Diethyl 2,6-dimethyl-4-(4-pyrid­yl)-1,4-dihydro­pyridine-3,5-dicarboxyl­ate

Li, Y.

doi:10.1107/S1600536810016934

organic compounds

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ISSN: 2056-9890

Volume 66| Part 6| June 2010| Page o1334

https://doi.org/10.1107/S1600536810016934

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Diethyl 2,6-dimethyl-4-(4-pyridyl)-1,4-dihydropyridine-3,5-dicarboxylate

Yumei Li ^a ^*

^aDepartment of Chemistry, Dezhou University, Shandong 253023, People's Republic of China
^*Correspondence e-mail: liyumei_dzc@yahoo.com.cn

(Received 20 April 2010; accepted 10 May 2010; online 15 May 2010)

In the title compound, C₁₈H₂₂N₂O₄, the dihedral angle between the two rings is 87.90 (6)°. The mean devation of the atoms in the dihydropyridine plane is 0.082 (3) Å. In the crystal, molecules are linked by intermolecular N—H⋯N hydrogen bonds, generating chains.

Related literature

For general background to the biological activity of 1,4-dihydropyridine derivatives, see: Gaudio et al. (1994 ).

Experimental

Crystal data

C₁₈H₂₂N₂O₄
M_r = 330.38
Monoclinic, P 2₁ /n
a = 11.5550 (2) Å
b = 13.1707 (2) Å
c = 11.8020 (2) Å
β = 92.705 (2)°
V = 1794.11 (5) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 296 K
0.12 × 0.10 × 0.08 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2001 ) T_min = 0.990, T_max = 0.993
9122 measured reflections
3152 independent reflections
2308 reflections with I > 2σ(I)
R_int = 0.032

Refinement

R[F² > 2σ(F²)] = 0.045
wR(F²) = 0.128
S = 1.03
3152 reflections
227 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.15 e Å⁻³
Δρ_min = −0.19 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2N⋯N1ⁱ	0.86 (2)	2.13 (2)	2.984 (2)	171.8 (18)
Symmetry code: (i) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2004 ); cell refinement: SAINT-Plus (Bruker, 2001); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536810016934/om2336sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810016934/om2336Isup2.hkl

checkCIF report

Comment top

The synthesis of 1,4-dihydropyridine derivatives has attracted continuous research interest due to various vasodilator, anti-hypertensive, bronchodilator, heptaprotective, anti-tumor, anti-mutagenic, geroprotective and anti-diabetic agents (Gaudio et al., 1994).

The molecular structure of the title compound is shown in Fig 1. The dihedral angle between the two rings is 87.90 (6) °. The mean devation of the dihydropyridine plane is 0.082 (3)Å. The intermolecular hydrogen bonding of N(2)—H(2A)···N(1) leads to a consolidation of the structure (Fig. 2; Table 1).

Related literature top

For general background to the biological activity of 1,4-dihydropyridine derivatives, see: Gaudio et al. (1994).

Experimental top

Diethyl 2,6-dimethyl-4-(4-pyridyl)-1,4-dihydropyridine-3,5-dicarboxylate was purchased from Jinan Henghua Science & Technology Co. Ltd. Diethyl 2,6-dimethyl-4-(4-pyridyl)-1,4-dihydropyridine-3,5-dicarboxylate (1 mmoL 0.39 g) was dissolved in 20 ml ethanol, which was evaporated in an open flask at room temperature. One week later, yellow block crystals suitable for the X-ray experiment were obained. Anal. C₁₈H₂₂N₂O₄: C, 65.37; H, 6.66; N, 8.48 %. Found: C, 65.32; H, 6.45; N, 8.39 %.

Structure description top

For general background to the biological activity of 1,4-dihydropyridine derivatives, see: Gaudio et al. (1994).

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT-Plus (Bruker, 2001); data reduction: SAINT-Plus (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Diethyl 2,6-dimethyl-4-(4-pyridyl)-1,4-dihydropyridine-3,5-dicarboxylate top

Crystal data top

C₁₈H₂₂N₂O₄	F(000) = 704
M_r = 330.38	D_x = 1.223 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 2361 reflections
a = 11.5550 (2) Å	θ = 2.3–24.5°
b = 13.1707 (2) Å	µ = 0.09 mm⁻¹
c = 11.8020 (2) Å	T = 296 K
β = 92.705 (2)°	Block, yellow
V = 1794.11 (5) Å³	0.12 × 0.10 × 0.08 mm
Z = 4

Data collection top

Bruker APEXII CCD diffractometer	3152 independent reflections
Radiation source: fine-focus sealed tube	2308 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.032
φ and ω scans	θ_max = 25.0°, θ_min = 2.3°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −11→13
T_min = 0.990, T_max = 0.993	k = −15→15
9122 measured reflections	l = −14→13

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)] = 0.045	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.128	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ²(F_o²) + (0.0645P)² + 0.2873P] where P = (F_o² + 2F_c²)/3
3152 reflections	(Δ/σ)_max = 0.001
227 parameters	Δρ_max = 0.15 e Å⁻³
0 restraints	Δρ_min = −0.19 e Å⁻³

Crystal data top

C₁₈H₂₂N₂O₄	V = 1794.11 (5) Å³
M_r = 330.38	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 11.5550 (2) Å	µ = 0.09 mm⁻¹
b = 13.1707 (2) Å	T = 296 K
c = 11.8020 (2) Å	0.12 × 0.10 × 0.08 mm
β = 92.705 (2)°

Data collection top

Bruker APEXII CCD diffractometer	3152 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2001)	2308 reflections with I > 2σ(I)
T_min = 0.990, T_max = 0.993	R_int = 0.032
9122 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.045	0 restraints
wR(F²) = 0.128	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	Δρ_max = 0.15 e Å⁻³
3152 reflections	Δρ_min = −0.19 e Å⁻³
227 parameters

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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	Occ. (<1)
O1	0.33862 (13)	0.01201 (15)	0.15684 (14)	0.0917 (6)
O2	0.50534 (12)	−0.07176 (10)	0.16753 (11)	0.0597 (4)
O3	0.80150 (10)	0.08444 (10)	0.58574 (10)	0.0539 (4)
O4	0.81559 (11)	−0.01782 (11)	0.43654 (12)	0.0630 (4)
N1	0.82662 (14)	0.18151 (15)	0.07048 (14)	0.0616 (5)
N2	0.47955 (13)	0.18372 (12)	0.43985 (13)	0.0472 (4)
H2N	0.4391 (17)	0.2279 (15)	0.4751 (16)	0.058 (6)*
C1	0.76016 (19)	0.23648 (17)	0.13643 (17)	0.0626 (6)
H1	0.7595	0.3066	0.1272	0.075*
C2	0.69267 (17)	0.19512 (14)	0.21726 (16)	0.0527 (5)
H2	0.6482	0.2374	0.2610	0.063*
C3	0.69017 (13)	0.09216 (12)	0.23420 (13)	0.0376 (4)
C4	0.75744 (16)	0.03451 (15)	0.16496 (15)	0.0525 (5)
H4	0.7586	−0.0358	0.1717	0.063*
C5	0.82298 (17)	0.08201 (18)	0.08560 (17)	0.0631 (6)
H5	0.8674	0.0415	0.0399	0.076*
C6	0.76250 (15)	0.04661 (14)	0.48574 (14)	0.0431 (4)
C7	0.91311 (16)	0.04589 (17)	0.62964 (17)	0.0601 (5)
H7A	0.9739	0.0664	0.5806	0.072*
H7B	0.9116	−0.0277	0.6328	0.072*
C8	0.9350 (2)	0.0879 (2)	0.7438 (2)	0.0949 (9)
H8A	0.9386	0.1606	0.7394	0.142*
H8B	1.0072	0.0622	0.7754	0.142*
H8C	0.8734	0.0684	0.7911	0.142*
C9	0.43413 (16)	0.00167 (16)	0.20127 (15)	0.0514 (5)
C10	0.4620 (2)	−0.13703 (19)	0.0762 (2)	0.0795 (7)
H10A	0.4463	−0.0974	0.0079	0.095*
H10B	0.3905	−0.1694	0.0967	0.095*
C11	0.5496 (3)	−0.2133 (3)	0.0566 (3)	0.1604 (18)
H11A	0.6205	−0.1805	0.0384	0.241*
H11B	0.5236	−0.2562	−0.0053	0.241*
H11C	0.5624	−0.2536	0.1238	0.241*
C12	0.61631 (13)	0.04467 (13)	0.32414 (13)	0.0373 (4)
H12	0.6308	−0.0286	0.3252	0.045*
C13	0.48786 (14)	0.06167 (13)	0.29414 (14)	0.0405 (4)
C14	0.42771 (14)	0.13185 (13)	0.34979 (14)	0.0424 (4)
C15	0.58549 (14)	0.15725 (13)	0.49037 (14)	0.0425 (4)
C16	0.65116 (13)	0.08686 (12)	0.44024 (13)	0.0381 (4)
C17	0.61248 (18)	0.21403 (17)	0.59884 (16)	0.0614 (6)
H17A	0.6361	0.1669	0.6575	0.092*	0.60 (2)
H17B	0.5447	0.2499	0.6205	0.092*	0.60 (2)
H17C	0.6739	0.2615	0.5878	0.092*	0.60 (2)
H17D	0.6004	0.2854	0.5864	0.092*	0.40 (2)
H17E	0.6918	0.2023	0.6233	0.092*	0.40 (2)
H17F	0.5625	0.1907	0.6561	0.092*	0.40 (2)
C18	0.30334 (15)	0.16157 (17)	0.32620 (17)	0.0584 (5)
H18A	0.2596	0.1466	0.3913	0.088*	0.59 (2)
H18B	0.2721	0.1242	0.2620	0.088*	0.59 (2)
H18C	0.2989	0.2330	0.3102	0.088*	0.59 (2)
H18D	0.2941	0.1892	0.2511	0.088*	0.41 (2)
H18E	0.2816	0.2116	0.3804	0.088*	0.41 (2)
H18F	0.2548	0.1028	0.3321	0.088*	0.41 (2)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0504 (9)	0.1327 (15)	0.0895 (11)	0.0078 (9)	−0.0249 (9)	−0.0411 (11)
O2	0.0560 (8)	0.0669 (9)	0.0552 (8)	−0.0058 (7)	−0.0078 (7)	−0.0177 (7)
O3	0.0388 (7)	0.0738 (9)	0.0480 (7)	0.0130 (6)	−0.0106 (6)	−0.0075 (6)
O4	0.0505 (8)	0.0732 (9)	0.0643 (9)	0.0217 (7)	−0.0080 (7)	−0.0164 (7)
N1	0.0482 (10)	0.0823 (13)	0.0547 (10)	−0.0138 (9)	0.0065 (8)	0.0115 (9)
N2	0.0358 (8)	0.0622 (10)	0.0436 (9)	0.0121 (7)	−0.0003 (7)	−0.0067 (8)
C1	0.0689 (14)	0.0555 (12)	0.0637 (13)	−0.0175 (11)	0.0050 (11)	0.0075 (10)
C2	0.0552 (12)	0.0487 (11)	0.0551 (11)	−0.0048 (9)	0.0113 (9)	−0.0026 (9)
C3	0.0289 (8)	0.0479 (10)	0.0355 (9)	−0.0015 (7)	−0.0038 (7)	−0.0004 (7)
C4	0.0520 (11)	0.0542 (12)	0.0522 (11)	0.0069 (9)	0.0121 (9)	0.0029 (9)
C5	0.0491 (12)	0.0853 (17)	0.0563 (13)	0.0091 (11)	0.0171 (10)	0.0050 (11)
C6	0.0383 (10)	0.0507 (10)	0.0401 (10)	0.0015 (8)	0.0004 (8)	0.0003 (8)
C7	0.0367 (10)	0.0759 (14)	0.0662 (13)	0.0114 (10)	−0.0129 (9)	−0.0020 (11)
C8	0.0617 (15)	0.144 (2)	0.0762 (16)	0.0252 (16)	−0.0278 (13)	−0.0237 (17)
C9	0.0433 (11)	0.0666 (13)	0.0441 (11)	−0.0083 (9)	0.0010 (9)	−0.0025 (9)
C10	0.0852 (17)	0.0833 (17)	0.0684 (14)	−0.0116 (14)	−0.0149 (13)	−0.0286 (13)
C11	0.172 (4)	0.139 (3)	0.164 (3)	0.065 (3)	−0.066 (3)	−0.101 (3)
C12	0.0350 (9)	0.0402 (9)	0.0366 (9)	−0.0001 (7)	0.0009 (7)	0.0014 (7)
C13	0.0342 (9)	0.0510 (10)	0.0362 (9)	−0.0058 (8)	0.0011 (7)	0.0040 (8)
C14	0.0329 (9)	0.0555 (11)	0.0386 (9)	−0.0012 (8)	0.0011 (7)	0.0066 (8)
C15	0.0363 (9)	0.0543 (11)	0.0366 (9)	0.0025 (8)	−0.0002 (8)	0.0015 (8)
C16	0.0324 (9)	0.0443 (10)	0.0374 (9)	0.0013 (7)	−0.0002 (7)	0.0008 (7)
C17	0.0537 (12)	0.0806 (14)	0.0493 (11)	0.0159 (10)	−0.0048 (9)	−0.0170 (10)
C18	0.0339 (10)	0.0825 (14)	0.0586 (12)	0.0053 (9)	−0.0019 (9)	0.0038 (11)

Geometric parameters (Å, º) top

O1—C9	1.207 (2)	C9—C13	1.465 (2)
O2—C9	1.342 (2)	C10—C11	1.452 (4)
O2—C10	1.449 (2)	C10—H10A	0.9700
O3—C6	1.339 (2)	C10—H10B	0.9700
O3—C7	1.458 (2)	C11—H11A	0.9600
O4—C6	1.211 (2)	C11—H11B	0.9600
N1—C5	1.324 (3)	C11—H11C	0.9600
N1—C1	1.333 (3)	C12—C16	1.515 (2)
N2—C14	1.377 (2)	C12—C13	1.526 (2)
N2—C15	1.381 (2)	C12—H12	0.9800
N2—H2N	0.86 (2)	C13—C14	1.346 (2)
C1—C2	1.373 (3)	C14—C18	1.503 (2)
C1—H1	0.9300	C15—C16	1.352 (2)
C2—C3	1.371 (2)	C15—C17	1.503 (2)
C2—H2	0.9300	C17—H17A	0.9600
C3—C4	1.381 (2)	C17—H17B	0.9600
C3—C12	1.527 (2)	C17—H17C	0.9600
C4—C5	1.382 (3)	C17—H17D	0.9600
C4—H4	0.9300	C17—H17E	0.9600
C5—H5	0.9300	C17—H17F	0.9600
C6—C16	1.470 (2)	C18—H18A	0.9600
C7—C8	1.467 (3)	C18—H18B	0.9600
C7—H7A	0.9700	C18—H18C	0.9600
C7—H7B	0.9700	C18—H18D	0.9600
C8—H8A	0.9600	C18—H18E	0.9600
C8—H8B	0.9600	C18—H18F	0.9600
C8—H8C	0.9600

C9—O2—C10	116.92 (16)	H11A—C11—H11B	109.5
C6—O3—C7	116.02 (14)	C10—C11—H11C	109.5
C5—N1—C1	115.87 (17)	H11A—C11—H11C	109.5
C14—N2—C15	123.55 (16)	H11B—C11—H11C	109.5
C14—N2—H2N	118.7 (13)	C16—C12—C13	111.71 (13)
C15—N2—H2N	116.8 (13)	C16—C12—C3	110.18 (13)
N1—C1—C2	123.51 (19)	C13—C12—C3	110.37 (13)
N1—C1—H1	118.2	C16—C12—H12	108.2
C2—C1—H1	118.2	C13—C12—H12	108.2
C3—C2—C1	120.68 (18)	C3—C12—H12	108.2
C3—C2—H2	119.7	C14—C13—C9	121.67 (16)
C1—C2—H2	119.7	C14—C13—C12	120.43 (15)
C2—C3—C4	116.16 (16)	C9—C13—C12	117.87 (15)
C2—C3—C12	121.52 (15)	C13—C14—N2	120.11 (15)
C4—C3—C12	122.32 (15)	C13—C14—C18	126.85 (16)
C3—C4—C5	119.59 (18)	N2—C14—C18	113.03 (16)
C3—C4—H4	120.2	C16—C15—N2	119.26 (15)
C5—C4—H4	120.2	C16—C15—C17	128.02 (15)
N1—C5—C4	124.17 (19)	N2—C15—C17	112.72 (15)
N1—C5—H5	117.9	C15—C16—C6	125.97 (15)
C4—C5—H5	117.9	C15—C16—C12	121.10 (14)
O4—C6—O3	121.74 (15)	C6—C16—C12	112.88 (14)
O4—C6—C16	122.14 (16)	C15—C17—H17A	109.5
O3—C6—C16	116.11 (15)	C15—C17—H17B	109.5
O3—C7—C8	107.81 (17)	H17A—C17—H17B	109.5
O3—C7—H7A	110.1	C15—C17—H17C	109.5
C8—C7—H7A	110.1	H17A—C17—H17C	109.5
O3—C7—H7B	110.1	H17B—C17—H17C	109.5
C8—C7—H7B	110.1	C15—C17—H17D	109.5
H7A—C7—H7B	108.5	C15—C17—H17E	109.5
C7—C8—H8A	109.5	H17D—C17—H17E	109.5
C7—C8—H8B	109.5	C15—C17—H17F	109.5
H8A—C8—H8B	109.5	H17D—C17—H17F	109.5
C7—C8—H8C	109.5	H17E—C17—H17F	109.5
H8A—C8—H8C	109.5	C14—C18—H18A	109.5
H8B—C8—H8C	109.5	C14—C18—H18B	109.5
O1—C9—O2	120.87 (17)	H18A—C18—H18B	109.5
O1—C9—C13	127.63 (19)	C14—C18—H18C	109.5
O2—C9—C13	111.50 (15)	H18A—C18—H18C	109.5
O2—C10—C11	108.0 (2)	H18B—C18—H18C	109.5
O2—C10—H10A	110.1	C14—C18—H18D	109.5
C11—C10—H10A	110.1	C14—C18—H18E	109.5
O2—C10—H10B	110.1	H18D—C18—H18E	109.5
C11—C10—H10B	110.1	C14—C18—H18F	109.5
H10A—C10—H10B	108.4	H18D—C18—H18F	109.5
C10—C11—H11A	109.5	H18E—C18—H18F	109.5
C10—C11—H11B	109.5

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2N···N1ⁱ	0.86 (2)	2.13 (2)	2.984 (2)	171.8 (18)

Symmetry code: (i) x−1/2, −y+1/2, z+1/2.

Experimental details

Crystal data
Chemical formula	C₁₈H₂₂N₂O₄
M_r	330.38
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	296
a, b, c (Å)	11.5550 (2), 13.1707 (2), 11.8020 (2)
β (°)	92.705 (2)
V (Å³)	1794.11 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.12 × 0.10 × 0.08

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2001)
T_min, T_max	0.990, 0.993
No. of measured, independent and observed [I > 2σ(I)] reflections	9122, 3152, 2308
R_int	0.032
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.045, 0.128, 1.03
No. of reflections	3152
No. of parameters	227
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.15, −0.19

Computer programs: APEX2 (Bruker, 2004), SAINT-Plus (Bruker, 2001), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2N···N1ⁱ	0.86 (2)	2.13 (2)	2.984 (2)	171.8 (18)

Symmetry code: (i) x−1/2, −y+1/2, z+1/2.

References

Bruker (2001). SAINT-Plus and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Bruker (2004). APEX2. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Gaudio, A. C., Korolkovas, A. & Takahata, Y. (1994). J. Pharm. Sci. A83, 1110–1115. CrossRef Web of Science Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar

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Volume 66| Part 6| June 2010| Page o1334

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