1-Acetyl-3-ferrocenyl-5-(2-nitro­phen­yl)-2-pyrazoline

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

doi:10.1107/S1600536808004236

. 2008 Mar 5;64(Pt 4):m514–m515. doi: 10.1107/S1600536808004236

1-Acetyl-3-ferrocenyl-5-(2-nitrophenyl)-2-pyrazoline

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

PMCID: PMC2960933 PMID: 21201984

Abstract

In the title compound, [Fe(C₅H₅)(C₁₆H₁₄N₃O₃)], the pyrazoline ring and the substituted cyclopentadienyl ring are nearly coplanar, with a dihedral angle of 8.17 (2)°, while the nitro-substituted benzene ring is twisted out of the pyrazoline ring plane by 70.76 (1)°. The molecules in the crystal structure are held together by three intermolecular C—H⋯O hydrogen bonds. There is also an intramolecular C—H⋯N hydrogen bond. The H atoms of the methyl group are disordered equally over two positions.

Related literature

For related literature, see: Amr et al. (2006 ▶); Biot et al. (2004 ▶); Cremer & Pople (1975 ▶); Fang et al. (2003 ▶); Fouda et al. (2007 ▶); Guirado et al. (2004 ▶); Jaouen et al. (2004 ▶); Karthikeyan et al. (2007 ▶); Küçükgüzel et al. (2000 ▶); Kudar et al. (2005 ▶); Özdemir et al. (2007 ▶); Shi et al. (2006a ▶,b ▶); Shi et al. (2006 ▶); Zora et al. (2006 ▶, 2008 ▶).

Experimental

Crystal data

[Fe(C₅H₅)(C₁₆H₁₄N₃O₃)]
M _r = 417.24
Orthorhombic,
a = 8.6691 (6) Å
b = 13.4779 (7) Å
c = 31.4930 (15) Å
V = 3679.7 (4) Å³
Z = 8
Mo Kα radiation
μ = 0.85 mm⁻¹
T = 296 K
0.50 × 0.31 × 0.06 mm

Data collection

Stoe IPDSII diffractometer
Absorption correction: integration (X-RED32; Stoe & Cie, 2002 ▶) T _min = 0.636, T _max = 0.862
17799 measured reflections
3613 independent reflections
2409 reflections with I > 2σ(I)
R _int = 0.061

Refinement

R[F ² > 2σ(F ²)] = 0.037
wR(F ²) = 0.086
S = 0.94
3613 reflections
253 parameters
H-atom parameters constrained
Δρ_max = 0.19 e Å⁻³
Δρ_min = −0.29 e Å⁻³

Data collection: X-AREA (Stoe & Cie, 2002 ▶); cell refinement: X-AREA; data reduction: X-RED32 (Stoe & Cie, 2002 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶) and PLATON (Spek, 2003 ▶).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808004236/hy2116sup1.cif

e-64-0m514-sup1.cif^{(30.8KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808004236/hy2116Isup2.hkl

e-64-0m514-Isup2.hkl^{(173.7KB, hkl)}

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

Table 1. Selected bond lengths (Å).

C12—Fe1	2.035 (3)
C13—Fe1	2.044 (3)
C14—Fe1	2.051 (3)
C15—Fe1	2.034 (3)
C16—Fe1	2.016 (3)
C17—Fe1	2.047 (3)
C18—Fe1	2.033 (3)
C19—Fe1	2.036 (3)
C20—Fe1	2.035 (3)
C21—Fe1	2.045 (3)

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Table 2. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C11—H11A⋯N3	0.96	2.29	2.788 (4)	112
C8—H8A⋯O3ⁱ	0.97	2.57	3.476 (3)	154
C8—H8B⋯O2ⁱⁱ	0.97	2.63	3.551 (4)	158
C21—H21⋯O2ⁱⁱ	0.93	2.46	3.136 (4)	130

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

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 IPDSII diffractometer purchased under grant F.279 of the University Research Fund.

supplementary crystallographic information

Comment

Pyrazolines are widely studied as 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. 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 was synthesized and its crystal structure was determined.

The molecular structure of the title compound is shown in Fig. 1. The puckering parameters (Cremer & Pople, 1975) are q₂=0.037 (3)Å and φ=43.3 (8)° for the pyrazoline ring, q₂=0.008 (3)Å and φ=156.3 (2)° for the substituted cyclopentadienyl (Cp) ring and q₂=0.004 (3)Å and φ=69.6 (5)° for the unsubstituted Cp ring. The dihedral angle of 8.17 (2)° between the pyrazoline ring and the substituted Cp ring indicates that they are conjugated with each other; this is in accord with the C9—C12 bond [1.456 (4) Å], showing a double-bond character (Shi et al., 2006a). Furthermore, N3—C9 bond length [1.284 (3) Å] increases as a result of this conjugation. This observation is in good agreement with those reported for 2,6-bis(3-ferrocenyl-5-methyl-1H-pyrazol-1-ylcarbonyl)pyridine (Shi et al., 2006b) and 1,3-bis(3-ferrocenyl-5-methyl-1H-pyrazol-1-ylcarbonyl)benzene (Shi et al., 2006).

The Fe—Cg_s and Fe—Cg_as distances are 1.6398 (14) and 1.6544 (14) Å, respectively, and the Cg_s—Fe—Cg_as angle is 177.78 (7)°, where Cg_s and Cg_as are the centroids of the substituted and unsubstituted Cp rings. The small dihedral angle of 3.68 (2)° between the unsubstituted and substituted Cp rings indicates that the two Cp rings are parallel to each other (Shi et al., 2006a). The C12—Cg_s—Cg_as—C20 torsion angle of 3.71 (2)° indicates that the two Cp rings of the ferrocenyl group is nearly in an eclipsed conformation, as was previously observed in a ferrocene-containing compound (Zora et al., 2008). The C—C bond distances in the Cp rings range from 1.389 (4) to 1.434 (4) Å, while Fe—C bond lengths range between 2.016 (3) and 2.051 (3)Å (Table 1), all of which are as expected (Zora et al., 2006).

The pyrazoline ring and the nitro substituted phenyl group make a dihedral angle of 70.76 (1)°. The dihedral angle between the nitro plane and pheny ring is 18.30 (5)°. The dihedral angles between the phenyl ring and the substituted and unsubstituted Cp planes are 76.16 (1) and 76.12 (1)°, respectively. The molecules in crystal are held together by three intermolecular C—H···O hydrogen bonds (Table 2; Fig. 2). There is one intramolecular C—H···N hydrogen bond.

Experimental

A mixture of 1-ferrocenyl-3-(2-nitrophenyl)-2-propenone (0.09 g, 0.24 mmol), 80% hydrazine hydrate (0.264 g, 5.28 mmol) and glacial acetic acid (10 ml) was refluxed under nitrogen atmosphere for 5 h. TLC indicated the formation of the reaction product. It was poured into ice-water to give dark 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 50.5%; m.p. 425–426 K). IR (KBr, cm^-1): 1653 (C?O), 1601 (C?C), 1574 (C?N), 1527 (asym N?O), 1333 (sym N?O), 1107 (C—N). ¹H-NMR (CDCl₃, p.p.m.): 2.33 (s, 1H, CH₃), 2.89 (dd, 1H, pyrazoline H₄), 3.84 (dd, 1H, pyrazoline H₄), 4.04 (s, 5H, ferrocene), 4.36 (s, 2H, ferrocene), 4.53 (s, 1H, ferrocene), 4.60 (s, 1H, ferrocene), 6.03 (dd, 1H, pyrazoline H₅), 7.23–8.05 (m, 4H, aromatic). ¹³C-NMR (CDCl₃, p.p.m.): 21.75 (CH₃), 43.83 (C4), 56.52 (C5), 67.30, 67.78 (C2', C5'), 69.46 (C6'–C10'), 70.61, 71.10 (C3', C4'), 74.86 (C1'), 125.56 (C8), 126.37 (C9), 128.50 (C11), 134.28 (C10), 137.33 (C6), 147.08 (C7), 156.63 (C3), 168.30 (C?O).