Dimethyl 4-(4-hy-droxy-phen-yl)-2,6-dimethyl-1,4-dihydro-pyridine-3,5-dicarboxyl-ate.

The title mol-ecule, C(17)H(19)NO(5), was prepared by a Hantzsch dihydro-pyridine synthesis from 4-hy-droxy-benzaldehyde, methyl acetoacetate and NH(4)HCO(3). In the mol-ecular structure of the title compound, the dihydro-pyridine ring adopts a flattened boat conformation and the plane of the base of the boat forms a dihedral angle of 80.8 (2)° with the aromatic six-membered ring. The packing is stabilized by strong inter-molecular N-H⋯O(carbon-yl), O(hydrox-y)-H⋯O(carbon-yl) and weak intra-molecular C-H⋯O hydrogen bonds.

Related literature

For background to the bioactivity and synthesis of 1,4-dihydro­pyridines, see: Yang et al. (2010 ▶); Davies et al. (2005 ▶); Warrior et al. (2005 ▶); Ko & Yao (2006 ▶); Rose & Draeger (1992 ▶). For related structures, see: Bai et al. (2009 ▶); Fun et al. (2009 ▶); Thenmozhi et al. (2009 ▶). For hydrogen-bond definitions, see: Desiraju & Steiner (1999 ▶). For the synthetic method, see: n class="Chemical">Tamaddon et al. (2010 ▶).

Experimental

Crystal data

C17H19NO5

M = 317.33

Monoclinic,

a = 13.245 (3) Å

b = 9.3480 (19) Å

c = 13.754 (3) Å

β = 110.14 (3)°

V = 1598.8 (6) Å3

Z = 4

Mo Kα radiation

μ = 0.10 mm−1

T = 293 K

0.20 × 0.10 × 0.10 mm

Data collection

Nonius CAD-4 diffractometer

Absorption correction: ψ scan For semi-empirical (using intensity measurements) absorption, see: North et al. (1968 ▶) T min = 0.981, T max = 0.990

4588 measured reflections

2931 independent reflections

1212 reflections with I > 2σ(I)

R int = 0.104

3 standard reflections every 200 reflections intensity decay: 1%

Refinement

R[F 2 > 2σ(F 2)] = 0.074

wR(F 2) = 0.081

S = 1.00

2931 reflections

209 parameters

1 restraint

H-atom parameters constrained

Δρmax = 0.16 e Å−3

Δρmin = −0.17 e Å−3

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994 ▶); cell refinement: CAD-4 EXPRESS; data reduction: XCAD4 (Harms & Wocadlo, 1996 ▶); 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 datablock(s) I, global. DOI: 10.1107/S1600536811032521/zl2397sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811032521/zl2397Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536811032521/zl2397Isup3.mol

Supplementary material file. DOI: 10.1107/S1600536811032521/zl2397Isup4.cml

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

C17H19NO5	F(000) = 672
Mr = 317.33	Dx = 1.318 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 25 reflections
a = 13.245 (3) Å	θ = 9–12°
b = 9.3480 (19) Å	µ = 0.10 mm−1
c = 13.754 (3) Å	T = 293 K
β = 110.14 (3)°	Block, yellow
V = 1598.8 (6) Å3	0.20 × 0.10 × 0.10 mm
Z = 4

Nonius CAD 4 diffractometer	1212 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.104
graphite	θmax = 25.4°, θmin = 1.8°
ω/2θ scans	h = 0→15
Absorption correction: ψ scan For semi-empirical (using intensity measurements) absorption, see: North et al. (1968)	k = −4→11
Tmin = 0.981, Tmax = 0.990	l = −16→15
4588 measured reflections	3 standard reflections every 200 reflections
2931 independent reflections	intensity decay: 1%

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)] = 0.074	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.081	H-atom parameters constrained
S = 1.00	w = 1/[σ2(Fo2) + (0.005P)2] where P = (Fo2 + 2Fc2)/3
2931 reflections	(Δ/σ)max < 0.001
209 parameters	Δρmax = 0.16 e Å−3
1 restraint	Δρmin = −0.17 e Å−3

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.

	x	y	z	Uiso*/Ueq
N1	0.6521 (3)	0.2025 (3)	0.3016 (2)	0.0547 (9)
H1A	0.6515	0.1445	0.2529	0.066*
O1	1.0141 (2)	−0.0866 (3)	0.7601 (2)	0.0705 (9)
H1B	0.9967	−0.1157	0.8083	0.106*
C1	0.8797 (3)	0.1492 (4)	0.5474 (3)	0.0460 (10)
H1C	0.8910	0.1793	0.4875	0.055*
O2	0.5444 (2)	0.3203 (4)	0.5778 (2)	0.0866 (11)
C2	0.9528 (3)	0.0542 (4)	0.6113 (3)	0.0609 (12)
H2A	1.0116	0.0232	0.5947	0.073*
O3	0.4353 (2)	0.1763 (3)	0.4605 (2)	0.0698 (9)
C3	0.9371 (3)	0.0055 (4)	0.7006 (3)	0.0498 (10)
O4	0.8684 (2)	0.5538 (3)	0.3923 (2)	0.0706 (9)
C4	0.8511 (3)	0.0495 (4)	0.7228 (3)	0.0601 (12)
H4A	0.8396	0.0157	0.7816	0.072*
O5	0.8363 (2)	0.5462 (3)	0.5423 (2)	0.0600 (8)
C5	0.7786 (3)	0.1468 (4)	0.6570 (3)	0.0578 (12)
H5A	0.7195	0.1763	0.6735	0.069*
C6	0.7922 (3)	0.2018 (4)	0.5662 (3)	0.0422 (9)
C7	0.7113 (3)	0.3079 (4)	0.4988 (3)	0.0466 (9)
H7A	0.7036	0.3853	0.5438	0.056*
C8	0.5986 (3)	0.2431 (4)	0.4446 (3)	0.0480 (10)
C9	0.5808 (3)	0.1810 (4)	0.3502 (3)	0.0442 (9)
C10	0.7253 (3)	0.3108 (4)	0.3254 (3)	0.0461 (10)
C11	0.7525 (3)	0.3737 (4)	0.4184 (3)	0.0530 (11)
C12	0.4874 (3)	0.0857 (4)	0.2903 (3)	0.0674 (14)
H12A	0.4384	0.0774	0.3276	0.101*
H12B	0.5139	−0.0073	0.2819	0.101*
H12C	0.4508	0.1269	0.2234	0.101*
C13	0.7703 (3)	0.3459 (5)	0.2409 (3)	0.0789 (16)
H13A	0.8426	0.3807	0.2715	0.118*
H13B	0.7266	0.4180	0.1962	0.118*
H13C	0.7703	0.2613	0.2013	0.118*
C14	0.5229 (3)	0.2511 (4)	0.4999 (3)	0.0518 (11)
C15	0.3573 (3)	0.1894 (5)	0.5099 (3)	0.1006 (19)
H15A	0.2957	0.1319	0.4740	0.151*
H15B	0.3359	0.2877	0.5088	0.151*
H15C	0.3878	0.1575	0.5804	0.151*
C16	0.8259 (3)	0.4957 (4)	0.4461 (3)	0.0506 (10)
C17	0.9061 (3)	0.6675 (4)	0.5735 (3)	0.0797 (15)
H17A	0.9123	0.6948	0.6426	0.120*
H17B	0.8770	0.7457	0.5271	0.120*
H17C	0.9759	0.6433	0.5717	0.120*

	U11	U22	U33	U12	U13	U23
N1	0.077 (3)	0.042 (2)	0.048 (2)	0.0006 (19)	0.0258 (18)	0.0007 (17)
O1	0.074 (2)	0.085 (2)	0.0554 (19)	0.0210 (18)	0.0265 (16)	0.0311 (17)
C1	0.060 (3)	0.049 (3)	0.036 (2)	0.010 (2)	0.0251 (19)	−0.0016 (17)
O2	0.075 (2)	0.127 (3)	0.059 (2)	−0.018 (2)	0.0253 (17)	−0.038 (2)
C2	0.058 (3)	0.073 (3)	0.057 (3)	0.004 (2)	0.027 (2)	0.024 (2)
O3	0.0503 (18)	0.104 (3)	0.063 (2)	−0.0190 (18)	0.0301 (16)	−0.0103 (19)
C3	0.056 (3)	0.053 (2)	0.045 (2)	−0.006 (2)	0.024 (2)	0.001 (2)
O4	0.085 (2)	0.075 (2)	0.0512 (19)	−0.0162 (18)	0.0227 (16)	0.0111 (16)
C4	0.066 (3)	0.075 (3)	0.045 (3)	0.003 (3)	0.026 (2)	0.014 (2)
O5	0.087 (2)	0.0338 (16)	0.071 (2)	−0.0074 (15)	0.0426 (18)	−0.0083 (15)
C5	0.052 (3)	0.075 (3)	0.054 (3)	0.011 (2)	0.029 (2)	0.007 (2)
C6	0.048 (2)	0.042 (2)	0.041 (2)	−0.0051 (18)	0.0206 (19)	0.0032 (17)
C7	0.054 (3)	0.049 (2)	0.039 (2)	0.012 (2)	0.0183 (19)	−0.0042 (19)
C8	0.065 (3)	0.042 (2)	0.036 (2)	0.0020 (19)	0.015 (2)	−0.0039 (17)
C9	0.042 (2)	0.045 (2)	0.047 (2)	0.0111 (19)	0.0175 (18)	0.007 (2)
C10	0.058 (3)	0.046 (2)	0.046 (2)	0.000 (2)	0.032 (2)	0.0108 (19)
C11	0.077 (3)	0.043 (2)	0.037 (2)	0.014 (2)	0.019 (2)	−0.0060 (19)
C12	0.064 (3)	0.097 (4)	0.040 (2)	−0.004 (3)	0.016 (2)	−0.021 (3)
C13	0.086 (4)	0.103 (4)	0.054 (3)	−0.005 (3)	0.032 (3)	−0.003 (3)
C14	0.051 (3)	0.059 (3)	0.040 (2)	0.002 (2)	0.009 (2)	−0.002 (2)
C15	0.055 (3)	0.136 (5)	0.112 (4)	0.008 (4)	0.031 (3)	−0.018 (4)
C16	0.059 (3)	0.049 (3)	0.053 (3)	0.002 (2)	0.031 (2)	0.016 (2)
C17	0.096 (4)	0.052 (3)	0.075 (3)	−0.008 (3)	0.009 (3)	0.000 (3)

N1—C9	1.346 (4)	C7—C11	1.522 (4)
N1—C10	1.361 (4)	C7—C8	1.544 (5)
N1—H1A	0.8600	C7—H7A	0.9800
O1—C3	1.370 (4)	C8—C9	1.367 (4)
O1—H1B	0.8200	C8—C14	1.455 (5)
C1—C6	1.363 (4)	C9—C12	1.517 (4)
C1—C2	1.383 (4)	C10—C11	1.340 (5)
C1—H1C	0.9300	C10—C13	1.514 (4)
O2—C14	1.199 (4)	C11—C16	1.461 (5)
C2—C3	1.391 (4)	C12—H12A	0.9600
C2—H2A	0.9300	C12—H12B	0.9600
O3—C14	1.302 (4)	C12—H12C	0.9600
O3—C15	1.424 (4)	C13—H13A	0.9600
C3—C4	1.341 (4)	C13—H13B	0.9600
O4—C16	1.203 (4)	C13—H13C	0.9600
C4—C5	1.403 (5)	C15—H15A	0.9600
C4—H4A	0.9300	C15—H15B	0.9600
O5—C16	1.366 (4)	C15—H15C	0.9600
O5—C17	1.433 (4)	C17—H17A	0.9600
C5—C6	1.417 (4)	C17—H17B	0.9600
C5—H5A	0.9300	C17—H17C	0.9600
C6—C7	1.520 (5)
C9—N1—C10	123.7 (3)	C11—C10—N1	119.4 (3)
C9—N1—H1A	118.2	C11—C10—C13	126.2 (4)
C10—N1—H1A	118.2	N1—C10—C13	114.4 (4)
C3—O1—H1B	109.5	C10—C11—C16	121.8 (4)
C6—C1—C2	124.5 (3)	C10—C11—C7	118.1 (4)
C6—C1—H1C	117.8	C16—C11—C7	119.9 (3)
C2—C1—H1C	117.8	C9—C12—H12A	109.5
C1—C2—C3	119.1 (4)	C9—C12—H12B	109.5
C1—C2—H2A	120.5	H12A—C12—H12B	109.5
C3—C2—H2A	120.5	C9—C12—H12C	109.5
C14—O3—C15	116.3 (3)	H12A—C12—H12C	109.5
C4—C3—O1	124.9 (4)	H12B—C12—H12C	109.5
C4—C3—C2	119.8 (4)	C10—C13—H13A	109.5
O1—C3—C2	115.2 (3)	C10—C13—H13B	109.5
C3—C4—C5	119.9 (4)	H13A—C13—H13B	109.5
C3—C4—H4A	120.1	C10—C13—H13C	109.5
C5—C4—H4A	120.1	H13A—C13—H13C	109.5
C16—O5—C17	113.8 (3)	H13B—C13—H13C	109.5
C4—C5—C6	122.4 (4)	O2—C14—O3	124.5 (4)
C4—C5—H5A	118.8	O2—C14—C8	120.0 (4)
C6—C5—H5A	118.8	O3—C14—C8	115.5 (4)
C1—C6—C5	114.3 (4)	O3—C15—H15A	109.5
C1—C6—C7	126.0 (3)	O3—C15—H15B	109.5
C5—C6—C7	119.8 (3)	H15A—C15—H15B	109.5
C6—C7—C11	110.6 (3)	O3—C15—H15C	109.5
C6—C7—C8	113.6 (3)	H15A—C15—H15C	109.5
C11—C7—C8	109.7 (3)	H15B—C15—H15C	109.5
C6—C7—H7A	107.6	O4—C16—O5	121.8 (4)
C11—C7—H7A	107.6	O4—C16—C11	127.0 (4)
C8—C7—H7A	107.6	O5—C16—C11	111.0 (3)
C9—C8—C14	126.5 (4)	O5—C17—H17A	109.5
C9—C8—C7	116.5 (3)	O5—C17—H17B	109.5
C14—C8—C7	117.0 (3)	H17A—C17—H17B	109.5
N1—C9—C8	119.2 (4)	O5—C17—H17C	109.5
N1—C9—C12	113.5 (3)	H17A—C17—H17C	109.5
C8—C9—C12	127.3 (3)	H17B—C17—H17C	109.5
C6—C1—C2—C3	1.0 (7)	C7—C8—C9—C12	167.3 (4)
C1—C2—C3—C4	0.9 (7)	C9—N1—C10—C11	21.1 (6)
C1—C2—C3—O1	−179.1 (4)	C9—N1—C10—C13	−160.3 (3)
O1—C3—C4—C5	178.6 (4)	N1—C10—C11—C16	−176.5 (3)
C2—C3—C4—C5	−1.3 (7)	C13—C10—C11—C16	5.0 (7)
C3—C4—C5—C6	0.0 (7)	N1—C10—C11—C7	7.9 (6)
C2—C1—C6—C5	−2.1 (6)	C13—C10—C11—C7	−170.6 (4)
C2—C1—C6—C7	179.0 (4)	C6—C7—C11—C10	92.2 (4)
C4—C5—C6—C1	1.6 (6)	C8—C7—C11—C10	−33.9 (5)
C4—C5—C6—C7	−179.4 (4)	C6—C7—C11—C16	−83.5 (4)
C1—C6—C7—C11	−12.1 (5)	C8—C7—C11—C16	150.4 (3)
C5—C6—C7—C11	169.1 (3)	C15—O3—C14—O2	5.5 (7)
C1—C6—C7—C8	111.8 (4)	C15—O3—C14—C8	−176.4 (4)
C5—C6—C7—C8	−67.0 (4)	C9—C8—C14—O2	−172.9 (4)
C6—C7—C8—C9	−88.5 (4)	C7—C8—C14—O2	8.7 (6)
C11—C7—C8—C9	35.9 (5)	C9—C8—C14—O3	8.9 (6)
C6—C7—C8—C14	90.1 (4)	C7—C8—C14—O3	−169.5 (4)
C11—C7—C8—C14	−145.5 (3)	C17—O5—C16—O4	−3.2 (6)
C10—N1—C9—C8	−18.3 (6)	C17—O5—C16—C11	−179.1 (3)
C10—N1—C9—C12	162.1 (4)	C10—C11—C16—O4	0.8 (7)
C14—C8—C9—N1	169.3 (4)	C7—C11—C16—O4	176.3 (4)
C7—C8—C9—N1	−12.3 (5)	C10—C11—C16—O5	176.4 (4)
C14—C8—C9—C12	−11.2 (7)	C7—C11—C16—O5	−8.0 (5)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O4i	0.86	2.10	2.936 (4)	164
O1—H1B···O2ii	0.82	1.92	2.742 (4)	179
C7—H7A···O2	0.98	2.39	2.781 (5)	103
C7—H7A···O5	0.98	2.32	2.717 (5)	103
C12—H12A···O3	0.96	2.06	2.790 (5)	131
C13—H13A···O4	0.96	2.26	2.818 (5)	116

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O4i	0.86	2.10	2.936 (4)	164
O1—H1B⋯O2ii	0.82	1.92	2.742 (4)	179
C7—H7A⋯O2	0.98	2.39	2.781 (5)	103
C7—H7A⋯O5	0.98	2.32	2.717 (5)	103
C12—H12A⋯O3	0.96	2.06	2.790 (5)	131
C13—H13A⋯O4	0.96	2.26	2.818 (5)	116

Symmetry codes: (i) ; (ii) .