N-(2,6-Dimethyl­phen­yl)maleamic acid

Gowda, B.T.; Tokarčík, M.; Kožíšek, J.; Shakuntala, K.; Fuess, H.

doi:10.1107/S1600536809042470

organic compounds

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ISSN: 2056-9890

Volume 65| Part 11| November 2009| Page o2807

https://doi.org/10.1107/S1600536809042470

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N-(2,6-Dimethylphenyl)maleamic acid

B. Thimme Gowda,^a ^* Miroslav Tokarčík,^b Jozef Kožíšek,^b K. Shakuntala ^a and Hartmut Fuess ^c

^aDepartment of Chemistry, Mangalore University, Mangalagangotri 574 199, Mangalore, India, ^bFaculty of Chemical and Food Technology, Slovak Technical University, Radlinského 9, SK-812 37 Bratislava, Slovak Republic, and ^cInstitute of Materials Science, Darmstadt University of Technology, Petersenstrasse 23, D-64287 Darmstadt, Germany
^*Correspondence e-mail: gowdabt@yahoo.com

(Received 15 October 2009; accepted 15 October 2009; online 23 October 2009)

The asymmetric unit of the title compound, C₁₂H₁₃NO₃, contains two independent molecules. The conformation of the N—H bond and the C=O bond in the amide segment are anti to each other. The molecular conformation of each molecule is stabilized by an intramolecular O—H⋯O hydrogen bond. In the crystal, molecules are connected through intermolecular N—H⋯O hydrogen bonds. In addition, there is a carbonyl–carbonyl dipolar interaction with an O⋯C contact of 2.926 (3) Å.

Related literature

For our sudies on the effect of ring- and side-chain substitutions on the crystal structures of amides, see: Gowda et al. (2009a ,b ,c ); Prasad et al. (2002 ). For bond-length data, see: Allen et al. (1998 ). For modes of interlinking carboxylic acids by hydrogen bonds, see: Leiserowitz (1976 ); Jagannathan et al. (1994 ).

Experimental

Crystal data

C₁₂H₁₃NO₃
M_r = 219.23
Orthorhombic, P 2₁ 2₁ 2₁
a = 12.5268 (4) Å
b = 12.9226 (4) Å
c = 14.6835 (5) Å
V = 2376.95 (13) Å³
Z = 8
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 295 K
0.56 × 0.54 × 0.48 mm

Data collection

Oxford Diffraction Xcalibur Ruby Gemini diffractometer
Absorption correction: multi-scan (CrysAlis Pro; Oxford Diffraction, 2009 $[Oxford Diffraction (2009). CrysAlis Pro. Oxford Diffraction Ltd, Yarnton, England.]$ ) T_min = 0.940, T_max = 0.955
38472 measured reflections
2533 independent reflections
2201 reflections with I > 2σ(I)
R_int = 0.025

Refinement

R[F² > 2σ(F²)] = 0.032
wR(F²) = 0.089
S = 1.07
2533 reflections
305 parameters
2 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.14 e Å⁻³
Δρ_min = −0.12 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N⋯O3ⁱ	0.87 (2)	2.01 (2)	2.824 (2)	156 (2)
N2—H2N⋯O5ⁱⁱ	0.839 (19)	2.04 (2)	2.856 (2)	166 (2)
O2—H2A⋯O1	0.94 (3)	1.53 (3)	2.465 (2)	173 (2)
O6—H6A⋯O4	0.96 (4)	1.52 (4)	2.462 (2)	163 (4)
Symmetry codes: (i) $[-x, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) $[x-{\script{1\over 2}}, -y+{\script{3\over 2}}, -z]$ .

Data collection: CrysAlis Pro (Oxford Diffraction, 2009 $[Oxford Diffraction (2009). CrysAlis Pro. Oxford Diffraction Ltd, Yarnton, England.]$ ); cell refinement: CrysAlis Pro; data reduction: CrysAlis Pro; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997 ) and DIAMOND (Brandenburg, 2002 ); software used to prepare material for publication: SHELXL97, PLATON (Spek, 2009 ) and WinGX (Farrugia, 1999 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536809042470/bt5099sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536809042470/bt5099Isup2.hkl

checkCIF report

Comment top

The amide moiety is an important constituent of many biologically important compounds. As a part of studying the effect of ring and side chain substitutions on the crystal structures of this class of compounds (Gowda et al., 2009a,b,c; Prasad et al., 2002), the crystal structure of N-(2,6-dimethylphenyl)-maleamic acid (I) has been determined. The asymmetric unit of the cell contains two independent molecules (Fig. 1). The conformations of the N—H and C=O bonds in the amide segment of the structure are anti to each other and those of the amide O atom and the carbonyl O atom of the acid segment are also anti to each other. But the amide O atom is anti to the H atom attached to the adjacent C atom, while the carboxyl O atom is syn to the H atom attached to its adjacent C atom (Fig.1). In the present study, the rare anti conformation of the C=O and O—H bonds of the acid group has been observed, similar to that obsrved in N-(3,5-dichlorophenyl)succinamic acid (Gowda et al., 2009c), but contrary to the more general syn conformation observed for C=O and O—H bonds of the acid group in N-(2,6-dimethylphenyl)succinamic acid (Gowda et al., 2009b). The various modes of interlinking carboxylic acids by hydrogen bonds is described elsewhere (Leiserowitz, 1976). The packing of molecules involving dimeric hydrogen bonded association of each carboxyl group with a centrosymmetrically related neighbor has also been observed (Jagannathan et al., 1994). One intramolecular hydrogen O—H···O bond is present within each maleamic acid moiety. The crystal packing is determined by intermolecular N–H···O hydrogen bonds (Table 1) as seen in Fig. 2. Other intermolecular interactions, which seem to play some role, are the carbonyl-carbonyl interactions, first analyzed in the paper of Allen et al. (1998). These dipolar interactions are observed through a short O···C contact of 2.926 (3) Å between the O4 atom of amide moiety in molecule 2 and the C10 atom of the carboxyl moiety in molecule 1 at the position x + 1,y,z. The amido group –NHCO– forms dihedral angles of 80.5 (1)° and 64.0 (2)° with the aromatic ring in the first and second molecules, respectively.

Related literature top

For our sudies on the effect of ring- and side-chain

substitutions on the crystal structures of amides, see: Gowda et al. (2009a,b,c); Prasad et al. (2002). For bond-length data, see: Allen et al. (1998). For modes of interlinking carboxylic acids by hydrogen

bonds, see: Leiserowitz (1976); Jagannathan et al. (1994).

Experimental top

The solution of maleic anhydride (0.025 mol) in toluene (25 ml) was treated dropwise with the solution of 2,6-dimethylaniline (0.025 mol) also in toluene (20 ml) with constant stirring. The resulting mixture was stirred for about 30 min and set aside for an additional 30 min at room temperature for the completion of reaction. The mixture was then treated with dilute hydrochloric acid to remove the unreacted 2,6-dimethylaniline. The resultant solid N-(2,6-dimethylphenyl)maleamic acid was filtered under suction and washed thoroughly with water to remove the unreacted maleic anhydride and maleic acid. It was recrystallized to constant melting point from ethanol. The purity of the compound was checked by elemental analysis and characterized by its infrared spectra. The single crystals used in X-ray diffraction studies were grown in an ethanol solution by slow evaporation at room temperature.

Structure description top

For our sudies on the effect of ring- and side-chain

bonds, see: Leiserowitz (1976); Jagannathan et al. (1994).

Computing details top

Data collection: CrysAlis PRO (Oxford Diffraction, 2009); cell refinement: CrysAlis PRO (Oxford Diffraction, 2009); data reduction: CrysAlis PRO (Oxford Diffraction, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997) and DIAMOND (Brandenburg, 2002); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009) and WinGX (Farrugia, 1999).

Figures top

	Fig. 1. Molecular structure of the two molecules in the asymmetric unit of the title compound showing the atom labelling scheme. Displacement ellipsoids are drawn at the 30% probability level. H atoms are represented as small spheres of arbitrary radii.
	Fig. 2. Part of the crystal structure of the title compound with hydrogen bonds shown as dashed lines. Symmetry codes (i): -x,y - 1/2,-z + 1/2; (ii) x - 1/2,-y + 3/2,-z.

N-(2,6-Dimethylphenyl)maleamic acid top

Crystal data top

C₁₂H₁₃NO₃	F(000) = 928
M_r = 219.23	D_x = 1.225 Mg m⁻³
Orthorhombic, P2₁2₁2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 20238 reflections
a = 12.5268 (4) Å	θ = 2.1–29.4°
b = 12.9226 (4) Å	µ = 0.09 mm⁻¹
c = 14.6835 (5) Å	T = 295 K
V = 2376.95 (13) Å³	Prism, colourless
Z = 8	0.56 × 0.54 × 0.48 mm

Data collection top

Oxford Diffraction Xcalibur Ruby Gemini diffractometer	2533 independent reflections
Graphite monochromator	2201 reflections with I > 2σ(I)
Detector resolution: 10.434 pixels mm^-1	R_int = 0.025
ω scans	θ_max = 25.6°, θ_min = 2.1°
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009)	h = −15→15
T_min = 0.940, T_max = 0.955	k = −15→15
38472 measured reflections	l = −17→17

Refinement top

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)] = 0.032	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.089	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	w = 1/[σ²(F_o²) + (0.0646P)²] where P = (F_o² + 2F_c²)/3
2533 reflections	(Δ/σ)_max < 0.001
305 parameters	Δρ_max = 0.14 e Å⁻³
2 restraints	Δρ_min = −0.12 e Å⁻³

Crystal data top

C₁₂H₁₃NO₃	V = 2376.95 (13) Å³
M_r = 219.23	Z = 8
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 12.5268 (4) Å	µ = 0.09 mm⁻¹
b = 12.9226 (4) Å	T = 295 K
c = 14.6835 (5) Å	0.56 × 0.54 × 0.48 mm

Data collection top

Oxford Diffraction Xcalibur Ruby Gemini diffractometer	2533 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009)	2201 reflections with I > 2σ(I)
T_min = 0.940, T_max = 0.955	R_int = 0.025
38472 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.032	2 restraints
wR(F²) = 0.089	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	Δρ_max = 0.14 e Å⁻³
2533 reflections	Δρ_min = −0.12 e Å⁻³
305 parameters

Special details top

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.

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

	x	y	z	U_iso*/U_eq
C1	0.25341 (16)	0.39170 (14)	0.10573 (14)	0.0489 (5)
C2	0.34832 (18)	0.37146 (16)	0.15245 (15)	0.0570 (5)
C3	0.44161 (19)	0.3689 (2)	0.10282 (19)	0.0703 (7)
H3	0.5057	0.3534	0.1317	0.084*
C4	0.4408 (2)	0.3891 (2)	0.0114 (2)	0.0824 (8)
H4	0.5045	0.3875	−0.0211	0.099*
C5	0.3477 (2)	0.4115 (2)	−0.03281 (17)	0.0767 (7)
H5	0.3494	0.4271	−0.0946	0.092*
C6	0.2509 (2)	0.41152 (16)	0.01250 (16)	0.0617 (6)
C7	0.10578 (16)	0.47012 (14)	0.18861 (14)	0.0486 (5)
C8	0.00863 (15)	0.44838 (14)	0.24183 (14)	0.0475 (4)
H8	−0.0079	0.3787	0.2493	0.057*
C9	−0.05843 (15)	0.51409 (14)	0.28054 (14)	0.0469 (5)
H9	−0.1152	0.4829	0.3107	0.056*
C10	−0.05898 (16)	0.62944 (15)	0.28426 (14)	0.0483 (5)
C11	0.3486 (3)	0.3555 (2)	0.25411 (18)	0.0814 (7)
H11A	0.4185	0.3342	0.2734	0.122*
H11B	0.2976	0.303	0.2698	0.122*
H11C	0.3299	0.4191	0.2839	0.122*
C12	0.1475 (3)	0.4315 (3)	−0.0362 (2)	0.0929 (9)
H12A	0.1169	0.495	−0.0146	0.139*
H12B	0.0989	0.3755	−0.0246	0.139*
H12C	0.1605	0.4365	−0.1005	0.139*
N1	0.15528 (13)	0.38779 (12)	0.15561 (12)	0.0514 (4)
H1N	0.1307 (18)	0.3268 (17)	0.1688 (16)	0.062*
O1	0.14060 (13)	0.55904 (11)	0.17420 (12)	0.0726 (5)
O2	0.01844 (12)	0.68259 (10)	0.24839 (12)	0.0591 (4)
H2A	0.067 (2)	0.640 (2)	0.2168 (18)	0.071*
O3	−0.13208 (14)	0.67180 (12)	0.32315 (12)	0.0728 (5)
C21	0.69266 (14)	0.49032 (15)	0.15611 (12)	0.0432 (4)
C22	0.64858 (15)	0.48672 (16)	0.24349 (13)	0.0500 (5)
C23	0.65844 (19)	0.39448 (19)	0.29159 (15)	0.0641 (6)
H23	0.6292	0.3896	0.3496	0.077*
C24	0.7103 (2)	0.3108 (2)	0.25536 (18)	0.0734 (7)
H24	0.7175	0.2504	0.2893	0.088*
C25	0.7512 (2)	0.31594 (19)	0.16950 (16)	0.0676 (6)
H25	0.7851	0.2581	0.1453	0.081*
C26	0.74363 (16)	0.40489 (16)	0.11727 (14)	0.0517 (5)
C27	0.76542 (15)	0.64136 (16)	0.07866 (12)	0.0452 (4)
C28	0.73911 (15)	0.73479 (15)	0.02517 (12)	0.0455 (4)
H28	0.6669	0.7505	0.0205	0.055*
C29	0.80542 (15)	0.79940 (14)	−0.01721 (13)	0.0459 (4)
H29	0.7718	0.8548	−0.0457	0.055*
C30	0.92344 (16)	0.79890 (17)	−0.02710 (16)	0.0556 (5)
C31	0.5931 (2)	0.5778 (2)	0.28480 (16)	0.0700 (6)
H31A	0.5664	0.5593	0.3439	0.105*
H31B	0.5347	0.5982	0.2465	0.105*
H31C	0.6425	0.6342	0.2906	0.105*
C32	0.7872 (2)	0.4054 (2)	0.02141 (17)	0.0750 (7)
H32A	0.8546	0.4408	0.0205	0.112*
H32B	0.7379	0.4403	−0.0181	0.112*
H32C	0.7969	0.3355	0.0009	0.112*
N2	0.68287 (12)	0.58427 (13)	0.10535 (11)	0.0455 (4)
H2N	0.6232 (16)	0.6091 (17)	0.0914 (15)	0.055*
O4	0.85813 (11)	0.61612 (13)	0.09830 (11)	0.0665 (4)
O5	0.96486 (13)	0.85754 (14)	−0.08053 (13)	0.0768 (5)
O6	0.98128 (12)	0.73556 (19)	0.02073 (15)	0.0970 (8)
H6A	0.944 (3)	0.685 (3)	0.057 (3)	0.116*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0508 (11)	0.0374 (9)	0.0585 (11)	−0.0027 (9)	0.0129 (10)	−0.0054 (9)
C2	0.0592 (12)	0.0494 (12)	0.0623 (12)	−0.0093 (10)	0.0059 (11)	−0.0118 (10)
C3	0.0507 (12)	0.0769 (16)	0.0835 (17)	−0.0117 (12)	0.0087 (12)	−0.0201 (14)
C4	0.0672 (16)	0.0939 (19)	0.0861 (19)	−0.0245 (15)	0.0330 (15)	−0.0243 (16)
C5	0.0903 (19)	0.0815 (17)	0.0581 (13)	−0.0216 (15)	0.0227 (14)	−0.0082 (12)
C6	0.0706 (14)	0.0523 (12)	0.0622 (13)	−0.0056 (11)	0.0079 (12)	−0.0023 (10)
C7	0.0476 (11)	0.0342 (10)	0.0641 (12)	−0.0011 (9)	0.0063 (9)	0.0024 (9)
C8	0.0450 (10)	0.0319 (9)	0.0654 (11)	−0.0024 (8)	0.0027 (9)	0.0004 (9)
C9	0.0408 (10)	0.0411 (10)	0.0587 (11)	−0.0007 (8)	0.0003 (9)	0.0018 (9)
C10	0.0509 (11)	0.0404 (10)	0.0536 (11)	0.0064 (10)	−0.0065 (10)	−0.0059 (9)
C11	0.0836 (17)	0.0905 (18)	0.0702 (15)	0.0041 (15)	−0.0008 (14)	−0.0064 (14)
C12	0.096 (2)	0.107 (2)	0.0757 (17)	0.0050 (18)	−0.0048 (17)	0.0136 (16)
N1	0.0520 (9)	0.0336 (8)	0.0688 (10)	−0.0028 (7)	0.0148 (8)	0.0015 (8)
O1	0.0681 (10)	0.0378 (7)	0.1120 (13)	−0.0057 (7)	0.0323 (10)	0.0003 (8)
O2	0.0579 (9)	0.0351 (7)	0.0843 (10)	−0.0007 (7)	0.0032 (8)	−0.0074 (7)
O3	0.0757 (11)	0.0502 (8)	0.0924 (12)	0.0134 (8)	0.0203 (10)	−0.0100 (8)
C21	0.0318 (8)	0.0537 (11)	0.0440 (9)	−0.0060 (8)	−0.0052 (8)	0.0082 (8)
C22	0.0418 (10)	0.0618 (12)	0.0464 (10)	−0.0055 (9)	−0.0012 (9)	0.0078 (9)
C23	0.0655 (14)	0.0739 (14)	0.0528 (11)	−0.0056 (13)	−0.0001 (11)	0.0197 (11)
C24	0.0832 (17)	0.0629 (14)	0.0742 (15)	0.0040 (13)	−0.0054 (14)	0.0225 (13)
C25	0.0729 (14)	0.0562 (12)	0.0738 (14)	0.0096 (12)	−0.0027 (14)	0.0035 (11)
C26	0.0468 (10)	0.0558 (11)	0.0525 (10)	−0.0011 (10)	−0.0035 (9)	0.0008 (9)
C27	0.0366 (10)	0.0582 (11)	0.0407 (9)	−0.0030 (9)	−0.0040 (8)	0.0062 (8)
C28	0.0344 (9)	0.0538 (11)	0.0484 (10)	0.0008 (9)	0.0007 (9)	0.0040 (9)
C29	0.0424 (9)	0.0460 (10)	0.0494 (10)	−0.0002 (8)	0.0023 (9)	0.0035 (9)
C30	0.0449 (11)	0.0578 (12)	0.0643 (12)	−0.0118 (10)	0.0003 (10)	0.0091 (11)
C31	0.0711 (14)	0.0823 (16)	0.0565 (12)	0.0068 (13)	0.0147 (11)	0.0056 (12)
C32	0.0820 (17)	0.0803 (16)	0.0626 (13)	0.0058 (14)	0.0126 (13)	−0.0049 (13)
N2	0.0311 (7)	0.0567 (10)	0.0486 (8)	0.0000 (7)	0.0006 (7)	0.0115 (8)
O4	0.0365 (7)	0.0845 (11)	0.0784 (10)	−0.0085 (8)	−0.0110 (7)	0.0377 (9)
O5	0.0529 (9)	0.0795 (11)	0.0979 (13)	−0.0113 (8)	0.0134 (8)	0.0336 (10)
O6	0.0379 (8)	0.1251 (17)	0.1281 (16)	−0.0123 (10)	−0.0069 (9)	0.0741 (15)

Geometric parameters (Å, º) top

C1—C6	1.393 (3)	C21—C26	1.397 (3)
C1—C2	1.397 (3)	C21—C22	1.398 (3)
C1—N1	1.432 (3)	C21—N2	1.430 (2)
C2—C3	1.378 (3)	C22—C23	1.391 (3)
C2—C11	1.507 (4)	C22—C31	1.495 (3)
C3—C4	1.368 (4)	C23—C24	1.369 (4)
C3—H3	0.93	C23—H23	0.93
C4—C5	1.365 (4)	C24—C25	1.362 (4)
C4—H4	0.93	C24—H24	0.93
C5—C6	1.383 (4)	C25—C26	1.385 (3)
C5—H5	0.93	C25—H25	0.93
C6—C12	1.502 (4)	C26—C32	1.510 (3)
C7—O1	1.247 (2)	C27—O4	1.240 (2)
C7—N1	1.323 (3)	C27—N2	1.329 (2)
C7—C8	1.473 (3)	C27—C28	1.478 (3)
C8—C9	1.323 (3)	C28—C29	1.332 (3)
C8—H8	0.93	C28—H28	0.93
C9—C10	1.492 (3)	C29—C30	1.486 (3)
C9—H9	0.93	C29—H29	0.93
C10—O3	1.210 (2)	C30—O5	1.208 (2)
C10—O2	1.300 (3)	C30—O6	1.299 (3)
C11—H11A	0.96	C31—H31A	0.96
C11—H11B	0.96	C31—H31B	0.96
C11—H11C	0.96	C31—H31C	0.96
C12—H12A	0.96	C32—H32A	0.96
C12—H12B	0.96	C32—H32B	0.96
C12—H12C	0.96	C32—H32C	0.96
N1—H1N	0.87 (2)	N2—H2N	0.839 (19)
O2—H2A	0.94 (3)	O6—H6A	0.96 (4)

C6—C1—C2	122.42 (19)	C26—C21—C22	121.93 (17)
C6—C1—N1	119.32 (19)	C26—C21—N2	119.83 (16)
C2—C1—N1	118.21 (18)	C22—C21—N2	118.22 (18)
C3—C2—C1	117.8 (2)	C23—C22—C21	117.4 (2)
C3—C2—C11	121.3 (2)	C23—C22—C31	120.63 (18)
C1—C2—C11	120.9 (2)	C21—C22—C31	122.01 (18)
C4—C3—C2	120.5 (3)	C24—C23—C22	121.5 (2)
C4—C3—H3	119.7	C24—C23—H23	119.3
C2—C3—H3	119.7	C22—C23—H23	119.3
C5—C4—C3	120.9 (2)	C25—C24—C23	119.9 (2)
C5—C4—H4	119.5	C25—C24—H24	120
C3—C4—H4	119.5	C23—C24—H24	120
C4—C5—C6	121.3 (2)	C24—C25—C26	121.8 (2)
C4—C5—H5	119.3	C24—C25—H25	119.1
C6—C5—H5	119.3	C26—C25—H25	119.1
C5—C6—C1	116.9 (2)	C25—C26—C21	117.45 (19)
C5—C6—C12	121.8 (2)	C25—C26—C32	119.7 (2)
C1—C6—C12	121.3 (2)	C21—C26—C32	122.85 (19)
O1—C7—N1	120.98 (18)	O4—C27—N2	120.93 (17)
O1—C7—C8	123.68 (17)	O4—C27—C28	123.18 (17)
N1—C7—C8	115.34 (16)	N2—C27—C28	115.89 (16)
C9—C8—C7	129.05 (17)	C29—C28—C27	128.42 (18)
C9—C8—H8	115.5	C29—C28—H28	115.8
C7—C8—H8	115.5	C27—C28—H28	115.8
C8—C9—C10	131.31 (19)	C28—C29—C30	131.57 (18)
C8—C9—H9	114.3	C28—C29—H29	114.2
C10—C9—H9	114.3	C30—C29—H29	114.2
O3—C10—O2	121.11 (18)	O5—C30—O6	120.45 (19)
O3—C10—C9	118.2 (2)	O5—C30—C29	119.2 (2)
O2—C10—C9	120.65 (18)	O6—C30—C29	120.32 (19)
C2—C11—H11A	109.5	C22—C31—H31A	109.5
C2—C11—H11B	109.5	C22—C31—H31B	109.5
H11A—C11—H11B	109.5	H31A—C31—H31B	109.5
C2—C11—H11C	109.5	C22—C31—H31C	109.5
H11A—C11—H11C	109.5	H31A—C31—H31C	109.5
H11B—C11—H11C	109.5	H31B—C31—H31C	109.5
C6—C12—H12A	109.5	C26—C32—H32A	109.5
C6—C12—H12B	109.5	C26—C32—H32B	109.5
H12A—C12—H12B	109.5	H32A—C32—H32B	109.5
C6—C12—H12C	109.5	C26—C32—H32C	109.5
H12A—C12—H12C	109.5	H32A—C32—H32C	109.5
H12B—C12—H12C	109.5	H32B—C32—H32C	109.5
C7—N1—C1	124.14 (16)	C27—N2—C21	123.92 (16)
C7—N1—H1N	118.8 (16)	C27—N2—H2N	114.2 (16)
C1—N1—H1N	116.8 (15)	C21—N2—H2N	121.9 (16)
C10—O2—H2A	111.5 (15)	C30—O6—H6A	117 (2)

C6—C1—C2—C3	−1.6 (3)	C26—C21—C22—C23	0.8 (3)
N1—C1—C2—C3	175.98 (19)	N2—C21—C22—C23	179.67 (18)
C6—C1—C2—C11	177.0 (2)	C26—C21—C22—C31	−179.38 (19)
N1—C1—C2—C11	−5.4 (3)	N2—C21—C22—C31	−0.5 (3)
C1—C2—C3—C4	2.1 (3)	C21—C22—C23—C24	0.7 (3)
C11—C2—C3—C4	−176.5 (3)	C31—C22—C23—C24	−179.1 (2)
C2—C3—C4—C5	−0.4 (4)	C22—C23—C24—C25	−1.7 (4)
C3—C4—C5—C6	−2.0 (4)	C23—C24—C25—C26	1.1 (4)
C4—C5—C6—C1	2.5 (4)	C24—C25—C26—C21	0.3 (4)
C4—C5—C6—C12	−177.3 (3)	C24—C25—C26—C32	−178.1 (2)
C2—C1—C6—C5	−0.7 (3)	C22—C21—C26—C25	−1.3 (3)
N1—C1—C6—C5	−178.2 (2)	N2—C21—C26—C25	179.84 (18)
C2—C1—C6—C12	179.1 (2)	C22—C21—C26—C32	177.0 (2)
N1—C1—C6—C12	1.5 (3)	N2—C21—C26—C32	−1.8 (3)
O1—C7—C8—C9	1.8 (4)	O4—C27—C28—C29	7.2 (3)
N1—C7—C8—C9	−177.9 (2)	N2—C27—C28—C29	−172.82 (19)
C7—C8—C9—C10	−0.4 (4)	C27—C28—C29—C30	1.7 (4)
C8—C9—C10—O3	178.4 (2)	C28—C29—C30—O5	168.9 (2)
C8—C9—C10—O2	−3.2 (3)	C28—C29—C30—O6	−10.7 (4)
O1—C7—N1—C1	3.2 (3)	O4—C27—N2—C21	−1.2 (3)
C8—C7—N1—C1	−177.03 (18)	C28—C27—N2—C21	178.79 (17)
C6—C1—N1—C7	−84.2 (3)	C26—C21—N2—C27	−64.1 (3)
C2—C1—N1—C7	98.2 (2)	C22—C21—N2—C27	117.1 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O3ⁱ	0.87 (2)	2.01 (2)	2.824 (2)	156 (2)
N2—H2N···O5ⁱⁱ	0.84 (2)	2.04 (2)	2.856 (2)	166 (2)
O2—H2A···O1	0.94 (3)	1.53 (3)	2.465 (2)	173 (2)
O6—H6A···O4	0.96 (4)	1.52 (4)	2.462 (2)	163 (4)

Symmetry codes: (i) −x, y−1/2, −z+1/2; (ii) x−1/2, −y+3/2, −z.

Experimental details

Crystal data
Chemical formula	C₁₂H₁₃NO₃
M_r	219.23
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	295
a, b, c (Å)	12.5268 (4), 12.9226 (4), 14.6835 (5)
V (Å³)	2376.95 (13)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.56 × 0.54 × 0.48

Data collection
Diffractometer	Oxford Diffraction Xcalibur Ruby Gemini
Absorption correction	Multi-scan (CrysAlis PRO; Oxford Diffraction, 2009)
T_min, T_max	0.940, 0.955
No. of measured, independent and observed [I > 2σ(I)] reflections	38472, 2533, 2201
R_int	0.025
(sin θ/λ)_max (Å⁻¹)	0.608

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.032, 0.089, 1.07
No. of reflections	2533
No. of parameters	305
No. of restraints	2
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.14, −0.12

Computer programs: CrysAlis PRO (Oxford Diffraction, 2009), SHELXS97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997) and DIAMOND (Brandenburg, 2002), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009) and WinGX (Farrugia, 1999).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O3ⁱ	0.87 (2)	2.01 (2)	2.824 (2)	156 (2)
N2—H2N···O5ⁱⁱ	0.839 (19)	2.04 (2)	2.856 (2)	166 (2)
O2—H2A···O1	0.94 (3)	1.53 (3)	2.465 (2)	173 (2)
O6—H6A···O4	0.96 (4)	1.52 (4)	2.462 (2)	163 (4)

Symmetry codes: (i) −x, y−1/2, −z+1/2; (ii) x−1/2, −y+3/2, −z.

Acknowledgements

MT and JK thank the Grant Agency of the Slovak Republic (VEGA 1/0817/08) and Structural Funds, Interreg IIIA, for financial support in purchasing the diffractometer.

References

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