2-[(E)-4-Diethyl­amino-2-hy­droxy­benzyl­idene]hydrazinecarboxamide

Hoong-Kun Fun; Chin Wei Ooi; Shridhar Malladi; Arun M Isloor; Kammasandra N Shivananda

doi:10.1107/S1600536812000311

. 2012 Jan 14;68(Pt 2):o380. doi: 10.1107/S1600536812000311

2-[(E)-4-Diethylamino-2-hydroxybenzylidene]hydrazinecarboxamide

Hoong-Kun Fun ^a,^*,^‡, Chin Wei Ooi ^a, Shridhar Malladi ^b, Arun M Isloor ^b, Kammasandra N Shivananda ^c

PMCID: PMC3275058 PMID: 22347003

Abstract

Two molecules make up the asymmetric unit of the title compound, C₁₂H₁₈N₄O₂, and both feature an intramolecular O—H⋯N hydrogen bond, which generates an S(6) ring. The diethylamino group of one of the molecules is disordered over two sets of sites in a 0.59 (2):0.41 (2) ratio. In the crystal, N—H⋯O hydrogen bonds link the molecules into sheets lying parallel to the ac plane and C—H⋯π interactions are also observed.

Related literature

For a related structure and background references to semicarbazides and semicarbazones, see: Fun et al. (2011 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶). For reference bond-length data, see: Allen et al. (1987 ▶).

Experimental

Crystal data

C₁₂H₁₈N₄O₂
M _r = 250.30
Triclinic,
a = 8.794 (2) Å
b = 12.532 (3) Å
c = 14.292 (5) Å
α = 112.911 (7)°
β = 96.033 (7)°
γ = 107.296 (5)°
V = 1340.8 (7) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 296 K
0.35 × 0.12 × 0.03 mm

Data collection

Bruker APEX DUO CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T _min = 0.970, T _max = 0.998
15373 measured reflections
4567 independent reflections
2179 reflections with I > 2σ(I)
R _int = 0.082

Refinement

R[F ² > 2σ(F ²)] = 0.068
wR(F ²) = 0.220
S = 1.00
4567 reflections
378 parameters
H-atom parameters constrained
Δρ_max = 0.37 e Å⁻³
Δρ_min = −0.23 e Å⁻³

Data collection: APEX2 (Bruker, 2009 ▶); cell refinement: SAINT (Bruker, 2009 ▶); data reduction: SAINT; 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, 2009 ▶).

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812000311/hb6571sup1.cif

e-68-0o380-sup1.cif^{(28.2KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812000311/hb6571Isup2.hkl

e-68-0o380-Isup2.hkl^{(223.7KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536812000311/hb6571Isup3.cml

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

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

Cg1 is the centroid of the C1B–C6B benzene ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1A—H1O1⋯N2A	0.87	1.79	2.608 (4)	157
O1B—H2O1⋯N2B	0.87	1.91	2.654 (5)	142
N3A—H1N3⋯O2Aⁱ	0.95	1.90	2.832 (4)	168
N3B—H2N3⋯O2Bⁱⁱ	0.99	1.87	2.837 (4)	168
N4A—H1N4⋯O1B	0.79	2.40	3.077 (5)	144
N4A—H2N4⋯O2Bⁱⁱⁱ	0.90	2.01	2.901 (5)	172
N4B—H3N4⋯O2A^iv	0.78	2.14	2.911 (5)	167
N4B—H4N4⋯O1A	0.89	2.20	2.962 (5)	144
C9A—H9AB⋯Cg1^v	0.97	2.83	3.733 (19)	156
C10X—H10F⋯Cg1^v	0.96	2.71	3.46 (3)	136

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

Acknowledgments

HKF and CWO thank Universiti Sains Malaysia (USM) for the Research University Grant (1001/PFIZIK/811160). CWO also thanks the Malaysian Government and USM for the award of the post of research assistant under the Research University Grant (1001/PFIZIK/811151). AMI is thankful to the Department of Atomic Energy, Board for Research in Nuclear Sciences, Government of India, for the Young Scientist award.

supplementary crystallographic information

Comment

As part of our ongoing studies of semicarbazides (Fun et al., 2011), we now describe the structure of the title compound, (I).

The asymmetric unit of (I) consists of two crystallographically independent molecules A and B as shown in Fig. 1. The diethylamino group (N1/C9–C12) in the molecule A is observed to be disordered over two positions with a site-occupancy ratio of 0.59 (2): 0.41 (2). The intramolecular O1A—H1O1···N2A and O1B—H2O1···N2B hydrogen bonds generate S(6) ring motifs (Bernstein et al., 1995) in both molecules. The bond lengths (Allen et al., 1987) and angles are within normal ranges and are comparable to a related structure (Fun et al., 2011).

In the crystal (Fig. 2), N3A—H1N3···O2A, N3B—H2N3···O2B, N4B—H3N4···O2A, N4A—H2N4···O2B, N4A—H1N4···O1B and N4B—H4N4···O1A hydrogen bonds (Table 1) link the molecules into two-dimensional network parallel to the ac plane. The crystal structure is further consolidated by C—H···π interactions, involving the centroid of the benzene ring (C1B–C6B; Cg1; Table 1).

Experimental

Semicarbazide hydrochloride (0.86 g, 7.70 mmol) and freshly recrystallized sodium acetate (0.77 g, 9.40 mmol) were dissolved in water (10 ml). The reaction mixture was stirred at room temperature for 10 minutes. To this, N,N-diethylaminosalicylaldehyde (1.396 g, 7.23 mmol) was added and the mixture was shaken well. A little alcohol was added to dissolve the turbidity. The mixture was shaken for a further 10 minutes and allowed to stand. The title compound crystallizes out on standing for 6 h. The separated crystals were filtered, washed with cold water and recrystallized from ethanol. Yield: 1.4 g, 77.43%. M.p. 508–510 K.