The title compound, C
32H
26N
2Cl
2, exists as the
Z isomer. All three rings in the azabicylo[2.2.2]octane system adopt a boat conformation. Intermolecular C—H
Cl interactions form a dimer in the crystal structure.
Supporting information
CCDC reference: 296526
Key indicators
- Single-crystal X-ray study
- T = 273 K
- Mean (C-C) = 0.005 Å
- R factor = 0.055
- wR factor = 0.163
- Data-to-parameter ratio = 14.3
checkCIF/PLATON results
No syntax errors found
Alert level C
PLAT125_ALERT_4_C No _symmetry_space_group_name_Hall Given ....... ?
PLAT230_ALERT_2_C Hirshfeld Test Diff for C11 - C12 .. 5.99 su
PLAT241_ALERT_2_C Check High Ueq as Compared to Neighbors for C7
PLAT241_ALERT_2_C Check High Ueq as Compared to Neighbors for C23
PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for C18
PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for C21
PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for C31
PLAT331_ALERT_2_C Small Average Phenyl C-C Dist. C21 -C26 1.37 Ang.
PLAT340_ALERT_3_C Low Bond Precision on C-C bonds (x 1000) Ang ... 5
PLAT480_ALERT_4_C Long H...A H-Bond Reported H10 .. CL2 .. 3.06 Ang.
PLAT481_ALERT_4_C Long D...A H-Bond Reported C10 .. CL2 .. 3.97 Ang.
0 ALERT level A = In general: serious problem
0 ALERT level B = Potentially serious problem
11 ALERT level C = Check and explain
0 ALERT level G = General alerts; check
0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
7 ALERT type 2 Indicator that the structure model may be wrong or deficient
1 ALERT type 3 Indicator that the structure quality may be low
3 ALERT type 4 Improvement, methodology, query or suggestion
To a solution of N-benzylideneaniline (5.5 mmol) in CH2Cl2 (5 ml) at room temperature were sequentially added ZrCl4 (10 mol%) and cyclohexen-2-one (5.5 mmol). The mixture was stirred for 6 h. After completion of the reaction as indicated by thin-layer chromatography, the reaction was quenched with water, and the mixture diluted with CH2Cl2 (20 ml) and washed with water (10 ml). The aqueous layer was extracted with CH2Cl2 (2 x 10 ml). The combined organic layers were dried over Na2SO4 and concentrated in vacuo to yield a dark-brown residue, which was purified by column chromatography using 2–10% ethyl acetate in hexane as eluent to obtain the pure product.
H atoms were included in calculated positions (C—H = 0.93–0.98 Å) and refined as riding, with Uiso(H) values set at 1.2 or 1.5 (CH3) times Ueq(C).
Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL/PC (Sheldrick, 1990); software used to prepare material for publication: SHELXL97.
N-{3-(4-Chlorophenyl)-6-[(
Z)-(4-chlorophenyl)methylidene]-2-phenyl- 2-azabicyclo[2.2.2]oct-5-ylidene}aniline
top
Crystal data top
C32H26Cl2N2 | F(000) = 1064 |
Mr = 509.45 | Dx = 1.274 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
a = 14.3560 (6) Å | Cell parameters from 5389 reflections |
b = 10.0621 (4) Å | θ = 2.2–23.0° |
c = 18.3872 (8) Å | µ = 0.27 mm−1 |
β = 91.427 (1)° | T = 273 K |
V = 2655.24 (19) Å3 | Block, colorless |
Z = 4 | 0.20 × 0.12 × 0.07 mm |
Data collection top
Bruker SMART APEX CCD area-detector diffractometer | 3312 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.021 |
Graphite monochromator | θmax = 25.0°, θmin = 1.8° |
ω scans | h = −17→17 |
18622 measured reflections | k = −11→11 |
4657 independent reflections | l = −21→21 |
Refinement top
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)] = 0.055 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.163 | H-atom parameters constrained |
S = 1.04 | w = 1/[σ2(Fo2) + (0.0676P)2 + 0.9266P] where P = (Fo2 + 2Fc2)/3 |
4657 reflections | (Δ/σ)max = 0.001 |
325 parameters | Δρmax = 0.37 e Å−3 |
0 restraints | Δρmin = −0.36 e Å−3 |
Crystal data top
C32H26Cl2N2 | V = 2655.24 (19) Å3 |
Mr = 509.45 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 14.3560 (6) Å | µ = 0.27 mm−1 |
b = 10.0621 (4) Å | T = 273 K |
c = 18.3872 (8) Å | 0.20 × 0.12 × 0.07 mm |
β = 91.427 (1)° | |
Data collection top
Bruker SMART APEX CCD area-detector diffractometer | 3312 reflections with I > 2σ(I) |
18622 measured reflections | Rint = 0.021 |
4657 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.055 | 0 restraints |
wR(F2) = 0.163 | H-atom parameters constrained |
S = 1.04 | Δρmax = 0.37 e Å−3 |
4657 reflections | Δρmin = −0.36 e Å−3 |
325 parameters | |
Special details top
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Cl1 | 0.30109 (8) | 0.75288 (12) | 1.07831 (7) | 0.1443 (4) | |
Cl2 | −0.06461 (8) | 0.26491 (15) | 0.54980 (6) | 0.1609 (5) | |
N1 | 0.23800 (15) | 0.1089 (2) | 0.82629 (10) | 0.0765 (6) | |
N2 | −0.0294 (2) | 0.1096 (3) | 0.88518 (12) | 0.0965 (7) | |
C1 | 0.2240 (2) | 0.1253 (3) | 0.90536 (13) | 0.0943 (9) | |
H1 | 0.2695 | 0.1887 | 0.9257 | 0.113* | |
C3 | 0.16841 (17) | 0.0202 (2) | 0.79139 (12) | 0.0702 (6) | |
H3 | 0.2020 | −0.0553 | 0.7710 | 0.084* | |
C4 | 0.1036 (2) | −0.0345 (3) | 0.84999 (13) | 0.0822 (7) | |
H4 | 0.0575 | −0.0956 | 0.8285 | 0.099* | |
C5 | 0.0568 (2) | 0.0829 (3) | 0.88407 (13) | 0.0849 (8) | |
C6 | 0.1264 (2) | 0.1770 (3) | 0.91529 (13) | 0.0878 (8) | |
C7 | 0.2350 (3) | −0.0082 (4) | 0.94316 (17) | 0.1224 (14) | |
H7A | 0.2246 | 0.0015 | 0.9948 | 0.147* | |
H7B | 0.2976 | −0.0420 | 0.9370 | 0.147* | |
C8 | 0.1634 (3) | −0.1049 (4) | 0.90932 (18) | 0.1148 (12) | |
H8A | 0.1234 | −0.1384 | 0.9469 | 0.138* | |
H8B | 0.1955 | −0.1798 | 0.8882 | 0.138* | |
C9 | 0.32744 (18) | 0.1111 (2) | 0.79855 (15) | 0.0767 (7) | |
C10 | 0.4076 (2) | 0.1419 (3) | 0.84034 (19) | 0.1013 (10) | |
H10 | 0.4028 | 0.1599 | 0.8897 | 0.122* | |
C11 | 0.4941 (2) | 0.1458 (3) | 0.8082 (3) | 0.1206 (13) | |
H11 | 0.5464 | 0.1674 | 0.8366 | 0.145* | |
C12 | 0.5043 (3) | 0.1190 (4) | 0.7370 (3) | 0.1222 (12) | |
H12 | 0.5629 | 0.1209 | 0.7165 | 0.147* | |
C13 | 0.4273 (2) | 0.0892 (4) | 0.6959 (2) | 0.1082 (10) | |
H13 | 0.4336 | 0.0707 | 0.6467 | 0.130* | |
C14 | 0.34048 (19) | 0.0856 (3) | 0.72519 (15) | 0.0843 (7) | |
H14 | 0.2891 | 0.0658 | 0.6953 | 0.101* | |
C15 | 0.11243 (16) | 0.0845 (2) | 0.72970 (11) | 0.0627 (6) | |
C16 | 0.0628 (2) | 0.0058 (3) | 0.68123 (14) | 0.0848 (8) | |
H16 | 0.0666 | −0.0861 | 0.6857 | 0.102* | |
C17 | 0.0080 (2) | 0.0595 (4) | 0.62641 (15) | 0.1007 (10) | |
H17 | −0.0254 | 0.0048 | 0.5944 | 0.121* | |
C18 | 0.00325 (19) | 0.1946 (4) | 0.61984 (14) | 0.0916 (9) | |
C19 | 0.0515 (2) | 0.2752 (3) | 0.66644 (15) | 0.0885 (8) | |
H19 | 0.0480 | 0.3670 | 0.6613 | 0.106* | |
C20 | 0.10592 (18) | 0.2196 (2) | 0.72163 (13) | 0.0747 (7) | |
H20 | 0.1386 | 0.2749 | 0.7538 | 0.090* | |
C21 | −0.0969 (2) | 0.0246 (3) | 0.85195 (16) | 0.0916 (9) | |
C22 | −0.1264 (3) | −0.0890 (5) | 0.8840 (2) | 0.1272 (13) | |
H22 | −0.0977 | −0.1170 | 0.9272 | 0.153* | |
C23 | −0.1966 (4) | −0.1620 (5) | 0.8546 (4) | 0.156 (2) | |
H23 | −0.2163 | −0.2387 | 0.8779 | 0.187* | |
C24 | −0.2391 (3) | −0.1230 (5) | 0.7903 (4) | 0.1541 (17) | |
H24 | −0.2887 | −0.1716 | 0.7707 | 0.185* | |
C25 | −0.2077 (3) | −0.0112 (5) | 0.7549 (3) | 0.1422 (14) | |
H25 | −0.2338 | 0.0133 | 0.7100 | 0.171* | |
C26 | −0.1377 (3) | 0.0633 (4) | 0.78646 (19) | 0.1107 (10) | |
H26 | −0.1176 | 0.1403 | 0.7637 | 0.133* | |
C27 | 0.0997 (2) | 0.2887 (3) | 0.94778 (13) | 0.0884 (8) | |
H27 | 0.0355 | 0.2981 | 0.9514 | 0.106* | |
C28 | 0.1539 (2) | 0.3989 (3) | 0.97868 (13) | 0.0839 (8) | |
C29 | 0.1169 (2) | 0.4684 (3) | 1.03691 (15) | 0.0919 (8) | |
H29 | 0.0602 | 0.4412 | 1.0553 | 0.110* | |
C30 | 0.1616 (2) | 0.5756 (4) | 1.06797 (16) | 0.0997 (9) | |
H30 | 0.1360 | 0.6196 | 1.1072 | 0.120* | |
C31 | 0.2435 (2) | 0.6164 (3) | 1.04067 (17) | 0.0978 (9) | |
C32 | 0.2818 (2) | 0.5534 (4) | 0.98267 (19) | 0.1073 (10) | |
H32 | 0.3378 | 0.5832 | 0.9642 | 0.129* | |
C33 | 0.2369 (3) | 0.4453 (4) | 0.95173 (16) | 0.0996 (10) | |
H33 | 0.2629 | 0.4029 | 0.9121 | 0.120* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Cl1 | 0.1473 (9) | 0.1385 (9) | 0.1447 (9) | −0.0114 (6) | −0.0472 (7) | 0.0042 (6) |
Cl2 | 0.1312 (8) | 0.2484 (15) | 0.1006 (7) | 0.0052 (8) | −0.0478 (6) | 0.0461 (8) |
N1 | 0.0879 (15) | 0.0811 (13) | 0.0596 (11) | 0.0214 (11) | −0.0168 (10) | −0.0176 (10) |
N2 | 0.117 (2) | 0.1027 (18) | 0.0697 (14) | 0.0299 (16) | 0.0035 (13) | −0.0125 (13) |
C1 | 0.120 (2) | 0.101 (2) | 0.0602 (14) | 0.0494 (17) | −0.0237 (14) | −0.0184 (14) |
C3 | 0.0881 (16) | 0.0626 (14) | 0.0601 (13) | 0.0133 (12) | 0.0020 (12) | −0.0078 (11) |
C4 | 0.110 (2) | 0.0717 (15) | 0.0657 (14) | 0.0228 (14) | 0.0140 (14) | 0.0067 (12) |
C5 | 0.114 (2) | 0.0903 (19) | 0.0507 (13) | 0.0400 (17) | 0.0078 (14) | 0.0058 (13) |
C6 | 0.118 (2) | 0.0967 (19) | 0.0482 (13) | 0.0421 (18) | −0.0109 (13) | −0.0101 (13) |
C7 | 0.168 (3) | 0.134 (3) | 0.0645 (17) | 0.077 (3) | −0.0140 (19) | −0.0022 (18) |
C8 | 0.157 (3) | 0.103 (2) | 0.084 (2) | 0.055 (2) | 0.019 (2) | 0.0267 (18) |
C9 | 0.0824 (17) | 0.0603 (14) | 0.0862 (17) | 0.0179 (12) | −0.0203 (14) | −0.0133 (12) |
C10 | 0.110 (2) | 0.0806 (19) | 0.111 (2) | 0.0226 (17) | −0.0439 (19) | −0.0278 (16) |
C11 | 0.082 (2) | 0.096 (2) | 0.182 (4) | 0.0058 (17) | −0.045 (2) | −0.031 (2) |
C12 | 0.092 (2) | 0.113 (3) | 0.161 (4) | −0.0116 (19) | −0.003 (2) | −0.018 (3) |
C13 | 0.081 (2) | 0.126 (3) | 0.118 (2) | −0.0147 (18) | 0.0060 (18) | −0.011 (2) |
C14 | 0.0795 (17) | 0.0922 (19) | 0.0807 (17) | −0.0030 (14) | −0.0073 (13) | −0.0091 (14) |
C15 | 0.0710 (14) | 0.0647 (14) | 0.0524 (12) | −0.0038 (11) | 0.0011 (10) | −0.0054 (10) |
C16 | 0.106 (2) | 0.0803 (17) | 0.0680 (16) | −0.0185 (15) | −0.0019 (14) | −0.0139 (13) |
C17 | 0.101 (2) | 0.136 (3) | 0.0645 (16) | −0.035 (2) | −0.0138 (15) | −0.0139 (17) |
C18 | 0.0750 (17) | 0.135 (3) | 0.0643 (16) | −0.0136 (17) | −0.0118 (13) | 0.0165 (17) |
C19 | 0.0914 (19) | 0.0864 (18) | 0.0868 (18) | −0.0060 (15) | −0.0159 (15) | 0.0193 (15) |
C20 | 0.0820 (16) | 0.0698 (16) | 0.0714 (15) | −0.0081 (12) | −0.0185 (12) | −0.0001 (12) |
C21 | 0.109 (2) | 0.091 (2) | 0.0756 (18) | 0.0270 (18) | 0.0273 (16) | 0.0046 (16) |
C22 | 0.145 (3) | 0.126 (3) | 0.112 (3) | 0.024 (3) | 0.050 (3) | 0.032 (2) |
C23 | 0.152 (4) | 0.123 (4) | 0.196 (5) | 0.005 (3) | 0.076 (4) | 0.041 (4) |
C24 | 0.126 (3) | 0.115 (3) | 0.222 (6) | −0.021 (3) | 0.018 (4) | −0.013 (4) |
C25 | 0.156 (4) | 0.122 (3) | 0.147 (4) | −0.022 (3) | −0.025 (3) | 0.005 (3) |
C26 | 0.132 (3) | 0.096 (2) | 0.104 (2) | −0.008 (2) | −0.006 (2) | 0.0112 (19) |
C27 | 0.114 (2) | 0.096 (2) | 0.0550 (13) | 0.0381 (17) | −0.0016 (14) | −0.0044 (14) |
C28 | 0.104 (2) | 0.0944 (19) | 0.0531 (13) | 0.0388 (17) | −0.0034 (14) | −0.0016 (13) |
C29 | 0.0940 (19) | 0.109 (2) | 0.0729 (16) | 0.0197 (17) | 0.0023 (14) | −0.0172 (16) |
C30 | 0.102 (2) | 0.119 (3) | 0.0779 (18) | 0.0205 (19) | −0.0051 (17) | −0.0224 (17) |
C31 | 0.104 (2) | 0.106 (2) | 0.0822 (19) | 0.0237 (19) | −0.0208 (17) | 0.0069 (17) |
C32 | 0.102 (2) | 0.122 (3) | 0.098 (2) | 0.023 (2) | 0.0032 (19) | 0.026 (2) |
C33 | 0.117 (3) | 0.116 (3) | 0.0674 (17) | 0.044 (2) | 0.0165 (17) | 0.0123 (17) |
Geometric parameters (Å, º) top
Cl1—C31 | 1.737 (4) | C15—C20 | 1.371 (3) |
Cl2—C18 | 1.745 (3) | C15—C16 | 1.377 (3) |
N1—C9 | 1.394 (3) | C16—C17 | 1.374 (4) |
N1—C3 | 1.475 (3) | C16—H16 | 0.930 |
N1—C1 | 1.482 (3) | C17—C18 | 1.367 (5) |
N2—C5 | 1.267 (4) | C17—H17 | 0.930 |
N2—C21 | 1.419 (4) | C18—C19 | 1.357 (4) |
C1—C6 | 1.511 (4) | C19—C20 | 1.383 (3) |
C1—C7 | 1.519 (5) | C19—H19 | 0.930 |
C1—H1 | 0.980 | C20—H20 | 0.930 |
C3—C15 | 1.518 (3) | C21—C22 | 1.359 (5) |
C3—C4 | 1.542 (4) | C21—C26 | 1.382 (4) |
C3—H3 | 0.980 | C22—C23 | 1.350 (7) |
C4—C5 | 1.504 (4) | C22—H22 | 0.930 |
C4—C8 | 1.543 (4) | C23—C24 | 1.374 (7) |
C4—H4 | 0.980 | C23—H23 | 0.930 |
C5—C6 | 1.482 (4) | C24—C25 | 1.381 (6) |
C6—C27 | 1.333 (4) | C24—H24 | 0.930 |
C7—C8 | 1.536 (5) | C25—C26 | 1.371 (5) |
C7—H7A | 0.970 | C25—H25 | 0.930 |
C7—H7B | 0.970 | C26—H26 | 0.930 |
C8—H8A | 0.970 | C27—C28 | 1.462 (4) |
C8—H8B | 0.970 | C27—H27 | 0.930 |
C9—C14 | 1.390 (4) | C28—C33 | 1.383 (4) |
C9—C10 | 1.402 (4) | C28—C29 | 1.395 (4) |
C10—C11 | 1.389 (5) | C29—C30 | 1.372 (4) |
C10—H10 | 0.930 | C29—H29 | 0.930 |
C11—C12 | 1.349 (5) | C30—C31 | 1.355 (4) |
C11—H11 | 0.930 | C30—H30 | 0.930 |
C12—C13 | 1.357 (5) | C31—C32 | 1.368 (5) |
C12—H12 | 0.930 | C32—C33 | 1.380 (5) |
C13—C14 | 1.371 (4) | C32—H32 | 0.930 |
C13—H13 | 0.930 | C33—H33 | 0.930 |
C14—H14 | 0.930 | | |
| | | |
C9—N1—C3 | 118.08 (19) | C20—C15—C16 | 117.9 (2) |
C9—N1—C1 | 120.4 (2) | C20—C15—C3 | 122.4 (2) |
C3—N1—C1 | 112.8 (2) | C16—C15—C3 | 119.6 (2) |
C5—N2—C21 | 121.5 (3) | C17—C16—C15 | 121.8 (3) |
N1—C1—C6 | 107.79 (19) | C17—C16—H16 | 119.1 |
N1—C1—C7 | 109.6 (2) | C15—C16—H16 | 119.1 |
C6—C1—C7 | 109.6 (3) | C18—C17—C16 | 118.8 (3) |
N1—C1—H1 | 109.9 | C18—C17—H17 | 120.6 |
C6—C1—H1 | 109.9 | C16—C17—H17 | 120.6 |
C7—C1—H1 | 109.9 | C19—C18—C17 | 121.0 (3) |
N1—C3—C15 | 114.08 (19) | C19—C18—Cl2 | 119.4 (3) |
N1—C3—C4 | 109.0 (2) | C17—C18—Cl2 | 119.6 (2) |
C15—C3—C4 | 110.9 (2) | C18—C19—C20 | 119.5 (3) |
N1—C3—H3 | 107.5 | C18—C19—H19 | 120.3 |
C15—C3—H3 | 107.5 | C20—C19—H19 | 120.3 |
C4—C3—H3 | 107.5 | C15—C20—C19 | 121.1 (2) |
C5—C4—C3 | 107.1 (2) | C15—C20—H20 | 119.5 |
C5—C4—C8 | 108.2 (2) | C19—C20—H20 | 119.5 |
C3—C4—C8 | 108.9 (2) | C22—C21—C26 | 119.0 (4) |
C5—C4—H4 | 110.8 | C22—C21—N2 | 122.5 (4) |
C3—C4—H4 | 110.8 | C26—C21—N2 | 118.4 (3) |
C8—C4—H4 | 110.8 | C23—C22—C21 | 121.4 (4) |
N2—C5—C6 | 120.6 (2) | C23—C22—H22 | 119.3 |
N2—C5—C4 | 128.3 (3) | C21—C22—H22 | 119.3 |
C6—C5—C4 | 111.0 (3) | C22—C23—C24 | 120.0 (5) |
C27—C6—C5 | 120.9 (3) | C22—C23—H23 | 120.0 |
C27—C6—C1 | 128.5 (3) | C24—C23—H23 | 120.0 |
C5—C6—C1 | 110.6 (2) | C23—C24—C25 | 119.7 (5) |
C1—C7—C8 | 108.3 (3) | C23—C24—H24 | 120.1 |
C1—C7—H7A | 110.0 | C25—C24—H24 | 120.1 |
C8—C7—H7A | 110.0 | C26—C25—C24 | 119.3 (5) |
C1—C7—H7B | 110.0 | C26—C25—H25 | 120.3 |
C8—C7—H7B | 110.0 | C24—C25—H25 | 120.3 |
H7A—C7—H7B | 108.4 | C25—C26—C21 | 120.4 (4) |
C7—C8—C4 | 110.5 (3) | C25—C26—H26 | 119.8 |
C7—C8—H8A | 109.5 | C21—C26—H26 | 119.8 |
C4—C8—H8A | 109.5 | C6—C27—C28 | 131.1 (3) |
C7—C8—H8B | 109.5 | C6—C27—H27 | 114.5 |
C4—C8—H8B | 109.5 | C28—C27—H27 | 114.5 |
H8A—C8—H8B | 108.1 | C33—C28—C29 | 117.0 (3) |
C14—C9—N1 | 120.0 (2) | C33—C28—C27 | 124.9 (3) |
C14—C9—C10 | 116.4 (3) | C29—C28—C27 | 118.0 (3) |
N1—C9—C10 | 123.6 (3) | C30—C29—C28 | 122.1 (3) |
C11—C10—C9 | 120.2 (3) | C30—C29—H29 | 119.0 |
C11—C10—H10 | 119.9 | C28—C29—H29 | 119.0 |
C9—C10—H10 | 119.9 | C31—C30—C29 | 119.0 (3) |
C12—C11—C10 | 121.9 (3) | C31—C30—H30 | 120.5 |
C12—C11—H11 | 119.1 | C29—C30—H30 | 120.5 |
C10—C11—H11 | 119.1 | C30—C31—C32 | 121.2 (3) |
C11—C12—C13 | 118.5 (4) | C30—C31—Cl1 | 120.1 (3) |
C11—C12—H12 | 120.7 | C32—C31—Cl1 | 118.7 (3) |
C13—C12—H12 | 120.7 | C31—C32—C33 | 119.6 (3) |
C12—C13—C14 | 121.6 (4) | C31—C32—H32 | 120.2 |
C12—C13—H13 | 119.2 | C33—C32—H32 | 120.2 |
C14—C13—H13 | 119.2 | C32—C33—C28 | 121.1 (3) |
C13—C14—C9 | 121.5 (3) | C32—C33—H33 | 119.5 |
C13—C14—H14 | 119.3 | C28—C33—H33 | 119.5 |
C9—C14—H14 | 119.3 | | |
| | | |
C9—N1—C1—C6 | 156.0 (2) | N1—C9—C14—C13 | 178.9 (3) |
C3—N1—C1—C6 | −57.0 (3) | C10—C9—C14—C13 | 0.7 (4) |
C9—N1—C1—C7 | −84.8 (3) | N1—C3—C15—C20 | −19.0 (3) |
C3—N1—C1—C7 | 62.2 (3) | C4—C3—C15—C20 | 104.5 (3) |
C9—N1—C3—C15 | −90.2 (2) | N1—C3—C15—C16 | 163.7 (2) |
C1—N1—C3—C15 | 122.0 (2) | C4—C3—C15—C16 | −72.8 (3) |
C9—N1—C3—C4 | 145.2 (2) | C20—C15—C16—C17 | −0.3 (4) |
C1—N1—C3—C4 | −2.6 (3) | C3—C15—C16—C17 | 177.2 (2) |
N1—C3—C4—C5 | 60.3 (3) | C15—C16—C17—C18 | 0.4 (4) |
C15—C3—C4—C5 | −66.1 (3) | C16—C17—C18—C19 | −0.1 (5) |
N1—C3—C4—C8 | −56.5 (3) | C16—C17—C18—Cl2 | 179.0 (2) |
C15—C3—C4—C8 | 177.1 (2) | C17—C18—C19—C20 | −0.3 (5) |
C21—N2—C5—C6 | 176.4 (2) | Cl2—C18—C19—C20 | −179.5 (2) |
C21—N2—C5—C4 | 0.3 (4) | C16—C15—C20—C19 | −0.2 (4) |
C3—C4—C5—N2 | 118.6 (3) | C3—C15—C20—C19 | −177.5 (2) |
C8—C4—C5—N2 | −124.1 (3) | C18—C19—C20—C15 | 0.5 (4) |
C3—C4—C5—C6 | −57.8 (3) | C5—N2—C21—C22 | 79.1 (4) |
C8—C4—C5—C6 | 59.5 (3) | C5—N2—C21—C26 | −104.7 (3) |
N2—C5—C6—C27 | 2.8 (4) | C26—C21—C22—C23 | −2.3 (5) |
C4—C5—C6—C27 | 179.5 (2) | N2—C21—C22—C23 | 173.9 (4) |
N2—C5—C6—C1 | −178.2 (2) | C21—C22—C23—C24 | 0.9 (7) |
C4—C5—C6—C1 | −1.5 (3) | C22—C23—C24—C25 | 2.0 (8) |
N1—C1—C6—C27 | −121.6 (3) | C23—C24—C25—C26 | −3.4 (7) |
C7—C1—C6—C27 | 119.2 (3) | C24—C25—C26—C21 | 2.1 (7) |
N1—C1—C6—C5 | 59.5 (3) | C22—C21—C26—C25 | 0.8 (5) |
C7—C1—C6—C5 | −59.7 (3) | N2—C21—C26—C25 | −175.6 (3) |
N1—C1—C7—C8 | −58.5 (3) | C5—C6—C27—C28 | −176.2 (2) |
C6—C1—C7—C8 | 59.6 (3) | C1—C6—C27—C28 | 5.0 (5) |
C1—C7—C8—C4 | −1.1 (4) | C6—C27—C28—C33 | 34.1 (4) |
C5—C4—C8—C7 | −57.8 (3) | C6—C27—C28—C29 | −150.1 (3) |
C3—C4—C8—C7 | 58.3 (3) | C33—C28—C29—C30 | −1.9 (4) |
C3—N1—C9—C14 | 29.8 (3) | C27—C28—C29—C30 | −178.1 (3) |
C1—N1—C9—C14 | 175.1 (2) | C28—C29—C30—C31 | 0.9 (5) |
C3—N1—C9—C10 | −152.1 (2) | C29—C30—C31—C32 | 0.5 (5) |
C1—N1—C9—C10 | −6.8 (4) | C29—C30—C31—Cl1 | 179.4 (2) |
C14—C9—C10—C11 | 0.0 (4) | C30—C31—C32—C33 | −0.7 (5) |
N1—C9—C10—C11 | −178.1 (3) | Cl1—C31—C32—C33 | −179.6 (2) |
C9—C10—C11—C12 | −0.8 (5) | C31—C32—C33—C28 | −0.4 (4) |
C10—C11—C12—C13 | 0.8 (6) | C29—C28—C33—C32 | 1.6 (4) |
C11—C12—C13—C14 | −0.1 (6) | C27—C28—C33—C32 | 177.5 (3) |
C12—C13—C14—C9 | −0.7 (5) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C11—H11···Cl1i | 0.93 | 2.78 | 3.706 (3) | 177 |
C10—H10···Cl2ii | 0.93 | 3.06 | 3.974 (3) | 167 |
Symmetry codes: (i) −x+1, −y+1, −z+2; (ii) x+1/2, −y+1/2, z+1/2. |
Experimental details
Crystal data |
Chemical formula | C32H26Cl2N2 |
Mr | 509.45 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 273 |
a, b, c (Å) | 14.3560 (6), 10.0621 (4), 18.3872 (8) |
β (°) | 91.427 (1) |
V (Å3) | 2655.24 (19) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.27 |
Crystal size (mm) | 0.20 × 0.12 × 0.07 |
|
Data collection |
Diffractometer | Bruker SMART APEX CCD area-detector diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 18622, 4657, 3312 |
Rint | 0.021 |
(sin θ/λ)max (Å−1) | 0.595 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.055, 0.163, 1.04 |
No. of reflections | 4657 |
No. of parameters | 325 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.37, −0.36 |
Selected geometric parameters (Å, º) topCl1—C31 | 1.737 (4) | N2—C5 | 1.267 (4) |
Cl2—C18 | 1.745 (3) | C6—C27 | 1.333 (4) |
| | | |
N2—C5—C4 | 128.3 (3) | C6—C27—C28 | 131.1 (3) |
C27—C6—C1 | 128.5 (3) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C11—H11···Cl1i | 0.93 | 2.78 | 3.706 (3) | 177 |
C10—H10···Cl2ii | 0.93 | 3.06 | 3.974 (3) | 167 |
Symmetry codes: (i) −x+1, −y+1, −z+2; (ii) x+1/2, −y+1/2, z+1/2. |
In continuation of our ongoing structural elucidation of azabicyclo[2.2.2]octane derivatives obtained from the Diels–Alder reaction, we report here the crystal structure of the title compound, (I).
The molecular geometry of (I) (Fig. 1), in terms of bond distances and angles, is in good agreement with that of similar structures (Sonar et al., 2004; Ravikumar et al., 2005a,b). The torsion angles C5—C6—C27—C28 = −176.2 (2)° and C5—C6—N2—C21 = 176.4 (2)° indicate a trans configuration, and hence the Z isomer. Due to the double-bond strain, the bond angles C4—C5—N2, C6—C27—C28 and C1—C6—C27 deviate from ideal values (Table 1).
All three six-membered rings of the azabicyclo[2.2.2]octane system adopt the expected boat conformation, with asymmetry parameters (Nardelli, 1983) ΔCs(C1) = 0.009 (2), 0.017 (2), 0.027 (1) for the rings C1/C4–C8, N1/C1/C3/C4/C7/C8 and N1/C1/C3–C6, respectively. The C9–C14 phenyl ring and C15–C20 chlorophenyl ring make dihedral angles with the mean plane of atoms C1/C3/C4/N1 of the azabicyclo[2.2.2]octane cage of 30.7 (1) and 66.7 (1)°, respectively. Similarly, the dihedral angles are 77.9 (1) and 35.1 (1)°, respectively, for the C21–C26 phenyl ring and C28–C33 chlorophenyl ring with respect to the C1/C4/C5/C6 mean plane of the cage. The torsion angle C9—N1—C3—C15 is −90.2 (2)°, but N2—C5—C6—C27 is only 2.8 (4)°, as a consequence of the double bonds.
The crystal structure is stabilized by weak intermolecular C—H···Cl interactions (You et al., 2004) (Table 2). One of them leads to formation of a centrosymmetric dimer with a characteristic R22(26) motif (Bernstein et al., 1995) in the crystal packing (Fig. 2).