2-(4-Bromo­phen­oxy)propanohydrazide

Tashfeen Akhtar; M Khawar Rauf; Masahiro Ebihara; Shahid Hameed

doi:10.1107/S1600536809003134

. 2009 Jan 31;65(Pt 2):o441. doi: 10.1107/S1600536809003134

2-(4-Bromophenoxy)propanohydrazide

Tashfeen Akhtar ^a, M Khawar Rauf ^a, Masahiro Ebihara ^b, Shahid Hameed ^a,^*

PMCID: PMC2968209 PMID: 21582026

Abstract

The title compound, C₉H₁₁BrN₂O₂, is an important intermediate for the synthesis of heterocyclic compounds such as azoles, 2,5-disubstituted-1,3,4-oxadiazoles and 5-substituted 2-mercapto-1,3,4-oxadiazoles. The bromophenoxy group subtends a dihedral angle of 82.81 (7)° with the plane passing through the propanohydrazide moiety. The crystal structure is stabilized by intermolecular N—H⋯O hydrogen bonds that form columns extending along the b axis.

Related literature

For carboxyhydrazide derivatives with biological activities, see: Belkadi & Othman (2006 ▶); Goswami et al. (1984 ▶); Akhtar et al. (2008 ▶); Akhtar, Hameed et al. (2007 ▶); Ahmad et al. (1996 ▶); Akhtar et al. (2006 ▶); For related structures, see: Akhtar, Khawar Rauf et al. (2007 ▶); Zheng (2008 ▶).

Experimental

Crystal data

C₉H₁₁BrN₂O₂
M _r = 259.11
Monoclinic,
a = 10.2598 (14) Å
b = 4.8009 (7) Å
c = 23.322 (3) Å
β = 112.712 (6)°
V = 1059.7 (3) Å³
Z = 4
Mo Kα radiation
μ = 3.86 mm⁻¹
T = 113 (2) K
0.50 × 0.30 × 0.20 mm

Data collection

Rigaku/MSC Mercury CCD diffractometer
Absorption correction: integration (NUMABS; Higashi, 1999) T _min = 0.531, T _max = 0.759
8296 measured reflections
2418 independent reflections
2201 reflections with I > 2σ(I)
R _int = 0.039

Refinement

R[F ² > 2σ(F ²)] = 0.048
wR(F ²) = 0.076
S = 1.20
2418 reflections
137 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.59 e Å⁻³
Δρ_min = −0.75 e Å⁻³

Data collection: CrystalClear (Molecular Structure Corporation & Rigaku, 2001 ▶); cell refinement: CrystalClear; data reduction: TEXSAN (Molecular Structure Corporation & Rigaku, 2004 ▶); program(s) used to solve structure: SIR97 (Altomare et al., 1999 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEPII (Johnson, 1976 ▶); software used to prepare material for publication: SHELXL97 and TEXSAN.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809003134/si2151sup1.cif

e-65-0o441-sup1.cif^{(15.3KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809003134/si2151Isup2.hkl

e-65-0o441-Isup2.hkl^{(118.8KB, 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—H1⋯O1ⁱ	0.85 (3)	1.97 (3)	2.812 (3)	170 (3)
N2—H2A⋯O1ⁱⁱ	0.83 (3)	2.33 (3)	3.127 (3)	161 (3)

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

Acknowledgments

MKR is grateful to the HEC–Pakistan for financial support for a PhD program under scholarship No. ILC-0363104.

supplementary crystallographic information

Comment

Carboxylic acid hydrazides are important biological agents and intermediates in the synthesis of biologically active heterocycles with two nitrogen atoms at adjacent positions (Belkadi & Othman, 2006). The hydrazides when treated with isocyanates or isothiocyanates afford semicarbazides and thiosemicarbazides, respectively (Goswami et al., 1984). These are important intermediates in the synthesis of azoles under acidic or basic conditions (Akhtar et al., 2007a; Ahmad et al., 1996). In continuation of our previous studies (Akhtar et al., 2006; Akhtar et al., 2007b), the title compound, 2-(4-bromophenoxy)propane hydrazide,was synthesized as an intermediate in the synthesis of certain azole derivatives (Akhtar et al., 2008). The C—N bond length of 1.330 (3)Å is similar to C—N 1.321 (3) Å, indicating the single bond character.The N1—N2 bond length of 1.415 (3) Å in the title compound is longer than the N—N distance [1.366 (3)Å] in the crystal structure of N-propionyl-N'-(3-hydroxy-2-naphthoyl)hydrazide (Zheng, 2008). The Bromo group is coplanar with the phenyl plane C3/C4/C5/C6/C7/C8 with deviation from the plane of 0.030 (4) Å. The molecular packing diagram (Fig. 2) shows the presence of two intermolecular N—H···O hydrogen bonds, (Table 1), one of which is generated via translation along [0 1 0], the other via inversion symmetry.

Experimental

Methyl 2-(4-bromophenoxy)propionate (5.0 g, 0.0193 mol) was dissolved in methanol (20 ml) and hydrazine hydrate (80%, 3.50 mL, 0.0679 mol) added slowly with stirring. The reaction mixture was set to reflux. After completion of the reaction (TLC, 6 hrs), the reaction mixture was concentrated and poured to water. The precipitated solid was filtered and recrystallized from ethanol/ water. The spectroscopic and physical characterization data will be reported separately.