Cystal structre of 5-hy­droxy-2-nitro­benzaldehyde

Bano, H.; Yousuf, S.

doi:10.1107/S205698901500701X

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 71| Part 5| May 2015| Pages o328-o329

https://doi.org/10.1107/S205698901500701X

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Cystal structre of 5-hydroxy-2-nitrobenzaldehyde

Huma Bano ^a and Sammer Yousuf ^a ^*

^aH.E.J. Research Institute of Chemistry, International Center for Chemical and Biological Sciences, University of Karachi, Karachi 75270, Pakistan
^*Correspondence e-mail: dr.sammer.yousuf@gmail.com

Edited by H. Stoeckli-Evans, University of Neuchâtel, Switzerland (Received 6 April 2015; accepted 8 April 2015; online 22 April 2015)

In the title compound, C₇H₅NO₄, the nitro group and the aldehyde group are inclined to the benzene ring by 16.6 (3) and 15.6 (3)°, respectively. In the crystal, molecules are linked via O—H⋯O hydrogen bonds, forming chains along [100]. The chains are linked by C—H⋯O hydrogen bonds, forming a three-dimensional structure.

Keywords: crystal structure; nitro-substituted aromatics; O—H⋯O hydrogen bonds; C—H⋯O hydrogen bonds.

CCDC reference: 1058381

1. Related literature

For literature on nitro-substituted aromatic compounds and their various properties, see: Yan et al. (2006 ); Soojhawon et al. (2005 ). For crystal structures of related compounds, see: Tang et al. (2010 ); Tanak et al. (2009 ); Singh et al. (2009 ).

2. Experimental

2.1. Crystal data

C₇H₅NO₄
M_r = 167.12
Monoclinic, P 2₁ /c
a = 9.6648 (18) Å
b = 5.0917 (10) Å
c = 14.920 (3) Å
β = 106.159 (4)°
V = 705.2 (2) Å³
Z = 4
Mo Kα radiation
μ = 0.13 mm⁻¹
T = 273 K
0.48 × 0.32 × 0.15 mm

2.2. Data collection

Bruker SMART APEX CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2000 ) T_min = 0.939, T_max = 0.980
3884 measured reflections
1312 independent reflections
974 reflections with I > 2σ(I)
R_int = 0.024

2.3. Refinement

R[F² > 2σ(F²)] = 0.046
wR(F²) = 0.116
S = 1.04
1312 reflections
113 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.19 e Å⁻³
Δρ_min = −0.16 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H3B⋯O4ⁱ	0.88 (3)	1.82 (3)	2.699 (2)	174 (3)
C2—H2A⋯O1ⁱⁱ	0.93	2.48	3.364 (3)	158
C5—H5A⋯O3ⁱⁱⁱ	0.93	2.45	3.379 (3)	173
C7—H7A⋯O1^iv	0.93	2.49	3.264 (3)	140
Symmetry codes: (i) $[x, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (ii) -x, -y+2, -z; (iii) -x+1, -y, -z; (iv) $[-x, y-{\script{1\over 2}}, -z-{\script{1\over 2}}]$ .

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008) and Mercury (Macrae et al., 2008 ); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009 ).

Supporting information

CCDC reference: 1058381

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S205698901500701X/su5113sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S205698901500701X/su5113Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S205698901500701X/su5113Isup3.cml

checkCIF report

Synthesis and crystallization top

Colourless crystals of the title compound [Fluka; HPLC grade] were obtained by slow evaporation of a solution in methanol.

Refinement top

Crystal data, data collection and structure refinement details are summarized in Table 2. The hydroxyl H atom was located in a difference Fourier map and freely refined. The C-bound H atoms were positioned geometrically and constrained to ride on their parent atoms: C—H = 0.93 Å, with U_iso(H) = 1.2U_eq(C).

Comment top

Nitro substituted aromatic compounds are well known intermediates in various organic reactions, responsible for synthesis of pesticides, explosive materials and other bioactive phenyl derivatives (Yan et al., 2006). The nitro substituted aromatic compounds are also known to be widely distributed as pollutant in air and water reservoirs (Yan et al., 2006; Soojhawon et al., 2005). The title compound is a commercially available benzaldehyde derivative, composed of a planar hydroxy substituted nitrobenzaldehyde ring. The compound was crystal out as a part of our ongoing research project involving to crystallize and evaluate biological activities of commercially available molecular libraries.

The molecular structure of the title compound is illustrated in Fig. 1. Structurally it is a positional isomer of the previously reported 2-hydroxy-5-nitrobenzaldehyde with the difference that the positions of the hydroxy and nitro substituents are interchanged (Tanak et al., 2009). The nitro group (N1/O1/O2) and the aldehyde group (C6/C1/O4) are inclined to the benzene ring (C1—C6) by 16.6 (3) and 15.6 (3) °, respectively.

In the crystal, molecules are linked by O—H···O hydrogen bonds forming zigzag chains along [100]. The chains are linked via C—H···O hydrogen bonds forming a three dimensional structure (Table 2 and Fig. 2).

Related literature top

For literature on nitro-substituted aromatic compounds and their various properties, see: Yan et al. (2006); Soojhawon et al. (2005). For crystal structures of related compounds, see: Tang et al. (2010); Tanak et al. (2009); Singh et al. (2009).

Structure description top

For literature on nitro-substituted aromatic compounds and their various properties, see: Yan et al. (2006); Soojhawon et al. (2005). For crystal structures of related compounds, see: Tang et al. (2010); Tanak et al. (2009); Singh et al. (2009).

Synthesis and crystallization top

Colourless crystals of the title compound [Fluka; HPLC grade] were obtained by slow evaporation of a solution in methanol.

Refinement details top

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008) and Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures top

	Fig. 1. The molecular structure of title compound, with atom labelling. Displacement ellipsoids are drawn at 30% probability level.
	Fig. 2. The crystal packing of title compound, viewed along the b axis. Hydrogen bonds are shown as dashed lines (see Table 1 for details).

5-Hydroxy-2-nitrobenzaldehyde top

Crystal data top

C₇H₅NO₄	F(000) = 344
M_r = 167.12	D_x = 1.574 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ybc	Cell parameters from 924 reflections
a = 9.6648 (18) Å	θ = 2.8–23.7°
b = 5.0917 (10) Å	µ = 0.13 mm⁻¹
c = 14.920 (3) Å	T = 273 K
β = 106.159 (4)°	Block, colourles
V = 705.2 (2) Å³	0.48 × 0.32 × 0.15 mm
Z = 4

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	1312 independent reflections
Radiation source: fine-focus sealed tube	974 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.024
ω scan	θ_max = 25.5°, θ_min = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −11→11
T_min = 0.939, T_max = 0.980	k = −5→6
3884 measured reflections	l = −18→16

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)] = 0.046	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.116	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ²(F_o²) + (0.0518P)² + 0.1669P] where P = (F_o² + 2F_c²)/3
1312 reflections	(Δ/σ)_max < 0.001
113 parameters	Δρ_max = 0.19 e Å⁻³
0 restraints	Δρ_min = −0.16 e Å⁻³

Crystal data top

C₇H₅NO₄	V = 705.2 (2) Å³
M_r = 167.12	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 9.6648 (18) Å	µ = 0.13 mm⁻¹
b = 5.0917 (10) Å	T = 273 K
c = 14.920 (3) Å	0.48 × 0.32 × 0.15 mm
β = 106.159 (4)°

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	1312 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2000)	974 reflections with I > 2σ(I)
T_min = 0.939, T_max = 0.980	R_int = 0.024
3884 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.046	0 restraints
wR(F²) = 0.116	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	Δρ_max = 0.19 e Å⁻³
1312 reflections	Δρ_min = −0.16 e Å⁻³
113 parameters

Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
O1	0.0034 (2)	0.9749 (4)	−0.12613 (15)	0.0961 (7)
O2	0.1401 (2)	0.9319 (3)	−0.21588 (12)	0.0763 (6)
O3	0.42366 (18)	0.1329 (3)	0.09957 (10)	0.0571 (5)
O4	0.39446 (19)	0.3765 (4)	−0.22575 (10)	0.0671 (5)
N1	0.1039 (2)	0.8710 (4)	−0.14662 (14)	0.0577 (5)
C1	0.1847 (2)	0.6689 (4)	−0.08470 (13)	0.0440 (5)
C2	0.1690 (2)	0.6549 (4)	0.00439 (15)	0.0524 (6)
H2A	0.1050	0.7672	0.0218	0.063*
C3	0.2468 (2)	0.4774 (4)	0.06721 (14)	0.0504 (6)
H3A	0.2356	0.4691	0.1271	0.061*
C4	0.3419 (2)	0.3104 (4)	0.04173 (12)	0.0421 (5)
C5	0.3562 (2)	0.3232 (4)	−0.04816 (12)	0.0420 (5)
H5A	0.4192	0.2086	−0.0654	0.050*
C6	0.2793 (2)	0.5012 (4)	−0.11264 (12)	0.0408 (5)
C7	0.2988 (3)	0.4856 (4)	−0.20759 (14)	0.0543 (6)
H7A	0.2307	0.5677	−0.2560	0.065*
H3B	0.411 (3)	0.140 (5)	0.156 (2)	0.078 (8)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0934 (14)	0.1045 (16)	0.0934 (14)	0.0513 (13)	0.0311 (12)	0.0152 (12)
O2	0.1128 (15)	0.0612 (11)	0.0566 (10)	0.0066 (10)	0.0265 (10)	0.0107 (8)
O3	0.0801 (11)	0.0627 (10)	0.0343 (8)	0.0137 (8)	0.0256 (8)	0.0081 (7)
O4	0.0813 (11)	0.0887 (13)	0.0398 (8)	0.0127 (10)	0.0307 (8)	−0.0016 (8)
N1	0.0660 (13)	0.0515 (12)	0.0528 (11)	0.0033 (10)	0.0117 (10)	−0.0038 (9)
C1	0.0457 (11)	0.0436 (11)	0.0427 (11)	−0.0009 (9)	0.0123 (9)	−0.0025 (9)
C2	0.0578 (13)	0.0528 (13)	0.0542 (13)	0.0027 (11)	0.0280 (11)	−0.0087 (10)
C3	0.0650 (14)	0.0565 (13)	0.0377 (11)	−0.0020 (11)	0.0273 (11)	−0.0030 (10)
C4	0.0518 (12)	0.0423 (11)	0.0354 (10)	−0.0046 (9)	0.0175 (9)	−0.0022 (9)
C5	0.0479 (11)	0.0477 (12)	0.0342 (10)	−0.0005 (9)	0.0177 (9)	−0.0063 (9)
C6	0.0439 (11)	0.0466 (11)	0.0333 (10)	−0.0081 (9)	0.0129 (9)	−0.0064 (8)
C7	0.0685 (15)	0.0608 (14)	0.0337 (11)	0.0090 (12)	0.0144 (11)	0.0026 (10)

Geometric parameters (Å, º) top

O1—N1	1.218 (2)	C2—H2A	0.9300
O2—N1	1.219 (3)	C3—C4	1.381 (3)
O3—C4	1.344 (2)	C3—H3A	0.9300
O3—H3B	0.88 (3)	C4—C5	1.387 (3)
O4—C7	1.173 (2)	C5—C6	1.379 (3)
N1—C1	1.457 (3)	C5—H5A	0.9300
C1—C2	1.381 (3)	C6—C7	1.482 (3)
C1—C6	1.397 (3)	C7—H7A	0.9300
C2—C3	1.367 (3)

C4—O3—H3B	111.7 (17)	O3—C4—C3	123.70 (17)
O1—N1—O2	122.6 (2)	O3—C4—C5	116.94 (18)
O1—N1—C1	118.2 (2)	C3—C4—C5	119.36 (18)
O2—N1—C1	119.2 (2)	C6—C5—C4	121.73 (18)
C2—C1—C6	120.82 (19)	C6—C5—H5A	119.1
C2—C1—N1	117.63 (19)	C4—C5—H5A	119.1
C6—C1—N1	121.50 (18)	C5—C6—C1	117.64 (17)
C3—C2—C1	120.47 (19)	C5—C6—C7	116.39 (18)
C3—C2—H2A	119.8	C1—C6—C7	125.87 (19)
C1—C2—H2A	119.8	O4—C7—C6	124.3 (2)
C2—C3—C4	119.97 (18)	O4—C7—H7A	117.8
C2—C3—H3A	120.0	C6—C7—H7A	117.8
C4—C3—H3A	120.0

O1—N1—C1—C2	−16.9 (3)	C3—C4—C5—C6	1.0 (3)
O2—N1—C1—C2	162.27 (19)	C4—C5—C6—C1	−0.5 (3)
O1—N1—C1—C6	165.7 (2)	C4—C5—C6—C7	−176.99 (18)
O2—N1—C1—C6	−15.2 (3)	C2—C1—C6—C5	−0.2 (3)
C6—C1—C2—C3	0.4 (3)	N1—C1—C6—C5	177.18 (18)
N1—C1—C2—C3	−177.03 (19)	C2—C1—C6—C7	175.9 (2)
C1—C2—C3—C4	0.0 (3)	N1—C1—C6—C7	−6.7 (3)
C2—C3—C4—O3	179.1 (2)	C5—C6—C7—O4	−17.1 (3)
C2—C3—C4—C5	−0.7 (3)	C1—C6—C7—O4	166.8 (2)
O3—C4—C5—C6	−178.86 (18)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3B···O4ⁱ	0.88 (3)	1.82 (3)	2.699 (2)	174 (3)
C2—H2A···O1ⁱⁱ	0.93	2.48	3.364 (3)	158
C5—H5A···O3ⁱⁱⁱ	0.93	2.45	3.379 (3)	173
C7—H7A···O1^iv	0.93	2.49	3.264 (3)	140

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3B···O4ⁱ	0.88 (3)	1.82 (3)	2.699 (2)	174 (3)
C2—H2A···O1ⁱⁱ	0.93	2.48	3.364 (3)	158
C5—H5A···O3ⁱⁱⁱ	0.93	2.45	3.379 (3)	173
C7—H7A···O1^iv	0.93	2.49	3.264 (3)	140

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

Acknowledgements

The authors acknowledge the financial support of the Higher Education Commission of Pakistan (HEC) through the research project entitled `Structural Studies of New Inhibitors of Urease Enzyme – An Approach towards the Treatment of Gastric Ulcer, Urolitheasis and Other Complications'.

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CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 71| Part 5| May 2015| Pages o328-o329

https://doi.org/10.1107/S205698901500701X

Open

access