4-Hydr­oxy-3-nitro­benzaldehyde

Rizal, M.R.; Azizul, I.; Ng, S.W.

doi:10.1107/S1600536808011148

organic compounds

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ISSN: 2056-9890

Volume 64| Part 5| May 2008| Page o915

doi:10.1107/S1600536808011148

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4-Hydroxy-3-nitrobenzaldehyde

Mohd. Razali Rizal,^a Isha Azizul ^a and Seik Weng Ng ^a ^*

^aDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
^*Correspondence e-mail: seikweng@um.edu.my

(Received 27 February 2008; accepted 20 April 2008; online 26 April 2008)

The hydroxyl group in each of the two independent molecules of the title compound, C₇H₅NO₄, participates in two O—H⋯O hydrogen bonds, viz. one intramolecular bond to the nitro group and one intermolecular bond to the aldehyde group of the same molecule in the next unit, resulting in a linear chain structure. The dihedral angle between the aromatic ring and the nitro group is 10.9 (3)° in one molecule and 9.9 (2)° in the other.

Related literature

For the structure of 2-nitrophenol, see: Iwasaki & Kawano (1978 ). For the structure of 4-hydroxybenzaldehyde, see: Jasinski et al. (2008 ).

Experimental

Crystal data

C₇H₅NO₄
M_r = 167.12
Triclinic, $[P \overline 1]$
a = 8.042 (1) Å
b = 8.036 (1) Å
c = 12.242 (2) Å
α = 71.975 (2)°
β = 70.820 (2)°
γ = 67.323 (2)°
V = 674.1 (2) Å³
Z = 4
Mo Kα radiation
μ = 0.14 mm⁻¹
T = 100 (2) K
0.40 × 0.05 × 0.05 mm

Data collection

Bruker SMART APEX diffractometer
Absorption correction: none
4245 measured reflections
3068 independent reflections
2134 reflections with I > 2σ(I)
R_int = 0.016

Refinement

R[F² > 2σ(F²)] = 0.045
wR(F²) = 0.121
S = 0.99
3068 reflections
225 parameters
2 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.31 e Å⁻³
Δρ_min = −0.32 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O4—H4o⋯O1ⁱ	0.84 (1)	2.13 (3)	2.676 (2)	122 (3)
O4—H4o⋯O3	0.84 (1)	1.91 (2)	2.638 (2)	144 (3)
O8—H8o⋯O5ⁱⁱ	0.84 (1)	2.10 (3)	2.687 (2)	128 (3)
O8—H8o⋯O7	0.84 (1)	1.94 (2)	2.635 (2)	139 (3)
Symmetry codes: (i) x+1, y-1, z; (ii) x-1, y+1, z.

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: X-SEED (Barbour, 2001 ); software used to prepare material for publication: publCIF (Westrip, 2008 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808011148/fl2191sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808011148/fl2191Isup2.hkl

checkCIF report

Comment top

A nitro group either ortho or para to a hydroxyl group can significantly increase the acidity of the resulting phenol. The crystal structures of a large number of 2-nitrophenol compounds have reported; the title compound represents another example. The hydroxyl group of the two independent molecules of the title compound (Fig. 1) is intramolecularly linked to the nitro group by an O–H···O hydrogen bond; the hydroxy group is intermolecularly linked to the aldehyde group of the molecule in the next unit cell by an similar hydrogen bond to result in a linear chain structure (Fig. 2). 2-Nitrophenol itself features an intramolecular hydrogen bond of 2.602 Å (Iwasaki & Kawano, 1978). On the other hand, 4-hydroxybenzaldehyde exists as a hydrogen-bonded chain [O–H···O 2.731 (2) Å] (Jasinski et al., 2008).

Related literature top

For the structure of 2-nitrophenol, see: Iwasaki & Kawano (1978). For the structure of 4-hydroxybenzaldehyde, see: Jasinski et al. (2008).

Experimental top

The commercially available compound (Sigma Aldrich) was recrystallized from water.

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: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2008).

Figures top

	Fig. 1. Thermal ellipsoid plot of the two independent molecules of the title compound at the 70% probability level; hydrogen atoms are drawn as spheres of arbitrary radius.
	Fig. 2. Chain structure of 4-hydroxy-3-nitrobenzaldehyde. Dashed lines denote hydrogen bonds.

4-Hydroxy-3-nitrobenzaldehyde top

Crystal data top

C₇H₅NO₄	Z = 4
M_r = 167.12	F(000) = 344
Triclinic, P1	D_x = 1.647 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.042 (1) Å	Cell parameters from 1123 reflections
b = 8.036 (1) Å	θ = 3.0–28.8°
c = 12.242 (2) Å	µ = 0.14 mm⁻¹
α = 71.975 (2)°	T = 100 K
β = 70.820 (2)°	Prism, yellow
γ = 67.323 (2)°	0.40 × 0.05 × 0.05 mm
V = 674.1 (2) Å³

Data collection top

Bruker SMART APEXII diffractometer	2134 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.016
Graphite monochromator	θ_max = 27.5°, θ_min = 1.8°
ϕ and ω scans	h = −10→10
4245 measured reflections	k = −10→9
3068 independent reflections	l = −15→15

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)] = 0.045	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.121	H atoms treated by a mixture of independent and constrained refinement
S = 0.99	w = 1/[σ²(F_o²) + (0.0598P)² + 0.2315P] where P = (F_o² + 2F_c²)/3
3068 reflections	(Δ/σ)_max = 0.001
225 parameters	Δρ_max = 0.31 e Å⁻³
2 restraints	Δρ_min = −0.32 e Å⁻³

Crystal data top

C₇H₅NO₄	γ = 67.323 (2)°
M_r = 167.12	V = 674.1 (2) Å³
Triclinic, P1	Z = 4
a = 8.042 (1) Å	Mo Kα radiation
b = 8.036 (1) Å	µ = 0.14 mm⁻¹
c = 12.242 (2) Å	T = 100 K
α = 71.975 (2)°	0.40 × 0.05 × 0.05 mm
β = 70.820 (2)°

Data collection top

Bruker SMART APEXII diffractometer	2134 reflections with I > 2σ(I)
4245 measured reflections	R_int = 0.016
3068 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.045	2 restraints
wR(F²) = 0.121	H atoms treated by a mixture of independent and constrained refinement
S = 0.99	Δρ_max = 0.31 e Å⁻³
3068 reflections	Δρ_min = −0.32 e Å⁻³
225 parameters

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

	x	y	z	U_iso*/U_eq
O1	0.4321 (2)	0.8384 (2)	0.8786 (1)	0.0221 (3)
O2	0.9772 (2)	0.2412 (2)	1.1704 (1)	0.0225 (4)
O3	1.1859 (2)	0.0816 (2)	1.0449 (1)	0.0224 (4)
O4	1.1227 (2)	0.1121 (2)	0.8402 (1)	0.0204 (3)
O5	1.0630 (2)	0.6755 (2)	0.4971 (1)	0.0220 (3)
O6	0.4719 (2)	1.2568 (2)	0.7806 (1)	0.0277 (4)
O7	0.2851 (2)	1.4257 (2)	0.6664 (1)	0.0231 (4)
O8	0.3813 (2)	1.4045 (2)	0.4424 (1)	0.0199 (3)
N1	1.0379 (2)	0.2049 (2)	1.0719 (2)	0.0173 (4)
N2	0.4272 (2)	1.2985 (2)	0.6866 (2)	0.0189 (4)
C1	0.5276 (3)	0.7418 (3)	0.9488 (2)	0.0175 (4)
C2	0.6821 (3)	0.5734 (3)	0.9247 (2)	0.0157 (4)
C3	0.7856 (3)	0.4675 (3)	1.0075 (2)	0.0160 (4)
C4	0.9342 (3)	0.3115 (3)	0.9816 (2)	0.0153 (4)
C5	0.9815 (3)	0.2577 (3)	0.8741 (2)	0.0162 (4)
C6	0.8705 (3)	0.3642 (3)	0.7931 (2)	0.0193 (4)
C7	0.7247 (3)	0.5181 (3)	0.8181 (2)	0.0185 (4)
C8	0.9568 (3)	0.7675 (3)	0.5691 (2)	0.0181 (4)
C9	0.8044 (3)	0.9364 (3)	0.5399 (2)	0.0157 (4)
C10	0.6886 (3)	1.0378 (3)	0.6244 (2)	0.0157 (4)
C11	0.5444 (3)	1.1966 (3)	0.5950 (2)	0.0157 (4)
C12	0.5144 (3)	1.2565 (3)	0.4804 (2)	0.0155 (4)
C13	0.6380 (3)	1.1535 (3)	0.3950 (2)	0.0174 (4)
C14	0.7784 (3)	0.9973 (3)	0.4242 (2)	0.0173 (4)
H4o	1.185 (4)	0.068 (4)	0.892 (2)	0.06 (1)*
H8o	0.308 (3)	1.452 (4)	0.499 (2)	0.05 (1)*
H1	0.5013	0.7765	1.0216	0.021*
H3	0.7557	0.5010	1.0812	0.019*
H6	0.8969	0.3290	0.7203	0.023*
H7	0.6514	0.5884	0.7623	0.022*
H8	0.9724	0.7290	0.6477	0.022*
H10	0.7070	0.9998	0.7023	0.019*
H13	0.6238	1.1931	0.3161	0.021*
H14	0.8593	0.9290	0.3655	0.021*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0187 (8)	0.0176 (8)	0.0236 (8)	0.0041 (6)	−0.0081 (6)	−0.0052 (6)
O2	0.0246 (8)	0.0218 (8)	0.0174 (7)	−0.0016 (7)	−0.0057 (6)	−0.0057 (6)
O3	0.0171 (8)	0.0177 (8)	0.0261 (8)	0.0048 (6)	−0.0082 (6)	−0.0059 (6)
O4	0.0169 (8)	0.0172 (8)	0.0234 (8)	0.0048 (6)	−0.0073 (6)	−0.0096 (6)
O5	0.0191 (8)	0.0171 (8)	0.0251 (8)	0.0038 (6)	−0.0071 (6)	−0.0083 (6)
O6	0.0294 (9)	0.0283 (9)	0.0199 (8)	0.0037 (7)	−0.0080 (7)	−0.0121 (7)
O7	0.0175 (8)	0.0186 (8)	0.0241 (8)	0.0047 (6)	−0.0035 (6)	−0.0075 (6)
O8	0.0155 (8)	0.0171 (7)	0.0197 (8)	0.0049 (6)	−0.0051 (6)	−0.0060 (6)
N1	0.0170 (9)	0.0152 (9)	0.0187 (9)	−0.0028 (7)	−0.0058 (7)	−0.0035 (7)
N2	0.0171 (9)	0.0166 (9)	0.0189 (9)	−0.0004 (7)	−0.0029 (7)	−0.0063 (7)
C1	0.0149 (10)	0.0145 (10)	0.0201 (10)	−0.0005 (8)	−0.0023 (8)	−0.0065 (8)
C2	0.0104 (9)	0.0135 (10)	0.0198 (10)	−0.0007 (8)	−0.0025 (8)	−0.0040 (8)
C3	0.0149 (10)	0.0149 (10)	0.0163 (10)	−0.0025 (8)	−0.0033 (8)	−0.0038 (8)
C4	0.0134 (10)	0.0138 (10)	0.0167 (10)	−0.0026 (8)	−0.0055 (8)	−0.0006 (8)
C5	0.0117 (10)	0.0142 (10)	0.0204 (10)	−0.0006 (8)	−0.0038 (8)	−0.0048 (8)
C6	0.0177 (11)	0.0187 (11)	0.0197 (10)	0.0010 (8)	−0.0060 (9)	−0.0085 (8)
C7	0.0149 (10)	0.0175 (10)	0.0202 (10)	−0.0001 (8)	−0.0070 (8)	−0.0034 (8)
C8	0.0167 (10)	0.0153 (10)	0.0199 (10)	−0.0018 (8)	−0.0057 (8)	−0.0034 (8)
C9	0.0145 (10)	0.0119 (10)	0.0195 (10)	−0.0020 (8)	−0.0054 (8)	−0.0031 (8)
C10	0.0154 (10)	0.0147 (10)	0.0155 (10)	−0.0034 (8)	−0.0047 (8)	−0.0017 (8)
C11	0.0132 (10)	0.0135 (10)	0.0182 (10)	−0.0018 (8)	−0.0021 (8)	−0.0053 (8)
C12	0.0123 (10)	0.0121 (9)	0.0196 (10)	−0.0013 (8)	−0.0040 (8)	−0.0032 (8)
C13	0.0153 (10)	0.0170 (10)	0.0171 (10)	0.0000 (8)	−0.0057 (8)	−0.0043 (8)
C14	0.0150 (10)	0.0152 (10)	0.0189 (10)	0.0006 (8)	−0.0033 (8)	−0.0075 (8)

Geometric parameters (Å, º) top

O1—C1	1.222 (2)	C8—C9	1.475 (3)
O2—N1	1.223 (2)	C9—C10	1.380 (3)
O3—N1	1.242 (2)	C9—C14	1.406 (3)
O4—C5	1.341 (2)	C10—C11	1.397 (3)
O5—C8	1.214 (3)	C11—C12	1.405 (3)
O6—N2	1.226 (2)	C12—C13	1.408 (3)
O7—N2	1.241 (2)	C13—C14	1.368 (3)
O8—C12	1.335 (2)	O4—H4o	0.84 (1)
N1—C4	1.457 (3)	O8—H8o	0.84 (1)
N2—C11	1.447 (3)	C1—H1	0.9500
C1—C2	1.473 (3)	C3—H3	0.9500
C2—C3	1.385 (3)	C6—H6	0.9500
C2—C7	1.403 (3)	C7—H7	0.9500
C3—C4	1.394 (3)	C8—H8	0.9500
C4—C5	1.399 (3)	C10—H10	0.9500
C5—C6	1.408 (3)	C13—H13	0.9500
C6—C7	1.370 (3)	C14—H14	0.9500

O2—N1—O3	122.8 (2)	C10—C11—N2	117.7 (2)
O2—N1—C4	119.0 (2)	C12—C11—N2	121.0 (2)
O3—N1—C4	118.1 (2)	O8—C12—C11	126.7 (2)
O6—N2—O7	122.6 (2)	O8—C12—C13	115.7 (2)
O6—N2—C11	119.1 (2)	C11—C12—C13	117.7 (2)
O7—N2—C11	118.3 (2)	C14—C13—C12	120.9 (2)
O1—C1—C2	122.4 (2)	C13—C14—C9	120.9 (2)
C3—C2—C7	119.4 (2)	C5—O4—H4o	106 (2)
C3—C2—C1	120.4 (2)	C12—O8—H8o	110 (2)
C7—C2—C1	120.3 (2)	O1—C1—H1	118.8
C2—C3—C4	119.4 (2)	C2—C1—H1	118.8
C3—C4—C5	121.8 (2)	C2—C3—H3	120.3
C3—C4—N1	117.1 (2)	C4—C3—H3	120.3
C5—C4—N1	121.1 (2)	C7—C6—H6	119.7
O4—C5—C4	126.4 (2)	C5—C6—H6	119.7
O4—C5—C6	115.9 (2)	C6—C7—H7	119.5
C4—C5—C6	117.7 (2)	C2—C7—H7	119.5
C7—C6—C5	120.6 (2)	O5—C8—H8	118.5
C6—C7—C2	121.1 (2)	C9—C8—H8	118.5
O5—C8—C9	122.9 (2)	C9—C10—H10	120.1
C10—C9—C14	119.4 (2)	C11—C10—H10	120.1
C10—C9—C8	120.8 (2)	C14—C13—H13	119.5
C14—C9—C8	119.8 (2)	C12—C13—H13	119.5
C9—C10—C11	119.8 (2)	C13—C14—H14	119.6
C10—C11—C12	121.3 (2)	C9—C14—H14	119.6

O1—C1—C2—C3	−179.5 (2)	O5—C8—C9—C10	−179.1 (2)
O1—C1—C2—C7	0.0 (3)	O5—C8—C9—C14	−0.3 (3)
C7—C2—C3—C4	2.1 (3)	C14—C9—C10—C11	1.7 (3)
C1—C2—C3—C4	−178.3 (2)	C8—C9—C10—C11	−179.5 (2)
C2—C3—C4—C5	−0.4 (3)	C9—C10—C11—C12	−0.3 (3)
C2—C3—C4—N1	−179.8 (2)	C9—C10—C11—N2	−179.8 (2)
O2—N1—C4—C3	9.5 (3)	O6—N2—C11—C10	9.2 (3)
O3—N1—C4—C3	−169.8 (2)	O7—N2—C11—C10	−171.1 (2)
O2—N1—C4—C5	−170.0 (2)	O6—N2—C11—C12	−170.3 (2)
O3—N1—C4—C5	10.7 (3)	O7—N2—C11—C12	9.4 (3)
C3—C4—C5—O4	179.0 (2)	C10—C11—C12—O8	179.6 (2)
N1—C4—C5—O4	−1.6 (3)	N2—C11—C12—O8	−0.9 (3)
C3—C4—C5—C6	−1.6 (3)	C10—C11—C12—C13	−1.6 (3)
N1—C4—C5—C6	177.8 (2)	N2—C11—C12—C13	177.9 (2)
O4—C5—C6—C7	−178.7 (2)	O8—C12—C13—C14	−179.0 (2)
C4—C5—C6—C7	1.9 (3)	C11—C12—C13—C14	2.1 (3)
C5—C6—C7—C2	−0.1 (3)	C12—C13—C14—C9	−0.8 (3)
C3—C2—C7—C6	−2.0 (3)	C10—C9—C14—C13	−1.2 (3)
C1—C2—C7—C6	178.5 (2)	C8—C9—C14—C13	180.0 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O4—H4o···O1ⁱ	0.84 (1)	2.13 (3)	2.676 (2)	122 (3)
O4—H4o···O3	0.84 (1)	1.91 (2)	2.638 (2)	144 (3)
O8—H8o···O5ⁱⁱ	0.84 (1)	2.10 (3)	2.687 (2)	128 (3)
O8—H8o···O7	0.84 (1)	1.94 (2)	2.635 (2)	139 (3)

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

Experimental details

Crystal data
Chemical formula	C₇H₅NO₄
M_r	167.12
Crystal system, space group	Triclinic, P1
Temperature (K)	100
a, b, c (Å)	8.042 (1), 8.036 (1), 12.242 (2)
α, β, γ (°)	71.975 (2), 70.820 (2), 67.323 (2)
V (Å³)	674.1 (2)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.14
Crystal size (mm)	0.40 × 0.05 × 0.05

Data collection
Diffractometer	Bruker SMART APEXII diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	4245, 3068, 2134
R_int	0.016
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.045, 0.121, 0.99
No. of reflections	3068
No. of parameters	225
No. of restraints	2
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.31, −0.32

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001), publCIF (Westrip, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O4—H4o···O1ⁱ	0.84 (1)	2.13 (3)	2.676 (2)	122 (3)
O4—H4o···O3	0.84 (1)	1.91 (2)	2.638 (2)	144 (3)
O8—H8o···O5ⁱⁱ	0.84 (1)	2.10 (3)	2.687 (2)	128 (3)
O8—H8o···O7	0.84 (1)	1.94 (2)	2.635 (2)	139 (3)

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

Acknowledgements

We thank the University of Malaya for the purchase of the diffractometer.

References

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