Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270106007530/sk3008sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270106007530/sk3008Isup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270106007530/sk3008IIsup3.hkl |
CCDC references: 605700; 605701
For the synthesis of compounds (I) and (II), equimolar amounts of 2,4-dichlorobenzaldehyde, and 5-methyl-1,3-cyclohexanedione for (I) or 5-phenyl-1,3-cyclohexanedione for (II), together with methyl aminocrotonoate were refluxed in methanol for 8 h. The solution was then poured into water, and the precipitate which formed was filtered off, dried, and recrystallized from ethanol. The m.p. for the crystals containing the diastereoisomeric mixtures were 523 and 421 K, respectively.
For (I), the methyl-substituted atom of the oxocyclohexene ring and its associated methyl group are disordered, as a result of the occurrence of diastereoisomeric molecules at the same crystallographic site. Two sets of positions were defined for these atoms and the site occupation factor for the atoms corresponding to the major isomer refined to 0.512 (6). Similarity restraints were applied to the chemically equivalent bond lengths and angles involving all disordered C atoms, while neighbouring atoms within and between each conformation of the disordered groups were restrained to have similar atomic displacement parameters.
For (II), the disorder of the phenyl-substituted atom of the oxocyclohexene ring and its associated phenyl group, as well as an adjacent methylene group, was treated exactly as described above. The site occupation factor for the atoms corresponding to the major isomer refined to 0.505 (7). The asymmetric unit also contains a water molecule disordered over two adjacent positions and the site occupation factor of the more occupied site refined to 0.879 (6). The H atoms of the lesser occupied site were not included in the model.
For each structure, the position of the amine H atom, and the positions of the H atoms of the major occupied site of the water molecule in (II), were determined from a difference Fourier map and refined freely with individual isotropic displacement parameters. The methyl H atoms were constrained to an ideal geometry, with C—H = 0.98 Å and Uiso(H) = 1.5Ueq(C), but were allowed to rotate freely about their C—C bonds. All other H atoms were placed in geometrically idealized positions and constrained to ride on their parent C atoms at distances of 0.95, 0.99 or 1.00 Å for phenyl, methylene or methine groups, respectively, and with Uiso(H) = 1.2Ueq(C).
For both compounds, data collection: COLLECT (Nonius, 2000); cell refinement: DENZO-SMN (Otwinowski & Minor, 1997); data reduction: DENZO-SMN and SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2003).
C19H19Cl2NO3 | F(000) = 792 |
Mr = 380.27 | Dx = 1.371 Mg m−3 |
Monoclinic, P21/n | Melting point: 523 K |
Hall symbol: -P 2yn | Mo Kα radiation, λ = 0.71073 Å |
a = 11.6670 (3) Å | Cell parameters from 13345 reflections |
b = 13.7746 (4) Å | θ = 2.0–25.0° |
c = 11.8897 (4) Å | µ = 0.37 mm−1 |
β = 105.4328 (19)° | T = 160 K |
V = 1841.88 (10) Å3 | Tablet, pale yellow |
Z = 4 | 0.22 × 0.22 × 0.07 mm |
Nonius KappaCCD area-detector diffractometer | 3252 independent reflections |
Radiation source: Nonius FR590 sealed tube generator | 2469 reflections with I > 2σ(I) |
Horizontally mounted graphite crystal monochromator | Rint = 0.072 |
Detector resolution: 9 pixels mm-1 | θmax = 25.0°, θmin = 2.2° |
ω scans with κ offsets | h = −13→13 |
Absorption correction: multi-scan (Blessing, 1995) | k = −16→16 |
Tmin = 0.871, Tmax = 0.979 | l = −14→14 |
23780 measured reflections |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: geom and difmap |
R[F2 > 2σ(F2)] = 0.049 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.139 | w = 1/[σ2(Fo2) + (0.073P)2 + 1.1256P] where P = (Fo2 + 2Fc2)/3 |
S = 1.04 | (Δ/σ)max = 0.001 |
3252 reflections | Δρmax = 0.71 e Å−3 |
254 parameters | Δρmin = −0.30 e Å−3 |
31 restraints | Extinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.011 (2) |
C19H19Cl2NO3 | V = 1841.88 (10) Å3 |
Mr = 380.27 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 11.6670 (3) Å | µ = 0.37 mm−1 |
b = 13.7746 (4) Å | T = 160 K |
c = 11.8897 (4) Å | 0.22 × 0.22 × 0.07 mm |
β = 105.4328 (19)° |
Nonius KappaCCD area-detector diffractometer | 3252 independent reflections |
Absorption correction: multi-scan (Blessing, 1995) | 2469 reflections with I > 2σ(I) |
Tmin = 0.871, Tmax = 0.979 | Rint = 0.072 |
23780 measured reflections |
R[F2 > 2σ(F2)] = 0.049 | 31 restraints |
wR(F2) = 0.139 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.04 | Δρmax = 0.71 e Å−3 |
3252 reflections | Δρmin = −0.30 e Å−3 |
254 parameters |
Experimental. Solvent used: Cooling Device: Oxford Cryosystems Cryostream 700 Crystal mount: glued on a glass fibre Mosaicity (°.): 0.491 (2) Frames collected: 194 Seconds exposure per frame: 26 Degrees rotation per frame: 2.0 Crystal-Detector distance (mm): 30.0 |
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 | 0.22102 (6) | 0.11917 (5) | 0.91939 (6) | 0.0436 (3) | |
Cl2 | −0.04745 (8) | 0.38039 (6) | 1.06080 (7) | 0.0573 (3) | |
O5 | 0.25975 (16) | 0.26195 (16) | 0.71309 (16) | 0.0457 (5) | |
O10 | −0.17030 (19) | −0.04887 (16) | 0.64133 (19) | 0.0551 (6) | |
O11 | −0.00920 (17) | −0.00143 (14) | 0.77785 (17) | 0.0432 (5) | |
N1 | −0.0879 (2) | 0.17511 (17) | 0.4283 (2) | 0.0374 (6) | |
H1 | −0.132 (3) | 0.191 (2) | 0.359 (3) | 0.049 (9)* | |
C2 | −0.1208 (2) | 0.10291 (19) | 0.4935 (2) | 0.0334 (6) | |
C3 | −0.0553 (2) | 0.08602 (19) | 0.6046 (2) | 0.0318 (6) | |
C4 | 0.0522 (2) | 0.14857 (18) | 0.6638 (2) | 0.0302 (6) | |
H4 | 0.1215 | 0.1044 | 0.6946 | 0.036* | |
C4A | 0.0836 (2) | 0.21715 (18) | 0.5769 (2) | 0.0302 (6) | |
C5 | 0.1923 (2) | 0.2724 (2) | 0.6137 (2) | 0.0367 (6) | |
C6 | 0.2229 (3) | 0.3432 (2) | 0.5298 (3) | 0.0514 (8) | |
H61 | 0.2768 | 0.3107 | 0.4898 | 0.062* | 0.488 (6) |
H62 | 0.2669 | 0.3983 | 0.5748 | 0.062* | 0.488 (6) |
H63 | 0.3105 | 0.3483 | 0.5468 | 0.062* | 0.512 (6) |
H64 | 0.1918 | 0.4080 | 0.5421 | 0.062* | 0.512 (6) |
C7A | 0.1152 (4) | 0.3832 (4) | 0.4370 (4) | 0.0505 (19) | 0.488 (6) |
H71 | 0.0671 | 0.4219 | 0.4791 | 0.061* | 0.488 (6) |
C19A | 0.1413 (10) | 0.4487 (7) | 0.3452 (7) | 0.086 (3) | 0.488 (6) |
H191 | 0.1792 | 0.4109 | 0.2951 | 0.129* | 0.488 (6) |
H192 | 0.1948 | 0.5009 | 0.3830 | 0.129* | 0.488 (6) |
H193 | 0.0669 | 0.4767 | 0.2977 | 0.129* | 0.488 (6) |
C7B | 0.1730 (4) | 0.3142 (4) | 0.4037 (4) | 0.0461 (16) | 0.512 (6) |
H72 | 0.2100 | 0.2512 | 0.3905 | 0.055* | 0.512 (6) |
C19B | 0.2082 (7) | 0.3908 (6) | 0.3286 (6) | 0.061 (2) | 0.512 (6) |
H194 | 0.1875 | 0.4551 | 0.3525 | 0.092* | 0.512 (6) |
H195 | 0.1660 | 0.3795 | 0.2467 | 0.092* | 0.512 (6) |
H196 | 0.2942 | 0.3875 | 0.3379 | 0.092* | 0.512 (6) |
C8 | 0.0394 (2) | 0.2989 (2) | 0.3806 (2) | 0.0402 (7) | |
H81 | −0.0365 | 0.3240 | 0.3303 | 0.048* | 0.488 (6) |
H82 | 0.0806 | 0.2637 | 0.3302 | 0.048* | 0.488 (6) |
H83 | 0.0003 | 0.3619 | 0.3860 | 0.048* | 0.512 (6) |
H84 | 0.0069 | 0.2732 | 0.3007 | 0.048* | 0.512 (6) |
C8A | 0.0131 (2) | 0.22939 (19) | 0.4671 (2) | 0.0322 (6) | |
C9 | −0.2300 (2) | 0.0493 (2) | 0.4284 (3) | 0.0453 (7) | |
H91 | −0.2121 | −0.0202 | 0.4275 | 0.068* | |
H92 | −0.2557 | 0.0736 | 0.3481 | 0.068* | |
H93 | −0.2935 | 0.0594 | 0.4670 | 0.068* | |
C10 | −0.0871 (2) | 0.00612 (19) | 0.6710 (2) | 0.0356 (6) | |
C12 | −0.0352 (3) | −0.0761 (2) | 0.8522 (3) | 0.0499 (8) | |
H121 | −0.1179 | −0.0698 | 0.8557 | 0.075* | |
H122 | 0.0182 | −0.0694 | 0.9308 | 0.075* | |
H123 | −0.0237 | −0.1400 | 0.8206 | 0.075* | |
C13 | 0.0305 (2) | 0.20598 (18) | 0.7668 (2) | 0.0306 (6) | |
C14 | 0.1005 (2) | 0.19828 (18) | 0.8809 (2) | 0.0326 (6) | |
C15 | 0.0781 (2) | 0.25244 (19) | 0.9711 (2) | 0.0350 (6) | |
H15 | 0.1278 | 0.2466 | 1.0484 | 0.042* | |
C16 | −0.0182 (3) | 0.3151 (2) | 0.9465 (2) | 0.0379 (6) | |
C17 | −0.0895 (2) | 0.3261 (2) | 0.8346 (2) | 0.0401 (7) | |
H17 | −0.1545 | 0.3701 | 0.8182 | 0.048* | |
C18 | −0.0641 (2) | 0.2712 (2) | 0.7464 (2) | 0.0357 (6) | |
H18 | −0.1131 | 0.2784 | 0.6690 | 0.043* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cl1 | 0.0422 (4) | 0.0492 (4) | 0.0331 (4) | 0.0138 (3) | −0.0011 (3) | 0.0054 (3) |
Cl2 | 0.0770 (6) | 0.0613 (5) | 0.0364 (4) | 0.0174 (4) | 0.0203 (4) | −0.0056 (4) |
O5 | 0.0346 (10) | 0.0656 (14) | 0.0307 (11) | −0.0077 (9) | −0.0021 (8) | −0.0049 (9) |
O10 | 0.0555 (13) | 0.0543 (13) | 0.0520 (13) | −0.0192 (11) | 0.0084 (11) | 0.0061 (11) |
O11 | 0.0494 (11) | 0.0390 (11) | 0.0382 (11) | 0.0014 (9) | 0.0067 (9) | 0.0104 (9) |
N1 | 0.0335 (12) | 0.0443 (14) | 0.0275 (12) | −0.0053 (10) | −0.0037 (10) | 0.0045 (10) |
C2 | 0.0289 (13) | 0.0358 (14) | 0.0344 (15) | −0.0026 (11) | 0.0063 (11) | −0.0038 (12) |
C3 | 0.0316 (13) | 0.0319 (13) | 0.0313 (14) | −0.0004 (11) | 0.0073 (11) | −0.0025 (11) |
C4 | 0.0288 (13) | 0.0338 (14) | 0.0246 (13) | 0.0032 (11) | 0.0015 (10) | −0.0012 (11) |
C4A | 0.0286 (13) | 0.0344 (13) | 0.0255 (13) | 0.0000 (11) | 0.0036 (10) | −0.0032 (11) |
C5 | 0.0343 (14) | 0.0438 (16) | 0.0292 (14) | −0.0043 (12) | 0.0035 (12) | −0.0078 (12) |
C6 | 0.0457 (17) | 0.064 (2) | 0.0395 (17) | −0.0250 (15) | 0.0023 (14) | −0.0011 (15) |
C7A | 0.069 (4) | 0.047 (3) | 0.029 (3) | −0.022 (3) | 0.002 (3) | 0.002 (3) |
C19A | 0.110 (6) | 0.075 (5) | 0.056 (4) | −0.036 (4) | −0.010 (4) | 0.010 (4) |
C7B | 0.049 (3) | 0.054 (3) | 0.036 (3) | −0.012 (3) | 0.013 (2) | 0.004 (3) |
C19B | 0.059 (4) | 0.071 (4) | 0.048 (4) | −0.020 (3) | 0.004 (3) | 0.020 (3) |
C8 | 0.0426 (16) | 0.0443 (16) | 0.0295 (14) | −0.0040 (13) | 0.0024 (12) | 0.0052 (12) |
C8A | 0.0307 (13) | 0.0362 (14) | 0.0268 (14) | 0.0012 (11) | 0.0023 (11) | −0.0023 (11) |
C9 | 0.0371 (15) | 0.0503 (18) | 0.0428 (17) | −0.0095 (13) | 0.0003 (13) | −0.0036 (14) |
C10 | 0.0369 (15) | 0.0331 (14) | 0.0367 (15) | 0.0024 (12) | 0.0093 (12) | −0.0009 (12) |
C12 | 0.063 (2) | 0.0442 (17) | 0.0438 (18) | 0.0044 (15) | 0.0161 (15) | 0.0138 (14) |
C13 | 0.0339 (13) | 0.0316 (13) | 0.0255 (13) | 0.0004 (11) | 0.0067 (10) | 0.0029 (11) |
C14 | 0.0322 (13) | 0.0333 (14) | 0.0299 (14) | 0.0027 (11) | 0.0038 (11) | 0.0050 (11) |
C15 | 0.0430 (15) | 0.0379 (15) | 0.0220 (13) | −0.0004 (12) | 0.0050 (11) | 0.0048 (11) |
C16 | 0.0481 (16) | 0.0370 (15) | 0.0315 (14) | 0.0016 (13) | 0.0157 (12) | −0.0009 (12) |
C17 | 0.0397 (15) | 0.0435 (16) | 0.0371 (16) | 0.0081 (13) | 0.0104 (12) | 0.0026 (13) |
C18 | 0.0347 (14) | 0.0415 (15) | 0.0283 (14) | 0.0071 (12) | 0.0039 (11) | 0.0017 (12) |
Cl1—C14 | 1.741 (3) | C19A—H192 | 0.9800 |
Cl2—C16 | 1.737 (3) | C19A—H193 | 0.9800 |
O5—C5 | 1.242 (3) | C7B—C19B | 1.508 (6) |
O10—C10 | 1.208 (3) | C7B—C8 | 1.523 (4) |
O11—C10 | 1.355 (3) | C7B—H72 | 1.0000 |
O11—C12 | 1.440 (3) | C19B—H194 | 0.9800 |
N1—C8A | 1.367 (3) | C19B—H195 | 0.9800 |
N1—C2 | 1.377 (3) | C19B—H196 | 0.9800 |
N1—H1 | 0.88 (3) | C8—C8A | 1.496 (4) |
C2—C3 | 1.359 (4) | C8—H81 | 0.9900 |
C2—C9 | 1.497 (4) | C8—H82 | 0.9900 |
C3—C10 | 1.458 (4) | C8—H83 | 0.9900 |
C3—C4 | 1.530 (4) | C8—H84 | 0.9900 |
C4—C4A | 1.515 (4) | C9—H91 | 0.9800 |
C4—C13 | 1.534 (3) | C9—H92 | 0.9800 |
C4—H4 | 1.0000 | C9—H93 | 0.9800 |
C4A—C8A | 1.356 (3) | C12—H121 | 0.9800 |
C4A—C5 | 1.444 (4) | C12—H122 | 0.9800 |
C5—C6 | 1.503 (4) | C12—H123 | 0.9800 |
C6—C7B | 1.511 (4) | C13—C14 | 1.389 (4) |
C6—C7A | 1.537 (4) | C13—C18 | 1.393 (4) |
C6—H61 | 0.9900 | C14—C15 | 1.388 (4) |
C6—H62 | 0.9900 | C15—C16 | 1.385 (4) |
C6—H63 | 0.9900 | C15—H15 | 0.9500 |
C6—H64 | 0.9900 | C16—C17 | 1.377 (4) |
C7A—C8 | 1.505 (4) | C17—C18 | 1.388 (4) |
C7A—C19A | 1.508 (7) | C17—H17 | 0.9500 |
C7A—H71 | 1.0000 | C18—H18 | 0.9500 |
C19A—H191 | 0.9800 | ||
C10—O11—C12 | 115.6 (2) | H194—C19B—H196 | 109.5 |
C2—N1—C8A | 123.3 (2) | H195—C19B—H196 | 109.5 |
C8A—N1—H1 | 115 (2) | C8A—C8—C7A | 113.1 (3) |
C2—N1—H1 | 122 (2) | C8A—C8—C7B | 110.6 (3) |
N1—C2—C3 | 120.1 (2) | C8A—C8—H81 | 109.0 |
N1—C2—C9 | 113.1 (2) | C7A—C8—H81 | 109.0 |
C3—C2—C9 | 126.8 (2) | C8A—C8—H82 | 109.0 |
C2—C3—C10 | 119.8 (2) | C7A—C8—H82 | 109.0 |
C2—C3—C4 | 122.1 (2) | H81—C8—H82 | 107.8 |
C10—C3—C4 | 118.1 (2) | C8A—C8—H83 | 109.5 |
C3—C4—C4A | 110.7 (2) | C7B—C8—H83 | 109.5 |
C4A—C4—C13 | 110.1 (2) | C8A—C8—H84 | 109.5 |
C3—C4—C13 | 111.6 (2) | C7B—C8—H84 | 109.5 |
C4A—C4—H4 | 108.1 | H83—C8—H84 | 108.1 |
C3—C4—H4 | 108.1 | N1—C8A—C4A | 120.3 (2) |
C13—C4—H4 | 108.1 | C4A—C8A—C8 | 124.0 (2) |
C8A—C4A—C5 | 119.0 (2) | N1—C8A—C8 | 115.7 (2) |
C4—C4A—C8A | 122.7 (2) | C2—C9—H91 | 109.5 |
C5—C4A—C4 | 118.3 (2) | C2—C9—H92 | 109.5 |
O5—C5—C4A | 120.7 (3) | H91—C9—H92 | 109.5 |
O5—C5—C6 | 120.3 (2) | C2—C9—H93 | 109.5 |
C4A—C5—C6 | 119.0 (2) | H91—C9—H93 | 109.5 |
C5—C6—C7B | 113.0 (3) | H92—C9—H93 | 109.5 |
C5—C6—C7A | 114.6 (3) | O10—C10—O11 | 120.8 (3) |
C5—C6—H61 | 108.6 | O10—C10—C3 | 128.0 (3) |
C7A—C6—H61 | 108.6 | O11—C10—C3 | 111.2 (2) |
C5—C6—H62 | 108.6 | O11—C12—H121 | 109.5 |
C7A—C6—H62 | 108.6 | O11—C12—H122 | 109.5 |
H61—C6—H62 | 107.6 | H121—C12—H122 | 109.5 |
C5—C6—H63 | 109.0 | O11—C12—H123 | 109.5 |
C7B—C6—H63 | 109.0 | H121—C12—H123 | 109.5 |
C5—C6—H64 | 109.0 | H122—C12—H123 | 109.5 |
C7B—C6—H64 | 109.0 | C14—C13—C18 | 116.9 (2) |
H63—C6—H64 | 107.8 | C14—C13—C4 | 124.1 (2) |
C8—C7A—C19A | 110.3 (4) | C18—C13—C4 | 119.0 (2) |
C8—C7A—C6 | 108.3 (3) | C15—C14—C13 | 122.1 (2) |
C19A—C7A—C6 | 116.8 (5) | C15—C14—Cl1 | 116.0 (2) |
C8—C7A—H71 | 107.0 | C13—C14—Cl1 | 121.9 (2) |
C19A—C7A—H71 | 107.0 | C16—C15—C14 | 118.7 (2) |
C6—C7A—H71 | 107.0 | C16—C15—H15 | 120.6 |
C19B—C7B—C6 | 108.0 (4) | C14—C15—H15 | 120.6 |
C19B—C7B—C8 | 114.7 (4) | C17—C16—C15 | 121.4 (2) |
C6—C7B—C8 | 108.7 (3) | C17—C16—Cl2 | 120.3 (2) |
C19B—C7B—H72 | 108.4 | C15—C16—Cl2 | 118.3 (2) |
C6—C7B—H72 | 108.4 | C16—C17—C18 | 118.4 (3) |
C8—C7B—H72 | 108.4 | C16—C17—H17 | 120.8 |
C7B—C19B—H194 | 109.5 | C18—C17—H17 | 120.8 |
C7B—C19B—H195 | 109.5 | C17—C18—C13 | 122.6 (2) |
H194—C19B—H195 | 109.5 | C17—C18—H18 | 118.7 |
C7B—C19B—H196 | 109.5 | C13—C18—H18 | 118.7 |
C8A—N1—C2—C3 | 3.5 (4) | C5—C4A—C8A—C8 | −1.3 (4) |
C8A—N1—C2—C9 | −175.8 (2) | C4—C4A—C8A—C8 | 177.9 (2) |
N1—C2—C3—C10 | −176.7 (2) | C2—N1—C8A—C4A | −3.4 (4) |
C9—C2—C3—C10 | 2.5 (4) | C2—N1—C8A—C8 | 175.2 (2) |
N1—C2—C3—C4 | 3.3 (4) | C7A—C8—C8A—C4A | −26.0 (4) |
C9—C2—C3—C4 | −177.5 (3) | C7B—C8—C8A—C4A | 28.5 (4) |
C2—C3—C4—C4A | −8.9 (3) | C7A—C8—C8A—N1 | 155.4 (3) |
C10—C3—C4—C4A | 171.1 (2) | C7B—C8—C8A—N1 | −150.1 (3) |
C2—C3—C4—C13 | 114.1 (3) | C12—O11—C10—O10 | −1.8 (4) |
C10—C3—C4—C13 | −65.8 (3) | C12—O11—C10—C3 | 177.8 (2) |
C3—C4—C4A—C8A | 9.1 (3) | C2—C3—C10—O10 | −2.7 (4) |
C13—C4—C4A—C8A | −114.8 (3) | C4—C3—C10—O10 | 177.3 (3) |
C3—C4—C4A—C5 | −171.8 (2) | C2—C3—C10—O11 | 177.7 (2) |
C13—C4—C4A—C5 | 64.3 (3) | C4—C3—C10—O11 | −2.3 (3) |
C8A—C4A—C5—O5 | −179.0 (3) | C4A—C4—C13—C14 | −115.5 (3) |
C4—C4A—C5—O5 | 1.9 (4) | C3—C4—C13—C14 | 121.0 (3) |
C8A—C4A—C5—C6 | 1.1 (4) | C4A—C4—C13—C18 | 63.7 (3) |
C4—C4A—C5—C6 | −178.1 (2) | C3—C4—C13—C18 | −59.7 (3) |
O5—C5—C6—C7B | 151.2 (3) | C18—C13—C14—C15 | 0.1 (4) |
C4A—C5—C6—C7B | −28.9 (4) | C4—C13—C14—C15 | 179.4 (2) |
O5—C5—C6—C7A | −153.9 (3) | C18—C13—C14—Cl1 | 179.6 (2) |
C4A—C5—C6—C7A | 26.1 (4) | C4—C13—C14—Cl1 | −1.2 (4) |
C5—C6—C7A—C8 | −50.4 (5) | C13—C14—C15—C16 | 0.9 (4) |
C5—C6—C7A—C19A | −175.6 (5) | Cl1—C14—C15—C16 | −178.6 (2) |
C5—C6—C7B—C19B | 179.4 (5) | C14—C15—C16—C17 | −1.5 (4) |
C5—C6—C7B—C8 | 54.4 (5) | C14—C15—C16—Cl2 | 178.5 (2) |
C19A—C7A—C8—C8A | 178.3 (6) | C15—C16—C17—C18 | 1.2 (4) |
C6—C7A—C8—C8A | 49.4 (5) | Cl2—C16—C17—C18 | −178.8 (2) |
C19B—C7B—C8—C8A | −174.1 (5) | C16—C17—C18—C13 | −0.1 (4) |
C6—C7B—C8—C8A | −53.2 (4) | C14—C13—C18—C17 | −0.5 (4) |
C5—C4A—C8A—N1 | 177.3 (2) | C4—C13—C18—C17 | −179.8 (2) |
C4—C4A—C8A—N1 | −3.6 (4) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O5i | 0.88 (3) | 1.96 (3) | 2.835 (3) | 173 (3) |
Symmetry code: (i) x−1/2, −y+1/2, z−1/2. |
C24H21Cl2NO3·H2O | Z = 2 |
Mr = 460.35 | F(000) = 480 |
Triclinic, P1 | Dx = 1.353 Mg m−3 |
Hall symbol: -P 1 | Melting point: 421 K |
a = 9.4543 (5) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 9.7947 (6) Å | Cell parameters from 24569 reflections |
c = 13.4460 (9) Å | θ = 2.0–25.0° |
α = 76.436 (3)° | µ = 0.32 mm−1 |
β = 89.268 (4)° | T = 160 K |
γ = 69.471 (3)° | Tablet, pale yellow |
V = 1130.23 (12) Å3 | 0.22 × 0.22 × 0.10 mm |
Nonius KappaCCD area-detector diffractometer | 3980 independent reflections |
Radiation source: Nonius FR590 sealed tube generator | 3043 reflections with I > 2σ(I) |
Horizontally mounted graphite crystal monochromator | Rint = 0.046 |
Detector resolution: 9 pixels mm-1 | θmax = 25.0°, θmin = 2.3° |
ω scans with κ offsets | h = −11→11 |
Absorption correction: multi-scan (Blessing, 1995) | k = −11→11 |
Tmin = 0.822, Tmax = 0.977 | l = −15→16 |
14667 measured reflections |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: geom and difmap |
R[F2 > 2σ(F2)] = 0.053 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.150 | w = 1/[σ2(Fo2) + (0.0709P)2 + 0.6095P] where P = (Fo2 + 2Fc2)/3 |
S = 1.05 | (Δ/σ)max = 0.002 |
3980 reflections | Δρmax = 0.28 e Å−3 |
376 parameters | Δρmin = −0.35 e Å−3 |
248 restraints | Extinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.026 (6) |
C24H21Cl2NO3·H2O | γ = 69.471 (3)° |
Mr = 460.35 | V = 1130.23 (12) Å3 |
Triclinic, P1 | Z = 2 |
a = 9.4543 (5) Å | Mo Kα radiation |
b = 9.7947 (6) Å | µ = 0.32 mm−1 |
c = 13.4460 (9) Å | T = 160 K |
α = 76.436 (3)° | 0.22 × 0.22 × 0.10 mm |
β = 89.268 (4)° |
Nonius KappaCCD area-detector diffractometer | 3980 independent reflections |
Absorption correction: multi-scan (Blessing, 1995) | 3043 reflections with I > 2σ(I) |
Tmin = 0.822, Tmax = 0.977 | Rint = 0.046 |
14667 measured reflections |
R[F2 > 2σ(F2)] = 0.053 | 248 restraints |
wR(F2) = 0.150 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.05 | Δρmax = 0.28 e Å−3 |
3980 reflections | Δρmin = −0.35 e Å−3 |
376 parameters |
Experimental. Solvent used: Cooling Device: Oxford Cryosystems Cryostream 700 Crystal mount: glued on a glass fibre Mosaicity (°.): 1.398 (4) Frames collected: 196 Seconds exposure per frame: 80 Degrees rotation per frame: 2.0 Crystal-Detector distance (mm): 30.0 |
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 | 0.05915 (7) | 0.70403 (8) | 0.14084 (6) | 0.0634 (3) | |
Cl2 | 0.16289 (11) | 0.84845 (11) | 0.48377 (8) | 0.0914 (4) | |
O5 | 0.24207 (18) | 0.3319 (2) | 0.21871 (17) | 0.0649 (6) | |
O10 | 0.5516 (3) | 0.8073 (3) | 0.0033 (2) | 0.0958 (9) | |
O11 | 0.3256 (2) | 0.7987 (2) | 0.04186 (16) | 0.0711 (6) | |
N1 | 0.7296 (3) | 0.3496 (3) | 0.1748 (2) | 0.0569 (6) | |
H1 | 0.827 (5) | 0.298 (4) | 0.190 (3) | 0.086 (11)* | |
C2 | 0.6793 (3) | 0.4958 (3) | 0.1162 (2) | 0.0525 (7) | |
C3 | 0.5300 (3) | 0.5789 (3) | 0.1033 (2) | 0.0510 (6) | |
C4 | 0.4113 (3) | 0.5186 (3) | 0.1554 (2) | 0.0481 (6) | |
H4 | 0.3287 | 0.5382 | 0.1024 | 0.058* | |
C4A | 0.4812 (3) | 0.3508 (3) | 0.2002 (2) | 0.0478 (6) | |
C5 | 0.3815 (3) | 0.2675 (3) | 0.2317 (2) | 0.0550 (7) | |
C6A | 0.4561 (9) | 0.0966 (5) | 0.2631 (6) | 0.052 (2) | 0.505 (7) |
H61 | 0.4758 | 0.0578 | 0.2006 | 0.062* | 0.505 (7) |
H62 | 0.3859 | 0.0536 | 0.3023 | 0.062* | 0.505 (7) |
C7A | 0.6061 (5) | 0.0449 (6) | 0.3289 (5) | 0.0521 (14) | 0.505 (7) |
H71 | 0.5849 | 0.0885 | 0.3901 | 0.063* | 0.505 (7) |
C19A | 0.6779 (8) | −0.1226 (6) | 0.3663 (7) | 0.0511 (18) | 0.505 (7) |
C20A | 0.7161 (13) | −0.1872 (9) | 0.4701 (7) | 0.0630 (19) | 0.505 (7) |
H20A | 0.6917 | −0.1247 | 0.5169 | 0.076* | 0.505 (7) |
C21A | 0.7898 (15) | −0.3424 (10) | 0.5076 (6) | 0.070 (2) | 0.505 (7) |
H21A | 0.8155 | −0.3845 | 0.5791 | 0.084* | 0.505 (7) |
C22A | 0.825 (3) | −0.4342 (8) | 0.4399 (7) | 0.060 (2) | 0.505 (7) |
H22A | 0.8752 | −0.5397 | 0.4646 | 0.072* | 0.505 (7) |
C23A | 0.787 (2) | −0.3718 (8) | 0.3369 (7) | 0.057 (2) | 0.505 (7) |
H23A | 0.8122 | −0.4341 | 0.2899 | 0.069* | 0.505 (7) |
C24A | 0.7131 (17) | −0.2182 (9) | 0.3014 (6) | 0.0575 (19) | 0.505 (7) |
H24A | 0.6855 | −0.1772 | 0.2300 | 0.069* | 0.505 (7) |
C6B | 0.4452 (8) | 0.1085 (6) | 0.2998 (7) | 0.055 (2) | 0.495 (7) |
H63 | 0.3763 | 0.0542 | 0.2938 | 0.067* | 0.495 (7) |
H64 | 0.4543 | 0.1120 | 0.3724 | 0.067* | 0.495 (7) |
C7B | 0.6021 (5) | 0.0262 (5) | 0.2661 (5) | 0.0492 (14) | 0.495 (7) |
H72 | 0.5865 | 0.0196 | 0.1942 | 0.059* | 0.495 (7) |
C19B | 0.6757 (9) | −0.1317 (7) | 0.3300 (7) | 0.0524 (18) | 0.495 (7) |
C20B | 0.6947 (13) | −0.1575 (9) | 0.4355 (7) | 0.062 (2) | 0.495 (7) |
H20B | 0.6616 | −0.0745 | 0.4661 | 0.075* | 0.495 (7) |
C21B | 0.7615 (15) | −0.3029 (11) | 0.4980 (6) | 0.066 (2) | 0.495 (7) |
H21B | 0.7697 | −0.3187 | 0.5705 | 0.079* | 0.495 (7) |
C22B | 0.816 (3) | −0.4236 (8) | 0.4536 (7) | 0.061 (2) | 0.495 (7) |
H22B | 0.8623 | −0.5227 | 0.4953 | 0.073* | 0.495 (7) |
C23B | 0.801 (2) | −0.3992 (7) | 0.3488 (7) | 0.056 (2) | 0.495 (7) |
H23B | 0.8400 | −0.4812 | 0.3177 | 0.068* | 0.495 (7) |
C24B | 0.7301 (16) | −0.2549 (8) | 0.2884 (6) | 0.0544 (17) | 0.495 (7) |
H24B | 0.7185 | −0.2403 | 0.2162 | 0.065* | 0.495 (7) |
C8 | 0.7082 (3) | 0.1135 (3) | 0.2640 (2) | 0.0572 (7) | |
H81 | 0.7970 | 0.1010 | 0.3083 | 0.069* | 0.505 (7) |
H82 | 0.7460 | 0.0572 | 0.2110 | 0.069* | 0.505 (7) |
H83 | 0.7436 | 0.1035 | 0.3352 | 0.069* | 0.495 (7) |
H84 | 0.7980 | 0.0692 | 0.2275 | 0.069* | 0.495 (7) |
C8A | 0.6331 (3) | 0.2767 (3) | 0.2121 (2) | 0.0514 (6) | |
C9 | 0.8066 (3) | 0.5428 (4) | 0.0705 (2) | 0.0633 (8) | |
H91 | 0.7941 | 0.6422 | 0.0804 | 0.095* | |
H92 | 0.8048 | 0.5471 | −0.0030 | 0.095* | |
H93 | 0.9037 | 0.4696 | 0.1044 | 0.095* | |
C10 | 0.4765 (3) | 0.7359 (4) | 0.0452 (2) | 0.0616 (8) | |
C12 | 0.2577 (5) | 0.9594 (4) | 0.0045 (3) | 0.0976 (13) | |
H121 | 0.3369 | 1.0012 | −0.0155 | 0.146* | |
H122 | 0.2030 | 1.0027 | 0.0588 | 0.146* | |
H123 | 0.1868 | 0.9836 | −0.0551 | 0.146* | |
C13 | 0.3420 (3) | 0.5993 (3) | 0.23848 (19) | 0.0435 (6) | |
C14 | 0.1895 (3) | 0.6841 (3) | 0.2385 (2) | 0.0475 (6) | |
C15 | 0.1335 (3) | 0.7587 (3) | 0.3140 (2) | 0.0539 (7) | |
H15 | 0.0284 | 0.8146 | 0.3129 | 0.065* | |
C16 | 0.2334 (3) | 0.7501 (3) | 0.3908 (2) | 0.0552 (7) | |
C17 | 0.3854 (3) | 0.6670 (3) | 0.3956 (2) | 0.0505 (6) | |
H17 | 0.4529 | 0.6618 | 0.4492 | 0.061* | |
C18 | 0.4370 (3) | 0.5915 (3) | 0.31999 (19) | 0.0455 (6) | |
H18 | 0.5414 | 0.5317 | 0.3236 | 0.055* | |
O1A | 0.0435 (3) | 0.1849 (4) | 0.2342 (3) | 0.0950 (15) | 0.879 (6) |
H11 | 0.104 (6) | 0.222 (6) | 0.216 (4) | 0.142* | 0.879 (6) |
H12 | 0.034 (7) | 0.184 (8) | 0.294 (3) | 0.142* | 0.879 (6) |
O1B | 0.0987 (14) | 0.1256 (15) | 0.1547 (11) | 0.040 (5) | 0.121 (6) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cl1 | 0.0366 (4) | 0.0753 (5) | 0.0744 (5) | −0.0202 (3) | −0.0119 (3) | −0.0099 (4) |
Cl2 | 0.0764 (6) | 0.0996 (7) | 0.1126 (8) | −0.0238 (5) | 0.0157 (5) | −0.0652 (6) |
O5 | 0.0309 (9) | 0.0657 (12) | 0.0973 (15) | −0.0244 (9) | 0.0027 (9) | −0.0072 (11) |
O10 | 0.0793 (16) | 0.0812 (16) | 0.125 (2) | −0.0428 (13) | 0.0313 (15) | −0.0009 (15) |
O11 | 0.0529 (12) | 0.0768 (14) | 0.0700 (13) | −0.0266 (10) | −0.0035 (10) | 0.0134 (11) |
N1 | 0.0344 (12) | 0.0690 (16) | 0.0766 (16) | −0.0297 (11) | 0.0067 (11) | −0.0178 (13) |
C2 | 0.0454 (14) | 0.0737 (19) | 0.0544 (15) | −0.0375 (13) | 0.0074 (12) | −0.0206 (14) |
C3 | 0.0459 (14) | 0.0675 (17) | 0.0507 (15) | −0.0334 (13) | 0.0036 (11) | −0.0151 (13) |
C4 | 0.0366 (12) | 0.0626 (16) | 0.0523 (15) | −0.0269 (12) | 0.0014 (11) | −0.0131 (12) |
C4A | 0.0351 (12) | 0.0573 (15) | 0.0596 (16) | −0.0255 (11) | 0.0053 (11) | −0.0165 (12) |
C5 | 0.0316 (13) | 0.0625 (17) | 0.0734 (18) | −0.0234 (12) | 0.0033 (12) | −0.0110 (14) |
C6A | 0.031 (3) | 0.066 (3) | 0.060 (4) | −0.026 (2) | 0.013 (3) | −0.008 (3) |
C7A | 0.035 (2) | 0.062 (3) | 0.065 (3) | −0.023 (2) | 0.007 (2) | −0.018 (3) |
C19A | 0.029 (2) | 0.060 (3) | 0.064 (4) | −0.020 (2) | 0.011 (3) | −0.010 (3) |
C20A | 0.050 (4) | 0.067 (4) | 0.067 (4) | −0.017 (3) | −0.003 (4) | −0.013 (3) |
C21A | 0.050 (4) | 0.071 (4) | 0.073 (4) | −0.010 (3) | −0.007 (3) | −0.008 (3) |
C22A | 0.043 (4) | 0.061 (3) | 0.075 (4) | −0.021 (3) | 0.002 (4) | −0.010 (3) |
C23A | 0.043 (4) | 0.059 (3) | 0.070 (3) | −0.021 (3) | 0.005 (3) | −0.011 (3) |
C24A | 0.040 (4) | 0.059 (4) | 0.071 (3) | −0.022 (4) | 0.006 (3) | −0.006 (3) |
C6B | 0.031 (3) | 0.066 (3) | 0.069 (5) | −0.023 (2) | 0.017 (3) | −0.010 (3) |
C7B | 0.031 (2) | 0.059 (3) | 0.064 (3) | −0.0227 (19) | 0.006 (2) | −0.016 (2) |
C19B | 0.034 (3) | 0.060 (3) | 0.065 (4) | −0.021 (2) | 0.006 (3) | −0.010 (3) |
C20B | 0.046 (4) | 0.060 (4) | 0.073 (5) | −0.013 (3) | −0.002 (4) | −0.011 (4) |
C21B | 0.048 (4) | 0.073 (4) | 0.068 (3) | −0.017 (4) | −0.003 (3) | −0.011 (3) |
C22B | 0.042 (4) | 0.061 (3) | 0.077 (4) | −0.023 (3) | −0.001 (4) | −0.002 (3) |
C23B | 0.040 (4) | 0.054 (3) | 0.074 (4) | −0.022 (3) | −0.001 (3) | −0.003 (3) |
C24B | 0.037 (4) | 0.055 (3) | 0.073 (3) | −0.018 (3) | 0.009 (3) | −0.014 (3) |
C8 | 0.0310 (12) | 0.0623 (17) | 0.084 (2) | −0.0229 (12) | 0.0048 (12) | −0.0200 (15) |
C8A | 0.0361 (13) | 0.0626 (16) | 0.0674 (17) | −0.0276 (12) | 0.0087 (11) | −0.0229 (13) |
C9 | 0.0522 (16) | 0.091 (2) | 0.0643 (18) | −0.0466 (16) | 0.0125 (13) | −0.0200 (16) |
C10 | 0.0587 (18) | 0.080 (2) | 0.0552 (17) | −0.0380 (16) | 0.0086 (13) | −0.0125 (15) |
C12 | 0.082 (2) | 0.083 (2) | 0.098 (3) | −0.022 (2) | 0.006 (2) | 0.023 (2) |
C13 | 0.0356 (12) | 0.0465 (13) | 0.0518 (14) | −0.0223 (10) | −0.0003 (10) | −0.0064 (11) |
C14 | 0.0326 (12) | 0.0490 (14) | 0.0591 (16) | −0.0176 (10) | −0.0048 (11) | −0.0047 (12) |
C15 | 0.0373 (13) | 0.0468 (15) | 0.0746 (19) | −0.0126 (11) | 0.0030 (12) | −0.0134 (13) |
C16 | 0.0541 (16) | 0.0498 (15) | 0.0662 (17) | −0.0195 (12) | 0.0080 (13) | −0.0214 (13) |
C17 | 0.0458 (14) | 0.0513 (15) | 0.0565 (16) | −0.0219 (12) | −0.0021 (12) | −0.0099 (12) |
C18 | 0.0328 (12) | 0.0484 (14) | 0.0543 (15) | −0.0174 (10) | 0.0006 (10) | −0.0065 (11) |
O1A | 0.0345 (13) | 0.089 (2) | 0.157 (4) | −0.0373 (13) | −0.0025 (18) | 0.001 (2) |
O1B | 0.027 (7) | 0.056 (9) | 0.046 (9) | −0.025 (6) | 0.012 (6) | −0.015 (6) |
Cl1—C14 | 1.741 (3) | C6B—H63 | 0.9900 |
Cl2—C16 | 1.740 (3) | C6B—H64 | 0.9900 |
O5—C5 | 1.240 (3) | C7B—C19B | 1.500 (5) |
O10—C10 | 1.210 (3) | C7B—C8 | 1.526 (4) |
O11—C10 | 1.337 (3) | C7B—H72 | 1.0000 |
O11—C12 | 1.439 (4) | C19B—C24B | 1.380 (7) |
N1—C8A | 1.367 (3) | C19B—C20B | 1.384 (8) |
N1—C2 | 1.379 (4) | C20B—C21B | 1.398 (7) |
N1—H1 | 0.88 (4) | C20B—H20B | 0.9500 |
C2—C3 | 1.348 (4) | C21B—C22B | 1.385 (6) |
C2—C9 | 1.508 (3) | C21B—H21B | 0.9500 |
C3—C10 | 1.460 (4) | C22B—C23B | 1.372 (6) |
C3—C4 | 1.533 (3) | C22B—H22B | 0.9500 |
C4—C4A | 1.511 (4) | C23B—C24B | 1.385 (6) |
C4—C13 | 1.527 (4) | C23B—H23B | 0.9500 |
C4—H4 | 1.0000 | C24B—H24B | 0.9500 |
C4A—C8A | 1.355 (3) | C8—C8A | 1.497 (4) |
C4A—C5 | 1.449 (3) | C8—H81 | 0.9900 |
C5—C6B | 1.521 (4) | C8—H82 | 0.9900 |
C5—C6A | 1.525 (4) | C8—H83 | 0.9900 |
C6A—C7A | 1.539 (6) | C8—H84 | 0.9900 |
C6A—H61 | 0.9900 | C9—H91 | 0.9800 |
C6A—H62 | 0.9900 | C9—H92 | 0.9800 |
C7A—C19A | 1.499 (5) | C9—H93 | 0.9800 |
C7A—C8 | 1.518 (4) | C12—H121 | 0.9800 |
C7A—H71 | 1.0000 | C12—H122 | 0.9800 |
C19A—C24A | 1.381 (7) | C12—H123 | 0.9800 |
C19A—C20A | 1.384 (7) | C13—C14 | 1.389 (3) |
C20A—C21A | 1.399 (7) | C13—C18 | 1.397 (3) |
C20A—H20A | 0.9500 | C14—C15 | 1.381 (4) |
C21A—C22A | 1.384 (6) | C15—C16 | 1.377 (4) |
C21A—H21A | 0.9500 | C15—H15 | 0.9500 |
C22A—C23A | 1.372 (6) | C16—C17 | 1.374 (4) |
C22A—H22A | 0.9500 | C17—C18 | 1.380 (4) |
C23A—C24A | 1.384 (6) | C17—H17 | 0.9500 |
C23A—H23A | 0.9500 | C18—H18 | 0.9500 |
C24A—H24A | 0.9500 | O1A—H11 | 0.79 (3) |
C6B—C7B | 1.539 (6) | O1A—H12 | 0.81 (3) |
C10—O11—C12 | 117.9 (2) | C24B—C19B—C20B | 117.3 (4) |
C2—N1—C8A | 122.6 (2) | C24B—C19B—C7B | 123.1 (6) |
C8A—N1—H1 | 116 (2) | C20B—C19B—C7B | 119.5 (6) |
C2—N1—H1 | 121 (2) | C19B—C20B—C21B | 121.5 (5) |
N1—C2—C3 | 120.2 (2) | C19B—C20B—H20B | 119.3 |
N1—C2—C9 | 112.6 (2) | C21B—C20B—H20B | 119.3 |
C3—C2—C9 | 127.2 (3) | C22B—C21B—C20B | 119.5 (5) |
C2—C3—C10 | 120.5 (2) | C22B—C21B—H21B | 120.3 |
C2—C3—C4 | 122.2 (2) | C20B—C21B—H21B | 120.3 |
C10—C3—C4 | 117.1 (2) | C23B—C22B—C21B | 119.6 (4) |
C4A—C4—C13 | 110.6 (2) | C23B—C22B—H22B | 120.2 |
C3—C4—C4A | 110.3 (2) | C21B—C22B—H22B | 120.2 |
C13—C4—C3 | 110.8 (2) | C22B—C23B—C24B | 120.0 (4) |
C4A—C4—H4 | 108.3 | C22B—C23B—H23B | 120.0 |
C13—C4—H4 | 108.3 | C24B—C23B—H23B | 120.0 |
C3—C4—H4 | 108.3 | C19B—C24B—C23B | 122.0 (4) |
C8A—C4A—C5 | 119.3 (2) | C19B—C24B—H24B | 119.0 |
C4—C4A—C8A | 122.1 (2) | C23B—C24B—H24B | 119.0 |
C5—C4A—C4 | 118.5 (2) | C8A—C8—C7A | 114.3 (3) |
O5—C5—C4A | 120.5 (2) | C8A—C8—H81 | 108.7 |
O5—C5—C6B | 118.6 (3) | C7A—C8—H81 | 108.7 |
C4A—C5—C6B | 119.8 (4) | C8A—C8—H82 | 108.7 |
O5—C5—C6A | 122.2 (4) | C7A—C8—H82 | 108.7 |
C4A—C5—C6A | 116.4 (4) | H81—C8—H82 | 107.6 |
C5—C6A—C7A | 112.1 (4) | C8A—C8—H83 | 109.2 |
C5—C6A—H61 | 109.2 | C7B—C8—H83 | 109.2 |
C7A—C6A—H61 | 109.2 | C8A—C8—H84 | 109.2 |
C5—C6A—H62 | 109.2 | C7B—C8—H84 | 109.2 |
C7A—C6A—H62 | 109.2 | H83—C8—H84 | 107.9 |
H61—C6A—H62 | 107.9 | N1—C8A—C4A | 120.6 (3) |
C19A—C7A—C8 | 112.4 (5) | C4A—C8A—C8 | 124.3 (2) |
C19A—C7A—C6A | 113.5 (3) | N1—C8A—C8 | 115.1 (2) |
C8—C7A—C6A | 106.3 (5) | C2—C9—H91 | 109.5 |
C19A—C7A—H71 | 108.1 | C2—C9—H92 | 109.5 |
C8—C7A—H71 | 108.1 | H91—C9—H92 | 109.5 |
C6A—C7A—H71 | 108.1 | C2—C9—H93 | 109.5 |
C24A—C19A—C20A | 117.2 (4) | H91—C9—H93 | 109.5 |
C24A—C19A—C7A | 123.0 (6) | H92—C9—H93 | 109.5 |
C20A—C19A—C7A | 119.7 (6) | O10—C10—O11 | 121.0 (3) |
C19A—C20A—C21A | 121.5 (5) | O10—C10—C3 | 127.7 (3) |
C19A—C20A—H20A | 119.3 | O11—C10—C3 | 111.3 (2) |
C21A—C20A—H20A | 119.3 | O11—C12—H121 | 109.5 |
C22A—C21A—C20A | 119.6 (5) | O11—C12—H122 | 109.5 |
C22A—C21A—H21A | 120.2 | H121—C12—H122 | 109.5 |
C20A—C21A—H21A | 120.2 | O11—C12—H123 | 109.5 |
C23A—C22A—C21A | 119.6 (4) | H121—C12—H123 | 109.5 |
C23A—C22A—H22A | 120.2 | H122—C12—H123 | 109.5 |
C21A—C22A—H22A | 120.2 | C14—C13—C18 | 116.5 (2) |
C22A—C23A—C24A | 120.0 (4) | C14—C13—C4 | 124.7 (2) |
C22A—C23A—H23A | 120.0 | C18—C13—C4 | 118.8 (2) |
C24A—C23A—H23A | 120.0 | C15—C14—C13 | 122.3 (2) |
C19A—C24A—C23A | 122.1 (4) | C15—C14—Cl1 | 116.55 (18) |
C19A—C24A—H24A | 118.9 | C13—C14—Cl1 | 121.1 (2) |
C23A—C24A—H24A | 118.9 | C16—C15—C14 | 118.5 (2) |
C5—C6B—C7B | 109.0 (4) | C16—C15—H15 | 120.8 |
C5—C6B—H63 | 109.9 | C14—C15—H15 | 120.8 |
C7B—C6B—H63 | 109.9 | C17—C16—C15 | 121.9 (3) |
C5—C6B—H64 | 109.9 | C17—C16—Cl2 | 119.8 (2) |
C7B—C6B—H64 | 109.9 | C15—C16—Cl2 | 118.3 (2) |
H63—C6B—H64 | 108.3 | C16—C17—C18 | 118.0 (2) |
C19B—C7B—C8 | 110.2 (5) | C16—C17—H17 | 121.0 |
C19B—C7B—C6B | 113.0 (3) | C18—C17—H17 | 121.0 |
C8—C7B—C6B | 112.0 (6) | C17—C18—C13 | 122.7 (2) |
C19B—C7B—H72 | 107.1 | C17—C18—H18 | 118.6 |
C8—C7B—H72 | 107.1 | C13—C18—H18 | 118.6 |
C6B—C7B—H72 | 107.1 | H11—O1A—H12 | 107 (5) |
C8A—N1—C2—C3 | 7.7 (4) | C24B—C19B—C20B—C21B | −2.2 (17) |
C8A—N1—C2—C9 | −171.0 (3) | C7B—C19B—C20B—C21B | 179.4 (9) |
N1—C2—C3—C10 | 177.2 (2) | C19B—C20B—C21B—C22B | 3 (2) |
C9—C2—C3—C10 | −4.3 (4) | C20B—C21B—C22B—C23B | −1 (3) |
N1—C2—C3—C4 | 2.4 (4) | C21B—C22B—C23B—C24B | −1 (4) |
C9—C2—C3—C4 | −179.1 (3) | C20B—C19B—C24B—C23B | 0.0 (19) |
C2—C3—C4—C4A | −12.4 (3) | C7B—C19B—C24B—C23B | 178.3 (12) |
C10—C3—C4—C4A | 172.6 (2) | C22B—C23B—C24B—C19B | 2 (3) |
C2—C3—C4—C13 | 110.4 (3) | C19A—C7A—C8—C8A | 171.3 (4) |
C10—C3—C4—C13 | −64.5 (3) | C6A—C7A—C8—C8A | 46.6 (5) |
C13—C4—C4A—C8A | −108.6 (3) | C5—C4A—C8A—N1 | 174.1 (3) |
C3—C4—C4A—C8A | 14.3 (4) | C4—C4A—C8A—N1 | −6.3 (4) |
C13—C4—C4A—C5 | 71.0 (3) | C5—C4A—C8A—C8 | −5.0 (4) |
C3—C4—C4A—C5 | −166.1 (2) | C4—C4A—C8A—C8 | 174.6 (3) |
C8A—C4A—C5—O5 | −177.8 (3) | C2—N1—C8A—C4A | −5.8 (4) |
C4—C4A—C5—O5 | 2.6 (4) | C2—N1—C8A—C8 | 173.4 (2) |
C8A—C4A—C5—C6B | 14.4 (6) | C7A—C8—C8A—C4A | −16.3 (5) |
C4—C4A—C5—C6B | −165.2 (5) | C7B—C8—C8A—C4A | 21.5 (5) |
C8A—C4A—C5—C6A | −8.2 (5) | C7A—C8—C8A—N1 | 164.5 (3) |
C4—C4A—C5—C6A | 172.2 (4) | C7B—C8—C8A—N1 | −157.6 (3) |
O5—C5—C6A—C7A | −148.8 (5) | C12—O11—C10—O10 | −11.6 (5) |
C4A—C5—C6A—C7A | 41.8 (8) | C12—O11—C10—C3 | 168.5 (3) |
C5—C6A—C7A—C19A | 176.5 (6) | C2—C3—C10—O10 | 0.6 (5) |
C5—C6A—C7A—C8 | −59.3 (8) | C4—C3—C10—O10 | 175.6 (3) |
C8—C7A—C19A—C24A | −64.8 (10) | C2—C3—C10—O11 | −179.5 (3) |
C6A—C7A—C19A—C24A | 55.9 (12) | C4—C3—C10—O11 | −4.5 (4) |
C8—C7A—C19A—C20A | 113.1 (9) | C4A—C4—C13—C14 | −118.3 (2) |
C6A—C7A—C19A—C20A | −126.2 (9) | C3—C4—C13—C14 | 119.0 (3) |
C24A—C19A—C20A—C21A | 1.1 (16) | C4A—C4—C13—C18 | 63.1 (3) |
C7A—C19A—C20A—C21A | −176.9 (9) | C3—C4—C13—C18 | −59.6 (3) |
C19A—C20A—C21A—C22A | 0 (2) | C18—C13—C14—C15 | 0.7 (4) |
C20A—C21A—C22A—C23A | 0 (3) | C4—C13—C14—C15 | −177.9 (2) |
C21A—C22A—C23A—C24A | −1 (4) | C18—C13—C14—Cl1 | 179.57 (18) |
C20A—C19A—C24A—C23A | −1.8 (19) | C4—C13—C14—Cl1 | 0.9 (3) |
C7A—C19A—C24A—C23A | 176.1 (12) | C13—C14—C15—C16 | 1.1 (4) |
C22A—C23A—C24A—C19A | 2 (3) | Cl1—C14—C15—C16 | −177.8 (2) |
O5—C5—C6B—C7B | 153.3 (6) | C14—C15—C16—C17 | −1.6 (4) |
C4A—C5—C6B—C7B | −38.7 (10) | C14—C15—C16—Cl2 | 178.3 (2) |
C5—C6B—C7B—C19B | 179.2 (7) | C15—C16—C17—C18 | 0.3 (4) |
C5—C6B—C7B—C8 | 54.0 (10) | Cl2—C16—C17—C18 | −179.58 (19) |
C8—C7B—C19B—C24B | −107.0 (11) | C16—C17—C18—C13 | 1.6 (4) |
C6B—C7B—C19B—C24B | 126.8 (11) | C14—C13—C18—C17 | −2.0 (4) |
C8—C7B—C19B—C20B | 71.3 (9) | C4—C13—C18—C17 | 176.7 (2) |
C6B—C7B—C19B—C20B | −54.9 (12) |
D—H···A | D—H | H···A | D···A | D—H···A |
O1A—H11···O5 | 0.79 (3) | 1.96 (4) | 2.718 (3) | 159 (6) |
N1—H1···O1Ai | 0.88 (4) | 1.97 (4) | 2.854 (4) | 176 (3) |
Symmetry code: (i) x+1, y, z. |
Experimental details
(I) | (II) | |
Crystal data | ||
Chemical formula | C19H19Cl2NO3 | C24H21Cl2NO3·H2O |
Mr | 380.27 | 460.35 |
Crystal system, space group | Monoclinic, P21/n | Triclinic, P1 |
Temperature (K) | 160 | 160 |
a, b, c (Å) | 11.6670 (3), 13.7746 (4), 11.8897 (4) | 9.4543 (5), 9.7947 (6), 13.4460 (9) |
α, β, γ (°) | 90, 105.4328 (19), 90 | 76.436 (3), 89.268 (4), 69.471 (3) |
V (Å3) | 1841.88 (10) | 1130.23 (12) |
Z | 4 | 2 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 0.37 | 0.32 |
Crystal size (mm) | 0.22 × 0.22 × 0.07 | 0.22 × 0.22 × 0.10 |
Data collection | ||
Diffractometer | Nonius KappaCCD area-detector diffractometer | Nonius KappaCCD area-detector diffractometer |
Absorption correction | Multi-scan (Blessing, 1995) | Multi-scan (Blessing, 1995) |
Tmin, Tmax | 0.871, 0.979 | 0.822, 0.977 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 23780, 3252, 2469 | 14667, 3980, 3043 |
Rint | 0.072 | 0.046 |
(sin θ/λ)max (Å−1) | 0.596 | 0.595 |
Refinement | ||
R[F2 > 2σ(F2)], wR(F2), S | 0.049, 0.139, 1.04 | 0.053, 0.150, 1.05 |
No. of reflections | 3252 | 3980 |
No. of parameters | 254 | 376 |
No. of restraints | 31 | 248 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.71, −0.30 | 0.28, −0.35 |
Computer programs: COLLECT (Nonius, 2000), DENZO-SMN (Otwinowski & Minor, 1997), DENZO-SMN and SCALEPACK (Otwinowski & Minor, 1997), SIR92 (Altomare et al., 1994), SHELXL97 (Sheldrick, 1997), ORTEPII (Johnson, 1976), SHELXL97 and PLATON (Spek, 2003).
O5—C5 | 1.242 (3) | C2—C3 | 1.359 (4) |
O10—C10 | 1.208 (3) | C3—C10 | 1.458 (4) |
O11—C10 | 1.355 (3) | C3—C4 | 1.530 (4) |
N1—C8A | 1.367 (3) | C4—C4A | 1.515 (4) |
N1—C2 | 1.377 (3) | C4A—C8A | 1.356 (3) |
C2—N1—C8A | 123.3 (2) | C3—C4—C4A | 110.7 (2) |
N1—C2—C3 | 120.1 (2) | C4—C4A—C8A | 122.7 (2) |
N1—C2—C9 | 113.1 (2) | N1—C8A—C4A | 120.3 (2) |
C3—C2—C9 | 126.8 (2) | O10—C10—O11 | 120.8 (3) |
C2—C3—C10 | 119.8 (2) | O10—C10—C3 | 128.0 (3) |
C2—C3—C4 | 122.1 (2) | O11—C10—C3 | 111.2 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O5i | 0.88 (3) | 1.96 (3) | 2.835 (3) | 173 (3) |
Symmetry code: (i) x−1/2, −y+1/2, z−1/2. |
O5—C5 | 1.240 (3) | C2—C3 | 1.348 (4) |
O10—C10 | 1.210 (3) | C3—C10 | 1.460 (4) |
O11—C10 | 1.337 (3) | C3—C4 | 1.533 (3) |
N1—C8A | 1.367 (3) | C4—C4A | 1.511 (4) |
N1—C2 | 1.379 (4) | C4A—C8A | 1.355 (3) |
C2—N1—C8A | 122.6 (2) | C3—C4—C4A | 110.3 (2) |
N1—C2—C3 | 120.2 (2) | C4—C4A—C8A | 122.1 (2) |
N1—C2—C9 | 112.6 (2) | N1—C8A—C4A | 120.6 (3) |
C3—C2—C9 | 127.2 (3) | O10—C10—O11 | 121.0 (3) |
C2—C3—C10 | 120.5 (2) | O10—C10—C3 | 127.7 (3) |
C2—C3—C4 | 122.2 (2) | O11—C10—C3 | 111.3 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
O1A—H11···O5 | 0.79 (3) | 1.96 (4) | 2.718 (3) | 159 (6) |
N1—H1···O1Ai | 0.88 (4) | 1.97 (4) | 2.854 (4) | 176 (3) |
Symmetry code: (i) x+1, y, z. |
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1,4-Dihydropyridine (1,4-DHP) derivatives have yielded many drugs which act as calcium channel agonists or antagonists (Rose, 1989, 1990). Nifedipine is the prototype of this group, and both it and its structural analogues are used as antianginal and antihypertensive drugs (Janis & Triggle, 1984). Our interest is in the correlation between the three-dimensional structure and calcium antagonistic behaviour of condensed derivatives of 1,4-DHP (Linden et al., 1998, 2002, 2004, 2005; Şimşek et al., 2000, 2003; Kısmetli et al., 2004). Two new compounds have been prepared as further potentially active 1,4-DHP derivatives. These compounds differ only in the substituent at the 7-position on the oxocyclohexene ring and are methyl 4-(2,4-chlorophenyl)-2,7-dimethyl-5-oxo-1,4,5,6,7,8-hexahydroquinoline-3-carboxylate, (I), and methyl 4-(2,4-chlorophenyl)-2-methyl-7-phenyl-5-oxo-1,4,5,6,7,8-hexahydroquinoline-3-carboxylate monohydrate, (II). The syntheses are not stereo-specific, so the reactions produced mixtures of the 4,7-diastereoisomers of the racemic compounds. The stereoisomers could not be separated readily and, as subsequently revealed by the crystal structure determinations, crystallization yielded cocrystals in which both diastereoisomers were incorporated, rather than crystals of a single compound forming preferentially.
Views of the asymmetric units in the structures of (I) and (II) are shown in Figs. 1 and 2, respectively. Compound (II) crystallizes as the monohydrate, in which the water molecule is disordered over two sites. The centrosymmetric space groups indicate that the compounds are racemic. Although there is only one formula unit in the asymmetric unit of each structure, the molecules are disordered at atom C7 of the oxocyclohexene rings [and at atom C6 in (II)] and the disorder extends through the substituents at C7 [methyl in (I) and phenyl in (II)]. The disorder manifests itself as alternate directions of folding of the flap of the C7-envelope [in (I)] or half-chair [in (II)] conformations of the oxocyclohexene rings, but inspection of the positions of the substituents indicates that the two arrangements are related by inversion of the configuration at atom C7. As the configuration at atom C4 is constant in both of the disordered arrangements, the disorder is actually a consequence of the presence of a mixture of diastereoisomers in the crystal. The diastereoisomers with the same configuration at atom C4 have been inserted randomly and in almost equal quantities in the crystal lattice and the centrosymmetric space group accommodates the enantiomers of the diastereoisomeric pair. If the diastereoisomers were incorporated into the crystal lattice in a regular sequence, one would find two molecules (at least) in the asymmetric unit. That a random distribution of diastereoisomers occurs in the crystal suggests that the shape of the volume occupied by the diastereoisomeric molecules is very similar.
Despite the disorder, most of the bond lengths and angles in (I) and (II) have normal values. There are small angular distortions about atoms C2 and C10 (Tables 1 and 3), which result from steric interactions between the methyl substituent at C2 and atom O1O of the ester substituent at C3 [O10···C9 = 2.790 (4) and 2.814 (5) Å for (I) and (II), respectively)]. The presence of π-electron conjugation keeps the ester group at C3 almost coplanar [C2═ C3—C10═O10 = −2.7 (4) and 0.6 (5)° for (I) and (II), respectively] with the endocyclic double bond and prevents the ester group from rotating into a sterically more amenable orientation. These properties are consistent with those of related compounds (Linden et al., 2005).
The switch from the 7-methyl substituent in compound (I) to the 7-phenyl substituent in compound (II) has no major influence on the conformations of the molecules. The 1,4-DHP rings have the shallow boat conformations generally observed for 4-aryl-1,4-DHP derivatives (Linden et al., 2005), although the conformations in (I) and (II) are among the shallowest examples. In compound (I), atoms N1 and C4 are 0.035 (2) and 0.115 (2) Å, respectively, from the plane defined by atoms C2, C3, C4A and C8A. The deviation of atom N1 from this plane is so small that the ring could almost be described as having a shallow envelope conformation. The corresponding displacements in compound (II) are 0.058 (3) and 0.200 (3) Å, respectively. The shallowness of the boat conformations is indicated by the small values of the total puckering amplitudes, Q (Cremer & Pople, 1975), of 0.090 (3) and 0.141 (3) Å for compounds (I) and (II), respectively. Three structures of 1,4-DHP derivatives with similarly shallow boat conformations were reported recently (Quesada et al., 2006) and several examples containing a planar ring are also known (Pastor et al., 1994; Duque et al., 2000; Low et al., 2001; Linden et al., 2002; Mahendra et al., 2003).
The plane of the 2,4-dichlorophenyl ring in each of the title compounds is, as frequently observed (Linden et al., 2005), essentially parallel to the N1···C4 axis. Compound (I) has a N1···C4—C13—C18 torsion angle of 2.6 (3)°, while the corresponding torsion angle in compound (II) is 1.8 (3)°. The 2-chloro substituent lies above the C4—H bond in the sterically most favourable synperiplanar orientation. The Cambridge Structural Database (Release 5.27 with January 2006 updates; Allen, 2002) contains five examples of 4-aryl-1,4-DHP compounds with 2,4-disubstitution in the phenyl ring. Three of these compounds are 4-(2,4-dichlorophenyl)-2,6-dimethyl-3,5-dicarboxy-1,4-DHP derivatives (Mehdi & Ravikumar, 1992; Sagar et al., 1999; Caignan & Holt, 2000), while there is one 4-(2-chloro-4-nitrophenyl)- (Rovnyak et al., 1988) and one 4-(2,4-dinitrophenyl)- analogue (Fossheim et al., 1982). In each of these compounds, the 2,4-disubstituted phenyl ring has a synperiplanar orientation with respect to the 1,4-DHP ring, although with the 4-(2,4-dinitrophenyl)- derivative and one of the 4-(2,4-dichloro)- derivatives (Sagar et al., 1999), the plane of the phenyl ring is rotated slightly to make angles of about 16 and 31°, respectively, with the N1···C4 axis.
The use of geometric restraints to handle the disordered atoms in the structures of (I) and (II) makes it unwise to analyse the conformations of the oxocyclohexene rings in any detail. It suffices to say that the oxocyclohexene ring in each diastereoisomer of compound (I) has a C7-envelope conformation, while the corresponding conformation in each diastereoisomer of compound (II) is that of a slightly distorted half-chair twisted about the C6—C7 bond. It has been noted previously that atom C7 is the atom that deviates most from the ring plane in structures involving the 5-oxoquinoline or 1,8-dioxoacridine moiety (Linden et al., 2005).
In compound (I), an intermolecular N—H···O hydrogen bond between the amine group and the carbonyl O atom of the oxocyclohexene ring of a neighbouring molecule (Table 2) links the molecules into extended chains which run parallel to the [101] direction and can be described by a graph-set motif of C(6) (Bernstein et al., 1995). The same C(6) motif has been observed in the crystal structures of several other closely related 1,4-DHP compounds (Linden et al., 1998, 2002, 2004, 2005; Şimşek et al., 2000). In compound (II), the major site of the disordered water molecule accepts the N—H···O hydrogen bond from the 1,4-DHP molecule and, in turn, forms another intermolecular hydrogen bond with the carbonyl O atom of the oxocyclohexene ring of a neighbouring 1,4-DHP molecule (Table 4). These interactions link the 1,4-DHP and water molecules alternately into extended chains which run parallel to the [100] direction and can be described by a binary graph-set motif of C22(8). The minor site of the water molecule (12% occupancy) has not been considered in this analysis.