2-Hydr­oxy-5-nitro­benzamide

Abstract

In the title compound, C₇H₆N₂O₄, an intra­molecular O—H⋯O hydrogen bond generates an S(6) ring. In the crystal, inversion dimers linked by pairs of N—H⋯O hydrogen bonds occur. Weak C—H⋯O links consolidate the packing, leading to R ₂ ¹(7) and R ₂ ²(10) loops within (100) polymeric sheets.

Related literature

For related structures, see: Pertlik (1990 ▶); Raza et al. (2009 ▶).

Experimental

Crystal data

• C₇H₆N₂O₄

• M _r = 182.14

• Monoclinic,

• a = 5.1803 (3) Å

• b = 11.1037 (8) Å

• c = 13.7214 (10) Å

• β = 100.642 (4)°

• V = 775.69 (9) ų

• Z = 4

• Mo Kα radiation

• μ = 0.13 mm⁻¹

• T = 296 K

• 0.28 × 0.20 × 0.18 mm

Data collection

• Bruker Kappa APEXII CCD diffractometer

• Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T _min = 0.970, T _max = 0.976

• 4581 measured reflections

• 1799 independent reflections

• 1434 reflections with I > 2σ(I)

• R _int = 0.018

Refinement

• R[F ² > 2σ(F ²)] = 0.037

• wR(F ²) = 0.112

• S = 1.05

• 1799 reflections

• 125 parameters

• H atoms treated by a mixture of independent and constrained refinement

• Δρ_max = 0.23 e Å⁻³

• Δρ_min = −0.21 e Å⁻³

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 (Farrugia, 1997 ▶) and PLATON (Spek, 2009 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶) and PLATON.

Supplementary Material

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
O1—H1⋯O2	0.82	1.79	2.5196 (16)	148
N1—H1A⋯O2i	0.914 (19)	1.969 (19)	2.8807 (17)	174.9 (18)
N1—H1B⋯O3ii	0.88 (2)	2.167 (19)	3.0193 (17)	164.6 (15)
C4—H4⋯O1iii	0.93	2.49	3.3915 (18)	164
C6—H6⋯O3ii	0.93	2.47	3.3826 (16)	169

Symmetry codes: (i) ; (ii) ; (iii) .

supplementary crystallographic information

Comment

The title compound (I, Fig. 1) is an intermediate for various derivatives. We have reported the preparation and crystal structure of (II) 2-hydroxy-3-nitrobenzamide (Raza et al., 2009) which is isomer of (I). The crystal structures of (III) 2-Hydroxybenzamide (Pertlik, 1990) has been published also.

In the asymmetric unit of (I), the benzene ring A (C1—C6) is of course planar. The nitro group B (N2/O3/O4) and the amide group C (C7/N1/O2) make dihedral angle of 8.49 (13)° and 8.48 (21)° respectively, with the benzene ring. The dihedral angle between B/C is 14.51 (22)°. There exist an intramolecular H-bonding of O–H···O type forming S(6) ring motif (Bernstein et al., 1995). The molecules of the title compound are dimerised forming a R₂²(10) and two R₂¹(7) ring motifs (Table 1, Fig. 2). The dimers are interlinked each other forming polymeric network and the dimers are surounded by six R₅⁴(16) ring motifs.

Experimental

A solution of 2-hydroxy-benzamide (1.37 g, 0.01 mol) in ethyl acetate (25 ml) was added as drops to a nitrating mixture of HNO₃ (3 ml, 1.89 g, 0.03 mol) and H₂SO₄ (2 ml, 1.96 g, 0.02 mol), with constant stirring, while the temperature was kept below 278 K. The reaction mixture was stirred at room temperature for 4–5 h, refluxed for 1 h, cooled, neutralized with aqueous NaHCO₃ (10%) and extracted with EtOAc (3 × 25 ml). The organic layer was combined, dried over anhydrous Na₂SO₄, filtered and rotary concentrated to afford light yellowish solid. The column chromatographic purification with 0, 2.5, and 5% EtOAc in petrol (0.5 l each) over a silica gel packed column (25.5 cm height) afforded the title compound.

Refinement

The coordintes of H-atoms of NH₂ group were refined. The other H-atoms were positioned geometrically (O–H = 0.82, C–H = 0.93 Å) and refined as riding with U_iso(H) = 1.2U_eq(C, N, O).

Figures

Fig. 1.

View of (I) with displacement ellipsoids drawn at the 50% probability level. The dashed line represents the intramolecular H-bond.

Fig. 2.

The projectional view of the title compound showing that molecules are dimerized and dimers are linked in the formation of two dimensional polymeric sheets with various ring motifs.

Crystal data

C7H6N2O4	F(000) = 376
Mr = 182.14	Dx = 1.560 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 1799 reflections
a = 5.1803 (3) Å	θ = 2.4–27.8°
b = 11.1037 (8) Å	µ = 0.13 mm−1
c = 13.7214 (10) Å	T = 296 K
β = 100.642 (4)°	Prisms, light yellow
V = 775.69 (9) Å3	0.28 × 0.20 × 0.18 mm
Z = 4

Data collection

Bruker Kappa APEXII CCD diffractometer	1799 independent reflections
Radiation source: fine-focus sealed tube	1434 reflections with I > 2σ(I)
graphite	Rint = 0.018
Detector resolution: 7.50 pixels mm-1	θmax = 27.8°, θmin = 2.4°
ω scans	h = −6→6
Absorption correction: multi-scan (SADABS; Bruker, 2005)	k = −14→13
Tmin = 0.970, Tmax = 0.976	l = −17→16
4581 measured reflections

Refinement

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)] = 0.037	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.112	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ2(Fo2) + (0.0629P)2 + 0.0918P] where P = (Fo2 + 2Fc2)/3
1799 reflections	(Δ/σ)max < 0.001
125 parameters	Δρmax = 0.23 e Å−3
0 restraints	Δρmin = −0.21 e Å−3

Special details

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 e.s.d.'s 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 (Ų)

	x	y	z	Uiso*/Ueq
O1	0.5646 (2)	0.40418 (9)	0.31899 (9)	0.0527 (4)
O2	0.2337 (2)	0.46688 (9)	0.42269 (9)	0.0538 (4)
O3	0.1375 (2)	−0.09501 (9)	0.42368 (9)	0.0604 (4)
O4	0.4447 (2)	−0.15349 (9)	0.34804 (9)	0.0599 (4)
N1	0.0539 (3)	0.33482 (11)	0.51407 (10)	0.0505 (4)
N2	0.3188 (2)	−0.07405 (10)	0.37931 (8)	0.0425 (4)
C1	0.3227 (2)	0.26057 (11)	0.39880 (9)	0.0352 (3)
C2	0.5024 (3)	0.28970 (12)	0.33611 (10)	0.0393 (4)
C3	0.6220 (3)	0.19813 (14)	0.28969 (11)	0.0460 (4)
C4	0.5642 (3)	0.07915 (13)	0.30371 (10)	0.0427 (4)
C5	0.3840 (2)	0.05179 (11)	0.36410 (9)	0.0363 (4)
C6	0.2636 (2)	0.13973 (11)	0.41112 (9)	0.0351 (3)
C7	0.1992 (3)	0.36003 (11)	0.44683 (10)	0.0390 (4)
H1	0.48184	0.44981	0.34877	0.0632*
H1A	−0.032 (4)	0.3969 (16)	0.5380 (14)	0.0606*
H1B	0.028 (3)	0.2603 (18)	0.5307 (13)	0.0606*
H3	0.74118	0.21799	0.24920	0.0552*
H4	0.64399	0.01822	0.27341	0.0513*
H6	0.14354	0.11839	0.45083	0.0421*

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
O1	0.0632 (7)	0.0386 (5)	0.0644 (7)	−0.0088 (5)	0.0331 (5)	0.0035 (5)
O2	0.0678 (7)	0.0286 (5)	0.0737 (7)	0.0004 (4)	0.0362 (5)	0.0027 (4)
O3	0.0834 (8)	0.0346 (5)	0.0760 (8)	−0.0045 (5)	0.0481 (6)	0.0018 (5)
O4	0.0723 (7)	0.0372 (6)	0.0751 (8)	0.0129 (5)	0.0267 (6)	−0.0080 (5)
N1	0.0732 (8)	0.0274 (6)	0.0610 (8)	0.0076 (5)	0.0389 (7)	0.0020 (5)
N2	0.0535 (7)	0.0333 (6)	0.0433 (6)	0.0050 (5)	0.0156 (5)	−0.0021 (4)
C1	0.0383 (6)	0.0321 (6)	0.0378 (6)	0.0010 (5)	0.0135 (5)	0.0011 (5)
C2	0.0412 (6)	0.0381 (7)	0.0411 (7)	−0.0044 (5)	0.0143 (5)	0.0029 (5)
C3	0.0454 (7)	0.0500 (8)	0.0490 (8)	−0.0033 (6)	0.0254 (6)	−0.0015 (6)
C4	0.0435 (7)	0.0433 (7)	0.0458 (7)	0.0044 (5)	0.0199 (5)	−0.0056 (5)
C5	0.0407 (6)	0.0315 (6)	0.0389 (7)	0.0024 (5)	0.0133 (5)	−0.0015 (5)
C6	0.0390 (6)	0.0319 (6)	0.0382 (6)	0.0023 (5)	0.0170 (5)	0.0007 (5)
C7	0.0451 (7)	0.0298 (6)	0.0452 (7)	0.0008 (5)	0.0161 (5)	0.0002 (5)

Geometric parameters (Å, °)

O1—C2	1.3427 (17)	C1—C2	1.4167 (19)
O2—C7	1.2535 (16)	C1—C6	1.3935 (17)
O3—N2	1.2321 (15)	C2—C3	1.403 (2)
O4—N2	1.2210 (15)	C3—C4	1.376 (2)
O1—H1	0.8200	C4—C5	1.3914 (19)
N1—C7	1.324 (2)	C5—C6	1.3811 (17)
N2—C5	1.4615 (16)	C3—H3	0.9300
N1—H1A	0.914 (19)	C4—H4	0.9300
N1—H1B	0.88 (2)	C6—H6	0.9300
C1—C7	1.4896 (18)
C2—O1—H1	109.00	C3—C4—C5	118.70 (13)
O3—N2—C5	117.94 (10)	N2—C5—C4	119.47 (11)
O4—N2—C5	119.21 (10)	N2—C5—C6	118.23 (10)
O3—N2—O4	122.86 (11)	C4—C5—C6	122.30 (12)
C7—N1—H1A	117.9 (12)	C1—C6—C5	119.72 (10)
C7—N1—H1B	121.1 (11)	O2—C7—C1	119.41 (13)
H1A—N1—H1B	120.8 (16)	N1—C7—C1	119.83 (11)
C6—C1—C7	122.57 (11)	O2—C7—N1	120.76 (13)
C2—C1—C6	118.51 (11)	C2—C3—H3	120.00
C2—C1—C7	118.91 (11)	C4—C3—H3	120.00
O1—C2—C3	117.79 (13)	C3—C4—H4	121.00
C1—C2—C3	120.33 (12)	C5—C4—H4	121.00
O1—C2—C1	121.89 (12)	C1—C6—H6	120.00
C2—C3—C4	120.43 (14)	C5—C6—H6	120.00
O3—N2—C5—C4	−171.90 (12)	C2—C1—C7—N1	−172.50 (13)
O3—N2—C5—C6	8.36 (17)	C6—C1—C7—O2	−170.64 (13)
O4—N2—C5—C4	8.18 (18)	C6—C1—C7—N1	9.1 (2)
O4—N2—C5—C6	−171.57 (12)	O1—C2—C3—C4	−179.42 (14)
C6—C1—C2—O1	178.56 (12)	C1—C2—C3—C4	0.7 (2)
C6—C1—C2—C3	−1.51 (19)	C2—C3—C4—C5	0.4 (2)
C7—C1—C2—O1	0.12 (19)	C3—C4—C5—N2	179.58 (12)
C7—C1—C2—C3	−179.95 (15)	C3—C4—C5—C6	−0.7 (2)
C2—C1—C6—C5	1.28 (17)	N2—C5—C6—C1	179.54 (11)
C7—C1—C6—C5	179.66 (12)	C4—C5—C6—C1	−0.20 (18)
C2—C1—C7—O2	7.73 (19)

Hydrogen-bond geometry (Å, °)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O2	0.82	1.79	2.5196 (16)	148
N1—H1A···O2i	0.914 (19)	1.969 (19)	2.8807 (17)	174.9 (18)
N1—H1B···O3ii	0.88 (2)	2.167 (19)	3.0193 (17)	164.6 (15)
C4—H4···O1iii	0.93	2.49	3.3915 (18)	164
C6—H6···O3ii	0.93	2.47	3.3826 (16)	169

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