N′-[(Z)-4-(Dimethyl­amino)benzyl­idene]-4-nitro­benzohydrazide mono­hydrate

Hoong-Kun Fun; Samuel Robinson Jebas; K V Sujith; P S Patil; B Kalluraya

doi:10.1107/S1600536808028328

. 2008 Sep 13;64(Pt 10):o1907–o1908. doi: 10.1107/S1600536808028328

N′-[(Z)-4-(Dimethylamino)benzylidene]-4-nitrobenzohydrazide monohydrate

Hoong-Kun Fun ^a,^*, Samuel Robinson Jebas ^a,^‡, K V Sujith ^b, P S Patil ^c,^§, B Kalluraya ^b

PMCID: PMC2959418 PMID: 21201117

Abstract

In the asymmetric unit of the title compound, C₁₆H₁₆N₄O₃·H₂O, there are two symmetry-independent hydrazide molecules with almost identical geometries, and two independent water molecules. The dihedral angles between the two benzene rings in the two hydrazide molecules are 0.11 (5) and 0.77 (5)°. In one molecule, an intramolecular C—H⋯O hydrogen bond generates a ring of graph-set motif S(5). Intermolecular N—H⋯O, O—H⋯O, O—H⋯N and C—H⋯O hydrogen bonds and π–π stacking interactions between the benzene rings [centroid–centroid distances in the range 3.5021 (6)–3.6403 (6) Å] are observed, together with O⋯O [2.7226 (11) Å], O⋯N [2.7072 (10) Å] and N⋯O [2.7072 (10)–2.8582 (12) Å] short contacts. The hydrazine molecules are stacked along the b axis and adjacent molecules are linked by water molecules.

Related literature

For related literature on hydrazones, see: Rollas & Küçükgüzel (2007 ▶); Singh et al. (1992 ▶); Ergenç & Günay (1998 ▶); Durgun et al. (1993 ▶). For a related structure, see: Fun et al. (2008 ▶). For bond-length data, see: Allen et al. (1987 ▶). For graph-set analysis of hydrogen bonding, see: Bernstein et al. (1995 ▶).

Experimental

Crystal data

C₁₆H₁₆N₄O₃·H₂O
M _r = 330.34
Triclinic,
a = 6.5866 (2) Å
b = 7.1337 (2) Å
c = 34.4059 (12) Å
α = 92.113 (2)°
β = 90.918 (2)°
γ = 107.816 (1)°
V = 1537.42 (8) Å³
Z = 4
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 100.0 (1) K
0.41 × 0.13 × 0.10 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T _min = 0.959, T _max = 0.990
52996 measured reflections
11039 independent reflections
8656 reflections with I > 2σ(I)
R _int = 0.028

Refinement

R[F ² > 2σ(F ²)] = 0.048
wR(F ²) = 0.155
S = 1.07
11039 reflections
461 parameters
8 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.45 e Å⁻³
Δρ_min = −0.36 e Å⁻³

Data collection: APEX2 (Bruker, 2005 ▶); cell refinement: APEX2; data reduction: SAINT (Bruker, 2005 ▶); program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2003 ▶).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808028328/is2331sup1.cif

e-64-o1907-sup1.cif^{(29.8KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808028328/is2331Isup2.hkl

e-64-o1907-Isup2.hkl^{(528.9KB, hkl)}

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
N1A—H1NA⋯O1Wⁱ	0.850 (9)	2.024 (10)	2.8582 (11)	166.8 (16)
O2W—H2W2⋯O1Wⁱⁱ	0.839 (8)	2.066 (9)	2.8892 (12)	166.9 (16)
O2W—H1W2⋯N2Bⁱⁱⁱ	0.838 (8)	2.435 (11)	3.1989 (12)	151.8 (16)
O2W—H1W2⋯O1Bⁱⁱⁱ	0.838 (8)	2.453 (13)	3.1535 (11)	141.6 (15)
O1W—H2W1⋯O1A^iv	0.848 (9)	1.907 (10)	2.7227 (10)	160.9 (18)
O1W—H2W1⋯N2A^iv	0.848 (9)	2.550 (16)	3.1072 (11)	124.2 (14)
N1B—H1NB⋯O2W^v	0.859 (9)	2.073 (9)	2.9260 (12)	171.5 (16)
O1W—H1W1⋯O1Bⁱⁱⁱ	0.842 (9)	1.997 (9)	2.8304 (12)	170.2 (17)
C1A—H1AA⋯O1Wⁱ	0.93	2.49	3.3025 (13)	146
C8A—H8AA⋯O1Wⁱ	0.93	2.51	3.2886 (13)	141
C1B—H1BA⋯O2W^v	0.93	2.41	3.3276 (13)	169
C5B—H5BA⋯O1B	0.93	2.42	2.7555 (13)	101
C8B—H8BA⋯O2W^v	0.93	2.48	3.2977 (14)	147
C15A—H15C⋯O2B^vi	0.96	2.58	3.4738 (15)	156
C15B—H15F⋯O2A^vii	0.96	2.58	3.4773 (15)	156

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

Acknowledgments

FHK and SRJ thank the Malaysian Government and Universiti Sains Malaysia for the Science Fund grant No. 305/PFIZIK/613312. SRJ thanks Universiti Sains Malaysia for a post-doctoral research fellowship.

supplementary crystallographic information

Comment

Hydrazones possessing an azometine —NHN═CH— proton constitute an important class of compounds for new drug development. Therefore, many researchers have synthesized these compounds as target structures and evaluated their biological activities. These observations have been the guides for the development of new hydrazones. Hydrazones containing an azometine —NHN═CH— proton are synthesized by heating the appropriate substituted hydrazines/hydrazides with aldehydes and ketones in solvents like ethanol, methanol, tetrahydrofuran, butanol, glacial acetic acid, ethanol-glacial acetic acid. Another synthetic route for the synthesis of hydrazones is the coupling of aryldiazonium salts with active hydrogen compounds (Rollas & Küçükgüzel, 2007). Hydrazide-hydrazones compounds are not only intermediates but they are also very effective organic compounds in their own right. When they are used as intermediates, coupling products can be synthesized by using the active hydrogen component of the —CONHN═CH— azometine group (Singh et al., 1992). N-Alkyl hydrazides can be synthesized by reduction of hydrazones with NaBH₄ (Ergenç & Günay, 1998), substituted 1,3,4-oxadiazolines can be synthesized when hydrazones are heated in the presence of acetic anhydride (Durgun et al., 1993). Prompted by these review and in continuation of our work (Fun et al., 2008), we herein report the crystal structure of the title compound, (I).

There are two independent molecules (A and B) in the asymmetric unit of (I), with similar geometries (Fig. 1.) The bond lengths and angles are found to have normal values (Allen et al., 1987). The dihedral angle formed by the benzene (C1A–C6A) and (C9A–C14A) rings is 0.11 (5)° in molecule A and that between the benzene (C1B–C6B) and (C9B–C14B) rings is 0.77 (5)° in molecule B, indicating that they are coplanar. In molecule B, an intramolecular C—H···O hydrogen bond generates an S(5) ring motif (Bernstein et al., 1995).

The crystal packing is consolidated by N—H···O, O—H···O, O—H···N and C—H···O inter and intramolecular hydrogen bonding (Table 1). Furthermore, the packing is strengthened by π–π stacking interactions involving the benzene (C1A–C6A) (Cg1) and the symmetry related (C9B–C14B) ring (Cg4) [Cg1···Cg4ⁱ = 3.5021 Å; Cg1—Cg4ⁱⁱ = 3.6403 (6) Å; symmetry codes: (i) 2-x, 1-y, 1-z; (ii) 2-x, -y, 1-z] and the benzene (C9A–C14A) ring (Cg2) and the symmetry related (C9B–C14B) ring (Cg3) [Cg2···Cg3ⁱ = 3.6065 (6) Å; Cg2—Cg3ⁱⁱ = 3.5274 (6) Å; symmetry codes: (i) 2-x, 1-y, 1-z; (ii) 2-x, -y, 1-z] together with O···O = 2.7226 (11) Å, O···N = 2.7072 (10) Å and N···O = 2.7072 (10)–2.8582 (12) Å short contacts. In the crystal packing, the molecules are stacked along the b axis and the adjacent molecules are linked by water molecules to form an infinite one dimensional chain along the [010] direction.

Experimental

The title compound was obtained by refluxing 4-nitrrophenyl hydrazide (0.01 mol) and 4-(dimethylamino)benzaldehyde (0.01 mol) in ethanol (30 ml) with the addition of 3 drops of concentrated Sulfuric acid for 3 h. Excess ethanol was removed from the reaction mixture under reduced pressure. The solid product obtained was filtered, washed with water and dried. Crystals suitable for X-ray analysis were obtained from ethanol by slow evaporation.