N′-[(5-Methyl-3-oxo-2-phenyl-2,3-dihydro-1H-pyrazol-4-yl)(thio­phen-2-yl)methyl­idene]benzohydrazide

Hualing Zhu; Jinhua Zhu; Luxia Bu; Jun Shi; Juan Wang

doi:10.1107/S1600536812014821

. 2012 Apr 13;68(Pt 5):o1368–o1369. doi: 10.1107/S1600536812014821

N′-[(5-Methyl-3-oxo-2-phenyl-2,3-dihydro-1H-pyrazol-4-yl)(thiophen-2-yl)methylidene]benzohydrazide

Hualing Zhu ^a,^*, Jinhua Zhu ^b, Luxia Bu ^c, Jun Shi ^a, Juan Wang ^a

PMCID: PMC3344500 PMID: 22590262

Abstract

In the title compound, C₂₂H₁₈N₄O₂S, the seven-membered ring generated by an intramolecular N—H⋯O hydrogen bond adopts an envelope conformation in both of the two independent molecules in the asymmetric unit. In the crystal, molecules are linked into C(9) chains along [100] by N—H⋯O hydrogen bonds. The molecules are also weakly linked by C—H⋯O and C—H⋯N interactions, forming dimers with edge-connected R ₂ ²(9) rings. The dimers are interlinked by further weak C—H⋯N hydrogen bonds into chains along [010].

Related literature

For the biological activity of hydrazones, see: Mahalingam et al. (2009 ▶); Kocyigit-Kaymakcioglu et al. (2009 ▶); Zhang et al. (2007 ▶); Gemma et al. (2006 ▶). For uses of hydrazones, see: Gupta et al. (2007 ▶). For applications of pyrazolone derivatives, see: Li et al. (2000 ▶); Shi et al. (2005 ▶); Zhang et al. (2008 ▶). For related structures, see: Qiu (2009 ▶); Ren (2009 ▶).

Experimental

Crystal data

C₂₂H₁₈N₄O₂S
M _r = 402.46
Orthorhombic,
a = 13.562 (5) Å
b = 16.729 (6) Å
c = 17.258 (6) Å
V = 3916 (2) Å³
Z = 8
Mo Kα radiation
μ = 0.19 mm⁻¹
T = 113 K
0.20 × 0.18 × 0.12 mm

Data collection

Rigaku Saturn724 CCD diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2008 ▶) T _min = 0.963, T _max = 0.977
41426 measured reflections
9266 independent reflections
7812 reflections with I > 2σ(I)
R _int = 0.082

Refinement

R[F ² > 2σ(F ²)] = 0.050
wR(F ²) = 0.103
S = 1.00
9266 reflections
541 parameters
7 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.53 e Å⁻³
Δρ_min = −0.57 e Å⁻³
Absolute structure: Flack (1983 ▶), 4123 Friedel pairs
Flack parameter: −0.01 (6)

Data collection: CrystalClear (Rigaku, 2008 ▶); cell refinement: CrystalClear ; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: CrystalStructure (Rigaku, 2008 ▶).

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812014821/fj2536sup1.cif

e-68-o1368-sup1.cif^{(43.9KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812014821/fj2536Isup2.hkl

e-68-o1368-Isup2.hkl^{(444.1KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536812014821/fj2536Isup3.cml

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
N2—H2A⋯O2ⁱ	0.91 (1)	1.79 (1)	2.677 (3)	165 (2)
C15—H15⋯O3ⁱⁱ	0.95	2.44	3.383 (3)	171
N6—H6A⋯O4ⁱⁱⁱ	0.89 (1)	1.80 (1)	2.674 (3)	167 (3)
C36—H36⋯N3^iv	0.95	2.63	3.326 (3)	131
C14—H14⋯N7ⁱⁱ	0.95	2.55	3.322 (3)	139
N4—H4A⋯O1	0.91 (1)	1.93 (2)	2.757 (3)	152 (2)
N8—H8A⋯O3	0.91 (1)	1.86 (1)	2.715 (3)	157 (2)

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

Acknowledgments

The authors are grateful for financial support from the Spark Program Foundation of the Science and Technology Department of China (research No. 2010 GA610009). This work was supported by the Tianjin City Science and Technology Support Planning Project under grant No. 09ZCKFSF01200. The authors also thank the Natural Science and Technology Committee of Tianjin Agricultural College for financial support (research No. 2011 N06).

supplementary crystallographic information

Comment

Hydrazones derived from the condensation reactions of hydrazides with aldehydes or ketones show excellent biological properties, such as antimicrobial(Mahalingam et al., 2009), antitubercular(Kocyigit-Kaymakcioglu et al., 2009), anticancer (Zhang et al.,2007) and antimalarial (Gemma et al.,2006). The hydrazones are also important for their use as plasticizers and stabilizers for polymers, polymerization initiators, antioxidants and as indicators (Gupta et al., 2007). Derivatives of 1-phenyl-3-methyl-4-acyl-5-pyrazolone have found extensive application in coordination chemistry (Shi et al., 2005) and in antibacterial activation (Zhang et al., 2008; Li et al., 2000). Recently, a large number of hydrazone compounds have been reported (Qiu, 2009; Ren et al., 2009). The possible properties and using of hydrazones and the pyrazolone derivatives make it attractive to study these compounds.

The molecular structure of the title compound is shown in Fig. 1. There are two kinds of molecules in the asymmetric unit, which partly differ from each other geometrically. For example, the distance being 1.925 (15) Å between H4A and O1 of the hydrogen bond N4—H4A···O1 in the first kind of molecules is longer than that of the hydrogen bond N8—H8A···O3 in the second kind of molecules which is 1.855 (13) Å. In each independent molecule, the seven-membered ring generated by the intramolecular N—H···O hydrogen bond adopts an envelope conformation. The coplanar atom O1,C7,C8, C11(with the largest deviation of -0.0229 (23) Å for atom C8) and the coplanar atom O3,C29,C30, C33(with the largest deviation of -0.0061 (22) Å for atom C29) form the mean planes of the envelopes, the mean planes and the bonded pyrazole ring are essentially planar, with the dihedral angle of 4.26 (11) ° and 0.56 (9) ° respectively. Plane of N3,N4, H4A and Plane of N7,N8, H8A form the up-warping parts of the envelopes, making a dihedral angle of 61.07 (9)° and 63.20 (98)° with the corresponding mean planes respectively. The pyrazole rings of the two molecules make dihedral angles of 23.16 (8)°, 58.23 (8)°, 31.23 (7)° and 20.06 (7)°, 52.36 (8)°, 20.46 (7)° with the benzene ring of pyrazolone, the thiophen ring and benzene ring of benzoyl hydrazine, respectively.

Two intermolecular N2—H2A···O2 and N6—H6A···O4 hydrogen bonds are observed in the structure(Table1,Fig.2), which link the molecules to form chains of molecules C(9) along [100]. N2 acts as a hydrogen-bond donor to atom O2 at (x + 1/2, 1.5 - y, 2 - z), N6 acts as a hydrogen-bond donor to atom O4 at (x + 1/2, 1/2 - y, - z). Weak C15—H15···O3 and C14—H14···N7 interactions link the molecules to form dimmers with edge-connected R₂²(9) rings, the dimmers are interlinked by weak interaction C36–H36···N3 into one dimensional chains along [010] (Table 1, Fig. 3).

Experimental

The title compound was synthesized by refluxing the mixture of 1-phenyl-3-methyl-4-(2-thenoyl)pyrazolone-5 (30m mol) and benzoyl hydrazine (30m mol) in ethanol (150 ml) over a steam bath for about 6 h, then the solution was cooled down to room temperature. After seven days, pale yellow block was obtained and dried in air. The product was recrystallized from ethanol which afforded pale yellow crystals suitable for X–ray analysis.