A redetermination of 2-nitro-benzoic acid.

The crystal structure of the title compound, C(7)H(5)NO(4), was first reported by Kurahashi, Fukuyo & Shimada [(1967). Bull. Chem. Soc. Jpn, 40, 1296]. It has been re-examined, improving the precision of the derived geometric parameters. The asymmetric unit comprises a non-planar independent mol-ecule, as the nitro and the carb-oxy substituents force each other to be twisted away from the plane of the aromatic ring by 54.9 (2) and 24.0 (2)°, respectively. The mol-ecules form a conventional dimeric unit via centrosymmetric inter-molecular hydrogen bonds.

Related literature

For the previous structure determination, see: Kurahashi et al. (1967 ▶); Sakore et al. (1967 ▶); Tavale & Pant (1973 ▶). For the effect of nitro and carboxy substitution on the geometry of polysubstituted benzene rings, see: Colapietro et al. (1984 ▶); Domenicano et al. (1989 ▶). For the formation of hydrogen-bonded dimers in monocarboylic acids, see:Leiserowitz (1976 ▶). For computation of ring patterns formed by hydrogen bonds in crystal structures, see: Etter et al. (1990 ▶); Bernstein et al. (1995 ▶); Motherwell et al. (1999 ▶).

Experimental

Crystal data

C7H5NO4

M = 167.12

Triclinic,

a = 5.0147 (15) Å

b = 7.527 (2) Å

c = 10.620 (2) Å

α = 69.41 (2)°

β = 86.07 (2)°

γ = 71.01 (3)°

V = 354.35 (18) Å3

Z = 2

Mo Kα radiation

μ = 0.13 mm−1

T = 298 K

0.15 × 0.15 × 0.10 mm

Data collection

Oxford Diffraction Xcalibur S CCD diffractometer

Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2006 ▶) T min = 0.879, T max = 0.980

3862 measured reflections

1872 independent reflections

1087 reflections with I > 2σ(I)

R int = 0.050

Refinement

R[F 2 > 2σ(F 2)] = 0.077

wR(F 2) = 0.148

S = 1.07

1872 reflections

113 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.26 e Å−3

Δρmin = −0.20 e Å−3

Data collection: CrysAlis CCD (Oxford Diffraction, 2006 ▶); cell refinement: CrysAlis RED (Oxford Diffraction, 2006 ▶); data reduction: CrysAlis RED; program(s) used to solve structure: SIR97 (Altomare et al., 1999 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809011830/kp2213sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809011830/kp2213Isup2.hkl

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

C7H5NO4	Z = 2
Mr = 167.12	F(000) = 172
Triclinic, P1	Dx = 1.566 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 5.0147 (15) Å	Cell parameters from 861 reflections
b = 7.527 (2) Å	θ = 3.0–32.5°
c = 10.620 (2) Å	µ = 0.13 mm−1
α = 69.41 (2)°	T = 298 K
β = 86.07 (2)°	Tablets, colourless
γ = 71.01 (3)°	0.15 × 0.15 × 0.10 mm
V = 354.35 (18) Å3

Oxford Diffraction Xcalibur S CCD diffractometer	1872 independent reflections
Radiation source: Enhance (Mo) X-ray Source	1087 reflections with I > 2σ(I)
graphite	Rint = 0.050
Detector resolution: 16.0696 pixels mm-1	θmax = 29.0°, θmin = 3.0°
ω and φ scans	h = −6→6
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2006)	k = −10→10
Tmin = 0.879, Tmax = 0.980	l = −14→14
3862 measured reflections

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)] = 0.077	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.148	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	w = 1/[σ2(Fo2) + (0.0536P)2 + 0.0451P] where P = (Fo2 + 2Fc2)/3
1872 reflections	(Δ/σ)max < 0.001
113 parameters	Δρmax = 0.26 e Å−3
0 restraints	Δρmin = −0.20 e Å−3

Experimental. Absorption correction: CrysAlis RED, Oxford Diffraction Ltd., Version 1.171.32.29 (release 10-06-2008 CrysAlis171 .NET) (compiled Jun 10 2008,16:49:55) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.

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.

	x	y	z	Uiso*/Ueq
O1	0.8083 (4)	0.3762 (3)	0.6058 (2)	0.0471 (6)
O2	1.2483 (4)	0.2482 (3)	0.5512 (2)	0.0481 (6)
H2	1.221 (7)	0.378 (5)	0.504 (3)	0.068 (11)*
O3	0.7790 (4)	0.2147 (3)	0.8921 (2)	0.0537 (6)
O4	0.4118 (4)	0.1514 (3)	0.8517 (2)	0.0533 (6)
N1	0.6642 (5)	0.1288 (3)	0.8481 (2)	0.0344 (5)
C1	1.0287 (5)	0.0235 (3)	0.6923 (2)	0.0305 (6)
C2	0.8416 (5)	−0.0231 (4)	0.7933 (2)	0.0297 (6)
C3	0.8224 (6)	−0.2123 (4)	0.8508 (3)	0.0381 (7)
H3	0.6904	−0.2375	0.9147	0.046*
C4	1.0025 (6)	−0.3648 (4)	0.8123 (3)	0.0450 (7)
H4	0.9927	−0.4941	0.8503	0.054*
C5	1.1971 (6)	−0.3249 (4)	0.7172 (3)	0.0440 (8)
H5	1.3219	−0.4286	0.6933	0.053*
C6	1.2084 (6)	−0.1327 (4)	0.6572 (3)	0.0393 (7)
H6	1.3386	−0.1080	0.5922	0.047*
C7	1.0188 (5)	0.2327 (4)	0.6144 (3)	0.0334 (6)

	U11	U22	U33	U12	U13	U23
O1	0.0457 (12)	0.0296 (10)	0.0542 (13)	−0.0083 (9)	0.0228 (10)	−0.0080 (9)
O2	0.0461 (13)	0.0350 (12)	0.0543 (13)	−0.0151 (9)	0.0236 (10)	−0.0071 (10)
O3	0.0600 (14)	0.0563 (13)	0.0657 (14)	−0.0290 (11)	0.0177 (11)	−0.0391 (12)
O4	0.0361 (12)	0.0638 (14)	0.0638 (15)	−0.0131 (10)	0.0160 (10)	−0.0321 (12)
N1	0.0411 (14)	0.0319 (12)	0.0275 (12)	−0.0140 (10)	0.0117 (10)	−0.0071 (10)
C1	0.0335 (14)	0.0287 (14)	0.0275 (13)	−0.0088 (11)	0.0023 (11)	−0.0090 (11)
C2	0.0312 (13)	0.0300 (14)	0.0270 (13)	−0.0084 (10)	0.0045 (11)	−0.0106 (11)
C3	0.0486 (17)	0.0355 (15)	0.0323 (15)	−0.0205 (12)	0.0114 (13)	−0.0097 (12)
C4	0.062 (2)	0.0263 (14)	0.0437 (17)	−0.0150 (13)	0.0056 (15)	−0.0079 (13)
C5	0.0530 (18)	0.0312 (15)	0.0436 (17)	−0.0052 (12)	0.0085 (14)	−0.0169 (13)
C6	0.0402 (16)	0.0393 (16)	0.0357 (15)	−0.0105 (12)	0.0132 (13)	−0.0138 (13)
C7	0.0392 (15)	0.0320 (14)	0.0304 (14)	−0.0148 (12)	0.0131 (12)	−0.0116 (11)

O1—C7	1.222 (3)	C2—C3	1.372 (3)
O2—C7	1.310 (3)	C3—C4	1.380 (3)
O2—H2	0.90 (3)	C3—H3	0.9300
O3—N1	1.208 (3)	C4—C5	1.381 (4)
O4—N1	1.221 (3)	C4—H4	0.9300
N1—C2	1.474 (3)	C5—C6	1.379 (4)
C1—C6	1.381 (3)	C5—H5	0.9300
C1—C2	1.402 (3)	C6—H6	0.9300
C1—C7	1.485 (3)
C7—O2—H2	108 (2)	C3—C4—C5	119.8 (2)
O3—N1—O4	124.6 (2)	C3—C4—H4	120.1
O3—N1—C2	118.2 (2)	C5—C4—H4	120.1
O4—N1—C2	117.1 (2)	C6—C5—C4	120.6 (2)
C6—C1—C2	117.2 (2)	C6—C5—H5	119.7
C6—C1—C7	119.9 (2)	C4—C5—H5	119.7
C2—C1—C7	122.7 (2)	C5—C6—C1	120.9 (2)
C3—C2—C1	122.5 (2)	C5—C6—H6	119.6
C3—C2—N1	116.4 (2)	C1—C6—H6	119.6
C1—C2—N1	121.1 (2)	O1—C7—O2	123.4 (2)
C2—C3—C4	118.9 (2)	O1—C7—C1	122.2 (2)
C2—C3—H3	120.6	O2—C7—C1	114.4 (2)
C4—C3—H3	120.6
C6—C1—C2—C3	−3.7 (4)	C2—C3—C4—C5	−0.1 (4)
C7—C1—C2—C3	169.9 (3)	C3—C4—C5—C6	−1.9 (4)
C6—C1—C2—N1	173.2 (2)	C4—C5—C6—C1	1.1 (4)
C7—C1—C2—N1	−13.3 (4)	C2—C1—C6—C5	1.6 (4)
O3—N1—C2—C3	122.6 (3)	C7—C1—C6—C5	−172.1 (3)
O4—N1—C2—C3	−53.9 (3)	C6—C1—C7—O1	152.9 (3)
O3—N1—C2—C1	−54.5 (3)	C2—C1—C7—O1	−20.5 (4)
O4—N1—C2—C1	129.1 (3)	C6—C1—C7—O2	−23.9 (4)
C1—C2—C3—C4	2.9 (4)	C2—C1—C7—O2	162.7 (2)
N1—C2—C3—C4	−174.1 (2)

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···O1i	0.90 (3)	1.77 (4)	2.660 (3)	173 (3)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2⋯O1i	0.90 (3)	1.77 (4)	2.660 (3)	173 (3)

Symmetry code: (i) .