Diethyl 4-[5-(biphenyl-4-yl)-1H-pyrazol-4-yl]-2,6-dimethyl-1,4-dihydro­pyridine-3,5-dicarboxyl­ate ethanol monosolvate

Hoong-Kun Fun; Madhukar Hemamalini; A M Vijesh; Arun M Isloor; T Arulmoli

doi:10.1107/S160053681102349X

. 2011 Jun 22;67(Pt 7):o1768–o1769. doi: 10.1107/S160053681102349X

Diethyl 4-[5-(biphenyl-4-yl)-1H-pyrazol-4-yl]-2,6-dimethyl-1,4-dihydropyridine-3,5-dicarboxylate ethanol monosolvate

Hoong-Kun Fun ^a,^*,^‡, Madhukar Hemamalini ^a, A M Vijesh ^b,^§, Arun M Isloor ^b, T Arulmoli ^c

PMCID: PMC3152003 PMID: 21837147

Abstract

In the title compound, C₂₈H₂₉N₃O₄·C₂H₆O, the benzene ring makes dihedral angles of 33.72 (13) and 32.86 (13)°, respectively, with the adjacent pyrazole and phenyl rings. In the crystal, the components are connected via intermolecular N—H⋯O, N—H⋯N, O—H⋯O and C—H⋯O hydrogen bonds, forming a layer parallel to the bc plane.

Related literature

For applications of Hantzsch 1,4-dihydropyridines, see: Surendra Kumar et al. (2011 ▶); Swarnalatha et al. (2011 ▶); Tasaka et al. (2001 ▶). For bond-length data, see: Allen et al. (1987 ▶).

Experimental

Crystal data

C₂₈H₂₉N₃O₄·C₂H₆O
M _r = 517.61
Orthorhombic,
a = 34.884 (2) Å
b = 10.2322 (7) Å
c = 7.8449 (6) Å
V = 2800.1 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 296 K
0.74 × 0.23 × 0.23 mm

Data collection

Bruker APEXII DUO CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T _min = 0.941, T _max = 0.981
19567 measured reflections
4972 independent reflections
4032 reflections with I > 2σ(I)
R _int = 0.031

Refinement

R[F ² > 2σ(F ²)] = 0.045
wR(F ²) = 0.127
S = 1.04
4972 reflections
343 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.22 e Å⁻³
Δρ_min = −0.20 e Å⁻³

Data collection: APEX2 (Bruker, 2009 ▶); cell refinement: SAINT (Bruker, 2009 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 ▶).

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S160053681102349X/is2733sup1.cif

e-67-o1768-sup1.cif^{(26.5KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S160053681102349X/is2733Isup2.hkl

e-67-o1768-Isup2.hkl^{(238.6KB, hkl)}

Supplementary material file. DOI: 10.1107/S160053681102349X/is2733Isup3.cml

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
N1—H1N1⋯O5	0.83	2.09	2.880 (3)	158
N3—H1N3⋯N2ⁱ	0.92	2.10	2.958 (2)	155
O5—H1O5⋯O1ⁱⁱ	0.91	1.88	2.776 (3)	172
C11—H11A⋯O2	0.93	2.50	3.414 (2)	167
C25—H25A⋯O3	0.96	2.13	2.864 (4)	132

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

Acknowledgments

HKF and MH thank the Malaysian Government and Universiti Sains Malaysia for the Research University Grant No. 1001/PFIZIK/811160. MH also thanks Universiti Sains Malaysia for a post-doctoral research fellowship. AMI thanks the Board for Research in Nuclear Sciences, Government of India, for a Young Scientist award. AMV is thankful to the management, SeQuent Scientific Ltd, New Mangalore, India, for their invaluable support and allocation of resources for this work.

supplementary crystallographic information

Comment

Hantzsch 1,4-dihydropyridines (1,4-DHPs) and their derivatives are an important class of bioactive molecules in the pharmaceutical field. They possess anti-inflammatory, anti-microbial (Surendra Kumar et al., 2011), anti-oxidant and antiulcer activities (Swarnalatha et al., 2011). DHPs are commercially used as calcium channel blockers for the treatment of cardiovascular diseases, including hypertension. Recently, the syntheses of DHPs with respect to Multidrug Resistance (MDR) reversal in tumor cell gave a new dimension to their applications (Tasaka et al., 2001). Keeping in view of the biological importance of 1,4-dihydropyridines, we hereby report the crystal structure of the title compound.

The asymmetric unit of the title compound is shown in Fig. 1. The rings A (N3/C16–C20), B (N1/N2/C13–C15), C (C7–C12) and D (C1–C6) are essentially planar. The dihedral angle between the best planes of these rings are A/B = 89.23 (11)°, A/C = 59.92 (11)°, A/D = 33.06 (12)°, B/C = 33.72 (13)°, B/D = 66.58 (13)° and C/D = 32.86 (13)°. The bond lengths (Allen et al., 1987) and angles are normal.

In the crystal packing (Fig. 2), the molecules are connected via intermolecular N1—H1N1···O5, N3—H1N3···N2, O5—H1O5···O1, C11—H11A···O2 and C25—H25A···O3 (Table 1) hydrogen bonds, forming sheets lying parallel to the bc-plane.

Experimental

3-(4-Biphenyl)-1H-pyrazole-4-carbaldehyde (0.2g, 0.80 mmol), ethylacetoacetate (0.21g, 1.6 mmol) and ammonium acetate (0.07g, 0.90 mmol) in ethanol (20 ml) were refluxed for 8 hours in an oil bath. After the completion of the reaction, the reaction mixture was concentrated and then poured onto crushed ice. The precipitated product was filtered and washed with water. The resulting solid was recrystallized from hot ethanol (0.28 g, 74%). M.p. 465–467 K.