(2E)-2-[1-(2-Hy­droxy-4-meth­oxy­phenyl)ethyl­idene]-N-phenyl­hydrazine­carbox­amide monohydrate

C F Annie; Jinsa Mary Jacob; M Sithambaresan; M R Prathapachandra Kurup

doi:10.1107/S1600536812039414

. 2012 Sep 22;68(Pt 10):o2985–o2986. doi: 10.1107/S1600536812039414

(2E)-2-[1-(2-Hydroxy-4-methoxyphenyl)ethylidene]-N-phenylhydrazinecarboxamide monohydrate

C F Annie ^a, Jinsa Mary Jacob ^a, M Sithambaresan ^b,^*, M R Prathapachandra Kurup ^a

PMCID: PMC3470348 PMID: 23125761

Abstract

The title compound, C₁₆H₁₇N₃O₃·H₂O, exists in the E conformation with respect to the azomethine C=N double bond. While the phenyl ring is almost coplanar with the central hydrazinecarboxamide group [dihedral angle = 14.18 (11)°], it is twisted slightly with respect to the other aromatic ring in the molecule, with a dihedral angle of 22.88 (13)°. The packing is dominated by O—H⋯O, N—H⋯O and C—H⋯O hydrogen-bond interactions, forming a three-dimensional supramolecular structure which is augmented by two types of C—H⋯π interactions. An intramolecular O—H⋯N interaction is also present in the molecule.

Related literature

For the application of hydrazinecarboxamides as enzyme inhibitors and as a source of self-complementary bidirectional hydrogen-bonding motifs, see: Lam et al. (1994 ▶); Chorev & Goodman (1993 ▶); Zhao et al. (1990 ▶). For the synthesis of related compounds, see: Sreekanth et al. (2004 ▶). For standard bond-length data, see: Allen et al. (1987 ▶). For related structures, see: Sithambaresan & Kurup (2011 ▶); Siji et al. (2010 ▶).

Experimental

Crystal data

C₁₆H₁₇N₃O₃·H₂O
M _r = 317.34
Monoclinic,
a = 12.4020 (18) Å
b = 13.7808 (19) Å
c = 9.3919 (10) Å
β = 96.813 (7)°
V = 1593.8 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 296 K
0.50 × 0.30 × 0.25 mm

Data collection

Bruker Kappa APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS (Bruker, 2004 ▶) T _min = 0.966, T _max = 0.976
12097 measured reflections
2809 independent reflections
1807 reflections with I > 2σ(I)
R _int = 0.083

Refinement

R[F ² > 2σ(F ²)] = 0.053
wR(F ²) = 0.172
S = 1.02
2809 reflections
230 parameters
6 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.22 e Å⁻³
Δρ_min = −0.19 e Å⁻³

Data collection: APEX2 (Bruker, 2004 ▶); cell refinement: APEX2 and SAINT (Bruker, 2004 ▶); data reduction: SAINT and XPREP (Bruker, 2004 ▶); program(s) used to solve structure: SHELXL97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶) and DIAMOND (Brandenburg, 2010 ▶); software used to prepare material for publication: SHELXL97 and publCIF (Westrip, 2010 ▶).

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812039414/bv2210sup1.cif

e-68-o2985-sup1.cif^{(25KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812039414/bv2210Isup2.hkl

e-68-o2985-Isup2.hkl^{(137.9KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536812039414/bv2210Isup3.cml

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

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

Cg1 is the centroid of the C1–C6 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2′⋯N1	0.88 (1)	1.71 (2)	2.526 (2)	154 (3)
N2—H2N⋯O1S ⁱ	0.88 (1)	2.08 (1)	2.900 (3)	154 (2)
N3—H3⋯O1S ⁱ	0.88 (1)	2.11 (2)	2.918 (3)	153 (3)
O1S—H1A⋯O2	0.86 (2)	2.12 (2)	2.925 (3)	156 (3)
O1S—H1B⋯O3ⁱⁱ	0.84 (2)	1.90 (2)	2.730 (3)	174 (3)
C8—H8C⋯O3ⁱⁱⁱ	0.96	2.51	3.457 (3)	167
C11—H11⋯O3	0.93	2.31	2.881 (3)	119
C13—H13⋯O1^iv	0.93	2.60	3.489 (3)	160
C8—H8A⋯Cg1^v	0.96	2.92	3.543 (3)	123
C16—H16C⋯Cg1^vi	0.96	2.79	3.645 (4)	148

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

Acknowledgments

CFA is grateful to the University Grants Commission, New Delhi, India, for the award of a Teacher Fellowship. The authors are grateful to the Sophisticated Analytical Instruments Facility, Cochin University of Science and Technology, Kochi 22, India, for the single-crystal X-ray diffraction measurements.

supplementary crystallographic information

Comment

Hydrazinecarboxamides have gained considerable importance in recent years in the design of enzyme inhibitors (Lam et al., 1994), as replacement for the amide (–CO–NH–) bond in peptidomimetics (Chorev & Goodman, 1993) and as sources of self-complementary bidirectional hydrogen bonding motif in supramolecular chemistry (Zhao et al., 1990). As a continuous work on the hydrazinecarboxamide compounds, a new hydrazinecarboxamide compound, (2E)-2-[1-(2-hydroxy-4-methoxyphenyl)ethylidene]-N-phenylhydrazinecarboxamide monohydrate, was prepared and structurally characterized. The ORTEP view of the title compound is shown in Fig. 1.

The compound crystallizes in monoclinic space group P2₁/c. The molecule adopts an E configuration with respect to C7═N1 bond (Sithambaresan & Kurup, 2011; Siji et al., 2010) and it exists in amido form with C9═O3 bond length of 1.212 (3) Å which is very close to a formal C═O bond length [1.21 Å] (Allen et al., 1987). The phenyl ring is almost coplanar with the central hydrazinecarboxamide moiety with maximum deviation of -0.060 (3) Å for the C1 atom. The two aromatic rings are twisted with dihedral angle of 22.88 (13)°.

While the intramolecular O—H···N and C—H···O hydrogen bonds increase the rigidity of the molecule, intermolecular O—H···O, N—H···O, C—H···O hydrogen bonding interactions (Table 1) links the adjacent molecules directly and through water molecule forming an infinite three-dimensional supramolecular structure in the lattice (Fig. 2). Phenylhydrazinecarboxamide molecules also interact through two types of C—H···π interactions (Fig. 3) with the H···π distances of 2.92 and 2.79 Å and very weak π–π interactions with a shortest centroid–centroid distance of 5.0552 (18) Å. The parallel arrangement of the molecules along b axis is shown in Fig. 4.

Experimental

The title compound was prepared by adapting a reported procedure (Sreekanth et al., 2004). To a warm ethanolic solution of N-phenylsemicarbazide (0.302 g, 2 mmol), an ethanolic solution of 1-(2-hydroxy-4-methoxyphenyl)ethanone (0.332 g, 2 mmol) was added and the resulting solution was refluxed for 3 h after adding three drops of glacial acetic acid. On cooling the solution colorless crystals were separated out. Single crystals suitable for X-ray diffraction studies were obtained by slow evaporation from its ethanolic solution.