2-[5-Methyl-2-(propan-2-yl)phen­oxy]-N′-{2-[5-methyl-2-(propan-2-yl)phen­oxy]acet­yl}acetohydrazide

Hoong-Kun Fun; Ching Kheng Quah; Nithinchandra; Balakrishna Kalluraya

doi:10.1107/S1600536811033964

. 2011 Aug 27;67(Pt 9):o2414. doi: 10.1107/S1600536811033964

2-[5-Methyl-2-(propan-2-yl)phenoxy]-N′-{2-[5-methyl-2-(propan-2-yl)phenoxy]acetyl}acetohydrazide

Hoong-Kun Fun ^a,^*,^‡, Ching Kheng Quah ^a,^§, Nithinchandra ^b, Balakrishna Kalluraya ^b

PMCID: PMC3200946 PMID: 22059000

Abstract

The complete molecule of the title compound, C₂₄H₃₂N₂O₄, is generated by a crystallographic inversion center. The 1,2-diethylhydrazine moiety is nearly planar, with a maximum deviation of 0.024 (1) Å, and is inclined at a dihedral angle of 54.20 (4)° with the phenyl ring. In the crystal, [001] chains are formed, with adjacent molecules in the chain linked by pair of intermolecular N—H⋯O hydrogen bonds, generating R ² ₂(10) ring motifs. Intermolecular C—H⋯O hydrogen bonds and C—H⋯π interactions are also observed.

Related literature

For general background to and the biological activity of hydrazides, see: Bedia et al. (2006 ▶); Rollas et al. (2002 ▶); Terzioglu & Gürsoy (2003 ▶); Bratenko et al. (1999 ▶); Rai et al. (2008 ▶). For standard bond-length data, see: Allen et al. (1987 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶). For the stability of the temperature controller used for the data collection, see: Cosier & Glazer (1986 ▶).

Experimental

Crystal data

C₂₄H₃₂N₂O₄
M _r = 412.52
Orthorhombic,
a = 23.6018 (8) Å
b = 11.2077 (4) Å
c = 8.6653 (3) Å
V = 2292.16 (14) Å³
Z = 4
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 100 K
0.98 × 0.23 × 0.18 mm

Data collection

Bruker SMART APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T _min = 0.914, T _max = 0.986
38738 measured reflections
3337 independent reflections
2946 reflections with I > 2σ(I)
R _int = 0.030

Refinement

R[F ² > 2σ(F ²)] = 0.041
wR(F ²) = 0.111
S = 1.04
3337 reflections
143 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.34 e Å⁻³
Δρ_min = −0.21 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/S1600536811033964/hb6377sup1.cif

e-67-o2414-sup1.cif^{(17.1KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811033964/hb6377Isup2.hkl

e-67-o2414-Isup2.hkl^{(163.8KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536811033964/hb6377Isup3.cml

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

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

Cg1 is the centroid of the C1–C6 phenyl ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N1⋯O2ⁱ	0.902 (16)	1.916 (15)	2.7759 (11)	158.8 (13)
C11—H11A⋯O2ⁱⁱ	0.96	2.58	3.4830 (14)	157
C7—H7B⋯Cg1ⁱⁱⁱ	0.97	2.68	3.3706 (10)	129

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

Acknowledgments

HKF and CKQ thank Universiti Sains Malaysia for the Research University Grant (No. 1001/PFIZIK/811160).

supplementary crystallographic information

Comment

Hydrazides have been demonstrated to possess antimicrobial, anticonvulsant, analgesic, antiinflammatory, antiplatelet, antitubercular, anticancer and antitumoral activities (Bedia et al., 2006; Rollas et al., 2002; Terzioglu & Gürsoy, 2003). These are key intermediates in the preparation of hydrazones. Hydrazones are versatile intermediates and important building blocks. Hydrazones of aliphatic and aromatic methyl ketones yield pyrazole-4-carboxaldehyde on formylation with Vilsmeier reagent (Bratenko et al., 1999). Aryl hydrazones are important building blocks for the synthesis of a variety of heterocyclic compounds such as pyrazolines and pyrazoles (Rai et al., 2008). The condensation of ethyl [5-methyl-2-(propan-2-yl)phenoxy]acetate with hydrazides of corresponding ester in presence of a catalytic amount of sodium acetate yielded the titled compound. The hydrazides are in turn obtained by refluxing ester with hydrazine hydrate in presence of ethanol .

The title molecule, Fig. 1, is lying across a crystallographic inversion center (symmetry code: -x+1, -y+1, -z). The 1,2-diethylhydrazine moeity (O2/O2A/N1/N1A/C7/C7A/C8/C8A) is nearly planar, with a maximum deviation of 0.024 (1) Å at atoms N1 and N1A, and is inclined at an angle of 54.20 (4)° with the phenyl ring (C1-C6). Bond lengths (Allen et al., 1987) and angles are within normal ranges.

In the crystal packing, the molecules are linked via a pair of intermolecular N1–H1N1···O2 hydrogen bonds (Table 1), generating R²₂ (10) ring motifs (Bernstein et al., 1995). The molecules are further linked into one-dimensional chains along [001] via adjacent ring motifs and intermolecular C11–H11A···O2 hydrogen bonds (Table 1). The crystal structure is further stabilized by C7—H7B···Cg1 (Table 1) interactions, where Cg1 is the centroid of the C1-C6 phenyl ring.

Experimental

2-[5-Methyl-2-(propan-2-yl)phenoxy]acethydrazide (0.01 mol) and ethyl [5-methyl-2-(propan-2-yl)phenoxy]acetate (0.01 mol) in ethanol and a catalytic amount of anhydrous sodium acetate was refluxed for 2-3 h. The excess of ethanol was removed by distillation and the reaction mixture was kept overnight. The solid product separated was filtered. It was then recrystallized from ethanol. Colourless needles were obtained from ethanol by slow evaporation.