2-Methyl­amino-5-nitro­benzoic acid

Raza, A.R.; Rubab, S.L.; Tahir, M.N.

doi:10.1107/S160053681001946X

organic compounds

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ISSN: 2056-9890

Volume 66| Part 6| June 2010| Page o1484

https://doi.org/10.1107/S160053681001946X

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2-Methylamino-5-nitrobenzoic acid

Abdul Rauf Raza,^a Syeda Laila Rubab ^a and M. Nawaz Tahir ^b ^*

^aDepartment of Chemistry, University of Sargodha, Sargodha, Pakistan, and ^bDepartment of Physics, University of Sargodha, Sargodha, Pakistan
^*Correspondence e-mail: dmntahir_uos@yahoo.com

(Received 22 May 2010; accepted 24 May 2010; online 29 May 2010)

The title compound, C₈H₈N₂O₄, is almost planar (r.m.s. deviation = 0.037 Å) and an intramolecular N—H⋯O hydrogen bond generates an S(6) ring. In the crystal, inversion dimers linked by pairs of O—H⋯O hydrogen bonds generate R₂²(8) loops. Intermolecular N—H⋯O hydrogen bonds (involving the same H atom that forms the intramolecular hydrogen bond) link the dimers into infinite sheets lying parallel to (102).

Related literature

For background to the medicinal properties of benzodiazepines, see: Blank et al. (2009 ); Kamal et al. (2010 ). For a related structure, see: Dhaneshwar & Pant (1972 ). For graph-set theory, see: Bernstein et al. (1995 ).

Experimental

Crystal data

C₈H₈N₂O₄
M_r = 196.16
Monoclinic, P 2₁ /c
a = 7.2541 (12) Å
b = 14.037 (2) Å
c = 8.5972 (14) Å
β = 103.673 (6)°
V = 850.6 (2) Å³
Z = 4
Mo Kα radiation
μ = 0.13 mm⁻¹
T = 296 K
0.34 × 0.12 × 0.10 mm

Data collection

Bruker Kappa APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ) T_min = 0.979, T_max = 0.988
6739 measured reflections
1667 independent reflections
931 reflections with I > 2σ(I)
R_int = 0.051

Refinement

R[F² > 2σ(F²)] = 0.051
wR(F²) = 0.156
S = 0.95
1667 reflections
129 parameters
H-atom parameters constrained
Δρ_max = 0.25 e Å⁻³
Δρ_min = −0.27 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O1	0.86	2.03	2.694 (3)	134
N1—H1⋯O4ⁱ	0.86	2.52	3.165 (3)	133
O2—H2⋯O1ⁱⁱ	0.82	1.86	2.679 (3)	177
Symmetry codes: (i) $[x-1, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (ii) -x+1, -y+1, -z+1.

Data collection: APEX2 (Bruker, 2007 ); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ) and PLATON (Spek, 2009 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ) and PLATON.

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S160053681001946X/hb5463sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S160053681001946X/hb5463Isup2.hkl

checkCIF report

Comment top

The benzodiazepines constitute a very diverse class of heterocyclic compounds with plethora of biological activities such as anti-caner (Kamal et al., 2010) and anti-HIV (Blank et al., 2009) agent. The title compound (I, Fig. 1) was synthesized as a precursor for the synthesis of benzodiazepine derivative and it will also be utilized for the metal complexation.

The crystal structures of N-methylanthranilic acid (II) (Dhaneshwar & Pant, 1972) has been published. The title compound differs from (II) due to substitution of nitro group at at position five.

The asymmetric unit of title compound is essentially planar with r. m. s. deviation of 0.0366 Å from the least square plane of (C1—C8/N1/N2/O1/O2/O3). There exist a S(6) ring motif (Bernstein et al., 1995) due to N—H···O type of intramolecular H-bondings. The molecules are dimerised due to inversion related O—H···O type of H-bondings with R₂²(8) ring motifs. The dimers are interlinked in the form of infinite two dimensional polymeric sheets due to H-bonding of N—H···O type (Fig. 2).

Related literature top

For background to the medicinal properties of benzodiazepines, see: Blank et al. (2009); Kamal et al. (2010). For a related structure, see: Dhaneshwar & Pant (1972). For graph-set theory, see: Bernstein et al. (1995);

Experimental top

To HNO₃ (1.83 g, 0.03 mol) taken in an ice chilled round bottom flask the H₂SO₄ (2.6 g, 0.026 mol) was added as drops with constant stirring. A solution of N-methylanthranilic acid (2 g, 0.01 mol) in EtOAc (25 ml) was added as drops to the nitrating mixture in ice chilled water bath and stirred for half an hour followed by 3 hours reflux. The reaction mixture was neutralized and extracted with EtOAc (3 × 30 ml). The organic layer was dried over anhydrous Na₂SO₄ and concentrated under reduce pressure that afforded purple needles of (I) upon standing.

Structure description top

The crystal structures of N-methylanthranilic acid (II) (Dhaneshwar & Pant, 1972) has been published. The title compound differs from (II) due to substitution of nitro group at at position five.

For background to the medicinal properties of benzodiazepines, see: Blank et al. (2009); Kamal et al. (2010). For a related structure, see: Dhaneshwar & Pant (1972). For graph-set theory, see: Bernstein et al. (1995);

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2009); software used to prepare material for publication: WinGX (Farrugia, 1999) and PLATON (Spek, 2009).

Figures top

	Fig. 1. View of (I) with displacement ellipsoids drawn at the 50% probability level. The dotted line indicate the intramolecular H-bond.
	Fig. 2. The partial packing diagram of (I), which shows that molecules form polymeric chains extending along the b-axis.

2-Methylamino-5-nitrobenzoic acid top

Crystal data top

C₈H₈N₂O₄	F(000) = 408
M_r = 196.16	D_x = 1.532 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 931 reflections
a = 7.2541 (12) Å	θ = 2.8–26.0°
b = 14.037 (2) Å	µ = 0.13 mm⁻¹
c = 8.5972 (14) Å	T = 296 K
β = 103.673 (6)°	Needle, colorless
V = 850.6 (2) Å³	0.34 × 0.12 × 0.10 mm
Z = 4

Data collection top

Bruker Kappa APEXII CCD diffractometer	1667 independent reflections
Radiation source: fine-focus sealed tube	931 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.051
Detector resolution: 7.50 pixels mm^-1	θ_max = 26.0°, θ_min = 2.8°
ω scans	h = −8→8
Absorption correction: multi-scan (SADABS; Bruker, 2005)	k = −17→12
T_min = 0.979, T_max = 0.988	l = −10→10
6739 measured reflections

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)] = 0.051	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.156	H-atom parameters constrained
S = 0.95	w = 1/[σ²(F_o²) + (0.0901P)²] where P = (F_o² + 2F_c²)/3
1667 reflections	(Δ/σ)_max < 0.001
129 parameters	Δρ_max = 0.25 e Å⁻³
0 restraints	Δρ_min = −0.27 e Å⁻³

Crystal data top

C₈H₈N₂O₄	V = 850.6 (2) Å³
M_r = 196.16	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 7.2541 (12) Å	µ = 0.13 mm⁻¹
b = 14.037 (2) Å	T = 296 K
c = 8.5972 (14) Å	0.34 × 0.12 × 0.10 mm
β = 103.673 (6)°

Data collection top

Bruker Kappa APEXII CCD diffractometer	1667 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	931 reflections with I > 2σ(I)
T_min = 0.979, T_max = 0.988	R_int = 0.051
6739 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.051	0 restraints
wR(F²) = 0.156	H-atom parameters constrained
S = 0.95	Δρ_max = 0.25 e Å⁻³
1667 reflections	Δρ_min = −0.27 e Å⁻³
129 parameters

Special details top

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell esds are taken into account in the estimation of distances, angles and torsion angles

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
O1	0.5419 (3)	0.38658 (12)	0.5049 (2)	0.0518 (7)
O2	0.7127 (3)	0.49628 (11)	0.4158 (3)	0.0573 (8)
O3	1.2269 (3)	0.42409 (14)	0.1896 (3)	0.0729 (9)
O4	1.3096 (3)	0.27893 (14)	0.1606 (3)	0.0672 (8)
N1	0.6259 (3)	0.20268 (13)	0.4642 (3)	0.0468 (8)
N2	1.2080 (3)	0.33798 (16)	0.2050 (3)	0.0520 (9)
C1	0.7967 (3)	0.33700 (15)	0.3914 (3)	0.0356 (8)
C2	0.7635 (3)	0.23711 (16)	0.4028 (3)	0.0380 (8)
C3	0.8868 (3)	0.17368 (17)	0.3470 (3)	0.0421 (9)
C4	1.0304 (4)	0.20647 (17)	0.2851 (3)	0.0445 (9)
C5	1.0588 (3)	0.30381 (17)	0.2745 (3)	0.0412 (9)
C6	0.9435 (4)	0.36766 (16)	0.3270 (3)	0.0405 (8)
C7	0.6728 (4)	0.40694 (16)	0.4424 (3)	0.0404 (9)
C8	0.5800 (4)	0.10286 (17)	0.4683 (4)	0.0530 (11)
H1	0.55963	0.24247	0.50427	0.0562*
H2	0.63612	0.53160	0.44325	0.0859*
H3	0.86864	0.10833	0.35312	0.0505*
H4	1.10970	0.16375	0.24988	0.0534*
H6	0.96473	0.43263	0.31904	0.0486*
H8A	0.68822	0.06878	0.52857	0.0796*
H8B	0.54575	0.07839	0.36101	0.0796*
H8C	0.47552	0.09499	0.51789	0.0796*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0570 (13)	0.0296 (10)	0.0792 (14)	0.0016 (8)	0.0367 (11)	0.0003 (9)
O2	0.0657 (13)	0.0256 (11)	0.0921 (16)	0.0005 (9)	0.0418 (12)	−0.0015 (9)
O3	0.0793 (16)	0.0436 (12)	0.1119 (19)	−0.0089 (10)	0.0550 (14)	0.0108 (12)
O4	0.0582 (13)	0.0610 (13)	0.0958 (17)	0.0082 (10)	0.0448 (12)	0.0052 (12)
N1	0.0541 (14)	0.0254 (11)	0.0716 (16)	−0.0034 (10)	0.0363 (13)	−0.0040 (10)
N2	0.0497 (15)	0.0443 (14)	0.0687 (17)	0.0010 (12)	0.0273 (13)	0.0050 (12)
C1	0.0406 (15)	0.0224 (12)	0.0464 (16)	0.0003 (10)	0.0156 (12)	−0.0020 (10)
C2	0.0416 (15)	0.0307 (13)	0.0447 (15)	−0.0026 (11)	0.0160 (13)	−0.0013 (11)
C3	0.0464 (16)	0.0261 (12)	0.0584 (17)	0.0005 (11)	0.0216 (14)	−0.0032 (12)
C4	0.0461 (16)	0.0333 (15)	0.0586 (18)	0.0050 (12)	0.0212 (14)	−0.0029 (12)
C5	0.0414 (15)	0.0366 (15)	0.0497 (16)	−0.0023 (11)	0.0190 (13)	0.0030 (12)
C6	0.0438 (15)	0.0288 (13)	0.0502 (16)	−0.0012 (11)	0.0137 (13)	−0.0003 (11)
C7	0.0467 (16)	0.0264 (14)	0.0494 (16)	−0.0001 (11)	0.0141 (14)	−0.0006 (12)
C8	0.069 (2)	0.0257 (14)	0.076 (2)	−0.0092 (12)	0.0404 (16)	−0.0070 (13)

Geometric parameters (Å, º) top

O1—C7	1.230 (4)	C1—C6	1.380 (4)
O2—C7	1.319 (3)	C2—C3	1.423 (3)
O3—N2	1.227 (3)	C3—C4	1.357 (4)
O4—N2	1.228 (3)	C4—C5	1.388 (3)
O2—H2	0.8200	C5—C6	1.373 (4)
N1—C8	1.443 (3)	C3—H3	0.9300
N1—C2	1.326 (3)	C4—H4	0.9300
N2—C5	1.437 (3)	C6—H6	0.9300
N1—H1	0.8600	C8—H8A	0.9600
C1—C7	1.466 (3)	C8—H8B	0.9600
C1—C2	1.430 (3)	C8—H8C	0.9600

C7—O2—H2	109.00	N2—C5—C6	119.7 (2)
C2—N1—C8	124.3 (2)	C1—C6—C5	121.1 (2)
O3—N2—C5	119.2 (2)	O1—C7—O2	121.4 (2)
O4—N2—C5	118.1 (2)	O1—C7—C1	124.5 (2)
O3—N2—O4	122.7 (2)	O2—C7—C1	114.2 (2)
C2—N1—H1	118.00	C2—C3—H3	119.00
C8—N1—H1	118.00	C4—C3—H3	119.00
C6—C1—C7	119.8 (2)	C3—C4—H4	120.00
C2—C1—C6	119.5 (2)	C5—C4—H4	120.00
C2—C1—C7	120.7 (2)	C1—C6—H6	119.00
N1—C2—C3	119.9 (2)	C5—C6—H6	119.00
N1—C2—C1	122.7 (2)	N1—C8—H8A	109.00
C1—C2—C3	117.4 (2)	N1—C8—H8B	109.00
C2—C3—C4	121.5 (2)	N1—C8—H8C	109.00
C3—C4—C5	119.9 (2)	H8A—C8—H8B	109.00
C4—C5—C6	120.6 (2)	H8A—C8—H8C	110.00
N2—C5—C4	119.6 (2)	H8B—C8—H8C	109.00

C8—N1—C2—C1	175.8 (3)	C2—C1—C7—O1	4.1 (4)
C8—N1—C2—C3	−5.1 (4)	C2—C1—C7—O2	−175.9 (2)
O3—N2—C5—C4	176.8 (3)	C6—C1—C7—O1	−178.0 (2)
O3—N2—C5—C6	−2.0 (4)	C6—C1—C7—O2	2.0 (4)
O4—N2—C5—C4	−1.9 (4)	N1—C2—C3—C4	−179.3 (2)
O4—N2—C5—C6	179.4 (3)	C1—C2—C3—C4	−0.1 (4)
C6—C1—C2—N1	179.6 (2)	C2—C3—C4—C5	−0.3 (4)
C6—C1—C2—C3	0.4 (4)	C3—C4—C5—N2	−178.4 (2)
C7—C1—C2—N1	−2.5 (4)	C3—C4—C5—C6	0.4 (4)
C7—C1—C2—C3	178.4 (2)	N2—C5—C6—C1	178.7 (2)
C2—C1—C6—C5	−0.4 (4)	C4—C5—C6—C1	0.0 (4)
C7—C1—C6—C5	−178.3 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1	0.86	2.03	2.694 (3)	134
N1—H1···O4ⁱ	0.86	2.52	3.165 (3)	133
O2—H2···O1ⁱⁱ	0.82	1.86	2.679 (3)	177

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

Experimental details

Crystal data
Chemical formula	C₈H₈N₂O₄
M_r	196.16
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	296
a, b, c (Å)	7.2541 (12), 14.037 (2), 8.5972 (14)
β (°)	103.673 (6)
V (Å³)	850.6 (2)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.13
Crystal size (mm)	0.34 × 0.12 × 0.10

Data collection
Diffractometer	Bruker Kappa APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2005)
T_min, T_max	0.979, 0.988
No. of measured, independent and observed [I > 2σ(I)] reflections	6739, 1667, 931
R_int	0.051
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.051, 0.156, 0.95
No. of reflections	1667
No. of parameters	129
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.25, −0.27

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2009), WinGX (Farrugia, 1999) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1	0.86	2.03	2.694 (3)	134
N1—H1···O4ⁱ	0.86	2.52	3.165 (3)	133
O2—H2···O1ⁱⁱ	0.82	1.86	2.679 (3)	177

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

Acknowledgements

The authors acknowledge the provision of funds for the purchase of diffractometer and encouragement by Dr Muhammad Akram Chaudhary, Vice Chancellor, University of Sargodha. ARR also acknowledges the Higher Education Commission, Government of Pakistan, for generous support of a research project (20-819).

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