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

In the title compound, C₂₁H₂₇NO₆, the 1,4-di­hydro­pyridine ring adopts a shallow boat conformation, with the 3-eth­oxy-4-hy­droxy­phenyl substituent in an axial orientation [dihedral angle between ring planes = 85.49 (12)°]. In the crystal, N—H...O and O—H...O hydrogen bonds link the mol­ecules into (001) sheets. The packing is consolidated by C—H...O and π–π stacking inter­actions, which leads to a three-dimensional network.

Computing details

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT (Bruker, 1998); 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 4-(3-ethoxy-4-hydroxyphenyl)-2,6-dimethyl-1,4-dihydropyridine-3,5-dicarboxylate

Crystal data

C21H27NO6	F(000) = 832
Mr = 389.44	Dx = 1.295 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 9.6064 (16) Å	Cell parameters from 3520 reflections
b = 15.924 (2) Å	θ = 2.0–25.0°
c = 13.129 (2) Å	µ = 0.10 mm^−1
β = 96.013 (5)°	T = 100 K
V = 1997.4 (5) Å^3	Block, colorless
Z = 4	0.16 × 0.15 × 0.15 mm

Data collection

Bruker SMART APEX CCD diffractometer	3520 independent reflections
Radiation source: fine-focus sealed tube	2204 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.087
ω scans	θmax = 25.0°, θmin = 2.0°
Absorption correction: multi-scan (SADABS; Bruker, 1998)	h = −11→11
Tmin = 0.985, Tmax = 0.986	k = −17→18
15758 measured reflections	l = −15→15

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.056	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.151	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	w = 1/[σ^2(Fo^2) + (0.0777P)^2] where P = (Fo^2 + 2Fc^2)/3
3520 reflections	(Δ/σ)max < 0.001
259 parameters	Δρmax = 0.30 e Å^−3
0 restraints	Δρmin = −0.32 e Å^−3

Special details

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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 (Ų)

	x	y	z	Uiso*/Ueq
C1	0.1199 (3)	0.27480 (17)	0.8627 (2)	0.0200 (7)
H1A	0.0768	0.3244	0.8282	0.030*
H1B	0.1505	0.2885	0.9343	0.030*
H1C	0.0515	0.2290	0.8600	0.030*
C2	0.4545 (3)	0.16274 (15)	0.8465 (2)	0.0174 (6)
C3	0.5028 (3)	0.18745 (15)	0.7580 (2)	0.0175 (6)
C4	0.4016 (3)	0.22685 (16)	0.67425 (19)	0.0157 (6)
H4	0.4548	0.2680	0.6358	0.019*
C5	0.2851 (3)	0.27365 (15)	0.71935 (19)	0.0152 (6)
C6	0.2435 (3)	0.24810 (16)	0.8102 (2)	0.0173 (6)
C7	0.5302 (3)	0.11523 (17)	0.9340 (2)	0.0245 (7)
H7A	0.6121	0.0872	0.9109	0.037*
H7B	0.4673	0.0731	0.9587	0.037*
H7C	0.5606	0.1543	0.9896	0.037*
C8	0.6507 (3)	0.17556 (16)	0.7410 (2)	0.0198 (7)
C9	0.8343 (3)	0.22798 (18)	0.6487 (2)	0.0263 (7)
H9A	0.8765	0.1717	0.6612	0.032*
H9B	0.8845	0.2681	0.6970	0.032*
C10	0.8471 (4)	0.2542 (3)	0.5425 (3)	0.0666 (13)
H10A	0.8004	0.2130	0.4951	0.100*
H10B	0.9463	0.2577	0.5316	0.100*
H10C	0.8032	0.3093	0.5301	0.100*
C11	0.2228 (3)	0.34133 (16)	0.6544 (2)	0.0173 (6)
C12	0.0678 (3)	0.45631 (16)	0.6272 (2)	0.0256 (7)
H12A	0.0267	0.4335	0.5606	0.031*
H12B	0.1427	0.4964	0.6144	0.031*
C13	−0.0426 (3)	0.49978 (18)	0.6804 (2)	0.0365 (9)
H13A	−0.1158	0.4595	0.6933	0.055*
H13B	−0.0836	0.5454	0.6371	0.055*
H13C	−0.0005	0.5229	0.7457	0.055*
C14	0.3440 (3)	0.15860 (16)	0.59973 (19)	0.0158 (6)
C15	0.2251 (3)	0.11367 (16)	0.6148 (2)	0.0192 (6)
H15	0.1758	0.1268	0.6718	0.023*
C16	0.1759 (3)	0.04974 (16)	0.5487 (2)	0.0211 (7)
H16	0.0943	0.0192	0.5607	0.025*
C17	0.2463 (3)	0.03096 (16)	0.4654 (2)	0.0204 (7)
C18	0.3672 (3)	0.07531 (16)	0.4488 (2)	0.0179 (6)
C19	0.4164 (3)	0.13826 (16)	0.5158 (2)	0.0169 (6)
H19	0.4995	0.1678	0.5049	0.020*
C20	0.5481 (3)	0.09391 (16)	0.3377 (2)	0.0208 (7)
H20A	0.6276	0.0823	0.3901	0.025*
H20B	0.5315	0.1553	0.3351	0.025*
C21	0.5797 (3)	0.06224 (17)	0.2347 (2)	0.0258 (7)
H21A	0.6027	0.0023	0.2396	0.039*
H21B	0.6594	0.0933	0.2127	0.039*
H21C	0.4977	0.0705	0.1847	0.039*
N1	0.3203 (2)	0.18583 (13)	0.86434 (16)	0.0177 (5)
H1	0.2813	0.1594	0.9130	0.021*
O1	0.68648 (18)	0.22551 (11)	0.66499 (14)	0.0221 (5)
O2	0.7345 (2)	0.12903 (13)	0.78730 (16)	0.0373 (6)
O3	0.12502 (18)	0.38864 (11)	0.69286 (14)	0.0231 (5)
O4	0.25831 (19)	0.35563 (11)	0.56969 (14)	0.0229 (5)
O5	0.1961 (2)	−0.03123 (12)	0.39926 (14)	0.0288 (5)
H5	0.2464	−0.0345	0.3508	0.043*
O6	0.42503 (19)	0.05071 (10)	0.36239 (13)	0.0223 (5)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0189 (16)	0.0278 (16)	0.0138 (14)	−0.0007 (13)	0.0048 (13)	−0.0006 (13)
C2	0.0195 (16)	0.0164 (15)	0.0159 (15)	−0.0018 (12)	0.0002 (13)	−0.0022 (12)
C3	0.0197 (15)	0.0157 (15)	0.0176 (15)	−0.0003 (12)	0.0036 (13)	−0.0021 (12)
C4	0.0161 (15)	0.0174 (15)	0.0140 (14)	−0.0021 (12)	0.0033 (12)	−0.0012 (12)
C5	0.0162 (15)	0.0140 (14)	0.0154 (14)	−0.0025 (12)	0.0026 (12)	−0.0050 (12)
C6	0.0175 (15)	0.0172 (15)	0.0172 (15)	−0.0009 (12)	0.0010 (13)	−0.0023 (12)
C7	0.0290 (18)	0.0265 (16)	0.0179 (16)	0.0017 (14)	0.0026 (14)	0.0017 (13)
C8	0.0256 (17)	0.0200 (16)	0.0140 (15)	−0.0010 (14)	0.0034 (14)	−0.0032 (13)
C9	0.0165 (16)	0.0268 (17)	0.0367 (18)	−0.0040 (13)	0.0087 (14)	−0.0052 (15)
C10	0.029 (2)	0.127 (4)	0.047 (2)	0.005 (2)	0.0204 (19)	0.028 (2)
C11	0.0154 (15)	0.0172 (15)	0.0201 (16)	−0.0046 (12)	0.0048 (13)	−0.0065 (13)
C12	0.0296 (18)	0.0226 (16)	0.0251 (17)	0.0089 (14)	0.0046 (14)	0.0081 (13)
C13	0.0288 (19)	0.038 (2)	0.044 (2)	0.0140 (15)	0.0100 (16)	0.0063 (16)
C14	0.0144 (15)	0.0177 (15)	0.0150 (15)	0.0005 (12)	−0.0005 (12)	0.0025 (12)
C15	0.0221 (16)	0.0207 (15)	0.0151 (14)	0.0006 (13)	0.0036 (13)	0.0007 (13)
C16	0.0189 (16)	0.0236 (16)	0.0211 (16)	−0.0055 (13)	0.0045 (13)	0.0013 (13)
C17	0.0268 (17)	0.0169 (15)	0.0168 (15)	−0.0020 (13)	−0.0008 (13)	−0.0021 (13)
C18	0.0196 (16)	0.0186 (15)	0.0159 (15)	0.0058 (13)	0.0044 (13)	0.0005 (13)
C19	0.0146 (14)	0.0171 (15)	0.0190 (15)	0.0013 (12)	0.0018 (12)	0.0039 (13)
C20	0.0201 (16)	0.0204 (16)	0.0221 (16)	0.0012 (13)	0.0032 (13)	0.0024 (13)
C21	0.0283 (17)	0.0270 (17)	0.0236 (16)	0.0067 (14)	0.0097 (14)	−0.0006 (14)
N1	0.0192 (13)	0.0205 (13)	0.0142 (12)	−0.0031 (10)	0.0060 (10)	0.0053 (10)
O1	0.0166 (11)	0.0250 (11)	0.0255 (11)	−0.0004 (9)	0.0055 (9)	0.0030 (9)
O2	0.0276 (13)	0.0487 (14)	0.0368 (13)	0.0149 (11)	0.0086 (11)	0.0188 (11)
O3	0.0231 (11)	0.0248 (10)	0.0230 (11)	0.0096 (9)	0.0094 (9)	0.0038 (9)
O4	0.0301 (12)	0.0226 (11)	0.0173 (11)	0.0037 (9)	0.0088 (9)	0.0020 (9)
O5	0.0351 (13)	0.0277 (11)	0.0249 (12)	−0.0104 (10)	0.0086 (10)	−0.0106 (10)
O6	0.0259 (12)	0.0230 (11)	0.0192 (11)	−0.0019 (9)	0.0087 (9)	−0.0043 (9)

Geometric parameters (Å, º)

C1—C6	1.497 (3)	C11—O3	1.343 (3)
C1—H1A	0.9800	C12—O3	1.451 (3)
C1—H1B	0.9800	C12—C13	1.499 (4)
C1—H1C	0.9800	C12—H12A	0.9900
C2—C3	1.354 (3)	C12—H12B	0.9900
C2—N1	1.384 (3)	C13—H13A	0.9800
C2—C7	1.498 (4)	C13—H13B	0.9800
C3—C8	1.473 (4)	C13—H13C	0.9800
C3—C4	1.525 (4)	C14—C15	1.379 (3)
C4—C5	1.516 (3)	C14—C19	1.401 (3)
C4—C14	1.527 (3)	C15—C16	1.389 (3)
C4—H4	1.0000	C15—H15	0.9500
C5—C6	1.359 (3)	C16—C17	1.377 (4)
C5—C11	1.463 (4)	C16—H16	0.9500
C6—N1	1.387 (3)	C17—O5	1.371 (3)
C7—H7A	0.9800	C17—C18	1.396 (4)
C7—H7B	0.9800	C18—O6	1.372 (3)
C7—H7C	0.9800	C18—C19	1.384 (4)
C8—O2	1.210 (3)	C19—H19	0.9500
C8—O1	1.349 (3)	C20—O6	1.434 (3)
C9—O1	1.458 (3)	C20—C21	1.504 (3)
C9—C10	1.473 (4)	C20—H20A	0.9900
C9—H9A	0.9900	C20—H20B	0.9900
C9—H9B	0.9900	C21—H21A	0.9800
C10—H10A	0.9800	C21—H21B	0.9800
C10—H10B	0.9800	C21—H21C	0.9800
C10—H10C	0.9800	N1—H1	0.8800
C11—O4	1.218 (3)	O5—H5	0.8400
C6—C1—H1A	109.5	O3—C12—H12A	110.1
C6—C1—H1B	109.5	C13—C12—H12A	110.1
H1A—C1—H1B	109.5	O3—C12—H12B	110.1
C6—C1—H1C	109.5	C13—C12—H12B	110.1
H1A—C1—H1C	109.5	H12A—C12—H12B	108.4
H1B—C1—H1C	109.5	C12—C13—H13A	109.5
C3—C2—N1	118.5 (2)	C12—C13—H13B	109.5
C3—C2—C7	128.5 (2)	H13A—C13—H13B	109.5
N1—C2—C7	113.0 (2)	C12—C13—H13C	109.5
C2—C3—C8	121.0 (3)	H13A—C13—H13C	109.5
C2—C3—C4	119.2 (2)	H13B—C13—H13C	109.5
C8—C3—C4	119.7 (2)	C15—C14—C19	118.7 (2)
C5—C4—C3	111.2 (2)	C15—C14—C4	121.8 (2)
C5—C4—C14	111.5 (2)	C19—C14—C4	119.4 (2)
C3—C4—C14	109.3 (2)	C14—C15—C16	121.5 (2)
C5—C4—H4	108.2	C14—C15—H15	119.2
C3—C4—H4	108.2	C16—C15—H15	119.2
C14—C4—H4	108.2	C17—C16—C15	119.5 (3)
C6—C5—C11	126.3 (2)	C17—C16—H16	120.2
C6—C5—C4	119.5 (2)	C15—C16—H16	120.2
C11—C5—C4	114.1 (2)	O5—C17—C16	119.4 (2)
C5—C6—N1	118.4 (2)	O5—C17—C18	120.6 (2)
C5—C6—C1	129.8 (2)	C16—C17—C18	120.0 (2)
N1—C6—C1	111.8 (2)	O6—C18—C19	126.3 (2)
C2—C7—H7A	109.5	O6—C18—C17	113.6 (2)
C2—C7—H7B	109.5	C19—C18—C17	120.1 (2)
H7A—C7—H7B	109.5	C18—C19—C14	120.2 (2)
C2—C7—H7C	109.5	C18—C19—H19	119.9
H7A—C7—H7C	109.5	C14—C19—H19	119.9
H7B—C7—H7C	109.5	O6—C20—C21	106.9 (2)
O2—C8—O1	121.7 (2)	O6—C20—H20A	110.3
O2—C8—C3	127.1 (3)	C21—C20—H20A	110.3
O1—C8—C3	111.2 (2)	O6—C20—H20B	110.3
O1—C9—C10	109.0 (3)	C21—C20—H20B	110.3
O1—C9—H9A	109.9	H20A—C20—H20B	108.6
C10—C9—H9A	109.9	C20—C21—H21A	109.5
O1—C9—H9B	109.9	C20—C21—H21B	109.5
C10—C9—H9B	109.9	H21A—C21—H21B	109.5
H9A—C9—H9B	108.3	C20—C21—H21C	109.5
C9—C10—H10A	109.5	H21A—C21—H21C	109.5
C9—C10—H10B	109.5	H21B—C21—H21C	109.5
H10A—C10—H10B	109.5	C2—N1—C6	123.9 (2)
C9—C10—H10C	109.5	C2—N1—H1	118.0
H10A—C10—H10C	109.5	C6—N1—H1	118.0
H10B—C10—H10C	109.5	C8—O1—C9	116.9 (2)
O4—C11—O3	120.8 (2)	C11—O3—C12	115.4 (2)
O4—C11—C5	122.2 (2)	C17—O5—H5	109.5
O3—C11—C5	117.0 (2)	C18—O6—C20	117.7 (2)
O3—C12—C13	108.0 (2)
N1—C2—C3—C8	171.1 (2)	C3—C4—C14—C19	−88.5 (3)
C7—C2—C3—C8	−5.8 (4)	C19—C14—C15—C16	−0.5 (4)
N1—C2—C3—C4	−9.9 (4)	C4—C14—C15—C16	−177.8 (2)
C7—C2—C3—C4	173.2 (2)	C14—C15—C16—C17	−0.6 (4)
C2—C3—C4—C5	30.2 (3)	C15—C16—C17—O5	−178.9 (2)
C8—C3—C4—C5	−150.7 (2)	C15—C16—C17—C18	0.9 (4)
C2—C3—C4—C14	−93.3 (3)	O5—C17—C18—O6	0.6 (4)
C8—C3—C4—C14	85.7 (3)	C16—C17—C18—O6	−179.1 (2)
C3—C4—C5—C6	−28.9 (3)	O5—C17—C18—C19	179.6 (2)
C14—C4—C5—C6	93.4 (3)	C16—C17—C18—C19	−0.1 (4)
C3—C4—C5—C11	154.3 (2)	O6—C18—C19—C14	177.9 (2)
C14—C4—C5—C11	−83.4 (3)	C17—C18—C19—C14	−1.0 (4)
C11—C5—C6—N1	−176.3 (2)	C15—C14—C19—C18	1.2 (4)
C4—C5—C6—N1	7.3 (4)	C4—C14—C19—C18	178.6 (2)
C11—C5—C6—C1	6.3 (5)	C3—C2—N1—C6	−15.6 (4)
C4—C5—C6—C1	−170.1 (2)	C7—C2—N1—C6	161.8 (2)
C2—C3—C8—O2	17.7 (4)	C5—C6—N1—C2	17.0 (4)
C4—C3—C8—O2	−161.2 (3)	C1—C6—N1—C2	−165.1 (2)
C2—C3—C8—O1	−161.4 (2)	O2—C8—O1—C9	−6.7 (4)
C4—C3—C8—O1	19.6 (3)	C3—C8—O1—C9	172.5 (2)
C6—C5—C11—O4	−173.5 (3)	C10—C9—O1—C8	156.5 (3)
C4—C5—C11—O4	3.1 (4)	O4—C11—O3—C12	−0.3 (3)
C6—C5—C11—O3	7.5 (4)	C5—C11—O3—C12	178.7 (2)
C4—C5—C11—O3	−175.9 (2)	C13—C12—O3—C11	177.8 (2)
C5—C4—C14—C15	−34.5 (3)	C19—C18—O6—C20	−0.2 (4)
C3—C4—C14—C15	88.8 (3)	C17—C18—O6—C20	178.7 (2)
C5—C4—C14—C19	148.2 (2)	C21—C20—O6—C18	−173.6 (2)

Hydrogen-bond geometry (Å, º)

Cg1 and Cg2 are the centroids of the C14–C19 and N1/C2–C6 rings, respectively.

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O4^i	0.88	2.11	2.898 (4)	149
O5—H5···O2^ii	0.84	2.38	3.035 (5)	135
C13—H13C···O5^i	0.98	2.62	3.519 (3)	152
C1—H1B···Cg1^iii	0.98	2.69	3.370 (2)	136
C20—H20B···Cg2^iii	0.99	2.66	3.654 (2)	146

Symmetry codes: (i) x, −y+1/2, z+1/2; (ii) −x+1, −y, −z+1; (iii) −x, y+1/2, −z+1/2.