In the title compound, C
34H
34N
4O
11·C
4H
8O
2, the dihydropyridine rings display envelope configuration. The solvent molecule links to the anhydride
via weak C—H
O hydrogen bonding.
Supporting information
CCDC reference: 296732
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (C-C) = 0.005 Å
- R factor = 0.065
- wR factor = 0.206
- Data-to-parameter ratio = 13.8
checkCIF/PLATON results
No syntax errors found
Alert level C
PLAT199_ALERT_1_C Check the Reported _cell_measurement_temperature 293 K
PLAT200_ALERT_1_C Check the Reported _diffrn_ambient_temperature . 293 K
PLAT220_ALERT_2_C Large Non-Solvent C Ueq(max)/Ueq(min) ... 2.94 Ratio
PLAT220_ALERT_2_C Large Non-Solvent O Ueq(max)/Ueq(min) ... 2.97 Ratio
PLAT222_ALERT_3_C Large Non-Solvent H Ueq(max)/Ueq(min) ... 3.45 Ratio
PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for N2
PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for N4
PLAT244_ALERT_4_C Low 'Solvent' Ueq as Compared to Neighbors for C36
PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor .... 2.19
PLAT340_ALERT_3_C Low Bond Precision on C-C bonds (x 1000) Ang ... 5
PLAT360_ALERT_2_C Short C(sp3)-C(sp3) Bond C37 - C38 ... 1.35 Ang.
0 ALERT level A = In general: serious problem
0 ALERT level B = Potentially serious problem
11 ALERT level C = Check and explain
0 ALERT level G = General alerts; check
2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
6 ALERT type 2 Indicator that the structure model may be wrong or deficient
2 ALERT type 3 Indicator that the structure quality may be low
1 ALERT type 4 Improvement, methodology, query or suggestion
5-Ethoxycarbonyl-2,6-dimethyl-4-(3-nitrophenyl)-1,4-dihydropyridine- 3-carboxylic acid (0.45 g, 1 mmol) was dissolved in CH2Cl2 (30 ml), and dicyclohexylcarbodiimide (0.21 g, 1 mmol) in CH2Cl2 (10 ml) was dropped into the above solution at 278 K. The reaction mixture was stirred at 276–279 K for 4 h. The solvent CH2Cl2 was removed by vacuum evaporation at 293 K. The destination compound was purified by chromatography on a silica gel column (eluted by ethyl acetate and petroleum, 3:7) at room temperature. The product (0.41 g) was obtained in a yield of 94%. Recrystallization from a dichloromethane/ethyl acetate solution gave single crystals of (I).
Methyl H atoms were placed in calculated positions with C—H = 0.96 Å and torsion refined to fit the electron density with Uiso(H) = 1.5Ueq(C). Other H atoms were placed in calculated positions with C—H = 0.93–0.98 Å and N—H = 0.86 Å, and constrained to ride on their parent atoms with Uiso(H) = 1.2Ueq(carrier).
Data collection: PROCESS-AUTO (Rigaku, 1998); cell refinement: PROCESS-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2002); software used to prepare material for publication: SHELXTL.
5-Ethoxycarbonyl-2,6-dimethyl-4-(3-nitrophenyl)-1,4-dihydro-pyridine- 3-carboxylic anhydride ethyl acetate solvate
top
Crystal data top
C34H34N4O11·C4H8O2 | Z = 2 |
Mr = 762.76 | F(000) = 804 |
Triclinic, P1 | Dx = 1.342 Mg m−3 |
Hall symbol: -P 1 | Melting point = 450–451 K |
a = 10.896 (2) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 12.017 (2) Å | Cell parameters from 15558 reflections |
c = 16.162 (3) Å | θ = 3.2–25.5° |
α = 99.59 (3)° | µ = 0.10 mm−1 |
β = 106.29 (3)° | T = 293 K |
γ = 105.69 (3)° | Block, yellow |
V = 1887.1 (9) Å3 | 0.28 × 0.22 × 0.10 mm |
Data collection top
Rigaku R-AXIS RAPID diffractometer | 4362 reflections with I > 2σ(I) |
Radiation source: rotating anode | Rint = 0.038 |
Graphite monochromator | θmax = 25.5°, θmin = 3.2° |
ω scans | h = −13→13 |
18422 measured reflections | k = −14→14 |
6953 independent reflections | l = −19→19 |
Refinement top
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.065 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.206 | H-atom parameters constrained |
S = 1.08 | w = 1/[σ2(Fo2) + (0.1184P)2] where P = (Fo2 + 2Fc2)/3 |
6953 reflections | (Δ/σ)max = 0.001 |
504 parameters | Δρmax = 0.57 e Å−3 |
0 restraints | Δρmin = −0.45 e Å−3 |
Crystal data top
C34H34N4O11·C4H8O2 | γ = 105.69 (3)° |
Mr = 762.76 | V = 1887.1 (9) Å3 |
Triclinic, P1 | Z = 2 |
a = 10.896 (2) Å | Mo Kα radiation |
b = 12.017 (2) Å | µ = 0.10 mm−1 |
c = 16.162 (3) Å | T = 293 K |
α = 99.59 (3)° | 0.28 × 0.22 × 0.10 mm |
β = 106.29 (3)° | |
Data collection top
Rigaku R-AXIS RAPID diffractometer | 4362 reflections with I > 2σ(I) |
18422 measured reflections | Rint = 0.038 |
6953 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.065 | 0 restraints |
wR(F2) = 0.206 | H-atom parameters constrained |
S = 1.08 | Δρmax = 0.57 e Å−3 |
6953 reflections | Δρmin = −0.45 e Å−3 |
504 parameters | |
Special details top
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
O1 | 0.3869 (2) | 0.50900 (18) | 0.11858 (13) | 0.0586 (5) | |
O2 | 0.5820 (3) | 0.6080 (3) | 0.10492 (19) | 0.0967 (9) | |
O3 | 0.1157 (3) | 0.4971 (3) | 0.4347 (2) | 0.1420 (15) | |
O4 | 0.0521 (3) | 0.4272 (3) | 0.2952 (2) | 0.0983 (9) | |
O5 | 0.4989 (2) | 0.1678 (2) | 0.36098 (16) | 0.0705 (6) | |
O6 | 0.33349 (17) | 0.17678 (15) | 0.24507 (12) | 0.0479 (4) | |
O7 | 0.2374 (2) | 0.18901 (19) | 0.35081 (13) | 0.0681 (6) | |
O8 | 0.6393 (3) | −0.1781 (3) | 0.2608 (2) | 0.1137 (11) | |
O9 | 0.6059 (3) | −0.0693 (3) | 0.1715 (2) | 0.1117 (11) | |
O10 | −0.0790 (2) | −0.2303 (2) | −0.08999 (14) | 0.0800 (7) | |
O11 | 0.1436 (2) | −0.14129 (18) | −0.02035 (12) | 0.0632 (6) | |
O12 | 0.0855 (5) | 0.7276 (5) | 0.3950 (3) | 0.184 (2) | |
O13 | 0.1371 (4) | 0.9037 (3) | 0.4833 (3) | 0.1408 (14) | |
N1 | 0.7668 (2) | 0.4367 (2) | 0.29037 (17) | 0.0590 (6) | |
H1D | 0.8535 | 0.4587 | 0.3153 | 0.071* | |
N2 | 0.1399 (3) | 0.4761 (2) | 0.3657 (2) | 0.0704 (8) | |
N3 | −0.1162 (2) | −0.0783 (2) | 0.15706 (15) | 0.0537 (6) | |
H3A | −0.1905 | −0.1024 | 0.1679 | 0.064* | |
N4 | 0.5678 (3) | −0.1315 (3) | 0.2177 (2) | 0.0774 (8) | |
C1 | 0.1708 (4) | 0.5116 (4) | 0.0361 (3) | 0.0974 (13) | |
H1A | 0.1228 | 0.5443 | −0.0074 | 0.146* | |
H1B | 0.1555 | 0.5340 | 0.0912 | 0.146* | |
H1C | 0.1388 | 0.4258 | 0.0148 | 0.146* | |
C2 | 0.3182 (4) | 0.5589 (3) | 0.0511 (2) | 0.0726 (9) | |
H2A | 0.3351 | 0.5356 | −0.0040 | 0.087* | |
H2B | 0.3513 | 0.6457 | 0.0714 | 0.087* | |
C3 | 0.5221 (3) | 0.5391 (3) | 0.13875 (19) | 0.0585 (7) | |
C4 | 0.5810 (3) | 0.4801 (2) | 0.20378 (17) | 0.0481 (6) | |
C5 | 0.7152 (3) | 0.4987 (3) | 0.23253 (19) | 0.0537 (7) | |
C6 | 0.8237 (3) | 0.5814 (3) | 0.2086 (2) | 0.0793 (10) | |
H6A | 0.7884 | 0.6369 | 0.1817 | 0.119* | |
H6B | 0.8508 | 0.5352 | 0.1671 | 0.119* | |
H6C | 0.9007 | 0.6248 | 0.2616 | 0.119* | |
C7 | 0.6882 (3) | 0.3422 (2) | 0.31032 (18) | 0.0487 (6) | |
C8 | 0.7672 (3) | 0.2741 (3) | 0.3592 (2) | 0.0679 (9) | |
H8A | 0.7104 | 0.1922 | 0.3456 | 0.102* | |
H8B | 0.7974 | 0.3094 | 0.4224 | 0.102* | |
H8C | 0.8444 | 0.2771 | 0.3410 | 0.102* | |
C9 | 0.5518 (2) | 0.3174 (2) | 0.28333 (17) | 0.0420 (6) | |
C10 | 0.4863 (2) | 0.4002 (2) | 0.24045 (16) | 0.0399 (5) | |
H10A | 0.4033 | 0.3508 | 0.1906 | 0.048* | |
C11 | 0.4469 (2) | 0.4729 (2) | 0.30959 (15) | 0.0367 (5) | |
C12 | 0.3119 (2) | 0.4478 (2) | 0.30282 (17) | 0.0407 (6) | |
H12A | 0.2429 | 0.3920 | 0.2534 | 0.049* | |
C13 | 0.2829 (3) | 0.5081 (2) | 0.37171 (18) | 0.0462 (6) | |
C14 | 0.3790 (3) | 0.5935 (2) | 0.44488 (19) | 0.0519 (7) | |
H14A | 0.3549 | 0.6322 | 0.4895 | 0.062* | |
C15 | 0.5130 (3) | 0.6205 (2) | 0.45048 (18) | 0.0509 (6) | |
H15A | 0.5809 | 0.6793 | 0.4987 | 0.061* | |
C16 | 0.5456 (3) | 0.5593 (2) | 0.38350 (17) | 0.0445 (6) | |
H16A | 0.6362 | 0.5769 | 0.3884 | 0.053* | |
C17 | 0.4665 (3) | 0.2170 (2) | 0.30386 (18) | 0.0466 (6) | |
C18 | 0.2275 (3) | 0.1374 (2) | 0.27749 (18) | 0.0459 (6) | |
C19 | 0.1148 (2) | 0.0392 (2) | 0.21225 (16) | 0.0399 (6) | |
C20 | −0.0079 (3) | 0.0098 (2) | 0.22210 (18) | 0.0484 (6) | |
C21 | −0.0416 (3) | 0.0664 (3) | 0.2993 (2) | 0.0715 (9) | |
H21A | 0.0018 | 0.1517 | 0.3153 | 0.107* | |
H21B | −0.0099 | 0.0358 | 0.3494 | 0.107* | |
H21C | −0.1381 | 0.0479 | 0.2824 | 0.107* | |
C22 | −0.1134 (3) | −0.1310 (2) | 0.07489 (17) | 0.0454 (6) | |
C23 | −0.2531 (3) | −0.2037 (3) | 0.0100 (2) | 0.0646 (8) | |
H23A | −0.2473 | −0.2664 | −0.0326 | 0.097* | |
H23B | −0.2920 | −0.1529 | −0.0207 | 0.097* | |
H23C | −0.3093 | −0.2384 | 0.0418 | 0.097* | |
C24 | 0.0062 (3) | −0.1113 (2) | 0.06206 (16) | 0.0423 (6) | |
C25 | 0.0137 (3) | −0.1674 (2) | −0.02374 (18) | 0.0510 (6) | |
C26 | 0.1673 (4) | −0.2005 (4) | −0.0973 (2) | 0.0832 (11) | |
H26A | 0.1314 | −0.1720 | −0.1486 | 0.100* | |
H26B | 0.1222 | −0.2863 | −0.1120 | 0.100* | |
C27 | 0.3136 (5) | −0.1735 (5) | −0.0755 (3) | 0.1079 (15) | |
H27A | 0.3317 | −0.2068 | −0.1272 | 0.162* | |
H27B | 0.3470 | −0.2078 | −0.0280 | 0.162* | |
H27C | 0.3581 | −0.0883 | −0.0569 | 0.162* | |
C28 | 0.1392 (2) | −0.0350 (2) | 0.13605 (16) | 0.0389 (5) | |
H28A | 0.1930 | 0.0201 | 0.1110 | 0.047* | |
C29 | 0.2221 (2) | −0.1100 (2) | 0.17451 (15) | 0.0386 (5) | |
C30 | 0.3545 (3) | −0.0891 (2) | 0.17608 (17) | 0.0462 (6) | |
H30A | 0.3932 | −0.0322 | 0.1499 | 0.055* | |
C31 | 0.4280 (3) | −0.1543 (3) | 0.2171 (2) | 0.0553 (7) | |
C32 | 0.3777 (4) | −0.2385 (3) | 0.2573 (2) | 0.0687 (9) | |
H32A | 0.4306 | −0.2793 | 0.2859 | 0.082* | |
C33 | 0.2447 (4) | −0.2606 (3) | 0.2539 (3) | 0.0746 (10) | |
H33A | 0.2062 | −0.3190 | 0.2790 | 0.090* | |
C34 | 0.1692 (3) | −0.1971 (3) | 0.2137 (2) | 0.0576 (7) | |
H34A | 0.0803 | −0.2129 | 0.2126 | 0.069* | |
C35 | −0.0780 (5) | 0.7699 (6) | 0.4520 (4) | 0.147 (2) | |
H35A | −0.1023 | 0.8398 | 0.4664 | 0.220* | |
H35B | −0.0710 | 0.7322 | 0.5002 | 0.220* | |
H35C | −0.1464 | 0.7149 | 0.3985 | 0.220* | |
C36 | 0.0499 (6) | 0.8038 (5) | 0.4382 (3) | 0.1156 (16) | |
C37 | 0.2697 (6) | 0.9385 (6) | 0.4697 (5) | 0.148 (2) | |
H37A | 0.3088 | 0.8754 | 0.4751 | 0.177* | |
H37B | 0.2569 | 0.9494 | 0.4100 | 0.177* | |
C38 | 0.3552 (7) | 1.0415 (6) | 0.5308 (6) | 0.179 (3) | |
H38A | 0.4400 | 1.0643 | 0.5205 | 0.268* | |
H38B | 0.3705 | 1.0296 | 0.5897 | 0.268* | |
H38C | 0.3158 | 1.1036 | 0.5258 | 0.268* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
O1 | 0.0542 (12) | 0.0670 (13) | 0.0531 (11) | 0.0188 (10) | 0.0143 (10) | 0.0219 (10) |
O2 | 0.0763 (17) | 0.119 (2) | 0.0955 (18) | 0.0094 (16) | 0.0328 (16) | 0.0624 (17) |
O3 | 0.092 (2) | 0.170 (3) | 0.148 (3) | 0.011 (2) | 0.085 (2) | −0.022 (2) |
O4 | 0.0395 (13) | 0.135 (2) | 0.101 (2) | 0.0202 (15) | 0.0219 (15) | 0.0007 (18) |
O5 | 0.0540 (13) | 0.0688 (14) | 0.0823 (15) | 0.0167 (11) | 0.0092 (12) | 0.0341 (12) |
O6 | 0.0352 (10) | 0.0439 (10) | 0.0494 (10) | 0.0007 (8) | 0.0077 (8) | 0.0057 (8) |
O7 | 0.0579 (13) | 0.0689 (13) | 0.0547 (12) | 0.0055 (10) | 0.0163 (11) | −0.0115 (10) |
O8 | 0.0691 (18) | 0.144 (3) | 0.141 (3) | 0.067 (2) | 0.0239 (18) | 0.039 (2) |
O9 | 0.0567 (16) | 0.151 (3) | 0.157 (3) | 0.0430 (18) | 0.057 (2) | 0.068 (2) |
O10 | 0.0725 (16) | 0.0886 (16) | 0.0471 (12) | 0.0048 (13) | 0.0071 (12) | −0.0043 (12) |
O11 | 0.0645 (13) | 0.0777 (14) | 0.0449 (11) | 0.0223 (11) | 0.0232 (10) | 0.0048 (10) |
O12 | 0.165 (4) | 0.187 (4) | 0.163 (4) | 0.025 (3) | 0.074 (4) | −0.023 (3) |
O13 | 0.097 (3) | 0.110 (3) | 0.173 (4) | 0.009 (2) | 0.029 (3) | 0.002 (3) |
N1 | 0.0251 (11) | 0.0760 (16) | 0.0660 (15) | 0.0077 (11) | 0.0129 (11) | 0.0130 (13) |
N2 | 0.0517 (17) | 0.0704 (17) | 0.093 (2) | 0.0197 (14) | 0.0391 (18) | 0.0094 (15) |
N3 | 0.0325 (12) | 0.0622 (14) | 0.0568 (14) | 0.0059 (11) | 0.0161 (11) | 0.0063 (11) |
N4 | 0.0482 (16) | 0.091 (2) | 0.089 (2) | 0.0331 (16) | 0.0164 (16) | 0.0106 (17) |
C1 | 0.081 (3) | 0.128 (4) | 0.093 (3) | 0.050 (3) | 0.020 (2) | 0.048 (3) |
C2 | 0.081 (2) | 0.077 (2) | 0.0582 (19) | 0.0296 (19) | 0.0132 (18) | 0.0244 (16) |
C3 | 0.0543 (18) | 0.0628 (18) | 0.0519 (16) | 0.0078 (15) | 0.0211 (15) | 0.0132 (14) |
C4 | 0.0403 (14) | 0.0511 (15) | 0.0458 (14) | 0.0066 (12) | 0.0172 (13) | 0.0048 (12) |
C5 | 0.0398 (15) | 0.0605 (17) | 0.0502 (16) | 0.0044 (13) | 0.0177 (14) | 0.0037 (13) |
C6 | 0.0493 (19) | 0.104 (3) | 0.069 (2) | −0.0057 (18) | 0.0285 (18) | 0.0182 (19) |
C7 | 0.0378 (14) | 0.0526 (15) | 0.0528 (15) | 0.0158 (12) | 0.0166 (13) | 0.0034 (12) |
C8 | 0.0488 (17) | 0.078 (2) | 0.082 (2) | 0.0343 (17) | 0.0186 (17) | 0.0196 (18) |
C9 | 0.0320 (12) | 0.0417 (13) | 0.0445 (13) | 0.0097 (11) | 0.0108 (11) | −0.0004 (10) |
C10 | 0.0282 (12) | 0.0410 (13) | 0.0408 (13) | 0.0043 (10) | 0.0083 (11) | 0.0039 (10) |
C11 | 0.0321 (12) | 0.0369 (12) | 0.0397 (12) | 0.0103 (10) | 0.0107 (11) | 0.0112 (10) |
C12 | 0.0310 (12) | 0.0372 (13) | 0.0486 (14) | 0.0081 (10) | 0.0101 (11) | 0.0093 (11) |
C13 | 0.0411 (14) | 0.0468 (14) | 0.0598 (16) | 0.0192 (12) | 0.0235 (14) | 0.0195 (12) |
C14 | 0.0594 (18) | 0.0481 (15) | 0.0521 (16) | 0.0216 (14) | 0.0236 (15) | 0.0093 (12) |
C15 | 0.0501 (16) | 0.0476 (15) | 0.0448 (14) | 0.0136 (13) | 0.0082 (13) | 0.0045 (12) |
C16 | 0.0344 (13) | 0.0463 (14) | 0.0488 (14) | 0.0121 (11) | 0.0116 (12) | 0.0094 (11) |
C17 | 0.0406 (14) | 0.0433 (14) | 0.0465 (15) | 0.0127 (12) | 0.0074 (13) | 0.0027 (12) |
C18 | 0.0424 (14) | 0.0423 (14) | 0.0497 (15) | 0.0129 (12) | 0.0161 (13) | 0.0053 (12) |
C19 | 0.0393 (13) | 0.0355 (12) | 0.0429 (13) | 0.0106 (11) | 0.0142 (12) | 0.0083 (10) |
C20 | 0.0395 (14) | 0.0525 (15) | 0.0508 (15) | 0.0149 (12) | 0.0159 (13) | 0.0071 (12) |
C21 | 0.0560 (19) | 0.085 (2) | 0.069 (2) | 0.0208 (17) | 0.0313 (17) | −0.0036 (17) |
C22 | 0.0392 (14) | 0.0384 (13) | 0.0482 (14) | 0.0034 (11) | 0.0091 (12) | 0.0104 (11) |
C23 | 0.0443 (17) | 0.0677 (19) | 0.0605 (18) | 0.0014 (14) | 0.0055 (15) | 0.0124 (15) |
C24 | 0.0419 (14) | 0.0373 (13) | 0.0425 (13) | 0.0083 (11) | 0.0111 (12) | 0.0116 (10) |
C25 | 0.0573 (18) | 0.0441 (15) | 0.0415 (15) | 0.0096 (13) | 0.0107 (14) | 0.0084 (12) |
C26 | 0.108 (3) | 0.104 (3) | 0.0523 (19) | 0.050 (2) | 0.041 (2) | 0.0108 (18) |
C27 | 0.127 (4) | 0.139 (4) | 0.091 (3) | 0.068 (3) | 0.069 (3) | 0.024 (3) |
C28 | 0.0337 (13) | 0.0369 (13) | 0.0415 (13) | 0.0056 (10) | 0.0138 (11) | 0.0068 (10) |
C29 | 0.0383 (13) | 0.0369 (13) | 0.0398 (13) | 0.0098 (11) | 0.0164 (11) | 0.0075 (10) |
C30 | 0.0399 (14) | 0.0468 (14) | 0.0491 (15) | 0.0121 (12) | 0.0167 (13) | 0.0072 (11) |
C31 | 0.0419 (15) | 0.0573 (17) | 0.0642 (18) | 0.0215 (14) | 0.0159 (15) | 0.0056 (14) |
C32 | 0.074 (2) | 0.072 (2) | 0.073 (2) | 0.0427 (19) | 0.0213 (19) | 0.0281 (17) |
C33 | 0.079 (2) | 0.079 (2) | 0.097 (3) | 0.041 (2) | 0.046 (2) | 0.052 (2) |
C34 | 0.0554 (17) | 0.0609 (18) | 0.0729 (19) | 0.0244 (15) | 0.0344 (17) | 0.0308 (15) |
C35 | 0.088 (4) | 0.177 (6) | 0.123 (4) | −0.003 (4) | 0.041 (3) | −0.023 (4) |
C36 | 0.102 (4) | 0.121 (4) | 0.079 (3) | 0.000 (3) | 0.015 (3) | 0.000 (3) |
C37 | 0.112 (5) | 0.128 (5) | 0.154 (5) | −0.001 (4) | 0.032 (4) | 0.004 (4) |
C38 | 0.140 (6) | 0.144 (6) | 0.204 (7) | 0.023 (5) | 0.039 (6) | −0.002 (5) |
Geometric parameters (Å, º) top
O1—C2 | 1.453 (4) | C12—H12A | 0.9300 |
O1—C3 | 1.345 (4) | C13—C14 | 1.367 (4) |
O2—C3 | 1.212 (3) | C14—C15 | 1.379 (4) |
O3—N2 | 1.218 (4) | C14—H14A | 0.9300 |
O4—N2 | 1.192 (4) | C15—C16 | 1.389 (3) |
O5—C17 | 1.199 (3) | C15—H15A | 0.9300 |
O6—C17 | 1.391 (3) | C16—H16A | 0.9300 |
O6—C18 | 1.399 (3) | C18—C19 | 1.445 (4) |
O7—C18 | 1.203 (3) | C19—C20 | 1.350 (3) |
O8—N4 | 1.211 (4) | C19—C28 | 1.526 (3) |
O9—N4 | 1.217 (4) | C20—C21 | 1.504 (4) |
O10—C25 | 1.204 (4) | C21—H21A | 0.9600 |
O11—C25 | 1.347 (3) | C21—H21B | 0.9600 |
O11—C26 | 1.451 (3) | C21—H21C | 0.9600 |
O12—C36 | 1.269 (6) | C22—C24 | 1.341 (3) |
O13—C36 | 1.256 (6) | C22—C23 | 1.504 (4) |
O13—C37 | 1.482 (6) | C23—H23A | 0.9600 |
N1—C7 | 1.370 (3) | C23—H23B | 0.9600 |
N1—C5 | 1.381 (4) | C23—H23C | 0.9600 |
N1—H1D | 0.8600 | C24—C25 | 1.472 (3) |
N2—C13 | 1.471 (4) | C24—C28 | 1.521 (4) |
N3—C20 | 1.369 (4) | C26—C27 | 1.462 (6) |
N3—C22 | 1.385 (3) | C26—H26A | 0.9700 |
N3—H3A | 0.8600 | C26—H26B | 0.9700 |
N4—C31 | 1.469 (4) | C27—H27A | 0.9600 |
C1—C2 | 1.485 (5) | C27—H27B | 0.9600 |
C1—H1A | 0.9600 | C27—H27C | 0.9600 |
C1—H1B | 0.9600 | C28—C29 | 1.526 (3) |
C1—H1C | 0.9600 | C28—H28A | 0.9800 |
C2—H2A | 0.9700 | C29—C30 | 1.388 (3) |
C2—H2B | 0.9700 | C29—C34 | 1.388 (4) |
C3—C4 | 1.461 (4) | C30—C31 | 1.381 (4) |
C4—C5 | 1.347 (4) | C30—H30A | 0.9300 |
C4—C10 | 1.528 (3) | C31—C32 | 1.366 (4) |
C5—C6 | 1.512 (4) | C32—C33 | 1.383 (5) |
C6—H6A | 0.9600 | C32—H32A | 0.9300 |
C6—H6B | 0.9600 | C33—C34 | 1.374 (4) |
C6—H6C | 0.9600 | C33—H33A | 0.9300 |
C7—C9 | 1.356 (4) | C34—H34A | 0.9300 |
C7—C8 | 1.501 (4) | C35—C36 | 1.434 (7) |
C8—H8A | 0.9600 | C35—H35A | 0.9600 |
C8—H8B | 0.9600 | C35—H35B | 0.9600 |
C8—H8C | 0.9600 | C35—H35C | 0.9600 |
C9—C17 | 1.459 (4) | C37—C38 | 1.352 (8) |
C9—C10 | 1.522 (4) | C37—H37A | 0.9700 |
C10—C11 | 1.531 (3) | C37—H37B | 0.9700 |
C10—H10A | 0.9800 | C38—H38A | 0.9600 |
C11—C12 | 1.387 (3) | C38—H38B | 0.9600 |
C11—C16 | 1.387 (4) | C38—H38C | 0.9600 |
C12—C13 | 1.385 (3) | | |
| | | |
C3—O1—C2 | 115.9 (2) | C20—C19—C18 | 120.0 (2) |
C17—O6—C18 | 118.9 (2) | C20—C19—C28 | 120.8 (2) |
C25—O11—C26 | 116.9 (3) | C18—C19—C28 | 119.0 (2) |
C36—O13—C37 | 118.7 (5) | C19—C20—N3 | 119.6 (2) |
C7—N1—C5 | 123.9 (2) | C19—C20—C21 | 126.2 (3) |
C7—N1—H1D | 118.1 | N3—C20—C21 | 114.2 (2) |
C5—N1—H1D | 118.1 | C20—C21—H21A | 109.5 |
O4—N2—O3 | 122.1 (3) | C20—C21—H21B | 109.5 |
O4—N2—C13 | 119.9 (2) | H21A—C21—H21B | 109.5 |
O3—N2—C13 | 118.0 (3) | C20—C21—H21C | 109.5 |
C20—N3—C22 | 124.1 (2) | H21A—C21—H21C | 109.5 |
C20—N3—H3A | 118.0 | H21B—C21—H21C | 109.5 |
C22—N3—H3A | 118.0 | C24—C22—N3 | 119.1 (2) |
O8—N4—O9 | 122.1 (3) | C24—C22—C23 | 128.7 (2) |
O8—N4—C31 | 119.7 (3) | N3—C22—C23 | 112.1 (2) |
O9—N4—C31 | 118.1 (3) | C22—C23—H23A | 109.5 |
C2—C1—H1A | 109.5 | C22—C23—H23B | 109.5 |
C2—C1—H1B | 109.5 | H23A—C23—H23B | 109.5 |
H1A—C1—H1B | 109.5 | C22—C23—H23C | 109.5 |
C2—C1—H1C | 109.5 | H23A—C23—H23C | 109.5 |
H1A—C1—H1C | 109.5 | H23B—C23—H23C | 109.5 |
H1B—C1—H1C | 109.5 | C22—C24—C25 | 120.8 (2) |
O1—C2—C1 | 107.5 (3) | C22—C24—C28 | 121.7 (2) |
O1—C2—H2A | 110.2 | C25—C24—C28 | 117.4 (2) |
C1—C2—H2A | 110.2 | O10—C25—O11 | 121.5 (2) |
O1—C2—H2B | 110.2 | O10—C25—C24 | 127.6 (3) |
C1—C2—H2B | 110.2 | O11—C25—C24 | 110.9 (2) |
H2A—C2—H2B | 108.5 | O11—C26—C27 | 108.3 (3) |
O2—C3—O1 | 121.1 (3) | O11—C26—H26A | 110.0 |
O2—C3—C4 | 127.0 (3) | C27—C26—H26A | 110.0 |
O1—C3—C4 | 111.9 (2) | O11—C26—H26B | 110.0 |
C5—C4—C3 | 120.9 (2) | C27—C26—H26B | 110.0 |
C5—C4—C10 | 121.1 (3) | H26A—C26—H26B | 108.4 |
C3—C4—C10 | 117.9 (2) | C26—C27—H27A | 109.5 |
C4—C5—N1 | 119.6 (2) | C26—C27—H27B | 109.5 |
C4—C5—C6 | 127.8 (3) | H27A—C27—H27B | 109.5 |
N1—C5—C6 | 112.6 (3) | C26—C27—H27C | 109.5 |
C5—C6—H6A | 109.5 | H27A—C27—H27C | 109.5 |
C5—C6—H6B | 109.5 | H27B—C27—H27C | 109.5 |
H6A—C6—H6B | 109.5 | C24—C28—C29 | 112.43 (19) |
C5—C6—H6C | 109.5 | C24—C28—C19 | 111.33 (19) |
H6A—C6—H6C | 109.5 | C29—C28—C19 | 108.39 (19) |
H6B—C6—H6C | 109.5 | C24—C28—H28A | 108.2 |
C9—C7—N1 | 119.3 (3) | C29—C28—H28A | 108.2 |
C9—C7—C8 | 127.0 (3) | C19—C28—H28A | 108.2 |
N1—C7—C8 | 113.7 (2) | C30—C29—C34 | 118.0 (2) |
C7—C8—H8A | 109.5 | C30—C29—C28 | 121.4 (2) |
C7—C8—H8B | 109.5 | C34—C29—C28 | 120.5 (2) |
H8A—C8—H8B | 109.5 | C31—C30—C29 | 118.9 (2) |
C7—C8—H8C | 109.5 | C31—C30—H30A | 120.5 |
H8A—C8—H8C | 109.5 | C29—C30—H30A | 120.5 |
H8B—C8—H8C | 109.5 | C32—C31—C30 | 123.4 (3) |
C7—C9—C17 | 120.0 (2) | C32—C31—N4 | 118.4 (3) |
C7—C9—C10 | 121.2 (2) | C30—C31—N4 | 118.2 (3) |
C17—C9—C10 | 118.4 (2) | C31—C32—C33 | 117.3 (3) |
C9—C10—C4 | 110.9 (2) | C31—C32—H32A | 121.3 |
C9—C10—C11 | 108.56 (19) | C33—C32—H32A | 121.3 |
C4—C10—C11 | 112.24 (19) | C34—C33—C32 | 120.6 (3) |
C9—C10—H10A | 108.4 | C34—C33—H33A | 119.7 |
C4—C10—H10A | 108.4 | C32—C33—H33A | 119.7 |
C11—C10—H10A | 108.4 | C33—C34—C29 | 121.7 (3) |
C12—C11—C16 | 118.5 (2) | C33—C34—H34A | 119.2 |
C12—C11—C10 | 120.5 (2) | C29—C34—H34A | 119.2 |
C16—C11—C10 | 120.8 (2) | C36—C35—H35A | 109.5 |
C13—C12—C11 | 118.1 (2) | C36—C35—H35B | 109.5 |
C13—C12—H12A | 120.9 | H35A—C35—H35B | 109.5 |
C11—C12—H12A | 120.9 | C36—C35—H35C | 109.5 |
C14—C13—C12 | 123.9 (2) | H35A—C35—H35C | 109.5 |
C14—C13—N2 | 118.6 (2) | H35B—C35—H35C | 109.5 |
C12—C13—N2 | 117.5 (3) | O13—C36—O12 | 119.0 (5) |
C13—C14—C15 | 117.9 (2) | O13—C36—C35 | 118.6 (5) |
C13—C14—H14A | 121.1 | O12—C36—C35 | 121.0 (5) |
C15—C14—H14A | 121.1 | C38—C37—O13 | 110.1 (6) |
C14—C15—C16 | 119.5 (3) | C38—C37—H37A | 109.6 |
C14—C15—H15A | 120.2 | O13—C37—H37A | 109.6 |
C16—C15—H15A | 120.2 | C38—C37—H37B | 109.6 |
C11—C16—C15 | 122.0 (2) | O13—C37—H37B | 109.6 |
C11—C16—H16A | 119.0 | H37A—C37—H37B | 108.1 |
C15—C16—H16A | 119.0 | C37—C38—H38A | 109.5 |
O5—C17—O6 | 120.2 (2) | C37—C38—H38B | 109.5 |
O5—C17—C9 | 128.3 (3) | H38A—C38—H38B | 109.5 |
O6—C17—C9 | 111.5 (2) | C37—C38—H38C | 109.5 |
O7—C18—O6 | 119.0 (2) | H38A—C38—H38C | 109.5 |
O7—C18—C19 | 128.9 (2) | H38B—C38—H38C | 109.5 |
O6—C18—C19 | 111.99 (19) | | |
| | | |
C3—O1—C2—C1 | 177.8 (3) | O7—C18—C19—C20 | 13.7 (4) |
C2—O1—C3—O2 | 3.2 (4) | O6—C18—C19—C20 | −163.1 (2) |
C2—O1—C3—C4 | −177.2 (2) | O7—C18—C19—C28 | −162.4 (3) |
O2—C3—C4—C5 | −0.5 (5) | O6—C18—C19—C28 | 20.8 (3) |
O1—C3—C4—C5 | 179.9 (2) | C18—C19—C20—N3 | 175.8 (2) |
O2—C3—C4—C10 | 177.5 (3) | C28—C19—C20—N3 | −8.1 (4) |
O1—C3—C4—C10 | −2.1 (3) | C18—C19—C20—C21 | −3.2 (4) |
C3—C4—C5—N1 | −176.5 (2) | C28—C19—C20—C21 | 172.8 (3) |
C10—C4—C5—N1 | 5.5 (4) | C22—N3—C20—C19 | −8.4 (4) |
C3—C4—C5—C6 | 2.8 (4) | C22—N3—C20—C21 | 170.8 (3) |
C10—C4—C5—C6 | −175.1 (3) | C20—N3—C22—C24 | 11.9 (4) |
C7—N1—C5—C4 | 10.9 (4) | C20—N3—C22—C23 | −167.1 (3) |
C7—N1—C5—C6 | −168.6 (3) | N3—C22—C24—C25 | 178.9 (2) |
C5—N1—C7—C9 | −10.2 (4) | C23—C22—C24—C25 | −2.3 (4) |
C5—N1—C7—C8 | 168.0 (2) | N3—C22—C24—C28 | 1.5 (4) |
N1—C7—C9—C17 | 179.9 (2) | C23—C22—C24—C28 | −179.7 (3) |
C8—C7—C9—C17 | 1.9 (4) | C26—O11—C25—O10 | −5.1 (4) |
N1—C7—C9—C10 | −6.8 (4) | C26—O11—C25—C24 | 174.0 (2) |
C8—C7—C9—C10 | 175.2 (2) | C22—C24—C25—O10 | 2.6 (4) |
C7—C9—C10—C4 | 20.2 (3) | C28—C24—C25—O10 | −179.9 (3) |
C17—C9—C10—C4 | −166.4 (2) | C22—C24—C25—O11 | −176.4 (2) |
C7—C9—C10—C11 | −103.6 (3) | C28—C24—C25—O11 | 1.1 (3) |
C17—C9—C10—C11 | 69.8 (3) | C25—O11—C26—C27 | −172.2 (3) |
C5—C4—C10—C9 | −19.5 (3) | C22—C24—C28—C29 | 106.4 (3) |
C3—C4—C10—C9 | 162.5 (2) | C25—C24—C28—C29 | −71.1 (3) |
C5—C4—C10—C11 | 102.1 (3) | C22—C24—C28—C19 | −15.4 (3) |
C3—C4—C10—C11 | −75.9 (3) | C25—C24—C28—C19 | 167.1 (2) |
C9—C10—C11—C12 | −106.8 (3) | C20—C19—C28—C24 | 18.8 (3) |
C4—C10—C11—C12 | 130.3 (2) | C18—C19—C28—C24 | −165.2 (2) |
C9—C10—C11—C16 | 68.7 (3) | C20—C19—C28—C29 | −105.4 (3) |
C4—C10—C11—C16 | −54.2 (3) | C18—C19—C28—C29 | 70.7 (3) |
C16—C11—C12—C13 | −1.9 (3) | C24—C28—C29—C30 | 123.8 (2) |
C10—C11—C12—C13 | 173.7 (2) | C19—C28—C29—C30 | −112.7 (2) |
C11—C12—C13—C14 | 2.0 (4) | C24—C28—C29—C34 | −59.8 (3) |
C11—C12—C13—N2 | −177.0 (2) | C19—C28—C29—C34 | 63.7 (3) |
O4—N2—C13—C14 | 160.6 (3) | C34—C29—C30—C31 | −0.8 (4) |
O3—N2—C13—C14 | −22.1 (4) | C28—C29—C30—C31 | 175.6 (2) |
O4—N2—C13—C12 | −20.4 (4) | C29—C30—C31—C32 | −0.5 (4) |
O3—N2—C13—C12 | 156.9 (3) | C29—C30—C31—N4 | 179.6 (2) |
C12—C13—C14—C15 | −0.4 (4) | O8—N4—C31—C32 | −7.4 (5) |
N2—C13—C14—C15 | 178.5 (2) | O9—N4—C31—C32 | 169.9 (3) |
C13—C14—C15—C16 | −1.2 (4) | O8—N4—C31—C30 | 172.5 (3) |
C12—C11—C16—C15 | 0.3 (4) | O9—N4—C31—C30 | −10.2 (4) |
C10—C11—C16—C15 | −175.3 (2) | C30—C31—C32—C33 | 1.8 (5) |
C14—C15—C16—C11 | 1.3 (4) | N4—C31—C32—C33 | −178.3 (3) |
C18—O6—C17—O5 | 38.3 (3) | C31—C32—C33—C34 | −1.9 (5) |
C18—O6—C17—C9 | −143.5 (2) | C32—C33—C34—C29 | 0.7 (5) |
C7—C9—C17—O5 | 20.9 (4) | C30—C29—C34—C33 | 0.7 (4) |
C10—C9—C17—O5 | −152.6 (3) | C28—C29—C34—C33 | −175.8 (3) |
C7—C9—C17—O6 | −157.1 (2) | C37—O13—C36—O12 | 12.6 (9) |
C10—C9—C17—O6 | 29.4 (3) | C37—O13—C36—C35 | 179.6 (5) |
C17—O6—C18—O7 | 37.7 (3) | C36—O13—C37—C38 | −172.8 (6) |
C17—O6—C18—C19 | −145.1 (2) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1D···O4i | 0.86 | 2.39 | 3.121 (4) | 143 |
N3—H3A···O9ii | 0.86 | 2.37 | 3.131 (4) | 147 |
C6—H6C···O12i | 0.96 | 2.36 | 3.317 (6) | 178 |
C23—H23C···O2iii | 0.96 | 2.44 | 3.348 (5) | 157 |
Symmetry codes: (i) x+1, y, z; (ii) x−1, y, z; (iii) x−1, y−1, z. |
Experimental details
Crystal data |
Chemical formula | C34H34N4O11·C4H8O2 |
Mr | 762.76 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 293 |
a, b, c (Å) | 10.896 (2), 12.017 (2), 16.162 (3) |
α, β, γ (°) | 99.59 (3), 106.29 (3), 105.69 (3) |
V (Å3) | 1887.1 (9) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.10 |
Crystal size (mm) | 0.28 × 0.22 × 0.10 |
|
Data collection |
Diffractometer | Rigaku R-AXIS RAPID diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 18422, 6953, 4362 |
Rint | 0.038 |
(sin θ/λ)max (Å−1) | 0.606 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.065, 0.206, 1.08 |
No. of reflections | 6953 |
No. of parameters | 504 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.57, −0.45 |
Selected bond lengths (Å) topO1—C2 | 1.453 (4) | O10—C25 | 1.204 (4) |
O1—C3 | 1.345 (4) | O11—C25 | 1.347 (3) |
O2—C3 | 1.212 (3) | O11—C26 | 1.451 (3) |
O5—C17 | 1.199 (3) | O12—C36 | 1.269 (6) |
O6—C17 | 1.391 (3) | O13—C36 | 1.256 (6) |
O6—C18 | 1.399 (3) | O13—C37 | 1.482 (6) |
O7—C18 | 1.203 (3) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1D···O4i | 0.86 | 2.39 | 3.121 (4) | 143 |
N3—H3A···O9ii | 0.86 | 2.37 | 3.131 (4) | 147 |
C6—H6C···O12i | 0.96 | 2.36 | 3.317 (6) | 178 |
C23—H23C···O2iii | 0.96 | 2.44 | 3.348 (5) | 157 |
Symmetry codes: (i) x+1, y, z; (ii) x−1, y, z; (iii) x−1, y−1, z. |
4-Aryl-1,4-dihydropyridine-3,5-dicarboxylic diesters of the nefidipine type have become almost indispensable for the treatment of cardiovascular diseases since they first appeared on the market in 1975 (Yiu & Edward, 1999; Goldmann & Stoltefuss, 1991). The title compound, (I), is related to the preparation of the above compounds.
The molecular structure of (I) is shown in Fig. 1. Both dihydropyridine rings display the envelope configuration, with atoms C10 and C28 displaced from the mean planes formed by the other atoms in the same ring by 0.287 (1) and 0.217 (1) Å, respectively. The dihedral angle between the C11-containing benzene ring and the N1/C4/C5/C7/C9 plane is 87.42 (5)°, while the dihedral angle between the C29-containing benzene ring and the N3/C19/C20/C22/C24 plane is 85.04 (5)°. This is comparable to the situation found in nefidipine (Hofmann & Cimiraglia, 1990; Ramusino & Varì, 1999). The C17—O6 and C18—O6 bond distances (Table 1) are much longer than the C17—O5 and C18—O7 bond distances, respectively, and show the single-bond feature.
Both classic N—H···O and weak C—H···O hydrogen bonds occur in the crystal structure (Table 2). The solvent molecule links with the anhydride via weak C—H···O hydrogen bonding.