Literature DB >> 21579500

Diethyl 4-(4-cyano-phen-yl)-2,6-dimethyl-1,4-dihydro-pyridine-3,5-dicarboxyl-ate.

Abstract

In the title compound, C(20)H(22)N(2)O(4), the dihedral angle between the roughly planar n class="Chemical">dihydro-pyridine ring (r.m.s. deviation = 0.092 Å) and the benzene ring is 87.09 (6)°. One of the eth-oxy side chains is disordered over two orientations in a 0.669 (14):0.331 (14) ratio. In the crystal, mol-ecules are linked by N-H⋯N hydrogen bonds, generating chains.

Entities: Chemical Disease Species

Year: 2010 PMID： 21579500 PMCID： PMC2979369 DOI： 10.1107/S1600536810018155

Source DB: PubMed Journal: Acta Crystallogr Sect E Struct Rep Online ISSN： 1600-5368

Related literature

For general background to dihydropyridine derivatives, see: Gaudio et al. (1994 ▶).

Experimental

Crystal data

C20H22N2O4 M = 354.40 Monoclinic, a = 10.4596 (13) Å b = 9.5117 (12) Å c = 19.160 (2) Å β = 91.493 (1)° V = 1905.6 (4) Å3 Z = 4 Mo Kα radiation μ = 0.09 mm−1 T = 296 K 0.12 × 0.10 × 0.08 mm

Data collection

Bruker APEXII CCD diffractometer Absorption correction: multi-scan (SADABS; Bruker, 2001 ▶) T min = 0.990, T max = 0.993 10000 measured reflections 3298 independent reflections 2408 reflections with I > 2σ(I) R int = 0.020

Refinement

R[F 2 > 2σ(F 2)] = 0.051 wR(F 2) = 0.162 S = 1.02 3298 reflections 249 parameters 2 restraints H-atom parameters constrained Δρmax = 0.31 e Å−3 Δρmin = −0.28 e Å−3 Data collection: APEX2 (Bruker, 2004 ▶); cell refinement: SAINT-Plus (Bruker, 2001 ▶); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL. Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810018155/hb5444sup1.cif Structure factors: contains datablocks I. DOI: 10.1107/S1600536810018155/hb5444Isup2.hkl Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C₂₀H₂₂N₂O₄	F(000) = 752
M_r = 354.40	D_x = 1.235 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 3532 reflections
a = 10.4596 (13) Å	θ = 2.4–25.9°
b = 9.5117 (12) Å	µ = 0.09 mm⁻¹
c = 19.160 (2) Å	T = 296 K
β = 91.493 (1)°	Block, colorless
V = 1905.6 (4) Å³	0.12 × 0.10 × 0.08 mm
Z = 4

Bruker APEXII CCD diffractometer	3298 independent reflections
Radiation source: fine-focus sealed tube	2408 reflections with I > 2σ(I)
graphite	R_int = 0.020
phi and ω scans	θ_max = 25.0°, θ_min = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −12→10
T_min = 0.990, T_max = 0.993	k = −9→11
10000 measured reflections	l = −22→22

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.051	H-atom parameters constrained
wR(F²) = 0.162	w = 1/[σ²(F_o²) + (0.0857P)² + 0.6251P] where P = (F_o² + 2F_c²)/3
S = 1.02	(Δ/σ)_max = 0.001
3298 reflections	Δρ_max = 0.31 e Å⁻³
249 parameters	Δρ_min = −0.28 e Å⁻³
2 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.012 (2)

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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	U_iso*/U_eq	Occ. (<1)
C1	0.5366 (2)	0.1062 (3)	0.32734 (12)	0.0574 (6)
C2	0.4507 (2)	0.0690 (2)	0.27004 (10)	0.0483 (5)
C3	0.3890 (2)	−0.0596 (3)	0.26959 (12)	0.0607 (6)
H3	0.4024	−0.1222	0.3063	0.073*
C4	0.3078 (2)	−0.0948 (2)	0.21466 (12)	0.0573 (6)
H4	0.2670	−0.1817	0.2145	0.069*
C5	0.28599 (19)	−0.0030 (2)	0.15987 (10)	0.0419 (5)
C6	0.3497 (2)	0.1239 (2)	0.16056 (12)	0.0535 (6)
H6	0.3378	0.1854	0.1233	0.064*
C7	0.4306 (2)	0.1614 (2)	0.21529 (12)	0.0552 (6)
H7	0.4713	0.2483	0.2154	0.066*
C8	0.19219 (19)	−0.0393 (2)	0.09975 (11)	0.0444 (5)
H8	0.1533	−0.1305	0.1098	0.053*
C9	0.2616 (2)	−0.0512 (2)	0.03111 (12)	0.0507 (6)
C10	0.2559 (2)	0.0529 (3)	−0.01647 (11)	0.0528 (6)
C11	0.08375 (19)	0.1693 (2)	0.04492 (10)	0.0445 (5)
C12	0.08624 (18)	0.0706 (2)	0.09551 (10)	0.0425 (5)
C13	−0.0033 (2)	0.0607 (2)	0.15302 (12)	0.0490 (5)
C14	−0.1644 (3)	0.1750 (3)	0.21848 (15)	0.0738 (8)
H14A	−0.1152	0.1750	0.2621	0.089*
H14B	−0.2190	0.0925	0.2175	0.089*
C15	−0.2415 (3)	0.3012 (3)	0.2130 (2)	0.0980 (11)
H15A	−0.1871	0.3823	0.2168	0.147*
H15B	−0.3019	0.3025	0.2498	0.147*
H15C	−0.2864	0.3024	0.1687	0.147*
C16	−0.0089 (2)	0.2888 (3)	0.03443 (13)	0.0586 (6)
H16A	−0.0883	0.2659	0.0557	0.088*
H16B	−0.0235	0.3045	−0.0146	0.088*
H16C	0.0261	0.3724	0.0555	0.088*
C17	0.3287 (3)	0.0650 (4)	−0.08253 (13)	0.0756 (8)
H17A	0.4001	0.1272	−0.0752	0.113*
H17B	0.2735	0.1017	−0.1190	0.113*
H17C	0.3592	−0.0261	−0.0958	0.113*
C18	0.3377 (2)	−0.1776 (3)	0.01887 (15)	0.0676 (7)
C19	0.3950 (6)	−0.3990 (5)	0.0605 (3)	0.158 (2)
H19A	0.3515	−0.4556	0.0251	0.190*	0.669 (14)
H19B	0.4793	−0.3765	0.0437	0.190*	0.669 (14)
H19C	0.4473	−0.3909	0.0196	0.190*	0.331 (14)
H19D	0.4514	−0.4147	0.1007	0.190*	0.331 (14)
C20A	0.4079 (13)	−0.4759 (9)	0.1207 (5)	0.185 (6)	0.669 (14)
H20A	0.4549	−0.5603	0.1116	0.278*	0.669 (14)
H20B	0.3248	−0.4999	0.1371	0.278*	0.669 (14)
H20C	0.4530	−0.4213	0.1556	0.278*	0.669 (14)
C20B	0.3114 (12)	−0.5133 (12)	0.0522 (12)	0.141 (9)	0.331 (14)
H20D	0.3600	−0.5980	0.0467	0.212*	0.331 (14)
H20E	0.2573	−0.4988	0.0116	0.212*	0.331 (14)
H20F	0.2598	−0.5213	0.0927	0.212*	0.331 (14)
N1	0.6066 (2)	0.1329 (3)	0.37179 (12)	0.0765 (7)
N2	0.17490 (18)	0.1647 (2)	−0.00618 (9)	0.0534 (5)
H2	0.1813	0.2363	−0.0333	0.064*
O1	0.4059 (2)	−0.2026 (3)	−0.02939 (13)	0.1062 (8)
O2	0.3246 (2)	−0.2705 (2)	0.06982 (13)	0.0967 (7)
O3	−0.07949 (16)	0.17231 (17)	0.16008 (9)	0.0641 (5)
O4	−0.00600 (19)	−0.0369 (2)	0.19268 (11)	0.0824 (6)

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0631 (14)	0.0625 (15)	0.0467 (13)	0.0055 (12)	−0.0004 (11)	−0.0063 (11)
C2	0.0482 (12)	0.0555 (13)	0.0413 (11)	0.0057 (10)	−0.0013 (9)	−0.0061 (9)
C3	0.0722 (15)	0.0591 (15)	0.0503 (13)	−0.0007 (12)	−0.0094 (12)	0.0147 (11)
C4	0.0642 (14)	0.0456 (13)	0.0617 (14)	−0.0084 (11)	−0.0080 (11)	0.0095 (10)
C5	0.0410 (10)	0.0396 (11)	0.0452 (11)	0.0051 (9)	0.0025 (8)	−0.0017 (8)
C6	0.0648 (14)	0.0462 (13)	0.0489 (12)	−0.0052 (11)	−0.0103 (11)	0.0075 (10)
C7	0.0603 (13)	0.0466 (12)	0.0582 (13)	−0.0064 (11)	−0.0068 (11)	−0.0006 (10)
C8	0.0446 (11)	0.0371 (11)	0.0513 (12)	−0.0006 (9)	−0.0025 (9)	−0.0032 (9)
C9	0.0453 (12)	0.0539 (13)	0.0525 (12)	0.0024 (10)	−0.0052 (10)	−0.0144 (10)
C10	0.0461 (12)	0.0658 (15)	0.0464 (12)	−0.0015 (11)	−0.0022 (9)	−0.0127 (11)
C11	0.0433 (11)	0.0461 (12)	0.0436 (11)	0.0011 (9)	−0.0056 (9)	−0.0029 (9)
C12	0.0398 (11)	0.0418 (11)	0.0456 (11)	−0.0011 (9)	−0.0029 (9)	−0.0042 (9)
C13	0.0465 (12)	0.0448 (12)	0.0557 (12)	−0.0004 (10)	0.0026 (10)	0.0015 (10)
C14	0.0735 (17)	0.0753 (18)	0.0740 (17)	0.0031 (14)	0.0293 (14)	−0.0027 (14)
C15	0.088 (2)	0.074 (2)	0.135 (3)	0.0022 (16)	0.058 (2)	−0.0069 (19)
C16	0.0624 (14)	0.0569 (14)	0.0562 (13)	0.0106 (11)	−0.0044 (11)	0.0070 (11)
C17	0.0687 (16)	0.106 (2)	0.0526 (14)	0.0028 (15)	0.0107 (12)	−0.0091 (14)
C18	0.0628 (15)	0.0681 (17)	0.0715 (17)	0.0159 (13)	−0.0080 (13)	−0.0218 (14)
C19	0.203 (5)	0.090 (3)	0.183 (5)	0.084 (4)	0.027 (4)	−0.008 (3)
C20A	0.279 (14)	0.093 (5)	0.186 (9)	0.083 (7)	0.039 (9)	0.046 (6)
C20B	0.128 (12)	0.070 (9)	0.23 (2)	0.017 (7)	0.035 (12)	0.030 (10)
N1	0.0915 (16)	0.0847 (16)	0.0522 (12)	−0.0014 (13)	−0.0187 (12)	−0.0122 (11)
N2	0.0585 (11)	0.0569 (11)	0.0450 (10)	0.0036 (9)	0.0028 (8)	0.0062 (8)
O1	0.1042 (16)	0.1076 (18)	0.1084 (17)	0.0390 (14)	0.0303 (14)	−0.0284 (14)
O2	0.1248 (18)	0.0670 (13)	0.0989 (16)	0.0474 (13)	0.0125 (13)	−0.0023 (12)
O3	0.0684 (10)	0.0557 (10)	0.0694 (11)	0.0101 (8)	0.0264 (9)	0.0053 (8)
O4	0.0811 (13)	0.0715 (12)	0.0963 (14)	0.0160 (10)	0.0341 (11)	0.0318 (11)

C1—N1	1.137 (3)	C14—H14A	0.9700
C1—C2	1.444 (3)	C14—H14B	0.9700
C2—C7	1.380 (3)	C15—H15A	0.9600
C2—C3	1.383 (3)	C15—H15B	0.9600
C3—C4	1.377 (3)	C15—H15C	0.9600
C3—H3	0.9300	C16—H16A	0.9600
C4—C5	1.380 (3)	C16—H16B	0.9600
C4—H4	0.9300	C16—H16C	0.9600
C5—C6	1.378 (3)	C17—H17A	0.9600
C5—C8	1.533 (3)	C17—H17B	0.9600
C6—C7	1.377 (3)	C17—H17C	0.9600
C6—H6	0.9300	C18—O1	1.206 (3)
C7—H7	0.9300	C18—O2	1.326 (4)
C8—C9	1.523 (3)	C19—C20A	1.370 (8)
C8—C12	1.524 (3)	C19—C20B	1.401 (9)
C8—H8	0.9800	C19—O2	1.440 (4)
C9—C10	1.346 (3)	C19—H19A	0.9700
C9—C18	1.464 (3)	C19—H19B	0.9700
C10—N2	1.377 (3)	C19—H19C	0.9700
C10—C17	1.499 (3)	C19—H19D	0.9700
C11—C12	1.349 (3)	C20A—H20A	0.9600
C11—N2	1.385 (3)	C20A—H20B	0.9600
C11—C16	1.504 (3)	C20A—H20C	0.9600
C12—C13	1.467 (3)	C20B—H20D	0.9600
C13—O4	1.201 (3)	C20B—H20E	0.9600
C13—O3	1.336 (3)	C20B—H20F	0.9600
C14—O3	1.447 (3)	N2—H2	0.8600
C14—C15	1.448 (4)

N1—C1—C2	178.1 (3)	H15B—C15—H15C	109.5
C7—C2—C3	119.8 (2)	C11—C16—H16A	109.5
C7—C2—C1	120.1 (2)	C11—C16—H16B	109.5
C3—C2—C1	120.1 (2)	H16A—C16—H16B	109.5
C4—C3—C2	119.9 (2)	C11—C16—H16C	109.5
C4—C3—H3	120.0	H16A—C16—H16C	109.5
C2—C3—H3	120.0	H16B—C16—H16C	109.5
C3—C4—C5	120.9 (2)	C10—C17—H17A	109.5
C3—C4—H4	119.5	C10—C17—H17B	109.5
C5—C4—H4	119.5	H17A—C17—H17B	109.5
C6—C5—C4	118.5 (2)	C10—C17—H17C	109.5
C6—C5—C8	120.27 (18)	H17A—C17—H17C	109.5
C4—C5—C8	121.25 (19)	H17B—C17—H17C	109.5
C7—C6—C5	121.4 (2)	O1—C18—O2	120.5 (3)
C7—C6—H6	119.3	O1—C18—C9	128.2 (3)
C5—C6—H6	119.3	O2—C18—C9	111.2 (2)
C6—C7—C2	119.5 (2)	C20A—C19—C20B	74.2 (9)
C6—C7—H7	120.3	C20A—C19—O2	112.8 (5)
C2—C7—H7	120.3	C20B—C19—O2	110.7 (7)
C9—C8—C12	111.57 (17)	C20A—C19—H19A	109.0
C9—C8—C5	110.82 (16)	O2—C19—H19A	109.0
C12—C8—C5	109.63 (16)	C20A—C19—H19B	109.0
C9—C8—H8	108.2	C20B—C19—H19B	134.7
C12—C8—H8	108.2	O2—C19—H19B	109.0
C5—C8—H8	108.2	H19A—C19—H19B	107.8
C10—C9—C18	120.7 (2)	C20A—C19—H19C	132.7
C10—C9—C8	121.06 (19)	C20B—C19—H19C	109.5
C18—C9—C8	118.2 (2)	O2—C19—H19C	109.5
C9—C10—N2	119.2 (2)	H19A—C19—H19C	75.2
C9—C10—C17	127.9 (2)	C20B—C19—H19D	109.5
N2—C10—C17	112.9 (2)	O2—C19—H19D	109.5
C12—C11—N2	119.03 (18)	H19A—C19—H19D	137.2
C12—C11—C16	128.49 (19)	H19B—C19—H19D	76.0
N2—C11—C16	112.47 (18)	H19C—C19—H19D	108.1
C11—C12—C13	125.70 (19)	C19—C20A—H20A	109.5
C11—C12—C8	121.06 (18)	C19—C20A—H20B	109.5
C13—C12—C8	113.16 (18)	H20A—C20A—H20B	109.5
O4—C13—O3	121.7 (2)	C19—C20A—H20C	109.5
O4—C13—C12	123.4 (2)	H20A—C20A—H20C	109.5
O3—C13—C12	114.78 (19)	H20B—C20A—H20C	109.5
O3—C14—C15	108.1 (2)	C19—C20B—H20D	109.5
O3—C14—H14A	110.1	C19—C20B—H20E	109.5
C15—C14—H14A	110.1	H20D—C20B—H20E	109.5
O3—C14—H14B	110.1	C19—C20B—H20F	109.5
C15—C14—H14B	110.1	H20D—C20B—H20F	109.5
H14A—C14—H14B	108.4	H20E—C20B—H20F	109.5
C14—C15—H15A	109.5	C10—N2—C11	124.26 (19)
C14—C15—H15B	109.5	C10—N2—H2	117.9
H15A—C15—H15B	109.5	C11—N2—H2	117.9
C14—C15—H15C	109.5	C18—O2—C19	114.2 (3)
H15A—C15—H15C	109.5	C13—O3—C14	118.16 (19)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···N1ⁱ	0.86	2.32	3.098 (3)	150

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2⋯N1ⁱ	0.86	2.32	3.098 (3)	150

Symmetry code: (i) .

2 in total

1. A short history of SHELX.

Authors: George M Sheldrick
Journal: Acta Crystallogr A Date: 2007-12-21 Impact factor: 2.290

2. Quantitative structure-activity relationships for 1,4-dihydropyridine calcium channel antagonists (nifedipine analogues): a quantum chemical/classical approach.

Authors: A C Gaudio; A Korolkovas; Y Takahata
Journal: J Pharm Sci Date: 1994-08 Impact factor: 3.534

2 in total