2-{(E)-1-[2-(2-Nitro­phen­yl)hydrazin-1-yl­idene]eth­yl}benzene-1,3-diol mono­hydrate

R Alan Howie; James L Wardell; Solange M S V Wardell; Edward R T Tiekink

doi:10.1107/S1600536812006241

. 2012 Feb 17;68(Pt 3):o765–o766. doi: 10.1107/S1600536812006241

2-{(E)-1-[2-(2-Nitrophenyl)hydrazin-1-ylidene]ethyl}benzene-1,3-diol monohydrate

R Alan Howie ^a, James L Wardell ^b,^‡, Solange M S V Wardell ^c, Edward R T Tiekink ^d,^*

PMCID: PMC3295529 PMID: 22412640

Abstract

The hydrazone molecule in title monohydrate, C₁₄H₁₃N₃O₄·H₂O, is almost coplanar, the dihedral angle between the terminal benzene rings being 3.22 (15)°; the nitro group is coplanar with the benzene ring to which it is bonded [O—N—C—C = −2.8 (4)°]. The hydroxy group forms an intramolecular hydrogen bond with the imine N atom, and the conformation about the imine bond [1.305 (3) Å] is E. In the crystal, supramolecular layers in the (203) plane are connected into a double layer via water–nitro O—H⋯O hydrogen bonds, along with π–π interactions [ring centroid–centroid distance = 3.7859 (19) Å].

Related literature

For background on the influence of substituents upon the supramolecular structures of hydrazones, see: Glidewell et al. (2004 ▶); Ferguson et al. (2005 ▶); Baddeley et al. (2009 ▶).

Experimental

Crystal data

C₁₄H₁₃N₃O₄·H₂O
M _r = 305.29
Monoclinic,
a = 7.6448 (6) Å
b = 21.405 (2) Å
c = 8.5755 (7) Å
β = 106.976 (5)°
V = 1342.1 (2) Å³
Z = 4
Mo Kα radiation
μ = 0.12 mm⁻¹
T = 120 K
0.45 × 0.25 × 0.02 mm

Data collection

Bruker–Nonius Roper CCD camera on κ-goniostat diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2007 ▶) T _min = 0.776, T _max = 0.998
16295 measured reflections
3068 independent reflections
1492 reflections with I > 2σ(I)
R _int = 0.110

Refinement

R[F ² > 2σ(F ²)] = 0.066
wR(F ²) = 0.194
S = 1.01
3068 reflections
221 parameters
6 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.37 e Å⁻³
Δρ_min = −0.30 e Å⁻³

Data collection: COLLECT (Hooft, 1998 ▶); cell refinement: DENZO (Otwinowski & Minor, 1997 ▶) and COLLECT; data reduction: DENZO and COLLECT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶) and DIAMOND (Brandenburg, 2006 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812006241/pv2513sup1.cif

e-68-0o765-sup1.cif^{(18.8KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812006241/pv2513Isup2.hkl

e-68-0o765-Isup2.hkl^{(147.5KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536812006241/pv2513Isup3.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
O1—H1O⋯N1	0.85 (2)	1.69 (2)	2.489 (3)	157 (4)
N2—H2N⋯O3	0.88 (2)	1.93 (2)	2.602 (3)	132 (2)
O2—H2O⋯O1wⁱ	0.84 (3)	1.90 (3)	2.742 (3)	174 (2)
O1W—H1W⋯O1ⁱⁱ	0.84 (2)	2.08 (3)	2.910 (3)	169 (3)
O1W—H2W⋯O4ⁱⁱⁱ	0.85 (3)	2.50 (3)	3.256 (3)	150 (3)
C11—H11⋯O3^iv	0.95	2.52	3.447 (4)	166

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

Acknowledgments

The use of the EPSRC X-ray crystallographic service at the University of Southampton, England, and the valuable assistance of the staff there is gratefully acknowledged. JLW acknowledges support from CAPES (Brazil). We also thank the Ministry of Higher Education (Malaysia) for funding structural studies through the High-Impact Research scheme (UM·C/HIR/MOHE/SC/12).

supplementary crystallographic information

Comment

The crystal structure of the title compound (I), has been determined in connection with on-going investigations into the structural chemistry of hydrazones, focusing in particular upon the influence of substituents upon their supramolecular structures, with a special emphasis on derivatives having potential biological activities. These studies have included investigations on substituted phenylhydrazines with substituted benzaldehydes (Glidewell et al., 2004; Ferguson et al., 2005) and 2-hydroxyacetophenone (Baddeley et al., 2009).

In (I) (Fig. 1), the dihedral angle between the benzene rings is 3.22 (15)°, indicating an approximately planar molecule. The nitro group is co-planar with the benzene ring to which it is bonded as seen in the value of the O3—N3—C10—C9 torsion angle of -2.8 (4)°. The hydroxy group forms an intramolecular hydrogen bond with the imine-N1 atom, Table 1. The configuration about the N1═C7 imine bond [1.305 (3) Å] is E.

With the exception of the O1w—H2w···O4ⁱⁱⁱ hydrogen bond, all the interactions listed in Table 1 combine to form supramolecular layers parallel to (203). These are connected into double layers via the O1w—H2w···O4ⁱⁱⁱ hydrogen bonds and π–π interactions [ring centroid···centroid distance = 3.7859 (19) Å, angle between rings = 3.22 (15)° for i: 1 - x, -y, 1 - z]. Layers stack without specific interactions between them (Fig. 2).

Experimental

A solution of 2-nitrophenylhydrazine and 2,6-dihydroxyacetophenone (2 mmol each) in ethanol (20 ml) was refluxed for 1 h, rotary evaporated and the residue recrystallized from methanol, m.p. 452–454 K.