N′-[(E)-3-Bromo-5-chloro-2-hy­droxy­benzyl­idene]furan-2-carbohydrazide

A Sundar; S Ranjith; G Rajagopal

doi:10.1107/S160053681401085X

. 2014 May 17;70(Pt 6):o670. doi: 10.1107/S160053681401085X

N′-[(E)-3-Bromo-5-chloro-2-hydroxybenzylidene]furan-2-carbohydrazide

A Sundar ^a, S Ranjith ^b, G Rajagopal ^a,^*

PMCID: PMC4051112 PMID: 24940251

Abstract

In the title compound, C₁₂H₈BrClN₂O₃, the furan ring makes a dihedral angle of 17.2 (2)° with the six-membered ring. An intramolecular O–H⋯N hydrogen bond stabilizes the molecular conformation. In the crystal, N–H⋯O hydrogen bonds connect the molecules into chains running along the c-axis direction. The crystal packing is additionally stabilized by C—H⋯O interactions into a three-dimensional supramolecular architecture.

Related literature

Heterocyclic carbohydrazides form stable metal chelates which find applications in molecular sensing, see: Bakir & Brown (2002 ▶). For the biological activity of hydrazones derived from isoniazid (systematic name: isonicotinohydrazide), see: Rollas & Kucukguzel (2007 ▶). For related structures, see: Prabhu et al. (2011 ▶); Bikas et al. (2010 ▶); Prasanna et al. (2013 ▶). graphic file with name e-70-0o670-scheme1.jpg

Experimental

Crystal data

C₁₂H₈BrClN₂O₃
M _r = 343.56
Monoclinic,
a = 16.7237 (9) Å
b = 7.7455 (4) Å
c = 10.1868 (5) Å
β = 93.557 (2)°
V = 1316.99 (12) Å³
Z = 4
Mo Kα radiation
μ = 3.33 mm⁻¹
T = 293 K
0.35 × 0.30 × 0.25 mm

Data collection

Bruker AAPEXII CCD Diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2004 ▶) T _min = 0.324, T _max = 0.435
13728 measured reflections
2996 independent reflections
2029 reflections with I > 2σ(I)
R _int = 0.032

Refinement

R[F ² > 2σ(F ²)] = 0.034
wR(F ²) = 0.085
S = 1.02
2996 reflections
172 parameters
H-atom parameters constrained
Δρ_max = 0.39 e Å⁻³
Δρ_min = −0.34 e Å⁻³

Data collection: APEX2 (Bruker, 2004 ▶); cell refinement: APEX2 and SAINT (Bruker, 2004 ▶); data reduction: SAINT and XPREP (Bruker, 2004 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ▶); software used to prepare material for publication: PLATON (Spek, 2009 ▶).

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S160053681401085X/bt6980sup1.cif

e-70-0o670-sup1.cif^{(20.4KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S160053681401085X/bt6980Isup2.hkl

e-70-0o670-Isup2.hkl^{(144KB, hkl)}

Click here for additional data file.^{(2KB, cml)}

Supporting information file. DOI: 10.1107/S160053681401085X/bt6980Isup3.cml

CCDC reference: 1002445

Additional supporting information: 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—H1A⋯O2ⁱ	0.86	2.14	2.953 (2)	157
C3—H3⋯O1ⁱⁱ	0.93	2.44	3.324 (3)	159
C6—H6⋯O2ⁱ	0.93	2.50	3.263 (3)	139
O3—H3A⋯N2	0.82	1.84	2.564 (3)	146

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

Acknowledgments

The authors wish to acknowledge the SAIF, IIT Madras, for the data collection.

supplementary crystallographic information

1. Comment

Heterocyclic carbohydrazides are compounds with a wide spectrum of biological and analytical applications. They form stable metal chelates which find applications in molecular sensing (Bakir & Brown, 2002). A number of hydrazones derived from isoniazid were reported to be active antitubercular agents and were found to be less toxic than isoniazid (Rollas & Kucukguzel, 2007). Against this background, and in order to obtain detailed information on the molecular conformation in the solid state, an X-ray study of the title compound was carried out.

The X-ray analysis confirms the molecular structure and atom connectivity as illustrated in Fig. 1. The molecule exists in a E configuration with respect to the C6=N2 bond, with the C7—C6—N2—N1 torsion angle of 179.1 (2)°. The bond lengths and angles in the carbohydrazide group of the title compound can be compared with the related structures (Prabhu et al., 2011; Bikas et al., 2010). The furan ring makes a dihedral angle of 17.2 (2)° with the six-membered ring. The N2—N1—C5—O2 torsion angle of -0.1 (4)° indicates the cis configuration of the O2 atom with respect to the hydrazine nitrogen atom N2. The bond distances C6═N2 [1.275 (3) Å] and C5═O2 [1.224 (3) Å] are very close to the formal double C═N and C═O bond lengths (Prasanna, et al., 2013) confirming that the carbohydrazide exists in solid state as an amido tautomer. An intramolecular O–H···N hydrogen bond stabilized the molecular conformation. Intermolecular N–H···O hydrogen bonds connect the molecules to chains running along the c axis. The crystal packing is further stabilized by C–H···O hydrogen bonds.

2. Experimental

N'-[(E)-(3-bromo-5-chloro-2-hydroxyphenyl)methylidene]furan-2-carbohydrazide, ligand was synthesized by Schiff-base condensation furan-2-carbohydrazide and 3-bromo-5-chlorosalicylaldehyde as shown in Scheme-1. 3-bromo-5-chloro salicylaldehyde (3.0 mmol) in methanol (0.75 g) was stirred in a round bottom flask followed by drop wise addition of methanolic solution of furan-2-carbohydrazide (3.0 mmol). The reaction mixture was stirred for 3 h. The resulting white solid was removed by filtration and washed with cold ethanol and dried in vacuum over anhydrous CaCl₂·M.p:180°C, yield: 80%. Single crystals suitable for the X-ray diffraction are obtained by slow evaporation of a solution of the title compound in DMF at room temperature.