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

Fun, H.-K.; Ooi, C.W.; Malladi, S.; Shivananda, K.N.; Isloor, A.M.

doi:10.1107/S1600536812008173

organic compounds

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ISSN: 2056-9890

Volume 68| Part 3| March 2012| Pages o892-o893

doi:10.1107/S1600536812008173

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

Hoong-Kun Fun,^a ^*‡ Chin Wei Ooi,^a Shridhar Malladi,^b K. N. Shivananda ^c and Arun M. Isloor ^b

^aX-ray Crystallography Unit, School of Physics, Universiti Sains Malaysia, 11800 USM, Penang, Malaysia, ^bMedicinal Chemistry Division, Department of Chemistry, National Institute of Technology–Karnataka, Surathkal, Mangalore 575 025, India, and ^cSchulich Faculty of Chemistry, Technion Israel Institute of Technology, Haifa 32000, Israel
^*Correspondence e-mail: hkfun@usm.my

(Received 21 February 2012; accepted 23 February 2012; online 29 February 2012)

In the title compound, C₂₂H₂₅N₃O₄, the dihydropyridine ring adopts a flattened boat conformation. The pyrazole ring makes a dihedral angle of 29.04 (5)° with the benzene ring. The molecular structure is stabilized by an intramolecular C—H⋯O hydrogen bond which generates an S(9) ring motif. In the crystal, molecules are linked via N—H⋯O and C—H⋯N hydrogen bonds into a two-dimensional network parallel to the ab plane. The crystal structure is further consolidated by weak C—H⋯π interactions.

Related literature

For details and applications of dihydropyridine, see: Stout & Meyers (1982 ); Böcker & Guengerich (1986 ); Vo et al. (1995 ). For hydrogen-bond motifs, see: Bernstein et al. (1995 ). For ring conformation, see: Cremer & Pople (1975 ). For a related structure, see: Fun et al. (2011 ). For bond-length data, see: Allen et al. (1987 ). For the stability of the temperature controller used for data collection, see: Cosier & Glazer (1986 ).

Experimental

Crystal data

C₂₂H₂₅N₃O₄
M_r = 395.45
Monoclinic, P 2₁ /c
a = 9.7700 (4) Å
b = 8.6431 (4) Å
c = 24.8878 (9) Å
β = 105.646 (2)°
V = 2023.73 (14) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 100 K
0.32 × 0.32 × 0.20 mm

Data collection

Bruker APEX DUO CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ) T_min = 0.972, T_max = 0.982
27563 measured reflections
7361 independent reflections
5987 reflections with I > 2σ(I)
R_int = 0.031

Refinement

R[F² > 2σ(F²)] = 0.041
wR(F²) = 0.118
S = 1.04
7361 reflections
266 parameters
H-atom parameters constrained
Δρ_max = 0.47 e Å⁻³
Δρ_min = −0.19 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

Cg1 and Cg2 are the centroids of the N1/N2/C7–C9 and C1–C6 rings.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H1⋯O3ⁱ	0.89	2.09	2.9597 (12)	167
N1—H2⋯O1ⁱⁱ	0.90	1.96	2.8506 (10)	171
C3—H3A⋯N2ⁱⁱⁱ	0.93	2.51	3.4202 (13)	164
C5—H5A⋯O4	0.93	2.50	3.4266 (12)	172
C21—H21C⋯N2^iv	0.96	2.45	3.3300 (14)	153
C16—H16A⋯Cg1^v	0.97	2.80	3.5318 (11)	133
C17—H17C⋯Cg2	0.96	2.99	3.7750 (15)	140
C19—H19A⋯Cg2^vi	0.97	2.88	3.7079 (11)	144
Symmetry codes: (i) $[-x+2, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) x, y-1, z; (iii) x-1, y, z; (iv) x, y+1, z; (v) -x+1, -y+1, -z; (vi) $[-x+1, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

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 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536812008173/is5081sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812008173/is5081Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812008173/is5081Isup3.cml

checkCIF report

Comment top

1,4-Dihydropyridine (DHP) (Stout & Meyers, 1982) scaffold is a heterocyclic unit with remarkable pharmacological efficiency. They are widely used clinically as calcium channel blockers for the treatment of cardiovascular diseases. For example, nifedipine and nitrendipine are used for the treatment of hypertension and angina pectorism with nisoldipine being a potent vasodilator and nimodipine exhibiting selectivity for cerebral vasculature (Böcker & Guengerich, 1986). A number of DHP derivatives are employed as potential drug candidates for the treatment of congestive heart failure (Vo et al., 1995). Prompted by the diverse activities of 1,4-dihydropyridines, we have synthesized the title compound to study its crystal structure.

In the title compound (Fig. 1), the dihydropyridine (N3/C10–C14) ring adopts a flattened boat conformation with puckering parameters (Cremer & Pople, 1975) Q = 0.2966 (9) Å, θ = 73.57 (17)° and ϕ = 185.61 (19)°. The pyrazole ring (N1/N2/C7–C9) is essentially planar [maximum deviation of 0.003 (1) Å at atoms C8 and C9] and makes a dihedral angle of 29.04 (5)° with the benzene ring (C1–C6). The molecular structure is stabilized by an intramolecular C5—H5A···O4 hydrogen bond (Table 1) which generates an S(9) ring motif (Bernstein et al., 1995). The bond lengths (Allen et al., 1987) and angles are within normal ranges are comparable to the related structure (Fun et al., 2011).

In the crystal structure (Fig. 2), the molecules are linked via intermolecular N3—H1···O3, N1—H2···O1, C3—H3A···N2 and C21—H21C···N2 hydrogen bonds (Table 1) into two-dimensional networks parallel to the ab plane. The crystal structure is further consolidated by weak C—H···π interactions, involving the centroids of the pyrazole ring (N1/N2/C7–C9; Cg1; Table 1) and benzene ring (C1–C6; Cg2; Table 1).

Related literature top

For details and applications of dihydropyridine, see: Stout & Meyers (1982); Böcker & Guengerich (1986); Vo et al. (1995). For hydrogen-bond motifs, see: Bernstein et al. (1995). For ring conformation, see: Cremer & Pople (1975). For a related structure, see: Fun et al. (2011). For bond-length data, see: Allen et al. (1987). For the stability of the temperature controller used for data collection, see: Cosier & Glazer (1986).

Experimental top

3-Phenyl-1H-pyrazole-4-carbaldehyde (0.172 g, 1.0 mmol), ethylacetoacetate (0.26 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. Yield: 0.285 g, 72.15%. M.p.: 476–478 K.

Computing details top

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

Figures top

	Fig. 1. The molecular structure of the title compound, showing 50% probability displacement ellipsoids and the atom-numbering scheme. Intramolecular hydrogen bond was shown as dash line.
	Fig. 2. The crystal packing of the title compound, viewed along the b axis. H atoms not involved in the intermolecular interactions (dashed lines) have been omitted for clarity.

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

Crystal data top

C₂₂H₂₅N₃O₄	F(000) = 840
M_r = 395.45	D_x = 1.298 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 8661 reflections
a = 9.7700 (4) Å	θ = 3.3–32.7°
b = 8.6431 (4) Å	µ = 0.09 mm⁻¹
c = 24.8878 (9) Å	T = 100 K
β = 105.646 (2)°	Block, colourless
V = 2023.73 (14) Å³	0.32 × 0.32 × 0.20 mm
Z = 4

Data collection top

Bruker APEX DUO CCD area-detector diffractometer	7361 independent reflections
Radiation source: fine-focus sealed tube	5987 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.031
ϕ and ω scans	θ_max = 32.7°, θ_min = 1.7°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −14→14
T_min = 0.972, T_max = 0.982	k = −13→12
27563 measured reflections	l = −37→37

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.118	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.0611P)² + 0.510P] where P = (F_o² + 2F_c²)/3
7361 reflections	(Δ/σ)_max < 0.001
266 parameters	Δρ_max = 0.47 e Å⁻³
0 restraints	Δρ_min = −0.19 e Å⁻³

Crystal data top

C₂₂H₂₅N₃O₄	V = 2023.73 (14) Å³
M_r = 395.45	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 9.7700 (4) Å	µ = 0.09 mm⁻¹
b = 8.6431 (4) Å	T = 100 K
c = 24.8878 (9) Å	0.32 × 0.32 × 0.20 mm
β = 105.646 (2)°

Data collection top

Bruker APEX DUO CCD area-detector diffractometer	7361 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2009)	5987 reflections with I > 2σ(I)
T_min = 0.972, T_max = 0.982	R_int = 0.031
27563 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.041	0 restraints
wR(F²) = 0.118	H-atom parameters constrained
S = 1.04	Δρ_max = 0.47 e Å⁻³
7361 reflections	Δρ_min = −0.19 e Å⁻³
266 parameters

Special details top

Experimental. The crystal was placed in the cold stream of an Oxford Cryosystems Cobra open-flow nitrogen cryostat (Cosier & Glazer, 1986) operating at 100.0 (1) K.

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
O1	0.58615 (8)	0.77001 (8)	0.04877 (3)	0.01973 (14)
O2	0.46241 (7)	0.57230 (8)	0.07072 (3)	0.01770 (14)
O3	0.81230 (7)	0.30340 (9)	0.29673 (3)	0.02111 (15)
O4	0.59607 (7)	0.39878 (9)	0.25573 (3)	0.01732 (14)
N1	0.64943 (8)	0.08372 (9)	0.08152 (3)	0.01486 (14)
H2	0.6195	−0.0121	0.0695	0.018*
N2	0.78581 (8)	0.12321 (10)	0.08546 (3)	0.01612 (15)
N3	0.93751 (8)	0.59581 (10)	0.17656 (3)	0.01588 (15)
H1	1.0205	0.6446	0.1854	0.019*
C1	0.34348 (10)	0.08036 (11)	0.05798 (4)	0.01656 (16)
H1A	0.3823	0.0415	0.0305	0.020*
C2	0.20104 (10)	0.05325 (12)	0.05454 (4)	0.01944 (18)
H2A	0.1454	−0.0036	0.0249	0.023*
C3	0.14161 (10)	0.11085 (13)	0.09525 (4)	0.02181 (19)
H3A	0.0463	0.0930	0.0930	0.026*
C4	0.22583 (10)	0.19531 (13)	0.13937 (4)	0.02233 (19)
H4A	0.1863	0.2343	0.1667	0.027*
C5	0.36860 (10)	0.22241 (12)	0.14327 (4)	0.01838 (17)
H5A	0.4239	0.2786	0.1732	0.022*
C6	0.42916 (9)	0.16544 (10)	0.10232 (4)	0.01384 (15)
C7	0.58005 (9)	0.18941 (10)	0.10518 (3)	0.01267 (15)
C8	0.80244 (9)	0.25795 (11)	0.11222 (4)	0.01455 (15)
H8A	0.8866	0.3143	0.1208	0.017*
C9	0.67828 (9)	0.30610 (10)	0.12621 (3)	0.01221 (15)
C10	0.66775 (8)	0.45725 (10)	0.15560 (3)	0.01229 (14)
H10A	0.5715	0.4685	0.1599	0.015*
C11	0.77430 (9)	0.45646 (10)	0.21308 (3)	0.01313 (15)
C12	0.90530 (9)	0.51818 (11)	0.22054 (4)	0.01474 (16)
C13	0.83443 (9)	0.64531 (10)	0.13003 (4)	0.01427 (15)
C14	0.69904 (9)	0.59162 (10)	0.12121 (3)	0.01304 (15)
C15	0.58227 (9)	0.65490 (10)	0.07696 (4)	0.01430 (15)
C16	0.33872 (10)	0.62787 (13)	0.02848 (4)	0.02195 (19)
H16A	0.3522	0.6144	−0.0084	0.026*
H16B	0.3235	0.7369	0.0341	0.026*
C17	0.21408 (12)	0.53514 (17)	0.03417 (6)	0.0380 (3)
H17A	0.1310	0.5647	0.0054	0.057*
H17B	0.1985	0.5542	0.0701	0.057*
H17C	0.2327	0.4271	0.0306	0.057*
C18	0.73457 (9)	0.37847 (11)	0.25931 (4)	0.01416 (15)
C19	0.54490 (10)	0.33281 (13)	0.30055 (4)	0.02049 (18)
H19A	0.6029	0.3677	0.3365	0.025*
H19B	0.5482	0.2207	0.2995	0.025*
C20	0.39406 (10)	0.38793 (14)	0.29101 (4)	0.0240 (2)
H20A	0.3571	0.3525	0.3209	0.036*
H20B	0.3369	0.3475	0.2563	0.036*
H20C	0.3919	0.4989	0.2898	0.036*
C21	0.88930 (10)	0.75484 (12)	0.09397 (4)	0.01890 (17)
H21A	0.8378	0.7398	0.0556	0.028*
H21B	0.9885	0.7354	0.0984	0.028*
H21C	0.8767	0.8594	0.1048	0.028*
C22	1.02486 (10)	0.51553 (13)	0.27302 (4)	0.02183 (19)
H22A	0.9870	0.5049	0.3046	0.033*
H22B	1.0778	0.6102	0.2761	0.033*
H22C	1.0864	0.4297	0.2719	0.033*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0228 (3)	0.0136 (3)	0.0205 (3)	−0.0022 (3)	0.0019 (3)	0.0027 (2)
O2	0.0125 (3)	0.0169 (3)	0.0205 (3)	−0.0013 (2)	−0.0009 (2)	0.0040 (2)
O3	0.0191 (3)	0.0240 (4)	0.0201 (3)	0.0072 (3)	0.0052 (2)	0.0062 (3)
O4	0.0129 (3)	0.0244 (4)	0.0156 (3)	0.0005 (2)	0.0055 (2)	0.0038 (2)
N1	0.0135 (3)	0.0128 (3)	0.0189 (3)	−0.0013 (3)	0.0055 (3)	−0.0025 (3)
N2	0.0128 (3)	0.0155 (4)	0.0205 (3)	−0.0002 (3)	0.0053 (3)	−0.0011 (3)
N3	0.0111 (3)	0.0180 (4)	0.0180 (3)	−0.0029 (3)	0.0031 (3)	0.0005 (3)
C1	0.0158 (4)	0.0175 (4)	0.0166 (4)	−0.0030 (3)	0.0046 (3)	−0.0020 (3)
C2	0.0148 (4)	0.0208 (4)	0.0214 (4)	−0.0044 (3)	0.0027 (3)	−0.0024 (3)
C3	0.0139 (4)	0.0231 (5)	0.0293 (5)	−0.0038 (3)	0.0073 (3)	−0.0022 (4)
C4	0.0173 (4)	0.0260 (5)	0.0268 (5)	−0.0043 (4)	0.0112 (3)	−0.0063 (4)
C5	0.0155 (4)	0.0208 (4)	0.0202 (4)	−0.0044 (3)	0.0071 (3)	−0.0052 (3)
C6	0.0128 (3)	0.0135 (4)	0.0157 (3)	−0.0022 (3)	0.0046 (3)	0.0000 (3)
C7	0.0124 (3)	0.0126 (4)	0.0134 (3)	−0.0010 (3)	0.0041 (3)	−0.0007 (3)
C8	0.0117 (3)	0.0141 (4)	0.0176 (4)	−0.0001 (3)	0.0035 (3)	0.0000 (3)
C9	0.0112 (3)	0.0120 (4)	0.0131 (3)	−0.0006 (3)	0.0028 (3)	0.0001 (3)
C10	0.0109 (3)	0.0125 (4)	0.0132 (3)	−0.0003 (3)	0.0027 (3)	−0.0006 (3)
C11	0.0114 (3)	0.0145 (4)	0.0132 (3)	0.0002 (3)	0.0028 (3)	−0.0007 (3)
C12	0.0122 (3)	0.0157 (4)	0.0158 (4)	−0.0008 (3)	0.0028 (3)	−0.0020 (3)
C13	0.0140 (3)	0.0127 (4)	0.0163 (3)	−0.0007 (3)	0.0043 (3)	−0.0010 (3)
C14	0.0129 (3)	0.0115 (4)	0.0144 (3)	−0.0002 (3)	0.0031 (3)	−0.0004 (3)
C15	0.0147 (3)	0.0120 (4)	0.0157 (3)	−0.0006 (3)	0.0033 (3)	−0.0017 (3)
C16	0.0156 (4)	0.0219 (5)	0.0234 (4)	0.0011 (3)	−0.0033 (3)	0.0044 (4)
C17	0.0173 (5)	0.0401 (7)	0.0481 (7)	−0.0053 (5)	−0.0058 (5)	0.0133 (6)
C18	0.0129 (3)	0.0144 (4)	0.0150 (3)	0.0007 (3)	0.0035 (3)	−0.0015 (3)
C19	0.0205 (4)	0.0250 (5)	0.0185 (4)	−0.0006 (4)	0.0096 (3)	0.0046 (3)
C20	0.0181 (4)	0.0350 (6)	0.0214 (4)	−0.0031 (4)	0.0098 (3)	−0.0007 (4)
C21	0.0171 (4)	0.0170 (4)	0.0237 (4)	−0.0021 (3)	0.0074 (3)	0.0034 (3)
C22	0.0147 (4)	0.0285 (5)	0.0192 (4)	−0.0039 (4)	−0.0009 (3)	0.0004 (4)

Geometric parameters (Å, º) top

O1—C15	1.2239 (11)	C9—C10	1.5141 (12)
O2—C15	1.3442 (11)	C10—C14	1.5219 (12)
O2—C16	1.4529 (11)	C10—C11	1.5254 (11)
O3—C18	1.2181 (11)	C10—H10A	0.9800
O4—C18	1.3434 (10)	C11—C12	1.3524 (12)
O4—C19	1.4560 (11)	C11—C18	1.4730 (12)
N1—N2	1.3531 (10)	C12—C22	1.4993 (12)
N1—C7	1.3623 (11)	C13—C14	1.3626 (12)
N1—H2	0.9024	C13—C21	1.4995 (13)
N2—C8	1.3296 (12)	C14—C15	1.4613 (12)
N3—C13	1.3817 (11)	C16—C17	1.4961 (16)
N3—C12	1.3905 (11)	C16—H16A	0.9700
N3—H1	0.8870	C16—H16B	0.9700
C1—C2	1.3910 (12)	C17—H17A	0.9600
C1—C6	1.4002 (12)	C17—H17B	0.9600
C1—H1A	0.9300	C17—H17C	0.9600
C2—C3	1.3887 (14)	C19—C20	1.5055 (14)
C2—H2A	0.9300	C19—H19A	0.9700
C3—C4	1.3886 (14)	C19—H19B	0.9700
C3—H3A	0.9300	C20—H20A	0.9600
C4—C5	1.3918 (13)	C20—H20B	0.9600
C4—H4A	0.9300	C20—H20C	0.9600
C5—C6	1.3987 (12)	C21—H21A	0.9600
C5—H5A	0.9300	C21—H21B	0.9600
C6—C7	1.4713 (11)	C21—H21C	0.9600
C7—C9	1.3933 (12)	C22—H22A	0.9600
C8—C9	1.4120 (12)	C22—H22B	0.9600
C8—H8A	0.9300	C22—H22C	0.9600

C15—O2—C16	115.90 (7)	C14—C13—N3	119.09 (8)
C18—O4—C19	116.48 (7)	C14—C13—C21	127.35 (8)
N2—N1—C7	113.24 (7)	N3—C13—C21	113.56 (7)
N2—N1—H2	118.7	C13—C14—C15	121.38 (8)
C7—N1—H2	127.2	C13—C14—C10	120.18 (8)
C8—N2—N1	104.02 (7)	C15—C14—C10	118.36 (7)
C13—N3—C12	122.73 (7)	O1—C15—O2	121.75 (8)
C13—N3—H1	118.1	O1—C15—C14	126.70 (8)
C12—N3—H1	114.8	O2—C15—C14	111.53 (8)
C2—C1—C6	120.83 (8)	O2—C16—C17	107.09 (9)
C2—C1—H1A	119.6	O2—C16—H16A	110.3
C6—C1—H1A	119.6	C17—C16—H16A	110.3
C3—C2—C1	120.19 (9)	O2—C16—H16B	110.3
C3—C2—H2A	119.9	C17—C16—H16B	110.3
C1—C2—H2A	119.9	H16A—C16—H16B	108.6
C4—C3—C2	119.35 (8)	C16—C17—H17A	109.5
C4—C3—H3A	120.3	C16—C17—H17B	109.5
C2—C3—H3A	120.3	H17A—C17—H17B	109.5
C3—C4—C5	120.83 (9)	C16—C17—H17C	109.5
C3—C4—H4A	119.6	H17A—C17—H17C	109.5
C5—C4—H4A	119.6	H17B—C17—H17C	109.5
C4—C5—C6	120.19 (9)	O3—C18—O4	121.96 (8)
C4—C5—H5A	119.9	O3—C18—C11	126.86 (8)
C6—C5—H5A	119.9	O4—C18—C11	111.18 (7)
C5—C6—C1	118.60 (8)	O4—C19—C20	106.20 (8)
C5—C6—C7	122.03 (8)	O4—C19—H19A	110.5
C1—C6—C7	119.36 (8)	C20—C19—H19A	110.5
N1—C7—C9	105.97 (7)	O4—C19—H19B	110.5
N1—C7—C6	119.57 (8)	C20—C19—H19B	110.5
C9—C7—C6	134.41 (8)	H19A—C19—H19B	108.7
N2—C8—C9	112.62 (8)	C19—C20—H20A	109.5
N2—C8—H8A	123.7	C19—C20—H20B	109.5
C9—C8—H8A	123.7	H20A—C20—H20B	109.5
C7—C9—C8	104.15 (7)	C19—C20—H20C	109.5
C7—C9—C10	132.57 (7)	H20A—C20—H20C	109.5
C8—C9—C10	123.24 (7)	H20B—C20—H20C	109.5
C9—C10—C14	109.67 (7)	C13—C21—H21A	109.5
C9—C10—C11	109.33 (7)	C13—C21—H21B	109.5
C14—C10—C11	109.94 (7)	H21A—C21—H21B	109.5
C9—C10—H10A	109.3	C13—C21—H21C	109.5
C14—C10—H10A	109.3	H21A—C21—H21C	109.5
C11—C10—H10A	109.3	H21B—C21—H21C	109.5
C12—C11—C18	120.81 (8)	C12—C22—H22A	109.5
C12—C11—C10	120.55 (8)	C12—C22—H22B	109.5
C18—C11—C10	118.53 (7)	H22A—C22—H22B	109.5
C11—C12—N3	119.27 (8)	C12—C22—H22C	109.5
C11—C12—C22	126.85 (8)	H22A—C22—H22C	109.5
N3—C12—C22	113.87 (8)	H22B—C22—H22C	109.5

C7—N1—N2—C8	−0.22 (10)	C18—C11—C12—N3	−177.72 (8)
C6—C1—C2—C3	0.12 (15)	C10—C11—C12—N3	6.18 (13)
C1—C2—C3—C4	−0.14 (16)	C18—C11—C12—C22	1.13 (15)
C2—C3—C4—C5	−0.14 (17)	C10—C11—C12—C22	−174.97 (9)
C3—C4—C5—C6	0.44 (16)	C13—N3—C12—C11	15.77 (13)
C4—C5—C6—C1	−0.45 (15)	C13—N3—C12—C22	−163.22 (9)
C4—C5—C6—C7	−179.10 (9)	C12—N3—C13—C14	−13.03 (13)
C2—C1—C6—C5	0.17 (14)	C12—N3—C13—C21	167.59 (8)
C2—C1—C6—C7	178.86 (9)	N3—C13—C14—C15	171.93 (8)
N2—N1—C7—C9	−0.16 (10)	C21—C13—C14—C15	−8.78 (14)
N2—N1—C7—C6	177.68 (7)	N3—C13—C14—C10	−11.41 (13)
C5—C6—C7—N1	151.31 (9)	C21—C13—C14—C10	167.88 (8)
C1—C6—C7—N1	−27.33 (12)	C9—C10—C14—C13	−90.92 (9)
C5—C6—C7—C9	−31.60 (15)	C11—C10—C14—C13	29.33 (11)
C1—C6—C7—C9	149.76 (10)	C9—C10—C14—C15	85.84 (9)
N1—N2—C8—C9	0.52 (10)	C11—C10—C14—C15	−153.91 (7)
N1—C7—C9—C8	0.44 (9)	C16—O2—C15—O1	0.21 (13)
C6—C7—C9—C8	−176.93 (9)	C16—O2—C15—C14	178.67 (8)
N1—C7—C9—C10	178.03 (9)	C13—C14—C15—O1	−9.87 (14)
C6—C7—C9—C10	0.66 (17)	C10—C14—C15—O1	173.41 (9)
N2—C8—C9—C7	−0.62 (10)	C13—C14—C15—O2	171.76 (8)
N2—C8—C9—C10	−178.49 (8)	C10—C14—C15—O2	−4.96 (11)
C7—C9—C10—C14	−118.96 (10)	C15—O2—C16—C17	−171.85 (9)
C8—C9—C10—C14	58.24 (10)	C19—O4—C18—O3	2.98 (13)
C7—C9—C10—C11	120.42 (10)	C19—O4—C18—C11	−177.36 (8)
C8—C9—C10—C11	−62.38 (10)	C12—C11—C18—O3	−33.38 (14)
C9—C10—C11—C12	93.77 (10)	C10—C11—C18—O3	142.81 (9)
C14—C10—C11—C12	−26.69 (11)	C12—C11—C18—O4	146.98 (9)
C9—C10—C11—C18	−82.43 (9)	C10—C11—C18—O4	−36.83 (11)
C14—C10—C11—C18	157.11 (7)	C18—O4—C19—C20	172.95 (8)

Hydrogen-bond geometry (Å, º) top

Cg1 and Cg2 are the centroids of the N1/N2/C7–C9 and C1–C6 rings.

D—H···A	D—H	H···A	D···A	D—H···A
N3—H1···O3ⁱ	0.89	2.09	2.9597 (12)	167
N1—H2···O1ⁱⁱ	0.90	1.96	2.8506 (10)	171
C3—H3A···N2ⁱⁱⁱ	0.93	2.51	3.4202 (13)	164
C5—H5A···O4	0.93	2.50	3.4266 (12)	172
C21—H21C···N2^iv	0.96	2.45	3.3300 (14)	153
C16—H16A···Cg1^v	0.97	2.80	3.5318 (11)	133
C17—H17C···Cg2	0.96	2.99	3.7750 (15)	140
C19—H19A···Cg2^vi	0.97	2.88	3.7079 (11)	144

Symmetry codes: (i) −x+2, y+1/2, −z+1/2; (ii) x, y−1, z; (iii) x−1, y, z; (iv) x, y+1, z; (v) −x+1, −y+1, −z; (vi) −x+1, y+1/2, −z+1/2.

Experimental details

Crystal data
Chemical formula	C₂₂H₂₅N₃O₄
M_r	395.45
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	100
a, b, c (Å)	9.7700 (4), 8.6431 (4), 24.8878 (9)
β (°)	105.646 (2)
V (Å³)	2023.73 (14)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.32 × 0.32 × 0.20

Data collection
Diffractometer	Bruker APEX DUO CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2009)
T_min, T_max	0.972, 0.982
No. of measured, independent and observed [I > 2σ(I)] reflections	27563, 7361, 5987
R_int	0.031
(sin θ/λ)_max (Å⁻¹)	0.760

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.041, 0.118, 1.04
No. of reflections	7361
No. of parameters	266
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.47, −0.19

Computer programs: APEX2 (Bruker, 2009), SAINT (Bruker, 2009), SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

Cg1 and Cg2 are the centroids of the N1/N2/C7–C9 and C1–C6 rings.

D—H···A	D—H	H···A	D···A	D—H···A
N3—H1···O3ⁱ	0.89	2.09	2.9597 (12)	167
N1—H2···O1ⁱⁱ	0.90	1.96	2.8506 (10)	171
C3—H3A···N2ⁱⁱⁱ	0.93	2.51	3.4202 (13)	164
C5—H5A···O4	0.93	2.50	3.4266 (12)	172
C21—H21C···N2^iv	0.96	2.45	3.3300 (14)	153
C16—H16A···Cg1^v	0.97	2.80	3.5318 (11)	133
C17—H17C···Cg2	0.96	2.99	3.7750 (15)	140
C19—H19A···Cg2^vi	0.97	2.88	3.7079 (11)	144

Symmetry codes: (i) −x+2, y+1/2, −z+1/2; (ii) x, y−1, z; (iii) x−1, y, z; (iv) x, y+1, z; (v) −x+1, −y+1, −z; (vi) −x+1, y+1/2, −z+1/2.

Footnotes

‡Thomson Reuters ResearcherID: A-3561-2009.

Acknowledgements

HKF and CWO thank Universiti Sains Malaysia (USM) for the Research University Grant (No. 1001/PFIZIK/811160). CWO thanks the Malaysian government and USM for the award of the post of research assistant under the Research University Grant (No. 1001/PFIZIK/811151). AMI is grateful to the Director of the 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 the Young Scientist award.

References

Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19. CrossRef Web of Science Google Scholar
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Volume 68| Part 3| March 2012| Pages o892-o893

doi:10.1107/S1600536812008173

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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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

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Experimental

Crystal data

Data collection

Refinement

Supporting information

Footnotes

Acknowledgements

References

organic compounds

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