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

In the title compound, C(22)H(25)N(3)O(4), the dihydro-pyridine ring adopts a flattened boat conformation. The pyrazole ring makes a dihedral angle of 29.04 (5)° with the benzene ring. The mol-ecular structure is stabilized by an intra-molecular C-H⋯O hydrogen bond which generates an S(9) ring motif. In the crystal, mol-ecules 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 inter-actions.

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 = 395.45

Monoclinic,

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[F 2 > 2σ(F 2)] = 0.041

wR(F 2) = 0.118

S = 1.04

7361 reflections

266 parameters

H-atom parameters constrained

Δρmax = 0.47 e Å−3

Δρmin = −0.19 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/S1600536812008173/is5081sup1.cif

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

Supplementary material file. DOI: 10.1107/S1600536812008173/is5081Isup3.cml

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

C22H25N3O4	F(000) = 840
Mr = 395.45	Dx = 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

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

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(Fo2) + (0.0611P)2 + 0.510P] where P = (Fo2 + 2Fc2)/3
7361 reflections	(Δ/σ)max < 0.001
266 parameters	Δρmax = 0.47 e Å−3
0 restraints	Δρmin = −0.19 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
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*

	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)

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)

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···N2iv	0.96	2.45	3.3300 (14)	153
C16—H16A···Cg1v	0.97	2.80	3.5318 (11)	133
C17—H17C···Cg2	0.96	2.99	3.7750 (15)	140
C19—H19A···Cg2vi	0.97	2.88	3.7079 (11)	144

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⋯N2iv	0.96	2.45	3.3300 (14)	153
C16—H16A⋯Cg1v	0.97	2.80	3.5318 (11)	133
C17—H17C⋯Cg2	0.96	2.99	3.7750 (15)	140
C19—H19A⋯Cg2vi	0.97	2.88	3.7079 (11)	144

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