4-(But-3-enylamino)-3-nitro­benzoic acid

Shivanagere Nagojappa Narendra Babu; Aisyah Saad Abdul Rahim; Hasnah Osman; Samuel Robinson Jebas; Hoong-Kun Fun

doi:10.1107/S1600536809021692

. 2009 Jun 13;65(Pt 7):o1560–o1561. doi: 10.1107/S1600536809021692

4-(But-3-enylamino)-3-nitrobenzoic acid

Shivanagere Nagojappa Narendra Babu ^a, Aisyah Saad Abdul Rahim ^a,^‡, Hasnah Osman ^b, Samuel Robinson Jebas ^c,^§, Hoong-Kun Fun ^c,^*,^¶

PMCID: PMC2969436 PMID: 21582843

Abstract

The asymmetric unit of the title compound, C₁₁H₁₂N₂O₄, contains 12 crystallographically independent molecules, labelled A to L. The nitro and carboxyl groups are twisted slightly out of the plane of the attached benzene ring in all independent molecules except molecules G and D. The nitro group is coplanar with the benzene ring in molecule G and the carboxyl group is coplanar with the benzene ring in molecule D. The orientation of the butyl group with respect to the rest of the molecule is different in some of the independent molecules, with the C—C—C—C torsion angles varying from 104.2 (5) to 126.6 (7)°. In each independent molecule, an intramolecular N—H⋯O hydrogen bond generates an S(6) ring motif. In the crystal structure, the 12 independent molecules exist as six pairs of O—H⋯O hydrogen-bonded R ₂ ²(8) dimers. In addition, C—H⋯O hydrogen bonds are observed.

Related literature

For heterocyclic compounds of pharmacological interest, see: Ishida et al. (2006 ▶); Kuzniewski et al. (2008 ▶); Wu et al. (2000 ▶). For bond-length data, see: Allen et al. (1987 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶). For the stability of the temperature controller used in the data collection, see: Cosier & Glazer (1986 ▶).

Experimental

Crystal data

C₁₁H₁₂N₂O₄
M _r = 236.23
Monoclinic,
a = 13.3461 (5) Å
b = 66.777 (3) Å
c = 15.0195 (6) Å
β = 99.632 (2)°
V = 13196.9 (9) Å³
Z = 48
Mo Kα radiation
μ = 0.11 mm⁻¹
T = 100 K
0.33 × 0.29 × 0.13 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T _min = 0.965, T _max = 0.985
173518 measured reflections
21275 independent reflections
16663 reflections with I > 2σ(I)
R _int = 0.096

Refinement

R[F ² > 2σ(F ²)] = 0.078
wR(F ²) = 0.213
S = 1.08
21275 reflections
1837 parameters
2 restraints
H-atom parameters constrained
Δρ_max = 0.73 e Å⁻³
Δρ_min = −0.38 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 ▶).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809021692/ci2814sup1.cif

e-65-o1560-sup1.cif^{(84.2KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809021692/ci2814Isup2.hkl

e-65-o1560-Isup2.hkl^{(1MB, hkl)}

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

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1A—H1AA⋯O1A	0.86	2.00	2.643 (4)	130
N1B—H1BA⋯O1B	0.86	1.99	2.628 (5)	130
N1C—H1CA⋯O1C	0.86	1.98	2.631 (4)	132
N1D—H1DA⋯O1D	0.86	1.99	2.634 (5)	130
N1E—H1EA⋯O1E	0.86	2.01	2.637 (5)	129
N1F—H1FA⋯O1F	0.86	2.00	2.641 (4)	130
N1G—H1GA⋯O1G	0.86	1.98	2.624 (5)	130
N1H—H1HA⋯O1H	0.86	1.97	2.621 (5)	131
N1I—H1IA⋯O1I	0.86	1.99	2.632 (4)	130
N1J—H1JA⋯O1J	0.86	1.99	2.627 (4)	131
N1K—H1KA⋯O1K	0.86	1.96	2.615 (4)	132
N1L—H1LA⋯O1L	0.86	2.01	2.645 (4)	130
O3A—H3AB⋯O4C	0.82	1.80	2.612 (5)	176
O3C—H3CB⋯O4A	0.82	1.82	2.630 (4)	172
O3B—H3BB⋯O4L	0.82	1.81	2.626 (5)	173
O3L—H3LB⋯O4B	0.82	1.80	2.613 (5)	169
O3D—H3DB⋯O4J	0.82	1.80	2.618 (5)	173
O3J—H3JB⋯O4D	0.82	1.81	2.626 (5)	175
O3E—H3EB⋯O4I	0.82	1.81	2.624 (5)	170
O3I—H3IB⋯O4E	0.82	1.82	2.635 (5)	174
O3G—H3GB⋯O4K	0.82	1.80	2.616 (5)	172
O3K—H3KB⋯O4G	0.82	1.83	2.633 (5)	163
O3F—H3FB⋯O4Hⁱ	0.82	1.79	2.605 (5)	172
O3H—H3HB⋯O4Fⁱⁱ	0.82	1.82	2.611 (5)	164
C6B—H6BA⋯O2Hⁱ	0.93	2.45	3.169 (5)	134
C6H—H6HA⋯O2Bⁱⁱⁱ	0.93	2.55	3.243 (5)	131
C6I—H6IA⋯O2Cⁱⁱ	0.93	2.53	3.218 (5)	131
C6K—H6KA⋯O2K^iv	0.93	2.40	3.149 (4)	138
C9C—H9CB⋯O1B	0.97	2.59	3.477 (6)	152

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) ; (iv) .

Acknowledgments

SNNB, ASAR and HO are grateful to Universiti Sains Malaysia (USM) for funding the synthetic chemistry work under the University Research grant No. 1001/PFARMASI/815026. HKF and SRJ thank the Malaysian Government and Universiti Sains Malaysia for the Science Fund grant No. 305/PFIZIK/613312. SNNB and SRJ thank Universiti Sains Malaysia for post-doctoral research fellowships. HKF also thanks Universiti Sains Malaysia for the Research University Golden Goose grant No.1001/PFIZIK/811012.

supplementary crystallographic information

Comment

Various heterocyclic compounds of pharmacological interests (Ishida et al., 2006; Kuzniewski et al., 2008; Wu et al., 2000) can be synthesized by nitro benzoic acid derivatives as the precursors. We report here the crystal structure of the title compound, which was synthesized as an intermediate.

The asymmetric unit of the title compound (Fig. 1) comprises of twelve crystallographically independent molecules labelled as A to L. The bond lengths (Allen et al., 1987) and bond angles are normal. The nitro group (N2/O1/O2) is twisted away from the attached benzene ring (C1-C6) in eleven molecules forming dihedral angles of 1.54 (1)° in molecule A [5.45 (2)° in B; 4.68 (2)° in C; 2.44 (1) in D; 5.10 (2)° in E; 5.84 (2)° in F; 3.29 (2)° in H; 6.96 (2)° in I; 7.48 (2)° in J; 2.44 (2)° in K and 4.67 (2)° in L]. In molecule G, the nitro group (N2/O1/O2) is almost coplanar with the attached benzene ring (C1-C6) forming a dihedral angle of 0.99 (2)°. The dihedral angles formed by the carboxyl groups (C7/O3/O4) with the attached benzene rings are 5.24 (1)° in molecule A [4.49 (2)° in B; 1.69 (2)° in C; 19.79 (2)° in E; 18.38 (2)° in F; 16.46 (3)° in G; 15.11 (2)° in H; 27.26 (2)° in I; 28.61 (2)° in J; 16.39 (2)° in K; 21.94 (2)° in L], indicating that they are twisted from the mean plane of the benzene ring. In molecule D, the carboxyl group is coplanar with the benzene ring [dihedral angle 0.26 (1)°]. The orientation of the butyl group of the but-3-enylamino unit (N1/C8-C11) is different in some of the independent molecules. The C8-C9-C10-C11 torsion angle is -121.7 (5)° in molecule A [-109.4 (6)° in B; -107.0 (6)° in C; 126.3 (7)° in D; 123.7 (5)° in E; 123.0 (5)° in F; 126.6 (7)° in G; -104.2 (5)° in H; -112.9 (5)° in I; 111.6 (5)° in J; -104.8 (5)° in K and 121.8 (6)° in L]. In each independent molecule, an intramolecular N—H···O hydrogen bond generates an S(6) ring motif (Bernstein et al., 1995).

In the crystal structure, the twelve independent molecules exist as six pairs of O—H···O hydrogen-bonded R₂²(8) dimers (Table 1 and Fig. 3). In addition, C—H···O hydrogen bonds are observed.

Experimental

A mixture of ethyl 4-(but-3-enylamino)-3-nitro-benzoate (0.25 g, 0.001 mol) and KOH (0.112 g, 0.002 mol) was refluxed in aqueous ethanol (5 ml) for 3 h. After completion of the reaction, ethanol was distilled off and the reaction mixture was diluted with water (5 ml). The aqueous layer was washed with dichloromethane (5 ml × 2) and acidified with concentrated HCl to afford a yellow solid. Yellow single crystals were obtained after recrystallization of the crude product with hot ethyl acetate.