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Acta Crystallogr Sect E Struct Rep Online. 2009 December 1; 65(Pt 12): o3260.
Published online 2009 November 28. doi:  10.1107/S1600536809050119
PMCID: PMC2971888

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 [triangle]); Raza et al. (2009 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-65-o3260-scheme1.jpg

Experimental

Crystal data

  • C7H6N2O4
  • M r = 182.14
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-o3260-efi1.jpg
  • 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 [triangle]) 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
  • Δρmax = 0.23 e Å−3
  • Δρmin = −0.21 e Å−3

Data collection: APEX2 (Bruker, 2007 [triangle]); cell refinement: SAINT (Bruker, 2007 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: ORTEP-3 (Farrugia, 1997 [triangle]) and PLATON (Spek, 2009 [triangle]); software used to prepare material for publication: WinGX (Farrugia, 1999 [triangle]) and PLATON.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

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

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

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

Acknowledgments

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.

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 Uiso(H) = 1.2Ueq(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

C7H6N2O4F(000) = 376
Mr = 182.14Dx = 1.560 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 1799 reflections
a = 5.1803 (3) Åθ = 2.4–27.8°
b = 11.1037 (8) ŵ = 0.13 mm1
c = 13.7214 (10) ÅT = 296 K
β = 100.642 (4)°Prisms, light yellow
V = 775.69 (9) Å30.28 × 0.20 × 0.18 mm
Z = 4

Data collection

Bruker Kappa APEXII CCD diffractometer1799 independent reflections
Radiation source: fine-focus sealed tube1434 reflections with I > 2σ(I)
graphiteRint = 0.018
Detector resolution: 7.50 pixels mm-1θmax = 27.8°, θmin = 2.4°
ω scansh = −6→6
Absorption correction: multi-scan (SADABS; Bruker, 2005)k = −14→13
Tmin = 0.970, Tmax = 0.976l = −17→16
4581 measured reflections

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.037Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.112H atoms treated by a mixture of independent and constrained refinement
S = 1.05w = 1/[σ2(Fo2) + (0.0629P)2 + 0.0918P] where P = (Fo2 + 2Fc2)/3
1799 reflections(Δ/σ)max < 0.001
125 parametersΔρmax = 0.23 e Å3
0 restraintsΔρmin = −0.21 e Å3

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 (Å2)

xyzUiso*/Ueq
O10.5646 (2)0.40418 (9)0.31899 (9)0.0527 (4)
O20.2337 (2)0.46688 (9)0.42269 (9)0.0538 (4)
O30.1375 (2)−0.09501 (9)0.42368 (9)0.0604 (4)
O40.4447 (2)−0.15349 (9)0.34804 (9)0.0599 (4)
N10.0539 (3)0.33482 (11)0.51407 (10)0.0505 (4)
N20.3188 (2)−0.07405 (10)0.37931 (8)0.0425 (4)
C10.3227 (2)0.26057 (11)0.39880 (9)0.0352 (3)
C20.5024 (3)0.28970 (12)0.33611 (10)0.0393 (4)
C30.6220 (3)0.19813 (14)0.28969 (11)0.0460 (4)
C40.5642 (3)0.07915 (13)0.30371 (10)0.0427 (4)
C50.3840 (2)0.05179 (11)0.36410 (9)0.0363 (4)
C60.2636 (2)0.13973 (11)0.41112 (9)0.0351 (3)
C70.1992 (3)0.36003 (11)0.44683 (10)0.0390 (4)
H10.481840.449810.348770.0632*
H1A−0.032 (4)0.3969 (16)0.5380 (14)0.0606*
H1B0.028 (3)0.2603 (18)0.5307 (13)0.0606*
H30.741180.217990.249200.0552*
H40.643990.018220.273410.0513*
H60.143540.118390.450830.0421*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
O10.0632 (7)0.0386 (5)0.0644 (7)−0.0088 (5)0.0331 (5)0.0035 (5)
O20.0678 (7)0.0286 (5)0.0737 (7)0.0004 (4)0.0362 (5)0.0027 (4)
O30.0834 (8)0.0346 (5)0.0760 (8)−0.0045 (5)0.0481 (6)0.0018 (5)
O40.0723 (7)0.0372 (6)0.0751 (8)0.0129 (5)0.0267 (6)−0.0080 (5)
N10.0732 (8)0.0274 (6)0.0610 (8)0.0076 (5)0.0389 (7)0.0020 (5)
N20.0535 (7)0.0333 (6)0.0433 (6)0.0050 (5)0.0156 (5)−0.0021 (4)
C10.0383 (6)0.0321 (6)0.0378 (6)0.0010 (5)0.0135 (5)0.0011 (5)
C20.0412 (6)0.0381 (7)0.0411 (7)−0.0044 (5)0.0143 (5)0.0029 (5)
C30.0454 (7)0.0500 (8)0.0490 (8)−0.0033 (6)0.0254 (6)−0.0015 (6)
C40.0435 (7)0.0433 (7)0.0458 (7)0.0044 (5)0.0199 (5)−0.0056 (5)
C50.0407 (6)0.0315 (6)0.0389 (7)0.0024 (5)0.0133 (5)−0.0015 (5)
C60.0390 (6)0.0319 (6)0.0382 (6)0.0023 (5)0.0170 (5)0.0007 (5)
C70.0451 (7)0.0298 (6)0.0452 (7)0.0008 (5)0.0161 (5)0.0002 (5)

Geometric parameters (Å, °)

O1—C21.3427 (17)C1—C21.4167 (19)
O2—C71.2535 (16)C1—C61.3935 (17)
O3—N21.2321 (15)C2—C31.403 (2)
O4—N21.2210 (15)C3—C41.376 (2)
O1—H10.8200C4—C51.3914 (19)
N1—C71.324 (2)C5—C61.3811 (17)
N2—C51.4615 (16)C3—H30.9300
N1—H1A0.914 (19)C4—H40.9300
N1—H1B0.88 (2)C6—H60.9300
C1—C71.4896 (18)
C2—O1—H1109.00C3—C4—C5118.70 (13)
O3—N2—C5117.94 (10)N2—C5—C4119.47 (11)
O4—N2—C5119.21 (10)N2—C5—C6118.23 (10)
O3—N2—O4122.86 (11)C4—C5—C6122.30 (12)
C7—N1—H1A117.9 (12)C1—C6—C5119.72 (10)
C7—N1—H1B121.1 (11)O2—C7—C1119.41 (13)
H1A—N1—H1B120.8 (16)N1—C7—C1119.83 (11)
C6—C1—C7122.57 (11)O2—C7—N1120.76 (13)
C2—C1—C6118.51 (11)C2—C3—H3120.00
C2—C1—C7118.91 (11)C4—C3—H3120.00
O1—C2—C3117.79 (13)C3—C4—H4121.00
C1—C2—C3120.33 (12)C5—C4—H4121.00
O1—C2—C1121.89 (12)C1—C6—H6120.00
C2—C3—C4120.43 (14)C5—C6—H6120.00
O3—N2—C5—C4−171.90 (12)C2—C1—C7—N1−172.50 (13)
O3—N2—C5—C68.36 (17)C6—C1—C7—O2−170.64 (13)
O4—N2—C5—C48.18 (18)C6—C1—C7—N19.1 (2)
O4—N2—C5—C6−171.57 (12)O1—C2—C3—C4−179.42 (14)
C6—C1—C2—O1178.56 (12)C1—C2—C3—C40.7 (2)
C6—C1—C2—C3−1.51 (19)C2—C3—C4—C50.4 (2)
C7—C1—C2—O10.12 (19)C3—C4—C5—N2179.58 (12)
C7—C1—C2—C3−179.95 (15)C3—C4—C5—C6−0.7 (2)
C2—C1—C6—C51.28 (17)N2—C5—C6—C1179.54 (11)
C7—C1—C6—C5179.66 (12)C4—C5—C6—C1−0.20 (18)
C2—C1—C7—O27.73 (19)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
O1—H1···O20.821.792.5196 (16)148
N1—H1A···O2i0.914 (19)1.969 (19)2.8807 (17)174.9 (18)
N1—H1B···O3ii0.88 (2)2.167 (19)3.0193 (17)164.6 (15)
C4—H4···O1iii0.932.493.3915 (18)164
C6—H6···O3ii0.932.473.3826 (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.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: HB5244).

References

  • Bruker (2005). SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.
  • Bruker (2007). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.
  • Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565.
  • Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838.
  • Pertlik, F. (1990). Monatsh. Chem. 121, 129–139.
  • Raza, A. R., Danish, M., Tahir, M. N., Nisar, B. & Iqbal, M. S. (2009). Acta Cryst. E65, o1630. [PMC free article] [PubMed]
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Spek, A. L. (2009). Acta Cryst. D65, 148–155. [PMC free article] [PubMed]

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography