Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807054785/xu2347sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807054785/xu2347Isup2.hkl |
CCDC reference: 672847
Cinchonidine (15 mmol) and racemic acid 1,4-dihydropyridine monoester, ethyl 1,4-dihydro-2,6-dimethyl-4-(3-nitrophenyl)-3,5-pyridinedicarboxylate (15 mmol) were stirred in reflux ethanol (35 ml) until the dissolution was complete, and then kept at room temperature for 24 h. The crystals formed were collected by filtration to give Cinchonidine salt (3.1 g). The 1,4-dihydropyridine monoester was obtained by dissolving of the Cinchonidine salt and sodium hydroxide in water. The solution were acidified with HCl, filtered, washed with water to give (-)-ethyl 1,4-dihydro-2,6-dimethyl-4-(3-nitrophenyl)-3,5-pyridinedicarboxylate (1.54 g, yield 31%, [α]D20 = -4.4°). The absolute configuration of the enantiomer has not been assigned.
Optical active 1,4-dihydropyridine monoester (5 mmol), 2-bromo-1-(4-benzyloxyphenyl)ethan-1-one (5 mmol) and K2CO3 (5 mmol) in DMF (5 ml) were stirred overnight at room temperature. The mixture was extracted with ethyl acetate, washed successively with water and brine, and then dried and the solvent was removed. The residue was purified by crystallization to give target compound (yield 75%, [α]D20 = -93.1°).
Crystals suitable for X-ray analysis were obtained by slow evaporation from saturated methanol solution.
Methyl H atoms were placed in calculated positions, with C—H = 0.96 Å, and torsion angles were refined, with Uiso(H) = 1.5Ueq(C). Other H atoms were placed in geometrically idealized positions and refined as riding model, with N—H = 0.86 A°, C—H = 0.98 (methine), 0.93 (aromatic) and 0.97 Å (methylene). The constraint Uiso(H) = 1.2Ueq(carrier) was applied. In the absence of significant anomalous dispersion effects, Friedel pairs were merged.
Data collection: SMART (Bruker, 2001); cell refinement: SAINT-Plus (Bruker, 2003); data reduction: SAINT-Plus (Bruker, 2003); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1997); software used to prepare material for publication: SHELXTL (Bruker, 1997).
Fig. 1. Molecular structure of (I) showing 30% probability displacement ellipsoids. | |
Fig. 2. Packing diagram. |
C32H30N2O8 | Z = 1 |
Mr = 570.58 | F(000) = 300 |
Triclinic, P1 | Dx = 1.301 Mg m−3 |
Hall symbol: P 1 | Melting point: 122 K |
a = 7.3646 (7) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 8.1772 (8) Å | Cell parameters from 1853 reflections |
c = 13.329 (1) Å | µ = 0.09 mm−1 |
α = 97.905 (2)° | T = 295 K |
β = 100.352 (2)° | Block, yellow |
γ = 109.296 (2)° | 0.46 × 0.28 × 0.16 mm |
V = 728.33 (12) Å3 |
Bruker SMART 1000 CCD diffractometer | 1747 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.030 |
Graphite monochromator | θmax = 26.0°, θmin = 1.6° |
ω scans | h = −9→9 |
5566 measured reflections | k = −10→10 |
2808 independent reflections | l = −16→16 |
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)] = 0.045 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.144 | H-atom parameters constrained |
S = 1.02 | w = 1/[σ2(Fo2) + (0.0853P)2] where P = (Fo2 + 2Fc2)/3 |
2808 reflections | (Δ/σ)max < 0.001 |
382 parameters | Δρmax = 0.21 e Å−3 |
3 restraints | Δρmin = −0.21 e Å−3 |
C32H30N2O8 | γ = 109.296 (2)° |
Mr = 570.58 | V = 728.33 (12) Å3 |
Triclinic, P1 | Z = 1 |
a = 7.3646 (7) Å | Mo Kα radiation |
b = 8.1772 (8) Å | µ = 0.09 mm−1 |
c = 13.329 (1) Å | T = 295 K |
α = 97.905 (2)° | 0.46 × 0.28 × 0.16 mm |
β = 100.352 (2)° |
Bruker SMART 1000 CCD diffractometer | 1747 reflections with I > 2σ(I) |
5566 measured reflections | Rint = 0.030 |
2808 independent reflections |
R[F2 > 2σ(F2)] = 0.045 | 3 restraints |
wR(F2) = 0.144 | H-atom parameters constrained |
S = 1.02 | Δρmax = 0.21 e Å−3 |
2808 reflections | Δρmin = −0.21 e Å−3 |
382 parameters |
Experimental. 1H NMR (CDCl3, 400 MHz) (p.p.m.): 1.22 (t, J = 7.2 Hz, 3H, CH3),2.39 (s, 3H, CH3), 2.42(s, 3H, CH3), 3.96–4.13 (m, 2H, CH2), 5.13 (s, 2H, CH2), 5.20 (s, 1H, DHP 4-H), 5.24, 5.29 (dd, J =16.4 Hz, J =16.4 Hz, 2H, CO2CH2CO), 5.98 (s, 1H, NH), 6.97–8.13 (m, 13H, Ar—H). |
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 | ||
C1 | 0.6718 (6) | 0.3591 (6) | 0.7572 (4) | 0.0533 (11) | |
C2 | 0.5034 (6) | 0.3903 (6) | 0.7313 (4) | 0.0513 (10) | |
C3 | 0.3081 (6) | 0.2467 (6) | 0.7268 (4) | 0.0536 (11) | |
H3 | 0.2150 | 0.3049 | 0.7396 | 0.064* | |
C4 | 0.3348 (6) | 0.1501 (5) | 0.8135 (3) | 0.0480 (10) | |
C5 | 0.5090 (6) | 0.1267 (6) | 0.8418 (4) | 0.0556 (11) | |
C6 | 0.5611 (8) | 0.0160 (8) | 0.9149 (5) | 0.0800 (16) | |
H6A | 0.5869 | 0.0777 | 0.9856 | 0.120* | |
H6B | 0.6771 | −0.0053 | 0.9034 | 0.120* | |
H6C | 0.4526 | −0.0950 | 0.9023 | 0.120* | |
C7 | 0.8763 (7) | 0.4639 (7) | 0.7483 (5) | 0.0768 (15) | |
H7A | 0.8718 | 0.4784 | 0.6777 | 0.115* | |
H7B | 0.9635 | 0.4022 | 0.7671 | 0.115* | |
H7C | 0.9243 | 0.5783 | 0.7943 | 0.115* | |
C8 | 0.1677 (6) | 0.0884 (5) | 0.8604 (4) | 0.0500 (10) | |
C9 | 0.0365 (8) | −0.0586 (8) | 0.9877 (5) | 0.0772 (15) | |
H9A | −0.0854 | −0.1386 | 0.9389 | 0.093* | |
H9B | 0.0125 | 0.0431 | 1.0207 | 0.093* | |
C10 | 0.1013 (11) | −0.1492 (11) | 1.0668 (6) | 0.111 (2) | |
H10A | 0.1136 | −0.2552 | 1.0329 | 0.167* | |
H10B | 0.0055 | −0.1795 | 1.1079 | 0.167* | |
H10C | 0.2273 | −0.0721 | 1.1111 | 0.167* | |
C11 | 0.4911 (7) | 0.5559 (6) | 0.7029 (4) | 0.0564 (11) | |
C12 | 0.6556 (7) | 0.8139 (6) | 0.6503 (4) | 0.0625 (13) | |
H12A | 0.7818 | 0.9123 | 0.6706 | 0.075* | |
H12B | 0.5550 | 0.8575 | 0.6674 | 0.075* | |
C13 | 0.6058 (6) | 0.7412 (6) | 0.5350 (4) | 0.0586 (12) | |
C14 | 0.5909 (6) | 0.8605 (6) | 0.4637 (4) | 0.0572 (11) | |
C15 | 0.6281 (7) | 1.0397 (6) | 0.4971 (4) | 0.0591 (12) | |
H15 | 0.6646 | 1.0887 | 0.5683 | 0.071* | |
C16 | 0.6120 (7) | 1.1463 (6) | 0.4269 (4) | 0.0618 (12) | |
H16 | 0.6336 | 1.2650 | 0.4510 | 0.074* | |
C17 | 0.5640 (7) | 1.0775 (7) | 0.3213 (4) | 0.0659 (13) | |
C18 | 0.5269 (10) | 0.8964 (8) | 0.2864 (5) | 0.0866 (17) | |
H18 | 0.4928 | 0.8473 | 0.2154 | 0.104* | |
C19 | 0.5412 (9) | 0.7935 (7) | 0.3575 (4) | 0.0814 (17) | |
H19 | 0.5167 | 0.6741 | 0.3336 | 0.098* | |
C20 | 0.5785 (11) | 1.3511 (7) | 0.2736 (5) | 0.0891 (17) | |
H20A | 0.7176 | 1.4170 | 0.3065 | 0.107* | |
H20B | 0.5006 | 1.3707 | 0.3222 | 0.107* | |
C21 | 0.5186 (10) | 1.4100 (7) | 0.1744 (5) | 0.0808 (17) | |
C22 | 0.6499 (12) | 1.4713 (10) | 0.1165 (6) | 0.111 (2) | |
H22 | 0.7793 | 1.4753 | 0.1362 | 0.134* | |
C23 | 0.5874 (18) | 1.5295 (11) | 0.0251 (7) | 0.134 (3) | |
H23 | 0.6765 | 1.5753 | −0.0144 | 0.161* | |
C24 | 0.3984 (18) | 1.5174 (9) | −0.0035 (7) | 0.116 (3) | |
H24 | 0.3568 | 1.5530 | −0.0640 | 0.140* | |
C25 | 0.2676 (13) | 1.4550 (9) | 0.0537 (6) | 0.106 (2) | |
H25 | 0.1375 | 1.4486 | 0.0330 | 0.127* | |
C26 | 0.3276 (12) | 1.4010 (8) | 0.1424 (5) | 0.0929 (19) | |
H26 | 0.2370 | 1.3574 | 0.1816 | 0.111* | |
C27 | 0.2206 (6) | 0.1232 (7) | 0.6193 (4) | 0.0579 (12) | |
C28 | 0.1756 (7) | 0.1925 (9) | 0.5333 (4) | 0.0755 (15) | |
H28 | 0.1954 | 0.3125 | 0.5424 | 0.091* | |
C29 | 0.1031 (8) | 0.0886 (13) | 0.4355 (5) | 0.093 (2) | |
C30 | 0.0708 (9) | −0.0890 (15) | 0.4179 (6) | 0.111 (3) | |
H30 | 0.0221 | −0.1584 | 0.3506 | 0.133* | |
C31 | 0.1123 (9) | −0.1625 (10) | 0.5025 (6) | 0.098 (2) | |
H31 | 0.0912 | −0.2828 | 0.4921 | 0.117* | |
C32 | 0.1851 (7) | −0.0585 (7) | 0.6024 (5) | 0.0731 (14) | |
H32 | 0.2106 | −0.1098 | 0.6588 | 0.088* | |
N1 | 0.6607 (5) | 0.2105 (5) | 0.7986 (3) | 0.0565 (10) | |
H1 | 0.7535 | 0.1688 | 0.7972 | 0.068* | |
N2 | 0.0568 (10) | 0.1652 (16) | 0.3455 (6) | 0.128 (3) | |
O1 | 0.0167 (4) | 0.1171 (4) | 0.8359 (2) | 0.0587 (8) | |
O2 | 0.1918 (5) | −0.0024 (5) | 0.9338 (3) | 0.0745 (10) | |
O3 | 0.3392 (5) | 0.5796 (4) | 0.6805 (3) | 0.0800 (11) | |
O4 | 0.6662 (4) | 0.6790 (4) | 0.7062 (3) | 0.0647 (9) | |
O5 | 0.5795 (7) | 0.5867 (5) | 0.5045 (3) | 0.0899 (12) | |
O6 | 0.5427 (6) | 1.1658 (5) | 0.2441 (3) | 0.0836 (11) | |
O7 | 0.0752 (11) | 0.3189 (14) | 0.3632 (6) | 0.162 (3) | |
O8 | 0.0010 (11) | 0.0749 (14) | 0.2595 (5) | 0.183 (3) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.046 (2) | 0.050 (3) | 0.072 (3) | 0.026 (2) | 0.020 (2) | 0.013 (2) |
C2 | 0.044 (2) | 0.052 (3) | 0.069 (3) | 0.026 (2) | 0.018 (2) | 0.018 (2) |
C3 | 0.038 (2) | 0.064 (3) | 0.075 (3) | 0.034 (2) | 0.020 (2) | 0.021 (2) |
C4 | 0.039 (2) | 0.047 (2) | 0.065 (3) | 0.0227 (18) | 0.0138 (19) | 0.011 (2) |
C5 | 0.048 (2) | 0.055 (3) | 0.077 (3) | 0.030 (2) | 0.021 (2) | 0.020 (2) |
C6 | 0.063 (3) | 0.087 (4) | 0.119 (5) | 0.049 (3) | 0.030 (3) | 0.049 (3) |
C7 | 0.052 (3) | 0.068 (3) | 0.124 (5) | 0.030 (2) | 0.032 (3) | 0.031 (3) |
C8 | 0.043 (2) | 0.046 (2) | 0.063 (3) | 0.0201 (19) | 0.009 (2) | 0.012 (2) |
C9 | 0.067 (3) | 0.088 (4) | 0.100 (4) | 0.040 (3) | 0.033 (3) | 0.047 (3) |
C10 | 0.115 (5) | 0.124 (6) | 0.121 (6) | 0.058 (5) | 0.035 (4) | 0.065 (5) |
C11 | 0.053 (3) | 0.057 (3) | 0.071 (3) | 0.031 (2) | 0.021 (2) | 0.016 (2) |
C12 | 0.055 (3) | 0.040 (2) | 0.093 (4) | 0.019 (2) | 0.015 (2) | 0.017 (2) |
C13 | 0.053 (3) | 0.045 (3) | 0.075 (3) | 0.018 (2) | 0.017 (2) | 0.005 (2) |
C14 | 0.056 (3) | 0.041 (2) | 0.077 (3) | 0.022 (2) | 0.018 (2) | 0.009 (2) |
C15 | 0.059 (3) | 0.046 (3) | 0.071 (3) | 0.016 (2) | 0.019 (2) | 0.009 (2) |
C16 | 0.069 (3) | 0.042 (2) | 0.075 (4) | 0.021 (2) | 0.019 (3) | 0.010 (3) |
C17 | 0.074 (3) | 0.061 (3) | 0.070 (4) | 0.034 (2) | 0.016 (3) | 0.015 (3) |
C18 | 0.125 (5) | 0.067 (3) | 0.071 (4) | 0.052 (3) | 0.011 (3) | −0.001 (3) |
C19 | 0.116 (5) | 0.053 (3) | 0.076 (4) | 0.046 (3) | 0.005 (3) | 0.000 (3) |
C20 | 0.122 (5) | 0.058 (3) | 0.087 (4) | 0.034 (3) | 0.021 (3) | 0.014 (3) |
C21 | 0.115 (5) | 0.047 (3) | 0.070 (4) | 0.020 (3) | 0.019 (4) | 0.009 (3) |
C22 | 0.119 (5) | 0.112 (6) | 0.093 (5) | 0.023 (4) | 0.037 (4) | 0.022 (4) |
C23 | 0.178 (9) | 0.099 (6) | 0.083 (6) | −0.012 (6) | 0.047 (6) | 0.019 (4) |
C24 | 0.174 (9) | 0.066 (4) | 0.089 (5) | 0.023 (5) | 0.021 (6) | 0.017 (4) |
C25 | 0.142 (6) | 0.078 (4) | 0.102 (5) | 0.056 (4) | 0.014 (5) | 0.008 (4) |
C26 | 0.133 (6) | 0.073 (4) | 0.088 (5) | 0.051 (4) | 0.035 (4) | 0.024 (3) |
C27 | 0.032 (2) | 0.078 (3) | 0.064 (3) | 0.020 (2) | 0.0151 (19) | 0.010 (3) |
C28 | 0.046 (3) | 0.109 (4) | 0.073 (4) | 0.022 (3) | 0.020 (3) | 0.028 (3) |
C29 | 0.054 (3) | 0.142 (7) | 0.070 (5) | 0.019 (4) | 0.019 (3) | 0.019 (5) |
C30 | 0.059 (4) | 0.161 (9) | 0.079 (5) | 0.017 (5) | 0.012 (3) | −0.018 (5) |
C31 | 0.066 (4) | 0.098 (5) | 0.105 (6) | 0.021 (3) | 0.013 (4) | −0.024 (5) |
C32 | 0.054 (3) | 0.073 (4) | 0.089 (4) | 0.026 (3) | 0.015 (3) | 0.003 (3) |
N1 | 0.044 (2) | 0.053 (2) | 0.088 (3) | 0.0314 (17) | 0.0222 (19) | 0.021 (2) |
N2 | 0.086 (4) | 0.201 (9) | 0.078 (5) | 0.020 (5) | 0.026 (4) | 0.042 (6) |
O1 | 0.0424 (17) | 0.068 (2) | 0.078 (2) | 0.0295 (15) | 0.0182 (14) | 0.0267 (17) |
O2 | 0.060 (2) | 0.095 (3) | 0.100 (3) | 0.0494 (19) | 0.0328 (18) | 0.055 (2) |
O3 | 0.065 (2) | 0.071 (2) | 0.134 (3) | 0.0450 (19) | 0.039 (2) | 0.047 (2) |
O4 | 0.0558 (19) | 0.0481 (19) | 0.090 (2) | 0.0204 (15) | 0.0090 (16) | 0.0197 (17) |
O5 | 0.134 (3) | 0.043 (2) | 0.095 (3) | 0.036 (2) | 0.029 (2) | 0.0092 (19) |
O6 | 0.122 (3) | 0.056 (2) | 0.076 (2) | 0.041 (2) | 0.017 (2) | 0.0108 (19) |
O7 | 0.133 (5) | 0.211 (8) | 0.117 (5) | 0.023 (6) | 0.004 (4) | 0.086 (6) |
O8 | 0.159 (6) | 0.289 (10) | 0.069 (4) | 0.050 (6) | 0.022 (3) | 0.024 (5) |
C1—C2 | 1.343 (5) | C15—H15 | 0.9300 |
C1—N1 | 1.386 (6) | C16—C17 | 1.376 (7) |
C1—C7 | 1.502 (7) | C16—H16 | 0.9300 |
C2—C11 | 1.481 (6) | C17—O6 | 1.350 (6) |
C2—C3 | 1.511 (6) | C17—C18 | 1.407 (7) |
C3—C4 | 1.507 (6) | C18—C19 | 1.363 (8) |
C3—C27 | 1.525 (7) | C18—H18 | 0.9300 |
C3—H3 | 0.9800 | C19—H19 | 0.9300 |
C4—C5 | 1.354 (5) | C20—O6 | 1.434 (6) |
C4—C8 | 1.454 (6) | C20—C21 | 1.510 (9) |
C5—N1 | 1.372 (6) | C20—H20A | 0.9700 |
C5—C6 | 1.501 (6) | C20—H20B | 0.9700 |
C6—H6A | 0.9600 | C21—C22 | 1.355 (9) |
C6—H6B | 0.9600 | C21—C26 | 1.369 (9) |
C6—H6C | 0.9600 | C22—C23 | 1.423 (12) |
C7—H7A | 0.9600 | C22—H22 | 0.9300 |
C7—H7B | 0.9600 | C23—C24 | 1.341 (13) |
C7—H7C | 0.9600 | C23—H23 | 0.9300 |
C8—O1 | 1.209 (4) | C24—C25 | 1.347 (11) |
C8—O2 | 1.328 (5) | C24—H24 | 0.9300 |
C9—O2 | 1.440 (6) | C25—C26 | 1.368 (10) |
C9—C10 | 1.468 (8) | C25—H25 | 0.9300 |
C9—H9A | 0.9700 | C26—H26 | 0.9300 |
C9—H9B | 0.9700 | C27—C28 | 1.383 (7) |
C10—H10A | 0.9600 | C27—C32 | 1.398 (7) |
C10—H10B | 0.9600 | C28—C29 | 1.360 (9) |
C10—H10C | 0.9600 | C28—H28 | 0.9300 |
C11—O3 | 1.191 (5) | C29—C30 | 1.370 (11) |
C11—O4 | 1.337 (5) | C29—N2 | 1.466 (10) |
C12—O4 | 1.429 (5) | C30—C31 | 1.382 (11) |
C12—C13 | 1.501 (7) | C30—H30 | 0.9300 |
C12—H12A | 0.9700 | C31—C32 | 1.384 (9) |
C12—H12B | 0.9700 | C31—H31 | 0.9300 |
C13—O5 | 1.211 (5) | C32—H32 | 0.9300 |
C13—C14 | 1.467 (7) | N1—H1 | 0.8600 |
C14—C19 | 1.381 (7) | N2—O8 | 1.195 (10) |
C14—C15 | 1.390 (6) | N2—O7 | 1.203 (11) |
C15—C16 | 1.380 (7) | ||
C2—C1—N1 | 117.2 (4) | C17—C16—C15 | 120.3 (4) |
C2—C1—C7 | 129.1 (4) | C17—C16—H16 | 119.9 |
N1—C1—C7 | 113.8 (4) | C15—C16—H16 | 119.9 |
C1—C2—C11 | 124.9 (4) | O6—C17—C16 | 126.6 (4) |
C1—C2—C3 | 119.1 (4) | O6—C17—C18 | 114.5 (5) |
C11—C2—C3 | 115.9 (3) | C16—C17—C18 | 118.9 (5) |
C4—C3—C2 | 109.4 (3) | C19—C18—C17 | 119.6 (5) |
C4—C3—C27 | 113.0 (4) | C19—C18—H18 | 120.2 |
C2—C3—C27 | 111.7 (4) | C17—C18—H18 | 120.2 |
C4—C3—H3 | 107.5 | C18—C19—C14 | 122.3 (5) |
C2—C3—H3 | 107.5 | C18—C19—H19 | 118.9 |
C27—C3—H3 | 107.5 | C14—C19—H19 | 118.9 |
C5—C4—C8 | 125.0 (4) | O6—C20—C21 | 106.6 (5) |
C5—C4—C3 | 118.7 (4) | O6—C20—H20A | 110.4 |
C8—C4—C3 | 116.4 (3) | C21—C20—H20A | 110.4 |
C4—C5—N1 | 118.0 (4) | O6—C20—H20B | 110.4 |
C4—C5—C6 | 128.4 (4) | C21—C20—H20B | 110.4 |
N1—C5—C6 | 113.6 (4) | H20A—C20—H20B | 108.6 |
C5—C6—H6A | 109.5 | C22—C21—C26 | 119.4 (7) |
C5—C6—H6B | 109.5 | C22—C21—C20 | 121.4 (7) |
H6A—C6—H6B | 109.5 | C26—C21—C20 | 119.2 (6) |
C5—C6—H6C | 109.5 | C21—C22—C23 | 119.2 (8) |
H6A—C6—H6C | 109.5 | C21—C22—H22 | 120.4 |
H6B—C6—H6C | 109.5 | C23—C22—H22 | 120.4 |
C1—C7—H7A | 109.5 | C24—C23—C22 | 119.3 (8) |
C1—C7—H7B | 109.5 | C24—C23—H23 | 120.4 |
H7A—C7—H7B | 109.5 | C22—C23—H23 | 120.4 |
C1—C7—H7C | 109.5 | C23—C24—C25 | 121.5 (8) |
H7A—C7—H7C | 109.5 | C23—C24—H24 | 119.3 |
H7B—C7—H7C | 109.5 | C25—C24—H24 | 119.3 |
O1—C8—O2 | 121.5 (4) | C24—C25—C26 | 119.5 (8) |
O1—C8—C4 | 123.3 (4) | C24—C25—H25 | 120.3 |
O2—C8—C4 | 115.3 (3) | C26—C25—H25 | 120.3 |
O2—C9—C10 | 107.6 (5) | C25—C26—C21 | 121.2 (7) |
O2—C9—H9A | 110.2 | C25—C26—H26 | 119.4 |
C10—C9—H9A | 110.2 | C21—C26—H26 | 119.4 |
O2—C9—H9B | 110.2 | C28—C27—C32 | 117.5 (5) |
C10—C9—H9B | 110.2 | C28—C27—C3 | 119.2 (5) |
H9A—C9—H9B | 108.5 | C32—C27—C3 | 123.3 (4) |
C9—C10—H10A | 109.5 | C29—C28—C27 | 121.3 (6) |
C9—C10—H10B | 109.5 | C29—C28—H28 | 119.4 |
H10A—C10—H10B | 109.5 | C27—C28—H28 | 119.4 |
C9—C10—H10C | 109.5 | C28—C29—C30 | 121.6 (7) |
H10A—C10—H10C | 109.5 | C28—C29—N2 | 120.3 (8) |
H10B—C10—H10C | 109.5 | C30—C29—N2 | 118.1 (8) |
O3—C11—O4 | 122.4 (4) | C29—C30—C31 | 118.4 (7) |
O3—C11—C2 | 123.3 (4) | C29—C30—H30 | 120.8 |
O4—C11—C2 | 114.3 (3) | C31—C30—H30 | 120.8 |
O4—C12—C13 | 110.2 (4) | C30—C31—C32 | 120.5 (7) |
O4—C12—H12A | 109.6 | C30—C31—H31 | 119.7 |
C13—C12—H12A | 109.6 | C32—C31—H31 | 119.7 |
O4—C12—H12B | 109.6 | C31—C32—C27 | 120.6 (6) |
C13—C12—H12B | 109.6 | C31—C32—H32 | 119.7 |
H12A—C12—H12B | 108.1 | C27—C32—H32 | 119.7 |
O5—C13—C14 | 122.7 (5) | C5—N1—C1 | 123.2 (3) |
O5—C13—C12 | 118.8 (4) | C5—N1—H1 | 118.4 |
C14—C13—C12 | 118.5 (4) | C1—N1—H1 | 118.4 |
C19—C14—C15 | 117.6 (4) | O8—N2—O7 | 123.0 (10) |
C19—C14—C13 | 118.8 (4) | O8—N2—C29 | 119.9 (11) |
C15—C14—C13 | 123.6 (4) | O7—N2—C29 | 117.0 (9) |
C16—C15—C14 | 121.3 (5) | C8—O2—C9 | 118.1 (3) |
C16—C15—H15 | 119.3 | C11—O4—C12 | 114.9 (3) |
C14—C15—H15 | 119.3 | C17—O6—C20 | 117.7 (4) |
N1—C1—C2—C11 | 169.2 (5) | O6—C20—C21—C26 | 90.2 (8) |
C7—C1—C2—C11 | −10.9 (10) | C26—C21—C22—C23 | 1.6 (13) |
N1—C1—C2—C3 | −12.7 (8) | C20—C21—C22—C23 | −178.5 (7) |
C7—C1—C2—C3 | 167.3 (6) | C21—C22—C23—C24 | −1.8 (15) |
C1—C2—C3—C4 | 37.5 (7) | C22—C23—C24—C25 | 0.9 (15) |
C11—C2—C3—C4 | −144.2 (4) | C23—C24—C25—C26 | 0.1 (14) |
C1—C2—C3—C27 | −88.2 (6) | C22—C21—C26—C25 | −0.6 (11) |
C11—C2—C3—C27 | 90.2 (5) | C20—C21—C26—C25 | 179.6 (7) |
C2—C3—C4—C5 | −34.7 (7) | C24—C25—C26—C21 | −0.3 (12) |
C27—C3—C4—C5 | 90.4 (6) | C4—C3—C27—C28 | 175.7 (4) |
C2—C3—C4—C8 | 145.3 (4) | C2—C3—C27—C28 | −60.5 (5) |
C27—C3—C4—C8 | −89.6 (5) | C4—C3—C27—C32 | −5.1 (6) |
C8—C4—C5—N1 | −172.5 (5) | C2—C3—C27—C32 | 118.6 (5) |
C3—C4—C5—N1 | 7.5 (8) | C32—C27—C28—C29 | −1.5 (8) |
C8—C4—C5—C6 | 8.7 (9) | C3—C27—C28—C29 | 177.7 (5) |
C3—C4—C5—C6 | −171.3 (6) | C27—C28—C29—C30 | 0.7 (10) |
C5—C4—C8—O1 | 177.0 (6) | C27—C28—C29—N2 | 179.9 (6) |
C3—C4—C8—O1 | −3.0 (7) | C28—C29—C30—C31 | 0.2 (11) |
C5—C4—C8—O2 | −2.5 (8) | N2—C29—C30—C31 | −179.0 (7) |
C3—C4—C8—O2 | 177.5 (5) | C29—C30—C31—C32 | −0.1 (11) |
C1—C2—C11—O3 | −179.9 (6) | C30—C31—C32—C27 | −0.7 (10) |
C3—C2—C11—O3 | 1.9 (8) | C28—C27—C32—C31 | 1.5 (8) |
C1—C2—C11—O4 | −0.6 (8) | C3—C27—C32—C31 | −177.6 (6) |
C3—C2—C11—O4 | −178.8 (5) | C4—C5—N1—C1 | 22.3 (8) |
O4—C12—C13—O5 | 1.0 (7) | C6—C5—N1—C1 | −158.7 (6) |
O4—C12—C13—C14 | −179.2 (4) | C2—C1—N1—C5 | −19.6 (8) |
O5—C13—C14—C19 | 1.0 (9) | C7—C1—N1—C5 | 160.5 (6) |
C12—C13—C14—C19 | −178.6 (5) | C28—C29—N2—O7 | −3.1 (13) |
O5—C13—C14—C15 | −177.5 (6) | C30—C29—N2—O7 | 176.1 (10) |
C12—C13—C14—C15 | 2.8 (8) | C28—C29—N2—O8 | 176.7 (8) |
C19—C14—C15—C16 | 1.4 (8) | C30—C29—N2—O8 | −4.1 (12) |
C13—C14—C15—C16 | 180.0 (5) | O1—C8—O2—C9 | −3.0 (8) |
C14—C15—C16—C17 | −2.1 (8) | C4—C8—O2—C9 | 176.5 (5) |
C15—C16—C17—O6 | 179.8 (6) | C10—C9—O2—C8 | −177.6 (7) |
C15—C16—C17—C18 | 1.5 (9) | O3—C11—O4—C12 | −19.1 (8) |
O6—C17—C18—C19 | −178.8 (7) | C2—C11—O4—C12 | 161.6 (5) |
C16—C17—C18—C19 | −0.3 (11) | C13—C12—O4—C11 | −73.8 (6) |
C17—C18—C19—C14 | −0.4 (12) | C16—C17—O6—C20 | 1.9 (10) |
C15—C14—C19—C18 | −0.2 (10) | C18—C17—O6—C20 | −179.8 (7) |
C13—C14—C19—C18 | −178.8 (7) | C21—C20—O6—C17 | −173.0 (6) |
O6—C20—C21—C22 | −89.7 (9) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O1i | 0.86 | 2.11 | 2.940 (5) | 163 |
Symmetry code: (i) x+1, y, z. |
Experimental details
Crystal data | |
Chemical formula | C32H30N2O8 |
Mr | 570.58 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 295 |
a, b, c (Å) | 7.3646 (7), 8.1772 (8), 13.329 (1) |
α, β, γ (°) | 97.905 (2), 100.352 (2), 109.296 (2) |
V (Å3) | 728.33 (12) |
Z | 1 |
Radiation type | Mo Kα |
µ (mm−1) | 0.09 |
Crystal size (mm) | 0.46 × 0.28 × 0.16 |
Data collection | |
Diffractometer | Bruker SMART 1000 CCD diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 5566, 2808, 1747 |
Rint | 0.030 |
(sin θ/λ)max (Å−1) | 0.617 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.045, 0.144, 1.02 |
No. of reflections | 2808 |
No. of parameters | 382 |
No. of restraints | 3 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.21, −0.21 |
Computer programs: SMART (Bruker, 2001), SAINT-Plus (Bruker, 2003), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 1997).
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O1i | 0.86 | 2.11 | 2.940 (5) | 163 |
Symmetry code: (i) x+1, y, z. |
1,4-dihydropyridine derivatives have been widely investigated from the pharmacological point of view since Nifedipine was found to be highly effective calcium antagonist in 1975, and many compounds similar to Nifedipine in structure have already been widely used as therapeutic agents for the treatment of cerebra circulatory disorder, hypertension and so on (Goldmann & Stoltefuss 1991). According to the structure–activity relationship of 1,4-dihydropyridine calcium antagonists, a serials of new compounds were designed and synthesized (Wu et al., 2006). The optical active title compound has been synthesized by the reaction of optical active 1,4-dihydropyridine monoester with a\-bromoalkylaryl ketone under mild conditions.
The 1,4-dihydropyridne (DHP) ring has a flattened boat conformation, N1 and C3 deviating from the mean plane by -0.185 (4) Å and -0.247 (5) Å, respectively. The dihedral angle found between plane C1/C2/C4/C5 and C2/C3/C4, C1/N1/N5 are 31.1° and 18.4°, respectively. Both the 3-nitrophenyl ring (C27–C32) and the DHP ring (N1, C1, C2, C3, C4, C5) are almost perpendicular to each other, the dihedral angle found between them is 80.8 (3)°. The phenyl rings C14/C15/C16/C17/C18/C19 and C21/C22/C23/C24/C25/C26 are almost perpendicular to each other, too, the dihedral angle found between them is 87.5 (3)°. The structure has intermolecular hydrogen bonds of the type N—H···O between the amine of one molecule and the carbonyl oxygen of neighbouring molecule.