2-[5-(1,3-Benzodioxol-5-yl)-3-ferrocenyl-4,5-dihydro-1H-pyrazol-1-yl]-4-phenyl-1,3-thia­zole

Wei-Yong Liu; Yong-Sheng Xie; Bai-Shan Wang; Bao-Xiang Zhao

doi:10.1107/S160053681003638X

. 2010 Sep 18;66(Pt 10):m1275. doi: 10.1107/S160053681003638X

2-[5-(1,3-Benzodioxol-5-yl)-3-ferrocenyl-4,5-dihydro-1H-pyrazol-1-yl]-4-phenyl-1,3-thiazole

Wei-Yong Liu ^a, Yong-Sheng Xie ^b, Bai-Shan Wang ^a, Bao-Xiang Zhao ^a,^*

PMCID: PMC2983240 PMID: 21587419

Abstract

In the title compound, [Fe(C₅H₅)(C₂₄H₁₈N₃O₂S)], the pyrazoline ring adopts a twist conformation. The thiazole ring forms dihedral angles of 83.7 (2) and 34.4 (2)° with the benzene ring of the benzodioxole ring and the fused phenyl ring, respectively. The molecular conformation is stabilized by an intramolecular C—H⋯π interaction. The crystal packing features intermolecular C—H⋯N, C—H⋯O hydrogen bonds and weak C—H⋯π interactions.

Related literature

For the biological activity of ferrocenyl derivatives, see: Jaouen et al. (2004 ▶); Xie et al. (2008 ▶, 2010 ▶). For the crystal structures of pyrazoline derivatives, see: Gong et al. (2010 ▶). For puckering parameters, see: Cremer & Pople (1975 ▶).

Experimental

Crystal data

[Fe(C₅H₅)(C₂₄H₁₈N₃O₂S)]
M _r = 533.41
Triclinic,
a = 10.228 (5) Å
b = 11.018 (5) Å
c = 12.604 (6) Å
α = 107.776 (8)°
β = 100.416 (8)°
γ = 112.767 (7)°
V = 1172.7 (10) Å³
Z = 2
Mo Kα radiation
μ = 0.77 mm⁻¹
T = 293 K
0.15 × 0.10 × 0.10 mm

Data collection

Bruker SMART area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.894, T _max = 0.927
6579 measured reflections
4716 independent reflections
3140 reflections with I > 2σ(I)
R _int = 0.024

Refinement

R[F ² > 2σ(F ²)] = 0.050
wR(F ²) = 0.124
S = 1.02
4716 reflections
325 parameters
H-atom parameters constrained
Δρ_max = 0.30 e Å⁻³
Δρ_min = −0.30 e Å⁻³

Data collection: SMART (Bruker, 2004 ▶); cell refinement: SAINT (Bruker, 2004 ▶); 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.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S160053681003638X/rz2480sup1.cif

e-66-m1275-sup1.cif^{(23.5KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S160053681003638X/rz2480Isup2.hkl

e-66-m1275-Isup2.hkl^{(231KB, hkl)}

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

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

Cg1, Cg2, Cg3 and Cg4 are the centroids of the C13–C18, C25–C29, C1–C6 and C20–C24 rings, respectively.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C15—H15⋯N3ⁱ	0.93	2.49	3.402 (6)	168
C28—H28⋯O2ⁱⁱ	0.98	2.43	3.337 (6)	153
C22—H22⋯Cg1ⁱⁱⁱ	0.98	2.97	3.709 (5)	133
C26—H26⋯Cg1	0.98	2.90	3.844 (5)	163
C5—H5⋯Cg2^iv	0.93	2.91	3.658 (5)	138
C8—H8⋯Cg3^v	0.93	2.98	3.590 (4)	125
C11—H11A⋯Cg4^vi	0.97	2.85	3.670 (4)	142

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

Acknowledgments

This study was supported by the Natural Science Foundation of Shandong Province (Z2008B10).

supplementary crystallographic information

Comment

Derivatives of pyrazoline possess widespread pharmacological activities. Among them ferrocenyl compounds display interesting antitumor (Jaouen et al., 2004) activities. In our recent study, incorporation of a ferrocene fragment into a heterocyclic ring may enhance their antitumor activities (Xie et al., 2008; Xie et al., 2010, which is rationalized as being due to their different membrane permeation properties and anomalous metabolism. In continuation of previous structural studies of pyrazoline derivatives (Gong et al., 2010), the title compound (I) was synthesized and its crystal structure was determined.

The molecular structure of the title compound is shown in Fig. 1. The conformation of the central pyrazole ring is twist on C11—C12 as indicated by the ring-puckering parameters q2 = 0.204 (4) Å and φ2 = 309.1 (11) ° (Cremer & Pople, 1975), with maximum deviations from the mean plane of the ring of 0.120 (4) and -0.125 (4) Å for atoms C11 and C12, respectively. The thiazole ring forms dihedral angles with the benzene ring of the benzodioxole ring (C13–C18) and the C20–C24 cyclopentadienyl ring of 83.7 (2)° and 47.7 (2)°, respectively, while the dihedral angle between the thiazole and the conjoint phenyl ring (C1–C6) is 34.4 (2)°. The torsion angle C20—Cg4—Cg2—C26 (Cg4 and Cg2 are the centroids of the C20–C24 and C25–C29 rings, respectively) of 3.8° indicates an almost eclipsed orientation of two cyclopentadienyl rings. The molecular conformation is stabilized by an intramolecular C—H···π (C26–H26···Cg1; Table 1) interaction. In the crystal packing (Fig. 2), zigzag chains are formed through intermolecular C—H···N and C—H···O hydrogen bonds, wherein each molecule is connected to two neighbouring molecules. Furthermore, the structure is stabilized by weak intermolecular C—H···π hydrogen contacts (Table 1).

Experimental

5-(Benzo[d][1,3]dioxol-5-yl)-3-ferrocenyl-4,5-dihydro-1H-pyrazole-1-carbothioamide (400 mg, 0.92 mmol), 2-bromo-1-phenylethanone (182 mg, 0.92 mmol) and dichloromethane (8 mL) were added to a round-bottomed flask. The mixture was stirred and heated at reflux under nitrogen for 2 h. The solvent was removed on a rotary evaporator. The residue was purified by column chromatography (silica gel; petroleum ether–EtOAc 3:1 v/v) to afford title compound. Single crystals suitable for X-ray analysis were obtained by slow evaporation of a solution of the solid in dichloromethane at room temperature for 3 days.