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

In the title compound, C(19)H(23)NO(6), the 1,4-dihydro-pyridine ring is twisted slightly from planarity, with a maximum deviation of 0.101 (1) Å, and adopts a very flattened boat conformation. The dihedral angle formed between the plane through the four C atoms of the 1,4-dihydro-pyridine ring and the benzene ring is 84.67 (7)°. In the crystal structure, inter-molecular N-H⋯O and C-H⋯O hydrogen bonds link the mol-ecules into a three-dimensional network.

Related literature

For background to the biological activity of 1,4-dihydro­pyridines, see: Gaudio et al. (1994 ▶); Bocker & Guengerich (1986 ▶); Gordeev et al. (1996 ▶); Sunkel et al. (1992 ▶); Vo et al. (1995 ▶); Cooper et al. (1992 ▶). For the synthesis of Hantzsch pyridines, see: Rathore et al. (2009 ▶). For a related structure, see: Shahani et al. (2009 ▶). For reference bond-length data, see: Allen et al. (1987 ▶). For puckering parameters, see: Cremer & Pople (1975 ▶). For the stability of the temperature controller used for the data collection, see: Cosier & Glazer (1986 ▶).

Experimental

Crystal data

C19H23NO6

M = 361.38

Triclinic,

a = 7.3883 (6) Å

b = 10.0775 (8) Å

c = 12.3833 (10) Å

α = 105.372 (2)°

β = 90.255 (2)°

γ = 91.611 (2)°

V = 888.60 (12) Å3

Z = 2

Mo Kα radiation

μ = 0.10 mm−1

T = 100 K

0.51 × 0.41 × 0.18 mm

Data collection

Bruker APEXII DUO CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T min = 0.950, T max = 0.982

15520 measured reflections

4693 independent reflections

3996 reflections with I > 2σ(I)

R int = 0.023

Refinement

R[F 2 > 2σ(F 2)] = 0.038

wR(F 2) = 0.117

S = 1.05

4693 reflections

327 parameters

All H-atom parameters refined

Δρmax = 0.39 e Å−3

Δρmin = −0.21 e Å−3

Data collection: APEX2 (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/S160053681001679X/wn2383sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S160053681001679X/wn2383Isup2.hkl

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

C19H23NO6	Z = 2
Mr = 361.38	F(000) = 384
Triclinic, P1	Dx = 1.351 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.3883 (6) Å	Cell parameters from 8704 reflections
b = 10.0775 (8) Å	θ = 2.3–30.1°
c = 12.3833 (10) Å	µ = 0.10 mm−1
α = 105.372 (2)°	T = 100 K
β = 90.255 (2)°	Block, colourless
γ = 91.611 (2)°	0.51 × 0.41 × 0.18 mm
V = 888.60 (12) Å3

Bruker APEXII DUO CCD area-detector diffractometer	4693 independent reflections
Radiation source: fine-focus sealed tube	3996 reflections with I > 2σ(I)
graphite	Rint = 0.023
φ and ω scans	θmax = 29.0°, θmin = 1.7°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −10→9
Tmin = 0.950, Tmax = 0.982	k = −13→13
15520 measured reflections	l = −16→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)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.117	All H-atom parameters refined
S = 1.05	w = 1/[σ2(Fo2) + (0.0633P)2 + 0.3175P] where P = (Fo2 + 2Fc2)/3
4693 reflections	(Δ/σ)max < 0.001
327 parameters	Δρmax = 0.39 e Å−3
0 restraints	Δρmin = −0.21 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 > 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	0.13177 (12)	0.35766 (10)	0.50655 (8)	0.0253 (2)
O2	−0.09815 (12)	0.19240 (10)	0.56457 (8)	0.0271 (2)
O3	0.21291 (12)	−0.12807 (9)	0.77077 (7)	0.02175 (19)
O4	0.49285 (13)	−0.19568 (10)	0.71696 (9)	0.0311 (2)
O5	0.05882 (11)	0.30006 (9)	1.00996 (7)	0.01900 (18)
O6	0.26916 (11)	0.44327 (8)	1.11470 (7)	0.01862 (18)
N1	0.67178 (13)	0.18380 (10)	0.94785 (8)	0.0175 (2)
C1	0.39341 (15)	0.27760 (12)	0.73593 (10)	0.0175 (2)
C2	0.35435 (16)	0.33318 (12)	0.64648 (10)	0.0189 (2)
C3	0.18797 (16)	0.30518 (12)	0.59181 (9)	0.0178 (2)
C4	0.06117 (15)	0.21698 (12)	0.62489 (10)	0.0179 (2)
C5	0.10199 (15)	0.16280 (11)	0.71366 (9)	0.0166 (2)
C6	0.26780 (14)	0.19386 (11)	0.77130 (9)	0.0147 (2)
C7	0.30862 (14)	0.13710 (11)	0.87152 (9)	0.0141 (2)
C8	0.45041 (15)	0.02726 (11)	0.84314 (9)	0.0161 (2)
C9	0.62445 (15)	0.05553 (12)	0.87803 (10)	0.0172 (2)
C10	0.54594 (15)	0.27558 (11)	1.00303 (9)	0.0156 (2)
C11	0.36775 (14)	0.25185 (11)	0.97297 (9)	0.0146 (2)
C12	0.26124 (19)	0.43765 (14)	0.46362 (11)	0.0240 (3)
C13	−0.21854 (18)	0.08780 (16)	0.58366 (12)	0.0281 (3)
C14	0.39486 (16)	−0.10892 (12)	0.77100 (10)	0.0188 (2)
C15	0.14106 (19)	−0.25176 (13)	0.69309 (11)	0.0254 (3)
C16	0.77848 (16)	−0.04195 (13)	0.85144 (11)	0.0223 (2)
C17	0.62731 (15)	0.39180 (13)	1.09351 (10)	0.0195 (2)
C18	0.21850 (15)	0.33172 (11)	1.03232 (9)	0.0147 (2)
C19	0.12427 (16)	0.52520 (12)	1.17271 (10)	0.0201 (2)
H1A	0.509 (2)	0.3021 (17)	0.7758 (14)	0.027 (4)*
H2A	0.446 (2)	0.3860 (16)	0.6208 (14)	0.025 (4)*
H5A	0.015 (2)	0.1061 (15)	0.7381 (13)	0.019 (4)*
H7A	0.195 (2)	0.0945 (15)	0.8880 (13)	0.019 (4)*
H12A	0.193 (3)	0.4694 (18)	0.4082 (16)	0.036 (5)*
H12B	0.306 (2)	0.5163 (17)	0.5209 (14)	0.027 (4)*
H12C	0.357 (2)	0.3847 (17)	0.4310 (14)	0.026 (4)*
H13A	−0.160 (2)	0.0001 (18)	0.5738 (14)	0.027 (4)*
H13B	−0.272 (2)	0.1130 (16)	0.6595 (14)	0.023 (4)*
H13C	−0.316 (3)	0.0809 (19)	0.5306 (16)	0.040 (5)*
H15A	0.196 (2)	−0.3330 (18)	0.7040 (15)	0.030 (4)*
H15B	0.009 (3)	−0.2556 (18)	0.7063 (15)	0.038 (5)*
H15C	0.163 (3)	−0.2468 (18)	0.6172 (16)	0.034 (4)*
H16A	0.887 (3)	−0.001 (2)	0.8987 (17)	0.044 (5)*
H16B	0.812 (3)	−0.0635 (19)	0.7690 (16)	0.038 (5)*
H16C	0.746 (3)	−0.128 (2)	0.8611 (17)	0.044 (5)*
H17A	0.594 (2)	0.4817 (16)	1.0829 (13)	0.025 (4)*
H17B	0.576 (2)	0.3880 (17)	1.1657 (15)	0.032 (4)*
H17C	0.760 (3)	0.3858 (18)	1.0926 (15)	0.034 (4)*
H19A	0.058 (2)	0.5670 (17)	1.1248 (15)	0.031 (4)*
H19B	0.046 (3)	0.4709 (18)	1.2075 (15)	0.034 (4)*
H19C	0.187 (2)	0.5943 (18)	1.2325 (15)	0.032 (4)*
H1N1	0.786 (3)	0.2040 (17)	0.9681 (15)	0.031 (4)*

	U11	U22	U33	U12	U13	U23
O1	0.0210 (4)	0.0347 (5)	0.0258 (4)	−0.0061 (4)	−0.0070 (3)	0.0186 (4)
O2	0.0165 (4)	0.0412 (5)	0.0284 (5)	−0.0104 (4)	−0.0108 (3)	0.0188 (4)
O3	0.0172 (4)	0.0185 (4)	0.0264 (4)	−0.0006 (3)	−0.0042 (3)	0.0006 (3)
O4	0.0259 (5)	0.0216 (4)	0.0420 (6)	0.0043 (4)	0.0084 (4)	0.0011 (4)
O5	0.0101 (4)	0.0214 (4)	0.0246 (4)	−0.0004 (3)	−0.0016 (3)	0.0046 (3)
O6	0.0120 (4)	0.0197 (4)	0.0216 (4)	−0.0002 (3)	−0.0008 (3)	0.0012 (3)
N1	0.0081 (4)	0.0219 (5)	0.0234 (5)	−0.0006 (3)	−0.0009 (3)	0.0078 (4)
C1	0.0122 (5)	0.0209 (5)	0.0197 (5)	−0.0025 (4)	−0.0032 (4)	0.0064 (4)
C2	0.0162 (5)	0.0207 (5)	0.0208 (5)	−0.0040 (4)	−0.0011 (4)	0.0077 (4)
C3	0.0173 (5)	0.0199 (5)	0.0167 (5)	−0.0002 (4)	−0.0020 (4)	0.0063 (4)
C4	0.0123 (5)	0.0223 (5)	0.0190 (5)	−0.0021 (4)	−0.0038 (4)	0.0058 (4)
C5	0.0123 (5)	0.0191 (5)	0.0189 (5)	−0.0023 (4)	−0.0011 (4)	0.0059 (4)
C6	0.0121 (5)	0.0155 (5)	0.0162 (5)	0.0010 (4)	−0.0010 (4)	0.0037 (4)
C7	0.0094 (5)	0.0159 (5)	0.0177 (5)	−0.0008 (4)	−0.0012 (4)	0.0056 (4)
C8	0.0131 (5)	0.0166 (5)	0.0199 (5)	0.0010 (4)	0.0014 (4)	0.0070 (4)
C9	0.0136 (5)	0.0197 (5)	0.0210 (5)	0.0019 (4)	0.0028 (4)	0.0099 (4)
C10	0.0118 (5)	0.0192 (5)	0.0178 (5)	−0.0008 (4)	0.0001 (4)	0.0084 (4)
C11	0.0114 (5)	0.0170 (5)	0.0164 (5)	−0.0007 (4)	−0.0010 (4)	0.0064 (4)
C12	0.0246 (6)	0.0260 (6)	0.0240 (6)	−0.0037 (5)	−0.0018 (5)	0.0119 (5)
C13	0.0171 (6)	0.0402 (8)	0.0290 (7)	−0.0107 (5)	−0.0077 (5)	0.0141 (6)
C14	0.0189 (5)	0.0177 (5)	0.0216 (5)	0.0018 (4)	0.0008 (4)	0.0083 (4)
C15	0.0271 (7)	0.0188 (6)	0.0275 (6)	−0.0011 (5)	−0.0094 (5)	0.0017 (5)
C16	0.0141 (5)	0.0243 (6)	0.0320 (6)	0.0050 (4)	0.0037 (4)	0.0132 (5)
C17	0.0106 (5)	0.0248 (6)	0.0229 (5)	−0.0032 (4)	−0.0039 (4)	0.0064 (4)
C18	0.0126 (5)	0.0163 (5)	0.0165 (5)	−0.0008 (4)	−0.0010 (4)	0.0070 (4)
C19	0.0152 (5)	0.0214 (5)	0.0218 (5)	0.0019 (4)	0.0011 (4)	0.0021 (4)

O1—C3	1.3679 (14)	C7—H7A	0.980 (16)
O1—C12	1.4268 (15)	C8—C9	1.3530 (16)
O2—C4	1.3721 (13)	C8—C14	1.4713 (16)
O2—C13	1.4282 (15)	C9—C16	1.5044 (16)
O3—C14	1.3526 (15)	C10—C11	1.3637 (15)
O3—C15	1.4434 (14)	C10—C17	1.4991 (16)
O4—C14	1.2108 (15)	C11—C18	1.4654 (15)
O5—C18	1.2245 (14)	C12—H12A	0.974 (19)
O6—C18	1.3452 (13)	C12—H12B	0.962 (17)
O6—C19	1.4442 (14)	C12—H12C	0.927 (18)
N1—C10	1.3805 (14)	C13—H13A	0.972 (17)
N1—C9	1.3856 (15)	C13—H13B	0.992 (16)
N1—H1N1	0.879 (19)	C13—H13C	0.96 (2)
C1—C6	1.3860 (15)	C15—H15A	0.963 (18)
C1—C2	1.3997 (16)	C15—H15B	0.99 (2)
C1—H1A	0.977 (18)	C15—H15C	0.968 (19)
C2—C3	1.3860 (16)	C16—H16A	1.01 (2)
C2—H2A	0.956 (17)	C16—H16B	1.018 (19)
C3—C4	1.4090 (16)	C16—H16C	0.93 (2)
C4—C5	1.3862 (15)	C17—H17A	0.986 (16)
C5—C6	1.4002 (15)	C17—H17B	0.983 (18)
C5—H5A	0.952 (16)	C17—H17C	0.983 (19)
C6—C7	1.5300 (15)	C19—H19A	0.955 (18)
C7—C11	1.5176 (15)	C19—H19B	0.964 (19)
C7—C8	1.5194 (15)	C19—H19C	0.977 (19)
C3—O1—C12	117.10 (10)	O1—C12—H12A	104.1 (11)
C4—O2—C13	117.19 (9)	O1—C12—H12B	111.7 (10)
C14—O3—C15	115.84 (10)	H12A—C12—H12B	109.0 (14)
C18—O6—C19	116.00 (9)	O1—C12—H12C	111.0 (10)
C10—N1—C9	123.01 (10)	H12A—C12—H12C	111.1 (15)
C10—N1—H1N1	116.4 (12)	H12B—C12—H12C	109.8 (15)
C9—N1—H1N1	119.8 (11)	O2—C13—H13A	112.5 (10)
C6—C1—C2	121.00 (10)	O2—C13—H13B	112.9 (9)
C6—C1—H1A	120.0 (10)	H13A—C13—H13B	107.8 (13)
C2—C1—H1A	118.9 (10)	O2—C13—H13C	105.0 (11)
C3—C2—C1	120.15 (10)	H13A—C13—H13C	111.4 (15)
C3—C2—H2A	120.4 (10)	H13B—C13—H13C	107.3 (15)
C1—C2—H2A	119.3 (10)	O4—C14—O3	122.11 (11)
O1—C3—C2	125.46 (10)	O4—C14—C8	126.90 (11)
O1—C3—C4	115.17 (10)	O3—C14—C8	110.99 (10)
C2—C3—C4	119.36 (10)	O3—C15—H15A	111.8 (11)
O2—C4—C5	124.82 (10)	O3—C15—H15B	106.8 (11)
O2—C4—C3	115.45 (10)	H15A—C15—H15B	109.8 (15)
C5—C4—C3	119.73 (10)	O3—C15—H15C	109.4 (11)
C4—C5—C6	121.17 (10)	H15A—C15—H15C	109.0 (15)
C4—C5—H5A	119.9 (9)	H15B—C15—H15C	109.9 (16)
C6—C5—H5A	118.9 (9)	C9—C16—H16A	109.7 (11)
C1—C6—C5	118.54 (10)	C9—C16—H16B	111.5 (11)
C1—C6—C7	120.84 (9)	H16A—C16—H16B	109.3 (16)
C5—C6—C7	120.61 (9)	C9—C16—H16C	111.6 (12)
C11—C7—C8	110.65 (9)	H16A—C16—H16C	111.3 (16)
C11—C7—C6	111.02 (8)	H16B—C16—H16C	103.2 (16)
C8—C7—C6	111.31 (9)	C10—C17—H17A	111.1 (10)
C11—C7—H7A	109.2 (9)	C10—C17—H17B	108.8 (10)
C8—C7—H7A	108.6 (9)	H17A—C17—H17B	105.9 (14)
C6—C7—H7A	105.9 (9)	C10—C17—H17C	109.5 (10)
C9—C8—C14	120.87 (10)	H17A—C17—H17C	109.0 (14)
C9—C8—C7	121.20 (10)	H17B—C17—H17C	112.5 (15)
C14—C8—C7	117.85 (9)	O5—C18—O6	121.78 (10)
C8—C9—N1	119.50 (10)	O5—C18—C11	123.15 (10)
C8—C9—C16	126.29 (11)	O6—C18—C11	115.07 (9)
N1—C9—C16	114.19 (10)	O6—C19—H19A	112.1 (11)
C11—C10—N1	119.03 (10)	O6—C19—H19B	110.5 (11)
C11—C10—C17	127.59 (10)	H19A—C19—H19B	111.5 (16)
N1—C10—C17	113.37 (9)	O6—C19—H19C	103.4 (11)
C10—C11—C18	124.66 (10)	H19A—C19—H19C	111.4 (15)
C10—C11—C7	121.19 (10)	H19B—C19—H19C	107.6 (15)
C18—C11—C7	114.15 (9)
C6—C1—C2—C3	0.14 (18)	C14—C8—C9—C16	−0.70 (18)
C12—O1—C3—C2	6.09 (18)	C7—C8—C9—C16	−177.18 (10)
C12—O1—C3—C4	−174.62 (11)	C10—N1—C9—C8	13.87 (16)
C1—C2—C3—O1	177.31 (11)	C10—N1—C9—C16	−164.32 (10)
C1—C2—C3—C4	−1.96 (18)	C9—N1—C10—C11	−12.47 (16)
C13—O2—C4—C5	−9.85 (18)	C9—N1—C10—C17	166.41 (10)
C13—O2—C4—C3	170.68 (11)	N1—C10—C11—C18	172.89 (10)
O1—C3—C4—O2	2.12 (16)	C17—C10—C11—C18	−5.82 (18)
C2—C3—C4—O2	−178.53 (11)	N1—C10—C11—C7	−7.50 (16)
O1—C3—C4—C5	−177.37 (10)	C17—C10—C11—C7	173.78 (10)
C2—C3—C4—C5	1.97 (17)	C8—C7—C11—C10	22.90 (14)
O2—C4—C5—C6	−179.60 (11)	C6—C7—C11—C10	−101.21 (12)
C3—C4—C5—C6	−0.16 (18)	C8—C7—C11—C18	−157.45 (9)
C2—C1—C6—C5	1.66 (17)	C6—C7—C11—C18	78.44 (11)
C2—C1—C6—C7	−178.00 (10)	C15—O3—C14—O4	−6.40 (17)
C4—C5—C6—C1	−1.65 (17)	C15—O3—C14—C8	173.30 (10)
C4—C5—C6—C7	178.01 (10)	C9—C8—C14—O4	−16.87 (19)
C1—C6—C7—C11	52.50 (13)	C7—C8—C14—O4	159.72 (12)
C5—C6—C7—C11	−127.15 (11)	C9—C8—C14—O3	163.45 (10)
C1—C6—C7—C8	−71.23 (13)	C7—C8—C14—O3	−19.96 (14)
C5—C6—C7—C8	109.12 (11)	C19—O6—C18—O5	−1.71 (15)
C11—C7—C8—C9	−21.56 (14)	C19—O6—C18—C11	178.71 (9)
C6—C7—C8—C9	102.39 (12)	C10—C11—C18—O5	−172.80 (11)
C11—C7—C8—C14	161.86 (9)	C7—C11—C18—O5	7.57 (15)
C6—C7—C8—C14	−74.20 (12)	C10—C11—C18—O6	6.78 (16)
C14—C8—C9—N1	−178.65 (10)	C7—C11—C18—O6	−172.85 (9)
C7—C8—C9—N1	4.87 (16)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N1···O5i	0.88 (2)	2.21 (2)	3.0750 (13)	166.7 (16)
C12—H12C···O4ii	0.926 (16)	2.550 (17)	3.4120 (17)	155.0 (13)
C15—H15C···O2iii	0.968 (19)	2.501 (19)	3.4136 (17)	157.0 (17)
C17—H17C···O5i	0.98 (2)	2.52 (2)	3.4318 (14)	154.9 (15)
C19—H19A···O5iv	0.954 (17)	2.562 (18)	3.5023 (15)	168.7 (13)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N1⋯O5i	0.88 (2)	2.21 (2)	3.0750 (13)	166.7 (16)
C12—H12C⋯O4ii	0.926 (16)	2.550 (17)	3.4120 (17)	155.0 (13)
C15—H15C⋯O2iii	0.968 (19)	2.501 (19)	3.4136 (17)	157.0 (17)
C17—H17C⋯O5i	0.98 (2)	2.52 (2)	3.4318 (14)	154.9 (15)
C19—H19A⋯O5iv	0.954 (17)	2.562 (18)	3.5023 (15)	168.7 (13)

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