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

In the title compound, C(18)H(21)NO(5), the dihydro-pyridine ring adopts a flattened-boat conformation and its planar part forms a dihedral angle of 84.60 (2)° with the benzene ring. In the crystal, inter-molecular N-H⋯O and C-H⋯O hydrogen bonds result in the formation of zigzag layers parallel to (001). These layers are inter-connected via C-H⋯π inter-actions.

Related literature

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

Experimental

Crystal data

C18H21NO5

M = 331.36

Triclinic,

a = 7.4106 (3) Å

b = 9.5715 (5) Å

c = 11.7771 (6) Å

α = 83.029 (1)°

β = 83.834 (1)°

γ = 77.424 (1)°

V = 806.46 (7) Å3

Z = 2

Mo Kα radiation

μ = 0.10 mm−1

T = 100 K

0.35 × 0.34 × 0.24 mm

Data collection

Bruker SMART APEX DUO CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T min = 0.966, T max = 0.976

19600 measured reflections

4664 independent reflections

4319 reflections with I > 2σ(I)

R int = 0.019

Refinement

R[F 2 > 2σ(F 2)] = 0.037

wR(F 2) = 0.110

S = 1.05

4664 reflections

226 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.48 e Å−3

Δρmin = −0.22 e Å−3

Data collection: APEX DUO (Bruker, 2009 ▶); cell refinement: SAINT (Bruker, 2009 ▶); 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/S1600536810004940/ci5029sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810004940/ci5029Isup2.hkl

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

C18H21NO5	Z = 2
Mr = 331.36	F(000) = 352
Triclinic, P1	Dx = 1.365 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.4106 (3) Å	Cell parameters from 9874 reflections
b = 9.5715 (5) Å	θ = 2.8–37.5°
c = 11.7771 (6) Å	µ = 0.10 mm−1
α = 83.029 (1)°	T = 100 K
β = 83.834 (1)°	Block, colourless
γ = 77.424 (1)°	0.35 × 0.34 × 0.24 mm
V = 806.46 (7) Å3

Bruker SMART APEX DUO CCD area-detector diffractometer	4664 independent reflections
Radiation source: fine-focus sealed tube	4319 reflections with I > 2σ(I)
graphite	Rint = 0.019
φ and ω scans	θmax = 30.0°, θmin = 2.7°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −10→10
Tmin = 0.966, Tmax = 0.976	k = −13→13
19600 measured reflections	l = −15→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)] = 0.037	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.110	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ2(Fo2) + (0.0628P)2 + 0.2437P] where P = (Fo2 + 2Fc2)/3
4664 reflections	(Δ/σ)max = 0.001
226 parameters	Δρmax = 0.48 e Å−3
0 restraints	Δρmin = −0.22 e Å−3

Experimental. The crystal was placed in the cold stream of an Oxford Cryosystems 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 > 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
O1	0.19666 (9)	0.64176 (7)	0.02070 (6)	0.01872 (14)
O2	0.45751 (9)	−0.03547 (8)	0.19907 (6)	0.02053 (15)
O3	0.76827 (9)	−0.08374 (7)	0.16829 (6)	0.01754 (14)
O4	0.13686 (9)	0.26414 (7)	0.49736 (6)	0.01760 (14)
O5	0.29405 (9)	0.35204 (8)	0.61485 (6)	0.01934 (14)
N1	0.78947 (10)	0.17746 (8)	0.42720 (6)	0.01437 (14)
C1	0.22940 (12)	0.30263 (9)	0.19929 (7)	0.01528 (16)
H1A	0.1636	0.2291	0.2132	0.018*
C2	0.17064 (12)	0.41859 (9)	0.11955 (7)	0.01588 (16)
H2A	0.0667	0.4221	0.0806	0.019*
C3	0.26760 (11)	0.52967 (9)	0.09799 (7)	0.01404 (16)
C4	0.42555 (12)	0.52171 (9)	0.15453 (8)	0.01685 (17)
H4A	0.4930	0.5942	0.1393	0.020*
C5	0.48191 (12)	0.40434 (9)	0.23414 (8)	0.01621 (17)
H5A	0.5875	0.3997	0.2718	0.019*
C6	0.38473 (11)	0.29392 (9)	0.25892 (7)	0.01226 (15)
C7	0.44663 (11)	0.16962 (9)	0.34963 (7)	0.01211 (15)
H7A	0.3513	0.1114	0.3631	0.015*
C8	0.62773 (11)	0.07428 (8)	0.30836 (7)	0.01266 (15)
C9	0.79129 (11)	0.08547 (9)	0.34450 (7)	0.01310 (15)
C10	0.63106 (11)	0.23953 (9)	0.49133 (7)	0.01351 (15)
C11	0.46306 (11)	0.22785 (9)	0.46145 (7)	0.01275 (15)
C12	0.28140 (14)	0.76387 (10)	0.00644 (9)	0.02215 (19)
H12A	0.2151	0.8376	−0.0455	0.033*
H12B	0.4079	0.7363	−0.0243	0.033*
H12C	0.2782	0.7998	0.0794	0.033*
C13	0.60706 (12)	−0.01947 (9)	0.22266 (7)	0.01414 (16)
C14	0.74903 (14)	−0.16612 (11)	0.07708 (9)	0.02279 (19)
H14A	0.8698	−0.2091	0.0444	0.034*
H14B	0.6814	−0.1038	0.0188	0.034*
H14C	0.6831	−0.2403	0.1073	0.034*
C15	0.28484 (11)	0.28084 (9)	0.52454 (7)	0.01380 (16)
C16	0.11938 (13)	0.41561 (11)	0.67270 (8)	0.02036 (18)
H16A	0.1416	0.4659	0.7338	0.031*
H16B	0.0540	0.3414	0.7037	0.031*
H16C	0.0462	0.4819	0.6191	0.031*
C17	0.98251 (11)	0.00466 (9)	0.30817 (8)	0.01614 (16)
H17A	0.9862	−0.0969	0.3206	0.024*
H17B	1.0712	0.0281	0.3526	0.024*
H17C	1.0122	0.0312	0.2282	0.024*
C18	0.67039 (12)	0.31346 (10)	0.58865 (8)	0.01716 (17)
H18A	0.5985	0.4101	0.5848	0.026*
H18B	0.8000	0.3156	0.5830	0.026*
H18C	0.6379	0.2619	0.6604	0.026*
H1N1	0.895 (2)	0.1892 (17)	0.4467 (13)	0.030 (4)*

	U11	U22	U33	U12	U13	U23
O1	0.0186 (3)	0.0164 (3)	0.0206 (3)	−0.0040 (2)	−0.0063 (2)	0.0048 (2)
O2	0.0147 (3)	0.0233 (3)	0.0262 (3)	−0.0051 (2)	−0.0037 (2)	−0.0088 (3)
O3	0.0143 (3)	0.0177 (3)	0.0218 (3)	−0.0029 (2)	−0.0008 (2)	−0.0080 (2)
O4	0.0111 (3)	0.0237 (3)	0.0187 (3)	−0.0042 (2)	−0.0016 (2)	−0.0036 (2)
O5	0.0127 (3)	0.0272 (3)	0.0193 (3)	−0.0035 (2)	0.0003 (2)	−0.0099 (3)
N1	0.0095 (3)	0.0180 (3)	0.0168 (3)	−0.0037 (2)	−0.0026 (2)	−0.0036 (3)
C1	0.0140 (4)	0.0160 (4)	0.0171 (4)	−0.0055 (3)	−0.0041 (3)	0.0002 (3)
C2	0.0139 (4)	0.0177 (4)	0.0168 (4)	−0.0039 (3)	−0.0055 (3)	0.0001 (3)
C3	0.0140 (3)	0.0141 (3)	0.0131 (3)	−0.0013 (3)	−0.0014 (3)	−0.0005 (3)
C4	0.0166 (4)	0.0161 (4)	0.0192 (4)	−0.0068 (3)	−0.0043 (3)	0.0015 (3)
C5	0.0140 (4)	0.0178 (4)	0.0182 (4)	−0.0056 (3)	−0.0057 (3)	0.0009 (3)
C6	0.0111 (3)	0.0132 (3)	0.0125 (3)	−0.0021 (3)	−0.0014 (3)	−0.0017 (3)
C7	0.0098 (3)	0.0135 (3)	0.0133 (3)	−0.0027 (3)	−0.0021 (3)	−0.0010 (3)
C8	0.0117 (3)	0.0119 (3)	0.0144 (3)	−0.0025 (3)	−0.0016 (3)	−0.0010 (3)
C9	0.0120 (3)	0.0126 (3)	0.0146 (3)	−0.0029 (3)	−0.0010 (3)	−0.0003 (3)
C10	0.0124 (4)	0.0148 (3)	0.0134 (3)	−0.0028 (3)	−0.0021 (3)	−0.0006 (3)
C11	0.0109 (3)	0.0146 (3)	0.0128 (3)	−0.0028 (3)	−0.0012 (3)	−0.0010 (3)
C12	0.0258 (5)	0.0168 (4)	0.0238 (4)	−0.0066 (3)	−0.0043 (3)	0.0043 (3)
C13	0.0141 (4)	0.0123 (3)	0.0161 (4)	−0.0030 (3)	−0.0017 (3)	−0.0006 (3)
C14	0.0205 (4)	0.0232 (4)	0.0270 (5)	−0.0042 (3)	−0.0016 (3)	−0.0131 (4)
C15	0.0131 (3)	0.0148 (3)	0.0132 (3)	−0.0028 (3)	−0.0013 (3)	0.0000 (3)
C16	0.0149 (4)	0.0243 (4)	0.0218 (4)	−0.0022 (3)	0.0021 (3)	−0.0087 (3)
C17	0.0101 (3)	0.0161 (4)	0.0223 (4)	−0.0023 (3)	−0.0014 (3)	−0.0030 (3)
C18	0.0132 (4)	0.0221 (4)	0.0178 (4)	−0.0038 (3)	−0.0037 (3)	−0.0059 (3)

O1—C3	1.3697 (10)	C7—C8	1.5180 (11)
O1—C12	1.4276 (11)	C7—H7A	0.98
O2—C13	1.2163 (10)	C8—C9	1.3565 (11)
O3—C13	1.3516 (10)	C8—C13	1.4698 (11)
O3—C14	1.4433 (11)	C9—C17	1.5040 (11)
O4—C15	1.2226 (10)	C10—C11	1.3603 (11)
O5—C15	1.3461 (10)	C10—C18	1.5026 (11)
O5—C16	1.4416 (11)	C11—C15	1.4637 (11)
N1—C10	1.3843 (10)	C12—H12A	0.96
N1—C9	1.3872 (11)	C12—H12B	0.96
N1—H1N1	0.871 (16)	C12—H12C	0.96
C1—C2	1.3885 (11)	C14—H14A	0.96
C1—C6	1.3938 (11)	C14—H14B	0.96
C1—H1A	0.93	C14—H14C	0.96
C2—C3	1.3925 (12)	C16—H16A	0.96
C2—H2A	0.93	C16—H16B	0.96
C3—C4	1.3912 (12)	C16—H16C	0.96
C4—C5	1.3928 (11)	C17—H17A	0.96
C4—H4A	0.93	C17—H17B	0.96
C5—C6	1.3901 (11)	C17—H17C	0.96
C5—H5A	0.93	C18—H18A	0.96
C6—C7	1.5252 (11)	C18—H18B	0.96
C7—C11	1.5172 (11)	C18—H18C	0.96
C3—O1—C12	116.97 (7)	C10—C11—C15	124.91 (8)
C13—O3—C14	115.18 (7)	C10—C11—C7	120.70 (7)
C15—O5—C16	116.31 (7)	C15—C11—C7	114.13 (7)
C10—N1—C9	124.03 (7)	O1—C12—H12A	109.5
C10—N1—H1N1	116.8 (10)	O1—C12—H12B	109.5
C9—N1—H1N1	118.7 (10)	H12A—C12—H12B	109.5
C2—C1—C6	121.53 (8)	O1—C12—H12C	109.5
C2—C1—H1A	119.2	H12A—C12—H12C	109.5
C6—C1—H1A	119.2	H12B—C12—H12C	109.5
C1—C2—C3	119.85 (8)	O2—C13—O3	121.96 (8)
C1—C2—H2A	120.1	O2—C13—C8	123.36 (8)
C3—C2—H2A	120.1	O3—C13—C8	114.65 (7)
O1—C3—C4	124.45 (8)	O3—C14—H14A	109.5
O1—C3—C2	115.92 (7)	O3—C14—H14B	109.5
C4—C3—C2	119.63 (8)	H14A—C14—H14B	109.5
C3—C4—C5	119.49 (8)	O3—C14—H14C	109.5
C3—C4—H4A	120.3	H14A—C14—H14C	109.5
C5—C4—H4A	120.3	H14B—C14—H14C	109.5
C6—C5—C4	121.82 (8)	O4—C15—O5	121.67 (8)
C6—C5—H5A	119.1	O4—C15—C11	123.13 (8)
C4—C5—H5A	119.1	O5—C15—C11	115.20 (7)
C5—C6—C1	117.64 (7)	O5—C16—H16A	109.5
C5—C6—C7	120.39 (7)	O5—C16—H16B	109.5
C1—C6—C7	121.96 (7)	H16A—C16—H16B	109.5
C11—C7—C8	111.44 (6)	O5—C16—H16C	109.5
C11—C7—C6	109.82 (6)	H16A—C16—H16C	109.5
C8—C7—C6	110.88 (6)	H16B—C16—H16C	109.5
C11—C7—H7A	108.2	C9—C17—H17A	109.5
C8—C7—H7A	108.2	C9—C17—H17B	109.5
C6—C7—H7A	108.2	H17A—C17—H17B	109.5
C9—C8—C13	125.21 (7)	C9—C17—H17C	109.5
C9—C8—C7	120.89 (7)	H17A—C17—H17C	109.5
C13—C8—C7	113.77 (7)	H17B—C17—H17C	109.5
C8—C9—N1	118.88 (7)	C10—C18—H18A	109.5
C8—C9—C17	127.61 (8)	C10—C18—H18B	109.5
N1—C9—C17	113.47 (7)	H18A—C18—H18B	109.5
C11—C10—N1	118.71 (7)	C10—C18—H18C	109.5
C11—C10—C18	127.85 (8)	H18A—C18—H18C	109.5
N1—C10—C18	113.43 (7)	H18B—C18—H18C	109.5
C6—C1—C2—C3	−0.14 (13)	C10—N1—C9—C8	12.37 (12)
C12—O1—C3—C4	−6.29 (13)	C10—N1—C9—C17	−165.74 (7)
C12—O1—C3—C2	173.39 (8)	C9—N1—C10—C11	−10.00 (12)
C1—C2—C3—O1	−178.08 (8)	C9—N1—C10—C18	169.89 (7)
C1—C2—C3—C4	1.62 (13)	N1—C10—C11—C15	176.50 (7)
O1—C3—C4—C5	178.06 (8)	C18—C10—C11—C15	−3.38 (14)
C2—C3—C4—C5	−1.60 (13)	N1—C10—C11—C7	−9.74 (12)
C3—C4—C5—C6	0.12 (14)	C18—C10—C11—C7	170.39 (8)
C4—C5—C6—C1	1.32 (13)	C8—C7—C11—C10	24.10 (10)
C4—C5—C6—C7	−177.87 (8)	C6—C7—C11—C10	−99.17 (9)
C2—C1—C6—C5	−1.31 (13)	C8—C7—C11—C15	−161.50 (7)
C2—C1—C6—C7	177.87 (8)	C6—C7—C11—C15	75.23 (8)
C5—C6—C7—C11	53.55 (10)	C14—O3—C13—O2	2.95 (12)
C1—C6—C7—C11	−125.60 (8)	C14—O3—C13—C8	−174.88 (7)
C5—C6—C7—C8	−70.05 (10)	C9—C8—C13—O2	173.87 (8)
C1—C6—C7—C8	110.80 (9)	C7—C8—C13—O2	−10.26 (12)
C11—C7—C8—C9	−21.76 (10)	C9—C8—C13—O3	−8.34 (12)
C6—C7—C8—C9	100.90 (9)	C7—C8—C13—O3	167.53 (7)
C11—C7—C8—C13	162.17 (7)	C16—O5—C15—O4	−4.05 (12)
C6—C7—C8—C13	−75.16 (8)	C16—O5—C15—C11	175.05 (7)
C13—C8—C9—N1	−179.23 (7)	C10—C11—C15—O4	−177.44 (8)
C7—C8—C9—N1	5.17 (12)	C7—C11—C15—O4	8.43 (11)
C13—C8—C9—C17	−1.42 (14)	C10—C11—C15—O5	3.48 (12)
C7—C8—C9—C17	−177.01 (8)	C7—C11—C15—O5	−170.65 (7)

Cg1 is the centroid of the C1–C6 ring.

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N1···O4i	0.87 (2)	2.23 (2)	3.0906 (10)	169 (1)
C14—H14A···O1ii	0.96	2.54	3.4631 (13)	162
C18—H18B···O4i	0.96	2.56	3.4558 (12)	156
C12—H12B···Cg1iii	0.96	2.79	3.6549 (11)	151

Table 1

Hydrogen-bond geometry (Å, °)

Cg1 is the centroid of the C1–C6 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N1⋯O4i	0.87 (2)	2.23 (2)	3.0906 (10)	169 (1)
C14—H14A⋯O1ii	0.96	2.54	3.4631 (13)	162
C18—H18B⋯O4i	0.96	2.56	3.4558 (12)	156
C12—H12B⋯Cg1iii	0.96	2.79	3.6549 (11)	151

Symmetry codes: (i) ; (ii) ; (iii) .