Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536805029569/rz6112sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536805029569/rz6112Isup2.hkl |
CCDC reference: 287698
Key indicators
- Single-crystal X-ray study
- T = 105 K
- Mean (C-C)= 0.002 Å
- R factor = 0.034
- wR factor = 0.098
- Data-to-parameter ratio = 18.9
checkCIF/PLATON results
No syntax errors found No errors found in this datablock
A mixture of 2,6-bis(2-chlorophenyl)-3,5-diphenylpiperidin-4-one (0.75 g, 0.0015 mol) and concentrated HCl (0.4 ml) was dissolvedin a 1:1 e thanol–water mixture (20 ml). The temperature of the solution was kept at 338–343 K and while stirring, a solution of NaNO2 (0.21 g, 0.003 mol) in a 1:1 e thanol–water mixture (15 ml) was added dropwise over a period of 1 h. The heating and stirring were continued for another 2 h. The reaction mixture was extracted four times with ether (100 ml) and the extracts were washed with water several times. The combined ether layer was dried over anhydrous sodium bisulfate. After removal of the ether, the crude product was recrystallized twice from ethyl acetate to give colourless crystals (yield: 68%, m.p. 493 K).
H atoms were placed at calculated positions and allowed to ride on their carrier atoms, with C—H = 0.93–0.98 Å and Uiso(H) = 1.2Ueq(C).
Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97.
C29H22Cl2N2O2 | F(000) = 1040 |
Mr = 501.39 | Dx = 1.386 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 3344 reflections |
a = 10.5812 (3) Å | θ = 2–23° |
b = 12.9766 (4) Å | µ = 0.30 mm−1 |
c = 17.5935 (5) Å | T = 105 K |
β = 95.863 (1)° | Needle, colourless |
V = 2403.09 (12) Å3 | 0.28 × 0.17 × 0.14 mm |
Z = 4 |
Bruker SMART APEX CCD diffractometer | 5972 independent reflections |
Radiation source: fine-focus sealed tube | 5061 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.036 |
ω scans | θmax = 28.3°, θmin = 1.9° |
Absorption correction: multi-scan (SADABS; Bruker, 1998) | h = −13→14 |
Tmin = 0.95, Tmax = 0.96 | k = −17→17 |
30319 measured reflections | l = −23→23 |
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)] = 0.034 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.098 | H-atom parameters constrained |
S = 1.05 | w = 1/[σ2(Fo2) + (0.0476P)2 + 1.0027P] where P = (Fo2 + 2Fc2)/3 |
5972 reflections | (Δ/σ)max = 0.001 |
316 parameters | Δρmax = 0.40 e Å−3 |
0 restraints | Δρmin = −0.26 e Å−3 |
C29H22Cl2N2O2 | V = 2403.09 (12) Å3 |
Mr = 501.39 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 10.5812 (3) Å | µ = 0.30 mm−1 |
b = 12.9766 (4) Å | T = 105 K |
c = 17.5935 (5) Å | 0.28 × 0.17 × 0.14 mm |
β = 95.863 (1)° |
Bruker SMART APEX CCD diffractometer | 5972 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 1998) | 5061 reflections with I > 2σ(I) |
Tmin = 0.95, Tmax = 0.96 | Rint = 0.036 |
30319 measured reflections |
R[F2 > 2σ(F2)] = 0.034 | 0 restraints |
wR(F2) = 0.098 | H-atom parameters constrained |
S = 1.05 | Δρmax = 0.40 e Å−3 |
5972 reflections | Δρmin = −0.26 e Å−3 |
316 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 | ||
Cl1 | 0.35419 (3) | 0.17177 (3) | 0.170940 (18) | 0.02837 (9) | |
Cl2 | −0.05881 (4) | 0.53122 (3) | 0.39363 (2) | 0.03962 (11) | |
O1 | 0.09933 (9) | 0.44604 (8) | 0.17883 (6) | 0.0277 (2) | |
O2 | 0.39941 (9) | 0.41054 (8) | 0.48952 (5) | 0.0256 (2) | |
N1 | 0.25167 (10) | 0.40901 (8) | 0.26596 (6) | 0.0192 (2) | |
C4 | 0.35635 (12) | 0.39987 (9) | 0.42367 (7) | 0.0194 (2) | |
C61 | 0.15895 (11) | 0.55918 (10) | 0.32579 (7) | 0.0207 (2) | |
N2 | 0.20701 (11) | 0.40881 (9) | 0.19229 (6) | 0.0230 (2) | |
C51 | 0.17659 (11) | 0.27849 (10) | 0.40780 (7) | 0.0202 (2) | |
C31 | 0.56092 (11) | 0.32645 (10) | 0.38349 (7) | 0.0203 (2) | |
C3 | 0.44378 (11) | 0.39175 (9) | 0.35936 (7) | 0.0184 (2) | |
H3 | 0.4736 | 0.4615 | 0.3495 | 0.022* | |
C22 | 0.44631 (12) | 0.28185 (10) | 0.16123 (7) | 0.0224 (2) | |
C21 | 0.45077 (11) | 0.35912 (10) | 0.21670 (7) | 0.0193 (2) | |
C66 | 0.24374 (12) | 0.62330 (11) | 0.29285 (8) | 0.0246 (3) | |
H66 | 0.3129 | 0.5943 | 0.2721 | 0.030* | |
C5 | 0.21300 (11) | 0.39241 (10) | 0.40171 (7) | 0.0198 (2) | |
H5 | 0.1714 | 0.4300 | 0.4406 | 0.024* | |
C52 | 0.12862 (12) | 0.21917 (11) | 0.34527 (7) | 0.0250 (3) | |
H52 | 0.1177 | 0.2487 | 0.2969 | 0.030* | |
C2 | 0.37289 (11) | 0.35206 (9) | 0.28442 (7) | 0.0180 (2) | |
H2 | 0.3521 | 0.2794 | 0.2917 | 0.022* | |
C62 | 0.05666 (12) | 0.60672 (11) | 0.35628 (8) | 0.0245 (3) | |
C6 | 0.16914 (11) | 0.44175 (10) | 0.32390 (7) | 0.0198 (2) | |
H6 | 0.0839 | 0.4151 | 0.3079 | 0.024* | |
C26 | 0.52472 (13) | 0.44584 (11) | 0.20560 (8) | 0.0248 (3) | |
H26 | 0.5304 | 0.4982 | 0.2419 | 0.030* | |
C63 | 0.04039 (14) | 0.71293 (12) | 0.35575 (8) | 0.0292 (3) | |
H63 | −0.0275 | 0.7424 | 0.3775 | 0.035* | |
C55 | 0.16119 (14) | 0.12902 (12) | 0.48906 (8) | 0.0300 (3) | |
H55 | 0.1727 | 0.0990 | 0.5373 | 0.036* | |
C25 | 0.59010 (14) | 0.45542 (12) | 0.14123 (8) | 0.0307 (3) | |
H25 | 0.6389 | 0.5138 | 0.1348 | 0.037* | |
C35 | 0.66844 (15) | 0.16147 (12) | 0.39667 (8) | 0.0336 (3) | |
H35 | 0.6670 | 0.0904 | 0.3898 | 0.040* | |
C36 | 0.55984 (14) | 0.21969 (11) | 0.37498 (8) | 0.0289 (3) | |
H36 | 0.4859 | 0.1869 | 0.3546 | 0.035* | |
C65 | 0.22740 (13) | 0.72966 (11) | 0.29032 (9) | 0.0291 (3) | |
H65 | 0.2843 | 0.7708 | 0.2670 | 0.035* | |
C56 | 0.19260 (13) | 0.23211 (11) | 0.47979 (7) | 0.0262 (3) | |
H56 | 0.2246 | 0.2706 | 0.5220 | 0.031* | |
C53 | 0.09692 (13) | 0.11618 (11) | 0.35467 (8) | 0.0284 (3) | |
H53 | 0.0649 | 0.0775 | 0.3126 | 0.034* | |
C64 | 0.12644 (14) | 0.77438 (11) | 0.32245 (9) | 0.0299 (3) | |
H64 | 0.1165 | 0.8456 | 0.3216 | 0.036* | |
C32 | 0.67132 (14) | 0.37360 (12) | 0.41636 (9) | 0.0341 (3) | |
H32 | 0.6736 | 0.4447 | 0.4228 | 0.041* | |
C23 | 0.51076 (14) | 0.29039 (12) | 0.09652 (8) | 0.0297 (3) | |
H23 | 0.5059 | 0.2381 | 0.0602 | 0.036* | |
C34 | 0.77803 (14) | 0.20924 (14) | 0.42839 (9) | 0.0378 (4) | |
H34 | 0.8509 | 0.1708 | 0.4421 | 0.045* | |
C54 | 0.11272 (13) | 0.07086 (11) | 0.42648 (8) | 0.0287 (3) | |
H54 | 0.0910 | 0.0021 | 0.4326 | 0.034* | |
C24 | 0.58237 (14) | 0.37804 (13) | 0.08689 (8) | 0.0337 (3) | |
H24 | 0.6254 | 0.3848 | 0.0436 | 0.040* | |
C33 | 0.77852 (15) | 0.31468 (15) | 0.43962 (11) | 0.0450 (4) | |
H33 | 0.8511 | 0.3466 | 0.4629 | 0.054* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cl1 | 0.03596 (18) | 0.02394 (16) | 0.02450 (16) | −0.00332 (12) | −0.00041 (12) | −0.00469 (12) |
Cl2 | 0.02990 (18) | 0.0404 (2) | 0.0524 (2) | 0.00942 (14) | 0.02263 (16) | 0.01542 (17) |
O1 | 0.0239 (5) | 0.0323 (5) | 0.0257 (5) | 0.0067 (4) | −0.0035 (4) | 0.0002 (4) |
O2 | 0.0273 (5) | 0.0310 (5) | 0.0182 (4) | −0.0030 (4) | 0.0010 (3) | −0.0021 (4) |
N1 | 0.0186 (5) | 0.0226 (5) | 0.0164 (5) | 0.0031 (4) | 0.0015 (4) | 0.0002 (4) |
C4 | 0.0222 (6) | 0.0165 (5) | 0.0194 (5) | −0.0003 (4) | 0.0023 (4) | −0.0002 (4) |
C61 | 0.0193 (5) | 0.0236 (6) | 0.0188 (5) | 0.0029 (4) | 0.0004 (4) | −0.0005 (5) |
N2 | 0.0247 (5) | 0.0250 (5) | 0.0185 (5) | 0.0029 (4) | −0.0011 (4) | −0.0004 (4) |
C51 | 0.0168 (5) | 0.0234 (6) | 0.0207 (6) | −0.0003 (4) | 0.0032 (4) | 0.0013 (5) |
C31 | 0.0190 (6) | 0.0256 (6) | 0.0165 (5) | 0.0017 (4) | 0.0026 (4) | 0.0013 (4) |
C3 | 0.0188 (5) | 0.0191 (5) | 0.0171 (5) | −0.0003 (4) | 0.0013 (4) | −0.0007 (4) |
C22 | 0.0211 (6) | 0.0252 (6) | 0.0203 (6) | 0.0019 (5) | −0.0004 (4) | −0.0007 (5) |
C21 | 0.0182 (5) | 0.0224 (6) | 0.0172 (5) | 0.0028 (4) | 0.0016 (4) | 0.0010 (4) |
C66 | 0.0207 (6) | 0.0260 (6) | 0.0275 (6) | 0.0009 (5) | 0.0043 (5) | −0.0008 (5) |
C5 | 0.0199 (5) | 0.0226 (6) | 0.0172 (5) | 0.0013 (4) | 0.0036 (4) | 0.0000 (4) |
C52 | 0.0247 (6) | 0.0306 (7) | 0.0194 (6) | −0.0047 (5) | 0.0001 (5) | 0.0021 (5) |
C2 | 0.0173 (5) | 0.0195 (5) | 0.0173 (5) | 0.0016 (4) | 0.0020 (4) | −0.0002 (4) |
C62 | 0.0217 (6) | 0.0290 (7) | 0.0235 (6) | 0.0038 (5) | 0.0052 (5) | 0.0034 (5) |
C6 | 0.0181 (5) | 0.0226 (6) | 0.0189 (5) | 0.0014 (4) | 0.0033 (4) | 0.0009 (4) |
C26 | 0.0257 (6) | 0.0246 (6) | 0.0249 (6) | −0.0003 (5) | 0.0067 (5) | −0.0009 (5) |
C63 | 0.0287 (7) | 0.0315 (7) | 0.0274 (7) | 0.0098 (5) | 0.0030 (5) | −0.0028 (5) |
C55 | 0.0343 (7) | 0.0322 (7) | 0.0232 (6) | −0.0039 (6) | 0.0021 (5) | 0.0066 (5) |
C25 | 0.0286 (7) | 0.0336 (7) | 0.0313 (7) | −0.0019 (6) | 0.0107 (5) | 0.0047 (6) |
C35 | 0.0406 (8) | 0.0336 (8) | 0.0263 (7) | 0.0151 (6) | 0.0026 (6) | 0.0007 (6) |
C36 | 0.0293 (7) | 0.0273 (7) | 0.0285 (7) | 0.0039 (5) | −0.0052 (5) | −0.0027 (5) |
C65 | 0.0253 (6) | 0.0260 (7) | 0.0356 (7) | −0.0037 (5) | 0.0018 (5) | 0.0000 (6) |
C56 | 0.0297 (7) | 0.0300 (7) | 0.0186 (6) | −0.0037 (5) | 0.0012 (5) | 0.0002 (5) |
C53 | 0.0289 (7) | 0.0310 (7) | 0.0250 (6) | −0.0084 (5) | 0.0011 (5) | −0.0024 (5) |
C64 | 0.0322 (7) | 0.0227 (6) | 0.0337 (7) | 0.0030 (5) | −0.0021 (6) | −0.0035 (5) |
C32 | 0.0254 (7) | 0.0327 (7) | 0.0423 (8) | −0.0049 (6) | −0.0057 (6) | 0.0058 (6) |
C23 | 0.0299 (7) | 0.0387 (8) | 0.0208 (6) | 0.0043 (6) | 0.0036 (5) | −0.0058 (5) |
C34 | 0.0236 (7) | 0.0527 (10) | 0.0381 (8) | 0.0133 (6) | 0.0074 (6) | 0.0178 (7) |
C54 | 0.0294 (7) | 0.0263 (7) | 0.0305 (7) | −0.0052 (5) | 0.0046 (5) | 0.0029 (5) |
C24 | 0.0316 (7) | 0.0475 (9) | 0.0238 (7) | 0.0020 (6) | 0.0113 (5) | 0.0020 (6) |
C33 | 0.0221 (7) | 0.0527 (10) | 0.0575 (11) | −0.0065 (7) | −0.0088 (7) | 0.0188 (8) |
Cl1—C22 | 1.7476 (14) | C62—C63 | 1.389 (2) |
Cl2—C62 | 1.7460 (14) | C6—H6 | 0.9800 |
O1—N2 | 1.2379 (14) | C26—C25 | 1.3916 (18) |
O2—C4 | 1.2087 (15) | C26—H26 | 0.9300 |
N1—N2 | 1.3336 (14) | C63—C64 | 1.385 (2) |
N1—C6 | 1.4710 (15) | C63—H63 | 0.9300 |
N1—C2 | 1.4872 (15) | C55—C54 | 1.389 (2) |
C4—C5 | 1.5296 (17) | C55—C56 | 1.392 (2) |
C4—C3 | 1.5365 (16) | C55—H55 | 0.9300 |
C61—C66 | 1.3926 (18) | C25—C24 | 1.383 (2) |
C61—C62 | 1.3994 (17) | C25—H25 | 0.9300 |
C61—C6 | 1.5283 (17) | C35—C34 | 1.381 (2) |
C51—C52 | 1.3951 (18) | C35—C36 | 1.395 (2) |
C51—C56 | 1.3969 (18) | C35—H35 | 0.9300 |
C51—C5 | 1.5342 (17) | C36—H36 | 0.9300 |
C31—C32 | 1.3912 (19) | C65—C64 | 1.386 (2) |
C31—C36 | 1.3934 (19) | C65—H65 | 0.9300 |
C31—C3 | 1.5255 (17) | C56—H56 | 0.9300 |
C3—C2 | 1.5376 (16) | C53—C54 | 1.388 (2) |
C3—H3 | 0.9800 | C53—H53 | 0.9300 |
C22—C23 | 1.3900 (19) | C64—H64 | 0.9300 |
C22—C21 | 1.3966 (18) | C32—C33 | 1.394 (2) |
C21—C26 | 1.3957 (18) | C32—H32 | 0.9300 |
C21—C2 | 1.5190 (16) | C23—C24 | 1.387 (2) |
C66—C65 | 1.391 (2) | C23—H23 | 0.9300 |
C66—H66 | 0.9300 | C34—C33 | 1.382 (3) |
C5—C6 | 1.5394 (17) | C34—H34 | 0.9300 |
C5—H5 | 0.9800 | C54—H54 | 0.9300 |
C52—C53 | 1.392 (2) | C24—H24 | 0.9300 |
C52—H52 | 0.9300 | C33—H33 | 0.9300 |
C2—H2 | 0.9800 | ||
N2—N1—C6 | 119.84 (10) | N1—C6—H6 | 107.1 |
N2—N1—C2 | 115.05 (10) | C61—C6—H6 | 107.1 |
C6—N1—C2 | 123.51 (10) | C5—C6—H6 | 107.1 |
O2—C4—C5 | 121.09 (11) | C25—C26—C21 | 121.22 (13) |
O2—C4—C3 | 121.15 (11) | C25—C26—H26 | 119.4 |
C5—C4—C3 | 117.76 (10) | C21—C26—H26 | 119.4 |
C66—C61—C62 | 116.91 (12) | C64—C63—C62 | 119.21 (13) |
C66—C61—C6 | 122.46 (11) | C64—C63—H63 | 120.4 |
C62—C61—C6 | 120.46 (11) | C62—C63—H63 | 120.4 |
O1—N2—N1 | 114.39 (10) | C54—C55—C56 | 120.16 (13) |
C52—C51—C56 | 118.55 (12) | C54—C55—H55 | 119.9 |
C52—C51—C5 | 123.39 (11) | C56—C55—H55 | 119.9 |
C56—C51—C5 | 118.06 (11) | C24—C25—C26 | 119.90 (14) |
C32—C31—C36 | 118.63 (13) | C24—C25—H25 | 120.0 |
C32—C31—C3 | 119.68 (12) | C26—C25—H25 | 120.0 |
C36—C31—C3 | 121.67 (11) | C34—C35—C36 | 120.09 (15) |
C31—C3—C4 | 111.49 (10) | C34—C35—H35 | 120.0 |
C31—C3—C2 | 111.34 (10) | C36—C35—H35 | 120.0 |
C4—C3—C2 | 112.13 (10) | C31—C36—C35 | 120.76 (14) |
C31—C3—H3 | 107.2 | C31—C36—H36 | 119.6 |
C4—C3—H3 | 107.2 | C35—C36—H36 | 119.6 |
C2—C3—H3 | 107.2 | C64—C65—C66 | 120.05 (13) |
C23—C22—C21 | 122.05 (13) | C64—C65—H65 | 120.0 |
C23—C22—Cl1 | 118.06 (10) | C66—C65—H65 | 120.0 |
C21—C22—Cl1 | 119.87 (10) | C55—C56—C51 | 120.80 (12) |
C26—C21—C22 | 117.42 (11) | C55—C56—H56 | 119.6 |
C26—C21—C2 | 121.01 (11) | C51—C56—H56 | 119.6 |
C22—C21—C2 | 121.50 (11) | C54—C53—C52 | 120.46 (13) |
C65—C66—C61 | 121.52 (12) | C54—C53—H53 | 119.8 |
C65—C66—H66 | 119.2 | C52—C53—H53 | 119.8 |
C61—C66—H66 | 119.2 | C63—C64—C65 | 119.94 (13) |
C4—C5—C51 | 107.03 (10) | C63—C64—H64 | 120.0 |
C4—C5—C6 | 113.54 (10) | C65—C64—H64 | 120.0 |
C51—C5—C6 | 114.07 (10) | C31—C32—C33 | 120.28 (15) |
C4—C5—H5 | 107.3 | C31—C32—H32 | 119.9 |
C51—C5—H5 | 107.3 | C33—C32—H32 | 119.9 |
C6—C5—H5 | 107.3 | C24—C23—C22 | 119.04 (13) |
C53—C52—C51 | 120.58 (12) | C24—C23—H23 | 120.5 |
C53—C52—H52 | 119.7 | C22—C23—H23 | 120.5 |
C51—C52—H52 | 119.7 | C35—C34—C33 | 119.52 (14) |
N1—C2—C21 | 108.88 (9) | C35—C34—H34 | 120.2 |
N1—C2—C3 | 110.80 (9) | C33—C34—H34 | 120.2 |
C21—C2—C3 | 113.34 (10) | C53—C54—C55 | 119.45 (13) |
N1—C2—H2 | 107.9 | C53—C54—H54 | 120.3 |
C21—C2—H2 | 107.9 | C55—C54—H54 | 120.3 |
C3—C2—H2 | 107.9 | C25—C24—C23 | 120.36 (13) |
C63—C62—C61 | 122.35 (13) | C25—C24—H24 | 119.8 |
C63—C62—Cl2 | 117.93 (10) | C23—C24—H24 | 119.8 |
C61—C62—Cl2 | 119.69 (11) | C34—C33—C32 | 120.65 (15) |
N1—C6—C61 | 110.57 (10) | C34—C33—H33 | 119.7 |
N1—C6—C5 | 110.47 (10) | C32—C33—H33 | 119.7 |
C61—C6—C5 | 114.26 (10) | ||
C6—N1—N2—O1 | 6.04 (17) | C66—C61—C62—Cl2 | 176.33 (10) |
C2—N1—N2—O1 | 172.10 (10) | C6—C61—C62—Cl2 | 0.91 (17) |
C32—C31—C3—C4 | −91.81 (14) | N2—N1—C6—C61 | −77.88 (14) |
C36—C31—C3—C4 | 86.81 (14) | C2—N1—C6—C61 | 117.29 (12) |
C32—C31—C3—C2 | 142.14 (12) | N2—N1—C6—C5 | 154.64 (11) |
C36—C31—C3—C2 | −39.23 (16) | C2—N1—C6—C5 | −10.19 (16) |
O2—C4—C3—C31 | 40.17 (16) | C66—C61—C6—N1 | −16.44 (16) |
C5—C4—C3—C31 | −138.96 (11) | C62—C61—C6—N1 | 158.72 (11) |
O2—C4—C3—C2 | 165.78 (11) | C66—C61—C6—C5 | 108.93 (13) |
C5—C4—C3—C2 | −13.35 (15) | C62—C61—C6—C5 | −75.91 (15) |
C23—C22—C21—C26 | −1.01 (19) | C4—C5—C6—N1 | 46.62 (14) |
Cl1—C22—C21—C26 | −179.30 (10) | C51—C5—C6—N1 | −76.37 (12) |
C23—C22—C21—C2 | 175.84 (12) | C4—C5—C6—C61 | −78.80 (13) |
Cl1—C22—C21—C2 | −2.45 (16) | C51—C5—C6—C61 | 158.20 (10) |
C62—C61—C66—C65 | −0.07 (19) | C22—C21—C26—C25 | 0.8 (2) |
C6—C61—C66—C65 | 175.25 (12) | C2—C21—C26—C25 | −176.05 (12) |
O2—C4—C5—C51 | −87.55 (14) | C61—C62—C63—C64 | 1.5 (2) |
C3—C4—C5—C51 | 91.58 (12) | Cl2—C62—C63—C64 | −176.26 (11) |
O2—C4—C5—C6 | 145.67 (12) | C21—C26—C25—C24 | 0.0 (2) |
C3—C4—C5—C6 | −35.20 (15) | C32—C31—C36—C35 | −2.1 (2) |
C52—C51—C5—C4 | −115.56 (13) | C3—C31—C36—C35 | 179.31 (12) |
C56—C51—C5—C4 | 64.38 (14) | C34—C35—C36—C31 | 1.3 (2) |
C52—C51—C5—C6 | 10.91 (16) | C61—C66—C65—C64 | 1.4 (2) |
C56—C51—C5—C6 | −169.15 (11) | C54—C55—C56—C51 | −0.3 (2) |
C56—C51—C52—C53 | 0.30 (19) | C52—C51—C56—C55 | −0.1 (2) |
C5—C51—C52—C53 | −179.76 (12) | C5—C51—C56—C55 | 179.94 (12) |
N2—N1—C2—C21 | 31.29 (14) | C51—C52—C53—C54 | −0.1 (2) |
C6—N1—C2—C21 | −163.22 (11) | C62—C63—C64—C65 | −0.1 (2) |
N2—N1—C2—C3 | 156.59 (10) | C66—C65—C64—C63 | −1.3 (2) |
C6—N1—C2—C3 | −37.93 (15) | C36—C31—C32—C33 | 0.5 (2) |
C26—C21—C2—N1 | 81.88 (14) | C3—C31—C32—C33 | 179.13 (14) |
C22—C21—C2—N1 | −94.85 (13) | C21—C22—C23—C24 | 0.4 (2) |
C26—C21—C2—C3 | −41.92 (16) | Cl1—C22—C23—C24 | 178.72 (11) |
C22—C21—C2—C3 | 141.34 (12) | C36—C35—C34—C33 | 1.1 (2) |
C31—C3—C2—N1 | 173.84 (10) | C52—C53—C54—C55 | −0.3 (2) |
C4—C3—C2—N1 | 48.15 (13) | C56—C55—C54—C53 | 0.5 (2) |
C31—C3—C2—C21 | −63.41 (13) | C26—C25—C24—C23 | −0.6 (2) |
C4—C3—C2—C21 | 170.90 (10) | C22—C23—C24—C25 | 0.4 (2) |
C66—C61—C62—C63 | −1.4 (2) | C35—C34—C33—C32 | −2.7 (3) |
C6—C61—C62—C63 | −176.78 (12) | C31—C32—C33—C34 | 1.9 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
C53—H53···O1i | 0.93 | 2.45 | 3.0470 (17) | 122 |
C32—H32···O2ii | 0.93 | 2.60 | 3.377 (2) | 142 |
C23—H23···O2iii | 0.93 | 2.50 | 3.3583 (18) | 154 |
Symmetry codes: (i) −x, y−1/2, −z+1/2; (ii) −x+1, −y+1, −z+1; (iii) x, −y+1/2, z−1/2. |
Experimental details
Crystal data | |
Chemical formula | C29H22Cl2N2O2 |
Mr | 501.39 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 105 |
a, b, c (Å) | 10.5812 (3), 12.9766 (4), 17.5935 (5) |
β (°) | 95.863 (1) |
V (Å3) | 2403.09 (12) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.30 |
Crystal size (mm) | 0.28 × 0.17 × 0.14 |
Data collection | |
Diffractometer | Bruker SMART APEX CCD diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 1998) |
Tmin, Tmax | 0.95, 0.96 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 30319, 5972, 5061 |
Rint | 0.036 |
(sin θ/λ)max (Å−1) | 0.667 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.034, 0.098, 1.05 |
No. of reflections | 5972 |
No. of parameters | 316 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.40, −0.26 |
Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2001), SAINT, SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), PLATON (Spek, 2003), SHELXL97.
C6—N1—N2—O1 | 6.04 (17) | C4—C3—C2—N1 | 48.15 (13) |
C2—N1—N2—O1 | 172.10 (10) | C31—C3—C2—C21 | −63.41 (13) |
C5—C4—C3—C2 | −13.35 (15) | C2—N1—C6—C5 | −10.19 (16) |
C3—C4—C5—C6 | −35.20 (15) | C4—C5—C6—N1 | 46.62 (14) |
C6—N1—C2—C3 | −37.93 (15) | C51—C5—C6—C61 | 158.20 (10) |
D—H···A | D—H | H···A | D···A | D—H···A |
C53—H53···O1i | 0.93 | 2.45 | 3.0470 (17) | 122 |
C32—H32···O2ii | 0.93 | 2.60 | 3.377 (2) | 142 |
C23—H23···O2iii | 0.93 | 2.50 | 3.3583 (18) | 154 |
Symmetry codes: (i) −x, y−1/2, −z+1/2; (ii) −x+1, −y+1, −z+1; (iii) x, −y+1/2, z−1/2. |
The piperidine ring is a distinct structural feature of a variety of alkaloid natural products and drug candidates. Watson et al. (2000) observed that during the past decade there were thousands of piperidine compounds mentioned in clinical and preclinical studies. Piperidinones, though relatively less prominent, have also been regarded as precursors of a host of biologically active compounds and natural alkaloids, prior to their conversion to piperidines. This paper reports the structure of the title compound, (I), a nitroso-piperidinone derivative, namely 2,6-bis(2-chloroyphenyl)-1-nitroso-3,5-diphenylpiperidin-4-one. Many nitroso–amines are carcinogenic (Magee et al., 1976) and certain N-nitroso–ureas are antitumour agents and antibiotics (Durand, 1989; Fujimoto et al., 1991). Thus, combining these moieties together may lead to many useful biologically active compounds. In addition to their possible biological significance, accurate X-ray crystallographic investigations on a variety of nitroso–piperidinone derivatives with various substituted phenyl rings at the 2-, 3-, 5- and 6-positions have been carried out in our laboratory with the aim of obtaining some information on the effect of substituents on the conformation of individual molecules and also on the crystal-packing features of these compounds. Recently, in our laboratory, we have elucidated the crystal structures of a few nitroso–piperidinone derivatives with varying substituted benzene rings at the 2- and 6-positions and unsubstituted phenyl rings at the 3- and 5-positions, namely the 4-methoxy (PIP1; Natarajan et al., 2005), 2-methyl (PIP2; Suresh et al., 2005a) and 2-methoxy (PIP3; Suresh et al., 2005b) analogues (I).
The molecular structure of compound (I) is illustrated in Fig. 1. The piperidinone ring adopts a twist–boat conformation, as observed in PIP1, PIP2 and PIP3. Atoms C2 and C5 deviate by 0.529 (2) and 0.499 (2) Å, respectively, from the least-squares plane defined by the other atoms (N1, C3, C4 and C6). The corresponding values are 0.592 (2) and 0.492 (2) Å for PIP1, 0.627 (1) and 0.560 (1) Å for PIP2, and 0.556 (1), 0.547 (1) Å for PIP3. The twist–boat conformation is also evident from the values observed for the torsion angles of the piperidinone ring (Table 1). The nitroso O atom is syn to the neighbouring axial chlorophenyl at C6 [C6—N1—N2—O1 = 6.04 (17)°]. The orientation of the nitroso O atom remains relatively unperturbed by the effect of the substituent. The value of this torsion angle is 5.3 (2)° for PIP1, −5.8 (1)° for PIP2 and 5.2 (1)° for PIP3. This may be attributed to the fact that the nitroso O atom encounters large steric effects due to the bulky substituents at the neighbouring 2- and 6-positions of the piperidinone ring. The configuration of the aryl rings at the 2- and 3- (equatorial, C21—C2—C3—C31 = −63.4°) and those at the 5- and 6-positions (axial, C61—C6—C5—C51 = 158.2°) are similar to those observed in PIP3, but are different from those of PIP1 and PIP2 where the aryl rings at the 2- and 3-positions are axially oriented and those at the 5- and 6-positions are equatorially oriented. The observations concerning the conformation of (I) agree well with the results of 1H NMR studies of piperidinone in solution (Alex Raja & Perumal, 2004) and establish that compound (I) adopts the same conformation in both solution and the solid state.
A sterically favoured short intramolecular distance is observed (H2···Cl1 = 2.544 Å). The crystal packing is stabilized by a three-dimensional network of C—H···O hydrogen bonds in which the nitroso and carbonyl O atoms participate as acceptors (Table 2 and Fig. 2). A weak Cl···Cl contact [Cl1···Cl2i = 3.696 (1) Å; symmetry code: (i) −x, +y − 1/2, −z + 1/2] is also observed. No significant C—H···.π or π–π interactions are present. Though the formation of centrosmmetric dimers seems an ubiquitous feature in the crystal packing of these compounds, the choice between interconnected layers and columns stabilized by van der Waals interactions among them could not be attributed to the change and nature of the substituents.