1-Acetyl-5-ferrocenyl-3-phenyl-2-pyrazoline

Nevzat Karadayı; Günseli Turgut Cin; Seda Demirel; Abban Çakıcı; Orhan Büyükgüngör

doi:10.1107/S1600536808043298

. 2009 Jan 8;65(Pt 2):m127–m128. doi: 10.1107/S1600536808043298

1-Acetyl-5-ferrocenyl-3-phenyl-2-pyrazoline

Nevzat Karadayı ^a, Günseli Turgut Cin ^b, Seda Demirel ^b, Abban Çakıcı ^b, Orhan Büyükgüngör ^c,^*

PMCID: PMC2968248 PMID: 21581746

Abstract

In the title compound, [Fe(C₅H₅)(C₁₆H₁₅N₂O)], the pyrazoline ring and the phenyl ring are nearly coplanar, making a dihedral angle of 6.54 (2)°, while the substituted cyclopentadienyl ring is twisted out of the pyrazoline ring plane by 81.32 (1)°. The molecules in the crystal structure are held together by weak C—H⋯O intermolecular hydrogen bonds and two C—H⋯π interactions.

Related literature

For background to the applications of pyrazolines, see: Amr et al. (2006 ▶); Biot et al. (2004 ▶); Fang et al. (2003 ▶); Fouda et al. (2007 ▶); Guirado et al. (2004 ▶); Jaouen et al. (2004 ▶); Johnson et al. (2007 ▶); Küçükgüzel et al. (2000 ▶); Karthikeyan et al. (2007 ▶); Özdemir et al. (2007 ▶). For bond-length data, see: Jian et al. (2008 ▶). For related structures, see: Turgut Cin et al. (2008 ▶); Kudar et al. (2005 ▶); Köysal et al. (2005 ▶).

Experimental

Crystal data

[Fe(C₅H₅)(C₁₆H₁₅N₂O)]
M _r = 372.24
Monoclinic,
a = 6.0762 (4) Å
b = 43.155 (2) Å
c = 7.3512 (4) Å
β = 116.218 (4)°
V = 1729.33 (17) Å³
Z = 4
Mo Kα radiation
μ = 0.88 mm⁻¹
T = 296 (2) K
0.49 × 0.33 × 0.05 mm

Data collection

STOE IPDS 2 diffractometer
Absorption correction: integration (X-RED32; Stoe & Cie, 2002 ▶) T _min = 0.662, T _max = 0.962
15964 measured reflections
3256 independent reflections
2765 reflections with I > 2σ(I)
R _int = 0.045

Refinement

R[F ² > 2σ(F ²)] = 0.035
wR(F ²) = 0.093
S = 1.04
3256 reflections
227 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.23 e Å⁻³
Δρ_min = −0.46 e Å⁻³

Data collection: X-AREA (Stoe & Cie, 2002 ▶); cell refinement: X-AREA; data reduction: X-RED (Stoe & Cie, 2002 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEPIII (Farrugia, 1997 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶) and PLATON (Spek, 2003 ▶).

Supplementary Material

Crystal structure: contains datablocks I. DOI: 10.1107/S1600536808043298/at2695sup1.cif

e-65-0m127-sup1.cif^{(30.1KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808043298/at2695Isup2.hkl

e-65-0m127-Isup2.hkl^{(156.5KB, 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
C5—H5⋯O1ⁱ	0.93	2.70	3.599 (3)	163 (1)
C16—H16⋯O1ⁱⁱ	0.93	2.29	3.201 (3)	167 (1)
C17—H17⋯Cg1ⁱⁱⁱ	0.93	2.71	3.64 (4)	174 (1)
C11—H11A⋯Cg2^iv	0.96	2.60	3.51 (5)	158 (1)

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) ; (iv) . Cg1 and Cg2 are the centroids of the C17—C21 and C1—C6 rings, respectively.

Acknowledgments

The authors acknowledge the Research Board of Akdeniz University (grant No. BAP-2007.01.0105.001) for financial support and the Faculty of Arts and Sciences, Ondokuz Mayıs University, for the Stoe IPDS 2 diffractometer (purchased under grand F.279 of the University Research Fund).

supplementary crystallographic information

Comment

Pyrazolines are well known nitrogen-containing five-membered heterocyclic compounds. Condensation of nitrogen-containing binucleophilic agents with α, β unsaturated ketones is one of the most suitable synthetic pathways for 2-pyrazolines (Kudar et al., 2005), which possess widespread pharmaceutical properties such as antimicrobial (Küçükgüzel et al., 2000), anticonvulsant (Karthikeyan et al., 2007), antidepressant (Özdemir et al., 2007), antiandrogenic (Amr et al., 2006), antifungal and anti-inflammatory (Guirado et al., 2004) activities. Furthermore, N-acetylated 2-pyrazolines are inhibitors of kinesin spindle protein (KSP); potentially useful for the treatment cancer (Johnson et al., 2007). Metallocenes are also known to exhibit a wide range of biological activity. Among them ferrocenyl compounds display interesting antibacterial (Fouda et al., 2007), antitumor (Jaouen et al., 2004), antimalarial and antifungal (Biot et al., 2004) activities. Therefore, incorporation of a ferrocene fragment into a heterocyclic ring may enhance their biological activities or generate new medicinal properties (Fang et al., 2003). As a part of an ongoing investigation of the chemistry of ferrocenyl pyrazolines, 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 dihedral angle of 6.54 (2)° between pyrazoline ring and the phenyl ring indicates that they are conjugated with each other; this is accord with the C1—C7 bond [1.474 (3) Å], which has double-bond character (Jian et al., 2008). Furthermore, N1—C7 bond length [1.286 (3) Å] increased as a result of this conjugation. This observation is in good agreement with those reported for 1-acetyl-3-ferrocenyl-5-(2-nitrophenyl)-2-pyrazoline (Turgut Cin et al., 2008), 5-ferrocenyl-3-(p-methoxyphenyl)-1-(2-pyridyl) -2-pyrazoline (Kudar et al., 2005) and 3-(4-fluorophenyl)-N-methyl-5- (4-methylphenyl)-2-pyrazoline-1-thiocarboxamide (Köysal et al., 2005).

The Fe—Cg_s and Fe—Cg_as distances are 1.6454 (13)Å and 1.6510 (15) Å, respectively, and the Cg_s—Fe—Cg_as angle is 178.90 (8)°, where Cg_s and Cg_as are the centroids of the substituted and unsubstituted Cp rings. The small dihedral angle of 3.2963 (2)° between the unsubstituted and substituted Cp rings exposes that the two Cp rings are parallel to each other. The average C12—Cg_s—Cg_as—C20 torsion angle of 4.789 (2)° brings that the two Cp rings of the ferrocenyl group is nearly in an eclipsed conformation.

The pyrazoline ring and substituted Cp ring make a dihedral angle of 81.32 (1)°. The dihedral angle between the phenyl ring and substituted Cp ring is 75.82 (1)°, whereas the phenyl ring plane deviates from the unsubstituted Cp ring with an angle of 76.60 (1)°. The molecules in the crystal held together by two weak intermolecular C5—H5···O1 and C16—H16···O1 hydrogen bonds and two C—H···π interactions (Table 1, Fig. 2).

Experimental

A mixture of 3-ferrocenyl-1-phenyl-propen-2-one (0.32 mmol, 0.1 g), 80% hydrazine monohydrate (7.04 mmol, 0.45 g) and glacial acetic acid (10 ml) was refluxed under nitrogen atmosphere for 4 h. TLC indicated the formation of the reaction product. It was poured into ice-water to give orange solid. The participate was separated by filtration and washed with water. The solid product was dried at room temperature. Single crystals of the title compound suitable for X-ray measurements were obtained by recrystallization from methanol at room temperature (Yield 82%; m.p. 456–457 K). IR (KBr, cm^-1): 1647 (C=O), 1596 (C=N), 1580 (C=C), 1102 (C—N), 507 (Cp—Fe—Cp). ¹H-NMR (CDCl₃, p.p.m..): 2.33 (s, 1H, CH₃), 3.50 (dd, 1H, pyr.), 3.68 (dd, 1H, pyr.), 4.02 (s, 1H, Fc), 4.12 (s, 1H, Fc), 4.16 (s, 5H, Fc), 4.18 (s, 1H, Fc), 4.51 (s, 1H, Fc), 5.51 (dd, 1H, pyr.), 7.47–7.81 (m, 5H, Arom.). ¹³C-NMR (CDCl₃, p.p.m.): 22.04 (CH₃), 39.54 (pyr. CH₂), 55.37 (pyr. CH), 65.57 (C_Fc), 68.22 (C_Fc), 68.37 (C_Fc), 68.58 (C_Fc), 70.34 (C_Fc), 87.38 (C_Fcipso), 126.53 (C_phenyl), 128.81 (C_phenyl), 130.27 (C_phenyl), 131.59 (C_phenyl), 153.88 (pyr. C=N), 168.87 (C=O).