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

In the title compound, C(21)H(27)NO(5), the dihydropyridine ring adopts a boat conformation. The ethoxy-phenyl ring is oriented approximately perpendicular to the planar part of the dihydropyridine ring, making a dihedral angle of 89.45 (6)°. An intra-molecular C-H⋯O hydrogen bond generates an S(6) ring motif. In the crystal structure, neighbouring mol-ecules are linked into chains along the a axis by N-H⋯O hydrogen bonds and the chains are inter-connected into two-dimensional networks parallel to the ab plane by C-H⋯O hydrogen bonds. The structure is further stabilized by weak C-H⋯π inter-actions.

Related literature

For general background to and applications of 1,4-dihydro­pyridine derivatives, see: Böcker & Guengerich (1986 ▶); Cooper et al. (1992 ▶); Vo et al. (1995 ▶); Gaudio et al. (1994 ▶); Gordeev et al. (1996 ▶); Sunkel et al. (1992 ▶). For ring conformations and ring puckering analysis, see: Boeyens (1978 ▶); Cremer & Pople (1975 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶). For bond-length data, see: Allen et al. (1987 ▶). For a related structure, see: Thenmozhi et al. (2009 ▶). For the stability of the temperature controller used for the data collection, see: Cosier & Glazer (1986 ▶).

Experimental

Crystal data

C21H27NO5

M = 373.44

Triclinic,

a = 7.5557 (1) Å

b = 9.5697 (1) Å

c = 14.0553 (2) Å

α = 85.844 (1)°

β = 87.679 (1)°

γ = 81.458 (1)°

V = 1001.91 (2) Å3

Z = 2

Mo Kα radiation

μ = 0.09 mm−1

T = 296 K

0.28 × 0.27 × 0.07 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer

Absorption correction: multi-scan (; Bruker, 2005 ▶) T min = 0.976, T max = 0.994

20664 measured reflections

5290 independent reflections

3602 reflections with I > 2σ(I)

R int = 0.027

Refinement

R[F 2 > 2σ(F 2)] = 0.055

wR(F 2) = 0.161

S = 1.02

5290 reflections

253 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.32 e Å−3

Δρmin = −0.24 e Å−3

Data collection: APEX2 (Bruker, 2005 ▶); cell refinement: SAINT (Bruker, 2005 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 ▶).

Crystal structure: contains datablocks global, I. DOI: 10.1107/S160053680903339X/ci2893sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S160053680903339X/ci2893Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C21H27NO5	Z = 2
Mr = 373.44	F(000) = 400
Triclinic, P1	Dx = 1.238 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.5557 (1) Å	Cell parameters from 5893 reflections
b = 9.5697 (1) Å	θ = 2.5–30.2°
c = 14.0553 (2) Å	µ = 0.09 mm−1
α = 85.844 (1)°	T = 296 K
β = 87.679 (1)°	Plate, colourless
γ = 81.458 (1)°	0.28 × 0.27 × 0.07 mm
V = 1001.91 (2) Å3

Bruker SMART APEXII CCD area-detector diffractometer	5290 independent reflections
Radiation source: fine-focus sealed tube	3602 reflections with I > 2σ(I)
graphite	Rint = 0.027
φ and ω scans	θmax = 29.0°, θmin = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −10→10
Tmin = 0.976, Tmax = 0.994	k = −11→13
20664 measured reflections	l = −19→19

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)] = 0.055	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.161	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	w = 1/[σ2(Fo2) + (0.0714P)2 + 0.3075P] where P = (Fo2 + 2Fc2)/3
5290 reflections	(Δ/σ)max = 0.001
253 parameters	Δρmax = 0.32 e Å−3
0 restraints	Δρmin = −0.24 e Å−3

Experimental. The crystal was placed in the cold stream of an Oxford Cyrosystems Cobra open-flow nitrogen cryostat (Cosier & Glazer, 1986) operating at 100.0 (1)K.

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 > 2sigma(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
O1	0.73624 (18)	0.59395 (15)	0.53338 (9)	0.0547 (4)
O2	1.01269 (16)	0.23542 (17)	0.96209 (10)	0.0603 (4)
O3	0.81388 (15)	0.34092 (15)	1.06441 (9)	0.0511 (3)
O4	0.5806 (2)	−0.10910 (17)	0.71435 (11)	0.0672 (4)
O5	0.85133 (17)	−0.04519 (14)	0.72123 (9)	0.0525 (3)
N1	0.41011 (18)	0.18714 (16)	0.92272 (10)	0.0402 (3)
C1	0.8807 (2)	0.28106 (19)	0.68730 (11)	0.0416 (4)
H1A	0.9720	0.2043	0.6870	0.050*
C2	0.8726 (2)	0.3840 (2)	0.61279 (12)	0.0452 (4)
H2A	0.9583	0.3761	0.5633	0.054*
C3	0.7373 (2)	0.49899 (19)	0.61149 (11)	0.0412 (4)
C4	0.6152 (2)	0.5125 (2)	0.68730 (13)	0.0479 (4)
H4A	0.5267	0.5911	0.6886	0.058*
C5	0.6254 (2)	0.40778 (19)	0.76151 (12)	0.0431 (4)
H5A	0.5421	0.4175	0.8120	0.052*
C6	0.7553 (2)	0.28953 (17)	0.76285 (10)	0.0333 (3)
C7	0.7547 (2)	0.16927 (17)	0.84131 (10)	0.0328 (3)
H7A	0.8750	0.1144	0.8434	0.039*
C8	0.7073 (2)	0.22640 (17)	0.93892 (10)	0.0330 (3)
C9	0.5348 (2)	0.24150 (17)	0.97270 (10)	0.0347 (3)
C10	0.4537 (2)	0.09203 (17)	0.85327 (11)	0.0373 (4)
C11	0.6234 (2)	0.07125 (17)	0.81710 (10)	0.0352 (3)
C12	0.5781 (3)	0.6937 (2)	0.51790 (14)	0.0552 (5)
H12A	0.5585	0.7572	0.5692	0.066*
H12B	0.4748	0.6447	0.5159	0.066*
C13	0.6041 (4)	0.7752 (3)	0.42475 (17)	0.0825 (8)
H13A	0.4990	0.8427	0.4120	0.124*
H13B	0.6242	0.7112	0.3746	0.124*
H13C	0.7056	0.8241	0.4278	0.124*
C14	0.8579 (2)	0.26575 (18)	0.98833 (11)	0.0365 (4)
C15	0.9594 (2)	0.3755 (2)	1.11817 (13)	0.0532 (5)
H15A	1.0388	0.4248	1.0765	0.064*
H15B	1.0280	0.2897	1.1461	0.064*
C16	0.8798 (3)	0.4675 (3)	1.19452 (16)	0.0695 (6)
H16A	0.9730	0.4874	1.2336	0.104*
H16B	0.7964	0.4198	1.2331	0.104*
H16C	0.8185	0.5546	1.1660	0.104*
C17	0.6761 (2)	−0.03516 (18)	0.74743 (11)	0.0411 (4)
C18	0.9092 (3)	−0.1407 (3)	0.64637 (16)	0.0676 (6)
H18A	0.8361	−0.1144	0.5909	0.081*
H18B	0.8960	−0.2370	0.6687	0.081*
C19	1.0976 (4)	−0.1317 (4)	0.6207 (2)	0.1091 (12)
H19A	1.1366	−0.1932	0.5706	0.164*
H19B	1.1694	−0.1601	0.6755	0.164*
H19C	1.1098	−0.0360	0.5993	0.164*
C20	0.4542 (2)	0.3115 (2)	1.05970 (12)	0.0461 (4)
H20A	0.5452	0.3102	1.1056	0.069*
H20B	0.3613	0.2614	1.0870	0.069*
H20C	0.4046	0.4078	1.0421	0.069*
C21	0.2974 (2)	0.0239 (2)	0.82690 (14)	0.0506 (5)
H21A	0.3381	−0.0725	0.8130	0.076*
H21B	0.2427	0.0748	0.7717	0.076*
H21C	0.2114	0.0261	0.8792	0.076*
H1N1	0.303 (3)	0.200 (2)	0.9447 (15)	0.063 (6)*

	U11	U22	U33	U12	U13	U23
O1	0.0620 (8)	0.0562 (8)	0.0433 (7)	−0.0086 (7)	0.0050 (6)	0.0103 (6)
O2	0.0287 (6)	0.0946 (11)	0.0613 (8)	−0.0088 (6)	0.0039 (5)	−0.0333 (8)
O3	0.0326 (6)	0.0773 (9)	0.0471 (7)	−0.0096 (6)	−0.0008 (5)	−0.0263 (6)
O4	0.0660 (9)	0.0695 (10)	0.0748 (10)	−0.0262 (8)	0.0099 (7)	−0.0365 (8)
O5	0.0489 (7)	0.0514 (8)	0.0592 (8)	−0.0065 (6)	0.0092 (6)	−0.0238 (6)
N1	0.0265 (7)	0.0497 (9)	0.0451 (8)	−0.0061 (6)	0.0012 (5)	−0.0090 (6)
C1	0.0363 (8)	0.0457 (10)	0.0419 (8)	−0.0037 (7)	0.0077 (7)	−0.0057 (7)
C2	0.0461 (10)	0.0515 (11)	0.0379 (8)	−0.0093 (8)	0.0135 (7)	−0.0056 (7)
C3	0.0469 (9)	0.0434 (10)	0.0352 (8)	−0.0143 (8)	0.0019 (7)	−0.0016 (7)
C4	0.0484 (10)	0.0450 (10)	0.0464 (9)	0.0020 (8)	0.0080 (8)	0.0000 (8)
C5	0.0427 (9)	0.0446 (10)	0.0394 (8)	−0.0015 (7)	0.0118 (7)	−0.0024 (7)
C6	0.0320 (7)	0.0376 (8)	0.0321 (7)	−0.0090 (6)	0.0020 (6)	−0.0075 (6)
C7	0.0282 (7)	0.0370 (8)	0.0326 (7)	−0.0019 (6)	0.0023 (5)	−0.0058 (6)
C8	0.0289 (7)	0.0381 (8)	0.0318 (7)	−0.0037 (6)	0.0001 (5)	−0.0035 (6)
C9	0.0304 (7)	0.0394 (9)	0.0340 (7)	−0.0040 (6)	−0.0003 (6)	−0.0020 (6)
C10	0.0350 (8)	0.0365 (9)	0.0407 (8)	−0.0058 (7)	−0.0051 (6)	−0.0015 (7)
C11	0.0373 (8)	0.0347 (8)	0.0333 (7)	−0.0046 (6)	−0.0018 (6)	−0.0016 (6)
C12	0.0630 (12)	0.0531 (12)	0.0514 (10)	−0.0148 (10)	−0.0137 (9)	0.0034 (9)
C13	0.108 (2)	0.0797 (17)	0.0598 (13)	−0.0203 (15)	−0.0214 (13)	0.0220 (12)
C14	0.0313 (8)	0.0452 (9)	0.0334 (7)	−0.0064 (7)	0.0008 (6)	−0.0042 (6)
C15	0.0381 (9)	0.0764 (14)	0.0486 (10)	−0.0115 (9)	−0.0083 (7)	−0.0171 (9)
C16	0.0631 (13)	0.0843 (17)	0.0649 (13)	−0.0092 (12)	−0.0098 (10)	−0.0308 (12)
C17	0.0466 (9)	0.0382 (9)	0.0387 (8)	−0.0076 (7)	0.0001 (7)	−0.0028 (7)
C18	0.0696 (14)	0.0679 (15)	0.0687 (13)	−0.0092 (11)	0.0135 (11)	−0.0369 (11)
C19	0.0758 (18)	0.135 (3)	0.128 (3)	−0.0290 (18)	0.0381 (17)	−0.086 (2)
C20	0.0338 (8)	0.0614 (12)	0.0430 (9)	−0.0055 (8)	0.0073 (7)	−0.0116 (8)
C21	0.0377 (9)	0.0557 (12)	0.0617 (11)	−0.0132 (8)	−0.0060 (8)	−0.0110 (9)

O1—C3	1.373 (2)	C10—C11	1.352 (2)
O1—C12	1.428 (2)	C10—C21	1.502 (2)
O2—C14	1.2115 (18)	C11—C17	1.465 (2)
O3—C14	1.3353 (19)	C12—C13	1.496 (3)
O3—C15	1.450 (2)	C12—H12A	0.97
O4—C17	1.210 (2)	C12—H12B	0.97
O5—C17	1.351 (2)	C13—H13A	0.96
O5—C18	1.455 (2)	C13—H13B	0.96
N1—C10	1.380 (2)	C13—H13C	0.96
N1—C9	1.380 (2)	C15—C16	1.488 (3)
N1—H1N1	0.85 (2)	C15—H15A	0.97
C1—C2	1.382 (2)	C15—H15B	0.97
C1—C6	1.393 (2)	C16—H16A	0.96
C1—H1A	0.93	C16—H16B	0.96
C2—C3	1.386 (3)	C16—H16C	0.96
C2—H2A	0.93	C18—C19	1.467 (3)
C3—C4	1.382 (2)	C18—H18A	0.97
C4—C5	1.389 (2)	C18—H18B	0.97
C4—H4A	0.93	C19—H19A	0.96
C5—C6	1.383 (2)	C19—H19B	0.96
C5—H5A	0.93	C19—H19C	0.96
C6—C7	1.535 (2)	C20—H20A	0.96
C7—C8	1.523 (2)	C20—H20B	0.96
C7—C11	1.527 (2)	C20—H20C	0.96
C7—H7A	0.98	C21—H21A	0.96
C8—C9	1.360 (2)	C21—H21B	0.96
C8—C14	1.466 (2)	C21—H21C	0.96
C9—C20	1.501 (2)
C3—O1—C12	117.87 (14)	C12—C13—H13A	109.5
C14—O3—C15	117.18 (13)	C12—C13—H13B	109.5
C17—O5—C18	115.21 (15)	H13A—C13—H13B	109.5
C10—N1—C9	123.89 (13)	C12—C13—H13C	109.5
C10—N1—H1N1	118.1 (15)	H13A—C13—H13C	109.5
C9—N1—H1N1	116.6 (15)	H13B—C13—H13C	109.5
C2—C1—C6	121.53 (16)	O2—C14—O3	121.24 (15)
C2—C1—H1A	119.2	O2—C14—C8	123.23 (14)
C6—C1—H1A	119.2	O3—C14—C8	115.52 (13)
C1—C2—C3	120.26 (15)	O3—C15—C16	107.77 (15)
C1—C2—H2A	119.9	O3—C15—H15A	110.2
C3—C2—H2A	119.9	C16—C15—H15A	110.2
O1—C3—C4	124.29 (16)	O3—C15—H15B	110.2
O1—C3—C2	116.40 (14)	C16—C15—H15B	110.2
C4—C3—C2	119.31 (15)	H15A—C15—H15B	108.5
C3—C4—C5	119.52 (16)	C15—C16—H16A	109.5
C3—C4—H4A	120.2	C15—C16—H16B	109.5
C5—C4—H4A	120.2	H16A—C16—H16B	109.5
C6—C5—C4	122.26 (15)	C15—C16—H16C	109.5
C6—C5—H5A	118.9	H16A—C16—H16C	109.5
C4—C5—H5A	118.9	H16B—C16—H16C	109.5
C5—C6—C1	117.05 (15)	O4—C17—O5	120.80 (16)
C5—C6—C7	121.32 (13)	O4—C17—C11	126.77 (16)
C1—C6—C7	121.55 (14)	O5—C17—C11	112.43 (14)
C8—C7—C11	110.43 (12)	O5—C18—C19	108.76 (19)
C8—C7—C6	111.55 (12)	O5—C18—H18A	109.9
C11—C7—C6	109.65 (12)	C19—C18—H18A	109.9
C8—C7—H7A	108.4	O5—C18—H18B	109.9
C11—C7—H7A	108.4	C19—C18—H18B	109.9
C6—C7—H7A	108.4	H18A—C18—H18B	108.3
C9—C8—C14	124.96 (14)	C18—C19—H19A	109.5
C9—C8—C7	120.06 (13)	C18—C19—H19B	109.5
C14—C8—C7	114.94 (12)	H19A—C19—H19B	109.5
C8—C9—N1	118.44 (14)	C18—C19—H19C	109.5
C8—C9—C20	129.12 (15)	H19A—C19—H19C	109.5
N1—C9—C20	112.44 (13)	H19B—C19—H19C	109.5
C11—C10—N1	119.10 (15)	C9—C20—H20A	109.5
C11—C10—C21	128.03 (15)	C9—C20—H20B	109.5
N1—C10—C21	112.87 (14)	H20A—C20—H20B	109.5
C10—C11—C17	120.26 (15)	C9—C20—H20C	109.5
C10—C11—C7	119.61 (14)	H20A—C20—H20C	109.5
C17—C11—C7	119.84 (13)	H20B—C20—H20C	109.5
O1—C12—C13	107.53 (18)	C10—C21—H21A	109.5
O1—C12—H12A	110.2	C10—C21—H21B	109.5
C13—C12—H12A	110.2	H21A—C21—H21B	109.5
O1—C12—H12B	110.2	C10—C21—H21C	109.5
C13—C12—H12B	110.2	H21A—C21—H21C	109.5
H12A—C12—H12B	108.5	H21B—C21—H21C	109.5
C6—C1—C2—C3	−0.3 (3)	C9—N1—C10—C11	−14.2 (2)
C12—O1—C3—C4	−15.4 (3)	C9—N1—C10—C21	166.34 (16)
C12—O1—C3—C2	165.31 (16)	N1—C10—C11—C17	176.38 (14)
C1—C2—C3—O1	−178.08 (16)	C21—C10—C11—C17	−4.2 (3)
C1—C2—C3—C4	2.6 (3)	N1—C10—C11—C7	−9.8 (2)
O1—C3—C4—C5	178.09 (17)	C21—C10—C11—C7	169.58 (16)
C2—C3—C4—C5	−2.7 (3)	C8—C7—C11—C10	29.0 (2)
C3—C4—C5—C6	0.4 (3)	C6—C7—C11—C10	−94.32 (16)
C4—C5—C6—C1	1.9 (3)	C8—C7—C11—C17	−157.19 (13)
C4—C5—C6—C7	−174.85 (16)	C6—C7—C11—C17	79.49 (17)
C2—C1—C6—C5	−1.9 (3)	C3—O1—C12—C13	−174.91 (18)
C2—C1—C6—C7	174.78 (16)	C15—O3—C14—O2	−4.4 (3)
C5—C6—C7—C8	−40.9 (2)	C15—O3—C14—C8	176.84 (15)
C1—C6—C7—C8	142.47 (15)	C9—C8—C14—O2	170.76 (18)
C5—C6—C7—C11	81.70 (18)	C7—C8—C14—O2	−11.3 (2)
C1—C6—C7—C11	−94.88 (17)	C9—C8—C14—O3	−10.5 (2)
C11—C7—C8—C9	−28.3 (2)	C7—C8—C14—O3	167.43 (14)
C6—C7—C8—C9	93.93 (17)	C14—O3—C15—C16	175.95 (18)
C11—C7—C8—C14	153.64 (13)	C18—O5—C17—O4	4.9 (3)
C6—C7—C8—C14	−84.16 (16)	C18—O5—C17—C11	−175.20 (16)
C14—C8—C9—N1	−173.78 (15)	C10—C11—C17—O4	2.0 (3)
C7—C8—C9—N1	8.3 (2)	C7—C11—C17—O4	−171.78 (17)
C14—C8—C9—C20	6.4 (3)	C10—C11—C17—O5	−177.96 (15)
C7—C8—C9—C20	−171.48 (16)	C7—C11—C17—O5	8.3 (2)
C10—N1—C9—C8	14.9 (2)	C17—O5—C18—C19	175.6 (2)
C10—N1—C9—C20	−165.23 (15)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N1···O2i	0.85 (2)	2.18 (2)	3.0045 (19)	165 (2)
C12—H12A···O4ii	0.97	2.51	3.458 (2)	166
C20—H20A···O3	0.96	2.14	2.7774 (19)	122
C16—H16A···Cg1iii	0.96	2.83	3.767 (2)	165

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N1⋯O2i	0.85 (2)	2.18 (2)	3.0045 (19)	165 (2)
C12—H12A⋯O4ii	0.97	2.51	3.458 (2)	166
C20—H20A⋯O3	0.96	2.14	2.7774 (19)	122
C16—H16A⋯Cg1iii	0.96	2.83	3.767 (2)	165

Symmetry codes: (i) ; (ii) ; (iii) . Cg1 is the centroid of the C1–C6 benzene ring.