1-(2,4-Dinitro­phen­yl)-5-ferrocenyl-3-methyl-1H-pyrazole

V Stalin Elanchezhian; M Kandaswamy; M N Ponnuswamy

doi:10.1107/S1600536807067384

. 2008 Jan 4;64(Pt 2):m265. doi: 10.1107/S1600536807067384

1-(2,4-Dinitrophenyl)-5-ferrocenyl-3-methyl-1H-pyrazole

V Stalin Elanchezhian ^a, M Kandaswamy ^a, M N Ponnuswamy ^b,^*

PMCID: PMC2960418 PMID: 21201250

Abstract

In the title compound, [Fe(C₅H₅)(C₁₅H₁₁N₄O₄)], the dinitrophenyl and cyclopentadienyl rings make dihedral angles of 53.61 (6) and 23.11 (9)°, respectively, with the pyrazole unit. The two cyclopentadienyl rings are in an eclipsed conformation. The crystal structure is stabilized by intermolecular C—H⋯O interactions, which link molecules into chains parallel to the b axis.

Related literature

For related literature, see: Beer et al. (1998 ▶); Erasmus et al. (1996 ▶); Fabbrizzi & Poggi (1995 ▶); Gilchrist (1997 ▶); Basurto et al. (2007 ▶); Shi et al. (2005 ▶).

Experimental

Crystal data

[Fe(C₅H₅)(C₁₅H₁₁N₄O₄)]
M _r = 432.22
Triclinic,
a = 7.1073 (2) Å
b = 11.5339 (3) Å
c = 11.7575 (3) Å
α = 103.822 (1)°
β = 93.061 (1)°
γ = 98.822 (2)°
V = 920.76 (4) Å³
Z = 2
Mo Kα radiation
μ = 0.85 mm⁻¹
T = 293 (2) K
0.25 × 0.15 × 0.15 mm

Data collection

Bruker Kappa APEXII diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.815, T _max = 0.882
24588 measured reflections
6096 independent reflections
4741 reflections with I > 2σ(I)
R _int = 0.027

Refinement

R[F ² > 2σ(F ²)] = 0.036
wR(F ²) = 0.107
S = 1.01
6096 reflections
263 parameters
10 restraints
H-atom parameters constrained
Δρ_max = 0.38 e Å⁻³
Δρ_min = −0.25 e Å⁻³

Data collection: APEX2 (Bruker, 2004 ▶); cell refinement: APEX2; data reduction: SAINT (Bruker, 2004 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997 ▶); molecular graphics: PLATON (Spek, 2003 ▶); software used to prepare material for publication: SHELXL97 and PARST (Nardelli, 1995 ▶).

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536807067384/gk2122sup1.cif

e-64-0m265-sup1.cif^{(30.4KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536807067384/gk2122Isup2.hkl

e-64-0m265-Isup2.hkl^{(292.3KB, 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
C8—H8⋯O4ⁱ	0.93	2.46	3.380 (3)	170

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Symmetry code: (i) Inline graphic .

Acknowledgments

We thank the CSIR, India, for financial support.

supplementary crystallographic information

Comment

The design of molecular receptors having the ability to selectively bind and sense cationic, anionic or even neutral guests via a macroscopic physical response is an area of intense activity (Fabbrizzi et al., 1995). Chemical sensors bearing ferrocene nuclei as part of the sensing unit have been widely studied (Basurto et al., 2007). Ferrocene has largely proved to be a simple and remarkably robust building block for the construction of redox-responsive receptors (Beer et al., 1998). To build a sensor molecule with dual response (redox &optical), the title compound has been synthesized and studied to understand the above said properties.

The pyrazole ring has delocalized bonds (Gilchrist,1997; Shi et al., 2005). The substitued cyclopentadienyl rings are parallel to each other. The cyclopentadienyl rings are oriented at angles of 23.11 (9)° and 23.45 (7)° with respect to the planar pyrazole ring. Furthermore, the pyrazole and dinitrophenyl rings make a dihedral angle of 53.61 (6) °. The nitro groups are planar and oriented at angles of 26.61 (12)° and 9.53 (10)° to the phenyl ring. The two cyclopentadienyl rings of the ferrocenyl group are in a nearly eclipsed conformation (Erasmus et al., 1996).

The molecules in crystal are connected via intermolecular C—H···O interaction into a chain extended along the [010] direction.

Experimental

2,4-Dinitrophenylhydrazine (1 g, 5 mmol) was added to a solution of ferrocenoylacetone (1.35 g, 5 mmol) and a catalytic amount of p-toluenesulfonic acid in 50 ml of toluene. Tthe mixture was refluxed with a Dean-Stark apparatus for 14 h. The solvent was evaporated under vacuum, and the resulting black residue was chromatographed on a silica-gel column using petroleum ether-ethylacetate (9:1) mixture as eluent. The red band was collected which offered dark-red crystal. (62% yield, m.p. 433–435 K).