2-Amino-5-nitro­benzoic acid

Odabaşoğlu, H.Y.; Büyükgüngör, O.; Avinç, O.O.; Odabaşoğlu, M.

doi:10.1107/S1600536812002474

organic compounds

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ISSN: 2056-9890

Volume 68| Part 2| February 2012| Page o511

doi:10.1107/S1600536812002474

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2-Amino-5-nitrobenzoic acid

Hakkı Yasin Odabaşoğlu,^a Orhan Büyükgüngör,^b ^* Osman Ozan Avinç ^a and Mustafa Odabaşoğlu ^c

^aDepartment of Textile Engineering, Faculty of Engineering, Pamukkale University, TR-20070 Kınıklı Denizli, Turkey, ^bDepartment of Physics, Faculty of Arts & Science, Ondokuz Mayıs University, TR-55139 Kurupelit Samsun, Turkey, and ^cDepartment of Chemical Technonolgy, Pamukkale University, TR-20070 Kınıklı Denizli, Turkey
^*Correspondence e-mail: orhanb@omu.edu.tr

(Received 12 January 2012; accepted 19 January 2012; online 25 January 2012)

In the title compound, C₇H₆N₂O₄, 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 and C—H⋯O hydrogen bonds then link the dimers, generating R₃³(16)R₂¹(6) motifs. The whole molecule is essentially planar, with the greatest deviation from the mean plane being 0.065 (2) Å.

Related literature

For related structures of carboxylic acides, see: Mrozek & Glowiak (2004 ); Raza et al. (2010 ); Grabowski & Krygowski (1985 ). For hydrogen-bond motifs, see: Bernstein et al. (1995 ). For general background to o-aminocarboxylic acids, see: Fierz et al. (1949 ); Shore (2002 ).

Experimental

Crystal data

C₇H₆N₂O₄
M_r = 182.14
Monoclinic, P 2₁ /c
a = 3.7026 (3) Å
b = 17.4638 (16) Å
c = 11.6953 (10) Å
β = 92.210 (7)°
V = 755.67 (11) Å³
Z = 4
Mo Kα radiation
μ = 0.13 mm⁻¹
T = 296 K
0.55 × 0.23 × 0.06 mm

Data collection

Stoe IPDS II diffractometer
Absorption correction: integration (X-RED32; Stoe & Cie, 2002 ) T_min = 0.964, T_max = 0.992
5176 measured reflections
1567 independent reflections
884 reflections with I > 2σ(I)
R_int = 0.077

Refinement

R[F² > 2σ(F²)] = 0.064
wR(F²) = 0.127
S = 0.99
1567 reflections
118 parameters
H-atom parameters constrained
Δρ_max = 0.18 e Å⁻³
Δρ_min = −0.15 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H7⋯O1	0.86	2.06	2.694 (3)	130
N1—H7⋯O4ⁱ	0.86	2.47	3.030 (3)	123
N1—H8⋯O3ⁱⁱ	0.86	2.39	3.192 (4)	155
O2—H2⋯O1ⁱⁱⁱ	0.82	1.81	2.631 (3)	174
C6—H6⋯O3ⁱⁱ	0.93	2.54	3.347 (4)	145 (3)
Symmetry codes: (i) $[-x+1, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (ii) $[x-1, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (iii) -x+2, -y+1, -z+2.

Data collection: X-AREA (Stoe & Cie, 2002); cell refinement: X-AREA; data reduction: X-RED32 (Stoe & Cie, 2002); 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 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536812002474/fk2050sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812002474/fk2050Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812002474/fk2050Isup3.cml

checkCIF report

Comment top

Most dyes contain groups known as auxochromes (colour helpers), examples of which are carboxylic acid, sulfonic acid, amino, and hydroxyl groups. While these groups are not responsible for colour, their presence can shift the colour of a colourant and they are most often used to influence dye solubility. Aminocarboxylic acids dissolve as easily in carbonate solution as does benzoic acid, and as easily in aqueous hydrochloric acid as does aniline. o-Aminocarboxylic acids are used for synthesis of azo dyes and indigo dyes (Fierz et al., 1949; Shore, 2002). Functional groups such as carboxylic acids are completely inert in the reaction conditions for the azo coupling reaction. Taking into account these important features of the o-aminocarboxylic acids for the dye synthesis, we have undertaken the X-ray diffraction study of the 2-amino-5-nitrobenzoic acid, (I) (Fig. 1), in order to understand the molecular features which stabilize its observed conformation.

In previous works, 5-amino-2-nitrobenzoic acid (Mrozek & Glowiak, 2004), 2-Methylamino-5-nitrobenzoic acid (Raza et al., 2010), 2,5-dinitrobenzoic acid (Grabowski & Krygowski, 1985) have been published whose molecular structures are similar to the title compound.

(I) is essentially planar, the largest deviation from the mean plane being -0.065 (2) Å for atom O1. The crystal packing is stabilized by N-H···O, O-H···O and C-H···O hydrogen bonds. There exists an S(6) ring motif (Bernstein et al., 1995) due to the N-H···O intramolecular bond. Molecules are connected by intermolecular O-H···O hydrogen bonds to form centrosymmetric dimers with R₂²(8) ring motifs. Other hydrogen bonds generate R₃³(16)R₂¹(6) motifs (Fig. 2 and Table 1).

Related literature top

For related structures of carboxylic acides, see: Mrozek & Glowiak (2004); Raza et al. (2010); Grabowski & Krygowski (1985). For hydrogen-bond motifs, see: Bernstein et al. (1995). For general background to o-aminocarboxylic acids, see: Fierz et al. (1949); Shore (2002).

Experimental top

Yellow needles of 2-amino-5-nitrobenzoic acid were obtained by slow evaporation of the analytical reagent (Alfa Aesar) from ethyl alcohol solution (m.p. 543 K).

Computing details top

Data collection: X-AREA (Stoe & Cie, 2002); cell refinement: X-AREA (Stoe & Cie, 2002); data reduction: X-RED32 (Stoe & Cie, 2002); 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); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top

	Fig. 1. Molecular structure of (I). Anisotropic displacement ellipsoids are drawn at the 40% probability level.
	Fig. 2. Crystal packing of (I), with hydrogen bonds drawn as dashed lines. [Symmetry codes: (i)x + 1/2, 1 - y, 2 - z; (ii)x - 1/2, y + 1/2, 3/2 - z; (iii)1/2 - x, 1/2 - y, z - 1/2].

2-Amino-5-nitrobenzoic acid top

Crystal data top

C₇H₆N₂O₄	F(000) = 376
M_r = 182.14	D_x = 1.601 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 4323 reflections
a = 3.7026 (3) Å	θ = 1.7–28.0°
b = 17.4638 (16) Å	µ = 0.13 mm⁻¹
c = 11.6953 (10) Å	T = 296 K
β = 92.210 (7)°	Needle, orange
V = 755.67 (11) Å³	0.55 × 0.23 × 0.06 mm
Z = 4

Data collection top

Stoe IPDS II diffractometer	1567 independent reflections
Radiation source: fine-focus sealed tube	884 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.077
Detector resolution: 6.67 pixels mm^-1	θ_max = 26.5°, θ_min = 2.1°
rotation method scans	h = −4→4
Absorption correction: integration (X-RED32; Stoe & Cie, 2002)	k = −21→21
T_min = 0.964, T_max = 0.992	l = −13→14
5176 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)] = 0.064	Hydrogen site location: geom and difmap
wR(F²) = 0.127	H-atom parameters constrained
S = 0.99	w = 1/[σ²(F_o²) + (0.0486P)²] where P = (F_o² + 2F_c²)/3
1567 reflections	(Δ/σ)_max < 0.001
118 parameters	Δρ_max = 0.18 e Å⁻³
0 restraints	Δρ_min = −0.15 e Å⁻³

Crystal data top

C₇H₆N₂O₄	V = 755.67 (11) Å³
M_r = 182.14	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 3.7026 (3) Å	µ = 0.13 mm⁻¹
b = 17.4638 (16) Å	T = 296 K
c = 11.6953 (10) Å	0.55 × 0.23 × 0.06 mm
β = 92.210 (7)°

Data collection top

Stoe IPDS II diffractometer	1567 independent reflections
Absorption correction: integration (X-RED32; Stoe & Cie, 2002)	884 reflections with I > 2σ(I)
T_min = 0.964, T_max = 0.992	R_int = 0.077
5176 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.064	0 restraints
wR(F²) = 0.127	H-atom parameters constrained
S = 0.99	Δρ_max = 0.18 e Å⁻³
1567 reflections	Δρ_min = −0.15 e Å⁻³
118 parameters

Special details top

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 > 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	0.6059 (8)	0.35123 (17)	0.7289 (3)	0.0393 (7)
C2	0.7771 (8)	0.34418 (16)	0.8394 (2)	0.0346 (7)
C3	0.8661 (8)	0.27231 (16)	0.8809 (3)	0.0370 (7)
H3	0.9810	0.2678	0.9527	0.044*
C4	0.7890 (8)	0.20744 (16)	0.8187 (3)	0.0380 (7)
C5	0.6210 (9)	0.21311 (18)	0.7098 (3)	0.0444 (8)
H5	0.5688	0.1692	0.6673	0.053*
C6	0.5351 (9)	0.28294 (17)	0.6667 (3)	0.0431 (8)
H6	0.4261	0.2862	0.5939	0.052*
C7	0.8660 (8)	0.41190 (17)	0.9097 (2)	0.0383 (7)
N1	0.5107 (8)	0.41812 (15)	0.6824 (2)	0.0548 (8)
H8	0.4074	0.4196	0.6154	0.066*
H7	0.5526	0.4599	0.7195	0.066*
N2	0.8912 (8)	0.13354 (14)	0.8636 (2)	0.0502 (7)
O1	0.7787 (6)	0.47709 (12)	0.88101 (17)	0.0513 (6)
O2	1.0433 (6)	0.39701 (12)	1.00684 (18)	0.0528 (7)
H2	1.0837	0.4371	1.0415	0.079*
O3	1.0514 (7)	0.12980 (13)	0.9571 (2)	0.0681 (8)
O4	0.8171 (9)	0.07683 (14)	0.8068 (2)	0.0845 (10)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0370 (18)	0.0391 (17)	0.0415 (17)	0.0007 (14)	−0.0015 (13)	0.0015 (13)
C2	0.0378 (17)	0.0336 (16)	0.0325 (15)	−0.0016 (14)	−0.0002 (12)	−0.0043 (13)
C3	0.0391 (18)	0.0395 (16)	0.0321 (16)	−0.0021 (14)	−0.0016 (13)	−0.0019 (12)
C4	0.0395 (18)	0.0330 (16)	0.0416 (18)	−0.0020 (13)	0.0014 (13)	−0.0032 (13)
C5	0.048 (2)	0.0421 (19)	0.0429 (18)	−0.0067 (15)	−0.0033 (14)	−0.0124 (14)
C6	0.0469 (19)	0.047 (2)	0.0346 (17)	−0.0021 (15)	−0.0062 (14)	−0.0048 (13)
C7	0.0434 (19)	0.0348 (18)	0.0365 (16)	−0.0006 (14)	−0.0019 (14)	−0.0014 (13)
N1	0.080 (2)	0.0407 (15)	0.0426 (15)	0.0062 (15)	−0.0147 (14)	0.0012 (12)
N2	0.0641 (19)	0.0336 (15)	0.0525 (17)	−0.0013 (14)	−0.0031 (14)	−0.0037 (13)
O1	0.0766 (17)	0.0322 (12)	0.0440 (12)	−0.0002 (11)	−0.0120 (11)	−0.0020 (10)
O2	0.0786 (17)	0.0343 (11)	0.0440 (13)	−0.0030 (11)	−0.0187 (12)	−0.0061 (9)
O3	0.101 (2)	0.0436 (14)	0.0573 (15)	0.0040 (13)	−0.0228 (15)	0.0032 (11)
O4	0.134 (3)	0.0334 (14)	0.084 (2)	−0.0019 (15)	−0.0263 (18)	−0.0118 (13)

Geometric parameters (Å, º) top

C1—N1	1.330 (4)	C5—H5	0.9300
C1—C6	1.416 (4)	C6—H6	0.9300
C1—C2	1.423 (4)	C7—O1	1.227 (3)
C2—C3	1.381 (4)	C7—O2	1.316 (3)
C2—C7	1.470 (4)	N1—H8	0.8600
C3—C4	1.370 (4)	N1—H7	0.8600
C3—H3	0.9300	N2—O4	1.218 (3)
C4—C5	1.399 (4)	N2—O3	1.226 (3)
C4—N2	1.439 (4)	O2—H2	0.8200
C5—C6	1.353 (4)

N1—C1—C6	119.3 (3)	C4—C5—H5	120.2
N1—C1—C2	123.3 (3)	C5—C6—C1	122.1 (3)
C6—C1—C2	117.4 (3)	C5—C6—H6	118.9
C3—C2—C1	119.3 (3)	C1—C6—H6	118.9
C3—C2—C7	119.3 (3)	O1—C7—O2	122.5 (3)
C1—C2—C7	121.4 (3)	O1—C7—C2	122.9 (3)
C4—C3—C2	121.5 (3)	O2—C7—C2	114.7 (3)
C4—C3—H3	119.2	C1—N1—H8	120.0
C2—C3—H3	119.2	C1—N1—H7	120.0
C3—C4—C5	120.1 (3)	H8—N1—H7	120.0
C3—C4—N2	120.1 (3)	O4—N2—O3	122.3 (3)
C5—C4—N2	119.8 (3)	O4—N2—C4	118.7 (3)
C6—C5—C4	119.5 (3)	O3—N2—C4	119.0 (3)
C6—C5—H5	120.2	C7—O2—H2	109.5

N1—C1—C2—C3	179.9 (3)	N1—C1—C6—C5	−179.1 (3)
C6—C1—C2—C3	0.1 (4)	C2—C1—C6—C5	0.8 (4)
N1—C1—C2—C7	−1.0 (4)	C3—C2—C7—O1	−176.2 (3)
C6—C1—C2—C7	179.1 (3)	C1—C2—C7—O1	4.8 (5)
C1—C2—C3—C4	−0.9 (4)	C3—C2—C7—O2	3.1 (4)
C7—C2—C3—C4	180.0 (3)	C1—C2—C7—O2	−176.0 (3)
C2—C3—C4—C5	1.0 (5)	C3—C4—N2—O4	179.5 (3)
C2—C3—C4—N2	178.9 (3)	C5—C4—N2—O4	−2.5 (5)
C3—C4—C5—C6	−0.1 (5)	C3—C4—N2—O3	−0.9 (5)
N2—C4—C5—C6	−178.1 (3)	C5—C4—N2—O3	177.0 (3)
C4—C5—C6—C1	−0.7 (5)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H7···O1	0.86	2.06	2.694 (3)	130
N1—H7···O4ⁱ	0.86	2.47	3.030 (3)	123
N1—H8···O3ⁱⁱ	0.86	2.39	3.192 (4)	155
O2—H2···O1ⁱⁱⁱ	0.82	1.81	2.631 (3)	174
C6—H6···O3ⁱⁱ	0.93	2.54	3.347 (4)	145 (3)

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

Experimental details

Crystal data
Chemical formula	C₇H₆N₂O₄
M_r	182.14
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	296
a, b, c (Å)	3.7026 (3), 17.4638 (16), 11.6953 (10)
β (°)	92.210 (7)
V (Å³)	755.67 (11)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.13
Crystal size (mm)	0.55 × 0.23 × 0.06

Data collection
Diffractometer	Stoe IPDS II diffractometer
Absorption correction	Integration (X-RED32; Stoe & Cie, 2002)
T_min, T_max	0.964, 0.992
No. of measured, independent and observed [I > 2σ(I)] reflections	5176, 1567, 884
R_int	0.077
(sin θ/λ)_max (Å⁻¹)	0.628

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.064, 0.127, 0.99
No. of reflections	1567
No. of parameters	118
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.18, −0.15

Computer programs: X-AREA (Stoe & Cie, 2002), X-RED32 (Stoe & Cie, 2002), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H7···O1	0.86	2.06	2.694 (3)	130.2
N1—H7···O4ⁱ	0.86	2.47	3.030 (3)	123.4
N1—H8···O3ⁱⁱ	0.86	2.39	3.192 (4)	155.2
O2—H2···O1ⁱⁱⁱ	0.82	1.81	2.631 (3)	174.1
C6—H6···O3ⁱⁱ	0.93	2.54	3.347 (4)	145 (3)

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

Acknowledgements

The authors acknowledge the Faculty of Arts and Sciences, Ondokuz Mayıs University, Turkey, for the use of the Stoe IPDS II diffractometer (purchased under grant F.279 of the University Research Fund).

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