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

Fun, H.-K.; Loh, W.-S.; Vijesh, A.M.; Isloor, A.M.; Malladi, S.

doi:10.1107/S160053681201344X

organic compounds

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ISSN: 2056-9890

Volume 68| Part 5| May 2012| Pages o1289-o1290

doi:10.1107/S160053681201344X

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

Hoong-Kun Fun,^a ^*‡ Wan-Sin Loh,^a § A. M. Vijesh,^b ¶ Arun M. Isloor ^b and Shridhar Malladi ^b

^aX-ray Crystallography Unit, School of Physics, Universiti Sains Malaysia, 11800 USM, Penang, Malaysia, and ^bDepartment of Chemistry, National Institute of Technology-Karnataka, Surathkal, Mangalore 575 025, India
^*Correspondence e-mail: hkfun@usm.my

(Received 26 March 2012; accepted 28 March 2012; online 4 April 2012)

In the title compound, C₂₂H₂₄ClN₃O₄, intramolecular C—H⋯O and C—H⋯N hydrogen bonds form S(9) and S(7) ring motifs, respectively. The 1,4-dihydropyridine ring adopts a flattened boat conformation. The benzene ring makes a dihedral angle of 33.36 (6)° with the pyrazole ring. In the crystal, pairs of N—H⋯N hydrogen bonds link the molecules into inversion dimers. The dimers are stacked in column along the a axis through N—H⋯O and C—H⋯N hydrogen bonds. The crystal packing also features C—H⋯π interactions involving the pyrazole ring.

Related literature

For background to and applications of 1,4-dihydropyridines, see: Janis & Triggle (1983 ); Boecker & Guengerich (1986 ); Gordeev et al. (1996 ); Buhler & Kiowski (1987 ); Vo et al. (1995 ). For hydrogen-bond motifs, see: Bernstein et al. (1995 ). For ring conformations, see: Cremer & Pople (1975 ). For a related structure, see: Fun et al. (2012 ). For the stability of the temperature controller used in the data collection, see: Cosier & Glazer (1986 ).

Experimental

Crystal data

C₂₂H₂₄ClN₃O₄
M_r = 429.89
Triclinic, $[P \overline 1]$
a = 8.5210 (5) Å
b = 10.7809 (6) Å
c = 11.2707 (7) Å
α = 90.411 (1)°
β = 97.205 (1)°
γ = 94.210 (1)°
V = 1024.28 (10) Å³
Z = 2
Mo Kα radiation
μ = 0.22 mm⁻¹
T = 100 K
0.38 × 0.18 × 0.17 mm

Data collection

Bruker SMART APEXII DUO CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ) T_min = 0.921, T_max = 0.964
17114 measured reflections
5885 independent reflections
5038 reflections with I > 2σ(I)
R_int = 0.027

Refinement

R[F² > 2σ(F²)] = 0.038
wR(F²) = 0.107
S = 1.04
5885 reflections
283 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.44 e Å⁻³
Δρ_min = −0.29 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

Cg1 is the centroid of the N1/N2/C7–C9 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N1⋯O4ⁱ	0.857 (17)	2.078 (17)	2.9291 (14)	172.2 (17)
N3—H1N3⋯N2ⁱⁱ	0.908 (19)	2.184 (19)	3.0427 (14)	157.5 (15)
C5—H5A⋯O1	0.93	2.27	3.1988 (16)	177
C8—H8A⋯N3	0.93	2.61	3.2546 (15)	127
C22—H22B⋯N2ⁱⁱⁱ	0.96	2.50	3.3741 (16)	151
C19—H19B⋯Cg1^iv	0.96	2.79	3.5562 (14)	137
Symmetry codes: (i) x+1, y, z; (ii) -x, -y+2, -z; (iii) x-1, y, z; (iv) -x, -y+2, -z+1.

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/S160053681201344X/is5103sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053681201344X/is5103Isup2.hkl

Supporting information file. DOI: 10.1107/S160053681201344X/is5103Isup3.cml

checkCIF report

Comment top

In recent years, considerable attention has been paid to the synthesis of 1,4-dihydropyridines owing to their significant biological activity. 1,4-Dihydropyridine-containing drugs (1,4-DHPs), such as nifedipine, nicardipine, amlodipine, felodipine and others have been found to be useful as calcium channel blockers (Janis & Triggle, 1983; Boecker & Guengerich, 1986; Gordeev et al., 1996) and are used most frequently as cardiovascular agents for the treatment of hypertension (Buhler & Kiowski, 1987). 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), intramolecular C5—H5A···O1 and C8—H8A···N3 hydrogen bonds form S(9) and S(7) ring motifs (Bernstein et al., 1995), respectively. The 1,4-dihydropyridine ring (C10–C12/N3/C13/C14) adopts a flattened boat conformation (Cremer & Pople, 1975) with the puckering parameters, Q = 0.4162 (11) Å; Θ = 74.64 (16)°; ϕ = 176.34 (17)°. The benzene ring (C1–C6) forms a dihedral angle of 33.36 (6)° with the pyrazole ring (N1/N2/C7–C9). The bond lengths and angles are within the normal ranges and are comparable with the related structure (Fun et al., 2012).

In the crystal packing (Fig. 2), intermolecular N1—H1N1···O4, N3—H1N3···N2 and C22—H22B···N2 hydrogen bonds (Table 1) link the molecules into a column along the a axis. The crystal packing is further stabilized by C—H···π interactions (Table 1) involving the pyrazole ring.

Related literature top

For background to and applications of 1,4-dihydropyridines, see: Janis & Triggle (1983); Boecker & Guengerich (1986); Gordeev et al. (1996); Buhler & Kiowski (1987); Vo et al. (1995). For hydrogen-bond motifs, see: Bernstein et al. (1995). For ring conformations, see: Cremer & Pople (1975). For a related structure, see: Fun et al. (2012). For the stability of the temperature controller used in the data collection, see: Cosier & Glazer (1986).

Experimental top

3-(4-Chlorophenyl)-1H-pyrazole-4-carbaldehyde (0.2 g, 1.1 mmol), ethylacetoacetate (0.3 g, 2.3 mmol) and ammonium acetate (0.09 g, 1.2 mmol) in ethanol (20 ml) were refluxed for 8 h in an oil bath. 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 hot ethanol (0.33 g, 67%). M.p.: 459–461 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. Dashed lines indicate the intramolecular hydrogen bonds.
	Fig. 2. A part of crystal packing diagram of the title compound, viewed along the a axis. H atoms not involved in the intermolecular interactions (dashed lines) have been omitted for clarity.

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

Crystal data top

C₂₂H₂₄ClN₃O₄	Z = 2
M_r = 429.89	F(000) = 452
Triclinic, P1	D_x = 1.394 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.5210 (5) Å	Cell parameters from 7118 reflections
b = 10.7809 (6) Å	θ = 2.4–32.6°
c = 11.2707 (7) Å	µ = 0.22 mm⁻¹
α = 90.411 (1)°	T = 100 K
β = 97.205 (1)°	Block, colourless
γ = 94.210 (1)°	0.38 × 0.18 × 0.17 mm
V = 1024.28 (10) Å³

Data collection top

Bruker SMART APEXII DUO CCD area-detector diffractometer	5885 independent reflections
Radiation source: fine-focus sealed tube	5038 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.027
ϕ and ω scans	θ_max = 30.0°, θ_min = 1.8°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −11→11
T_min = 0.921, T_max = 0.964	k = −15→15
17114 measured reflections	l = −15→15

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)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.107	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ²(F_o²) + (0.0519P)² + 0.4397P] where P = (F_o² + 2F_c²)/3
5885 reflections	(Δ/σ)_max = 0.001
283 parameters	Δρ_max = 0.44 e Å⁻³
0 restraints	Δρ_min = −0.29 e Å⁻³

Crystal data top

C₂₂H₂₄ClN₃O₄	γ = 94.210 (1)°
M_r = 429.89	V = 1024.28 (10) Å³
Triclinic, P1	Z = 2
a = 8.5210 (5) Å	Mo Kα radiation
b = 10.7809 (6) Å	µ = 0.22 mm⁻¹
c = 11.2707 (7) Å	T = 100 K
α = 90.411 (1)°	0.38 × 0.18 × 0.17 mm
β = 97.205 (1)°

Data collection top

Bruker SMART APEXII DUO CCD area-detector diffractometer	5885 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2009)	5038 reflections with I > 2σ(I)
T_min = 0.921, T_max = 0.964	R_int = 0.027
17114 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.038	0 restraints
wR(F²) = 0.107	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	Δρ_max = 0.44 e Å⁻³
5885 reflections	Δρ_min = −0.29 e Å⁻³
283 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
Cl1	0.40990 (4)	0.46308 (3)	0.70565 (3)	0.02708 (9)
O1	−0.04200 (12)	0.49719 (9)	0.17848 (9)	0.0248 (2)
O2	−0.23718 (10)	0.49196 (8)	0.02494 (8)	0.01812 (18)
O3	−0.12624 (10)	0.84126 (8)	0.44891 (7)	0.01690 (17)
O4	−0.34579 (10)	0.94038 (8)	0.39174 (8)	0.01770 (17)
N1	0.32527 (12)	0.89803 (9)	0.27948 (9)	0.01440 (19)
N2	0.26859 (12)	0.96583 (10)	0.18490 (9)	0.01621 (19)
N3	−0.24741 (11)	0.87179 (9)	0.03539 (9)	0.01423 (19)
C1	0.36646 (14)	0.76773 (12)	0.50778 (10)	0.0169 (2)
H1A	0.4078	0.8501	0.5120	0.020*
C2	0.41253 (14)	0.68690 (12)	0.59919 (11)	0.0197 (2)
H2A	0.4850	0.7149	0.6642	0.024*
C3	0.34984 (14)	0.56477 (12)	0.59271 (11)	0.0192 (2)
C4	0.24000 (15)	0.52106 (12)	0.49769 (12)	0.0213 (2)
H4A	0.1967	0.4392	0.4955	0.026*
C5	0.19539 (14)	0.60170 (12)	0.40547 (11)	0.0184 (2)
H5A	0.1232	0.5729	0.3406	0.022*
C6	0.25797 (13)	0.72537 (11)	0.40942 (10)	0.0139 (2)
C7	0.21629 (13)	0.80907 (10)	0.31024 (10)	0.0126 (2)
C8	0.11965 (13)	0.91862 (11)	0.15670 (10)	0.0156 (2)
H8A	0.0501	0.9477	0.0947	0.019*
C9	0.07844 (13)	0.81976 (10)	0.23091 (10)	0.0127 (2)
C10	−0.08660 (12)	0.75561 (10)	0.22759 (9)	0.0122 (2)
H10A	−0.0865	0.6963	0.2931	0.015*
C11	−0.20389 (13)	0.85225 (10)	0.24478 (10)	0.0127 (2)
C12	−0.26584 (12)	0.91545 (10)	0.14796 (10)	0.0129 (2)
C13	−0.21330 (13)	0.74984 (11)	0.01598 (10)	0.0144 (2)
C14	−0.14542 (13)	0.68669 (10)	0.11005 (10)	0.0132 (2)
C15	−0.13184 (13)	0.55150 (11)	0.10873 (10)	0.0156 (2)
C16	−0.24515 (15)	0.35748 (11)	0.02645 (11)	0.0192 (2)
H16A	−0.2669	0.3273	0.1041	0.023*
H16B	−0.1459	0.3273	0.0090	0.023*
C17	−0.37844 (15)	0.31492 (12)	−0.06902 (12)	0.0209 (2)
H17A	−0.3932	0.2258	−0.0697	0.031*
H17B	−0.3528	0.3425	−0.1456	0.031*
H17C	−0.4743	0.3494	−0.0526	0.031*
C18	−0.23545 (13)	0.88366 (10)	0.36557 (10)	0.0138 (2)
C19	−0.14246 (15)	0.86913 (13)	0.57282 (10)	0.0204 (2)
H19A	−0.2427	0.8322	0.5932	0.024*
H19B	−0.1386	0.9583	0.5862	0.024*
C20	−0.00580 (16)	0.81475 (14)	0.64767 (11)	0.0240 (3)
H20A	−0.0082	0.8352	0.7304	0.036*
H20B	0.0924	0.8484	0.6233	0.036*
H20C	−0.0145	0.7260	0.6370	0.036*
C21	−0.25953 (15)	0.70438 (12)	−0.11096 (10)	0.0185 (2)
H21A	−0.1851	0.6476	−0.1315	0.028*
H21B	−0.2592	0.7739	−0.1637	0.028*
H21C	−0.3638	0.6626	−0.1187	0.028*
C22	−0.34816 (14)	1.03355 (11)	0.14701 (11)	0.0170 (2)
H22A	−0.3285	1.0722	0.2250	0.026*
H22B	−0.4602	1.0152	0.1260	0.026*
H22C	−0.3086	1.0889	0.0895	0.026*
H1N1	0.424 (2)	0.9115 (16)	0.3055 (16)	0.024 (4)*
H1N3	−0.283 (2)	0.9163 (17)	−0.0293 (17)	0.028 (4)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.02373 (16)	0.03297 (19)	0.02383 (16)	0.00309 (12)	−0.00125 (11)	0.01615 (13)
O1	0.0259 (5)	0.0178 (4)	0.0280 (5)	0.0062 (4)	−0.0099 (4)	−0.0029 (4)
O2	0.0228 (4)	0.0133 (4)	0.0165 (4)	−0.0005 (3)	−0.0031 (3)	−0.0010 (3)
O3	0.0169 (4)	0.0239 (4)	0.0101 (4)	0.0046 (3)	0.0008 (3)	−0.0005 (3)
O4	0.0135 (4)	0.0216 (4)	0.0182 (4)	0.0023 (3)	0.0025 (3)	−0.0019 (3)
N1	0.0114 (4)	0.0169 (5)	0.0144 (4)	0.0002 (3)	−0.0002 (3)	0.0025 (3)
N2	0.0139 (4)	0.0187 (5)	0.0157 (4)	0.0008 (4)	0.0009 (3)	0.0051 (4)
N3	0.0151 (4)	0.0149 (5)	0.0123 (4)	0.0010 (3)	0.0002 (3)	0.0033 (3)
C1	0.0162 (5)	0.0192 (5)	0.0146 (5)	0.0001 (4)	0.0001 (4)	0.0015 (4)
C2	0.0170 (5)	0.0265 (6)	0.0145 (5)	−0.0001 (4)	−0.0020 (4)	0.0033 (4)
C3	0.0170 (5)	0.0244 (6)	0.0164 (5)	0.0043 (4)	0.0013 (4)	0.0089 (4)
C4	0.0204 (6)	0.0190 (6)	0.0230 (6)	−0.0005 (4)	−0.0023 (4)	0.0058 (5)
C5	0.0182 (5)	0.0178 (5)	0.0179 (5)	0.0009 (4)	−0.0026 (4)	0.0023 (4)
C6	0.0129 (5)	0.0173 (5)	0.0117 (5)	0.0029 (4)	0.0014 (4)	0.0019 (4)
C7	0.0120 (5)	0.0138 (5)	0.0120 (5)	0.0012 (4)	0.0009 (4)	0.0006 (4)
C8	0.0132 (5)	0.0183 (5)	0.0148 (5)	0.0010 (4)	0.0002 (4)	0.0038 (4)
C9	0.0125 (5)	0.0138 (5)	0.0116 (5)	0.0016 (4)	0.0006 (4)	0.0006 (4)
C10	0.0119 (4)	0.0132 (5)	0.0112 (4)	0.0006 (4)	0.0004 (3)	0.0008 (4)
C11	0.0111 (4)	0.0138 (5)	0.0130 (5)	−0.0003 (4)	0.0011 (4)	0.0000 (4)
C12	0.0100 (4)	0.0137 (5)	0.0146 (5)	−0.0007 (4)	0.0007 (4)	0.0009 (4)
C13	0.0136 (5)	0.0159 (5)	0.0132 (5)	−0.0007 (4)	0.0010 (4)	0.0002 (4)
C14	0.0127 (5)	0.0139 (5)	0.0127 (5)	0.0000 (4)	0.0008 (4)	−0.0006 (4)
C15	0.0147 (5)	0.0165 (5)	0.0154 (5)	0.0007 (4)	0.0014 (4)	−0.0020 (4)
C16	0.0239 (6)	0.0130 (5)	0.0197 (5)	0.0011 (4)	−0.0017 (4)	−0.0010 (4)
C17	0.0238 (6)	0.0172 (6)	0.0205 (6)	0.0001 (4)	−0.0015 (4)	−0.0022 (4)
C18	0.0125 (5)	0.0144 (5)	0.0137 (5)	−0.0016 (4)	0.0005 (4)	0.0003 (4)
C19	0.0195 (5)	0.0311 (7)	0.0110 (5)	0.0035 (5)	0.0025 (4)	−0.0025 (4)
C20	0.0230 (6)	0.0344 (7)	0.0138 (5)	0.0035 (5)	−0.0013 (4)	−0.0006 (5)
C21	0.0226 (6)	0.0200 (6)	0.0121 (5)	0.0006 (4)	−0.0001 (4)	0.0009 (4)
C22	0.0161 (5)	0.0163 (5)	0.0187 (5)	0.0035 (4)	0.0009 (4)	0.0033 (4)

Geometric parameters (Å, º) top

Cl1—C3	1.7387 (12)	C9—C10	1.5169 (15)
O1—C15	1.2117 (14)	C10—C11	1.5233 (15)
O2—C15	1.3430 (14)	C10—C14	1.5241 (15)
O2—C16	1.4467 (14)	C10—H10A	0.9800
O3—C18	1.3440 (13)	C11—C12	1.3611 (15)
O3—C19	1.4519 (14)	C11—C18	1.4625 (15)
O4—C18	1.2233 (14)	C12—C22	1.4977 (16)
N1—N2	1.3556 (13)	C13—C14	1.3552 (15)
N1—C7	1.3628 (15)	C13—C21	1.5042 (16)
N1—H1N1	0.859 (18)	C14—C15	1.4707 (16)
N2—C8	1.3313 (15)	C16—C17	1.5060 (17)
N3—C12	1.3814 (15)	C16—H16A	0.9700
N3—C13	1.3888 (15)	C16—H16B	0.9700
N3—H1N3	0.909 (19)	C17—H17A	0.9600
C1—C2	1.3915 (16)	C17—H17B	0.9600
C1—C6	1.4021 (15)	C17—H17C	0.9600
C1—H1A	0.9300	C19—C20	1.5075 (18)
C2—C3	1.3819 (19)	C19—H19A	0.9700
C2—H2A	0.9300	C19—H19B	0.9700
C3—C4	1.3862 (17)	C20—H20A	0.9600
C4—C5	1.3940 (16)	C20—H20B	0.9600
C4—H4A	0.9300	C20—H20C	0.9600
C5—C6	1.3974 (17)	C21—H21A	0.9600
C5—H5A	0.9300	C21—H21B	0.9600
C6—C7	1.4670 (15)	C21—H21C	0.9600
C7—C9	1.3965 (14)	C22—H22A	0.9600
C8—C9	1.4108 (16)	C22—H22B	0.9600
C8—H8A	0.9300	C22—H22C	0.9600

C15—O2—C16	116.30 (9)	C14—C13—N3	118.15 (10)
C18—O3—C19	116.69 (9)	C14—C13—C21	128.07 (11)
N2—N1—C7	112.89 (9)	N3—C13—C21	113.78 (10)
N2—N1—H1N1	116.7 (12)	C13—C14—C15	123.77 (10)
C7—N1—H1N1	130.0 (12)	C13—C14—C10	119.60 (10)
C8—N2—N1	104.07 (9)	C15—C14—C10	116.55 (9)
C12—N3—C13	121.59 (9)	O1—C15—O2	122.63 (11)
C12—N3—H1N3	118.7 (11)	O1—C15—C14	124.73 (11)
C13—N3—H1N3	117.8 (11)	O2—C15—C14	112.54 (10)
C2—C1—C6	120.24 (11)	O2—C16—C17	105.52 (10)
C2—C1—H1A	119.9	O2—C16—H16A	110.6
C6—C1—H1A	119.9	C17—C16—H16A	110.6
C3—C2—C1	119.54 (11)	O2—C16—H16B	110.6
C3—C2—H2A	120.2	C17—C16—H16B	110.6
C1—C2—H2A	120.2	H16A—C16—H16B	108.8
C2—C3—C4	121.43 (11)	C16—C17—H17A	109.5
C2—C3—Cl1	119.55 (9)	C16—C17—H17B	109.5
C4—C3—Cl1	119.01 (10)	H17A—C17—H17B	109.5
C3—C4—C5	118.96 (12)	C16—C17—H17C	109.5
C3—C4—H4A	120.5	H17A—C17—H17C	109.5
C5—C4—H4A	120.5	H17B—C17—H17C	109.5
C4—C5—C6	120.71 (11)	O4—C18—O3	122.26 (10)
C4—C5—H5A	119.6	O4—C18—C11	126.36 (10)
C6—C5—H5A	119.6	O3—C18—C11	111.38 (9)
C5—C6—C1	119.10 (10)	O3—C19—C20	106.57 (10)
C5—C6—C7	120.83 (10)	O3—C19—H19A	110.4
C1—C6—C7	120.03 (10)	C20—C19—H19A	110.4
N1—C7—C9	106.36 (9)	O3—C19—H19B	110.4
N1—C7—C6	120.39 (10)	C20—C19—H19B	110.4
C9—C7—C6	133.25 (10)	H19A—C19—H19B	108.6
N2—C8—C9	112.86 (10)	C19—C20—H20A	109.5
N2—C8—H8A	123.6	C19—C20—H20B	109.5
C9—C8—H8A	123.6	H20A—C20—H20B	109.5
C7—C9—C8	103.82 (10)	C19—C20—H20C	109.5
C7—C9—C10	131.02 (10)	H20A—C20—H20C	109.5
C8—C9—C10	124.80 (10)	H20B—C20—H20C	109.5
C9—C10—C11	109.34 (9)	C13—C21—H21A	109.5
C9—C10—C14	113.54 (9)	C13—C21—H21B	109.5
C11—C10—C14	107.27 (8)	H21A—C21—H21B	109.5
C9—C10—H10A	108.9	C13—C21—H21C	109.5
C11—C10—H10A	108.9	H21A—C21—H21C	109.5
C14—C10—H10A	108.9	H21B—C21—H21C	109.5
C12—C11—C18	121.40 (10)	C12—C22—H22A	109.5
C12—C11—C10	118.82 (10)	C12—C22—H22B	109.5
C18—C11—C10	119.51 (9)	H22A—C22—H22B	109.5
C11—C12—N3	118.42 (10)	C12—C22—H22C	109.5
C11—C12—C22	127.72 (10)	H22A—C22—H22C	109.5
N3—C12—C22	113.79 (9)	H22B—C22—H22C	109.5

C7—N1—N2—C8	0.62 (13)	C14—C10—C11—C18	146.53 (10)
C6—C1—C2—C3	−0.41 (19)	C18—C11—C12—N3	−172.34 (10)
C1—C2—C3—C4	−0.9 (2)	C10—C11—C12—N3	13.70 (15)
C1—C2—C3—Cl1	178.92 (10)	C18—C11—C12—C22	10.73 (18)
C2—C3—C4—C5	1.7 (2)	C10—C11—C12—C22	−163.24 (11)
Cl1—C3—C4—C5	−178.15 (10)	C13—N3—C12—C11	19.94 (16)
C3—C4—C5—C6	−1.14 (19)	C13—N3—C12—C22	−162.71 (10)
C4—C5—C6—C1	−0.12 (18)	C12—N3—C13—C14	−22.38 (16)
C4—C5—C6—C7	177.48 (11)	C12—N3—C13—C21	157.22 (10)
C2—C1—C6—C5	0.91 (18)	N3—C13—C14—C15	167.42 (10)
C2—C1—C6—C7	−176.72 (11)	C21—C13—C14—C15	−12.11 (19)
N2—N1—C7—C9	−0.39 (13)	N3—C13—C14—C10	−9.08 (16)
N2—N1—C7—C6	178.92 (10)	C21—C13—C14—C10	171.38 (11)
C5—C6—C7—N1	−145.13 (11)	C9—C10—C14—C13	−83.80 (13)
C1—C6—C7—N1	32.45 (16)	C11—C10—C14—C13	37.11 (14)
C5—C6—C7—C9	33.95 (19)	C9—C10—C14—C15	99.45 (12)
C1—C6—C7—C9	−148.47 (13)	C11—C10—C14—C15	−139.64 (10)
N1—N2—C8—C9	−0.62 (13)	C16—O2—C15—O1	3.64 (18)
N1—C7—C9—C8	0.00 (12)	C16—O2—C15—C14	−172.93 (10)
C6—C7—C9—C8	−179.18 (12)	C13—C14—C15—O1	162.09 (13)
N1—C7—C9—C10	−173.26 (11)	C10—C14—C15—O1	−21.31 (17)
C6—C7—C9—C10	7.6 (2)	C13—C14—C15—O2	−21.42 (16)
N2—C8—C9—C7	0.40 (13)	C10—C14—C15—O2	155.18 (10)
N2—C8—C9—C10	174.21 (10)	C15—O2—C16—C17	176.01 (10)
C7—C9—C10—C11	116.66 (13)	C19—O3—C18—O4	−1.74 (17)
C8—C9—C10—C11	−55.36 (14)	C19—O3—C18—C11	178.61 (10)
C7—C9—C10—C14	−123.60 (12)	C12—C11—C18—O4	20.74 (18)
C8—C9—C10—C14	64.38 (14)	C10—C11—C18—O4	−165.33 (11)
C9—C10—C11—C12	84.14 (12)	C12—C11—C18—O3	−159.62 (10)
C14—C10—C11—C12	−39.39 (13)	C10—C11—C18—O3	14.30 (14)
C9—C10—C11—C18	−89.94 (12)	C18—O3—C19—C20	−178.84 (11)

Hydrogen-bond geometry (Å, º) top

Cg1 is the centroid of the N1/N2/C7–C9 ring.

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N1···O4ⁱ	0.857 (17)	2.078 (17)	2.9291 (14)	172.2 (17)
N3—H1N3···N2ⁱⁱ	0.908 (19)	2.184 (19)	3.0427 (14)	157.5 (15)
C5—H5A···O1	0.93	2.27	3.1988 (16)	177
C8—H8A···N3	0.93	2.61	3.2546 (15)	127
C22—H22B···N2ⁱⁱⁱ	0.96	2.50	3.3741 (16)	151
C19—H19B···Cg1^iv	0.96	2.79	3.5562 (14)	137

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

Experimental details

Crystal data
Chemical formula	C₂₂H₂₄ClN₃O₄
M_r	429.89
Crystal system, space group	Triclinic, P1
Temperature (K)	100
a, b, c (Å)	8.5210 (5), 10.7809 (6), 11.2707 (7)
α, β, γ (°)	90.411 (1), 97.205 (1), 94.210 (1)
V (Å³)	1024.28 (10)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.22
Crystal size (mm)	0.38 × 0.18 × 0.17

Data collection
Diffractometer	Bruker SMART APEXII DUO CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2009)
T_min, T_max	0.921, 0.964
No. of measured, independent and observed [I > 2σ(I)] reflections	17114, 5885, 5038
R_int	0.027
(sin θ/λ)_max (Å⁻¹)	0.703

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.038, 0.107, 1.04
No. of reflections	5885
No. of parameters	283
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.44, −0.29

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

Hydrogen-bond geometry (Å, º) top

Cg1 is the centroid of the N1/N2/C7–C9 ring.

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N1···O4ⁱ	0.857 (17)	2.078 (17)	2.9291 (14)	172.2 (17)
N3—H1N3···N2ⁱⁱ	0.908 (19)	2.184 (19)	3.0427 (14)	157.5 (15)
C5—H5A···O1	0.93	2.27	3.1988 (16)	177
C8—H8A···N3	0.93	2.61	3.2546 (15)	127
C22—H22B···N2ⁱⁱⁱ	0.96	2.50	3.3741 (16)	151
C19—H19B···Cg1^iv	0.96	2.79	3.5562 (14)	137

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

Footnotes

‡Thomson Reuters ResearcherID: A-3561-2009.

§Thomson Reuters ResearcherID: C-7581-2009.

¶Additional address: SeQuent Scientific Ltd, No. 120 A & B Industrial Area, Baikampady, New Mangalore 575 011, Karnataka, India.

Acknowledgements

HKF and WSL thank Universiti Sains Malaysia (USM) for the Research University Grant (1001/PFIZIK/811160). WSL also thanks the Malaysian Government and USM for the award of the post of Research Officer under the Research University Grant (1001/PFIZIK/811160). AMI thanks the Department of Atomic Energy, Board for Research in Nuclear Sciences, Government of India for the Young Scientist award. AMV is thankful to Dr Arulmoli, Vice President (R&D) and the management, SeQuent Scientific Ltd, New Mangalore, India, for their invaluable support and allocation of resources for this work.

References

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Volume 68| Part 5| May 2012| Pages o1289-o1290

doi:10.1107/S160053681201344X

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

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

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Experimental

Crystal data

Data collection

Refinement

Supporting information

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Acknowledgements

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organic compounds

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