Dimethyl 2,6-dimethyl-4-(3-phenyl-1H-pyrazol-4-yl)-1,4-dihydro­pyridine-3,5-dicarboxyl­ate

Hoong-Kun Fun; Suhana Arshad; Shridhar Malladi; Kammasandra Nanjunda Shivananda; Arun M Isloor

doi:10.1107/S1600536812008306

. 2012 Mar 3;68(Pt 4):o922–o923. doi: 10.1107/S1600536812008306

Dimethyl 2,6-dimethyl-4-(3-phenyl-1H-pyrazol-4-yl)-1,4-dihydropyridine-3,5-dicarboxylate

Hoong-Kun Fun ^a,^*,^‡, Suhana Arshad ^a, Shridhar Malladi ^b, Kammasandra Nanjunda Shivananda ^c, Arun M Isloor ^b

PMCID: PMC3343908 PMID: 22589989

Abstract

In the title compound, C₂₀H₂₁N₃O₄, the 1,4-dihydropyridine ring adopts a boat conformation. An intramolecular C—H⋯O hydrogen bond generates an S(6) ring motif. The pyrazole ring makes dihedral angles of 87.81 (7) and 45.09 (7)° with the mean plane of the 1,4-dihydropyridine ring and the phenyl ring, respectively. In the crystal, molecules are linked by N—H⋯N, N—H⋯O and C—H⋯O hydrogen bonds into a three-dimensional network.

Related literature

For a related structure and background references, see: Fun et al. (2011 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶). For the stability of the temperature controller used for data collection, see: Cosier & Glazer (1986 ▶).

Experimental

Crystal data

C₂₀H₂₁N₃O₄
M _r = 367.40
Orthorhombic,
a = 13.9632 (6) Å
b = 10.9908 (5) Å
c = 11.8465 (5) Å
V = 1818.04 (14) Å³
Z = 4
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 100 K
0.38 × 0.22 × 0.14 mm

Data collection

Bruker SMART APEXII DUO CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T _min = 0.965, T _max = 0.987
17004 measured reflections
2788 independent reflections
2687 reflections with I > 2σ(I)
R _int = 0.030

Refinement

R[F ² > 2σ(F ²)] = 0.030
wR(F ²) = 0.080
S = 1.03
2788 reflections
256 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.30 e Å⁻³
Δρ_min = −0.24 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/S1600536812008306/hb6648sup1.cif

e-68-0o922-sup1.cif^{(28.8KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812008306/hb6648Isup2.hkl

e-68-0o922-Isup2.hkl^{(136.9KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536812008306/hb6648Isup3.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
C18—H18A⋯O3	0.98	2.29	2.9114 (18)	121
N3—H1N3⋯N2ⁱ	0.93 (2)	2.14 (2)	3.0529 (17)	167 (2)
N1—H1N1⋯O3ⁱⁱ	0.84 (3)	2.01 (3)	2.8438 (16)	173 (2)
C5—H5A⋯O1ⁱⁱⁱ	0.95	2.60	3.4895 (18)	157
C20—H20C⋯O1^iv	0.98	2.38	3.3524 (19)	170

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

Acknowledgments

HKF and SA thank Universiti Sains Malaysia (USM) for a Research University Grant (No. 1001/PFIZIK/811160). SA thanks the Malaysian government and USM for an award from the Academic Staff Training Scheme (ASTS). AMI is thankful to Director of National Institute of Technology Karnataka, Surathkal, India, for providing research facilities. AMI also thanks the Board for Research in Nuclear Sciences, Department of Atomic Energy, and the Government of India for a ’Young Scientist’ award.

supplementary crystallographic information

Comment

As part of our ongoing studies of dihydropyridine/pyrazole derivatives, we have synthesized the title compound, (I), to study its crystal structure.

The molecular structure in shown in Fig. 1. The 1,4-dihydropyridine ring (N3/C10–C14) adopts a boat conformation with puckering parameters Q = 0.3273 (13) Å, Θ= 106.1 (2)° and Φ= 356.4 (2)°. An intramolecular C18—H18A···O3 hydrogen bond (Table 1) forms an S(6) ring motif (Bernstein et al., 1995). The 1H-pyrazole ring (N1/N2/C7–C9) makes dihedral angles of 87.81 (7) and 45.09 (7)° with the mean plane of the 1,4-dihydropyridine (N3/C10–C14) ring and benzene (C1–C6) ring, respectively. Bond lengths and angles are comparable to the related structure (Fun et al., 2011).

In the crystal structure (Fig. 2), the molecules are linked via intermolecular N3—H1N3···N2, N1—H1N1···O3, C5—H5A···O1 and C20—H20C···O1 hydrogen bonds (Table 1) into three-dimensional network.

Experimental

3-Phenyl-1H-pyrazole-4-carbaldehyde (0.172 g, 1.0 mmol), methylacetoacetate (0.232 g, 2.0 mmol) and ammonium acetate (0.092 g, 1.2 mmol) in ethanol (7 ml) were refluxed for 5 h. After the completion of the reaction, the reaction mixture was concentrated and poured into crushed ice. The precipitated product was filtered and washed with water. The resulting solid was recrystallized from ethanol:water mixture as yellow blocks. Yield: 0.28 g, 76.21%. M.p.: 398–400 K.