2-Hydr­oxy-5-nitro­benzaldehyde

Tanak, H.; Macit, M.; Yavuz, M.; Işık, Ş.

doi:10.1107/S1600536809046807

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 65| Part 12| December 2009| Pages o3056-o3057

doi:10.1107/S1600536809046807

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2-Hydroxy-5-nitrobenzaldehyde

Hasan Tanak,^a ^* Mustafa Macit,^b Metin Yavuz ^a and Şamil Işık ^a

^aDepartment of Physics, Faculty of Arts & Science, Ondokuz Mayıs University, TR-55139 Kurupelit-Samsun, Turkey, and ^bDepartment of Chemistry, Faculty of Arts & Science, Ondokuz Mayıs University, 55139 Samsun, Turkey
^*Correspondence e-mail: htanak@omu.edu.tr

(Received 3 November 2009; accepted 5 November 2009; online 11 November 2009)

The title compound, C₇H₅NO₄, is essentially planar, with a maximum deviation from the mean plane of 0.0116 (11) Å for the hydroxy O atom. The molecular and crystal structure are stabilized by intra- and intermolecular interactions. An intramolecular O—H⋯O hydrogen bond generates a six-membered ring, producing an S(6) ring motif. The C—H⋯O interactions result in the formation of C(5) chains and R₂²(8) rings forming an approximately planar network parallel to (10 $[\overline{1}]$ ). These planes are interconnected through π–π interactions [centroid–centroid distance 3.582 (2) Å].

Related literature

Nitroaromatics are widely used as intermediates in explosives, dyestuffs, pesticides and organic synthesis, see: Yan et al. (2006 ). They occur in industrial wastes and as direct pollutants in the environment and are relatively soluble in water and detectable in rivers, ponds and soil, see: Yan et al. (2006); Soojhawon et al. (2005 ). Aromatic compounds with multiple nitro substituents are known to be resistant to electrophilic attack by oxygenases, see: Halas et al. (1983 ). For comparison bond lengths and angles in related structures, see: Rizal et al. (2008 ); Garden et al. (2004 ). For hydrogen-bond motifs, see: Bernstein et al. (1995 ).

Experimental

Crystal data

C₇H₅NO₄
M_r = 167.12
Monoclinic, P 2₁ /n
a = 7.2580 (17) Å
b = 8.3960 (13) Å
c = 11.704 (3) Å
β = 95.165 (18)°
V = 710.3 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.13 mm⁻¹
T = 296 K
0.54 × 0.28 × 0.15 mm

Data collection

Stoe IPDS II diffractometer
Absorption correction: integration (X-RED32; Stoe & Cie, 2002 ) T_min = 0.979, T_max = 0.992
4345 measured reflections
1396 independent reflections
944 reflections with I > 2σ(I)
R_int = 0.062

Refinement

R[F² > 2σ(F²)] = 0.050
wR(F²) = 0.119
S = 1.06
1396 reflections
112 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.16 e Å⁻³
Δρ_min = −0.15 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C2—H2⋯O4ⁱ	0.93	2.50	3.427 (3)	175
C6—H6⋯O3ⁱⁱ	0.93	2.53	3.433 (3)	163
C7—H7⋯O2ⁱⁱⁱ	0.93	2.50	3.176 (3)	130
O3—H3A⋯O4	0.93 (3)	1.73 (3)	2.613 (3)	157 (3)
Symmetry codes: (i) x, y-1, z; (ii) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (iii) x, y+1, z.

Data collection: X-AREA (Stoe & Cie, 2002); cell refinement: X-AREA; data reduction: X-RED32 (Stoe & Cie, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ) and PLATON (Spek, 2009 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809046807/dn2510sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809046807/dn2510Isup2.hkl

checkCIF report

Comment top

Nitroaromatics are widely used either as materials or as intermediates in explosives, dyestuffs, pesticides and organic synthesis (Yan et al., 2006). Nitroaromatics occur as industrial wastes and direct pollutants in the environment, and are relatively soluble in water and detectable in rivers, ponds and soil (Yan et al., 2006; Soojhawon et al., 2005). Morover, aromatic compounds with multiple nitro substituents are known to be resistant to electrophilic attack by oxygenases (Halas et al., 1983).

In the title compound (I, Fig. 1), the molecule is essentially planar with a maximum deviation from the mean plane of 0.0116 (11) Å for atom O3. The bond lengths and angles in (I) have normal values, and are comparable with those in the related structures (Rizal et al., 2008; Garden et al., 2004). The dihedral angle between the aromatic ring and the nitro group is 3.83 (3)°.

An intramolecular O3-H33···O4 interaction (Table 1, and Fig. 1) generates an S(6) ring motif (Bernstein et al., 1995). In the crystal structure, the molecules are linked by intermolecular C2-H2···O4, C6-H6···O3 and C7-H7···O7 interactions into a three-dimensional framework. The C-H···O interactions result in the formation of C(5) chain but also R₂²(8) ring forming an approximately planar network parallel to the (1 0 -1) plane (Fig. 2). These planes are interconnected through π-π interaction which occurs between Cg1 (the centroid of the C1-C6 ring) and its symmetry equivalent at (-x,-y,-z), with a centroid-to-centroid distance of 3.582 (2) Å, a plane-to-plane separation of 3.367 (1) Å and a slippage of 1.22 Å.

Related literature top

Nitroaromatics are widely used as intermediates in explosives, dyestuffs, pesticides and organic synthesis, see: Yan et al. (2006). They occur in industrial wastes and as direct pollutants in the environment and are relatively soluble in water and detectable in rivers, ponds and soil, see: Yan et al. (2006); Soojhawon et al. (2005). Aromatic compounds with multiple nitro substituents are known to be resistant to electrophilic attack by oxygenases, see: Halas et al. (1983). For comparison bond lengths and angles in related structures, see: Rizal et al. (2008); Garden et al. (2004). For hydrogen-bond motifs, see: Bernstein et al. (1995).

Experimental top

The commercially available compound (Acros Organics) was recrystallized from ethanol.

Computing details top

Data collection: X-AREA (Stoe & Cie, 2002); cell refinement: X-AREA (Stoe & Cie, 2002); data reduction: X-RED32 (Stoe & Cie, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2009); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top

	Fig. 1. The molecular structure of the title compound, showing the atom-numbering scheme and 50% probability diplacement ellipsoids. H atoms are represented as small spheres of arbitrary radii.
	Fig. 2. Partial packing view showing the formation of C-H···O hydrogen bonds represented as dashed lines. H atoms not involved in hydrogen bondings have been omitted for clarity. [Symmetry codes: (i) x, y-1, z; (ii) x+1/2, -y+1/2, z+1/2; (iii) x, y+1, z ]

2-Hydroxy-5-nitrobenzaldehyde top

Crystal data top

C₇H₅NO₄	F(000) = 344
M_r = 167.12	D_x = 1.563 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 8368 reflections
a = 7.2580 (17) Å	θ = 1.8–27.3°
b = 8.3960 (13) Å	µ = 0.13 mm⁻¹
c = 11.704 (3) Å	T = 296 K
β = 95.165 (18)°	Prism., red
V = 710.3 (3) Å³	0.54 × 0.28 × 0.15 mm
Z = 4

Data collection top

Stoe IPDS II diffractometer	1396 independent reflections
Radiation source: fine-focus sealed tube	944 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.062
Detector resolution: 6.67 pixels mm^-1	θ_max = 26.0°, θ_min = 3.0°
rotation method scans	h = −8→8
Absorption correction: integration (X-RED32; Stoe & Cie, 2002)	k = −10→10
T_min = 0.979, T_max = 0.992	l = −14→14
4345 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)] = 0.050	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.119	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ²(F_o²) + (0.05P)² + 0.0581P] where P = (F_o² + 2F_c²)/3
1396 reflections	(Δ/σ)_max < 0.001
112 parameters	Δρ_max = 0.16 e Å⁻³
0 restraints	Δρ_min = −0.15 e Å⁻³

Crystal data top

C₇H₅NO₄	V = 710.3 (3) Å³
M_r = 167.12	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 7.2580 (17) Å	µ = 0.13 mm⁻¹
b = 8.3960 (13) Å	T = 296 K
c = 11.704 (3) Å	0.54 × 0.28 × 0.15 mm
β = 95.165 (18)°

Data collection top

Stoe IPDS II diffractometer	1396 independent reflections
Absorption correction: integration (X-RED32; Stoe & Cie, 2002)	944 reflections with I > 2σ(I)
T_min = 0.979, T_max = 0.992	R_int = 0.062
4345 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.050	0 restraints
wR(F²) = 0.119	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	Δρ_max = 0.16 e Å⁻³
1396 reflections	Δρ_min = −0.15 e Å⁻³
112 parameters

Special details top

Experimental. 168 frames, detector distance = 120 mm

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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	0.4340 (3)	−0.1006 (2)	0.25586 (14)	0.0788 (6)
O2	0.3658 (3)	−0.3022 (2)	0.15003 (16)	0.0819 (6)
O3	0.1019 (3)	0.2346 (2)	−0.19209 (14)	0.0702 (6)
H3A	0.130 (4)	0.336 (4)	−0.162 (3)	0.105*
O4	0.2251 (3)	0.4736 (2)	−0.06415 (16)	0.0895 (7)
N1	0.3709 (3)	−0.1591 (2)	0.16564 (16)	0.0524 (5)
C1	0.3019 (3)	−0.0545 (2)	0.07198 (17)	0.0425 (5)
C2	0.2232 (3)	−0.1209 (2)	−0.03011 (17)	0.0459 (5)
H2	0.2154	−0.2309	−0.0385	0.055*
C3	0.1574 (3)	−0.0228 (3)	−0.11799 (18)	0.0494 (5)
H3	0.1037	−0.0659	−0.1863	0.059*
C4	0.1711 (3)	0.1417 (2)	−0.10464 (18)	0.0471 (5)
C5	0.2551 (3)	0.2073 (2)	−0.00295 (17)	0.0437 (5)
C6	0.3190 (3)	0.1067 (2)	0.08585 (17)	0.0431 (5)
H6	0.3730	0.1485	0.1544	0.052*
C7	0.2771 (3)	0.3784 (3)	0.0104 (2)	0.0631 (7)
H7	0.3338	0.4172	0.0792	0.076*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.1123 (15)	0.0673 (12)	0.0522 (10)	−0.0024 (11)	−0.0171 (10)	0.0069 (9)
O2	0.1202 (16)	0.0391 (10)	0.0829 (13)	0.0026 (9)	−0.0101 (11)	0.0101 (8)
O3	0.0914 (13)	0.0556 (11)	0.0590 (11)	0.0048 (9)	−0.0195 (9)	0.0061 (8)
O4	0.1338 (17)	0.0423 (10)	0.0871 (14)	0.0022 (11)	−0.0199 (12)	0.0094 (9)
N1	0.0593 (11)	0.0433 (12)	0.0547 (11)	−0.0005 (9)	0.0047 (9)	0.0071 (9)
C1	0.0418 (11)	0.0382 (12)	0.0475 (12)	−0.0002 (9)	0.0041 (9)	0.0023 (9)
C2	0.0486 (12)	0.0355 (10)	0.0535 (12)	−0.0007 (9)	0.0046 (9)	−0.0025 (9)
C3	0.0526 (12)	0.0492 (13)	0.0453 (12)	−0.0032 (10)	−0.0013 (9)	−0.0086 (10)
C4	0.0463 (11)	0.0458 (13)	0.0480 (12)	0.0029 (9)	−0.0018 (9)	0.0028 (10)
C5	0.0468 (11)	0.0366 (11)	0.0470 (12)	−0.0014 (9)	0.0007 (9)	−0.0008 (9)
C6	0.0457 (11)	0.0418 (12)	0.0413 (11)	−0.0031 (9)	0.0009 (9)	−0.0049 (9)
C7	0.0805 (17)	0.0424 (13)	0.0643 (15)	−0.0020 (12)	−0.0045 (12)	−0.0008 (12)

Geometric parameters (Å, º) top

O1—N1	1.216 (2)	C2—H2	0.9300
O2—N1	1.215 (2)	C3—C4	1.392 (3)
O3—C4	1.348 (2)	C3—H3	0.9300
O3—H3A	0.93 (3)	C4—C5	1.401 (3)
O4—C7	1.218 (3)	C5—C6	1.386 (3)
N1—C1	1.458 (3)	C5—C7	1.452 (3)
C1—C6	1.367 (3)	C6—H6	0.9300
C1—C2	1.394 (3)	C7—H7	0.9300
C2—C3	1.370 (3)

C4—O3—H3A	100.5 (19)	O3—C4—C3	118.12 (19)
O2—N1—O1	122.27 (19)	O3—C4—C5	121.43 (19)
O2—N1—C1	118.59 (19)	C3—C4—C5	120.45 (19)
O1—N1—C1	119.13 (18)	C6—C5—C4	119.19 (18)
C6—C1—C2	121.56 (19)	C6—C5—C7	119.77 (19)
C6—C1—N1	119.05 (18)	C4—C5—C7	121.04 (19)
C2—C1—N1	119.38 (18)	C1—C6—C5	119.59 (19)
C3—C2—C1	119.5 (2)	C1—C6—H6	120.2
C3—C2—H2	120.3	C5—C6—H6	120.2
C1—C2—H2	120.3	O4—C7—C5	123.3 (2)
C2—C3—C4	119.71 (19)	O4—C7—H7	118.4
C2—C3—H3	120.1	C5—C7—H7	118.4
C4—C3—H3	120.1

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···O4ⁱ	0.93	2.50	3.427 (3)	175
C6—H6···O3ⁱⁱ	0.93	2.53	3.433 (3)	163
C7—H7···O2ⁱⁱⁱ	0.93	2.50	3.176 (3)	130
O3—H3A···O4	0.93 (3)	1.73 (3)	2.613 (3)	157 (3)

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

Experimental details

Crystal data
Chemical formula	C₇H₅NO₄
M_r	167.12
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	296
a, b, c (Å)	7.2580 (17), 8.3960 (13), 11.704 (3)
β (°)	95.165 (18)
V (Å³)	710.3 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.13
Crystal size (mm)	0.54 × 0.28 × 0.15

Data collection
Diffractometer	Stoe IPDS II diffractometer
Absorption correction	Integration (X-RED32; Stoe & Cie, 2002)
T_min, T_max	0.979, 0.992
No. of measured, independent and observed [I > 2σ(I)] reflections	4345, 1396, 944
R_int	0.062
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.050, 0.119, 1.06
No. of reflections	1396
No. of parameters	112
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.16, −0.15

Computer programs: X-AREA (Stoe & Cie, 2002), X-RED32 (Stoe & Cie, 2002), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2009), WinGX (Farrugia, 1999).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···O4ⁱ	0.93	2.50	3.427 (3)	174.8
C6—H6···O3ⁱⁱ	0.93	2.53	3.433 (3)	163.2
C7—H7···O2ⁱⁱⁱ	0.93	2.50	3.176 (3)	129.6
O3—H3A···O4	0.93 (3)	1.73 (3)	2.613 (3)	157 (3)

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

Acknowledgements

This study was supported financially by the Research Center of Ondokuz Mayıs University (Project No. F-476). The authors acknowledge the Faculty of Arts and Sciences, Ondokuz Mayıs University, Turkey, for the use of the Stoe IPDS II diffractometer (purchased under grant No. F279 of the University Research Fund).

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