Diethyl 4-[5-(4-chloro-phen-yl)-1H-pyrazol-4-yl]-2,6-dimethyl-1,4-dihydro-pyridine-3,5-dicarboxyl-ate.

In the title compound, C(22)H(24)ClN(3)O(4), intra-molecular C-H⋯O and C-H⋯N hydrogen bonds form S(9) and S(7) ring motifs, respectively. The 1,4-dihydro-pyridine 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 mol-ecules 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 inter-actions 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 = 429.89

Triclinic,

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[F 2 > 2σ(F 2)] = 0.038

wR(F 2) = 0.107

S = 1.04

5885 reflections

283 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.44 e Å−3

Δρmin = −0.29 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 ▶).

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S160053681201344X/is5103sup1.cif

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

Supplementary material file. DOI: 10.1107/S160053681201344X/is5103Isup3.cml

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

C22H24ClN3O4	Z = 2
Mr = 429.89	F(000) = 452
Triclinic, P1	Dx = 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

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	Rint = 0.027
φ and ω scans	θmax = 30.0°, θmin = 1.8°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −11→11
Tmin = 0.921, Tmax = 0.964	k = −15→15
17114 measured reflections	l = −15→15

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(Fo2) + (0.0519P)2 + 0.4397P] where P = (Fo2 + 2Fc2)/3
5885 reflections	(Δ/σ)max = 0.001
283 parameters	Δρmax = 0.44 e Å−3
0 restraints	Δρmin = −0.29 e Å−3

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.

	x	y	z	Uiso*/Ueq
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)*

	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)

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)

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···Cg1iv	0.96	2.79	3.5562 (14)	137

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⋯Cg1iv	0.96	2.79	3.5562 (14)	137

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