Dimethyl 2,6-dimethyl-1,4-dihydro­pyridine-3,5-dicarboxyl­ate

Zhang, Z.; Xian, D.; Wang, J.; Zhang, G.

doi:10.1107/S1600536809035478

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 65| Part 10| October 2009| Page o2390

doi:10.1107/S1600536809035478

Open

access

Dimethyl 2,6-dimethyl-1,4-dihydropyridine-3,5-dicarboxylate

Zhenfeng Zhang,^a ^* Dong Xian,^a Jiange Wang ^b and Guisheng Zhang ^a

^aCollege of Chemistry and Environmental Science, Henan Normal University, Xinxiang 453007, People's Republic of China, and ^bCollege of Chemistry, Luoyang Normal University, Xinxiang 453007, People's Republic of China
^*Correspondence e-mail: zzf5188@sohu.com

(Received 18 August 2009; accepted 2 September 2009; online 9 September 2009)

In the crystal of the title compound, C₁₁H₁₅NO₄, the molecules are linked into sheets by N—H⋯O and C—H⋯O hydrogen bonds. Within the molecule, the 1,4-dihydropyridine 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-dihydropyridine ring. The conformation of the latter is governed mainly by two intramolecular C—H⋯O non-classical interactions.

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_r = 225.24
Triclinic, $[P \overline 1]$
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[F² > 2σ(F²)] = 0.040
wR(F²) = 0.115
S = 1.05
2047 reflections
148 parameters
H-atom parameters constrained
Δρ_max = 0.16 e Å⁻³
Δρ_min = −0.23 e Å⁻³

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) x-1, y, z; (ii) x+1, y, z-1.

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.

Supporting information

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

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

checkCIF report

Comment top

The 1,4-dihydropyridine, (1,4-DHP) derivatives, as analogues of NADH coenzymes, exhibit a wide range of biological activities, acting as powerful arteriolar vasodilators (Kazda & Towart, 1981) and antihypertensives (Janis & Triggle, 1983). In addition, 1,4-DHP compounds such as nifedipine, nisoldipine and nicardipine exhibit potential trypanocidal activity (Núñez-Vergara et al., 1998). The classical preparation method of 1,4-DHP is the Hantzsch (Hantzsch & Liebigs, 1882) and a number of 1,4-DHP derivatives have been synthesized via this method. We have prepared some 1,4-DHP derivatives by condensation reaction of β-enamino esters with aldehyde. As a typical example containing a planar 1,4-DHP ring, we now report the molecular and supramolecular structure of dimethyl 1,4-dihydro-2,6-dimethylpyridine-3,5-dicarboxylate, (I) (Fig. 1).

In the I, interestingly, 1,4-DHP ring exhibit perfectly coplanar conformation with r.m.s. deviation from the mean plane of 0.009 (3)Å. This conformation is significantly diverse from those found in other 1,4-DHP derivatives, where each of the 1,4-dihydropyrimidine rings adopts flat-boat conformation (Quesada et al., 2006; Ramesh, et al., 2008; Zhao & Teng, 2008; Bai et al., 2009). Another point of interest in the conformation concerns the ester portion of the molecule. In each molecule, there are two short non-classical intramolecular C–H···O interactions (Table 1), and these, we think, control and stabilize the conformations of the two methoxycarbonyl fragments, which are both coplanar with the 1,4-DHP ring, as shown by the torsion angles. However, for C2-methoxycarbonyl it is carbonyl atom O2 that participates in the intramolecular hydrogen bond, and for C4-methoxycarbonyl it is ethoxy O3 atom. Within the 1,4-DHP ring, the C1-C2 and C4-C5 distances shows markedly two double bonds. The N1–C1 and N1–C5 bonds are significantly shorter than the standard N–C experimental bond length of 1.47Å (Mak, et al., 2002). These features in bond distance suggest the existence of π-delocation in the C2/C1/N1/C5/C4 fragment.

Due to the above conformational features of I, its supramolecular structure exhibits some interesting feature. The molecules of the title compounds are linked into sheets by two independent intermolecular hydrogen bonds, one of N–H···O and one C–H···O type (Table 1), the formation of which is readily analyzed in terms of two one-dimensional substructures, one formed by the the N–H···O hydrogen bond and one formed by the C–H···O hydrogen bond. For the sake of simplicity, we shall omit any further consideration of other C–H···O intermolecular interaction involving C7-methyl group, which is too weak to influence the overall dimensionality of the supramolecular structure. In the first substructure, atom N1 in the molecule at (x, y, z) acts as a hydrogen-bond donor to the methoxycarbonyl atom O4 in the molecule at (x-1, y, z), thus forming by translation a C₂²(6) (Bernstein et al., 1995) chain running along the [1 0 0] direction (Fig. 2). In the second substructure, methyl atom C11 in the molecule at (x, y, z) acts as a hydrogen bond donor via H11B to methoxycarbonyl atom O2 in the milecule at (x+1, y, z-1), so forming by translation a C(9) (Bernstein et al., 1995) chain parallel to the [-1 0 1] direction (Fig. 2). The combination of the two chain motifs is sufficient to link all the molecules into a two-dimensional sheet parallel to (0 1 0). Two such sheets pass through each unit cell in the domains 0 < y < 1/2 and 1/2 < y < 1, and there are no direction-specific interactions between the two sheets.

Related literature top

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 top

Into a three-necked round-bottomed flask equipped with a stirrer were introduced methyl 3-aminobut-2-enoate (0.1 mol, 11.5 g), aqueous formaldehyde (0.05 mol, 37% 4.0 g) and ethanol (95%, 25 ml). The resulted mixture was refluxed with stirring for ca 20 min, and then the solution is cooled to room temperature. The precipitate was filtered off, washed with cool ethanol (95%), and the resulting solid product was recrystallized from hot ethanol to give crystals of I.

¹H NMR (DMSO, 400 MHz) of (I): δ 8.35 (s, 1H), δ 3.59 (s, 6H), δ 3.14 (s, 2H), δ 2.12 (s, 6H).

Computing details top

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT (Bruker, 1997); 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 (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of I, showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level. H atoms are shown as small spheres of arbitrary radius. Only one component of the disordered methyl groups is shown.
	Fig. 2. Part of the crystal structure of I, showing the formation of a (0 1 0) sheet. For the sake of clarity, H atoms not involved in the motif shown have been omitted. Intermolecular interactions are represented by dashed lines. Symmetry codes: (i) x+1, y, z; (ii) -x+1 ,y, z+1; (iii) x-1, y, z; (iv) x+1, y, z-1.

Dimethyl 2,6-dimethyl-1,4-dihydropyridine-3,5-dicarboxylate top

Crystal data top

C₁₁H₁₅NO₄	Z = 2
M_r = 225.24	F(000) = 240
Triclinic, P1	D_x = 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

Data collection top

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

Refinement top

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(F_o²) + (0.0612P)² + 0.1212P] where P = (F_o² + 2F_c²)/3
S = 1.05	(Δ/σ)_max < 0.001
2047 reflections	Δρ_max = 0.16 e Å⁻³
148 parameters	Δρ_min = −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)

Crystal data top

C₁₁H₁₅NO₄	γ = 64.351 (2)°
M_r = 225.24	V = 558.62 (17) Å³
Triclinic, P1	Z = 2
a = 7.3933 (13) Å	Mo Kα radiation
b = 7.8391 (14) Å	µ = 0.10 mm⁻¹
c = 11.1847 (19) Å	T = 293 K
α = 75.977 (2)°	0.49 × 0.43 × 0.25 mm
β = 75.274 (2)°

Data collection top

Bruker SMART CCD diffractometer	2047 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	1764 reflections with I > 2σ(I)
T_min = 0.952, T_max = 0.965	R_int = 0.015
3550 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.040	0 restraints
wR(F²) = 0.115	H-atom parameters constrained
S = 1.05	Δρ_max = 0.16 e Å⁻³
2047 reflections	Δρ_min = −0.23 e Å⁻³
148 parameters

Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	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)

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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)

Hydrogen-bond geometry (Å, º) top

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) x−1, y, z; (ii) x+1, y, z−1.

Experimental details

Crystal data
Chemical formula	C₁₁H₁₅NO₄
M_r	225.24
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	7.3933 (13), 7.8391 (14), 11.1847 (19)
α, β, γ (°)	75.977 (2), 75.274 (2), 64.351 (2)
V (Å³)	558.62 (17)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.10
Crystal size (mm)	0.49 × 0.43 × 0.25

Data collection
Diffractometer	Bruker SMART CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 2003)
T_min, T_max	0.952, 0.965
No. of measured, independent and observed [I > 2σ(I)] reflections	3550, 2047, 1764
R_int	0.015
(sin θ/λ)_max (Å⁻¹)	0.606

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.040, 0.115, 1.05
No. of reflections	2047
No. of parameters	148
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.16, −0.23

Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O4ⁱ	0.86	2.15	3.006 (2)	175.8
C11—H11B···O2ⁱⁱ	0.96	2.60	3.219 (2)	122.0
C6—H6D···O2	0.96	2.09	2.843 (2)	133.7
C7—H7D···O3	0.96	1.98	2.733 (2)	133.5

Symmetry codes: (i) x−1, y, z; (ii) x+1, y, z−1.

Acknowledgements

This work was supported by the Innovation Scientists and Technicians Troop Construction Projects of Henan Province (2008IRTSTHN002). The authors are grateful to the Physiochemical Analysis Measurement Laboratory, College of Chemistry, Luoyang Normal University, for performing the X-ray analysis.

References

Bai, M.-S., Chen, Y.-Y., Niu, D.-L. & Peng, L. (2009). Acta Cryst. E65, o799. Web of Science CSD CrossRef IUCr Journals Google Scholar
Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555–1573. CrossRef CAS Web of Science Google Scholar
Bruker (1997). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Hantzsch, A. & Liebigs, J. (1882). Ann. Chem. 215, 1–82. CrossRef Google Scholar
Janis, R. A. & Triggle, D. J. (1983). J. Med. Chem. 25, 775–785. CrossRef Web of Science Google Scholar
Kazda, S. & Towart, R. (1981). Br. J. Pharmacol. 72, 582–583. Google Scholar
Mak, T. C. W., Zhou, G. D. & Li, W. K. (2002). Advanced Inorganic Structural Chemistry, 2th ed. Beijing: Chinese. Google Scholar
Núñez-Vergara, L. J., Squella, J. A., Bollo-Dragnic, S., Marin-Catalán, R., Pino, L., Diaz-Araya, G. & Letelier, M. E. (1998). Gen. Pharmacol. 30, 85–87. PubMed Web of Science Google Scholar
Quesada, A., Argüello, J., Squella, J. A., Wardell, J. L., Low, J. N. & Glidewell, C. (2006). Acta Cryst. C62, o8–o12. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Ramesh, P., Subbiahpandi, A., Thirumurugan, P., Perumal, P. T. & Ponnuswamy, M. N. (2008). Acta Cryst. E64, o1891. Web of Science CSD CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2003). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Zhao, L.-L. & Teng, D. (2008). Acta Cryst. E64, o1772–o1773. Web of Science CSD CrossRef IUCr Journals Google Scholar