5-Hy­droxy-2-{(E)-[(3-nitro­phen­yl)iminio]meth­yl}phenolate

Muhammad Ashraf Shaheen; M Nawaz Tahir; Rana Muhammad Irfan; Shahid Iqbal; Saeed Ahmad

doi:10.1107/S1600536812033740

. 2012 Aug 1;68(Pt 9):o2622. doi: 10.1107/S1600536812033740

5-Hydroxy-2-{(E)-[(3-nitrophenyl)iminio]methyl}phenolate

Muhammad Ashraf Shaheen ^a, M Nawaz Tahir ^b,^*, Rana Muhammad Irfan ^a, Shahid Iqbal ^a, Saeed Ahmad ^c

PMCID: PMC3435650 PMID: 22969523

Abstract

The title compound, C₁₃H₁₀N₂O₄, crystallized as the zwitterionic tautomer. As a result, the phenolate C—O⁻ bond [1.296 (2) Å] is shorter than a normal Csp ²—O(H) bond, and the azomethine C=N bond [1.314 (2) Å] is longer than a normal C=N double bond. The molecule is nearly planar, the mean plane of the nitro-substituted benzene ring forming dihedral angles of 9.83 (7) and 8.45 (9)° with the other benzene ring and with the nitro group, respectively. The molecular conformation is stabilized by an intramolecular N—H⋯O hydrogen bond. In the crystal, strong O—H⋯O hydrogen bonds link the molecules into double-stranded chains along the b-axis direction. Within the chains there are π–π interactions involving the benzene rings of adjacent molecules [centroid–centroid distance = 3.669 (1) Å]. The chains are linked via C—H⋯O hydrogen bonds, forming R ₂ ¹(6), R ₂ ¹(7) and R ₂ ²(10) ring motifs.

Related literature

For related structures, see: Yeap et al. (1992 ▶); Hijji et al. (2009 ▶). For graph-set analysis of hydrogen bonds, see: Bernstein et al. (1995 ▶).

Experimental

Crystal data

C₁₃H₁₀N₂O₄
M _r = 258.23
Monoclinic,
a = 12.8518 (9) Å
b = 7.8501 (5) Å
c = 24.1316 (18) Å
β = 101.593 (3)°
V = 2384.9 (3) Å³
Z = 8
Mo Kα radiation
μ = 0.11 mm⁻¹
T = 296 K
0.30 × 0.25 × 0.22 mm

Data collection

Bruker Kappa APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T _min = 0.975, T _max = 0.985
5601 measured reflections
2126 independent reflections
1569 reflections with I > 2σ(I)
R _int = 0.025

Refinement

R[F ² > 2σ(F ²)] = 0.038
wR(F ²) = 0.105
S = 1.02
2126 reflections
173 parameters
H-atom parameters constrained
Δρ_max = 0.13 e Å⁻³
Δρ_min = −0.15 e Å⁻³

Data collection: APEX2 (Bruker, 2009 ▶); cell refinement: SAINT (Bruker, 2009 ▶); 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 for Windows (Farrugia, 1997 ▶) and PLATON (Spek, 2009 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶) and PLATON.

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812033740/yk2068sup1.cif

e-68-o2622-sup1.cif^{(21.4KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812033740/yk2068Isup2.hkl

e-68-o2622-Isup2.hkl^{(102.5KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536812033740/yk2068Isup3.cml

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

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2A⋯O3	0.86	1.87	2.5716 (19)	138
O4—H4A⋯O3ⁱ	0.82	1.79	2.6100 (17)	179
C2—H2⋯O2ⁱⁱ	0.93	2.54	3.446 (2)	164
C4—H4⋯O4ⁱⁱⁱ	0.93	2.54	3.268 (2)	135
C7—H7⋯O2ⁱⁱ	0.93	2.49	3.355 (2)	154
C10—H10⋯O3ⁱ	0.93	2.56	3.226 (2)	129

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) .

Acknowledgments

The authors acknowledge the provision of funds for the purchase of a diffractometer and encouragement by Dr Muhammad Akram Chaudhary, Vice Chancellor, University of Sargodha, Pakistan. The authors also acknowledge the technical support provided by Syed Muhammad Hussain Rizvi of Bana International, Karachi, Pakistan.

supplementary crystallographic information

Comment

The title compound (Fig. 1) has been synthesized as a precursor for complex formation and other studies.

In contrast to the closely related structure of 2-[(3-nitrophenylimino)methyl]phenol (Yeap et al., 1992), the title compound is a zwitterion, in which the hydroxy H⁺ ion is transferred to the imino N atom (Fig. 1). Analogous zwitterionic structure is observed for 2-{[(2-hydroxy-5-nitrophenyl)iminio]methyl}phenolate (Hijji et al., 2009).

The molecule consists of two roughly planar groups, the 3-nitroaniline fragment (C1—C6/N1/N2/O1/O2) and the rest of 2,4-dihydroxybenzaldehyde (C7—C13/O3/O4), the mean deviations from the planes are 0.070Å and 0.023Å, respectively. The dihedral angle between the planes of these groups is 9.37 (6)°.

Strong intramolecular N—H···O hydrogen bond (Table 1, Fig. 2) produce S(6) ring motif (Bernstein et al., 1995). Due to the intermolecular O—H···O hydrogen bonds, the C(6) chains along the b-axis direction are formed (Table 1, Fig. 2). The C—H···O interactions join these chains, generating the R₂¹(7) and R₂²(10) rings. motifs. Due to the C—H···O and O—H···O hydrogen bonds, the R₂¹(6) ring motif is also formed (Table 1, Fig. 2).

Experimental

3-Nitroaniline (0.138 g, 1.0 mmol) was dissolved in distilled methanol. Solution of 2,4-dihydroxybenzaldehyde (0.138 g, 1.0 mmol) in methanol was added dropwise. The mixture was refluxed for 2 h and orange prisms of the title compound were obtained after 48 h.