Diethyl 2,6-dimethyl-4-phenyl-1,4-dihydro-pyridine-3,5-dicarboxyl-ate.

The title mol-ecule, C(19)H(23)NO(4), was synthesized by the reaction of benzaldehyde, ethyl acetoacetate and NH(4)HCO(3). The dihydro-pyridine ring adopts a flattened boat conformation and the plane of the base of the boat forms a dihedral angle of 88.78 (9)° with the phenyl ring. The packing is stabilized by strong inter-molecular N-H⋯O and weak inter-molecular C-H⋯O hydrogen bonds.

Related literature

For general background, see: Cutshall et al. (2002 ▶); Henry (2004 ▶). For the crystal structure of the related compound diethyl 2,6-dimethyl-4-styryl-1,4-dihydro­pyridine-3,5-dicarb­oxyl­ate, see: Wang et al., (2007 ▶). For hydrogen bond definitions, see: Desiraju & Steiner (1999 ▶).

Experimental

Crystal data

C19H23NO4

M = 329.38

Monoclinic,

a = 9.7502 (12) Å

b = 7.3854 (9) Å

c = 24.326 (2) Å

β = 92.567 (1)°

V = 1749.9 (3) Å3

Z = 4

Mo Kα radiation

μ = 0.09 mm−1

T = 298 K

0.50 × 0.46 × 0.32 mm

Data collection

Siemens SMART 1000 CCD diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T min = 0.958, T max = 0.973

8718 measured reflections

3084 independent reflections

1989 reflections with I > 2σ(I)

R int = 0.033

Refinement

R[F 2 > 2σ(F 2)] = 0.045

wR(F 2) = 0.131

S = 1.01

3084 reflections

225 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.22 e Å−3

Δρmin = −0.18 e Å−3

Data collection: SMART (Siemens, 1996 ▶); cell refinement: SAINT (Siemens, 1996 ▶); data reduction: SAINT; 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: SHELXTL.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809009118/fb2141sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809009118/fb2141Isup2.hkl

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

C19H23NO4	F(000) = 704
Mr = 329.38	Dx = 1.250 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P2ybc	Cell parameters from 2342 reflections
a = 9.7502 (12) Å	θ = 2.6–27.7°
b = 7.3854 (9) Å	µ = 0.09 mm−1
c = 24.326 (2) Å	T = 298 K
β = 92.567 (1)°	Block, yellow
V = 1749.9 (3) Å3	0.50 × 0.46 × 0.32 mm
Z = 4

Siemens SMART 1000 CCD diffractometer	3084 independent reflections
Radiation source: fine-focus sealed tube	1989 reflections with I > 2σ(I)
graphite	Rint = 0.033
φ and ω scans	θmax = 25.0°, θmin = 1.7°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −7→11
Tmin = 0.958, Tmax = 0.973	k = −8→8
8718 measured reflections	l = −28→28

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.045	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.131	w = 1/[σ2(Fo2) + (0.0521P)2 + 0.8294P] where P = (Fo2 + 2Fc2)/3
S = 1.01	(Δ/σ)max < 0.001
3084 reflections	Δρmax = 0.22 e Å−3
225 parameters	Δρmin = −0.18 e Å−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
85 constraints	Extinction coefficient: 0.0027 (8)
Primary atom site location: structure-invariant direct methods

Experimental. The sample was cut out from a larger slab crystal.

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 > 2sigma(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
N1	0.3363 (2)	1.1267 (3)	0.55024 (8)	0.0405 (5)
H1	0.327 (3)	1.230 (4)	0.5394 (10)	0.049*
O1	0.57917 (16)	0.6975 (2)	0.65667 (7)	0.0476 (5)
O2	0.66266 (19)	0.9781 (3)	0.66376 (8)	0.0619 (6)
O3	0.14967 (17)	0.6965 (2)	0.46314 (6)	0.0468 (5)
O4	0.2624 (2)	0.5071 (2)	0.51964 (7)	0.0572 (5)
C1	0.4405 (2)	1.0939 (3)	0.58911 (9)	0.0376 (6)
C2	0.4587 (2)	0.9233 (3)	0.60794 (9)	0.0332 (5)
C3	0.3494 (2)	0.7821 (3)	0.59344 (8)	0.0324 (5)
H3	0.3937	0.6630	0.5927	0.039*
C4	0.2846 (2)	0.8200 (3)	0.53680 (8)	0.0318 (5)
C5	0.2721 (2)	0.9937 (3)	0.51905 (9)	0.0356 (5)
C6	0.2424 (2)	0.7790 (3)	0.63775 (8)	0.0323 (5)
C7	0.2655 (2)	0.6791 (4)	0.68509 (10)	0.0469 (6)
H7	0.3436	0.6070	0.6888	0.056*
C8	0.1752 (3)	0.6838 (4)	0.72719 (10)	0.0565 (8)
H8	0.1939	0.6175	0.7592	0.068*
C9	0.0577 (3)	0.7862 (4)	0.72192 (10)	0.0538 (7)
H9	−0.0035	0.7891	0.7501	0.065*
C10	0.0315 (3)	0.8837 (4)	0.67494 (10)	0.0497 (7)
H10	−0.0483	0.9524	0.6710	0.060*
C11	0.1231 (2)	0.8805 (3)	0.63333 (10)	0.0411 (6)
H11	0.1043	0.9481	0.6016	0.049*
C12	0.5222 (3)	1.2590 (3)	0.60462 (11)	0.0547 (7)
H12A	0.4892	1.3092	0.6379	0.082*
H12B	0.5126	1.3469	0.5756	0.082*
H12C	0.6172	1.2268	0.6102	0.082*
C13	0.5757 (2)	0.8760 (3)	0.64511 (9)	0.0387 (6)
C14	0.2330 (2)	0.6604 (3)	0.50671 (9)	0.0345 (5)
C15	0.1963 (3)	1.0650 (3)	0.46890 (10)	0.0508 (7)
H15A	0.2214	0.9965	0.4373	0.076*
H15B	0.2196	1.1900	0.4638	0.076*
H15C	0.0993	1.0543	0.4733	0.076*
C16	0.6846 (3)	0.6355 (4)	0.69600 (11)	0.0582 (8)
H16A	0.7690	0.7009	0.6902	0.070*
H16B	0.7019	0.5079	0.6898	0.070*
C17	0.6457 (4)	0.6618 (5)	0.75336 (12)	0.0819 (10)
H17A	0.6362	0.7888	0.7606	0.123*
H17B	0.7156	0.6118	0.7779	0.123*
H17C	0.5601	0.6018	0.7589	0.123*
C18	0.1024 (3)	0.5457 (3)	0.42944 (10)	0.0497 (7)
H18A	0.0477	0.4640	0.4507	0.060*
H18B	0.1800	0.4791	0.4162	0.060*
C19	0.0187 (4)	0.6213 (4)	0.38256 (12)	0.0757 (10)
H19A	−0.0562	0.6897	0.3962	0.114*
H19B	−0.0167	0.5242	0.3598	0.114*
H19C	0.0747	0.6988	0.3612	0.114*

	U11	U22	U33	U12	U13	U23
N1	0.0507 (13)	0.0230 (10)	0.0470 (12)	−0.0013 (10)	−0.0054 (10)	0.0019 (9)
O1	0.0410 (10)	0.0462 (11)	0.0542 (11)	0.0029 (8)	−0.0141 (8)	0.0051 (8)
O2	0.0573 (12)	0.0616 (12)	0.0647 (12)	−0.0180 (10)	−0.0213 (10)	0.0014 (10)
O3	0.0648 (11)	0.0324 (9)	0.0415 (9)	−0.0024 (8)	−0.0184 (8)	−0.0023 (7)
O4	0.0876 (14)	0.0259 (9)	0.0555 (11)	0.0040 (9)	−0.0245 (10)	0.0001 (8)
C1	0.0402 (14)	0.0340 (14)	0.0385 (13)	−0.0032 (11)	0.0009 (11)	−0.0053 (10)
C2	0.0344 (12)	0.0335 (13)	0.0316 (11)	−0.0016 (10)	0.0000 (10)	−0.0018 (10)
C3	0.0371 (13)	0.0252 (12)	0.0345 (12)	−0.0002 (10)	−0.0037 (10)	0.0014 (9)
C4	0.0373 (13)	0.0273 (12)	0.0305 (11)	0.0001 (10)	−0.0014 (10)	0.0010 (9)
C5	0.0425 (14)	0.0316 (12)	0.0327 (12)	0.0017 (11)	0.0009 (10)	0.0003 (10)
C6	0.0356 (13)	0.0285 (12)	0.0323 (12)	−0.0057 (10)	−0.0052 (9)	0.0015 (9)
C7	0.0388 (14)	0.0544 (17)	0.0468 (15)	−0.0019 (12)	−0.0055 (12)	0.0163 (12)
C8	0.0498 (16)	0.078 (2)	0.0414 (15)	−0.0118 (15)	−0.0034 (13)	0.0210 (14)
C9	0.0481 (16)	0.0715 (19)	0.0424 (15)	−0.0113 (15)	0.0079 (12)	0.0010 (14)
C10	0.0471 (15)	0.0519 (16)	0.0507 (16)	0.0061 (13)	0.0075 (13)	0.0032 (13)
C11	0.0452 (14)	0.0398 (14)	0.0382 (13)	0.0031 (12)	0.0006 (11)	0.0069 (11)
C12	0.0603 (17)	0.0389 (15)	0.0641 (17)	−0.0110 (13)	−0.0057 (14)	−0.0053 (13)
C13	0.0356 (13)	0.0459 (15)	0.0347 (13)	−0.0038 (12)	0.0019 (10)	−0.0027 (11)
C14	0.0421 (13)	0.0304 (13)	0.0309 (12)	−0.0003 (11)	−0.0005 (10)	0.0006 (10)
C15	0.0710 (18)	0.0355 (14)	0.0446 (15)	0.0015 (13)	−0.0099 (13)	0.0069 (11)
C16	0.0473 (16)	0.0625 (19)	0.0629 (18)	0.0087 (14)	−0.0179 (13)	0.0062 (14)
C17	0.091 (2)	0.098 (3)	0.0554 (19)	0.010 (2)	−0.0085 (17)	0.0202 (18)
C18	0.0689 (18)	0.0353 (14)	0.0436 (14)	−0.0102 (13)	−0.0112 (13)	−0.0056 (11)
C19	0.105 (3)	0.0559 (18)	0.0620 (19)	−0.0032 (18)	−0.0383 (18)	−0.0064 (15)

N1—C5	1.375 (3)	C8—H8	0.9300
N1—C1	1.378 (3)	C9—C10	1.365 (4)
N1—H1	0.81 (3)	C9—H9	0.9300
O1—C13	1.348 (3)	C10—C11	1.380 (3)
O1—C16	1.447 (3)	C10—H10	0.9300
O2—C13	1.208 (3)	C11—H11	0.9300
O3—C14	1.333 (3)	C12—H12A	0.9600
O3—C18	1.445 (3)	C12—H12B	0.9600
O4—C14	1.206 (3)	C12—H12C	0.9600
C1—C2	1.349 (3)	C15—H15A	0.9600
C1—C12	1.495 (3)	C15—H15B	0.9600
C2—C13	1.466 (3)	C15—H15C	0.9600
C2—C3	1.522 (3)	C16—C17	1.475 (4)
C3—C4	1.516 (3)	C16—H16A	0.9700
C3—C6	1.533 (3)	C16—H16B	0.9700
C3—H3	0.9800	C17—H17A	0.9600
C4—C5	1.357 (3)	C17—H17B	0.9600
C4—C14	1.464 (3)	C17—H17C	0.9600
C5—C15	1.493 (3)	C18—C19	1.482 (4)
C6—C7	1.378 (3)	C18—H18A	0.9700
C6—C11	1.384 (3)	C18—H18B	0.9700
C7—C8	1.381 (3)	C19—H19A	0.9600
C7—H7	0.9300	C19—H19B	0.9600
C8—C9	1.374 (4)	C19—H19C	0.9600
C5—N1—C1	123.83 (19)	C1—C12—H12B	109.5
C5—N1—H1	116.7 (19)	H12A—C12—H12B	109.5
C1—N1—H1	117.3 (19)	C1—C12—H12C	109.5
C13—O1—C16	117.3 (2)	H12A—C12—H12C	109.5
C14—O3—C18	117.68 (17)	H12B—C12—H12C	109.5
C2—C1—N1	118.6 (2)	O2—C13—O1	121.4 (2)
C2—C1—C12	128.0 (2)	O2—C13—C2	126.6 (2)
N1—C1—C12	113.4 (2)	O1—C13—C2	111.9 (2)
C1—C2—C13	121.2 (2)	O4—C14—O3	121.6 (2)
C1—C2—C3	118.8 (2)	O4—C14—C4	123.6 (2)
C13—C2—C3	119.83 (19)	O3—C14—C4	114.84 (19)
C4—C3—C2	110.05 (17)	C5—C15—H15A	109.5
C4—C3—C6	111.88 (17)	C5—C15—H15B	109.5
C2—C3—C6	109.81 (17)	H15A—C15—H15B	109.5
C4—C3—H3	108.3	C5—C15—H15C	109.5
C2—C3—H3	108.3	H15A—C15—H15C	109.5
C6—C3—H3	108.3	H15B—C15—H15C	109.5
C5—C4—C14	125.3 (2)	O1—C16—C17	112.2 (2)
C5—C4—C3	119.46 (19)	O1—C16—H16A	109.2
C14—C4—C3	115.16 (18)	C17—C16—H16A	109.2
C4—C5—N1	117.9 (2)	O1—C16—H16B	109.2
C4—C5—C15	128.8 (2)	C17—C16—H16B	109.2
N1—C5—C15	113.3 (2)	H16A—C16—H16B	107.9
C7—C6—C11	117.4 (2)	C16—C17—H17A	109.5
C7—C6—C3	120.3 (2)	C16—C17—H17B	109.5
C11—C6—C3	122.23 (19)	H17A—C17—H17B	109.5
C6—C7—C8	121.4 (2)	C16—C17—H17C	109.5
C6—C7—H7	119.3	H17A—C17—H17C	109.5
C8—C7—H7	119.3	H17B—C17—H17C	109.5
C9—C8—C7	120.1 (2)	O3—C18—C19	107.3 (2)
C9—C8—H8	119.9	O3—C18—H18A	110.3
C7—C8—H8	119.9	C19—C18—H18A	110.3
C10—C9—C8	119.5 (2)	O3—C18—H18B	110.3
C10—C9—H9	120.2	C19—C18—H18B	110.3
C8—C9—H9	120.2	H18A—C18—H18B	108.5
C9—C10—C11	120.1 (2)	C18—C19—H19A	109.5
C9—C10—H10	119.9	C18—C19—H19B	109.5
C11—C10—H10	119.9	H19A—C19—H19B	109.5
C10—C11—C6	121.4 (2)	C18—C19—H19C	109.5
C10—C11—H11	119.3	H19A—C19—H19C	109.5
C6—C11—H11	119.3	H19B—C19—H19C	109.5
C1—C12—H12A	109.5

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O4i	0.81 (3)	2.19 (3)	2.986 (3)	168 (3)
C3—H3···O1	0.98	2.35	2.733 (3)	103
C3—H3···O4	0.98	2.43	2.816 (3)	103
C7—H7···O1	0.93	2.55	3.169 (3)	124
C12—H12C···O2	0.96	2.27	2.841 (3)	116
C15—H15A···O3	0.96	2.42	2.762 (3)	101
C8—H8···O2ii	0.93	2.51	3.387 (3)	157

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O4i	0.81 (3)	2.19 (3)	2.986 (3)	168 (3)
C3—H3⋯O1	0.98	2.35	2.733 (3)	103
C3—H3⋯O4	0.98	2.43	2.816 (3)	103
C7—H7⋯O1	0.93	2.55	3.169 (3)	124
C12—H12C⋯O2	0.96	2.27	2.841 (3)	116
C15—H15A⋯O3	0.96	2.42	2.762 (3)	101
C8—H8⋯O2ii	0.93	2.51	3.387 (3)	157

Symmetry codes: (i) ; (ii) .