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

In the title mol-ecule, C(19)H(23)NO(5), the dihedral angle formed by the benzene ring and the planar part of the dihydro-pyridine ring is 83.52 (5)°. The dihydro-pyridine ring adopts a flattened boat conformation. In the crystal, mol-ecules are linked by N-H⋯O hydrogen bonds, generating chains running parallel to [100]. The crystal structure is consolidated by C-H⋯O contacts.

Related literature

For general background to Hantzsch 1,4-dihydro­pyridines (1,4-DHPS), 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 a related structure, see: Fun et al. (2009 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶). For geometric analysis, see: Cremer & Pople (1975 ▶). For the stability of the temperature controller used for the data collection, see: Cosier & Glazer (1986 ▶).

Experimental

Crystal data

C19H23NO5

M = 345.38

Triclinic,

a = 7.4108 (1) Å

b = 9.7459 (2) Å

c = 12.3359 (2) Å

α = 87.412 (1)°

β = 86.244 (1)°

γ = 76.402 (1)°

V = 863.72 (3) Å3

Z = 2

Mo Kα radiation

μ = 0.10 mm−1

T = 100 K

0.39 × 0.33 × 0.19 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer

Absorption correction: multi-scan (; Bruker, 2005 ▶) T min = 0.963, T max = 0.982

26880 measured reflections

4579 independent reflections

3972 reflections with I > 2σ(I)

R int = 0.026

Refinement

R[F 2 > 2σ(F 2)] = 0.036

wR(F 2) = 0.099

S = 1.05

4579 reflections

235 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.38 e Å−3

Δρmin = −0.23 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/S1600536809033364/tk2529sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809033364/tk2529Isup2.hkl

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

C19H23NO5	Z = 2
Mr = 345.38	F(000) = 368
Triclinic, P1	Dx = 1.328 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.4108 (1) Å	Cell parameters from 9914 reflections
b = 9.7459 (2) Å	θ = 2.7–37.4°
c = 12.3359 (2) Å	µ = 0.10 mm−1
α = 87.412 (1)°	T = 100 K
β = 86.244 (1)°	Block, colourless
γ = 76.402 (1)°	0.39 × 0.33 × 0.19 mm
V = 863.72 (3) Å3

Bruker SMART APEXII CCD area-detector diffractometer	4579 independent reflections
Radiation source: fine-focus sealed tube	3972 reflections with I > 2σ(I)
graphite	Rint = 0.026
φ and ω scans	θmax = 29.0°, θmin = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −10→9
Tmin = 0.963, Tmax = 0.982	k = −13→13
26880 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)] = 0.036	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.099	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ2(Fo2) + (0.0475P)2 + 0.2882P] where P = (Fo2 + 2Fc2)/3
4579 reflections	(Δ/σ)max = 0.001
235 parameters	Δρmax = 0.38 e Å−3
0 restraints	Δρmin = −0.23 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 e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s 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	0.19861 (10)	0.60173 (8)	0.03818 (6)	0.01954 (16)
O2	0.44712 (10)	−0.06125 (8)	0.22047 (7)	0.02351 (17)
O3	0.75904 (10)	−0.12488 (7)	0.20146 (6)	0.01800 (15)
O4	0.12920 (9)	0.26642 (8)	0.49547 (6)	0.01857 (16)
O5	0.28689 (10)	0.36872 (8)	0.60451 (6)	0.01980 (16)
N1	0.78173 (11)	0.17632 (9)	0.43091 (7)	0.01522 (17)
C1	0.47641 (14)	0.38112 (11)	0.24725 (8)	0.0186 (2)
H1A	0.5811	0.3780	0.2858	0.022*
C2	0.42251 (14)	0.49057 (11)	0.17125 (9)	0.0205 (2)
H2A	0.4905	0.5593	0.1594	0.025*
C3	0.26590 (13)	0.49643 (10)	0.11306 (8)	0.01547 (19)
C4	0.16801 (13)	0.39106 (10)	0.12993 (8)	0.01699 (19)
H4A	0.0646	0.3934	0.0904	0.020*
C5	0.22500 (13)	0.28219 (10)	0.20605 (8)	0.01653 (19)
H5A	0.1593	0.2118	0.2163	0.020*
C6	0.37885 (12)	0.27631 (10)	0.26738 (7)	0.01368 (18)
C7	0.43800 (12)	0.16185 (10)	0.35541 (7)	0.01319 (17)
H7A	0.3410	0.1087	0.3666	0.016*
C8	0.61931 (12)	0.05947 (10)	0.32117 (7)	0.01377 (18)
C9	0.78381 (13)	0.07461 (10)	0.35543 (8)	0.01377 (18)
C10	0.62373 (13)	0.24334 (10)	0.49089 (8)	0.01427 (18)
C11	0.45520 (12)	0.22955 (10)	0.46159 (7)	0.01390 (18)
C12	0.28242 (15)	0.72105 (11)	0.03018 (9)	0.0222 (2)
H12A	0.4125	0.6916	0.0059	0.027*
H12B	0.2744	0.7636	0.1004	0.027*
C13	0.17764 (17)	0.82565 (13)	−0.05091 (10)	0.0293 (3)
H13A	0.2306	0.9067	−0.0585	0.044*
H13B	0.0494	0.8544	−0.0258	0.044*
H13C	0.1863	0.7823	−0.1200	0.044*
C14	0.59716 (13)	−0.04608 (10)	0.24493 (8)	0.01548 (18)
C15	0.73788 (15)	−0.22168 (12)	0.12099 (9)	0.0234 (2)
H15A	0.8579	−0.2777	0.0980	0.035*
H15B	0.6800	−0.1695	0.0596	0.035*
H15C	0.6617	−0.2824	0.1517	0.035*
C16	0.27731 (13)	0.28733 (10)	0.52057 (8)	0.01461 (18)
C17	0.11161 (14)	0.43650 (12)	0.65823 (9)	0.0214 (2)
H17A	0.1336	0.4930	0.7155	0.032*
H17B	0.0500	0.3659	0.6882	0.032*
H17C	0.0348	0.4957	0.6067	0.032*
C18	0.97650 (13)	−0.00902 (10)	0.32325 (8)	0.01687 (19)
H18A	1.0010	0.0034	0.2465	0.025*
H18B	0.9854	−0.1073	0.3408	0.025*
H18C	1.0659	0.0235	0.3619	0.025*
C19	0.66430 (13)	0.32411 (11)	0.58374 (8)	0.01801 (19)
H19A	0.5904	0.4192	0.5801	0.027*
H19B	0.7937	0.3254	0.5792	0.027*
H19C	0.6347	0.2793	0.6513	0.027*
H1N1	0.886 (2)	0.1880 (15)	0.4495 (12)	0.027 (3)*

	U11	U22	U33	U12	U13	U23
O1	0.0198 (4)	0.0181 (3)	0.0215 (4)	−0.0055 (3)	−0.0063 (3)	0.0054 (3)
O2	0.0157 (3)	0.0248 (4)	0.0319 (4)	−0.0066 (3)	−0.0035 (3)	−0.0084 (3)
O3	0.0157 (3)	0.0167 (3)	0.0220 (4)	−0.0044 (3)	0.0005 (3)	−0.0051 (3)
O4	0.0112 (3)	0.0236 (4)	0.0213 (4)	−0.0047 (3)	−0.0010 (3)	−0.0018 (3)
O5	0.0128 (3)	0.0258 (4)	0.0209 (4)	−0.0040 (3)	0.0011 (3)	−0.0073 (3)
N1	0.0099 (4)	0.0184 (4)	0.0181 (4)	−0.0042 (3)	−0.0022 (3)	−0.0015 (3)
C1	0.0154 (4)	0.0212 (5)	0.0214 (5)	−0.0075 (4)	−0.0074 (4)	0.0029 (4)
C2	0.0202 (5)	0.0200 (5)	0.0244 (5)	−0.0104 (4)	−0.0067 (4)	0.0040 (4)
C3	0.0153 (4)	0.0158 (4)	0.0144 (4)	−0.0017 (3)	−0.0015 (3)	−0.0002 (3)
C4	0.0142 (4)	0.0197 (5)	0.0178 (4)	−0.0043 (3)	−0.0046 (3)	−0.0001 (4)
C5	0.0149 (4)	0.0169 (4)	0.0194 (5)	−0.0066 (3)	−0.0033 (3)	0.0003 (4)
C6	0.0120 (4)	0.0144 (4)	0.0143 (4)	−0.0021 (3)	−0.0012 (3)	−0.0013 (3)
C7	0.0100 (4)	0.0144 (4)	0.0158 (4)	−0.0038 (3)	−0.0021 (3)	0.0000 (3)
C8	0.0120 (4)	0.0135 (4)	0.0159 (4)	−0.0034 (3)	−0.0009 (3)	0.0008 (3)
C9	0.0128 (4)	0.0130 (4)	0.0154 (4)	−0.0033 (3)	−0.0008 (3)	0.0019 (3)
C10	0.0132 (4)	0.0149 (4)	0.0147 (4)	−0.0033 (3)	−0.0016 (3)	0.0013 (3)
C11	0.0115 (4)	0.0152 (4)	0.0151 (4)	−0.0034 (3)	−0.0009 (3)	0.0004 (3)
C12	0.0249 (5)	0.0192 (5)	0.0238 (5)	−0.0078 (4)	−0.0035 (4)	0.0042 (4)
C13	0.0284 (6)	0.0243 (5)	0.0333 (6)	−0.0047 (4)	−0.0020 (5)	0.0120 (5)
C14	0.0149 (4)	0.0138 (4)	0.0178 (4)	−0.0040 (3)	−0.0009 (3)	0.0012 (3)
C15	0.0231 (5)	0.0214 (5)	0.0270 (5)	−0.0065 (4)	0.0003 (4)	−0.0093 (4)
C16	0.0130 (4)	0.0157 (4)	0.0147 (4)	−0.0028 (3)	−0.0011 (3)	0.0023 (3)
C17	0.0153 (5)	0.0247 (5)	0.0229 (5)	−0.0019 (4)	0.0026 (4)	−0.0055 (4)
C18	0.0112 (4)	0.0172 (4)	0.0221 (5)	−0.0029 (3)	−0.0012 (3)	−0.0005 (4)
C19	0.0135 (4)	0.0222 (5)	0.0192 (5)	−0.0050 (3)	−0.0033 (3)	−0.0033 (4)

O1—C3	1.3745 (11)	C8—C9	1.3580 (13)
O1—C12	1.4384 (13)	C8—C14	1.4686 (13)
O2—C14	1.2143 (12)	C9—C18	1.5062 (13)
O3—C14	1.3551 (11)	C10—C11	1.3605 (12)
O3—C15	1.4403 (12)	C10—C19	1.5033 (13)
O4—C16	1.2237 (11)	C11—C16	1.4651 (13)
O5—C16	1.3479 (12)	C12—C13	1.5100 (15)
O5—C17	1.4443 (12)	C12—H12A	0.9700
N1—C10	1.3841 (12)	C12—H12B	0.9700
N1—C9	1.3872 (12)	C13—H13A	0.9600
N1—H1N1	0.852 (15)	C13—H13B	0.9600
C1—C6	1.3888 (13)	C13—H13C	0.9600
C1—C2	1.3909 (14)	C15—H15A	0.9600
C1—H1A	0.9300	C15—H15B	0.9600
C2—C3	1.3928 (13)	C15—H15C	0.9600
C2—H2A	0.9300	C17—H17A	0.9600
C3—C4	1.3912 (14)	C17—H17B	0.9600
C4—C5	1.3919 (13)	C17—H17C	0.9600
C4—H4A	0.9300	C18—H18A	0.9600
C5—C6	1.3978 (12)	C18—H18B	0.9600
C5—H5A	0.9300	C18—H18C	0.9600
C6—C7	1.5293 (12)	C19—H19A	0.9600
C7—C11	1.5188 (13)	C19—H19B	0.9600
C7—C8	1.5207 (12)	C19—H19C	0.9600
C7—H7A	0.9800
C3—O1—C12	117.11 (8)	O1—C12—C13	107.30 (9)
C14—O3—C15	114.71 (8)	O1—C12—H12A	110.3
C16—O5—C17	116.10 (8)	C13—C12—H12A	110.3
C10—N1—C9	123.78 (8)	O1—C12—H12B	110.3
C10—N1—H1N1	117.3 (10)	C13—C12—H12B	110.3
C9—N1—H1N1	118.0 (10)	H12A—C12—H12B	108.5
C6—C1—C2	122.08 (9)	C12—C13—H13A	109.5
C6—C1—H1A	119.0	C12—C13—H13B	109.5
C2—C1—H1A	119.0	H13A—C13—H13B	109.5
C1—C2—C3	119.51 (9)	C12—C13—H13C	109.5
C1—C2—H2A	120.2	H13A—C13—H13C	109.5
C3—C2—H2A	120.2	H13B—C13—H13C	109.5
O1—C3—C4	116.37 (8)	O2—C14—O3	121.92 (9)
O1—C3—C2	124.04 (9)	O2—C14—C8	123.53 (9)
C4—C3—C2	119.58 (9)	O3—C14—C8	114.53 (8)
C3—C4—C5	119.90 (9)	O3—C15—H15A	109.5
C3—C4—H4A	120.1	O3—C15—H15B	109.5
C5—C4—H4A	120.1	H15A—C15—H15B	109.5
C4—C5—C6	121.45 (9)	O3—C15—H15C	109.5
C4—C5—H5A	119.3	H15A—C15—H15C	109.5
C6—C5—H5A	119.3	H15B—C15—H15C	109.5
C1—C6—C5	117.45 (9)	O4—C16—O5	121.62 (9)
C1—C6—C7	120.24 (8)	O4—C16—C11	123.31 (9)
C5—C6—C7	122.30 (8)	O5—C16—C11	115.06 (8)
C11—C7—C8	110.84 (7)	O5—C17—H17A	109.5
C11—C7—C6	109.88 (7)	O5—C17—H17B	109.5
C8—C7—C6	111.28 (7)	H17A—C17—H17B	109.5
C11—C7—H7A	108.2	O5—C17—H17C	109.5
C8—C7—H7A	108.2	H17A—C17—H17C	109.5
C6—C7—H7A	108.2	H17B—C17—H17C	109.5
C9—C8—C14	125.40 (9)	C9—C18—H18A	109.5
C9—C8—C7	120.71 (8)	C9—C18—H18B	109.5
C14—C8—C7	113.77 (8)	H18A—C18—H18B	109.5
C8—C9—N1	118.66 (8)	C9—C18—H18C	109.5
C8—C9—C18	127.97 (9)	H18A—C18—H18C	109.5
N1—C9—C18	113.36 (8)	H18B—C18—H18C	109.5
C11—C10—N1	118.71 (8)	C10—C19—H19A	109.5
C11—C10—C19	127.90 (9)	C10—C19—H19B	109.5
N1—C10—C19	113.39 (8)	H19A—C19—H19B	109.5
C10—C11—C16	124.96 (9)	C10—C19—H19C	109.5
C10—C11—C7	120.47 (8)	H19A—C19—H19C	109.5
C16—C11—C7	114.33 (8)	H19B—C19—H19C	109.5
C6—C1—C2—C3	0.06 (16)	C10—N1—C9—C18	−164.68 (8)
C12—O1—C3—C4	171.89 (9)	C9—N1—C10—C11	−12.56 (14)
C12—O1—C3—C2	−7.98 (14)	C9—N1—C10—C19	167.12 (9)
C1—C2—C3—O1	178.41 (9)	N1—C10—C11—C16	176.37 (8)
C1—C2—C3—C4	−1.46 (15)	C19—C10—C11—C16	−3.25 (16)
O1—C3—C4—C5	−178.70 (9)	N1—C10—C11—C7	−9.52 (13)
C2—C3—C4—C5	1.18 (15)	C19—C10—C11—C7	170.86 (9)
C3—C4—C5—C6	0.51 (15)	C8—C7—C11—C10	26.43 (12)
C2—C1—C6—C5	1.58 (15)	C6—C7—C11—C10	−96.98 (10)
C2—C1—C6—C7	−177.17 (9)	C8—C7—C11—C16	−158.87 (8)
C4—C5—C6—C1	−1.86 (15)	C6—C7—C11—C16	77.72 (10)
C4—C5—C6—C7	176.86 (9)	C3—O1—C12—C13	−176.21 (9)
C1—C6—C7—C11	51.88 (11)	C15—O3—C14—O2	2.92 (14)
C5—C6—C7—C11	−126.81 (9)	C15—O3—C14—C8	−175.86 (8)
C1—C6—C7—C8	−71.27 (11)	C9—C8—C14—O2	176.04 (10)
C5—C6—C7—C8	110.05 (10)	C7—C8—C14—O2	−7.83 (14)
C11—C7—C8—C9	−24.86 (12)	C9—C8—C14—O3	−5.20 (14)
C6—C7—C8—C9	97.74 (10)	C7—C8—C14—O3	170.92 (8)
C11—C7—C8—C14	158.81 (8)	C17—O5—C16—O4	−3.79 (13)
C6—C7—C8—C14	−78.58 (10)	C17—O5—C16—C11	175.00 (8)
C14—C8—C9—N1	−177.70 (8)	C10—C11—C16—O4	−175.82 (9)
C7—C8—C9—N1	6.43 (13)	C7—C11—C16—O4	9.75 (13)
C14—C8—C9—C18	0.95 (16)	C10—C11—C16—O5	5.42 (14)
C7—C8—C9—C18	−174.92 (9)	C7—C11—C16—O5	−169.02 (8)
C10—N1—C9—C8	14.15 (14)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N1···O4i	0.854 (15)	2.230 (15)	3.0710 (11)	168.0 (13)
C4—H4A···O1ii	0.93	2.58	3.5104 (12)	174
C15—H15A···O1iii	0.96	2.60	3.5500 (14)	172
C19—H19B···O4i	0.96	2.57	3.4677 (12)	155

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N1⋯O4i	0.854 (15)	2.230 (15)	3.0710 (11)	168.0 (13)
C4—H4A⋯O1ii	0.93	2.58	3.5104 (12)	174
C15—H15A⋯O1iii	0.96	2.60	3.5500 (14)	172
C19—H19B⋯O4i	0.96	2.57	3.4677 (12)	155

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