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

In the title compound, C23H27N3O4, the dihydro-pyridine ring adopts a (1,4)B conformation. Intra-molecular C-H⋯O contacts occur. In the crystal, N-H⋯O and N-H⋯N hydrogen bonds and C-H⋯N contacts connect the mol-ecules into strands along the a-axis direction.

Related literature

For background to the biological and pharmaceutical importance of dihydro­pyridine compounds, see: Stout & Meyers (1982 ▶); Vijesh et al. (2011 ▶); Boecker & Guengerich (1986 ▶); Vo et al. (1995 ▶). For puckering analysis, see: Cremer & Pople (1975 ▶); Boeyens (1978 ▶). For graph-set analysis of hydrogen bonds, see: Etter et al. (1990 ▶); Bernstein et al. (1995 ▶).

Experimental

Crystal data

C23H27N3O4

M = 409.48

Triclinic,

a = 8.5905 (2) Å

b = 10.8253 (3) Å

c = 11.3702 (3) Å

α = 91.021 (1)°

β = 97.922 (1)°

γ = 93.445 (1)°

V = 1045.02 (5) Å3

Z = 2

Mo Kα radiation

μ = 0.09 mm−1

T = 200 K

0.36 × 0.31 × 0.16 mm

Data collection

Bruker APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2008 ▶) T min = 0.969, T max = 0.986

18073 measured reflections

4983 independent reflections

4313 reflections with I > 2σ(I)

R int = 0.017

Refinement

R[F 2 > 2σ(F 2)] = 0.041

wR(F 2) = 0.113

S = 1.05

4983 reflections

284 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.33 e Å−3

Δρmin = −0.21 e Å−3

Data collection: APEX2 (Bruker, 2010 ▶); cell refinement: SAINT (Bruker, 2010 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 2012 ▶) and Mercury (Macrae et al., 2008 ▶); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009 ▶).

Click here for additional data file.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812044649/hg5264sup1.cif

Click here for additional data file.

Supplementary material file. DOI: 10.1107/S1600536812044649/hg5264Isup2.cdx

Click here for additional data file.

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812044649/hg5264Isup3.hkl

Click here for additional data file.

Supplementary material file. DOI: 10.1107/S1600536812044649/hg5264Isup4.cml

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

C23H27N3O4	Z = 2
Mr = 409.48	F(000) = 436
Triclinic, P1	Dx = 1.301 Mg m−3
Hall symbol: -P 1	Melting point = 471–473 K
a = 8.5905 (2) Å	Mo Kα radiation, λ = 0.71073 Å
b = 10.8253 (3) Å	Cell parameters from 9960 reflections
c = 11.3702 (3) Å	θ = 2.7–28.3°
α = 91.021 (1)°	µ = 0.09 mm−1
β = 97.922 (1)°	T = 200 K
γ = 93.445 (1)°	Block, yellow
V = 1045.02 (5) Å3	0.36 × 0.31 × 0.16 mm

Bruker APEXII CCD diffractometer	4983 independent reflections
Radiation source: fine-focus sealed tube	4313 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.017
φ and ω scans	θmax = 28.0°, θmin = 2.4°
Absorption correction: multi-scan (SADABS; Bruker, 2008)	h = −11→11
Tmin = 0.969, Tmax = 0.986	k = −14→14
18073 measured reflections	l = −15→14

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) = 0.113	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ2(Fo2) + (0.0515P)2 + 0.4147P] where P = (Fo2 + 2Fc2)/3
4983 reflections	(Δ/σ)max < 0.001
284 parameters	Δρmax = 0.33 e Å−3
0 restraints	Δρmin = −0.21 e Å−3

	x	y	z	Uiso*/Ueq
O1	0.45908 (13)	0.00208 (9)	0.66938 (10)	0.0463 (3)
O2	0.25873 (11)	−0.00254 (8)	0.52185 (9)	0.0327 (2)
O3	0.15357 (10)	0.44024 (9)	0.88752 (8)	0.0317 (2)
O4	0.37379 (10)	0.34282 (9)	0.94459 (8)	0.0304 (2)
N11	0.25151 (12)	0.37638 (9)	0.53483 (9)	0.0245 (2)
H11B	0.2162 (19)	0.4218 (15)	0.4735 (15)	0.034 (4)*
N21	0.76600 (12)	0.46269 (10)	0.68190 (10)	0.0280 (2)
N22	0.82226 (12)	0.39623 (9)	0.77631 (9)	0.0242 (2)
H22	0.923 (2)	0.4087 (15)	0.8088 (14)	0.033 (4)*
C1	0.24030 (17)	0.21083 (13)	0.38718 (11)	0.0343 (3)
H1A	0.1319	0.1744	0.3764	0.051*
H1B	0.3115	0.1484	0.3679	0.051*
H1C	0.2478	0.2810	0.3345	0.051*
C2	0.15003 (15)	0.53629 (12)	0.64804 (12)	0.0297 (3)
H2A	0.1726	0.5759	0.7273	0.045*
H2B	0.0363	0.5174	0.6282	0.045*
H2C	0.1865	0.5924	0.5894	0.045*
C3	0.36694 (14)	0.05624 (11)	0.60280 (11)	0.0266 (2)
C4	0.25461 (18)	−0.13674 (12)	0.51954 (14)	0.0362 (3)
H4A	0.2425	−0.1689	0.5990	0.043*
H4B	0.3530	−0.1658	0.4957	0.043*
C5	0.11687 (18)	−0.17966 (13)	0.43120 (14)	0.0403 (3)
H5A	0.0216	−0.1448	0.4528	0.060*
H5B	0.1041	−0.2702	0.4305	0.060*
H5C	0.1342	−0.1521	0.3521	0.060*
C6	0.26466 (13)	0.38529 (11)	0.86200 (11)	0.0237 (2)
C7	0.35707 (17)	0.36804 (16)	1.06793 (12)	0.0378 (3)
H7A	0.2562	0.3296	1.0866	0.045*
H7B	0.3589	0.4584	1.0837	0.045*
C8	0.49288 (19)	0.31395 (17)	1.14178 (13)	0.0443 (4)
H8A	0.4903	0.3340	1.2258	0.066*
H8B	0.5918	0.3486	1.1184	0.066*
H8C	0.4855	0.2238	1.1294	0.066*
C9	0.90941 (19)	−0.02184 (15)	1.18484 (14)	0.0431 (4)
H9A	0.8981	0.0137	1.2629	0.065*
H9B	1.0204	−0.0360	1.1817	0.065*
H9C	0.8465	−0.1007	1.1719	0.065*
C11	0.41373 (12)	0.25920 (10)	0.72388 (10)	0.0203 (2)
H11	0.4153	0.1989	0.7895	0.024*
C12	0.35319 (13)	0.19111 (11)	0.60642 (10)	0.0226 (2)
C13	0.28586 (14)	0.25489 (11)	0.51391 (11)	0.0244 (2)
C14	0.23363 (13)	0.41889 (11)	0.64688 (11)	0.0228 (2)
C15	0.29660 (13)	0.35556 (10)	0.74185 (10)	0.0210 (2)
C21	0.57727 (13)	0.32159 (10)	0.72757 (10)	0.0211 (2)
C22	0.61806 (14)	0.41725 (12)	0.65375 (11)	0.0265 (3)
H22A	0.5473	0.4465	0.5902	0.032*
C23	0.71422 (13)	0.31013 (10)	0.80674 (10)	0.0214 (2)
C31	0.75666 (13)	0.22762 (11)	0.90584 (10)	0.0231 (2)
C32	0.86603 (15)	0.26894 (12)	1.00279 (11)	0.0282 (3)
H32	0.9084	0.3523	1.0074	0.034*
C33	0.91302 (16)	0.18844 (13)	1.09262 (12)	0.0327 (3)
H33	0.9883	0.2177	1.1578	0.039*
C34	0.85291 (15)	0.06632 (13)	1.08966 (12)	0.0321 (3)
C35	0.74117 (17)	0.02728 (13)	0.99461 (13)	0.0357 (3)
H35	0.6959	−0.0551	0.9921	0.043*
C36	0.69364 (15)	0.10560 (12)	0.90293 (12)	0.0311 (3)
H36	0.6180	0.0760	0.8381	0.037*

	U11	U22	U33	U12	U13	U23
O1	0.0470 (6)	0.0281 (5)	0.0564 (7)	0.0101 (4)	−0.0218 (5)	−0.0044 (5)
O2	0.0351 (5)	0.0228 (4)	0.0369 (5)	0.0006 (4)	−0.0064 (4)	−0.0024 (4)
O3	0.0226 (4)	0.0383 (5)	0.0348 (5)	0.0059 (4)	0.0047 (4)	−0.0034 (4)
O4	0.0269 (4)	0.0430 (5)	0.0215 (4)	0.0090 (4)	0.0015 (3)	−0.0001 (4)
N11	0.0230 (5)	0.0253 (5)	0.0242 (5)	0.0011 (4)	−0.0010 (4)	0.0067 (4)
N21	0.0209 (5)	0.0310 (5)	0.0316 (5)	0.0012 (4)	0.0004 (4)	0.0109 (4)
N22	0.0178 (5)	0.0265 (5)	0.0273 (5)	0.0015 (4)	−0.0012 (4)	0.0056 (4)
C1	0.0409 (7)	0.0360 (7)	0.0239 (6)	−0.0007 (6)	−0.0016 (5)	0.0017 (5)
C2	0.0244 (6)	0.0273 (6)	0.0373 (7)	0.0063 (5)	0.0012 (5)	0.0064 (5)
C3	0.0243 (6)	0.0256 (6)	0.0292 (6)	0.0018 (4)	0.0018 (5)	−0.0019 (5)
C4	0.0398 (7)	0.0222 (6)	0.0439 (8)	0.0016 (5)	−0.0033 (6)	−0.0025 (5)
C5	0.0424 (8)	0.0287 (7)	0.0462 (8)	−0.0004 (6)	−0.0042 (6)	−0.0033 (6)
C6	0.0189 (5)	0.0236 (5)	0.0277 (6)	−0.0015 (4)	0.0016 (4)	0.0002 (4)
C7	0.0341 (7)	0.0567 (9)	0.0229 (6)	0.0055 (6)	0.0049 (5)	−0.0031 (6)
C8	0.0413 (8)	0.0642 (10)	0.0255 (7)	0.0036 (7)	−0.0025 (6)	0.0007 (6)
C9	0.0408 (8)	0.0478 (9)	0.0400 (8)	0.0045 (7)	0.0001 (6)	0.0213 (7)
C11	0.0176 (5)	0.0212 (5)	0.0216 (5)	0.0016 (4)	0.0004 (4)	0.0029 (4)
C12	0.0199 (5)	0.0229 (5)	0.0245 (5)	−0.0003 (4)	0.0022 (4)	0.0000 (4)
C13	0.0209 (5)	0.0265 (6)	0.0248 (6)	−0.0025 (4)	0.0013 (4)	0.0012 (4)
C14	0.0158 (5)	0.0230 (5)	0.0287 (6)	−0.0008 (4)	0.0010 (4)	0.0031 (4)
C15	0.0164 (5)	0.0212 (5)	0.0251 (5)	0.0002 (4)	0.0016 (4)	0.0017 (4)
C21	0.0182 (5)	0.0224 (5)	0.0223 (5)	0.0031 (4)	0.0007 (4)	0.0019 (4)
C22	0.0195 (5)	0.0304 (6)	0.0287 (6)	0.0020 (4)	−0.0006 (4)	0.0089 (5)
C23	0.0188 (5)	0.0221 (5)	0.0229 (5)	0.0031 (4)	0.0012 (4)	0.0009 (4)
C31	0.0195 (5)	0.0258 (6)	0.0239 (5)	0.0046 (4)	0.0011 (4)	0.0033 (4)
C32	0.0265 (6)	0.0293 (6)	0.0272 (6)	−0.0008 (5)	−0.0008 (5)	0.0033 (5)
C33	0.0287 (6)	0.0409 (7)	0.0262 (6)	0.0007 (5)	−0.0047 (5)	0.0060 (5)
C34	0.0272 (6)	0.0384 (7)	0.0311 (6)	0.0052 (5)	0.0023 (5)	0.0127 (5)
C35	0.0344 (7)	0.0284 (6)	0.0419 (8)	−0.0012 (5)	−0.0030 (6)	0.0101 (6)
C36	0.0275 (6)	0.0286 (6)	0.0339 (7)	0.0007 (5)	−0.0070 (5)	0.0045 (5)

O1—C3	1.2041 (16)	C7—H7A	0.9900
O2—C3	1.3373 (15)	C7—H7B	0.9900
O2—C4	1.4508 (15)	C8—H8A	0.9800
O3—C6	1.2195 (15)	C8—H8B	0.9800
O4—C6	1.3403 (14)	C8—H8C	0.9800
O4—C7	1.4521 (15)	C9—C34	1.5050 (18)
N11—C14	1.3785 (16)	C9—H9A	0.9800
N11—C13	1.3886 (16)	C9—H9B	0.9800
N11—H11B	0.890 (17)	C9—H9C	0.9800
N21—C22	1.3292 (15)	C11—C21	1.5167 (15)
N21—N22	1.3527 (14)	C11—C15	1.5223 (15)
N22—C23	1.3586 (15)	C11—C12	1.5247 (15)
N22—H22	0.892 (17)	C11—H11	1.0000
C1—C13	1.5015 (17)	C12—C13	1.3505 (16)
C1—H1A	0.9800	C14—C15	1.3559 (16)
C1—H1B	0.9800	C21—C23	1.3926 (15)
C1—H1C	0.9800	C21—C22	1.4029 (16)
C2—C14	1.4977 (16)	C22—H22A	0.9500
C2—H2A	0.9800	C23—C31	1.4704 (15)
C2—H2B	0.9800	C31—C32	1.3945 (17)
C2—H2C	0.9800	C31—C36	1.3952 (17)
C3—C12	1.4720 (16)	C32—C33	1.3877 (17)
C4—C5	1.488 (2)	C32—H32	0.9500
C4—H4A	0.9900	C33—C34	1.388 (2)
C4—H4B	0.9900	C33—H33	0.9500
C5—H5A	0.9800	C34—C35	1.3845 (19)
C5—H5B	0.9800	C35—C36	1.3885 (18)
C5—H5C	0.9800	C35—H35	0.9500
C6—C15	1.4641 (16)	C36—H36	0.9500
C7—C8	1.496 (2)
C3—O2—C4	116.55 (10)	C34—C9—H9A	109.5
C6—O4—C7	116.94 (10)	C34—C9—H9B	109.5
C14—N11—C13	121.46 (10)	H9A—C9—H9B	109.5
C14—N11—H11B	117.7 (10)	C34—C9—H9C	109.5
C13—N11—H11B	119.0 (10)	H9A—C9—H9C	109.5
C22—N21—N22	103.83 (9)	H9B—C9—H9C	109.5
N21—N22—C23	112.96 (10)	C21—C11—C15	109.87 (9)
N21—N22—H22	119.8 (10)	C21—C11—C12	113.53 (9)
C23—N22—H22	127.1 (10)	C15—C11—C12	106.87 (9)
C13—C1—H1A	109.5	C21—C11—H11	108.8
C13—C1—H1B	109.5	C15—C11—H11	108.8
H1A—C1—H1B	109.5	C12—C11—H11	108.8
C13—C1—H1C	109.5	C13—C12—C3	123.65 (11)
H1A—C1—H1C	109.5	C13—C12—C11	119.48 (10)
H1B—C1—H1C	109.5	C3—C12—C11	116.82 (10)
C14—C2—H2A	109.5	C12—C13—N11	118.14 (11)
C14—C2—H2B	109.5	C12—C13—C1	128.04 (11)
H2A—C2—H2B	109.5	N11—C13—C1	113.82 (11)
C14—C2—H2C	109.5	C15—C14—N11	118.45 (10)
H2A—C2—H2C	109.5	C15—C14—C2	127.45 (11)
H2B—C2—H2C	109.5	N11—C14—C2	114.04 (10)
O1—C3—O2	122.52 (11)	C14—C15—C6	121.38 (10)
O1—C3—C12	124.48 (11)	C14—C15—C11	118.89 (10)
O2—C3—C12	112.88 (10)	C6—C15—C11	119.52 (10)
O2—C4—C5	106.23 (11)	C23—C21—C22	103.87 (10)
O2—C4—H4A	110.5	C23—C21—C11	130.71 (10)
C5—C4—H4A	110.5	C22—C21—C11	125.13 (10)
O2—C4—H4B	110.5	N21—C22—C21	113.03 (10)
C5—C4—H4B	110.5	N21—C22—H22A	123.5
H4A—C4—H4B	108.7	C21—C22—H22A	123.5
C4—C5—H5A	109.5	N22—C23—C21	106.30 (10)
C4—C5—H5B	109.5	N22—C23—C31	120.22 (10)
H5A—C5—H5B	109.5	C21—C23—C31	133.47 (11)
C4—C5—H5C	109.5	C32—C31—C36	118.69 (11)
H5A—C5—H5C	109.5	C32—C31—C23	120.25 (11)
H5B—C5—H5C	109.5	C36—C31—C23	121.01 (11)
O3—C6—O4	122.45 (11)	C33—C32—C31	120.06 (12)
O3—C6—C15	126.12 (11)	C33—C32—H32	120.0
O4—C6—C15	111.42 (10)	C31—C32—H32	120.0
O4—C7—C8	106.79 (11)	C32—C33—C34	121.70 (12)
O4—C7—H7A	110.4	C32—C33—H33	119.2
C8—C7—H7A	110.4	C34—C33—H33	119.2
O4—C7—H7B	110.4	C35—C34—C33	117.73 (12)
C8—C7—H7B	110.4	C35—C34—C9	120.89 (13)
H7A—C7—H7B	108.6	C33—C34—C9	121.37 (13)
C7—C8—H8A	109.5	C34—C35—C36	121.64 (13)
C7—C8—H8B	109.5	C34—C35—H35	119.2
H8A—C8—H8B	109.5	C36—C35—H35	119.2
C7—C8—H8C	109.5	C35—C36—C31	120.15 (12)
H8A—C8—H8C	109.5	C35—C36—H36	119.9
H8B—C8—H8C	109.5	C31—C36—H36	119.9
C22—N21—N22—C23	0.64 (14)	C21—C11—C15—C14	83.76 (12)
C4—O2—C3—O1	1.44 (19)	C12—C11—C15—C14	−39.82 (13)
C4—O2—C3—C12	−174.64 (11)	C21—C11—C15—C6	−91.09 (12)
C3—O2—C4—C5	174.86 (12)	C12—C11—C15—C6	145.33 (10)
C7—O4—C6—O3	−1.67 (18)	C15—C11—C21—C23	116.11 (13)
C7—O4—C6—C15	179.04 (11)	C12—C11—C21—C23	−124.30 (13)
C6—O4—C7—C8	−179.02 (12)	C15—C11—C21—C22	−56.77 (15)
O1—C3—C12—C13	159.81 (14)	C12—C11—C21—C22	62.82 (15)
O2—C3—C12—C13	−24.20 (17)	N22—N21—C22—C21	−0.49 (14)
O1—C3—C12—C11	−22.62 (18)	C23—C21—C22—N21	0.18 (14)
O2—C3—C12—C11	153.37 (10)	C11—C21—C22—N21	174.63 (11)
C21—C11—C12—C13	−83.11 (13)	N21—N22—C23—C21	−0.54 (14)
C15—C11—C12—C13	38.18 (14)	N21—N22—C23—C31	178.60 (10)
C21—C11—C12—C3	99.21 (12)	C22—C21—C23—N22	0.21 (13)
C15—C11—C12—C3	−139.50 (10)	C11—C21—C23—N22	−173.80 (11)
C3—C12—C13—N11	167.37 (11)	C22—C21—C23—C31	−178.77 (12)
C11—C12—C13—N11	−10.14 (16)	C11—C21—C23—C31	7.2 (2)
C3—C12—C13—C1	−12.1 (2)	N22—C23—C31—C32	32.05 (17)
C11—C12—C13—C1	170.34 (11)	C21—C23—C31—C32	−149.08 (13)
C14—N11—C13—C12	−22.13 (16)	N22—C23—C31—C36	−145.42 (12)
C14—N11—C13—C1	157.45 (11)	C21—C23—C31—C36	33.4 (2)
C13—N11—C14—C15	20.38 (16)	C36—C31—C32—C33	1.51 (19)
C13—N11—C14—C2	−162.15 (10)	C23—C31—C32—C33	−176.02 (11)
N11—C14—C15—C6	−171.78 (10)	C31—C32—C33—C34	−0.5 (2)
C2—C14—C15—C6	11.14 (18)	C32—C33—C34—C35	−1.2 (2)
N11—C14—C15—C11	13.47 (15)	C32—C33—C34—C9	177.43 (13)
C2—C14—C15—C11	−163.61 (11)	C33—C34—C35—C36	2.0 (2)
O3—C6—C15—C14	21.00 (18)	C9—C34—C35—C36	−176.65 (14)
O4—C6—C15—C14	−159.74 (11)	C34—C35—C36—C31	−1.1 (2)
O3—C6—C15—C11	−164.28 (11)	C32—C31—C36—C35	−0.75 (19)
O4—C6—C15—C11	14.98 (14)	C23—C31—C36—C35	176.77 (12)

D—H···A	D—H	H···A	D···A	D—H···A
N11—H11B···N21i	0.890 (17)	2.200 (17)	3.0352 (14)	156.2 (14)
N22—H22···O3ii	0.892 (17)	2.066 (17)	2.9580 (13)	178.6 (15)
C2—H2B···N21iii	0.98	2.52	3.4223 (16)	153
C36—H36···O1	0.95	2.30	3.2428 (17)	173

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N11—H11B⋯N21i	0.890 (17)	2.200 (17)	3.0352 (14)	156.2 (14)
N22—H22⋯O3ii	0.892 (17)	2.066 (17)	2.9580 (13)	178.6 (15)
C2—H2B⋯N21iii	0.98	2.52	3.4223 (16)	153
C36—H36⋯O1	0.95	2.30	3.2428 (17)	173

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