4-(4-Bromo­phenyl­hydrazono)-1-(5-bromo­pyrimidin-2-yl)-3-methyl-2-pyrazolin-5-one

M Subramanyam; B Lingappa; A Thiruvalluvar; R J Butcher; Balakrishna Kalluraya

doi:10.1107/S1600536807067943

. 2008 Jan 4;64(Pt 2):o362. doi: 10.1107/S1600536807067943

4-(4-Bromophenylhydrazono)-1-(5-bromopyrimidin-2-yl)-3-methyl-2-pyrazolin-5-one

M Subramanyam ^a, B Lingappa ^b, A Thiruvalluvar ^a,^*, R J Butcher ^c, Balakrishna Kalluraya ^b

PMCID: PMC2960163 PMID: 21201394

Abstract

The asymmetric unit of the title compound, C₁₄H₁₀Br₂N₆O, contains two crystallographically independent molecules. The pyrazole ring of one molecule makes dihedral angles of 22.0 (3) and 3.5 (3)° with the pyrimidine and benzene rings, respectively; the corresponding values in the other molecule are 9.2 (3) and 2.1 (3)°, respectively. The molecules are linked by N—H⋯O, C—H⋯N and C—H⋯Br hydrogen bonds.

Related literature

For related literature, see: Baraldi et al. (1996 ▶, 2003 ▶); Kalluraya & Rahiman (1997 ▶); Kalluraya et al. (2001 ▶); Lingappa et al. (2006 ▶, 2007 ▶). For related crystal structures, see: Thiruvalluvar, Subramanyam, Kalluraya et al. (2007a ▶,b ▶); Thiruvalluvar, Subramanyam, Lingappa et al. (2007 ▶).

Experimental

Crystal data

C₁₄H₁₀Br₂N₆O
M _r = 438.08
Triclinic,
a = 9.1647 (3) Å
b = 12.2833 (5) Å
c = 14.0288 (5) Å
α = 86.532 (3)°
β = 84.218 (3)°
γ = 78.747 (3)°
V = 1539.67 (10) Å³
Z = 4
Mo Kα radiation
μ = 5.28 mm⁻¹
T = 200 (2) K
0.44 × 0.39 × 0.28 mm

Data collection

Oxford Diffraction Gemini diffractometer
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2007 ▶) T _min = 0.205, T _max = 0.320 (expected range = 0.146–0.228)
24958 measured reflections
9542 independent reflections
6336 reflections with I > 2σ(I)
R _int = 0.057

Refinement

R[F ² > 2σ(F ²)] = 0.082
wR(F ²) = 0.139
S = 1.25
9542 reflections
415 parameters
H-atom parameters constrained
Δρ_max = 0.83 e Å⁻³
Δρ_min = −0.64 e Å⁻³

Data collection: CrysAlis CCD (Oxford Diffraction, 2007 ▶); cell refinement: CrysAlis CCD; data reduction: CrysAlis RED (Oxford Diffraction, 2007 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶); software used to prepare material for publication: PLATON (Spek, 2003 ▶).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536807067943/ez2116sup1.cif

e-64-0o362-sup1.cif^{(32.4KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536807067943/ez2116Isup2.hkl

e-64-0o362-Isup2.hkl^{(457.3KB, 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
N6A—H6A⋯O5A	0.88	2.14	2.821 (6)	134
N6B—H6B⋯O5B	0.88	2.10	2.782 (6)	134
C13A—H13A⋯N12Bⁱ	0.95	2.61	3.193 (7)	120
C15A—H15A⋯Br4ⁱⁱ	0.95	2.92	3.761 (6)	148
C15B—H15B⋯Br2ⁱⁱ	0.95	2.87	3.746 (6)	153
C31A—H31A⋯Br3ⁱ	0.98	2.88	3.858 (6)	173
C31B—H31D⋯Br1ⁱ	0.98	2.92	3.862 (6)	160
C45A—H45A⋯N16Bⁱⁱ	0.95	2.62	3.539 (7)	162

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

Acknowledgments

RJB acknowledges the NSF-MRI program for funding to purchase the X-ray CCD diffractometer. AT thanks the UGC, India, for the award of a Minor Research Project [file No. MRP-2355/06(UGC-SERO), link No. 2355, 10/01/2007].

supplementary crystallographic information

Comment

The chemistry of pyrimidine and its derivatives has been studied due to their diverse biological activities (Baraldi et al., 1996; Lingappa et al., 2006, 2007). Pyrazoles and their derivatives are found to be associated with diverse pharmacological activities. Pyrazoles constitute an important class of heterocycles, which display interesting biological properties such as fungicidal, anti-inflammatory, anti-arthritic, anti-depressant and antiviral activity (Baraldi et al., 2003; Kalluraya et al., 2001; Kalluraya & Rahiman, 1997). The title compound, has been analysed as part of our crystallographic studies on pyrimidine derivatives (Thiruvalluvar et al., 2007a,b; Thiruvalluvar, Subramanyam, Lingappa et al., 2007). The asymmetric unit of the title compound, C₁₄H₁₀Br₂N₆O, Fig. 1, contains two crystallographically independent molecules, A and B. The pyrazole ring of A makes dihedral angles of 22.0 (3)° and 3.5 (3)° with the pyrimidine ring and phenyl ring respectively; the corresponding values in molecule B are 9.2 (3)° and 2.1 (3)°. The molecules are linked by N—H···O, C—H···N and C—H···Br hydrogen bonds; see Fig. 2 and hydrogen bond table.

Experimental

Ethyl-2-(4-bromohydrazono-3-oxobutanoate (3.2 g, 0.01 mol) was dissolved in glacial acetic acid (15 ml). To this a solution of 2-hydrazino-5-bromo-pyrimidine (1.9 g, 0.01 mol) in glacial acetic acid (20 ml) was added and the mixture was refluxed for 4 h in an oil bath. It was cooled and allowed to stand overnight. The separated solid was filtered, dried and then recrystallized from ethanol to give reddish flakes. Further recrystallization from ethyl acetate gave the yellowish red crystals suitable for X-ray analysis (3.0 g, 70%).