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The crystal structure of the title compound, C20H23N3O7, consists of relatively isolated mol­ecules. The substituted 1,4-di­hydro­pyridine ring adopts a flattened boat conformation. Both ester groups, at positions 3 and 5, have cis,cis geometry. The phenyl ring is nearly planar and is approximately perpendicular to the 1,4-di­hydro­pyridine ring (dihedral angle 87.70°).

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270101009313/av1077sup1.cif
Contains datablocks default1, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270101009313/av1077Isup2.hkl
Contains datablock I

CCDC reference: 173370

Comment top

Many derivatives of 1,4-dihydropyridine (DHP) exhibit high affinity for calcium channel receptors and may act as agonists or antagonists, depending on the nature of the derivative, the physiological state of the channel and, in some cases, the side of the membrane containing the channel receptor to which the compound is added (Kokubun & Reuter, 1984). Amongst these 1,4-DHP is Nifedipine [2,6-dimethyl-3,5-dicarbomethoxy-4-(2-nitrophenyl)-1,4-dihydro- pyridine], which is one of the most potent of the calcium antagonists and is a powerful negative ionotropic and smooth-muscle relaxant species (Triggle et al., 1980). We have studied the crystal structure of methyl isopropyl 2-methoxyimino- -methyl-6-methyl-4-(3-nitrophenyl)-1,4-dihydropyridine-3,5-tricarboxylate, (I). \sch

The structure of (I) consists of discrete molecules. The 1,4-DHP ring exibits a boat conformation. The N1 and C3 atoms lie 0.110 (3) and 0.228 (3) Å, respectively, from the least-squares plane defined by the remaining four atoms of the DHP ring. The orientation of the 3-nitrophenyl ring relative to the 1,4-DHP ring, characterized by the torsion angle C2—C3—C10—C15, is -63.8 (4)°. Similar orientation of the phenyl ring is preferred in all the investigated phenyl-substituted derivatives (Mehdi & Ravikumar, 1992). It is probable that in this way the steric strain, which is imposed by the phenyl substitutent and the groups at the 3 and 5 positions, is minimized (Fossheim, 1986). The nitro-group is twisted 5.0 (3)° from the plane of the phenyl ring system. Langs & Triggle (1985) have observed that the majority of 1,4-DHP analogs have one of the ester groups at C3 and C5 of the 1,4-DHP ring in the cis conformation and the other in the trans conformation. A small number of very active antagonists are found to have cis,cis geometry. In the present compound both carbonyl groups are twisted in the same cis,cis direction. One ester group is slightly oriented out of the plane 1,4-DHP and the second ester group is coplanar with the 1,4-DHP ring (Table 1).

Experimental top

The title compound was prepared by known synthetic methods (Hantzsch, 1882) and recrystallized from an ethanol solution. Slow evaporation of an ethanol solution yielded yellow plate-like crystals.

Refinement top

The hydrogen atoms H1, H3, H6, H11, H13, H14, and H15 were located on the difference Fourier map and refined isotropically. The positions of the methyl H atoms were calculated geometrically and fixed (C···H 0.96 Å). Their isotropic displacement parameters were fixed at 1.5U(eq).

Computing details top

Data collection: Syntex P21 software; cell refinement: Syntex P21 software; data reduction: XP21 (Pavelčík, 1987); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: SHELXS97.

Figures top
[Figure 1] Fig. 1. A view of (I) with the atomic numbering scheme. Displacement ellipsoids are drawn at the 50% probablity level.
Methyl isopropyl 2-methoxyiminomethyl-6-methyl-4-(3-nitrophenyl)-1,4-dihydro- pyridine-3,5-dicarboxylate top
Crystal data top
C20H23N3O7Z = 2
Mr = 417.41F(000) = 440
Triclinic, P1Dx = 1.337 Mg m3
Dm = 1.34 (1) Mg m3
Dm measured by flotation in bromoform-hexane
a = 9.563 (4) ÅMo Kα radiation, λ = 0.71069 Å
b = 9.703 (4) ÅCell parameters from 25 reflections
c = 12.031 (6) Åθ = 8.2–21.4°
α = 93.99 (4)°µ = 0.10 mm1
β = 105.09 (4)°T = 293 K
γ = 103.66 (4)°Plate, yellow
V = 1037.1 (8) Å30.35 × 0.30 × 0.10 mm
Data collection top
Syntex P21
diffractometer
Rint = 0.000
Radiation source: fine-focus sealed tubeθmax = 25.1°, θmin = 1.8°
Graphite monochromatorh = 09
θ/2θ scansk = 1111
3527 measured reflectionsl = 1413
3527 independent reflections2 standard reflections every 100 min
1209 reflections with I > 2σ(I) intensity decay: none
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.052H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.068 w = 1/[σ2(Fo2) + (0.0112P)2]
where P = (Fo2 + 2Fc2)/3
S = 0.78(Δ/σ)max = 0.002
3527 reflectionsΔρmax = 0.14 e Å3
304 parametersΔρmin = 0.14 e Å3
0 restraintsExtinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0088 (6)
Crystal data top
C20H23N3O7γ = 103.66 (4)°
Mr = 417.41V = 1037.1 (8) Å3
Triclinic, P1Z = 2
a = 9.563 (4) ÅMo Kα radiation
b = 9.703 (4) ŵ = 0.10 mm1
c = 12.031 (6) ÅT = 293 K
α = 93.99 (4)°0.35 × 0.30 × 0.10 mm
β = 105.09 (4)°
Data collection top
Syntex P21
diffractometer
Rint = 0.000
3527 measured reflections2 standard reflections every 100 min
3527 independent reflections intensity decay: none
1209 reflections with I > 2σ(I)
Refinement top
R[F2 > 2σ(F2)] = 0.0520 restraints
wR(F2) = 0.068H atoms treated by a mixture of independent and constrained refinement
S = 0.78Δρmax = 0.14 e Å3
3527 reflectionsΔρmin = 0.14 e Å3
304 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
O10.6623 (2)0.3899 (2)0.99646 (18)0.0689 (7)
O20.3579 (2)0.1862 (2)0.64941 (18)0.0682 (7)
O30.5089 (2)0.0319 (2)0.69399 (18)0.0748 (8)
O40.1738 (4)0.4542 (3)0.4137 (3)0.1242 (14)
O50.3094 (4)0.3256 (3)0.3356 (2)0.1639 (17)
O60.0330 (3)0.2902 (2)0.98875 (18)0.0801 (9)
O70.0179 (2)0.3802 (2)0.81775 (17)0.0577 (7)
N10.3086 (3)0.0690 (3)0.9697 (2)0.0488 (8)
H10.348 (3)0.145 (3)1.0284 (19)0.049 (10)*
N20.5408 (3)0.2771 (3)0.9928 (2)0.0530 (8)
N30.2118 (4)0.3433 (4)0.4129 (3)0.0954 (14)
C10.3793 (3)0.0662 (3)0.8842 (3)0.0403 (9)
C20.3280 (3)0.0438 (3)0.7976 (3)0.0367 (8)
C30.1838 (3)0.1580 (4)0.7874 (3)0.0417 (9)
H30.209 (2)0.245 (2)0.7624 (17)0.018 (8)*
C40.1427 (3)0.1573 (3)0.8999 (3)0.0388 (9)
C50.2011 (3)0.0458 (4)0.9832 (3)0.0410 (9)
C60.5079 (4)0.1884 (4)0.9001 (3)0.0512 (10)
H60.561 (3)0.202 (3)0.8324 (19)0.063 (10)*
C70.6918 (3)0.4913 (3)1.0985 (2)0.0720 (11)
H7A0.77590.57011.10170.108*
H7B0.71430.44531.16660.108*
H7C0.60500.52611.09520.108*
C80.4098 (4)0.0570 (4)0.7115 (3)0.0477 (9)
C90.4334 (4)0.2175 (3)0.5645 (3)0.0938 (13)
H9A0.38670.31340.52520.141*
H9B0.53720.20870.60310.141*
H9C0.42640.15120.50900.141*
C100.0574 (3)0.1398 (4)0.6882 (2)0.0373 (8)
C110.0145 (4)0.2463 (4)0.5944 (3)0.0464 (10)
H110.024 (3)0.323 (3)0.592 (2)0.041 (10)*
C120.1339 (4)0.2294 (4)0.5107 (3)0.0526 (10)
C130.1847 (4)0.1109 (5)0.5149 (3)0.0598 (12)
H130.268 (3)0.107 (3)0.455 (2)0.068 (12)*
C140.1134 (5)0.0036 (5)0.6053 (3)0.0614 (12)
H140.145 (3)0.078 (3)0.616 (2)0.056 (11)*
C150.0070 (4)0.0188 (4)0.6912 (3)0.0486 (10)
H150.049 (3)0.060 (2)0.7479 (18)0.034 (9)*
C160.0239 (4)0.2786 (4)0.9096 (3)0.0496 (10)
C170.1482 (4)0.5021 (4)0.8082 (4)0.0655 (12)
H170.137 (3)0.535 (3)0.894 (2)0.106 (13)*
C180.1316 (4)0.6212 (3)0.7323 (3)0.0929 (14)
H18A0.04170.64750.76910.139*
H18B0.12560.59080.65900.139*
H18C0.21680.70220.71960.139*
C190.2868 (4)0.4518 (4)0.7581 (3)0.1017 (14)
H19A0.29060.37560.81160.153*
H19B0.37460.53010.74550.153*
H19C0.28300.41800.68560.153*
C200.1670 (3)0.0251 (3)1.0975 (2)0.0609 (10)
H20A0.22760.06601.14030.091*
H20B0.18890.10001.14160.091*
H20C0.06280.02801.08360.091*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0657 (18)0.0562 (16)0.0752 (18)0.0050 (15)0.0257 (14)0.0020 (14)
O20.0645 (17)0.0674 (18)0.0753 (17)0.0049 (14)0.0420 (14)0.0139 (14)
O30.0652 (18)0.075 (2)0.0792 (18)0.0077 (15)0.0392 (15)0.0028 (14)
O40.152 (3)0.091 (3)0.088 (2)0.016 (2)0.012 (2)0.029 (2)
O50.145 (3)0.174 (3)0.103 (3)0.041 (3)0.068 (2)0.043 (2)
O60.089 (2)0.084 (2)0.0693 (18)0.0022 (15)0.0475 (16)0.0172 (15)
O70.0575 (17)0.0540 (17)0.0557 (16)0.0005 (14)0.0181 (13)0.0135 (13)
N10.044 (2)0.048 (2)0.052 (2)0.0080 (18)0.0163 (17)0.0036 (17)
N20.0379 (18)0.047 (2)0.068 (2)0.0044 (16)0.0090 (16)0.0164 (17)
N30.087 (3)0.097 (4)0.063 (3)0.006 (3)0.012 (2)0.016 (3)
C10.034 (2)0.046 (3)0.047 (2)0.0143 (19)0.0177 (19)0.0182 (19)
C20.037 (2)0.036 (2)0.037 (2)0.0102 (18)0.0091 (18)0.0066 (17)
C30.038 (2)0.046 (3)0.042 (2)0.012 (2)0.0106 (18)0.0087 (19)
C40.031 (2)0.047 (2)0.037 (2)0.0094 (19)0.0065 (18)0.0080 (19)
C50.034 (2)0.056 (3)0.038 (2)0.018 (2)0.0112 (19)0.021 (2)
C60.044 (3)0.057 (3)0.050 (3)0.008 (2)0.016 (2)0.005 (2)
C70.074 (3)0.051 (2)0.076 (3)0.011 (2)0.002 (2)0.000 (2)
C80.036 (2)0.056 (3)0.048 (2)0.013 (2)0.0061 (19)0.005 (2)
C90.094 (3)0.107 (3)0.091 (3)0.019 (2)0.062 (3)0.023 (2)
C100.032 (2)0.041 (2)0.039 (2)0.0060 (19)0.0126 (17)0.0130 (18)
C110.042 (3)0.053 (3)0.045 (2)0.010 (2)0.013 (2)0.013 (2)
C120.043 (3)0.060 (3)0.048 (3)0.001 (2)0.011 (2)0.011 (2)
C130.047 (3)0.095 (4)0.043 (3)0.023 (3)0.015 (2)0.021 (3)
C140.071 (3)0.069 (3)0.063 (3)0.044 (3)0.026 (3)0.022 (3)
C150.054 (3)0.055 (3)0.045 (3)0.018 (2)0.022 (2)0.016 (2)
C160.047 (3)0.060 (3)0.044 (3)0.016 (2)0.012 (2)0.016 (2)
C170.053 (3)0.051 (3)0.083 (3)0.006 (2)0.018 (2)0.028 (2)
C180.109 (3)0.060 (3)0.092 (3)0.004 (3)0.026 (3)0.003 (2)
C190.054 (3)0.106 (3)0.128 (3)0.002 (3)0.014 (3)0.033 (3)
C200.055 (2)0.089 (3)0.044 (2)0.022 (2)0.0177 (19)0.0146 (19)
Geometric parameters (Å, º) top
O1—N21.384 (3)C7—H7B0.9600
O1—C71.440 (3)C7—H7C0.9600
O2—C81.326 (3)C9—H9A0.9600
O2—C91.450 (3)C9—H9B0.9600
O3—C81.196 (3)C9—H9C0.9600
O4—N31.214 (4)C10—C151.372 (4)
O5—N31.189 (4)C10—C111.383 (4)
O6—C161.214 (3)C11—C121.363 (4)
O7—C161.336 (3)C11—H110.91 (2)
O7—C171.474 (4)C12—C131.352 (4)
N1—C11.372 (4)C13—C141.361 (5)
N1—C51.376 (3)C13—H130.93 (2)
N1—H10.91 (2)C14—C151.377 (4)
N2—C61.280 (3)C14—H140.92 (2)
N3—C121.461 (4)C15—H150.92 (2)
C1—C21.341 (3)C17—C181.486 (4)
C1—C61.453 (4)C17—C191.512 (4)
C2—C81.467 (4)C17—H171.09 (3)
C2—C31.521 (4)C18—H18A0.9600
C3—C41.505 (4)C18—H18B0.9600
C3—C101.515 (4)C18—H18C0.9600
C3—H30.980 (19)C19—H19A0.9600
C4—C51.326 (4)C19—H19B0.9600
C4—C161.465 (4)C19—H19C0.9600
C5—C201.505 (3)C20—H20A0.9600
C6—H61.07 (2)C20—H20B0.9600
C7—H7A0.9600C20—H20C0.9600
N2—O1—C7108.9 (2)C15—C10—C11118.0 (3)
C8—O2—C9116.8 (3)C15—C10—C3120.7 (3)
C16—O7—C17117.9 (3)C11—C10—C3121.3 (3)
C1—N1—C5123.6 (3)C12—C11—C10119.4 (4)
C1—N1—H1117.3 (17)C12—C11—H11124.2 (16)
C5—N1—H1118.0 (16)C10—C11—H11116.4 (16)
C6—N2—O1110.1 (3)C13—C12—C11122.5 (4)
O5—N3—O4122.0 (4)C13—C12—N3118.2 (4)
O5—N3—C12119.8 (4)C11—C12—N3119.3 (4)
O4—N3—C12118.2 (4)C12—C13—C14119.0 (4)
C2—C1—N1119.6 (3)C12—C13—H13117.6 (18)
C2—C1—C6126.6 (3)C14—C13—H13123.4 (18)
N1—C1—C6113.7 (3)C13—C14—C15119.5 (4)
C1—C2—C8120.9 (3)C13—C14—H14123.5 (17)
C1—C2—C3120.4 (3)C15—C14—H14116.8 (17)
C8—C2—C3118.8 (3)C10—C15—C14121.6 (4)
C4—C3—C10111.4 (3)C10—C15—H15125.0 (16)
C4—C3—C2111.7 (3)C14—C15—H15113.4 (16)
C10—C3—C2110.3 (3)O6—C16—O7122.1 (3)
C4—C3—H3114.9 (13)O6—C16—C4126.5 (3)
C10—C3—H3106.3 (12)O7—C16—C4111.4 (3)
C2—C3—H3101.7 (13)O7—C17—C18106.0 (3)
C5—C4—C16120.7 (3)O7—C17—C19106.6 (3)
C5—C4—C3121.6 (3)C18—C17—C19113.9 (3)
C16—C4—C3117.3 (3)O7—C17—H17107.7 (16)
C4—C5—N1119.4 (3)C18—C17—H17106.8 (16)
C4—C5—C20128.3 (3)C19—C17—H17115.4 (17)
N1—C5—C20112.3 (3)C17—C18—H18A109.5
N2—C6—C1115.7 (3)C17—C18—H18B109.5
N2—C6—H6125.5 (14)H18A—C18—H18B109.5
C1—C6—H6118.7 (14)C17—C18—H18C109.5
O1—C7—H7A109.5H18A—C18—H18C109.5
O1—C7—H7B109.5H18B—C18—H18C109.5
H7A—C7—H7B109.5C17—C19—H19A109.5
O1—C7—H7C109.5C17—C19—H19B109.5
H7A—C7—H7C109.5H19A—C19—H19B109.5
H7B—C7—H7C109.5C17—C19—H19C109.5
O3—C8—O2121.5 (3)H19A—C19—H19C109.5
O3—C8—C2127.9 (3)H19B—C19—H19C109.5
O2—C8—C2110.6 (3)C5—C20—H20A109.5
O2—C9—H9A109.5C5—C20—H20B109.5
O2—C9—H9B109.5H20A—C20—H20B109.5
H9A—C9—H9B109.5C5—C20—H20C109.5
O2—C9—H9C109.5H20A—C20—H20C109.5
H9A—C9—H9C109.5H20B—C20—H20C109.5
H9B—C9—H9C109.5
C7—O1—N2—C6177.1 (3)C1—C2—C8—O2167.1 (3)
C5—N1—C1—C210.7 (5)C3—C2—C8—O212.6 (4)
C5—N1—C1—C6168.7 (3)C4—C3—C10—C1560.9 (4)
N1—C1—C2—C8173.9 (3)C2—C3—C10—C1563.8 (4)
C6—C1—C2—C85.4 (5)C4—C3—C10—C11116.5 (3)
N1—C1—C2—C35.8 (4)C2—C3—C10—C11118.8 (3)
C6—C1—C2—C3174.9 (3)C15—C10—C11—C121.7 (4)
C1—C2—C3—C418.6 (4)C3—C10—C11—C12175.8 (3)
C8—C2—C3—C4161.0 (3)C10—C11—C12—C130.7 (5)
C1—C2—C3—C10105.9 (3)C10—C11—C12—N3178.8 (3)
C8—C2—C3—C1074.4 (4)O5—N3—C12—C135.5 (6)
C10—C3—C4—C5106.1 (3)O4—N3—C12—C13174.3 (4)
C2—C3—C4—C517.8 (4)O5—N3—C12—C11175.0 (4)
C10—C3—C4—C1667.7 (4)O4—N3—C12—C115.2 (6)
C2—C3—C4—C16168.4 (3)C11—C12—C13—C140.6 (5)
C16—C4—C5—N1177.5 (3)N3—C12—C13—C14179.9 (3)
C3—C4—C5—N13.9 (5)C12—C13—C14—C151.0 (5)
C16—C4—C5—C203.2 (5)C11—C10—C15—C141.3 (5)
C3—C4—C5—C20176.9 (3)C3—C10—C15—C14176.2 (3)
C1—N1—C5—C411.8 (4)C13—C14—C15—C100.0 (5)
C1—N1—C5—C20167.6 (3)C17—O7—C16—O66.5 (5)
O1—N2—C6—C1178.6 (2)C17—O7—C16—C4173.3 (3)
C2—C1—C6—N2176.5 (3)C5—C4—C16—O61.0 (5)
N1—C1—C6—N22.9 (4)C3—C4—C16—O6173.0 (3)
C9—O2—C8—O33.8 (5)C5—C4—C16—O7179.2 (3)
C9—O2—C8—C2176.9 (3)C3—C4—C16—O76.9 (4)
C1—C2—C8—O313.8 (5)C16—O7—C17—C18157.2 (3)
C3—C2—C8—O3166.6 (3)C16—O7—C17—C1981.1 (4)

Experimental details

Crystal data
Chemical formulaC20H23N3O7
Mr417.41
Crystal system, space groupTriclinic, P1
Temperature (K)293
a, b, c (Å)9.563 (4), 9.703 (4), 12.031 (6)
α, β, γ (°)93.99 (4), 105.09 (4), 103.66 (4)
V3)1037.1 (8)
Z2
Radiation typeMo Kα
µ (mm1)0.10
Crystal size (mm)0.35 × 0.30 × 0.10
Data collection
DiffractometerSyntex P21
diffractometer
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
3527, 3527, 1209
Rint0.000
(sin θ/λ)max1)0.596
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.052, 0.068, 0.78
No. of reflections3527
No. of parameters304
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.14, 0.14

Computer programs: Syntex P21 software, XP21 (Pavelčík, 1987), SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), ORTEPII (Johnson, 1976), SHELXS97.

Selected geometric parameters (Å, º) top
O1—N21.384 (3)C1—C21.341 (3)
O3—C81.196 (3)C2—C31.521 (4)
O6—C161.214 (3)C3—C41.505 (4)
N1—C11.372 (4)C3—C101.515 (4)
N1—C51.376 (3)C4—C51.326 (4)
N3—C121.461 (4)
N2—O1—C7108.9 (2)C4—C3—C2111.7 (3)
C1—N1—C5123.6 (3)C15—C10—C3120.7 (3)
O5—N3—O4122.0 (4)C13—C12—C11122.5 (4)
C4—C3—C10111.4 (3)O6—C16—O7122.1 (3)
C5—N1—C1—C210.7 (5)C4—C3—C10—C1560.9 (4)
C1—C2—C3—C418.6 (4)C2—C3—C10—C1563.8 (4)
C2—C3—C4—C517.8 (4)O4—N3—C12—C115.2 (6)
C1—N1—C5—C411.8 (4)C5—C4—C16—O61.0 (5)
C1—C2—C8—O313.8 (5)C5—C4—C16—O7179.2 (3)
C1—C2—C8—O2167.1 (3)
 

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