Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536803005543/ww6065sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536803005543/ww6065Isup2.hkl |
CCDC reference: 214621
A mixture of 2,6-dichlorobenzonitrile oxide (3 mmol) and 2,5-bis(4-chlorobenzylidene)cyclopentanone (1.5 mmol) in dry benzene (30 ml) was heated under reflux for 40 h. After evaporation of the solvent, the residue was separated by column chromatography (silica gel, petroleum ether–ethyl acetate = 5:1) to give the title compound, (I). M.p. 535–536 K; IR (KBr): 1765 (C═O), 1595, 1581 (C═N and C═C) cm−1; 1H NMR (CDCl3, p.p.m.): 1.77–1.81 (2H, m), 1.99–2.02 (2H, m), 5.62 (2H, s), 7.18–7.37 (14H, m); 20 mg of (I) was dissolved in 15 ml chloroform and methanol mixed solvent, and the solution was kept at room temperature for 10 d, to give colorless single crystals of (I) by evaporation.
Data collection: SMART (Bruker, 1998); cell refinement: SMART; data reduction: SAINT and SHELXTL (Bruker, 1998); program(s) used to solve structure: SHELXTL (Bruker, 1998); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.
Fig. 1. The molecular structure of (I), drawn with 30% probability ellipsoids. | |
Fig. 2. The crystal structure of (I), viewed along the a axis, omitting the solvent molecules. |
C33H20Cl6N2O3·CHCl3·0.75CH4O | Z = 2 |
Mr = 848.61 | F(000) = 859 |
Triclinic, P1 | Dx = 1.456 Mg m−3 |
Hall symbol: -P 1 | Melting point = 535–536 K |
a = 9.896 (3) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 14.724 (4) Å | Cell parameters from 983 reflections |
c = 15.550 (5) Å | θ = 3.2–25.4° |
α = 111.815 (5)° | µ = 0.69 mm−1 |
β = 101.814 (5)° | T = 293 K |
γ = 103.510 (5)° | Plate, colorless |
V = 1935.5 (10) Å3 | 0.28 × 0.18 × 0.14 mm |
Bruker SMART CCD area-detector diffractometer | 6787 independent reflections |
Radiation source: fine-focus sealed tube | 4617 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.020 |
ϕ and ω scans | θmax = 25.0°, θmin = 2.2° |
Absorption correction: multi-scan (SADABS; Bruker, 1998) | h = −11→11 |
Tmin = 0.804, Tmax = 0.908 | k = −16→17 |
10032 measured reflections | l = −18→14 |
Refinement on F2 | 49 restraints |
Least-squares matrix: full | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.056 | w = 1/[σ2(Fo2) + (0.084P)2] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.195 | (Δ/σ)max = 0.001 |
S = 1.10 | Δρmax = 0.87 e Å−3 |
6787 reflections | Δρmin = −0.39 e Å−3 |
467 parameters |
C33H20Cl6N2O3·CHCl3·0.75CH4O | γ = 103.510 (5)° |
Mr = 848.61 | V = 1935.5 (10) Å3 |
Triclinic, P1 | Z = 2 |
a = 9.896 (3) Å | Mo Kα radiation |
b = 14.724 (4) Å | µ = 0.69 mm−1 |
c = 15.550 (5) Å | T = 293 K |
α = 111.815 (5)° | 0.28 × 0.18 × 0.14 mm |
β = 101.814 (5)° |
Bruker SMART CCD area-detector diffractometer | 6787 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 1998) | 4617 reflections with I > 2σ(I) |
Tmin = 0.804, Tmax = 0.908 | Rint = 0.020 |
10032 measured reflections |
R[F2 > 2σ(F2)] = 0.056 | 49 restraints |
wR(F2) = 0.195 | H-atom parameters constrained |
S = 1.10 | Δρmax = 0.87 e Å−3 |
6787 reflections | Δρmin = −0.39 e Å−3 |
467 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 | Occ. (<1) | |
Cl1 | 1.43071 (16) | 0.80436 (12) | 0.93787 (13) | 0.0848 (5) | |
Cl2 | 0.80995 (15) | 0.47773 (11) | 0.48562 (10) | 0.0645 (4) | |
Cl3 | 0.5833 (2) | 0.55659 (15) | 0.78489 (13) | 0.0894 (5) | |
Cl4 | 0.62958 (18) | −0.23588 (12) | 0.36408 (10) | 0.0832 (5) | |
Cl5 | 1.21776 (17) | 0.04500 (14) | 0.83836 (12) | 0.0828 (5) | |
Cl6 | 0.69207 (15) | 0.00826 (11) | 0.89947 (11) | 0.0703 (4) | |
O1 | 0.7322 (4) | 0.2990 (3) | 0.8195 (3) | 0.0656 (10) | |
O2 | 0.7584 (3) | 0.2869 (2) | 0.6236 (2) | 0.0473 (7) | |
O3 | 1.0241 (3) | 0.2756 (2) | 0.8806 (2) | 0.0504 (8) | |
N1 | 0.6962 (4) | 0.3497 (3) | 0.5905 (3) | 0.0429 (8) | |
N2 | 1.0459 (4) | 0.1997 (3) | 0.9111 (3) | 0.0480 (9) | |
C1 | 0.8236 (5) | 0.2923 (3) | 0.7803 (3) | 0.0405 (10) | |
C2 | 0.8673 (5) | 0.3514 (3) | 0.7219 (3) | 0.0382 (9) | |
C3 | 1.0151 (5) | 0.3413 (3) | 0.7165 (4) | 0.0476 (11) | |
H3A | 1.0942 | 0.3945 | 0.7746 | 0.057* | |
H3B | 1.0334 | 0.3466 | 0.6593 | 0.057* | |
C4 | 1.0001 (5) | 0.2323 (3) | 0.7095 (3) | 0.0450 (10) | |
H4A | 0.9444 | 0.1790 | 0.6435 | 0.054* | |
H4B | 1.0959 | 0.2259 | 0.7283 | 0.054* | |
C5 | 0.9193 (5) | 0.2231 (3) | 0.7806 (3) | 0.0393 (9) | |
C6 | 0.8462 (4) | 0.4586 (3) | 0.7540 (3) | 0.0360 (9) | |
H6 | 0.7927 | 0.4662 | 0.8013 | 0.043* | |
C7 | 0.7448 (4) | 0.4427 (3) | 0.6582 (3) | 0.0361 (9) | |
C8 | 0.9889 (5) | 0.5500 (3) | 0.7996 (3) | 0.0377 (9) | |
C9 | 1.0475 (5) | 0.6066 (3) | 0.9004 (3) | 0.0472 (11) | |
H9 | 0.9949 | 0.5918 | 0.9396 | 0.057* | |
C10 | 1.1826 (6) | 0.6843 (4) | 0.9433 (3) | 0.0560 (12) | |
H10 | 1.2214 | 0.7217 | 1.0111 | 0.067* | |
C11 | 1.2597 (5) | 0.7062 (4) | 0.8849 (4) | 0.0506 (11) | |
C12 | 1.2032 (5) | 0.6521 (4) | 0.7852 (4) | 0.0522 (11) | |
H12 | 1.2561 | 0.6674 | 0.7464 | 0.063* | |
C13 | 1.0679 (5) | 0.5749 (3) | 0.7427 (3) | 0.0477 (11) | |
H13 | 1.0290 | 0.5388 | 0.6749 | 0.057* | |
C14 | 0.6989 (4) | 0.5233 (3) | 0.6367 (3) | 0.0413 (10) | |
C15 | 0.7234 (5) | 0.5449 (4) | 0.5600 (3) | 0.0488 (11) | |
C16 | 0.6810 (6) | 0.6204 (4) | 0.5403 (4) | 0.0652 (15) | |
H16 | 0.6985 | 0.6333 | 0.4888 | 0.078* | |
C17 | 0.6124 (6) | 0.6761 (4) | 0.5982 (5) | 0.0744 (17) | |
H17 | 0.5849 | 0.7274 | 0.5858 | 0.089* | |
C18 | 0.5846 (6) | 0.6569 (4) | 0.6731 (4) | 0.0659 (15) | |
H18 | 0.5374 | 0.6943 | 0.7113 | 0.079* | |
C19 | 0.6272 (5) | 0.5814 (4) | 0.6918 (4) | 0.0528 (12) | |
C20 | 0.8377 (4) | 0.1155 (3) | 0.7700 (3) | 0.0372 (9) | |
H20 | 0.7505 | 0.1191 | 0.7898 | 0.045* | |
C21 | 0.9490 (5) | 0.1117 (3) | 0.8510 (3) | 0.0398 (9) | |
C22 | 0.7882 (4) | 0.0254 (3) | 0.6694 (3) | 0.0371 (9) | |
C23 | 0.8840 (5) | −0.0169 (4) | 0.6304 (3) | 0.0493 (11) | |
H23 | 0.9827 | 0.0085 | 0.6675 | 0.059* | |
C24 | 0.8357 (5) | −0.0975 (4) | 0.5360 (3) | 0.0522 (12) | |
H24 | 0.9015 | −0.1253 | 0.5100 | 0.063* | |
C25 | 0.6894 (5) | −0.1351 (3) | 0.4818 (3) | 0.0488 (11) | |
C26 | 0.5906 (5) | −0.0948 (4) | 0.5189 (3) | 0.0494 (11) | |
H26 | 0.4919 | −0.1212 | 0.4816 | 0.059* | |
C27 | 0.6400 (5) | −0.0143 (3) | 0.6126 (3) | 0.0451 (10) | |
H27 | 0.5738 | 0.0136 | 0.6380 | 0.054* | |
C28 | 0.9493 (5) | 0.0167 (3) | 0.8628 (3) | 0.0442 (11) | |
C29 | 1.0644 (6) | −0.0218 (4) | 0.8551 (3) | 0.0591 (13) | |
C30 | 1.0588 (9) | −0.1149 (5) | 0.8610 (4) | 0.082 (2) | |
H30 | 1.1353 | −0.1406 | 0.8539 | 0.099* | |
C31 | 0.9427 (10) | −0.1682 (5) | 0.8770 (4) | 0.092 (2) | |
H31 | 0.9401 | −0.2303 | 0.8803 | 0.110* | |
C32 | 0.8290 (8) | −0.1315 (4) | 0.8884 (4) | 0.0759 (18) | |
H32 | 0.7508 | −0.1672 | 0.9012 | 0.091* | |
C33 | 0.8329 (6) | −0.0396 (4) | 0.8804 (3) | 0.0562 (13) | |
C34 | 0.2388 (5) | 0.8183 (4) | 0.5982 (3) | 0.0537 (12) | |
H34 | 0.2587 | 0.7695 | 0.5434 | 0.064* | |
Cl7 | 0.06771 (16) | 0.75603 (13) | 0.60192 (14) | 0.0853 (5) | |
Cl8 | 0.23653 (15) | 0.92778 (11) | 0.57808 (10) | 0.0666 (4) | |
Cl9 | 0.37803 (15) | 0.85353 (12) | 0.70606 (10) | 0.0685 (4) | |
O4 | 0.4023 (19) | 0.4088 (13) | 0.8868 (14) | 0.192 (5) | 0.50 |
C35 | 0.4291 (18) | 0.3249 (15) | 0.9069 (13) | 0.126 (5) | 0.50 |
O5 | 0.5000 | 0.5000 | 1.0000 | 0.160 (6) | 0.50 |
C36 | 0.354 (2) | 0.504 (3) | 0.992 (3) | 0.135 (9) | 0.25 |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cl1 | 0.0544 (8) | 0.0721 (10) | 0.0903 (11) | −0.0021 (7) | 0.0050 (8) | 0.0209 (8) |
Cl2 | 0.0686 (8) | 0.0847 (9) | 0.0585 (7) | 0.0304 (7) | 0.0291 (6) | 0.0432 (7) |
Cl3 | 0.1173 (13) | 0.1138 (13) | 0.0987 (12) | 0.0812 (11) | 0.0748 (11) | 0.0646 (10) |
Cl4 | 0.0803 (10) | 0.0779 (10) | 0.0473 (7) | 0.0046 (8) | 0.0114 (7) | 0.0002 (7) |
Cl5 | 0.0749 (10) | 0.1027 (12) | 0.0828 (10) | 0.0555 (9) | 0.0256 (8) | 0.0379 (9) |
Cl6 | 0.0626 (8) | 0.0763 (9) | 0.0743 (9) | 0.0117 (7) | 0.0186 (7) | 0.0446 (8) |
O1 | 0.084 (2) | 0.074 (2) | 0.093 (3) | 0.053 (2) | 0.063 (2) | 0.060 (2) |
O2 | 0.064 (2) | 0.0342 (15) | 0.0413 (16) | 0.0199 (14) | 0.0103 (15) | 0.0154 (13) |
O3 | 0.0608 (19) | 0.0349 (16) | 0.0466 (17) | 0.0123 (14) | 0.0025 (15) | 0.0189 (14) |
N1 | 0.048 (2) | 0.043 (2) | 0.043 (2) | 0.0189 (17) | 0.0134 (17) | 0.0226 (17) |
N2 | 0.058 (2) | 0.043 (2) | 0.042 (2) | 0.0199 (19) | 0.0078 (18) | 0.0206 (18) |
C1 | 0.049 (2) | 0.039 (2) | 0.042 (2) | 0.0198 (19) | 0.018 (2) | 0.0219 (19) |
C2 | 0.044 (2) | 0.037 (2) | 0.038 (2) | 0.0174 (18) | 0.0152 (19) | 0.0182 (18) |
C3 | 0.050 (3) | 0.044 (2) | 0.056 (3) | 0.018 (2) | 0.025 (2) | 0.024 (2) |
C4 | 0.044 (2) | 0.044 (2) | 0.058 (3) | 0.024 (2) | 0.023 (2) | 0.025 (2) |
C5 | 0.043 (2) | 0.038 (2) | 0.038 (2) | 0.0158 (18) | 0.0119 (18) | 0.0175 (18) |
C6 | 0.046 (2) | 0.034 (2) | 0.037 (2) | 0.0186 (18) | 0.0190 (18) | 0.0196 (17) |
C7 | 0.040 (2) | 0.035 (2) | 0.037 (2) | 0.0146 (18) | 0.0141 (18) | 0.0179 (18) |
C8 | 0.047 (2) | 0.032 (2) | 0.038 (2) | 0.0170 (18) | 0.0116 (18) | 0.0182 (17) |
C9 | 0.062 (3) | 0.044 (2) | 0.037 (2) | 0.019 (2) | 0.017 (2) | 0.017 (2) |
C10 | 0.060 (3) | 0.052 (3) | 0.037 (2) | 0.014 (2) | 0.004 (2) | 0.010 (2) |
C11 | 0.044 (3) | 0.043 (3) | 0.057 (3) | 0.013 (2) | 0.008 (2) | 0.020 (2) |
C12 | 0.053 (3) | 0.052 (3) | 0.054 (3) | 0.014 (2) | 0.018 (2) | 0.028 (2) |
C13 | 0.056 (3) | 0.046 (3) | 0.037 (2) | 0.008 (2) | 0.012 (2) | 0.020 (2) |
C14 | 0.038 (2) | 0.038 (2) | 0.050 (2) | 0.0127 (18) | 0.0093 (19) | 0.0232 (19) |
C15 | 0.040 (2) | 0.053 (3) | 0.055 (3) | 0.013 (2) | 0.008 (2) | 0.031 (2) |
C16 | 0.056 (3) | 0.071 (4) | 0.076 (4) | 0.018 (3) | 0.006 (3) | 0.051 (3) |
C17 | 0.067 (3) | 0.061 (3) | 0.102 (5) | 0.030 (3) | 0.006 (3) | 0.050 (3) |
C18 | 0.058 (3) | 0.058 (3) | 0.083 (4) | 0.032 (3) | 0.015 (3) | 0.030 (3) |
C19 | 0.050 (3) | 0.053 (3) | 0.063 (3) | 0.025 (2) | 0.018 (2) | 0.028 (2) |
C20 | 0.041 (2) | 0.038 (2) | 0.040 (2) | 0.0179 (18) | 0.0111 (18) | 0.0216 (18) |
C21 | 0.046 (2) | 0.041 (2) | 0.034 (2) | 0.020 (2) | 0.0090 (19) | 0.0179 (19) |
C22 | 0.040 (2) | 0.035 (2) | 0.038 (2) | 0.0137 (18) | 0.0071 (18) | 0.0207 (18) |
C23 | 0.043 (2) | 0.052 (3) | 0.047 (3) | 0.020 (2) | 0.004 (2) | 0.019 (2) |
C24 | 0.055 (3) | 0.052 (3) | 0.044 (2) | 0.024 (2) | 0.012 (2) | 0.014 (2) |
C25 | 0.056 (3) | 0.043 (2) | 0.040 (2) | 0.009 (2) | 0.010 (2) | 0.017 (2) |
C26 | 0.038 (2) | 0.051 (3) | 0.048 (3) | 0.004 (2) | 0.004 (2) | 0.023 (2) |
C27 | 0.039 (2) | 0.048 (3) | 0.050 (3) | 0.014 (2) | 0.012 (2) | 0.025 (2) |
C28 | 0.063 (3) | 0.038 (2) | 0.031 (2) | 0.025 (2) | 0.006 (2) | 0.0153 (18) |
C29 | 0.082 (4) | 0.055 (3) | 0.039 (2) | 0.034 (3) | 0.008 (2) | 0.019 (2) |
C30 | 0.135 (6) | 0.068 (4) | 0.051 (3) | 0.069 (4) | 0.012 (4) | 0.022 (3) |
C31 | 0.170 (8) | 0.046 (3) | 0.058 (3) | 0.043 (4) | 0.015 (4) | 0.028 (3) |
C32 | 0.118 (5) | 0.043 (3) | 0.054 (3) | 0.014 (3) | 0.009 (3) | 0.026 (2) |
C33 | 0.080 (4) | 0.039 (2) | 0.037 (2) | 0.013 (2) | 0.005 (2) | 0.016 (2) |
C34 | 0.062 (3) | 0.056 (3) | 0.048 (3) | 0.025 (2) | 0.021 (2) | 0.023 (2) |
Cl7 | 0.0625 (9) | 0.0808 (10) | 0.1117 (13) | 0.0098 (7) | 0.0162 (8) | 0.0567 (10) |
Cl8 | 0.0662 (8) | 0.0770 (9) | 0.0775 (9) | 0.0284 (7) | 0.0251 (7) | 0.0522 (8) |
Cl9 | 0.0648 (8) | 0.0807 (9) | 0.0688 (8) | 0.0330 (7) | 0.0145 (7) | 0.0407 (7) |
O4 | 0.166 (9) | 0.175 (8) | 0.202 (9) | 0.020 (7) | 0.081 (7) | 0.061 (6) |
C35 | 0.084 (8) | 0.147 (8) | 0.118 (9) | 0.047 (7) | 0.031 (7) | 0.024 (6) |
O5 | 0.158 (9) | 0.164 (8) | 0.151 (9) | 0.079 (8) | 0.033 (7) | 0.056 (7) |
C36 | 0.129 (11) | 0.135 (13) | 0.142 (13) | 0.054 (10) | 0.023 (9) | 0.068 (8) |
Cl1—C11 | 1.742 (5) | C15—C16 | 1.386 (7) |
Cl2—C15 | 1.733 (5) | C16—C17 | 1.379 (8) |
Cl3—C19 | 1.730 (5) | C16—H16 | 0.9300 |
Cl4—C25 | 1.741 (5) | C17—C18 | 1.360 (9) |
Cl5—C29 | 1.730 (6) | C17—H17 | 0.9300 |
Cl6—C33 | 1.731 (6) | C18—C19 | 1.382 (7) |
O1—C1 | 1.192 (5) | C18—H18 | 0.9300 |
O2—N1 | 1.410 (4) | C20—C22 | 1.513 (6) |
O2—C2 | 1.472 (5) | C20—C21 | 1.521 (5) |
O3—N2 | 1.410 (4) | C20—H20 | 0.9800 |
O3—C5 | 1.471 (5) | C21—C28 | 1.476 (6) |
N1—C7 | 1.276 (5) | C22—C23 | 1.373 (6) |
N2—C21 | 1.274 (6) | C22—C27 | 1.400 (6) |
C1—C2 | 1.531 (6) | C23—C24 | 1.394 (6) |
C1—C5 | 1.544 (6) | C23—H23 | 0.9300 |
C2—C3 | 1.521 (6) | C24—C25 | 1.375 (6) |
C2—C6 | 1.547 (5) | C24—H24 | 0.9300 |
C3—C4 | 1.537 (6) | C25—C26 | 1.374 (7) |
C3—H3A | 0.9700 | C26—C27 | 1.385 (6) |
C3—H3B | 0.9700 | C26—H26 | 0.9300 |
C4—C5 | 1.517 (6) | C27—H27 | 0.9300 |
C4—H4A | 0.9700 | C28—C33 | 1.393 (7) |
C4—H4B | 0.9700 | C28—C29 | 1.393 (7) |
C5—C20 | 1.532 (6) | C29—C30 | 1.397 (8) |
C6—C7 | 1.516 (5) | C30—C31 | 1.356 (10) |
C6—C8 | 1.517 (6) | C30—H30 | 0.9300 |
C6—H6 | 0.9800 | C31—C32 | 1.372 (10) |
C7—C14 | 1.487 (5) | C31—H31 | 0.9300 |
C8—C13 | 1.384 (6) | C32—C33 | 1.397 (7) |
C8—C9 | 1.386 (6) | C32—H32 | 0.9300 |
C9—C10 | 1.377 (7) | C34—Cl9 | 1.748 (5) |
C9—H9 | 0.9300 | C34—Cl7 | 1.751 (5) |
C10—C11 | 1.377 (7) | C34—Cl8 | 1.756 (5) |
C10—H10 | 0.9300 | C34—H34 | 0.9800 |
C11—C12 | 1.368 (7) | O4—C35 | 1.449 (10) |
C12—C13 | 1.374 (6) | O4—O5 | 1.667 (18) |
C12—H12 | 0.9300 | O5—C36i | 1.438 (10) |
C13—H13 | 0.9300 | O5—C36 | 1.438 (10) |
C14—C15 | 1.395 (6) | O5—O4i | 1.667 (18) |
C14—C19 | 1.399 (6) | ||
N1—O2—C2 | 109.9 (3) | C18—C17—C16 | 120.9 (5) |
N2—O3—C5 | 108.9 (3) | C18—C17—H17 | 119.6 |
C7—N1—O2 | 109.6 (3) | C16—C17—H17 | 119.6 |
C21—N2—O3 | 109.1 (3) | C17—C18—C19 | 119.3 (5) |
O1—C1—C2 | 125.9 (4) | C17—C18—H18 | 120.3 |
O1—C1—C5 | 125.8 (4) | C19—C18—H18 | 120.3 |
C2—C1—C5 | 108.2 (3) | C18—C19—C14 | 122.6 (5) |
O2—C2—C3 | 108.1 (3) | C18—C19—Cl3 | 117.6 (4) |
O2—C2—C1 | 103.3 (3) | C14—C19—Cl3 | 119.8 (3) |
C3—C2—C1 | 103.7 (3) | C22—C20—C21 | 116.7 (3) |
O2—C2—C6 | 104.5 (3) | C22—C20—C5 | 116.8 (3) |
C3—C2—C6 | 120.8 (4) | C21—C20—C5 | 99.2 (3) |
C1—C2—C6 | 115.0 (3) | C22—C20—H20 | 107.8 |
C2—C3—C4 | 103.6 (3) | C21—C20—H20 | 107.8 |
C2—C3—H3A | 111.0 | C5—C20—H20 | 107.8 |
C4—C3—H3A | 111.0 | N2—C21—C28 | 120.8 (4) |
C2—C3—H3B | 111.0 | N2—C21—C20 | 114.2 (4) |
C4—C3—H3B | 111.0 | C28—C21—C20 | 125.0 (4) |
H3A—C3—H3B | 109.0 | C23—C22—C27 | 118.6 (4) |
C5—C4—C3 | 104.4 (3) | C23—C22—C20 | 122.5 (4) |
C5—C4—H4A | 110.9 | C27—C22—C20 | 118.8 (4) |
C3—C4—H4A | 110.9 | C22—C23—C24 | 121.0 (4) |
C5—C4—H4B | 110.9 | C22—C23—H23 | 119.5 |
C3—C4—H4B | 110.9 | C24—C23—H23 | 119.5 |
H4A—C4—H4B | 108.9 | C25—C24—C23 | 119.1 (4) |
O3—C5—C4 | 109.4 (3) | C25—C24—H24 | 120.5 |
O3—C5—C20 | 103.7 (3) | C23—C24—H24 | 120.5 |
C4—C5—C20 | 119.8 (3) | C26—C25—C24 | 121.3 (4) |
O3—C5—C1 | 104.3 (3) | C26—C25—Cl4 | 119.8 (4) |
C4—C5—C1 | 104.1 (3) | C24—C25—Cl4 | 118.9 (4) |
C20—C5—C1 | 114.5 (3) | C25—C26—C27 | 119.2 (4) |
C7—C6—C8 | 116.2 (3) | C25—C26—H26 | 120.4 |
C7—C6—C2 | 100.1 (3) | C27—C26—H26 | 120.4 |
C8—C6—C2 | 113.8 (3) | C26—C27—C22 | 120.8 (4) |
C7—C6—H6 | 108.8 | C26—C27—H27 | 119.6 |
C8—C6—H6 | 108.8 | C22—C27—H27 | 119.6 |
C2—C6—H6 | 108.8 | C33—C28—C29 | 116.9 (4) |
N1—C7—C14 | 118.4 (4) | C33—C28—C21 | 121.4 (4) |
N1—C7—C6 | 114.8 (3) | C29—C28—C21 | 121.7 (4) |
C14—C7—C6 | 126.8 (3) | C28—C29—C30 | 120.8 (6) |
C13—C8—C9 | 118.5 (4) | C28—C29—Cl5 | 120.6 (4) |
C13—C8—C6 | 121.3 (4) | C30—C29—Cl5 | 118.6 (5) |
C9—C8—C6 | 120.1 (4) | C31—C30—C29 | 120.5 (6) |
C10—C9—C8 | 120.8 (4) | C31—C30—H30 | 119.7 |
C10—C9—H9 | 119.6 | C29—C30—H30 | 119.7 |
C8—C9—H9 | 119.6 | C30—C31—C32 | 120.8 (5) |
C9—C10—C11 | 119.3 (4) | C30—C31—H31 | 119.6 |
C9—C10—H10 | 120.3 | C32—C31—H31 | 119.6 |
C11—C10—H10 | 120.3 | C31—C32—C33 | 118.7 (6) |
C12—C11—C10 | 120.8 (4) | C31—C32—H32 | 120.6 |
C12—C11—Cl1 | 119.2 (4) | C33—C32—H32 | 120.6 |
C10—C11—Cl1 | 120.0 (4) | C28—C33—C32 | 122.2 (6) |
C11—C12—C13 | 119.6 (5) | C28—C33—Cl6 | 119.6 (3) |
C11—C12—H12 | 120.2 | C32—C33—Cl6 | 118.2 (5) |
C13—C12—H12 | 120.2 | Cl9—C34—Cl7 | 110.8 (3) |
C12—C13—C8 | 120.9 (4) | Cl9—C34—Cl8 | 110.7 (3) |
C12—C13—H13 | 119.6 | Cl7—C34—Cl8 | 110.5 (3) |
C8—C13—H13 | 119.6 | Cl9—C34—H34 | 108.3 |
C15—C14—C19 | 115.9 (4) | Cl7—C34—H34 | 108.3 |
C15—C14—C7 | 122.2 (4) | Cl8—C34—H34 | 108.3 |
C19—C14—C7 | 121.8 (4) | C35—O4—O5 | 93.8 (13) |
C16—C15—C14 | 122.1 (5) | C36i—O5—C36 | 180.000 (15) |
C16—C15—Cl2 | 117.4 (4) | C36i—O5—O4 | 102.6 (18) |
C14—C15—Cl2 | 120.5 (3) | C36—O5—O4 | 77.4 (18) |
C17—C16—C15 | 119.2 (5) | C36i—O5—O4i | 77.4 (18) |
C17—C16—H16 | 120.4 | C36—O5—O4i | 102.6 (18) |
C15—C16—H16 | 120.4 | O4—O5—O4i | 180.000 (7) |
C2—O2—N1—C7 | −4.7 (4) | C19—C14—C15—Cl2 | −179.5 (3) |
C5—O3—N2—C21 | −12.0 (5) | C7—C14—C15—Cl2 | −0.1 (6) |
N1—O2—C2—C3 | −120.1 (3) | C14—C15—C16—C17 | 0.0 (8) |
N1—O2—C2—C1 | 130.4 (3) | Cl2—C15—C16—C17 | −179.6 (4) |
N1—O2—C2—C6 | 9.7 (4) | C15—C16—C17—C18 | −0.8 (8) |
O1—C1—C2—O2 | −84.5 (5) | C16—C17—C18—C19 | 0.7 (9) |
C5—C1—C2—O2 | 96.1 (4) | C17—C18—C19—C14 | 0.2 (8) |
O1—C1—C2—C3 | 162.8 (5) | C17—C18—C19—Cl3 | −177.7 (4) |
C5—C1—C2—C3 | −16.7 (4) | C15—C14—C19—C18 | −0.9 (7) |
O1—C1—C2—C6 | 28.7 (6) | C7—C14—C19—C18 | 179.7 (4) |
C5—C1—C2—C6 | −150.8 (3) | C15—C14—C19—Cl3 | 176.9 (3) |
O2—C2—C3—C4 | −74.5 (4) | C7—C14—C19—Cl3 | −2.6 (6) |
C1—C2—C3—C4 | 34.7 (4) | O3—C5—C20—C22 | −146.8 (3) |
C6—C2—C3—C4 | 165.4 (4) | C4—C5—C20—C22 | −24.6 (5) |
C2—C3—C4—C5 | −40.7 (4) | C1—C5—C20—C22 | 100.2 (4) |
N2—O3—C5—C4 | −107.8 (4) | O3—C5—C20—C21 | −20.5 (4) |
N2—O3—C5—C20 | 21.1 (4) | C4—C5—C20—C21 | 101.7 (4) |
N2—O3—C5—C1 | 141.3 (3) | C1—C5—C20—C21 | −133.5 (3) |
C3—C4—C5—O3 | −81.5 (4) | O3—N2—C21—C28 | 177.4 (4) |
C3—C4—C5—C20 | 159.1 (4) | O3—N2—C21—C20 | −3.0 (5) |
C3—C4—C5—C1 | 29.6 (4) | C22—C20—C21—N2 | 141.8 (4) |
O1—C1—C5—O3 | −72.9 (5) | C5—C20—C21—N2 | 15.5 (5) |
C2—C1—C5—O3 | 106.6 (4) | C22—C20—C21—C28 | −38.5 (6) |
O1—C1—C5—C4 | 172.4 (5) | C5—C20—C21—C28 | −164.9 (4) |
C2—C1—C5—C4 | −8.1 (4) | C21—C20—C22—C23 | −42.4 (6) |
O1—C1—C5—C20 | 39.7 (6) | C5—C20—C22—C23 | 74.7 (5) |
C2—C1—C5—C20 | −140.8 (3) | C21—C20—C22—C27 | 139.6 (4) |
O2—C2—C6—C7 | −10.2 (4) | C5—C20—C22—C27 | −103.3 (4) |
C3—C2—C6—C7 | 111.6 (4) | C27—C22—C23—C24 | 0.3 (7) |
C1—C2—C6—C7 | −122.7 (4) | C20—C22—C23—C24 | −177.6 (4) |
O2—C2—C6—C8 | −134.8 (3) | C22—C23—C24—C25 | −0.4 (7) |
C3—C2—C6—C8 | −13.0 (5) | C23—C24—C25—C26 | 0.1 (7) |
C1—C2—C6—C8 | 112.7 (4) | C23—C24—C25—Cl4 | −179.8 (4) |
O2—N1—C7—C14 | 176.8 (3) | C24—C25—C26—C27 | 0.3 (7) |
O2—N1—C7—C6 | −2.9 (5) | Cl4—C25—C26—C27 | −179.8 (3) |
C8—C6—C7—N1 | 131.5 (4) | C25—C26—C27—C22 | −0.4 (7) |
C2—C6—C7—N1 | 8.5 (5) | C23—C22—C27—C26 | 0.1 (6) |
C8—C6—C7—C14 | −48.1 (5) | C20—C22—C27—C26 | 178.1 (4) |
C2—C6—C7—C14 | −171.1 (4) | N2—C21—C28—C33 | 117.0 (5) |
C7—C6—C8—C13 | −39.8 (5) | C20—C21—C28—C33 | −62.6 (6) |
C2—C6—C8—C13 | 75.7 (5) | N2—C21—C28—C29 | −64.1 (6) |
C7—C6—C8—C9 | 144.3 (4) | C20—C21—C28—C29 | 116.3 (5) |
C2—C6—C8—C9 | −100.3 (4) | C33—C28—C29—C30 | 2.5 (7) |
C13—C8—C9—C10 | −1.3 (6) | C21—C28—C29—C30 | −176.4 (4) |
C6—C8—C9—C10 | 174.7 (4) | C33—C28—C29—Cl5 | −177.3 (3) |
C8—C9—C10—C11 | 0.3 (7) | C21—C28—C29—Cl5 | 3.8 (6) |
C9—C10—C11—C12 | 0.4 (7) | C28—C29—C30—C31 | −1.8 (8) |
C9—C10—C11—Cl1 | 180.0 (4) | Cl5—C29—C30—C31 | 178.1 (5) |
C10—C11—C12—C13 | 0.0 (7) | C29—C30—C31—C32 | −0.4 (9) |
Cl1—C11—C12—C13 | −179.6 (4) | C30—C31—C32—C33 | 1.8 (9) |
C11—C12—C13—C8 | −1.0 (7) | C29—C28—C33—C32 | −1.1 (7) |
C9—C8—C13—C12 | 1.7 (6) | C21—C28—C33—C32 | 177.8 (4) |
C6—C8—C13—C12 | −174.3 (4) | C29—C28—C33—Cl6 | 175.4 (3) |
N1—C7—C14—C15 | −57.0 (6) | C21—C28—C33—Cl6 | −5.7 (6) |
C6—C7—C14—C15 | 122.6 (5) | C31—C32—C33—C28 | −1.0 (8) |
N1—C7—C14—C19 | 122.3 (5) | C31—C32—C33—Cl6 | −177.6 (4) |
C6—C7—C14—C19 | −58.0 (6) | C35—O4—O5—C36i | 64 (2) |
C19—C14—C15—C16 | 0.8 (7) | C35—O4—O5—C36 | −116 (2) |
C7—C14—C15—C16 | −179.8 (4) | C35—O4—O5—O4i | −127 (54) |
Symmetry code: (i) −x+1, −y+1, −z+2. |
Experimental details
Crystal data | |
Chemical formula | C33H20Cl6N2O3·CHCl3·0.75CH4O |
Mr | 848.61 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 293 |
a, b, c (Å) | 9.896 (3), 14.724 (4), 15.550 (5) |
α, β, γ (°) | 111.815 (5), 101.814 (5), 103.510 (5) |
V (Å3) | 1935.5 (10) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.69 |
Crystal size (mm) | 0.28 × 0.18 × 0.14 |
Data collection | |
Diffractometer | Bruker SMART CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 1998) |
Tmin, Tmax | 0.804, 0.908 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 10032, 6787, 4617 |
Rint | 0.020 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.056, 0.195, 1.10 |
No. of reflections | 6787 |
No. of parameters | 467 |
No. of restraints | 49 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.87, −0.39 |
Computer programs: SMART (Bruker, 1998), SMART, SAINT and SHELXTL (Bruker, 1998), SHELXTL (Bruker, 1998), SHELXTL.
Cl1—C11 | 1.742 (5) | O2—N1 | 1.410 (4) |
O1—C1 | 1.192 (5) | O3—N2 | 1.410 (4) |
N1—O2—C2 | 109.9 (3) | O2—C2—C1 | 103.3 (3) |
N2—O3—C5 | 108.9 (3) | O2—C2—C6 | 104.5 (3) |
C7—N1—O2 | 109.6 (3) | O3—C5—C20 | 103.7 (3) |
C21—N2—O3 | 109.1 (3) | C7—C6—C2 | 100.1 (3) |
O1—C1—C5 | 125.8 (4) |
Spiro-compounds represent an important class of naturally occurring substances characterized by highly pronounced biological properties. (Kobayashi et al., 1991; James et al., 1991). 1,3-Dipolar cycloaddition reactions are important process for the construction of spiro-compounds (Caramella & Grunanger., 1984).
Compound (I) contains three spiro-linked rings, namely a cyclopentanone ring and two isoxazoline rings. The five-membered cyclopentanone ring has a twist conformation. The two isoxazoline rings are attached to this central ring through spiro-C atoms, giving approximate C2 symmetry. Attached to the isoxazoline rings are 4-chlorophenyl and 2,6-dichlorophenyl substituents.
The two isoxazoline rings (A and B) are non-planar, with envelope conformations. O2—N1—C7—C6 (ring A) and O3—N2—C21—C20 (ring B) form almost exactly planar arrangements; the torsion angle O2—N1—C7—C6 of −2.9 (5)° and O3—N2—C21—C20 of −3.0 (5)° are different from that of −0.9 (5)° in a related structure, viz. 4,11-bis(4-chlorophenyl)-3,10-bis(2,6-dichlorophenyl)-1,8-dioxa-2,9- diazadispiro[4.1.4.3]tetradeca-2,9-dien-6-one 0.75-hydrate (Li et al., 2003). Spiro-atom C2 lies 0.168 (3) Å from the O2/N1/C7/C6 plane in ring A and C5 is 0.345 (3) Å from the O3/N2/C21/C20 plane in ring B, these two atoms forming the flaps of the envelopes.
The bond lengths O2—N1 and O3—N2 are both 1.410 (4) Å, comparable to that of 1.413 (2) Å in a related structure, viz. 8-methyl-3-phenyl-1-oxa-2,8-diaza-spiro[4.5]dec-2-ene (Feng et al., 1997).
The dihedral angle between the two substituted phenyl rings on ring A is 94.9 (3)°, while that between the two substituted phenyl rings on ring B is 74.8 (3)°. The dihedral angle between the two isoxazoline ring envelope flaps (C6/C2/O2 and C20/C5/O3), which form the spiro linkages with the central ring, is 44.5 (3)°.