2-Amino-3-nitro­benzoic acid

Win, Y.-F.; Choong, C.-S.; Teoh, S.-G.; Quah, C.K.; Fun, H.-K.

doi:10.1107/S1600536812002036

organic compounds

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ISSN: 2056-9890

Volume 68| Part 2| February 2012| Page o488

doi:10.1107/S1600536812002036

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2-Amino-3-nitrobenzoic acid

Yip-Foo Win,^a Chen-Shang Choong,^a Siang-Guan Teoh,^b Ching Kheng Quah ^c ‡ and Hoong-Kun Fun ^c ^*§

^aDepartment of Chemical Science, Faculty of Science, Universiti Tunku Abdul Rahman, Perak Campus, Jalan Universiti, Bandar Barat, 31900 Kampar, Perak, Malaysia, ^bSchool of Chemical Sciences, Universiti Sains Malaysia, 11800 USM, Penang, Malaysia, and ^cX-ray Crystallography Unit, School of Physics, Universiti Sains Malaysia, 11800 USM, Penang, Malaysia
^*Correspondence e-mail: hkfun@usm.my

(Received 13 January 2012; accepted 17 January 2012; online 21 January 2012)

The title compound, C₇H₆N₂O₄, is approximately planar (r.m.s. deviation = 0.026 Å for the 13 non-H atoms). The molecular structure is stabilized by intramolecular N—H⋯O hydrogen bonds, which generate S(6) ring motifs. In the crystal, molecules are linked via intermolecular N—H⋯O, O—H⋯O and C—H⋯O hydrogen bonds into a three-dimensional network.

Related literature

For general background to the title compound and related structures, see: Win et al. (2010 , 2011a ,b ,c ). For standard 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 the data collection, see: Cosier & Glazer (1986 ).

Experimental

Crystal data

C₇H₆N₂O₄
M_r = 182.14
Monoclinic, P 2₁ /c
a = 9.0231 (3) Å
b = 7.4338 (2) Å
c = 11.0392 (4) Å
β = 92.114 (1)°
V = 739.96 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.14 mm⁻¹
T = 100 K
0.34 × 0.26 × 0.16 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ) T_min = 0.956, T_max = 0.979
22297 measured reflections
3247 independent reflections
2707 reflections with I > 2σ(I)
R_int = 0.030

Refinement

R[F² > 2σ(F²)] = 0.042
wR(F²) = 0.121
S = 1.04
3247 reflections
130 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.55 e Å⁻³
Δρ_min = −0.33 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H1N2⋯O2	0.892 (17)	1.958 (16)	2.6082 (11)	128.5 (13)
N2—H1N2⋯O1ⁱ	0.892 (17)	2.499 (17)	3.2885 (12)	147.8 (14)
N2—H2N2⋯O3	0.872 (15)	1.982 (16)	2.6582 (10)	133.4 (14)
O4—H1O4⋯O3ⁱⁱ	0.83 (2)	1.81 (2)	2.6397 (10)	176.2 (17)
C3—H3A⋯O1ⁱⁱⁱ	0.95	2.49	3.4349 (12)	176
Symmetry codes: (i) $[-x+2, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) -x+1, -y, -z+1; (iii) -x+2, -y+2, -z+1.

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); 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 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536812002036/qm2050sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812002036/qm2050Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812002036/qm2050Isup3.cml

checkCIF report

Comment top

In the study of organotin(IV) carboxylate complexes, 2-amino-5-nitrobenzoic, 2-amino-3-nitrobenzoic, 4-amino-3-nitrobenzoic and 5-amino-2-nitrobenzoic acids have been utilized in the synthesis work (Win et al., 2010, 2011a, 2011b, 2011c). The carboxylate anions of the acids are found to be bonded to tin(IV) atom moieties in both a monodentate and a bidentate manner resulting in structural diversity for organotin(IV) carboxylate complexes (Win et al., 2010, 2011a, 2011b, 2011c).

The title compound, Fig.1, is approximately planar (r.m.s. deviation = 0.026 Å for the 13 non-H atoms). Bond lengths (Allen et al., 1987) and angles are within normal ranges and are comparable to related structures (Win et al., 2010, 2011a, 2011b, 2011c). The molecular structure is stabilized by intramolecular N2–H1N2···O2 and N2–H2N2···O3 hydrogen bonds (Table 1), which generate S(6) ring motifs (Fig. 1, Bernstein et al., 1995).

In the crystal structure, Fig. 2, molecules are linked via intermolecular N2–H1N2···O1, O4–H1O4···O3 and C3–H3A···O1 hydrogen bonds (Table 1) into a three-dimensional network.

Related literature top

For general background to the title compound and related structures, see: Win et al. (2010, 2011a,b,c). For standard 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 the data collection, see: Cosier & Glazer (1986).

Experimental top

The attempt to prepare organotin(IV) carboxylate complexes by heating under reflux the mixture of 2-amino-3-nitrobenzoic acid (2 mmol) and dimethyltin(IV) oxide (4 mmol) for 4 h in 50 ml of methanol was unsuccessful. The resulting orange solution was filtered and orange crystals were obtained after 2 weeks. Unfortunately, the crystals obtained were found to be the starting material (2-amino-3-nitrobenzoic acid) with the melting point of 482 K.

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures top

	Fig. 1. The molecular structure of the title compound showing 50% probability displacement ellipsoids for non-H atoms. Intramolecular hydrogen bonds are shown as dashed lines.
	Fig. 2. The crystal structure of the title compound, viewed along the b axis. H atoms not involved in hydrogen bonds (dashed lines) have been omitted for clarity.

2-Amino-3-nitrobenzoic acid top

Crystal data top

C₇H₆N₂O₄	F(000) = 376
M_r = 182.14	D_x = 1.635 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 9956 reflections
a = 9.0231 (3) Å	θ = 2.9–34.8°
b = 7.4338 (2) Å	µ = 0.14 mm⁻¹
c = 11.0392 (4) Å	T = 100 K
β = 92.114 (1)°	Block, orange
V = 739.96 (4) Å³	0.34 × 0.26 × 0.16 mm
Z = 4

Data collection top

Bruker SMART APEXII CCD area-detector diffractometer	3247 independent reflections
Radiation source: fine-focus sealed tube	2707 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.030
ϕ and ω scans	θ_max = 35.0°, θ_min = 2.3°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −14→12
T_min = 0.956, T_max = 0.979	k = −11→11
22297 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)] = 0.042	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.121	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ²(F_o²) + (0.0662P)² + 0.1903P] where P = (F_o² + 2F_c²)/3
3247 reflections	(Δ/σ)_max = 0.001
130 parameters	Δρ_max = 0.55 e Å⁻³
0 restraints	Δρ_min = −0.33 e Å⁻³

Crystal data top

C₇H₆N₂O₄	V = 739.96 (4) Å³
M_r = 182.14	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 9.0231 (3) Å	µ = 0.14 mm⁻¹
b = 7.4338 (2) Å	T = 100 K
c = 11.0392 (4) Å	0.34 × 0.26 × 0.16 mm
β = 92.114 (1)°

Data collection top

Bruker SMART APEXII CCD area-detector diffractometer	3247 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2009)	2707 reflections with I > 2σ(I)
T_min = 0.956, T_max = 0.979	R_int = 0.030
22297 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.042	0 restraints
wR(F²) = 0.121	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	Δρ_max = 0.55 e Å⁻³
3247 reflections	Δρ_min = −0.33 e Å⁻³
130 parameters

Special details top

Experimental. The crystal was placed in the cold stream of an Oxford Cryosystems Cobra open-flow nitrogen cryostat (Cosier & Glazer, 1986) operating at 100.0 (1) K.

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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	1.00882 (10)	0.85440 (11)	0.40698 (8)	0.03096 (19)
O2	0.99701 (8)	0.61460 (10)	0.29827 (6)	0.02030 (14)
O3	0.62645 (7)	0.11784 (9)	0.43650 (6)	0.01909 (14)
O4	0.51199 (8)	0.18983 (10)	0.60595 (6)	0.01981 (14)
N1	0.95660 (8)	0.70510 (10)	0.38522 (6)	0.01587 (14)
N2	0.81247 (9)	0.35687 (11)	0.34730 (7)	0.01954 (16)
C1	0.64687 (9)	0.51128 (12)	0.62950 (7)	0.01552 (15)
H1A	0.5784	0.4697	0.6865	0.019*
C2	0.71159 (10)	0.67982 (12)	0.64617 (8)	0.01749 (16)
H2A	0.6870	0.7528	0.7131	0.021*
C3	0.81229 (9)	0.73922 (12)	0.56356 (7)	0.01620 (15)
H3A	0.8579	0.8536	0.5742	0.019*
C4	0.84738 (9)	0.63239 (11)	0.46482 (7)	0.01390 (14)
C5	0.78217 (8)	0.45981 (11)	0.44292 (7)	0.01334 (14)
C6	0.67970 (9)	0.40152 (11)	0.53140 (7)	0.01354 (14)
C7	0.60572 (9)	0.22530 (11)	0.51976 (7)	0.01458 (15)
H1N2	0.8797 (19)	0.393 (2)	0.2953 (15)	0.034 (4)*
H2N2	0.7714 (18)	0.251 (2)	0.3400 (14)	0.033 (4)*
H1O4	0.471 (2)	0.092 (3)	0.5901 (16)	0.044 (5)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0415 (4)	0.0181 (3)	0.0343 (4)	−0.0153 (3)	0.0144 (3)	−0.0043 (3)
O2	0.0229 (3)	0.0216 (3)	0.0168 (3)	−0.0046 (2)	0.0065 (2)	−0.0007 (2)
O3	0.0214 (3)	0.0154 (3)	0.0210 (3)	−0.0059 (2)	0.0076 (2)	−0.0043 (2)
O4	0.0231 (3)	0.0189 (3)	0.0180 (3)	−0.0087 (2)	0.0080 (2)	−0.0028 (2)
N1	0.0173 (3)	0.0151 (3)	0.0153 (3)	−0.0030 (2)	0.0017 (2)	0.0023 (2)
N2	0.0221 (3)	0.0175 (3)	0.0197 (3)	−0.0068 (3)	0.0094 (3)	−0.0058 (3)
C1	0.0162 (3)	0.0166 (3)	0.0139 (3)	−0.0015 (3)	0.0025 (2)	−0.0015 (3)
C2	0.0198 (3)	0.0165 (4)	0.0163 (3)	−0.0011 (3)	0.0029 (3)	−0.0036 (3)
C3	0.0179 (3)	0.0138 (3)	0.0169 (3)	−0.0013 (3)	0.0008 (3)	−0.0014 (3)
C4	0.0143 (3)	0.0133 (3)	0.0142 (3)	−0.0016 (2)	0.0016 (2)	0.0009 (2)
C5	0.0135 (3)	0.0134 (3)	0.0132 (3)	−0.0007 (2)	0.0019 (2)	−0.0003 (2)
C6	0.0135 (3)	0.0128 (3)	0.0144 (3)	−0.0016 (2)	0.0021 (2)	−0.0007 (2)
C7	0.0143 (3)	0.0145 (3)	0.0151 (3)	−0.0025 (3)	0.0024 (2)	0.0003 (3)

Geometric parameters (Å, º) top

O1—N1	1.2260 (10)	C1—C6	1.3964 (11)
O2—N1	1.2380 (10)	C1—H1A	0.9500
O3—C7	1.2371 (10)	C2—C3	1.3832 (12)
O4—C7	1.3227 (10)	C2—H2A	0.9500
O4—H1O4	0.83 (2)	C3—C4	1.3945 (11)
N1—C4	1.4490 (10)	C3—H3A	0.9500
N2—C5	1.3401 (11)	C4—C5	1.4283 (11)
N2—H1N2	0.893 (17)	C5—C6	1.4364 (11)
N2—H2N2	0.875 (18)	C6—C7	1.4737 (11)
C1—C2	1.3916 (12)

C7—O4—H1O4	108.3 (12)	C2—C3—H3A	119.8
O1—N1—O2	121.45 (7)	C4—C3—H3A	119.8
O1—N1—C4	118.94 (7)	C3—C4—C5	122.67 (7)
O2—N1—C4	119.59 (7)	C3—C4—N1	116.15 (7)
C5—N2—H1N2	119.8 (11)	C5—C4—N1	121.17 (7)
C5—N2—H2N2	119.3 (10)	N2—C5—C4	123.47 (7)
H1N2—N2—H2N2	120.7 (15)	N2—C5—C6	121.24 (7)
C2—C1—C6	121.91 (7)	C4—C5—C6	115.30 (7)
C2—C1—H1A	119.0	C1—C6—C5	120.75 (7)
C6—C1—H1A	119.0	C1—C6—C7	118.60 (7)
C3—C2—C1	118.87 (8)	C5—C6—C7	120.64 (7)
C3—C2—H2A	120.6	O3—C7—O4	121.60 (8)
C1—C2—H2A	120.6	O3—C7—C6	123.94 (7)
C2—C3—C4	120.47 (8)	O4—C7—C6	114.46 (7)

C6—C1—C2—C3	−0.58 (13)	N1—C4—C5—C6	177.80 (7)
C1—C2—C3—C4	0.47 (13)	C2—C1—C6—C5	−0.28 (13)
C2—C3—C4—C5	0.49 (13)	C2—C1—C6—C7	−179.61 (8)
C2—C3—C4—N1	−178.63 (8)	N2—C5—C6—C1	−178.81 (8)
O1—N1—C4—C3	−1.42 (12)	C4—C5—C6—C1	1.16 (11)
O2—N1—C4—C3	177.38 (7)	N2—C5—C6—C7	0.50 (13)
O1—N1—C4—C5	179.46 (8)	C4—C5—C6—C7	−179.53 (7)
O2—N1—C4—C5	−1.75 (12)	C1—C6—C7—O3	179.89 (8)
C3—C4—C5—N2	178.69 (8)	C5—C6—C7—O3	0.55 (13)
N1—C4—C5—N2	−2.24 (13)	C1—C6—C7—O4	0.60 (11)
C3—C4—C5—C6	−1.28 (12)	C5—C6—C7—O4	−178.73 (7)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H1N2···O2	0.892 (17)	1.958 (16)	2.6082 (11)	128.5 (13)
N2—H1N2···O1ⁱ	0.892 (17)	2.499 (17)	3.2885 (12)	147.8 (14)
N2—H2N2···O3	0.872 (15)	1.982 (16)	2.6582 (10)	133.4 (14)
O4—H1O4···O3ⁱⁱ	0.83 (2)	1.81 (2)	2.6397 (10)	176.2 (17)
C3—H3A···O1ⁱⁱⁱ	0.95	2.49	3.4349 (12)	176

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

Experimental details

Crystal data
Chemical formula	C₇H₆N₂O₄
M_r	182.14
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	100
a, b, c (Å)	9.0231 (3), 7.4338 (2), 11.0392 (4)
β (°)	92.114 (1)
V (Å³)	739.96 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.14
Crystal size (mm)	0.34 × 0.26 × 0.16

Data collection
Diffractometer	Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2009)
T_min, T_max	0.956, 0.979
No. of measured, independent and observed [I > 2σ(I)] reflections	22297, 3247, 2707
R_int	0.030
(sin θ/λ)_max (Å⁻¹)	0.807

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.042, 0.121, 1.04
No. of reflections	3247
No. of parameters	130
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.55, −0.33

Computer programs: APEX2 (Bruker, 2009), SAINT (Bruker, 2009), SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H1N2···O2	0.892 (17)	1.958 (16)	2.6082 (11)	128.5 (13)
N2—H1N2···O1ⁱ	0.892 (17)	2.499 (17)	3.2885 (12)	147.8 (14)
N2—H2N2···O3	0.872 (15)	1.982 (16)	2.6582 (10)	133.4 (14)
O4—H1O4···O3ⁱⁱ	0.83 (2)	1.81 (2)	2.6397 (10)	176.2 (17)
C3—H3A···O1ⁱⁱⁱ	0.9500	2.4900	3.4349 (12)	176.00

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

Footnotes

‡Thomson Reuters ResearcherID: A-5525-2009.

§Visiting Professor: College of Pharmacy, King Saud University Riyadh, Saudi Arabia. Thomson Reuters ResearcherID: A-3561-2009.

Acknowledgements

The authors would like to thank Universiti Tunku Abdul Rahman (UTAR) for the UTAR Research Fund (project No. IPSR/RMC/UTARRF/C1-11/C07) and Universiti Sains Malaysia (USM) for financial support as well as technical assistance and facilities. HKF and CKQ also thank USM for the Research University Grant (No. 1001/PFIZIK/811160).

References

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