 | C96—H96 | 0.9300 |
C64—C65 | 1.372 (7) | ||
C7—N1—C2 | 111.0 (3) | C66—C65—H65 | 120.7 |
C7—N1—C6 | 108.9 (3) | C65—C66—C61 | 121.1 (5) |
C2—N1—C6 | 109.4 (3) | C65—C66—H66 | 119.5 |
N1—C2—N3 | 114.2 (3) | C61—C66—H66 | 119.5 |
N1—C2—H2A | 108.7 | N1—C7—C71 | 111.5 (4) |
N3—C2—H2A | 108.7 | N1—C7—C8 | 109.7 (3) |
N1—C2—H2B | 108.7 | C71—C7—C8 | 114.0 (4) |
N3—C2—H2B | 108.7 | N1—C7—H7 | 107.1 |
H2A—C2—H2B | 107.6 | C71—C7—H7 | 107.1 |
C2—N3—C4 | 107.2 (3) | C8—C7—H7 | 107.1 |
C2—N3—C9 | 106.3 (3) | C76—C71—C72 | 117.5 (4) |
C4—N3—C9 | 114.2 (3) | C76—C71—C7 | 121.5 (4) |
N3—C4—C41 | 113.4 (3) | C72—C71—C7 | 120.9 (4) |
N3—C4—C5 | 109.9 (3) | C73—C72—C71 | 121.6 (4) |
C41—C4—C5 | 114.2 (3) | C73—C72—H72 | 119.2 |
N3—C4—H4 | 106.3 | C71—C72—H72 | 119.2 |
C41—C4—H4 | 106.3 | C72—C73—C74 | 119.3 (4) |
C5—C4—H4 | 106.3 | C72—C73—H73 | 120.4 |
C46—C41—C42 | 117.8 (4) | C74—C73—H73 | 120.4 |
C46—C41—C4 | 119.4 (4) | C73—C74—C75 | 120.8 (4) |
C42—C41—C4 | 122.8 (4) | C73—C74—Cl77 | 119.9 (4) |
C41—C42—C43 | 121.3 (5) | C75—C74—Cl77 | 119.4 (4) |
C41—C42—H42 | 119.3 | C76—C75—C74 | 119.3 (5) |
C43—C42—H42 | 119.3 | C76—C75—H75 | 120.3 |
C44—C43—C42 | 118.6 (5) | C74—C75—H75 | 120.3 |
C44—C43—H43 | 120.7 | C75—C76—C71 | 121.5 (4) |
C42—C43—H43 | 120.7 | C75—C76—H76 | 119.3 |
C45—C44—C43 | 121.5 (5) | C71—C76—H76 | 119.3 |
C45—C44—Cl47 | 120.1 (4) | C10—C8—C9 | 111.5 (4) |
C43—C44—Cl47 | 118.4 (4) | C10—C8—C7 | 105.5 (3) |
C44—C45—C46 | 118.9 (5) | C9—C8—C7 | 106.7 (3) |
C44—C45—H45 | 120.6 | C10—C8—H8 | 111.0 |
C46—C45—H45 | 120.6 | C9—C8—H8 | 111.0 |
C45—C46—C41 | 121.7 (5) | C7—C8—H8 | 111.0 |
C45—C46—H46 | 119.1 | N3—C9—C91 | 113.3 (3) |
C41—C46—H46 | 119.1 | N3—C9—C8 | 109.6 (3) |
C10—C5—C4 | 108.0 (3) | C91—C9—C8 | 116.9 (3) |
C10—C5—C6 | 106.9 (4) | N3—C9—H9 | 105.3 |
C4—C5—C6 | 109.0 (3) | C91—C9—H9 | 105.3 |
C10—C5—H5 | 110.9 | C8—C9—H9 | 105.3 |
C4—C5—H5 | 110.9 | C96—C91—C92 | 117.9 (4) |
C6—C5—H5 | 110.9 | C96—C91—C9 | 117.5 (4) |
N1—C6—C61 | 110.1 (4) | C92—C91—C9 | 124.6 (4) |
N1—C6—C5 | 109.1 (3) | C91—C92—C93 | 120.7 (5) |
C61—C6—C5 | 116.3 (4) | C91—C92—H92 | 119.7 |
N1—C6—H6 | 106.9 | C93—C92—H92 | 119.7 |
C61—C6—H6 | 106.9 | C94—C93—C92 | 119.8 (5) |
C5—C6—H6 | 106.9 | C94—C93—H93 | 120.1 |
C62—C61—C66 | 118.0 (5) | C92—C93—H93 | 120.1 |
C62—C61—C6 | 124.6 (4) | C95—C94—C93 | 120.8 (5) |
C66—C61—C6 | 117.3 (4) | C95—C94—Cl97 | 119.5 (4) |
C61—C62—C63 | 121.6 (5) | C93—C94—Cl97 | 119.7 (4) |
C61—C62—H62 | 119.2 | C94—C95—C96 | 119.3 (5) |
C63—C62—H62 | 119.2 | C94—C95—H95 | 120.4 |
C64—C63—C62 | 118.5 (5) | C96—C95—H95 | 120.4 |
C64—C63—H63 | 120.7 | C91—C96—C95 | 121.4 (4) |
C62—C63—H63 | 120.7 | C91—C96—H96 | 119.3 |
C63—C64—C65 | 122.0 (5) | C95—C96—H96 | 119.3 |
C63—C64—Cl67 | 120.0 (4) | O11—C10—C8 | 123.6 (4) |
C65—C64—Cl67 | 118.0 (4) | O11—C10—C5 | 123.7 (4) |
C64—C65—C66 | 118.7 (5) | C8—C10—C5 | 112.7 (4) |
C64—C65—H65 | 120.7 | ||
C7—N1—C2—N3 | −58.3 (5) | C2—N1—C7—C8 | 54.9 (4) |
C6—N1—C2—N3 | 61.9 (4) | C6—N1—C7—C8 | −65.5 (4) |
N1—C2—N3—C4 | −61.8 (4) | N1—C7—C71—C76 | 166.1 (4) |
N1—C2—N3—C9 | 60.8 (4) | C8—C7—C71—C76 | 41.1 (6) |
C2—N3—C4—C41 | −172.0 (4) | N1—C7—C71—C72 | −19.2 (6) |
C9—N3—C4—C41 | 70.5 (5) | C8—C7—C71—C72 | −144.2 (4) |
C2—N3—C4—C5 | 59.0 (4) | C76—C71—C72—C73 | −1.2 (7) |
C9—N3—C4—C5 | −58.5 (4) | C7—C71—C72—C73 | −176.1 (4) |
N3—C4—C41—C46 | 48.4 (6) | C71—C72—C73—C74 | 0.3 (7) |
C5—C4—C41—C46 | 175.2 (4) | C72—C73—C74—C75 | 1.2 (7) |
N3—C4—C41—C42 | −133.3 (4) | C72—C73—C74—Cl77 | −180.0 (4) |
C5—C4—C41—C42 | −6.4 (6) | C73—C74—C75—C76 | −1.7 (8) |
C46—C41—C42—C43 | −4.0 (7) | Cl77—C74—C75—C76 | 179.5 (4) |
C4—C41—C42—C43 | 177.6 (4) | C74—C75—C76—C71 | 0.7 (8) |
C41—C42—C43—C44 | 1.0 (8) | C72—C71—C76—C75 | 0.7 (7) |
C42—C43—C44—C45 | 2.4 (8) | C7—C71—C76—C75 | 175.6 (4) |
C42—C43—C44—Cl47 | −176.4 (4) | N1—C7—C8—C10 | 61.1 (4) |
C43—C44—C45—C46 | −2.6 (8) | C71—C7—C8—C10 | −173.0 (4) |
Cl47—C44—C45—C46 | 176.2 (4) | N1—C7—C8—C9 | −57.5 (4) |
C44—C45—C46—C41 | −0.7 (8) | C71—C7—C8—C9 | 68.4 (5) |
C42—C41—C46—C45 | 3.9 (7) | C2—N3—C9—C91 | 164.3 (3) |
C4—C41—C46—C45 | −177.6 (5) | C4—N3—C9—C91 | −77.7 (4) |
N3—C4—C5—C10 | 57.2 (4) | C2—N3—C9—C8 | −63.2 (4) |
C41—C4—C5—C10 | −71.4 (4) | C4—N3—C9—C8 | 54.9 (4) |
N3—C4—C5—C6 | −58.6 (4) | C10—C8—C9—N3 | −52.1 (4) |
C41—C4—C5—C6 | 172.8 (4) | C7—C8—C9—N3 | 62.7 (4) |
C7—N1—C6—C61 | −166.8 (4) | C10—C8—C9—C91 | 78.6 (5) |
C2—N1—C6—C61 | 71.7 (4) | C7—C8—C9—C91 | −166.7 (4) |
C7—N1—C6—C5 | 64.4 (4) | N3—C9—C91—C96 | −69.2 (5) |
C2—N1—C6—C5 | −57.1 (4) | C8—C9—C91—C96 | 162.0 (4) |
C10—C5—C6—N1 | −59.5 (4) | N3—C9—C91—C92 | 110.5 (5) |
C4—C5—C6—N1 | 57.0 (5) | C8—C9—C91—C92 | −18.4 (6) |
C10—C5—C6—C61 | 175.2 (4) | C96—C91—C92—C93 | 2.4 (7) |
C4—C5—C6—C61 | −68.3 (5) | C9—C91—C92—C93 | −177.3 (4) |
N1—C6—C61—C62 | −136.6 (5) | C91—C92—C93—C94 | 0.2 (8) |
C5—C6—C61—C62 | −11.9 (7) | C92—C93—C94—C95 | −2.8 (8) |
N1—C6—C61—C66 | 45.1 (5) | C92—C93—C94—Cl97 | 178.4 (4) |
C5—C6—C61—C66 | 169.8 (4) | C93—C94—C95—C96 | 2.6 (9) |
C66—C61—C62—C63 | −3.0 (7) | Cl97—C94—C95—C96 | −178.6 (4) |
C6—C61—C62—C63 | 178.7 (5) | C92—C91—C96—C95 | −2.5 (7) |
C61—C62—C63—C64 | 0.3 (8) | C9—C91—C96—C95 | 177.2 (5) |
C62—C63—C64—C65 | 3.4 (8) | C94—C95—C96—C91 | 0.1 (8) |
C62—C63—C64—Cl67 | −177.1 (4) | C9—C8—C10—O11 | −125.5 (4) |
C63—C64—C65—C66 | −4.2 (8) | C7—C8—C10—O11 | 119.0 (5) |
Cl67—C64—C65—C66 | 176.2 (4) | C9—C8—C10—C5 | 56.1 (5) |
C64—C65—C66—C61 | 1.4 (7) | C7—C8—C10—C5 | −59.4 (4) |
C62—C61—C66—C65 | 2.2 (7) | C4—C5—C10—O11 | 124.0 (4) |
C6—C61—C66—C65 | −179.5 (4) | C6—C5—C10—O11 | −118.8 (5) |
C2—N1—C7—C71 | −72.4 (4) | C4—C5—C10—C8 | −57.7 (4) |
C6—N1—C7—C71 | 167.1 (3) | C6—C5—C10—C8 | 59.5 (4) |
D—H···A | D—H | H···A | D···A | D—H···A |
C9—H9···O11i | 0.98 | 2.58 | 3.428 (5) | 144 |
C2—H2B···O11i | 0.97 | 2.50 | 3.357 (5) | 148 |
Symmetry code: (i) x+1, y, z. |
Experimental details
Crystal data | |
Chemical formula | C32H24Cl4N2O |
Mr | 594.33 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 293 |
a, b, c (Å) | 6.818 (3), 13.288 (4), 30.670 (14) |
β (°) | 94.47 (3) |
V (Å3) | 2770 (2) |
Z | 4 |
Radiation type | Cu Kα |
µ (mm−1) | 4.12 |
Crystal size (mm) | 0.34 × 0.22 × 0.18 |
Data collection | |
Diffractometer | Enraf-Nonius CAD-4 diffractometer |
Absorption correction | ψ scan (North et al., 1968) |
Tmin, Tmax | 0.42, 0.48 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 5739, 5268, 3549 |
Rint | 0.036 |
(sin θ/λ)max (Å−1) | 0.610 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.061, 0.149, 1.16 |
No. of reflections | 5268 |
No. of parameters | 353 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.37, −0.40 |
Computer programs: CAD-4 Software (Enraf-Nonius, 1989), CAD-4 Software, SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), XP (Siemens, 1990), SHELXL97.
D—H···A | D—H | H···A | D···A | D—H···A |
C9—H9···O11i | 0.98 | 2.58 | 3.428 (5) | 144 |
C2—H2B···O11i | 0.97 | 2.50 | 3.357 (5) | 148 |
Symmetry code: (i) x+1, y, z. |
The present X-ray investigations on the title compound, 4,8,9,10-tetrakis(4-chlorophenyl)-1,3-diazaadamantan-6-one, (I), was carried out with a view to observing possible differences in the crystal and molecular structures upon exchange of substituents and obtain some information about the nature of specific substituent or specific interactions. Moreover, crystallographic investigations on symmetrically shaped molecules are expected to provide insights into the nature and strength of intermolecular interactions and their role in effecting symmetry carry-over from the free state to the solid. Recently, the crystal structure of a methoxy-substituted analogue of the title compound, 4,8,9,10-tetrakis(4-methoxyphenyl)-1,3-diazaadamantan-6-one benzene solvate, was elucidated in our laboratory (Krishnakumar et al., 2001).
Fig. 1 shows the crystallographic numbering scheme adopted. No significant differences in the geometry of the diazaadamantanone cage are seen as it is known to be inherently rigid and symmetrical. All four six-membered rings which constitute the diazaadamantanone cage adopt chair conformations, which is the most preferred conformation for adamantanones, irrespective of substitutions. A molecular fit of (I) with its methoxy-substituted analogue shows a near perfect fit, except for a slight rotation of the two axially substituted phenyl rings. Thus, it seems that there is no loss of molecular symmetry as a result of chloro substitution, though the molecule does not lie across the mirror plane as in the case of the methoxy-substituted analogue.
It is known that the regular hexagonal geometry of benzene is perturbed when the ring is substituted with strong electron-donating or electron-withdrawing groups (Domenicano & Murray-Rust, 1979; Domenicano et al., 1983). However, in the title compound, the chloro substituent does not play any significant role in deforming the phenyl rings.
The crystal packing is stabilized by Cl···Cl interactions (Fig. 2) in addition to C—H···O hydrogen bonds. The two short Cl···Cl distances observed are: Cl47···Cl77(1 - x, y + 1/2, -z + 3/2) = 3.466 (3) Å and Cl67···Cl77(x - 1, y + 1, z) = 3.346 (3) Å. These values are significantly shorter than the sum of the van der Waals radii and demonstrate the special nature of Cl···Cl interactions (Schmidt, 1971; Williams & Hsu, 1985) and their dominant role in determining the packing modes in crystal structures.