2-(4-Methyl­anilino)acetohydrazide

Hoong-Kun Fun; Chin Sing Yeap; Shridhar Malladi; Mahesh Padaki; Arun M Isloor

doi:10.1107/S1600536809033169

. 2009 Aug 26;65(Pt 9):o2234. doi: 10.1107/S1600536809033169

2-(4-Methylanilino)acetohydrazide

Hoong-Kun Fun ^a,^*,^‡, Chin Sing Yeap ^a,^§, Shridhar Malladi ^b, Mahesh Padaki ^b, Arun M Isloor ^b

PMCID: PMC2969944 PMID: 21577633

Abstract

In the title molecule, C₉H₁₃N₃O, the non-hydrogen atoms of the hydrazide group are essentially planar [maximum deviation = 0.028 (1) Å for one of the N atoms]. The mean plane of this group forms a dihedral angle of 83.34 (5)° with the plane of the benzene ring. In the crystal structure, molecules are linked by intermolecular N—H⋯O, N—H⋯N and weak C—H⋯N hydrogen bonds into a two-dimensional network parallel to the ab plane. Additional stabilization is provided by a weak C—H⋯π interaction.

Related literature

For the biological activity of hydrazide derivatives, see: Ozdemir et al. (2009 ▶); Khattab (2005 ▶). For synthetic applications, see: Isloor et al. (2009 ▶); Holla & Udupa (1992 ▶). For a related structure, see: Zhang & Shi (2009 ▶). For the stability of the temperature controller used for the data collection, see: Cosier & Glazer (1986 ▶).

Experimental

Crystal data

C₉H₁₃N₃O
M _r = 179.22
Triclinic,
a = 5.1481 (1) Å
b = 5.9262 (2) Å
c = 15.4756 (4) Å
α = 87.002 (2)°
β = 84.282 (2)°
γ = 82.849 (2)°
V = 465.76 (2) Å³
Z = 2
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 100 K
0.52 × 0.15 × 0.07 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T _min = 0.956, T _max = 0.994
11697 measured reflections
2703 independent reflections
2301 reflections with I > 2σ(I)
R _int = 0.026

Refinement

R[F ² > 2σ(F ²)] = 0.039
wR(F ²) = 0.110
S = 1.03
2703 reflections
170 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.34 e Å⁻³
Δρ_min = −0.20 e Å⁻³

Data collection: APEX2 (Bruker, 2005 ▶); cell refinement: SAINT (Bruker, 2005 ▶); 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 datablocks global, I. DOI: 10.1107/S1600536809033169/lh2884sup1.cif

e-65-o2234-sup1.cif^{(16.5KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809033169/lh2884Isup2.hkl

e-65-o2234-Isup2.hkl^{(132.7KB, 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
N1—H1N1⋯O1ⁱ	0.875 (17)	2.162 (17)	3.0271 (11)	170.0 (13)
N2—H1N2⋯N3ⁱⁱ	0.887 (17)	2.287 (16)	3.0302 (12)	141.3 (13)
N3—H1N3⋯O1ⁱⁱⁱ	0.901 (14)	2.252 (13)	3.0614 (11)	149.4 (13)
N3—H2N3⋯O1^iv	0.914 (14)	2.281 (15)	3.0889 (12)	147.1 (12)
C7—H7B⋯N3^v	0.991 (15)	2.545 (14)	3.4341 (14)	149.2 (11)
C9—H9B⋯Cg^iv	0.96 (2)	2.94 (2)	3.7469 (16)	142.3 (14)

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) ; (iv) ; (v) . Cg is the centroid of the C1–C6 benzene ring.

Acknowledgments

HKF thanks Universiti Sains Malaysia (USM) for the Research University Golden Goose grant No. 1001/PFIZIK/811012. CSY thanks USM for the award of a USM Fellowship. AMI is grateful to the Head of the Department of Chemistry and Director, NITK, Surathkal, India, for providing research facilities.

supplementary crystallographic information

Comment

In organic chemistry, hydrazides are a class of organic compounds sharing a common functional group characterized by a nitrogen to nitrogen covalent bond with 4 substituents with at least one of them being an acyl group. They are also starting materials for many heterocycles including 1,2,4-triazoles (Isloor et al., 2009; Holla & Udupa, 1992). Many hydrazide derivatives have showed significant biological activities (Ozdemir et al., 2009; Khattab, 2005). In view of the biological and synthetic importance of hydrazides, we hereby report the crystal structure of the title compound (I).

The bond lengths and angles of the title compound (I), (Fig. 1) are comparable to its related structure (Zhang & Shi, 2009). A maximum deviation of 0.028 (1) Å for atom N2 from the mean plane of the hydrazide group form by atoms O1, N2, N3, C7 and C8 indicates that it is essentially coplanar. The mean plane of the hydrazide makes dihedral angle of 83.34 (5)° with C1–C6 benzene ring. In the crystal structure, the molecules are linked by intermolecular N1—H1N1···O1ⁱ, N2—H1N2···N3ⁱⁱ, N3—H1N3···O1ⁱⁱⁱ, N3—H2N3···O1^iv and C7—H7B···N3^v (see Table 1 for symmetry codes) hydrogen bonds into two-dimensional network parallel to ab plane (Fig. 2, Table 1). The crystal structure is also stabilized by a C—H···π interaction (Table 1).

Experimental

Ethyl [(4-methylphenyl)amino]acetate (19.3 g, 0.1 mol) and hydrazine hydrate (99%, 0.2 mol) in ethanol (200 ml) was heated on a water-bath for 6 h. Excess of ethanol was removed by distillation. On cooling, colourless block-shaped single crystals of 2-[(4-methylphenyl)amino]acetohydrazide begin to separate (Holla & Udupa, 1992). It was collected by filtration and recrystallized from ethanol. Yield: 13.2 g, 73.7%, M.p. 423–426 K.