Dimethyl 2,6-dimethyl-1,4-dihydro-pyridine-3,5-dicarboxyl-ate.

In the crystal of the title compound, C(11)H(15)NO(4), the mol-ecules are linked into sheets by N-H⋯O and C-H⋯O hydrogen bonds. Within the mol-ecule, the 1,4-dihydro-pyridine ring exhibits a distinctive planar conformation [r.m.s. deviation from the mean plane of 0.009 (3)Å], and the other non-H atoms are almost coplanar [r.m.s. deviation = 0.021 (3) Å] with the 1,4-dihydro-pyridine ring. The conformation of the latter is governed mainly by two intra-molecular C-H⋯O non-classical inter-actions.

Related literature

For general background to the biological activity of 1,4-dihydro­pyridine derivatives, see: Kazda & Towart (1981 ▶); Janis & Triggle (1983 ▶); Núñez-Vergara et al., (1998 ▶); Mak et al., (2002 ▶). For their synthesis, see: Hantzsch & Liebigs (1882 ▶). For related structures, see: Bai et al. (2009 ▶); Quesada et al. (2006 ▶); Ramesh et al. (2008 ▶); Zhao & Teng (2008 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶).

Experimental

Crystal data

C11H15NO4

M = 225.24

Triclinic,

a = 7.3933 (13) Å

b = 7.8391 (14) Å

c = 11.1847 (19) Å

α = 75.977 (2)°

β = 75.274 (2)°

γ = 64.351 (2)°

V = 558.62 (17) Å3

Z = 2

Mo Kα radiation

μ = 0.10 mm−1

T = 293 K

0.49 × 0.43 × 0.25 mm

Data collection

Bruker SMART CCD diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 2003 ▶) T min = 0.952, T max = 0.965

3550 measured reflections

2047 independent reflections

1764 reflections with I > 2σ(I)

R int = 0.015

Refinement

R[F 2 > 2σ(F 2)] = 0.040

wR(F 2) = 0.115

S = 1.05

2047 reflections

148 parameters

H-atom parameters constrained

Δρmax = 0.16 e Å−3

Δρmin = −0.23 e Å−3

Data collection: SMART (Bruker, 1997 ▶); cell refinement: SAINT (Bruker, 1997 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809035478/rk2162sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809035478/rk2162Isup2.hkl

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

C11H15NO4	Z = 2
Mr = 225.24	F(000) = 240
Triclinic, P1	Dx = 1.339 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.3933 (13) Å	Cell parameters from 2071 reflections
b = 7.8391 (14) Å	θ = 2.9–28.1°
c = 11.1847 (19) Å	µ = 0.10 mm−1
α = 75.977 (2)°	T = 293 K
β = 75.274 (2)°	Block, blue
γ = 64.351 (2)°	0.49 × 0.43 × 0.25 mm
V = 558.62 (17) Å3

Bruker SMART CCD diffractometer	2047 independent reflections
Radiation source: fine-focus sealed tube	1764 reflections with I > 2σ(I)
graphite	Rint = 0.015
φ and ω scans	θmax = 25.5°, θmin = 2.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	h = −8→8
Tmin = 0.952, Tmax = 0.965	k = −9→9
3550 measured reflections	l = −12→13

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.040	H-atom parameters constrained
wR(F2) = 0.115	w = 1/[σ2(Fo2) + (0.0612P)2 + 0.1212P] where P = (Fo2 + 2Fc2)/3
S = 1.05	(Δ/σ)max < 0.001
2047 reflections	Δρmax = 0.16 e Å−3
148 parameters	Δρmin = −0.23 e Å−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.26 (2)

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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	Occ. (<1)
C1	−0.2092 (2)	0.24631 (19)	0.60198 (13)	0.0371 (3)
C2	−0.0517 (2)	0.24220 (18)	0.64524 (13)	0.0355 (3)
C3	0.1441 (2)	0.2394 (2)	0.55870 (13)	0.0366 (3)
H3A	0.1702	0.3463	0.5677	0.044*
H3B	0.2561	0.1224	0.5837	0.044*
C4	0.13729 (19)	0.25116 (18)	0.42266 (12)	0.0328 (3)
C5	−0.0262 (2)	0.25369 (18)	0.38665 (12)	0.0348 (3)
C6	−0.4103 (2)	0.2499 (3)	0.67563 (16)	0.0519 (4)
H6A	−0.4925	0.2528	0.6204	0.078*	0.50
H6B	−0.4787	0.3618	0.7161	0.078*	0.50
H6C	−0.3888	0.1374	0.7376	0.078*	0.50
H6D	−0.4142	0.2485	0.7623	0.078*	0.50
H6E	−0.4280	0.1396	0.6666	0.078*	0.50
H6F	−0.5178	0.3639	0.6452	0.078*	0.50
C7	−0.0548 (2)	0.2638 (2)	0.25662 (14)	0.0467 (4)
H7A	−0.1855	0.2633	0.2596	0.070*	0.50
H7B	0.0502	0.1553	0.2209	0.070*	0.50
H7C	−0.0474	0.3794	0.2062	0.070*	0.50
H7D	0.0637	0.2687	0.1982	0.070*	0.50
H7E	−0.1720	0.3767	0.2369	0.070*	0.50
H7F	−0.0744	0.1526	0.2516	0.070*	0.50
C8	−0.0642 (2)	0.2376 (2)	0.77872 (14)	0.0430 (4)
C9	0.3211 (2)	0.25935 (19)	0.33790 (13)	0.0359 (3)
C10	0.1095 (4)	0.2341 (3)	0.93016 (16)	0.0699 (6)
H10A	−0.0084	0.3384	0.9621	0.105*
H10B	0.2303	0.2470	0.9358	0.105*
H10C	0.1084	0.1152	0.9784	0.105*
C11	0.5033 (3)	0.2757 (3)	0.13100 (16)	0.0647 (5)
H11A	0.5180	0.3911	0.1320	0.097*
H11B	0.4925	0.2720	0.0480	0.097*
H11C	0.6199	0.1669	0.1563	0.097*
N1	−0.19256 (17)	0.24966 (18)	0.47535 (11)	0.0401 (3)
H1	−0.2931	0.2492	0.4504	0.048*
O1	0.10679 (18)	0.23698 (18)	0.80131 (9)	0.0537 (3)
O2	−0.2029 (2)	0.2326 (2)	0.86306 (11)	0.0705 (4)
O3	0.32231 (16)	0.27138 (19)	0.21605 (10)	0.0547 (3)
O4	0.46494 (15)	0.25501 (17)	0.37415 (10)	0.0499 (3)

	U11	U22	U33	U12	U13	U23
C1	0.0345 (7)	0.0403 (7)	0.0361 (7)	−0.0168 (6)	−0.0018 (6)	−0.0055 (5)
C2	0.0353 (7)	0.0396 (7)	0.0318 (7)	−0.0161 (6)	−0.0029 (5)	−0.0060 (5)
C3	0.0323 (7)	0.0479 (8)	0.0329 (7)	−0.0183 (6)	−0.0047 (5)	−0.0082 (6)
C4	0.0314 (7)	0.0376 (7)	0.0307 (7)	−0.0148 (5)	−0.0047 (5)	−0.0062 (5)
C5	0.0341 (7)	0.0384 (7)	0.0338 (7)	−0.0161 (5)	−0.0059 (5)	−0.0052 (5)
C6	0.0397 (8)	0.0718 (11)	0.0470 (9)	−0.0287 (7)	0.0017 (7)	−0.0108 (7)
C7	0.0443 (8)	0.0679 (10)	0.0366 (8)	−0.0290 (7)	−0.0102 (6)	−0.0063 (7)
C8	0.0458 (8)	0.0471 (8)	0.0353 (8)	−0.0201 (6)	−0.0011 (6)	−0.0077 (6)
C9	0.0329 (7)	0.0415 (7)	0.0341 (7)	−0.0157 (6)	−0.0052 (5)	−0.0058 (5)
C10	0.0973 (15)	0.0926 (14)	0.0354 (9)	−0.0492 (12)	−0.0171 (9)	−0.0088 (8)
C11	0.0512 (10)	0.1089 (15)	0.0386 (9)	−0.0428 (10)	0.0079 (7)	−0.0144 (9)
N1	0.0324 (6)	0.0575 (7)	0.0369 (7)	−0.0239 (5)	−0.0061 (5)	−0.0066 (5)
O1	0.0599 (7)	0.0802 (8)	0.0319 (6)	−0.0359 (6)	−0.0090 (5)	−0.0106 (5)
O2	0.0668 (8)	0.1125 (11)	0.0357 (6)	−0.0465 (8)	0.0095 (6)	−0.0153 (6)
O3	0.0457 (6)	0.0966 (9)	0.0316 (6)	−0.0411 (6)	0.0011 (4)	−0.0101 (5)
O4	0.0356 (6)	0.0772 (8)	0.0430 (6)	−0.0284 (5)	−0.0049 (4)	−0.0103 (5)

C1—C2	1.356 (2)	C7—H7B	0.9600
C1—N1	1.3848 (18)	C7—H7C	0.9600
C1—C6	1.4976 (19)	C7—H7D	0.9600
C2—C8	1.465 (2)	C7—H7E	0.9600
C2—C3	1.5172 (18)	C7—H7F	0.9600
C3—C4	1.5142 (18)	C8—O2	1.2114 (19)
C3—H3A	0.9700	C8—O1	1.3489 (19)
C3—H3B	0.9700	C9—O4	1.2154 (17)
C4—C5	1.3587 (19)	C9—O3	1.3411 (17)
C4—C9	1.4634 (18)	C10—O1	1.4410 (19)
C5—N1	1.3771 (17)	C10—H10A	0.9600
C5—C7	1.5007 (19)	C10—H10B	0.9600
C6—H6A	0.9600	C10—H10C	0.9600
C6—H6B	0.9600	C11—O3	1.4396 (18)
C6—H6C	0.9600	C11—H11A	0.9600
C6—H6D	0.9600	C11—H11B	0.9600
C6—H6E	0.9600	C11—H11C	0.9600
C6—H6F	0.9600	N1—H1	0.8600
C7—H7A	0.9600
C2—C1—N1	119.37 (12)	C5—C7—H7C	109.5
C2—C1—C6	127.69 (13)	H7A—C7—H7C	109.5
N1—C1—C6	112.93 (12)	H7B—C7—H7C	109.5
C1—C2—C8	120.67 (12)	C5—C7—H7D	109.5
C1—C2—C3	121.77 (12)	H7A—C7—H7D	141.1
C8—C2—C3	117.56 (12)	H7B—C7—H7D	56.3
C4—C3—C2	112.94 (11)	H7C—C7—H7D	56.3
C4—C3—H3A	109.0	C5—C7—H7E	109.5
C2—C3—H3A	109.0	H7A—C7—H7E	56.3
C4—C3—H3B	109.0	H7B—C7—H7E	141.1
C2—C3—H3B	109.0	H7C—C7—H7E	56.3
H3A—C3—H3B	107.8	H7D—C7—H7E	109.5
C5—C4—C9	124.99 (12)	C5—C7—H7F	109.5
C5—C4—C3	121.76 (12)	H7A—C7—H7F	56.3
C9—C4—C3	113.25 (11)	H7B—C7—H7F	56.3
C4—C5—N1	119.50 (12)	H7C—C7—H7F	141.1
C4—C5—C7	127.93 (12)	H7D—C7—H7F	109.5
N1—C5—C7	112.57 (11)	H7E—C7—H7F	109.5
C1—C6—H6A	109.5	O2—C8—O1	121.07 (14)
C1—C6—H6B	109.5	O2—C8—C2	127.86 (15)
H6A—C6—H6B	109.5	O1—C8—C2	111.06 (12)
C1—C6—H6C	109.5	O4—C9—O3	121.45 (12)
H6A—C6—H6C	109.5	O4—C9—C4	122.90 (13)
H6B—C6—H6C	109.5	O3—C9—C4	115.65 (11)
C1—C6—H6D	109.5	O1—C10—H10A	109.5
H6A—C6—H6D	141.1	O1—C10—H10B	109.5
H6B—C6—H6D	56.3	H10A—C10—H10B	109.5
H6C—C6—H6D	56.3	O1—C10—H10C	109.5
C1—C6—H6E	109.5	H10A—C10—H10C	109.5
H6A—C6—H6E	56.3	H10B—C10—H10C	109.5
H6B—C6—H6E	141.1	O3—C11—H11A	109.5
H6C—C6—H6E	56.3	O3—C11—H11B	109.5
H6D—C6—H6E	109.5	H11A—C11—H11B	109.5
C1—C6—H6F	109.5	O3—C11—H11C	109.5
H6A—C6—H6F	56.3	H11A—C11—H11C	109.5
H6B—C6—H6F	56.3	H11B—C11—H11C	109.5
H6C—C6—H6F	141.1	C5—N1—C1	124.57 (11)
H6D—C6—H6F	109.5	C5—N1—H1	117.7
H6E—C6—H6F	109.5	C1—N1—H1	117.7
C5—C7—H7A	109.5	C8—O1—C10	115.57 (13)
C5—C7—H7B	109.5	C9—O3—C11	116.70 (12)
H7A—C7—H7B	109.5
N1—C1—C2—C8	−179.68 (12)	C1—C2—C8—O1	−179.05 (12)
C6—C1—C2—C8	1.0 (2)	C3—C2—C8—O1	1.79 (18)
N1—C1—C2—C3	−0.6 (2)	C5—C4—C9—O4	−179.32 (13)
C6—C1—C2—C3	−179.85 (13)	C3—C4—C9—O4	0.73 (19)
C1—C2—C3—C4	2.74 (19)	C5—C4—C9—O3	0.4 (2)
C8—C2—C3—C4	−178.11 (11)	C3—C4—C9—O3	−179.52 (11)
C2—C3—C4—C5	−3.18 (18)	C4—C5—N1—C1	1.1 (2)
C2—C3—C4—C9	176.77 (11)	C7—C5—N1—C1	−177.92 (12)
C9—C4—C5—N1	−178.51 (12)	C2—C1—N1—C5	−1.6 (2)
C3—C4—C5—N1	1.4 (2)	C6—C1—N1—C5	177.80 (12)
C9—C4—C5—C7	0.4 (2)	O2—C8—O1—C10	−1.3 (2)
C3—C4—C5—C7	−179.65 (13)	C2—C8—O1—C10	179.51 (13)
C1—C2—C8—O2	1.8 (2)	O4—C9—O3—C11	1.0 (2)
C3—C2—C8—O2	−177.38 (15)	C4—C9—O3—C11	−178.77 (14)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O4i	0.86	2.15	3.006 (2)	176
C11—H11B···O2ii	0.96	2.60	3.219 (2)	122
C6—H6D···O2	0.96	2.09	2.843 (2)	134
C7—H7D···O3	0.96	1.98	2.733 (2)	134

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O4i	0.86	2.15	3.006 (2)	176
C11—H11B⋯O2ii	0.96	2.60	3.219 (2)	122
C6—H6D⋯O2	0.96	2.09	2.843 (2)	134
C7—H7D⋯O3	0.96	1.98	2.733 (2)	134

Symmetry codes: (i) ; (ii) .