N-(3,4-Dimethyl­phen­yl)maleamic acid

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

doi:10.1107/S1600536809043682

N-(3,4-Dimethylphenyl)maleamic acid

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

The title compound, C₁₂H₁₃NO₃, crystallizes with four independent molecules in the asymmetric unit. The N—H bond and the C=O bond in the amide segment are anti to each other. The C=C double bond is cis configured and an intramolecular O—H

O hydrogen bond is formed in each molecule. The mean planes through the aromatic ring and the amide group –NHCO– are inclined at angles of 17.4 (3), 20.8 (2), 16.2 (2) and 11.2 (3)° in the four molecules. In the crystal, intermolecular N—H

O hydrogen bonds link the molecules into ribbons along the b axis.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536809043682/bt5110sup1.cif Contains datablocks I, global
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536809043682/bt5110Isup2.hkl Contains datablock I

CCDC reference: 754427

checkCIF report

Key indicators

Single-crystal X-ray study
T = 295 K
Mean (C-C) = 0.005 Å
R factor = 0.044
wR factor = 0.134
Data-to-parameter ratio = 9.1

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        C10
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        C70
PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor ....       2.23
PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor ....       2.12
PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor ....       2.81
PLAT910_ALERT_3_C Missing # of FCF Reflections Below Th(Min) .....          2
PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L=  0.600          2
PLAT912_ALERT_4_C Missing # of FCF Reflections Above STh/L=  0.600         16

Alert level G
REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is
            correct. If it is not, please give the correct count in the
            _publ_section_exptl_refinement section of the submitted CIF.
           From the CIF: _diffrn_reflns_theta_max           27.90
           From the CIF: _reflns_number_total               5279
           Count of symmetry unique reflns         5299
           Completeness (_total/calc)             99.62%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured         0
           Fraction of Friedel pairs measured     0.000
           Are heavy atom types Z>Si present         no
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......         10

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   8 ALERT level C = Check and explain
   2 ALERT level G = General alerts; check

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   5 ALERT type 2 Indicator that the structure model may be wrong or deficient
   3 ALERT type 3 Indicator that the structure quality may be low
   2 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

Comment top

As a part of studying the effect of ring and side chain substitutions on the crystal structures of biologically important amides (Gowda, Foro, Saraswathi & Fuess, 2009; Gowda, Foro, Saraswathi, Terao & Fuess, 2009; Gowda, Tokarčík et al., 2009; Prasad et al., 2002), the crystal structure of N-(3,4-dimethylphenyl)-maleamic acid (I) has been determined. The asymmetric unit of the cell contains four 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 structure of (I), 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-(2,6-dimethylphenyl)maleamic acid (Gowda, Tokarčík et al., 2009) and N-phenylmaleamic acid (Lo & Ng, 2009), 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).

In the maleamic moiety the C8—C9, C28—C29, C48—C49 and C68—C69 bond lengths of 1.322 (5), 1.343 (4), 1.320 (4) and 1.321 (4) Å clearly indicate the double bond character. Each maleamic moiety features one intramolecular hydrogen O–H···O bond (Table 1). The mean planes through the phenyl ring and the amido group –NHCO– are inclined at the angles of 17.4 (3), 20.8 (2), 16.2 (2) and 11.2 (3)° in the first, second, third and fourth molecules, respectively. In the crystal structure, the intermolecular N–H···O hydrogen bonds link the molecules into ribbons parallel to the ab-plane of the cell (Fig. 2).

Related literature top

For our study on the effect of ring and side-chain substitutions on the crystal structures of biologically important amides, see: Gowda, Foro, Saraswathi & Fuess (2009); Gowda, Foro, Saraswathi, Terao & Fuess (2009); Gowda, Tokarčík et al. (2009); Prasad et al. (2002). For modes of interlinking carboxylic acids by hydrogen bonds, see: Leiserowitz (1976). For a related structure, see: Lo & Ng (2009);

Experimental top

To a solution of maleic anhydride (0.025 mol) in toluene (25 ml) was added dropwise a solution of 3,4-dimethylaniline (0.025 mol) also in toluene (20 ml) with constant stirring. The resulting mixture was warmed with stirring for over 30 min and set aside for additional 30 min at room temperature for the completion of reaction. The mixture was then treated with dilute hydrochloric acid to remove the unreacted 3,4-dimethylaniline. The resultant solid N-(3,4-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

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 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 crystal structure of the title compound with N—H···O hydrogen bonds represented by dashed lines. Symmetry code (i): x,y - 1,z. H atoms not involved in intermolecular hydrogen bonding have been omitted.

N-(3,4-Dimethylphenyl)maleamic acid top

Crystal data top

C₁₂H₁₃NO₃	F(000) = 928
M_r = 219.23	D_x = 1.314 Mg m⁻³
Monoclinic, Pc	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P -2yc	Cell parameters from 31828 reflections
a = 11.9003 (2) Å	θ = 1.9–27.8°
b = 12.9991 (2) Å	µ = 0.10 mm⁻¹
c = 15.2641 (3) Å	T = 295 K
β = 110.207 (2)°	Truncated square pyramid, colourless
V = 2215.92 (7) Å³	0.48 × 0.32 × 0.31 mm
Z = 8

Data collection top

Oxford Diffraction Xcalibur Ruby Gemini diffractometer	5279 independent reflections
Graphite monochromator	4100 reflections with I > 2σ(I)
Detector resolution: 10.434 pixels mm^-1	R_int = 0.028
ω scans	θ_max = 27.9°, θ_min = 2.1°
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009)	h = −15→15
T_min = 0.958, T_max = 0.965	k = −17→17
67608 measured reflections	l = −20→20

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)] = 0.044	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.134	H-atom parameters constrained
S = 1.03	w = 1/[σ²(F_o²) + (0.0958P)² + 0.0272P] where P = (F_o² + 2F_c²)/3
5279 reflections	(Δ/σ)_max = 0.001
577 parameters	Δρ_max = 0.29 e Å⁻³
10 restraints	Δρ_min = −0.16 e Å⁻³

Crystal data top

C₁₂H₁₃NO₃	V = 2215.92 (7) Å³
M_r = 219.23	Z = 8
Monoclinic, Pc	Mo Kα radiation
a = 11.9003 (2) Å	µ = 0.10 mm⁻¹
b = 12.9991 (2) Å	T = 295 K
c = 15.2641 (3) Å	0.48 × 0.32 × 0.31 mm
β = 110.207 (2)°

Data collection top

Oxford Diffraction Xcalibur Ruby Gemini diffractometer	5279 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009)	4100 reflections with I > 2σ(I)
T_min = 0.958, T_max = 0.965	R_int = 0.028
67608 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.044	10 restraints
wR(F²) = 0.134	H-atom parameters constrained
S = 1.03	Δρ_max = 0.29 e Å⁻³
5279 reflections	Δρ_min = −0.16 e Å⁻³
577 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	Occ. (<1)
C1	0.5468 (2)	0.4000 (2)	0.1080 (2)	0.0430 (6)
C2	0.6117 (3)	0.4743 (2)	0.0804 (2)	0.0450 (6)
H2	0.5758	0.5365	0.056	0.054*
C3	0.7309 (3)	0.4559 (2)	0.0893 (2)	0.0462 (7)
C4	0.7851 (3)	0.3631 (2)	0.1243 (2)	0.0474 (7)
C5	0.7189 (3)	0.2888 (2)	0.1513 (2)	0.0493 (7)
H5	0.7544	0.2264	0.1755	0.059*
C6	0.6006 (3)	0.3075 (2)	0.1423 (2)	0.0484 (7)
H6	0.5571	0.2569	0.1596	0.058*
C7	0.3634 (3)	0.4981 (2)	0.0983 (2)	0.0468 (6)
C8	0.2429 (3)	0.4810 (3)	0.1042 (3)	0.0564 (8)
H8	0.2164	0.4132	0.0976	0.068*
C9	0.1684 (3)	0.5495 (2)	0.1176 (3)	0.0585 (8)
H9	0.0983	0.5213	0.1212	0.07*
C10	0.1759 (3)	0.6647 (2)	0.1281 (2)	0.0524 (7)
C11	0.7982 (3)	0.5385 (2)	0.0590 (3)	0.0589 (8)
H11A	0.8646	0.5613	0.1118	0.088*
H11B	0.7457	0.5955	0.0336	0.088*
H11C	0.8272	0.5115	0.0123	0.088*
C12	0.9124 (3)	0.3412 (3)	0.1342 (3)	0.0626 (9)
H12A	0.9338	0.2734	0.1594	0.094*	0.5
H12B	0.9639	0.3909	0.1754	0.094*	0.5
H12C	0.9211	0.3453	0.074	0.094*	0.5
H12D	0.9455	0.3996	0.1131	0.094*	0.5
H12E	0.9153	0.2822	0.0972	0.094*	0.5
H12F	0.9581	0.3278	0.1985	0.094*	0.5
N1	0.4259 (2)	0.41119 (17)	0.10310 (19)	0.0495 (6)
H1	0.3879	0.3549	0.1032	0.059*
O1	0.40148 (19)	0.58444 (16)	0.08902 (19)	0.0609 (6)
O2	0.2602 (2)	0.71471 (17)	0.1095 (2)	0.0745 (7)
H2A	0.3048	0.671	0.092	0.089*
O3	0.1018 (2)	0.70943 (18)	0.1511 (2)	0.0708 (7)
C21	−0.0264 (2)	0.63766 (18)	0.36357 (17)	0.0369 (5)
C22	−0.0921 (3)	0.7141 (2)	0.38831 (19)	0.0388 (6)
H22	−0.0562	0.7768	0.4112	0.047*
C23	−0.2114 (2)	0.69692 (19)	0.37893 (18)	0.0382 (6)
C24	−0.2663 (2)	0.6027 (2)	0.34333 (18)	0.0405 (6)
C25	−0.1979 (3)	0.5278 (2)	0.3203 (2)	0.0480 (7)
H25	−0.2328	0.4647	0.2978	0.058*
C26	−0.0802 (3)	0.5444 (2)	0.3298 (2)	0.0471 (7)
H26	−0.0366	0.4931	0.3135	0.056*
C27	0.1559 (3)	0.7351 (2)	0.3711 (2)	0.0429 (6)
C28	0.2785 (3)	0.7178 (2)	0.3698 (2)	0.0505 (7)
H28	0.3061	0.6503	0.3785	0.061*
C29	0.3543 (3)	0.7882 (2)	0.3577 (3)	0.0552 (8)
H29	0.4274	0.7609	0.3597	0.066*
C30	0.3450 (3)	0.8997 (2)	0.3418 (2)	0.0511 (7)
C31	−0.2811 (3)	0.7797 (2)	0.4058 (2)	0.0525 (7)
H31A	−0.2289	0.8363	0.4332	0.079*
H31B	−0.3142	0.7529	0.4503	0.079*
H31C	−0.3447	0.8029	0.3513	0.079*
C32	−0.3959 (3)	0.5826 (3)	0.3293 (2)	0.0548 (7)
H32A	−0.415	0.5124	0.3107	0.082*
H32B	−0.4455	0.6275	0.2816	0.082*
H32C	−0.41	0.5952	0.3866	0.082*
N2	0.09531 (19)	0.64905 (16)	0.37116 (16)	0.0417 (5)
H2N	0.1352	0.5928	0.3765	0.05*
O21	0.11403 (19)	0.82277 (15)	0.37276 (19)	0.0594 (6)
O22	0.2552 (2)	0.95070 (16)	0.3502 (2)	0.0701 (8)
H22A	0.2037	0.9074	0.3597	0.084*
O23	0.4227 (2)	0.94389 (17)	0.3212 (2)	0.0689 (7)
C41	0.6529 (2)	0.13584 (19)	0.35178 (18)	0.0367 (5)
C42	0.7424 (3)	0.2090 (2)	0.3831 (2)	0.0413 (6)
H42	0.7261	0.2714	0.406	0.05*
C43	0.8552 (2)	0.1909 (2)	0.38079 (19)	0.0400 (5)
C44	0.8820 (2)	0.0970 (2)	0.3492 (2)	0.0408 (6)
C45	0.7941 (3)	0.0228 (2)	0.3204 (2)	0.0488 (7)
H45	0.8121	−0.0407	0.3004	0.059*
C46	0.6794 (2)	0.04100 (19)	0.3205 (2)	0.0441 (6)
H46	0.6206	−0.0094	0.3	0.053*
C47	0.4769 (2)	0.23407 (19)	0.3576 (2)	0.0428 (6)
C48	0.3514 (3)	0.2177 (2)	0.3524 (3)	0.0518 (7)
H48	0.3262	0.1496	0.3481	0.062*
C49	0.2708 (3)	0.2873 (2)	0.3530 (3)	0.0578 (8)
H49	0.1977	0.2596	0.3505	0.069*
C50	0.2750 (3)	0.4020 (2)	0.3570 (2)	0.0538 (7)
C51	0.9488 (3)	0.2750 (2)	0.4126 (3)	0.0619 (9)
H51A	0.9188	0.3299	0.4405	0.093*
H51B	0.9664	0.3009	0.3599	0.093*
H51C	1.0204	0.2475	0.4576	0.093*
C52	1.0043 (3)	0.0740 (3)	0.3436 (3)	0.0600 (8)
H52A	1.0097	0.0021	0.3313	0.09*
H52B	1.0652	0.0917	0.4017	0.09*
H52C	1.0154	0.1137	0.2941	0.09*
N3	0.53418 (19)	0.14672 (16)	0.35181 (16)	0.0420 (5)
H3N	0.4942	0.0907	0.3476	0.05*
O41	0.52359 (19)	0.31979 (15)	0.3658 (2)	0.0668 (7)
O42	0.3700 (2)	0.45152 (16)	0.3612 (2)	0.0663 (7)
H42A	0.4274	0.4076	0.3639	0.08*
O43	0.1861 (2)	0.44801 (18)	0.3567 (2)	0.0835 (9)
C61	−0.1341 (3)	0.8982 (2)	0.11567 (19)	0.0422 (6)
C62	−0.2221 (3)	0.9730 (2)	0.0861 (2)	0.0452 (6)
H62	−0.2043	1.0366	0.0661	0.054*
C63	−0.3375 (3)	0.9533 (2)	0.0862 (2)	0.0468 (6)
C64	−0.3650 (3)	0.8579 (2)	0.1163 (2)	0.0489 (7)
C65	−0.2730 (3)	0.7836 (2)	0.1469 (2)	0.0507 (7)
H65	−0.2894	0.7198	0.1673	0.061*
C66	−0.1596 (3)	0.8041 (2)	0.1469 (2)	0.0502 (7)
H66	−0.0998	0.7546	0.1679	0.06*
C67	0.0405 (3)	0.9968 (2)	0.1050 (2)	0.0466 (7)
C68	0.1659 (3)	0.9812 (2)	0.1108 (2)	0.0523 (8)
H68	0.1915	0.9132	0.115	0.063*
C69	0.2463 (3)	1.0512 (2)	0.1108 (3)	0.0615 (8)
H69	0.3196	1.0235	0.1137	0.074*
C70	0.2430 (3)	1.1660 (2)	0.1070 (3)	0.0554 (8)
C71	−0.4309 (3)	1.0354 (3)	0.0559 (3)	0.0679 (9)
H71A	−0.4987	1.0102	0.0055	0.102*
H71B	−0.3985	1.0946	0.0354	0.102*
H71C	−0.4555	1.0542	0.1074	0.102*
C72	−0.4875 (3)	0.8336 (3)	0.1182 (3)	0.0653 (9)
H72A	−0.4884	0.7648	0.1407	0.098*	0.5
H72B	−0.5452	0.8394	0.0562	0.098*	0.5
H72C	−0.5074	0.8812	0.1587	0.098*	0.5
H72D	−0.5389	0.8921	0.0964	0.098*	0.5
H72E	−0.4821	0.8175	0.1809	0.098*	0.5
H72F	−0.5199	0.7757	0.0784	0.098*	0.5
N4	−0.0147 (2)	0.91139 (17)	0.11665 (17)	0.0450 (5)
H4N	0.0278	0.8563	0.1261	0.054*
O61	−0.0095 (2)	1.08224 (16)	0.0903 (2)	0.0649 (6)
O62	0.1442 (2)	1.21427 (16)	0.09843 (19)	0.0637 (6)
H62A	0.0882	1.1694	0.0969	0.076*
O63	0.3342 (2)	1.21084 (19)	0.1144 (3)	0.0878 (9)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0381 (14)	0.0391 (13)	0.0533 (15)	−0.0002 (11)	0.0177 (12)	−0.0032 (11)
C2	0.0439 (16)	0.0392 (14)	0.0527 (16)	−0.0027 (12)	0.0178 (13)	0.0025 (12)
C3	0.0528 (18)	0.0398 (14)	0.0507 (17)	−0.0023 (12)	0.0238 (14)	−0.0044 (11)
C4	0.0418 (16)	0.0443 (15)	0.0589 (17)	0.0038 (12)	0.0209 (14)	−0.0069 (12)
C5	0.0468 (16)	0.0394 (14)	0.0616 (18)	0.0040 (12)	0.0187 (15)	0.0006 (13)
C6	0.0461 (17)	0.0347 (13)	0.0676 (19)	0.0014 (12)	0.0240 (14)	0.0011 (12)
C7	0.0356 (14)	0.0372 (14)	0.0689 (18)	0.0015 (11)	0.0196 (13)	0.0007 (12)
C8	0.0403 (16)	0.0445 (16)	0.085 (2)	−0.0039 (13)	0.0220 (16)	−0.0029 (15)
C9	0.0415 (16)	0.0452 (16)	0.093 (2)	−0.0009 (13)	0.0282 (16)	0.0067 (15)
C10	0.0465 (16)	0.0411 (15)	0.0701 (19)	0.0039 (13)	0.0209 (14)	0.0039 (13)
C11	0.0536 (18)	0.0518 (17)	0.082 (2)	−0.0080 (14)	0.0370 (17)	−0.0011 (15)
C12	0.0453 (18)	0.065 (2)	0.080 (2)	0.0038 (15)	0.0249 (17)	−0.0128 (16)
N1	0.0429 (13)	0.0365 (12)	0.0731 (16)	−0.0020 (10)	0.0253 (12)	−0.0008 (11)
O1	0.0457 (11)	0.0383 (10)	0.1082 (18)	−0.0021 (9)	0.0386 (12)	−0.0003 (11)
O2	0.0640 (16)	0.0378 (12)	0.137 (2)	0.0040 (10)	0.0545 (16)	0.0031 (12)
O3	0.0603 (14)	0.0574 (14)	0.1057 (18)	0.0152 (11)	0.0428 (14)	0.0056 (12)
C21	0.0358 (13)	0.0307 (12)	0.0480 (15)	0.0021 (10)	0.0194 (11)	−0.0004 (10)
C22	0.0402 (14)	0.0299 (12)	0.0512 (15)	−0.0014 (10)	0.0220 (12)	−0.0030 (10)
C23	0.0389 (14)	0.0327 (12)	0.0469 (15)	0.0058 (10)	0.0197 (12)	0.0027 (10)
C24	0.0396 (14)	0.0398 (14)	0.0453 (14)	−0.0043 (11)	0.0187 (12)	0.0004 (11)
C25	0.0519 (18)	0.0355 (13)	0.0623 (19)	−0.0108 (12)	0.0270 (15)	−0.0101 (12)
C26	0.0515 (17)	0.0333 (13)	0.0658 (18)	−0.0012 (11)	0.0323 (14)	−0.0067 (11)
C27	0.0430 (15)	0.0326 (13)	0.0592 (17)	0.0004 (11)	0.0256 (13)	−0.0017 (11)
C28	0.0410 (15)	0.0294 (12)	0.087 (2)	0.0030 (11)	0.0293 (15)	−0.0044 (13)
C29	0.0320 (14)	0.0447 (16)	0.095 (2)	−0.0003 (12)	0.0291 (15)	−0.0055 (15)
C30	0.0359 (15)	0.0408 (15)	0.078 (2)	−0.0089 (12)	0.0219 (14)	−0.0089 (13)
C31	0.0512 (17)	0.0390 (14)	0.076 (2)	0.0089 (12)	0.0335 (16)	−0.0027 (13)
C32	0.0438 (16)	0.0537 (17)	0.0700 (19)	−0.0067 (14)	0.0238 (15)	−0.0015 (14)
N2	0.0338 (11)	0.0292 (10)	0.0679 (15)	0.0024 (8)	0.0249 (11)	−0.0017 (9)
O21	0.0489 (11)	0.0289 (9)	0.1141 (18)	0.0038 (8)	0.0455 (12)	−0.0007 (10)
O22	0.0547 (15)	0.0347 (11)	0.137 (2)	−0.0010 (9)	0.0542 (16)	0.0025 (12)
O23	0.0545 (13)	0.0493 (12)	0.1149 (19)	−0.0133 (11)	0.0444 (13)	−0.0027 (12)
C41	0.0361 (14)	0.0295 (11)	0.0482 (15)	0.0044 (10)	0.0190 (11)	0.0018 (10)
C42	0.0459 (15)	0.0303 (12)	0.0509 (15)	0.0042 (10)	0.0207 (12)	−0.0038 (10)
C43	0.0354 (13)	0.0326 (12)	0.0511 (15)	0.0018 (10)	0.0140 (12)	−0.0004 (11)
C44	0.0352 (14)	0.0378 (13)	0.0527 (15)	0.0093 (10)	0.0191 (12)	0.0015 (11)
C45	0.0478 (16)	0.0313 (12)	0.072 (2)	0.0049 (11)	0.0273 (15)	−0.0074 (12)
C46	0.0387 (14)	0.0286 (12)	0.0659 (18)	0.0019 (10)	0.0191 (13)	−0.0042 (11)
C47	0.0380 (14)	0.0272 (12)	0.0672 (18)	0.0044 (10)	0.0231 (13)	0.0005 (11)
C48	0.0461 (16)	0.0309 (13)	0.088 (2)	−0.0034 (12)	0.0348 (16)	−0.0037 (13)
C49	0.0366 (15)	0.0439 (16)	0.102 (2)	−0.0010 (13)	0.0352 (16)	−0.0026 (16)
C50	0.0421 (16)	0.0385 (15)	0.086 (2)	0.0077 (12)	0.0284 (15)	−0.0023 (13)
C51	0.0411 (16)	0.0489 (17)	0.094 (3)	−0.0070 (12)	0.0208 (17)	−0.0182 (16)
C52	0.0401 (17)	0.0526 (17)	0.095 (2)	0.0091 (13)	0.0330 (16)	−0.0054 (16)
N3	0.0379 (12)	0.0271 (10)	0.0672 (15)	0.0036 (9)	0.0263 (11)	−0.0011 (9)
O41	0.0426 (11)	0.0301 (10)	0.138 (2)	0.0009 (9)	0.0438 (13)	−0.0023 (11)
O42	0.0481 (13)	0.0353 (11)	0.124 (2)	0.0050 (9)	0.0399 (14)	−0.0040 (11)
O43	0.0504 (14)	0.0443 (12)	0.166 (3)	0.0117 (10)	0.0500 (17)	−0.0096 (14)
C61	0.0403 (15)	0.0354 (13)	0.0528 (16)	−0.0049 (11)	0.0187 (13)	−0.0022 (11)
C62	0.0409 (14)	0.0365 (13)	0.0579 (17)	−0.0006 (11)	0.0167 (13)	0.0060 (12)
C63	0.0440 (15)	0.0406 (14)	0.0541 (16)	0.0000 (12)	0.0148 (13)	0.0023 (12)
C64	0.0454 (15)	0.0376 (14)	0.0648 (18)	−0.0070 (11)	0.0206 (14)	−0.0049 (12)
C65	0.0520 (16)	0.0375 (14)	0.067 (2)	−0.0064 (12)	0.0262 (16)	0.0011 (13)
C66	0.0562 (17)	0.0351 (14)	0.0647 (18)	0.0001 (12)	0.0279 (15)	0.0029 (12)
C67	0.0427 (16)	0.0385 (14)	0.0654 (18)	−0.0033 (11)	0.0273 (14)	−0.0005 (12)
C68	0.0423 (16)	0.0370 (14)	0.085 (2)	0.0015 (12)	0.0310 (15)	0.0033 (14)
C69	0.0459 (17)	0.0450 (17)	0.101 (3)	−0.0004 (14)	0.0351 (17)	0.0058 (17)
C70	0.0466 (17)	0.0437 (16)	0.078 (2)	−0.0024 (14)	0.0241 (15)	0.0061 (14)
C71	0.0435 (17)	0.0501 (17)	0.108 (3)	0.0048 (13)	0.0232 (18)	0.0119 (17)
C72	0.0508 (18)	0.0541 (19)	0.091 (3)	−0.0094 (15)	0.0245 (18)	−0.0014 (17)
N4	0.0408 (12)	0.0311 (11)	0.0658 (15)	0.0031 (9)	0.0220 (12)	0.0025 (9)
O61	0.0446 (11)	0.0361 (10)	0.1192 (19)	0.0011 (9)	0.0348 (12)	0.0126 (11)
O62	0.0484 (13)	0.0386 (11)	0.1059 (18)	0.0005 (9)	0.0288 (13)	0.0048 (11)
O63	0.0550 (15)	0.0537 (14)	0.164 (3)	−0.0110 (11)	0.0502 (17)	0.0081 (16)

Geometric parameters (Å, º) top

C1—C6	1.378 (4)	C41—C42	1.384 (4)
C1—C2	1.390 (4)	C41—C46	1.397 (4)
C1—N1	1.423 (4)	C41—N3	1.420 (3)
C2—C3	1.399 (5)	C42—C43	1.374 (4)
C2—H2	0.93	C42—H42	0.93
C3—C4	1.385 (4)	C43—C44	1.389 (4)
C3—C11	1.505 (4)	C43—C51	1.516 (4)
C4—C5	1.395 (4)	C44—C45	1.379 (4)
C4—C12	1.498 (4)	C44—C52	1.518 (4)
C5—C6	1.388 (4)	C45—C46	1.386 (4)
C5—H5	0.93	C45—H45	0.93
C6—H6	0.93	C46—H46	0.93
C7—O1	1.237 (3)	C47—O41	1.232 (3)
C7—N1	1.341 (4)	C47—N3	1.343 (3)
C7—C8	1.483 (4)	C47—C48	1.483 (4)
C8—C9	1.322 (5)	C48—C49	1.320 (4)
C8—H8	0.93	C48—H48	0.93
C9—C10	1.505 (4)	C49—C50	1.493 (4)
C9—H9	0.93	C49—H49	0.93
C10—O3	1.206 (4)	C50—O43	1.214 (3)
C10—O2	1.306 (4)	C50—O42	1.283 (4)
C11—H11A	0.96	C51—H51A	0.96
C11—H11B	0.96	C51—H51B	0.96
C11—H11C	0.96	C51—H51C	0.96
C12—H12A	0.96	C52—H52A	0.96
C12—H12B	0.96	C52—H52B	0.96
C12—H12C	0.96	C52—H52C	0.96
C12—H12D	0.96	N3—H3N	0.86
C12—H12E	0.96	O42—H42A	0.88
C12—H12F	0.96	C61—C66	1.384 (4)
N1—H1	0.86	C61—C62	1.385 (4)
O2—H2A	0.88	C61—N4	1.426 (4)
C21—C26	1.384 (4)	C62—C63	1.398 (4)
C21—C22	1.395 (3)	C62—H62	0.93
C21—N2	1.420 (3)	C63—C64	1.400 (4)
C22—C23	1.394 (4)	C63—C71	1.494 (4)
C22—H22	0.93	C64—C65	1.413 (4)
C23—C24	1.406 (4)	C64—C72	1.502 (4)
C23—C31	1.500 (4)	C65—C66	1.377 (5)
C24—C25	1.390 (4)	C65—H65	0.93
C24—C32	1.505 (4)	C66—H66	0.93
C25—C26	1.375 (4)	C67—O61	1.243 (3)
C25—H25	0.93	C67—N4	1.333 (3)
C26—H26	0.93	C67—C68	1.479 (4)
C27—O21	1.247 (3)	C68—C69	1.321 (4)
C27—N2	1.332 (3)	C68—H68	0.93
C27—C28	1.483 (4)	C69—C70	1.493 (4)
C28—C29	1.343 (4)	C69—H69	0.93
C28—H28	0.93	C70—O63	1.203 (4)
C29—C30	1.467 (4)	C70—O62	1.299 (4)
C29—H29	0.93	C71—H71A	0.96
C30—O23	1.218 (4)	C71—H71B	0.96
C30—O22	1.301 (4)	C71—H71C	0.96
C31—H31A	0.96	C72—H72A	0.96
C31—H31B	0.96	C72—H72B	0.96
C31—H31C	0.96	C72—H72C	0.96
C32—H32A	0.96	C72—H72D	0.96
C32—H32B	0.96	C72—H72E	0.96
C32—H32C	0.96	C72—H72F	0.96
N2—H2N	0.86	N4—H4N	0.86
O22—H22A	0.88	O62—H62A	0.88

C6—C1—C2	119.2 (3)	C42—C41—C46	119.2 (2)
C6—C1—N1	116.0 (3)	C42—C41—N3	125.4 (2)
C2—C1—N1	124.8 (3)	C46—C41—N3	115.4 (2)
C1—C2—C3	120.2 (3)	C43—C42—C41	121.0 (2)
C1—C2—H2	119.9	C43—C42—H42	119.5
C3—C2—H2	119.9	C41—C42—H42	119.5
C4—C3—C2	120.5 (3)	C42—C43—C44	120.2 (2)
C4—C3—C11	121.0 (3)	C42—C43—C51	119.0 (2)
C2—C3—C11	118.5 (3)	C44—C43—C51	120.9 (2)
C3—C4—C5	118.9 (3)	C45—C44—C43	119.1 (2)
C3—C4—C12	121.6 (3)	C45—C44—C52	118.7 (2)
C5—C4—C12	119.5 (3)	C43—C44—C52	122.2 (3)
C6—C5—C4	120.4 (3)	C44—C45—C46	121.3 (2)
C6—C5—H5	119.8	C44—C45—H45	119.4
C4—C5—H5	119.8	C46—C45—H45	119.4
C1—C6—C5	120.8 (3)	C45—C46—C41	119.3 (2)
C1—C6—H6	119.6	C45—C46—H46	120.3
C5—C6—H6	119.6	C41—C46—H46	120.3
O1—C7—N1	123.5 (3)	O41—C47—N3	123.3 (3)
O1—C7—C8	122.9 (3)	O41—C47—C48	123.1 (2)
N1—C7—C8	113.6 (2)	N3—C47—C48	113.6 (2)
C9—C8—C7	128.5 (3)	C49—C48—C47	128.5 (3)
C9—C8—H8	115.8	C49—C48—H48	115.8
C7—C8—H8	115.8	C47—C48—H48	115.8
C8—C9—C10	131.9 (3)	C48—C49—C50	132.1 (3)
C8—C9—H9	114	C48—C49—H49	114
C10—C9—H9	114	C50—C49—H49	114
O3—C10—O2	121.1 (3)	O43—C50—O42	120.4 (3)
O3—C10—C9	119.2 (3)	O43—C50—C49	118.3 (3)
O2—C10—C9	119.6 (3)	O42—C50—C49	121.3 (3)
C3—C11—H11A	109.5	C43—C51—H51A	109.5
C3—C11—H11B	109.5	C43—C51—H51B	109.5
H11A—C11—H11B	109.5	H51A—C51—H51B	109.5
C3—C11—H11C	109.5	C43—C51—H51C	109.5
H11A—C11—H11C	109.5	H51A—C51—H51C	109.5
H11B—C11—H11C	109.5	H51B—C51—H51C	109.5
C4—C12—H12A	109.5	C44—C52—H52A	109.5
C4—C12—H12B	109.5	C44—C52—H52B	109.5
H12A—C12—H12B	109.5	H52A—C52—H52B	109.5
C4—C12—H12C	109.5	C44—C52—H52C	109.5
H12A—C12—H12C	109.5	H52A—C52—H52C	109.5
H12B—C12—H12C	109.5	H52B—C52—H52C	109.5
C4—C12—H12D	109.5	C47—N3—C41	127.8 (2)
H12A—C12—H12D	141.1	C47—N3—H3N	116.1
H12B—C12—H12D	56.3	C41—N3—H3N	116.1
H12C—C12—H12D	56.3	C50—O42—H42A	109.5
C4—C12—H12E	109.5	C66—C61—C62	120.1 (3)
H12A—C12—H12E	56.3	C66—C61—N4	116.0 (3)
H12B—C12—H12E	141.1	C62—C61—N4	123.9 (2)
H12C—C12—H12E	56.3	C61—C62—C63	120.2 (3)
H12D—C12—H12E	109.5	C61—C62—H62	119.9
C4—C12—H12F	109.5	C63—C62—H62	119.9
H12A—C12—H12F	56.3	C62—C63—C64	120.2 (3)
H12B—C12—H12F	56.3	C62—C63—C71	119.7 (3)
H12C—C12—H12F	141.1	C64—C63—C71	120.1 (3)
H12D—C12—H12F	109.5	C63—C64—C65	118.2 (3)
H12E—C12—H12F	109.5	C63—C64—C72	122.0 (3)
C7—N1—C1	128.4 (2)	C65—C64—C72	119.8 (3)
C7—N1—H1	115.8	C66—C65—C64	121.0 (3)
C1—N1—H1	115.8	C66—C65—H65	119.5
C10—O2—H2A	109.5	C64—C65—H65	119.5
C26—C21—C22	119.6 (2)	C65—C66—C61	120.2 (3)
C26—C21—N2	116.7 (2)	C65—C66—H66	119.9
C22—C21—N2	123.7 (2)	C61—C66—H66	119.9
C23—C22—C21	120.3 (2)	O61—C67—N4	122.8 (3)
C23—C22—H22	119.9	O61—C67—C68	123.0 (2)
C21—C22—H22	119.9	N4—C67—C68	114.3 (2)
C22—C23—C24	120.0 (2)	C69—C68—C67	128.4 (3)
C22—C23—C31	119.8 (2)	C69—C68—H68	115.8
C24—C23—C31	120.2 (2)	C67—C68—H68	115.8
C25—C24—C23	118.2 (2)	C68—C69—C70	132.8 (3)
C25—C24—C32	120.2 (3)	C68—C69—H69	113.6
C23—C24—C32	121.5 (2)	C70—C69—H69	113.6
C26—C25—C24	121.8 (3)	O63—C70—O62	122.1 (3)
C26—C25—H25	119.1	O63—C70—C69	118.0 (3)
C24—C25—H25	119.1	O62—C70—C69	119.9 (3)
C25—C26—C21	120.0 (2)	C63—C71—H71A	109.5
C25—C26—H26	120	C63—C71—H71B	109.5
C21—C26—H26	120	H71A—C71—H71B	109.5
O21—C27—N2	123.2 (3)	C63—C71—H71C	109.5
O21—C27—C28	122.7 (2)	H71A—C71—H71C	109.5
N2—C27—C28	114.1 (2)	H71B—C71—H71C	109.5
C29—C28—C27	127.6 (3)	C64—C72—H72A	109.5
C29—C28—H28	116.2	C64—C72—H72B	109.5
C27—C28—H28	116.2	H72A—C72—H72B	109.5
C28—C29—C30	132.9 (3)	C64—C72—H72C	109.5
C28—C29—H29	113.6	H72A—C72—H72C	109.5
C30—C29—H29	113.6	H72B—C72—H72C	109.5
O23—C30—O22	120.5 (3)	C64—C72—H72D	109.5
O23—C30—C29	119.1 (3)	H72A—C72—H72D	141.1
O22—C30—C29	120.3 (3)	H72B—C72—H72D	56.3
C23—C31—H31A	109.5	H72C—C72—H72D	56.3
C23—C31—H31B	109.5	C64—C72—H72E	109.5
H31A—C31—H31B	109.5	H72A—C72—H72E	56.3
C23—C31—H31C	109.5	H72B—C72—H72E	141.1
H31A—C31—H31C	109.5	H72C—C72—H72E	56.3
H31B—C31—H31C	109.5	H72D—C72—H72E	109.5
C24—C32—H32A	109.5	C64—C72—H72F	109.5
C24—C32—H32B	109.5	H72A—C72—H72F	56.3
H32A—C32—H32B	109.5	H72B—C72—H72F	56.3
C24—C32—H32C	109.5	H72C—C72—H72F	141.1
H32A—C32—H32C	109.5	H72D—C72—H72F	109.5
H32B—C32—H32C	109.5	H72E—C72—H72F	109.5
C27—N2—C21	128.7 (2)	C67—N4—C61	129.3 (2)
C27—N2—H2N	115.7	C67—N4—H4N	115.4
C21—N2—H2N	115.7	C61—N4—H4N	115.4
C30—O22—H22A	109.5	C70—O62—H62A	109.5

C6—C1—C2—C3	−1.3 (4)	C46—C41—C42—C43	2.2 (4)
N1—C1—C2—C3	179.2 (3)	N3—C41—C42—C43	179.5 (3)
C1—C2—C3—C4	0.9 (4)	C41—C42—C43—C44	−1.8 (4)
C1—C2—C3—C11	−179.8 (3)	C41—C42—C43—C51	177.8 (3)
C2—C3—C4—C5	−0.6 (4)	C42—C43—C44—C45	0.0 (4)
C11—C3—C4—C5	−179.9 (3)	C51—C43—C44—C45	−179.6 (3)
C2—C3—C4—C12	179.8 (3)	C42—C43—C44—C52	178.8 (3)
C11—C3—C4—C12	0.4 (4)	C51—C43—C44—C52	−0.8 (4)
C3—C4—C5—C6	0.6 (5)	C43—C44—C45—C46	1.4 (5)
C12—C4—C5—C6	−179.7 (3)	C52—C44—C45—C46	−177.4 (3)
C2—C1—C6—C5	1.4 (4)	C44—C45—C46—C41	−1.0 (5)
N1—C1—C6—C5	−179.1 (3)	C42—C41—C46—C45	−0.8 (4)
C4—C5—C6—C1	−1.1 (5)	N3—C41—C46—C45	−178.4 (3)
O1—C7—C8—C9	−13.3 (6)	O41—C47—C48—C49	1.8 (6)
N1—C7—C8—C9	167.3 (4)	N3—C47—C48—C49	−177.6 (4)
C7—C8—C9—C10	2.3 (8)	C47—C48—C49—C50	1.4 (7)
C8—C9—C10—O3	−171.1 (4)	C48—C49—C50—O43	−179.9 (4)
C8—C9—C10—O2	10.9 (7)	C48—C49—C50—O42	−0.4 (7)
O1—C7—N1—C1	6.8 (5)	O41—C47—N3—C41	−1.5 (5)
C8—C7—N1—C1	−173.9 (3)	C48—C47—N3—C41	178.0 (3)
C6—C1—N1—C7	159.6 (3)	C42—C41—N3—C47	18.9 (4)
C2—C1—N1—C7	−20.9 (5)	C46—C41—N3—C47	−163.7 (3)
C26—C21—C22—C23	−0.1 (4)	C66—C61—C62—C63	−1.0 (5)
N2—C21—C22—C23	−179.9 (2)	N4—C61—C62—C63	179.1 (3)
C21—C22—C23—C24	−0.8 (4)	C61—C62—C63—C64	0.1 (5)
C21—C22—C23—C31	180.0 (3)	C61—C62—C63—C71	178.8 (3)
C22—C23—C24—C25	1.4 (4)	C62—C63—C64—C65	0.5 (5)
C31—C23—C24—C25	−179.3 (3)	C71—C63—C64—C65	−178.2 (3)
C22—C23—C24—C32	−178.0 (3)	C62—C63—C64—C72	179.6 (3)
C31—C23—C24—C32	1.3 (4)	C71—C63—C64—C72	1.0 (5)
C23—C24—C25—C26	−1.2 (5)	C63—C64—C65—C66	−0.2 (5)
C32—C24—C25—C26	178.2 (3)	C72—C64—C65—C66	−179.3 (3)
C24—C25—C26—C21	0.3 (5)	C64—C65—C66—C61	−0.7 (5)
C22—C21—C26—C25	0.4 (4)	C62—C61—C66—C65	1.3 (5)
N2—C21—C26—C25	−179.9 (3)	N4—C61—C66—C65	−178.8 (3)
O21—C27—C28—C29	−9.7 (6)	O61—C67—C68—C69	7.0 (6)
N2—C27—C28—C29	170.8 (4)	N4—C67—C68—C69	−173.2 (4)
C27—C28—C29—C30	−0.3 (7)	C67—C68—C69—C70	1.3 (8)
C28—C29—C30—O23	−170.8 (4)	C68—C69—C70—O63	175.1 (5)
C28—C29—C30—O22	9.5 (7)	C68—C69—C70—O62	−3.2 (7)
O21—C27—N2—C21	7.0 (5)	O61—C67—N4—C61	−0.3 (5)
C28—C27—N2—C21	−173.6 (3)	C68—C67—N4—C61	179.8 (3)
C26—C21—N2—C27	155.7 (3)	C66—C61—N4—C67	−168.4 (3)
C22—C21—N2—C27	−24.5 (4)	C62—C61—N4—C67	11.4 (5)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O63ⁱ	0.86	2.00	2.851 (3)	168
N2—H2N···O43	0.86	2.03	2.865 (3)	163
N3—H3N···O23ⁱ	0.86	2.07	2.916 (3)	167
N4—H4N···O3	0.86	2.08	2.930 (3)	169
O2—H2A···O1	0.88	1.62	2.481 (3)	165
O22—H22A···O21	0.88	1.59	2.471 (3)	176
O42—H42A···O41	0.88	1.61	2.487 (3)	175
O62—H62A···O61	0.88	1.6	2.480 (3)	176

Symmetry code: (i) x, y−1, z.

Experimental details

Crystal data
Chemical formula	C₁₂H₁₃NO₃
M_r	219.23
Crystal system, space group	Monoclinic, Pc
Temperature (K)	295
a, b, c (Å)	11.9003 (2), 12.9991 (2), 15.2641 (3)
β (°)	110.207 (2)
V (Å³)	2215.92 (7)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.10
Crystal size (mm)	0.48 × 0.32 × 0.31

Data collection
Diffractometer	Oxford Diffraction Xcalibur Ruby Gemini
Absorption correction	Multi-scan (CrysAlis PRO; Oxford Diffraction, 2009)
T_min, T_max	0.958, 0.965
No. of measured, independent and observed [I > 2σ(I)] reflections	67608, 5279, 4100
R_int	0.028
(sin θ/λ)_max (Å⁻¹)	0.658

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.044, 0.134, 1.03
No. of reflections	5279
No. of parameters	577
No. of restraints	10
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.29, −0.16

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).