2-Hydr­oxy-5-nitro­benzamide

Raza, A.R.; Tahir, M.N.; Nisar, B.; Danish, M.; Iqbal, M.S.

doi:10.1107/S1600536809050119

organic compounds

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ISSN: 2056-9890

Volume 65| Part 12| December 2009| Page o3260

doi:10.1107/S1600536809050119

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2-Hydroxy-5-nitrobenzamide

Abdul Rauf Raza,^a M. Nawaz Tahir,^b ^* Bushra Nisar,^a Mohammad Danish ^a and Mohammad S. Iqbal ^c

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

(Received 21 November 2009; accepted 21 November 2009; online 28 November 2009)

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 R₂¹(7) and R₂²(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, P 2₁ /n
a = 5.1803 (3) Å
b = 11.1037 (8) Å
c = 13.7214 (10) Å
β = 100.642 (4)°
V = 775.69 (9) Å³
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[F² > 2σ(F²)] = 0.037
wR(F²) = 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

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) -x, -y+1, -z+1; (ii) -x, -y, -z+1; (iii) $[-x+{\script{3\over 2}}, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

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.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809050119/hb5244sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809050119/hb5244Isup2.hkl

checkCIF report

Comment top

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.

Related literature top

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

Experimental top

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.

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 (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 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.

2-Hydroxy-5-nitrobenzamide top

Crystal data top

C₇H₆N₂O₄	F(000) = 376
M_r = 182.14	D_x = 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 top

Bruker Kappa APEXII CCD diffractometer	1799 independent reflections
Radiation source: fine-focus sealed tube	1434 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.018
Detector resolution: 7.50 pixels mm^-1	θ_max = 27.8°, θ_min = 2.4°
ω scans	h = −6→6
Absorption correction: multi-scan (SADABS; Bruker, 2005)	k = −14→13
T_min = 0.970, T_max = 0.976	l = −17→16
4581 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)] = 0.037	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(F_o²) + (0.0629P)² + 0.0918P] where P = (F_o² + 2F_c²)/3
1799 reflections	(Δ/σ)_max < 0.001
125 parameters	Δρ_max = 0.23 e Å⁻³
0 restraints	Δρ_min = −0.21 e Å⁻³

Crystal data top

C₇H₆N₂O₄	V = 775.69 (9) Å³
M_r = 182.14	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 5.1803 (3) Å	µ = 0.13 mm⁻¹
b = 11.1037 (8) Å	T = 296 K
c = 13.7214 (10) Å	0.28 × 0.20 × 0.18 mm
β = 100.642 (4)°

Data collection top

Bruker Kappa APEXII CCD diffractometer	1799 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	1434 reflections with I > 2σ(I)
T_min = 0.970, T_max = 0.976	R_int = 0.018
4581 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.037	0 restraints
wR(F²) = 0.112	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	Δρ_max = 0.23 e Å⁻³
1799 reflections	Δρ_min = −0.21 e Å⁻³
125 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 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 (Å²) top

	x	y	z	U_iso*/U_eq
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 (Å²) top

	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, º) top

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, º) top

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.

Experimental details

Crystal data
Chemical formula	C₇H₆N₂O₄
M_r	182.14
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	296
a, b, c (Å)	5.1803 (3), 11.1037 (8), 13.7214 (10)
β (°)	100.642 (4)
V (Å³)	775.69 (9)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.13
Crystal size (mm)	0.28 × 0.20 × 0.18

Data collection
Diffractometer	Bruker Kappa APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2005)
T_min, T_max	0.970, 0.976
No. of measured, independent and observed [I > 2σ(I)] reflections	4581, 1799, 1434
R_int	0.018
(sin θ/λ)_max (Å⁻¹)	0.656

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.037, 0.112, 1.05
No. of reflections	1799
No. of parameters	125
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.23, −0.21

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

Selected geometric parameters (Å, º) top

O1—C2	1.3427 (17)	O4—N2	1.2210 (15)
O2—C7	1.2535 (16)	N1—C7	1.324 (2)
O3—N2	1.2321 (15)	N2—C5	1.4615 (16)

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)	O2—C7—C1	119.41 (13)
O1—C2—C3	117.79 (13)	N1—C7—C1	119.83 (11)
O1—C2—C1	121.89 (12)	O2—C7—N1	120.76 (13)

Hydrogen-bond geometry (Å, º) top

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.

Acknowledgements

The authors acknowledge the Higher Education Commision, Islamabad, Pakistan, and Bana International, Karachi, Pakistan, for funding the purchase of the diffractometer and for technical support, respectively.

References

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