Diethyl 2,6-dimethyl-4-p-tolyl-1,4-dihydro-pyridine-3,5-dicarboxyl-ate.

In the title compound, C(20)H(25)NO(4), the 1,4-dihydro-pyridine ring adopts a flattened-boat conformation and forms a dihedral angle of 89.77 (8)° with the benzene ring. Inter-molecular N-H⋯O hydrogen bonds result in the formation of extended chains parallel to the b axis.

Related literature

For general background 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 related 1,4-dihydro­pyridine structures, see: Fossheim et al. (1982 ▶); Teng et al. (2008 ▶); Bai et al. (2009 ▶). For the stability of the temperature controller used in the data collection, see: Cosier & Glazer (1986 ▶).

Experimental

Crystal data

C20H25NO4

M = 343.41

Monoclinic,

a = 10.0175 (1) Å

b = 7.4287 (1) Å

c = 25.0974 (3) Å

β = 105.528 (1)°

V = 1799.50 (4) Å3

Z = 4

Mo Kα radiation

μ = 0.09 mm−1

T = 100 K

0.31 × 0.15 × 0.05 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer

Absorption correction: multi-scan (; Bruker, 2005 ▶) T min = 0.973, T max = 0.996

20077 measured reflections

5309 independent reflections

3542 reflections with I > 2σ(I)

R int = 0.046

Refinement

R[F 2 > 2σ(F 2)] = 0.057

wR(F 2) = 0.147

S = 1.02

5309 reflections

231 parameters

H-atom parameters constrained

Δρmax = 0.33 e Å−3

Δρmin = −0.26 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/S1600536809035077/tk2533sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809035077/tk2533Isup2.hkl

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

C20H25NO4	F(000) = 736
Mr = 343.41	Dx = 1.268 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3769 reflections
a = 10.0175 (1) Å	θ = 2.9–27.7°
b = 7.4287 (1) Å	µ = 0.09 mm−1
c = 25.0974 (3) Å	T = 100 K
β = 105.528 (1)°	Plate, colourless
V = 1799.50 (4) Å3	0.31 × 0.15 × 0.05 mm
Z = 4

Bruker SMART APEXII CCD area-detector diffractometer	5309 independent reflections
Radiation source: fine-focus sealed tube	3542 reflections with I > 2σ(I)
graphite	Rint = 0.046
φ and ω scans	θmax = 30.1°, θmin = 2.1°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −14→14
Tmin = 0.973, Tmax = 0.996	k = −10→10
20077 measured reflections	l = −35→30

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)] = 0.057	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.147	H-atom parameters constrained
S = 1.02	w = 1/[σ2(Fo2) + (0.0648P)2 + 0.5567P] where P = (Fo2 + 2Fc2)/3
5309 reflections	(Δ/σ)max = 0.001
231 parameters	Δρmax = 0.33 e Å−3
0 restraints	Δρmin = −0.26 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	0.22376 (12)	0.93012 (15)	0.99648 (5)	0.0209 (3)
O2	0.11576 (12)	0.74263 (15)	1.04170 (5)	0.0193 (3)
O3	0.51279 (12)	0.43230 (17)	0.85637 (5)	0.0263 (3)
O4	0.43953 (12)	0.71714 (16)	0.86114 (5)	0.0226 (3)
N1	0.28643 (14)	0.30918 (19)	0.97456 (6)	0.0185 (3)
H1	0.2800	0.2043	0.9858	0.022*
C1	0.12624 (18)	0.8380 (2)	0.84689 (7)	0.0239 (4)
H1A	0.1920	0.9293	0.8559	0.029*
C2	0.01109 (18)	0.8600 (3)	0.80172 (7)	0.0257 (4)
H2A	0.0013	0.9654	0.7810	0.031*
C3	−0.08953 (17)	0.7263 (3)	0.78718 (7)	0.0229 (4)
C4	−0.07301 (18)	0.5727 (2)	0.81972 (7)	0.0245 (4)
H4A	−0.1401	0.4829	0.8115	0.029*
C5	0.04298 (17)	0.5511 (2)	0.86473 (7)	0.0216 (4)
H5A	0.0523	0.4465	0.8858	0.026*
C6	0.14465 (16)	0.6828 (2)	0.87865 (6)	0.0161 (3)
C7	0.27351 (16)	0.6541 (2)	0.92694 (6)	0.0155 (3)
H7A	0.3279	0.7655	0.9321	0.019*
C8	0.23295 (15)	0.6169 (2)	0.98026 (6)	0.0147 (3)
C9	0.23531 (15)	0.4472 (2)	1.00053 (6)	0.0162 (3)
C10	0.36055 (16)	0.3373 (2)	0.93593 (7)	0.0172 (3)
C11	0.36349 (15)	0.5037 (2)	0.91449 (7)	0.0164 (3)
C12	−0.21263 (19)	0.7489 (3)	0.73743 (8)	0.0305 (4)
H12A	−0.2578	0.6349	0.7279	0.046*
H12B	−0.1818	0.7931	0.7068	0.046*
H12C	−0.2765	0.8332	0.7460	0.046*
C13	0.19301 (15)	0.7769 (2)	1.00645 (6)	0.0159 (3)
C14	0.08916 (17)	0.8938 (2)	1.07421 (7)	0.0209 (4)
H14A	0.0075	0.8693	1.0868	0.025*
H14B	0.0716	1.0012	1.0514	0.025*
C15	0.2111 (2)	0.9245 (3)	1.12300 (8)	0.0320 (5)
H15A	0.1911	1.0216	1.1449	0.048*
H15B	0.2907	0.9545	1.1104	0.048*
H15C	0.2296	0.8170	1.1450	0.048*
C16	0.44652 (16)	0.5398 (2)	0.87521 (7)	0.0190 (3)
C17	0.50195 (18)	0.7686 (3)	0.81750 (7)	0.0264 (4)
H17A	0.5882	0.7034	0.8220	0.032*
H17B	0.5231	0.8962	0.8204	0.032*
C18	0.4070 (2)	0.7290 (3)	0.76142 (8)	0.0313 (4)
H18A	0.4428	0.7840	0.7335	0.047*
H18B	0.3165	0.7766	0.7592	0.047*
H18C	0.4008	0.6012	0.7557	0.047*
C19	0.19215 (18)	0.3867 (2)	1.05056 (7)	0.0200 (3)
H19A	0.2343	0.4630	1.0814	0.030*
H19B	0.2214	0.2646	1.0592	0.030*
H19C	0.0932	0.3939	1.0431	0.030*
C20	0.43324 (17)	0.1719 (2)	0.92385 (7)	0.0226 (4)
H20A	0.4138	0.1559	0.8846	0.034*
H20B	0.4011	0.0688	0.9399	0.034*
H20C	0.5313	0.1852	0.9394	0.034*

	U11	U22	U33	U12	U13	U23
O1	0.0275 (6)	0.0144 (6)	0.0225 (6)	0.0008 (5)	0.0094 (5)	0.0009 (5)
O2	0.0255 (6)	0.0153 (6)	0.0205 (6)	−0.0024 (5)	0.0120 (5)	−0.0047 (5)
O3	0.0255 (6)	0.0317 (8)	0.0250 (7)	0.0015 (5)	0.0126 (5)	−0.0034 (6)
O4	0.0257 (6)	0.0240 (7)	0.0217 (6)	−0.0031 (5)	0.0124 (5)	0.0043 (5)
N1	0.0245 (7)	0.0110 (7)	0.0214 (7)	−0.0001 (5)	0.0086 (6)	0.0007 (6)
C1	0.0240 (8)	0.0217 (9)	0.0259 (9)	−0.0020 (7)	0.0066 (7)	0.0049 (8)
C2	0.0272 (9)	0.0271 (10)	0.0233 (9)	0.0056 (7)	0.0076 (7)	0.0110 (8)
C3	0.0217 (8)	0.0322 (10)	0.0157 (8)	0.0069 (7)	0.0063 (6)	−0.0008 (7)
C4	0.0245 (8)	0.0242 (10)	0.0229 (9)	−0.0027 (7)	0.0031 (7)	−0.0037 (8)
C5	0.0267 (8)	0.0185 (9)	0.0184 (8)	−0.0019 (7)	0.0038 (7)	0.0026 (7)
C6	0.0184 (7)	0.0171 (8)	0.0146 (7)	0.0022 (6)	0.0076 (6)	−0.0006 (6)
C7	0.0180 (7)	0.0132 (8)	0.0159 (7)	−0.0017 (6)	0.0057 (6)	0.0001 (6)
C8	0.0164 (7)	0.0147 (8)	0.0127 (7)	−0.0010 (6)	0.0034 (6)	−0.0010 (6)
C9	0.0167 (7)	0.0165 (8)	0.0147 (7)	−0.0021 (6)	0.0033 (6)	−0.0011 (6)
C10	0.0170 (7)	0.0171 (8)	0.0172 (8)	−0.0016 (6)	0.0042 (6)	−0.0040 (7)
C11	0.0164 (7)	0.0168 (8)	0.0163 (8)	−0.0005 (6)	0.0047 (6)	−0.0031 (6)
C12	0.0288 (9)	0.0388 (12)	0.0212 (9)	0.0094 (8)	0.0023 (7)	0.0010 (8)
C13	0.0148 (7)	0.0181 (8)	0.0134 (7)	−0.0008 (6)	0.0015 (6)	0.0011 (6)
C14	0.0245 (8)	0.0176 (9)	0.0239 (9)	0.0005 (7)	0.0122 (7)	−0.0041 (7)
C15	0.0378 (11)	0.0348 (12)	0.0213 (9)	0.0069 (9)	0.0042 (8)	−0.0089 (8)
C16	0.0156 (7)	0.0243 (9)	0.0158 (8)	−0.0028 (6)	0.0022 (6)	−0.0029 (7)
C17	0.0266 (9)	0.0334 (11)	0.0219 (9)	−0.0067 (8)	0.0114 (7)	0.0030 (8)
C18	0.0316 (10)	0.0387 (12)	0.0233 (10)	−0.0062 (8)	0.0071 (8)	0.0032 (8)
C19	0.0271 (8)	0.0146 (8)	0.0195 (8)	−0.0006 (7)	0.0086 (7)	0.0015 (7)
C20	0.0218 (8)	0.0193 (9)	0.0275 (9)	0.0026 (7)	0.0079 (7)	−0.0015 (7)

O1—C13	1.223 (2)	C9—C19	1.502 (2)
O2—C13	1.3463 (19)	C10—C11	1.351 (2)
O2—C14	1.454 (2)	C10—C20	1.500 (2)
O3—C16	1.213 (2)	C11—C16	1.475 (2)
O4—C16	1.361 (2)	C12—H12A	0.9600
O4—C17	1.450 (2)	C12—H12B	0.9600
N1—C9	1.385 (2)	C12—H12C	0.9600
N1—C10	1.386 (2)	C14—C15	1.498 (2)
N1—H1	0.8370	C14—H14A	0.9700
C1—C6	1.386 (2)	C14—H14B	0.9700
C1—C2	1.394 (2)	C15—H15A	0.9600
C1—H1A	0.9300	C15—H15B	0.9600
C2—C3	1.392 (3)	C15—H15C	0.9600
C2—H2A	0.9300	C17—C18	1.502 (2)
C3—C4	1.387 (3)	C17—H17A	0.9700
C3—C12	1.511 (2)	C17—H17B	0.9700
C4—C5	1.396 (2)	C18—H18A	0.9600
C4—H4A	0.9300	C18—H18B	0.9600
C5—C6	1.387 (2)	C18—H18C	0.9600
C5—H5A	0.9300	C19—H19A	0.9600
C6—C7	1.531 (2)	C19—H19B	0.9600
C7—C11	1.520 (2)	C19—H19C	0.9600
C7—C8	1.524 (2)	C20—H20A	0.9600
C7—H7A	0.9800	C20—H20B	0.9600
C8—C9	1.357 (2)	C20—H20C	0.9600
C8—C13	1.465 (2)
C13—O2—C14	116.54 (13)	H12A—C12—H12C	109.5
C16—O4—C17	116.64 (14)	H12B—C12—H12C	109.5
C9—N1—C10	123.54 (14)	O1—C13—O2	122.08 (15)
C9—N1—H1	117.3	O1—C13—C8	123.33 (15)
C10—N1—H1	118.7	O2—C13—C8	114.57 (14)
C6—C1—C2	121.28 (17)	O2—C14—C15	110.15 (14)
C6—C1—H1A	119.4	O2—C14—H14A	109.6
C2—C1—H1A	119.4	C15—C14—H14A	109.6
C3—C2—C1	120.86 (16)	O2—C14—H14B	109.6
C3—C2—H2A	119.6	C15—C14—H14B	109.6
C1—C2—H2A	119.6	H14A—C14—H14B	108.1
C4—C3—C2	117.94 (16)	C14—C15—H15A	109.5
C4—C3—C12	121.34 (17)	C14—C15—H15B	109.5
C2—C3—C12	120.72 (17)	H15A—C15—H15B	109.5
C3—C4—C5	120.87 (16)	C14—C15—H15C	109.5
C3—C4—H4A	119.6	H15A—C15—H15C	109.5
C5—C4—H4A	119.6	H15B—C15—H15C	109.5
C6—C5—C4	121.24 (16)	O3—C16—O4	122.14 (15)
C6—C5—H5A	119.4	O3—C16—C11	127.33 (16)
C4—C5—H5A	119.4	O4—C16—C11	110.53 (14)
C1—C6—C5	117.77 (15)	O4—C17—C18	111.28 (14)
C1—C6—C7	121.68 (15)	O4—C17—H17A	109.4
C5—C6—C7	120.54 (14)	C18—C17—H17A	109.4
C11—C7—C8	111.04 (13)	O4—C17—H17B	109.4
C11—C7—C6	111.12 (13)	C18—C17—H17B	109.4
C8—C7—C6	110.72 (12)	H17A—C17—H17B	108.0
C11—C7—H7A	107.9	C17—C18—H18A	109.5
C8—C7—H7A	107.9	C17—C18—H18B	109.5
C6—C7—H7A	107.9	H18A—C18—H18B	109.5
C9—C8—C13	124.37 (14)	C17—C18—H18C	109.5
C9—C8—C7	121.06 (14)	H18A—C18—H18C	109.5
C13—C8—C7	114.56 (14)	H18B—C18—H18C	109.5
C8—C9—N1	118.86 (15)	C9—C19—H19A	109.5
C8—C9—C19	127.69 (15)	C9—C19—H19B	109.5
N1—C9—C19	113.42 (14)	H19A—C19—H19B	109.5
C11—C10—N1	119.30 (14)	C9—C19—H19C	109.5
C11—C10—C20	127.24 (15)	H19A—C19—H19C	109.5
N1—C10—C20	113.44 (14)	H19B—C19—H19C	109.5
C10—C11—C16	120.59 (15)	C10—C20—H20A	109.5
C10—C11—C7	120.89 (14)	C10—C20—H20B	109.5
C16—C11—C7	118.37 (14)	H20A—C20—H20B	109.5
C3—C12—H12A	109.5	C10—C20—H20C	109.5
C3—C12—H12B	109.5	H20A—C20—H20C	109.5
H12A—C12—H12B	109.5	H20B—C20—H20C	109.5
C3—C12—H12C	109.5
C6—C1—C2—C3	0.2 (3)	C9—N1—C10—C11	−12.4 (2)
C1—C2—C3—C4	1.4 (3)	C9—N1—C10—C20	166.21 (14)
C1—C2—C3—C12	−178.65 (17)	N1—C10—C11—C16	177.23 (14)
C2—C3—C4—C5	−1.7 (3)	C20—C10—C11—C16	−1.1 (2)
C12—C3—C4—C5	178.29 (16)	N1—C10—C11—C7	−7.3 (2)
C3—C4—C5—C6	0.6 (3)	C20—C10—C11—C7	174.40 (15)
C2—C1—C6—C5	−1.4 (3)	C8—C7—C11—C10	22.6 (2)
C2—C1—C6—C7	177.57 (15)	C6—C7—C11—C10	−101.07 (17)
C4—C5—C6—C1	1.0 (2)	C8—C7—C11—C16	−161.75 (13)
C4—C5—C6—C7	−177.94 (15)	C6—C7—C11—C16	74.54 (17)
C1—C6—C7—C11	−112.17 (17)	C14—O2—C13—O1	−9.6 (2)
C5—C6—C7—C11	66.73 (19)	C14—O2—C13—C8	172.05 (13)
C1—C6—C7—C8	123.94 (17)	C9—C8—C13—O1	160.80 (15)
C5—C6—C7—C8	−57.15 (19)	C7—C8—C13—O1	−19.1 (2)
C11—C7—C8—C9	−21.7 (2)	C9—C8—C13—O2	−20.9 (2)
C6—C7—C8—C9	102.23 (17)	C7—C8—C13—O2	159.24 (13)
C11—C7—C8—C13	158.16 (13)	C13—O2—C14—C15	−80.96 (18)
C6—C7—C8—C13	−77.91 (16)	C17—O4—C16—O3	7.0 (2)
C13—C8—C9—N1	−174.47 (14)	C17—O4—C16—C11	−172.52 (13)
C7—C8—C9—N1	5.4 (2)	C10—C11—C16—O3	3.5 (3)
C13—C8—C9—C19	3.4 (3)	C7—C11—C16—O3	−172.17 (15)
C7—C8—C9—C19	−176.74 (15)	C10—C11—C16—O4	−177.07 (14)
C10—N1—C9—C8	13.3 (2)	C7—C11—C16—O4	7.31 (19)
C10—N1—C9—C19	−164.90 (14)	C16—O4—C17—C18	80.78 (19)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1i	0.84	2.15	2.9684 (18)	166

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O1i	0.84	2.15	2.9684 (18)	166

Symmetry code: (i) .