Dimethyl 4-(4-formyl-phen-yl)-2,6-di-methyl-1,4-dihydro-pyridine-3,5-dicar-boxyl-ate.

The title compound, C(18)H(19)NO(5), is a product of the Hantzsch reaction of p-phthalaldehyde, methyl acetoacetate, and ammonium acetate. The 1,4-dihydro-pyridine ring of the mol-ecule adopts a flattened boat conformation. The benzene ring is almost perpendicular to the 1,4-dihydro-pyridine ring; the plane through the six C atoms of the benzene ring and the plane through the four C atoms that form the base of the boat-shaped 1,4-dihydro-pyridine ring (excluding the ring N atom and the opposite ring C atom) make a dihedral angle of 87.60 (3)°. Inter-molecular N-H⋯O hydrogen bonds result in the formation of extended chains along the a axis.

Related literature

For a related 1,4-dihydro­pyridine structure, see: Fossheim et al. (1982 ▶). For the synthesis of 1,4-dihydro­pyridines, see: Hantzsch & Liebigs (1882 ▶). For the biological activity of 1,4-dihydro­pyridines, see: Janis & Triggle (1983 ▶).

Experimental

Crystal data

C18H19NO5

M = 329.34

Triclinic,

a = 8.219 (2) Å

b = 10.432 (3) Å

c = 10.979 (3) Å

α = 111.364 (3)°

β = 102.799 (3)°

γ = 101.150 (4)°

V = 815.0 (4) Å3

Z = 2

Mo Kα radiation

μ = 0.10 mm−1

T = 298 (2) K

0.48 × 0.34 × 0.10 mm

Data collection

Bruker SMART CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS: Sheldrick, 2004 ▶) T min = 0.954, T max = 0.990

4173 measured reflections

2855 independent reflections

2352 reflections with I > 2σ(I)

R int = 0.015

Refinement

R[F 2 > 2σ(F 2)] = 0.052

wR(F 2) = 0.140

S = 1.04

2855 reflections

221 parameters

H-atom parameters constrained

Δρmax = 0.25 e Å−3

Δρmin = −0.23 e Å−3

Data collection: SMART (Bruker, 2001 ▶); cell refinement: SAINT (Bruker, 2001 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997 ▶); molecular graphics: SHELXTL (Sheldrick, 2001 ▶); software used to prepare material for publication: SHELXTL.

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536807063428/sq2008sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536807063428/sq2008Isup2.hkl

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

C18H19NO5	Z = 2
Mr = 329.34	F000 = 348
Triclinic, P1	Dx = 1.342 Mg m−3
Hall symbol: -P 1	Melting point: 479 K
a = 8.219 (2) Å	Mo Kα radiation λ = 0.71073 Å
b = 10.432 (3) Å	Cell parameters from 1572 reflections
c = 10.979 (3) Å	θ = 2.2–26.7º
α = 111.364 (3)º	µ = 0.10 mm−1
β = 102.799 (3)º	T = 298 (2) K
γ = 101.150 (4)º	Plate, colourless
V = 815.0 (4) Å3	0.48 × 0.34 × 0.10 mm

Bruker SMART CCD area-detector diffractometer	2855 independent reflections
Radiation source: fine-focus sealed tube	2352 reflections with I > 2σ(I)
Monochromator: graphite	Rint = 0.015
T = 298(2) K	θmax = 25.1º
phi and ω scans	θmin = 2.1º
Absorption correction: multi-scan(SADABS: Sheldrick, 2004)	h = −7→9
Tmin = 0.954, Tmax = 0.990	k = −12→12
4173 measured reflections	l = −13→11

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.052	H-atom parameters constrained
wR(F2) = 0.140	w = 1/[σ2(Fo2) + (0.0745P)2 + 0.2263P] where P = (Fo2 + 2Fc2)/3
S = 1.04	(Δ/σ)max < 0.001
2855 reflections	Δρmax = 0.25 e Å−3
221 parameters	Δρmin = −0.23 e Å−3
Primary atom site location: structure-invariant direct methods	Extinction correction: none

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
C1	0.0487 (3)	0.7111 (3)	0.2379 (2)	0.0540 (6)
H1A	0.1663	0.7527	0.2429	0.081*
H1B	−0.0263	0.7598	0.2053	0.081*
H1C	0.0087	0.6105	0.1753	0.081*
C2	0.1597 (3)	0.6835 (2)	0.4429 (2)	0.0369 (5)
C3	0.1430 (2)	0.7146 (2)	0.58051 (19)	0.0316 (4)
C4	0.2082 (3)	0.6488 (2)	0.6575 (2)	0.0360 (5)
C5	0.3136 (3)	0.5473 (2)	0.6249 (3)	0.0501 (6)
H5A	0.2939	0.5048	0.5272	0.075*
H5B	0.2792	0.4727	0.6538	0.075*
H5C	0.4355	0.5989	0.6725	0.075*
C6	−0.0172 (3)	0.7028 (3)	0.9224 (3)	0.0562 (6)
H6A	−0.0266	0.7913	0.9853	0.084*
H6B	0.0693	0.6730	0.9707	0.084*
H6C	−0.1282	0.6294	0.8845	0.084*
C7	0.0357 (3)	0.7258 (2)	0.8083 (2)	0.0369 (5)
C8	−0.0337 (2)	0.7922 (2)	0.73481 (19)	0.0326 (4)
C9	−0.1879 (3)	0.8380 (2)	0.7515 (2)	0.0403 (5)
C10	−0.3909 (3)	0.9447 (3)	0.6724 (3)	0.0648 (7)
H10A	−0.4883	0.8609	0.6436	0.097*
H10B	−0.4126	0.9901	0.6110	0.097*
H10C	−0.3759	1.0113	0.7646	0.097*
C11	0.0538 (2)	0.8272 (2)	0.63858 (18)	0.0298 (4)
H11	−0.0369	0.8235	0.5614	0.036*
C12	0.1873 (2)	0.9776 (2)	0.70850 (19)	0.0306 (4)
C13	0.2279 (3)	1.0506 (2)	0.6300 (2)	0.0352 (5)
H13	0.1695	1.0093	0.5356	0.042*
C14	0.3539 (3)	1.1837 (2)	0.6906 (2)	0.0387 (5)
H14	0.3797	1.2310	0.6368	0.046*
C15	0.4421 (2)	1.2473 (2)	0.8316 (2)	0.0360 (5)
C16	0.5802 (3)	1.3855 (2)	0.8933 (2)	0.0443 (5)
H16	0.5943	1.4329	0.8374	0.053*
C17	0.4002 (3)	1.1764 (2)	0.9107 (2)	0.0423 (5)
H17	0.4576	1.2186	1.0054	0.051*
C18	0.2739 (3)	1.0439 (2)	0.8499 (2)	0.0395 (5)
H18	0.2461	0.9981	0.9044	0.047*
O1	0.2601 (3)	0.6284 (2)	0.39502 (18)	0.0686 (5)
O2	0.0449 (2)	0.72623 (17)	0.37188 (14)	0.0483 (4)
O3	−0.23540 (19)	0.90263 (18)	0.66944 (17)	0.0504 (4)
O4	−0.2703 (2)	0.8207 (2)	0.8252 (2)	0.0747 (6)
O5	0.6775 (2)	1.44321 (17)	1.01131 (17)	0.0562 (5)
N1	0.1702 (2)	0.67213 (19)	0.77876 (18)	0.0412 (4)
H1	0.2335	0.6523	0.8389	0.049*

	U11	U22	U33	U12	U13	U23
C1	0.0704 (16)	0.0601 (15)	0.0303 (12)	0.0144 (12)	0.0190 (11)	0.0191 (11)
C2	0.0353 (10)	0.0365 (11)	0.0348 (11)	0.0084 (9)	0.0136 (9)	0.0106 (9)
C3	0.0284 (9)	0.0344 (10)	0.0300 (10)	0.0073 (8)	0.0094 (8)	0.0126 (8)
C4	0.0324 (10)	0.0351 (10)	0.0359 (11)	0.0063 (8)	0.0084 (8)	0.0136 (9)
C5	0.0477 (13)	0.0487 (13)	0.0603 (15)	0.0223 (11)	0.0167 (11)	0.0264 (12)
C6	0.0671 (16)	0.0706 (16)	0.0500 (14)	0.0234 (13)	0.0269 (12)	0.0401 (13)
C7	0.0367 (11)	0.0396 (11)	0.0322 (11)	0.0063 (9)	0.0105 (9)	0.0158 (9)
C8	0.0303 (10)	0.0386 (11)	0.0272 (10)	0.0072 (8)	0.0098 (8)	0.0134 (8)
C9	0.0353 (11)	0.0498 (12)	0.0351 (11)	0.0104 (9)	0.0154 (9)	0.0162 (10)
C10	0.0452 (14)	0.0819 (19)	0.088 (2)	0.0365 (13)	0.0322 (14)	0.0428 (16)
C11	0.0283 (9)	0.0377 (10)	0.0242 (9)	0.0097 (8)	0.0084 (8)	0.0140 (8)
C12	0.0305 (10)	0.0353 (10)	0.0307 (10)	0.0144 (8)	0.0129 (8)	0.0151 (8)
C13	0.0385 (11)	0.0391 (11)	0.0297 (10)	0.0129 (9)	0.0097 (8)	0.0166 (9)
C14	0.0419 (11)	0.0422 (12)	0.0427 (12)	0.0157 (9)	0.0182 (9)	0.0255 (10)
C15	0.0329 (10)	0.0365 (11)	0.0408 (11)	0.0133 (8)	0.0139 (9)	0.0162 (9)
C16	0.0418 (12)	0.0413 (12)	0.0522 (14)	0.0134 (10)	0.0155 (11)	0.0219 (11)
C17	0.0429 (12)	0.0461 (12)	0.0304 (11)	0.0070 (9)	0.0097 (9)	0.0126 (9)
C18	0.0436 (12)	0.0438 (12)	0.0301 (11)	0.0060 (9)	0.0127 (9)	0.0177 (9)
O1	0.0757 (12)	0.0995 (15)	0.0529 (11)	0.0537 (12)	0.0386 (10)	0.0324 (10)
O2	0.0566 (9)	0.0688 (10)	0.0300 (8)	0.0290 (8)	0.0194 (7)	0.0240 (7)
O3	0.0424 (9)	0.0688 (11)	0.0632 (11)	0.0303 (8)	0.0285 (8)	0.0392 (9)
O4	0.0658 (12)	0.1291 (18)	0.0740 (13)	0.0490 (12)	0.0508 (11)	0.0651 (13)
O5	0.0491 (9)	0.0482 (9)	0.0542 (11)	0.0042 (8)	0.0013 (8)	0.0173 (8)
N1	0.0425 (10)	0.0499 (11)	0.0385 (10)	0.0177 (8)	0.0100 (8)	0.0266 (8)

C1—O2	1.429 (2)	C9—O4	1.203 (2)
C1—H1A	0.9600	C9—O3	1.344 (2)
C1—H1B	0.9600	C10—O3	1.432 (3)
C1—H1C	0.9600	C10—H10A	0.9600
C2—O1	1.202 (2)	C10—H10B	0.9600
C2—O2	1.337 (3)	C10—H10C	0.9600
C2—C3	1.469 (3)	C11—C12	1.529 (3)
C3—C4	1.355 (3)	C11—H11	0.9800
C3—C11	1.522 (3)	C12—C18	1.390 (3)
C4—N1	1.381 (3)	C12—C13	1.394 (3)
C4—C5	1.489 (3)	C13—C14	1.381 (3)
C5—H5A	0.9600	C13—H13	0.9300
C5—H5B	0.9600	C14—C15	1.389 (3)
C5—H5C	0.9600	C14—H14	0.9300
C6—C7	1.495 (3)	C15—C17	1.386 (3)
C6—H6A	0.9600	C15—C16	1.463 (3)
C6—H6B	0.9600	C16—O5	1.211 (3)
C6—H6C	0.9600	C16—H16	0.9300
C7—C8	1.346 (3)	C17—C18	1.378 (3)
C7—N1	1.381 (3)	C17—H17	0.9300
C8—C9	1.463 (3)	C18—H18	0.9300
C8—C11	1.511 (2)	N1—H1	0.8600
O2—C1—H1A	109.5	O3—C10—H10B	109.5
O2—C1—H1B	109.5	H10A—C10—H10B	109.5
H1A—C1—H1B	109.5	O3—C10—H10C	109.5
O2—C1—H1C	109.5	H10A—C10—H10C	109.5
H1A—C1—H1C	109.5	H10B—C10—H10C	109.5
H1B—C1—H1C	109.5	C8—C11—C3	110.09 (15)
O1—C2—O2	121.76 (19)	C8—C11—C12	112.69 (15)
O1—C2—C3	127.5 (2)	C3—C11—C12	109.55 (15)
O2—C2—C3	110.72 (16)	C8—C11—H11	108.1
C4—C3—C2	121.94 (18)	C3—C11—H11	108.1
C4—C3—C11	119.60 (17)	C12—C11—H11	108.1
C2—C3—C11	118.44 (16)	C18—C12—C13	118.16 (18)
C3—C4—N1	118.15 (18)	C18—C12—C11	121.69 (16)
C3—C4—C5	127.55 (19)	C13—C12—C11	120.14 (16)
N1—C4—C5	114.27 (17)	C14—C13—C12	120.86 (18)
C4—C5—H5A	109.5	C14—C13—H13	119.6
C4—C5—H5B	109.5	C12—C13—H13	119.6
H5A—C5—H5B	109.5	C13—C14—C15	120.34 (18)
C4—C5—H5C	109.5	C13—C14—H14	119.8
H5A—C5—H5C	109.5	C15—C14—H14	119.8
H5B—C5—H5C	109.5	C17—C15—C14	119.14 (19)
C7—C6—H6A	109.5	C17—C15—C16	121.20 (19)
C7—C6—H6B	109.5	C14—C15—C16	119.65 (19)
H6A—C6—H6B	109.5	O5—C16—C15	125.3 (2)
C7—C6—H6C	109.5	O5—C16—H16	117.4
H6A—C6—H6C	109.5	C15—C16—H16	117.4
H6B—C6—H6C	109.5	C18—C17—C15	120.34 (19)
C8—C7—N1	118.71 (17)	C18—C17—H17	119.8
C8—C7—C6	126.71 (19)	C15—C17—H17	119.8
N1—C7—C6	114.59 (18)	C17—C18—C12	121.13 (18)
C7—C8—C9	121.16 (17)	C17—C18—H18	119.4
C7—C8—C11	119.69 (17)	C12—C18—H18	119.4
C9—C8—C11	119.07 (16)	C2—O2—C1	118.39 (17)
O4—C9—O3	121.06 (19)	C9—O3—C10	116.16 (17)
O4—C9—C8	127.2 (2)	C7—N1—C4	123.31 (16)
O3—C9—C8	111.71 (16)	C7—N1—H1	118.3
O3—C10—H10A	109.5	C4—N1—H1	118.3
O1—C2—C3—C4	−18.6 (3)	C8—C11—C12—C18	27.1 (2)
O2—C2—C3—C4	161.80 (17)	C3—C11—C12—C18	−95.8 (2)
O1—C2—C3—C11	159.8 (2)	C8—C11—C12—C13	−154.35 (17)
O2—C2—C3—C11	−19.8 (2)	C3—C11—C12—C13	82.7 (2)
C2—C3—C4—N1	−172.96 (17)	C18—C12—C13—C14	1.6 (3)
C11—C3—C4—N1	8.7 (3)	C11—C12—C13—C14	−177.05 (17)
C2—C3—C4—C5	4.6 (3)	C12—C13—C14—C15	−0.2 (3)
C11—C3—C4—C5	−173.75 (19)	C13—C14—C15—C17	−1.0 (3)
N1—C7—C8—C9	173.70 (18)	C13—C14—C15—C16	177.53 (18)
C6—C7—C8—C9	−6.5 (3)	C17—C15—C16—O5	6.6 (3)
N1—C7—C8—C11	−9.5 (3)	C14—C15—C16—O5	−171.9 (2)
C6—C7—C8—C11	170.29 (19)	C14—C15—C17—C18	0.7 (3)
C7—C8—C9—O4	−1.9 (3)	C16—C15—C17—C18	−177.79 (19)
C11—C8—C9—O4	−178.8 (2)	C15—C17—C18—C12	0.7 (3)
C7—C8—C9—O3	179.69 (18)	C13—C12—C18—C17	−1.8 (3)
C11—C8—C9—O3	2.8 (3)	C11—C12—C18—C17	176.73 (18)
C7—C8—C11—C3	31.4 (2)	O1—C2—O2—C1	−2.8 (3)
C9—C8—C11—C3	−151.73 (17)	C3—C2—O2—C1	176.83 (18)
C7—C8—C11—C12	−91.2 (2)	O4—C9—O3—C10	−1.8 (3)
C9—C8—C11—C12	85.7 (2)	C8—C9—O3—C10	176.73 (19)
C4—C3—C11—C8	−31.0 (2)	C8—C7—N1—C4	−17.3 (3)
C2—C3—C11—C8	150.61 (16)	C6—C7—N1—C4	162.9 (2)
C4—C3—C11—C12	93.5 (2)	C3—C4—N1—C7	17.6 (3)
C2—C3—C11—C12	−84.9 (2)	C5—C4—N1—C7	−160.32 (19)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O5i	0.86	2.27	3.107 (2)	163

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O5i	0.86	2.27	3.107 (2)	163

Symmetry code: (i) .