Ethyl 2-benzyl-3-[3-(4-chloro­phen­yl)-1-phenyl-1H-pyrazol-4-yl]-4,6-dioxo-5-phenyl­octa­hydro­pyrrolo­[3,4-c]pyrrole-1-carboxyl­ate

P Kamatchi; G Jagadeesan; M Pramesh; P T Perumal; S Aravindhan

doi:10.1107/S1600536812002450

. 2012 Jan 31;68(Pt 2):o552. doi: 10.1107/S1600536812002450

Ethyl 2-benzyl-3-[3-(4-chlorophenyl)-1-phenyl-1H-pyrazol-4-yl]-4,6-dioxo-5-phenyloctahydropyrrolo[3,4-c]pyrrole-1-carboxylate

P Kamatchi ^a, G Jagadeesan ^b, M Pramesh ^c, P T Perumal ^c, S Aravindhan ^b,^*

PMCID: PMC3275287 PMID: 22347143

Abstract

The title compound, C₃₇H₃₁ClN₄O₄, crystallizes with two molecules (A and B) in the asymmetric unit. The pyrrole rings in both molecules are connected via cis fusion, whereas one ring has a twisted conformation and the other assumes a half-chair conformation. In the crystal, the A molecules form inversion dimers via a pair of C—H⋯Cl interactions, while the B molecules form chains propagating in [1 Inline graphic 0], via C—H⋯O interactions. In the crystal, there are also a number of C—H⋯π interactions present.

Related literature

For the bioactivity of pyrazole derivatives, see: Sullivan et al. (2006 ▶); Patel et al. (2010 ▶); Siu et al. (2008 ▶). For conformation studies, see: Nardelli (1983 ▶).

Experimental

Crystal data

C₃₇H₃₁ClN₄O₄
M _r = 631.11
Triclinic,
a = 12.8293 (8) Å
b = 13.3467 (8) Å
c = 22.0754 (11) Å
α = 83.897 (4)°
β = 81.585 (5)°
γ = 62.213 (6)°
V = 3304.9 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.16 mm⁻¹
T = 293 K
0.2 × 0.2 × 0.2 mm

Data collection

Oxford Diffraction Xcalibur Eos diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009 ▶) T _min = 0.978, T _max = 0.984
29939 measured reflections
15365 independent reflections
7600 reflections with I > 2σ(I)
R _int = 0.027

Refinement

R[F ² > 2σ(F ²)] = 0.067
wR(F ²) = 0.225
S = 1.00
15365 reflections
831 parameters
259 restraints
H-atom parameters constrained
Δρ_max = 0.88 e Å⁻³
Δρ_min = −0.57 e Å⁻³

Data collection: CrysAlis PRO (Oxford Diffraction, 2009 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: PLATON (Spek, 2009 ▶); software used to prepare material for publication: PLATON and publCIF (Westrip, 2010 ▶).

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812002450/su2345sup1.cif

e-68-0o552-sup1.cif^{(49.9KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812002450/su2345Isup2.hkl

e-68-0o552-Isup2.hkl^{(735.9KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536812002450/su2345Isup3.cml

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

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

Cg1, Cg2 and Cg3 are the centroids of the C10–C15, C27′–C32′ and C33′–C38′ rings, respectively.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C7—H7⋯O44′	0.98	2.45	3.311 (3)	146
C42′—H42A⋯Cl1′ⁱ	0.96	2.76	3.707 (10)	170
C14′—H14′⋯Cg1	0.93	2.79	3.653 (4)	154
C17′—H17′⋯Cg2ⁱⁱ	0.93	2.95	3.738 (4)	143
C29—H29⋯Cg1ⁱⁱⁱ	0.93	2.87	3.633 (3)	140
C42′—H42B⋯Cg3^iv	0.96	2.80	3.866 (9)	153

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

Acknowledgments

PK and SA thank the UGC, India, for financial support.

supplementary crystallographic information

Comment

Pyrazoles exhibit a variety of pharmacological properties for e.g antibacterial and anti-inflammatory activities (Sullivan et al., 2006; Patel et al., 2010). One of the pyrazole derivatives shows nucleosidase inhibitory activity against Staphylococcus aureus (Siu et al., 2008). In view of their importance, the crystal structure determination of the title compound was carried out and the results are presented herein.

The molecular structure of the two independent molecules (A and B) of the title compound are shown in Figs. 1 and 2, respectively. In each molecule the pyrazole rings, (N24,N25,C26,C22,C23) in A and (N24',N25',C26',C22',C23') in B, are planar. In molecule A it is almost coplanar with the chlorophenyl ring attached to C26 as well as the phenyl ring attached at N24, with dihedral angles of 3.91 (16) and 4.88 (17) °, respectively. However, in molecule B the pyrazole ring is inclined to the chlorophenyl ring by 48.71 (17) °, and by 5.42 (18) ° to the phenyl ring at N24'.

The torsion angle H8—C8—C7—H7 in molecule A is 12.23 °, and H8'-C8'-C7'-H7' in molecule B is -14.81 °, which defines the ring fusion in the pyrrolo-pyrrole moieties as cis.

The pyrrole rings [(N5,C6—C8,C4) in A, and (N5',C6'-C8',C4') in B] assume half-chair (or envelope) conformations, with atoms C8 and C8' at the flap in molecules A and B, respectively, whereas the other pyrrole rings [(N2,C1,C7,C8,C3) in A and (N2',C1',C7',C8',C3') in B] have twisted conformations: defined by the asymmetry parameters (Nardelli, 1983), DS (N2) = 0.086 (2) Å and D2 (C8) = 0.010 (1) Å in molecule A, and DS (C3') = 0.018 (3) and D2 (C8') = 0.073 (2) in molecule B.

The partial double bond character of bonds C6—N5 [1.386 (3) Å] and C6'-N5' [1.390 (4) Å], and N5—C4 [1.395 (3) Å] and N5'-C4' [1.393 (3) Å], shows a high degree of electron delocalization.

In the crystal, the A molecules form inversion dimers via a pair of C—H···Cl interactions, while the B molecules form chains, propagating in [1 - 1 0], via C—H···O interactions (Fig. 3 and Table 1). There are also a number of C—H···π interactions present (Table 1).

Experimental

A mixture of pyrazole aldehyde (0.3 g), benzylethylglycinate (0.177 g) and maleimide (0.158 g) was refluxed in toluene(15 ml) until completion of the reaction as evidenced by TLC analysis. The solvent was evaporated under reduced pressure. The crude product was purified by column chromatography on silica gel [Merck, 100–200 mesh, ethylacetate–petroleum ether (10:90)] to afford pure product. Crystals, suitable for X-ray analysis, where obtained by slow evaporation of a solution in ethylacetate.