Hantzsch 1,4-dihydropyridine esters and analogs: candidates for generating reproducible one-dimensional packing motifs

Examination of the symmetric Hantzsch 1,4-dihydropyridine ester derivatives of the prototypical nifedipine molecule indicates the tendency of this class of molecule to form a common packing motif. Crystal structure analysis of 2,6-dimethyl-1,4-dihydropyridine-3,5-dicarboxylic diesters and analogs reveals that they form extended chains, characterized as the C(6) packing motif, via intermolecular (amine) N—H...O=C (C3,C5 carbonyl) hydrogen bonds. In addition, all the prepared derivatives also satisfy the basic structural requirements for their high binding efficiency to the receptor. The reproducible C(6) packing motif observed among these compounds has a use in the design of solid-state materials.

Computing details

For all compounds, data collection: SMART (Bruker, 2003); cell refinement: SAINT-Plus (Bruker, 2003); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXTL (Bruker, 2003); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-III (Farrugia, 1997), PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97 and PLATON.

Figures

(II) diethyl-2,6-dimethyl-1,4 dihydro-4-(3-nitrophenyl)-3,5-pyridine dicarboxylate

Crystal data

C19H22N2O6	Dx = 1.307 Mg m^−3
Mr = 374.39	Melting point: 433 K
Orthorhombic, Pna21	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2c -2n	Cell parameters from 2302 reflections
a = 14.3479 (10) Å	θ = 2.6–20.2°
b = 15.2867 (11) Å	µ = 0.10 mm^−1
c = 8.6765 (6) Å	T = 294 K
V = 1903.0 (2) Å^3	Plate, yellow
Z = 4	0.24 × 0.21 × 0.13 mm
F(000) = 792

Data collection

Bruker SMART CCD area-detector diffractometer	1999 independent reflections
Radiation source: fine-focus sealed tube	1592 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.046
φ and ω–scans	θmax = 26.0°, θmin = 2.0°
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	h = −17→17
Tmin = 0.890, Tmax = 0.985	k = −18→16
14270 measured reflections	l = −10→10

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.045	H-atom parameters constrained
wR(F^2) = 0.107	w = 1/[σ^2(Fo^2) + (0.0414P)^2 + 0.3319P] where P = (Fo^2 + 2Fc^2)/3
S = 1.11	(Δ/σ)max = 0.002
1999 reflections	Δρmax = 0.15 e Å^−3
248 parameters	Δρmin = −0.11 e Å^−3
2 restraints	Absolute structure: Flack H D (1983), Acta Cryst. A39, 876-881
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −10 (10)

Special details

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. Weighted least-squares planes through the starred atoms (Nardelli, Musatti, Domiano & Andreetti Ric·Sci.(1965),15(II—A),807). Equation of the plane: m1*X+m2*Y+m3*Z=d Plane 1 m1 = 0.07881(0.00278) m2 = 0.41642(0.00147) m3 = -0.90575(0.00062) D = -2.28919(0.00977) Atom d s d/s (d/s)**2 C2 * -0.0117 0.0038 - 3.062 9.373 C3 * 0.0108 0.0037 2.886 8.331 C5 * -0.0097 0.0036 - 2.712 7.356 C6 * 0.0103 0.0036 2.846 8.098 N1 - 0.1105 0.0033 - 33.474 1120.490 C4 - 0.2165 0.0035 - 62.343 3886.708 ============ Sum((d/s)**2) for starred atoms 33.158 Chi-squared at 95% for 1 degrees of freedom: 3.84 The group of atoms deviates significantly from planarity Plane 2 m1 = 0.16778(0.00250) m2 = 0.29023(0.00208) m3 = -0.94213(0.00091) D = -3.12265(0.02055) Atom d s d/s (d/s)**2 C3 * 0.0009 0.0038 0.250 0.062 C9 * -0.0054 0.0047 - 1.144 1.308 C10 * -0.0004 0.0066 - 0.066 0.004 O1 * 0.0030 0.0055 0.551 0.304 O2 * 0.0009 0.0032 0.281 0.079 C11 0.0079 0.0089 0.886 0.785 C4 - 0.1830 0.0035 - 52.227 2727.615 C2 0.1389 0.0039 35.976 1294.300 C7 0.1866 0.0050 37.232 1386.240 ============ Sum((d/s)**2) for starred atoms 1.757 Chi-squared at 95% for 2 degrees of freedom: 5.99 The group of atoms does not deviate significantly from planarity Plane 3 m1 = 0.06420(0.00190) m2 = 0.51036(0.00120) m3 = -0.85756(0.00069) D = -1.71797(0.00586) Atom d s d/s (d/s)**2 C5 * -0.0242 0.0035 - 6.858 47.034 C12 * 0.0053 0.0033 1.632 2.664 C13 * -0.0395 0.0039 - 10.108 102.171 O3 * 0.0061 0.0029 2.126 4.521 O4 * 0.0239 0.0027 8.863 78.561 C14 0.0684 0.0058 11.748 138.005 C4 - 0.0747 0.0034 - 21.775 474.158 C6 - 0.0502 0.0036 - 14.088 198.461 C8 - 0.0963 0.0042 - 22.691 514.870 ============ Sum((d/s)**2) for starred atoms 234.952 Chi-squared at 95% for 2 degrees of freedom: 5.99 The group of atoms deviates significantly from planarity Plane 4 m1 = -0.40437(0.00136) m2 = -0.80226(0.00092) m3 = -0.43916(0.00096) D = -6.31414(0.00587) Atom d s d/s (d/s)**2 C4 * -0.0188 0.0032 - 5.956 35.477 C15 * 0.0159 0.0031 5.085 25.857 C16 * 0.0070 0.0034 2.072 4.295 C17 * 0.0001 0.0036 0.019 0.000 C18 * -0.0150 0.0039 - 3.878 15.036 C19 * -0.0122 0.0041 - 2.947 8.684 C20 * 0.0181 0.0036 4.965 24.651 N2 0.0004 0.0036 0.115 0.013 O5 - 0.1419 0.0035 - 40.543 1643.716 O6 0.1794 0.0036 49.775 2477.540 ============ Sum((d/s)**2) for starred atoms 114.000 Chi-squared at 95% for 4 degrees of freedom: 9.49 The group of atoms deviates significantly from planarity Plane 5 m1 = -0.40952(0.00139) m2 = -0.80491(0.00093) m3 = -0.42944(0.00132) D = -6.24331(0.00900) Atom d s d/s (d/s)**2 C15 * -0.0024 0.0031 - 0.767 0.588 C16 * -0.0030 0.0034 - 0.888 0.788 C17 * 0.0055 0.0036 1.557 2.424 C18 * -0.0015 0.0039 - 0.386 0.149 C19 * -0.0070 0.0041 - 1.692 2.862 C20 * 0.0076 0.0036 2.104 4.428 C4 - 0.0544 0.0031 - 17.283 298.688 N2 0.0144 0.0036 3.975 15.802 O5 - 0.1349 0.0035 - 38.638 1492.919 O6 0.2069 0.0036 57.402 3295.011 ============ Sum((d/s)**2) for starred atoms 11.240 Chi-squared at 95% for 3 degrees of freedom: 7.81 The group of atoms deviates significantly from planarity Plane 6 m1 = -0.39318(0.00200) m2 = -0.72306(0.00154) m3 = -0.56797(0.00180) D = -6.98540(0.01658) Atom d s d/s (d/s)**2 N2 * -0.0096 0.0037 - 2.626 6.894 O5 * 0.0034 0.0036 0.939 0.882 O6 * 0.0032 0.0035 0.910 0.828 C17 * 0.0026 0.0036 0.732 0.536 C16 0.1972 0.0034 57.555 3312.552 C18 - 0.1886 0.0039 - 48.447 2347.121 ============ Sum((d/s)**2) for starred atoms 9.140 Chi-squared at 95% for 1 degrees of freedom: 3.84 The group of atoms deviates significantly from planarity Dihedral angles formed by LSQ-planes Plane - plane angle (s.u.) angle (s.u.) 1 2 9.10 (0.17) 170.90 (0.17) 1 3 6.11 (0.10) 173.89 (0.10) 1 4 88.18 (0.11) 91.82 (0.11) 1 5 88.77 (0.12) 91.23 (0.12) 1 6 79.49 (0.14) 100.51 (0.14) 2 3 14.80 (0.15) 165.20 (0.15) 2 4 83.51 (0.13) 96.49 (0.13) 2 5 84.13 (0.13) 95.87 (0.13) 2 6 74.97 (0.16) 105.03 (0.16) 3 4 86.63 (0.09) 93.37 (0.09) 3 5 86.05 (0.10) 93.95 (0.10) 3 6 84.68 (0.12) 95.32 (0.12) 4 5 0.65 (0.10) 179.35 (0.10) 4 6 8.70 (0.12) 171.30 (0.12) 5 6 9.28 (0.12) 170.72 (0.12) ====================================================================

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 (Ų)

	x	y	z	Uiso*/Ueq
O1	0.1099 (2)	0.5416 (2)	0.7079 (7)	0.1257 (18)
O2	−0.02997 (18)	0.49610 (16)	0.6423 (4)	0.0621 (8)
O3	−0.10235 (16)	0.21219 (16)	0.4399 (3)	0.0556 (7)
O4	0.00957 (15)	0.12283 (14)	0.3577 (3)	0.0481 (6)
O5	−0.2906 (2)	0.3970 (2)	0.8589 (5)	0.0913 (11)
O6	−0.2984 (2)	0.3136 (2)	1.0551 (4)	0.0884 (11)
N1	0.20504 (18)	0.28925 (19)	0.5691 (4)	0.0517 (8)
H1	0.2618	0.2729	0.5827	0.062*
N2	−0.2570 (2)	0.3430 (2)	0.9443 (4)	0.0606 (9)
C2	0.1800 (2)	0.3717 (2)	0.6197 (5)	0.0483 (9)
C3	0.0900 (2)	0.3948 (2)	0.6227 (4)	0.0448 (8)
C4	0.0136 (2)	0.3278 (2)	0.5863 (4)	0.0379 (8)
H4	−0.0325	0.3560	0.5195	0.045*
C5	0.0520 (2)	0.2491 (2)	0.5018 (4)	0.0372 (7)
C6	0.1449 (2)	0.2316 (2)	0.4985 (4)	0.0411 (8)
C7	0.2624 (3)	0.4263 (3)	0.6678 (6)	0.0707 (13)
H7A	0.2808	0.4634	0.5839	0.106*
H7B	0.3133	0.3886	0.6953	0.106*
H7C	0.2457	0.4617	0.7550	0.106*
C8	0.1945 (2)	0.1544 (3)	0.4298 (5)	0.0547 (10)
H8A	0.1828	0.1035	0.4916	0.082*
H8B	0.2602	0.1658	0.4270	0.082*
H8C	0.1721	0.1446	0.3270	0.082*
C9	0.0615 (3)	0.4837 (3)	0.6633 (5)	0.0626 (11)
C10	−0.0672 (3)	0.5807 (3)	0.6774 (8)	0.0884 (17)
H10A	−0.0367	0.6247	0.6145	0.106*
H10B	−0.0557	0.5945	0.7848	0.106*
C11	−0.1675 (4)	0.5815 (4)	0.6473 (11)	0.129 (3)
H11A	−0.1784	0.5717	0.5395	0.194*
H11B	−0.1928	0.6372	0.6766	0.194*
H11C	−0.1970	0.5361	0.7061	0.194*
C12	−0.0201 (2)	0.1946 (2)	0.4317 (4)	0.0382 (8)
C13	−0.0602 (2)	0.0643 (2)	0.2961 (5)	0.0490 (9)
H13A	−0.1010	0.0952	0.2256	0.059*
H13B	−0.0977	0.0399	0.3787	0.059*
C14	−0.0092 (3)	−0.0062 (4)	0.2140 (7)	0.0819 (15)
H14A	0.0267	0.0188	0.1318	0.123*
H14B	−0.0531	−0.0474	0.1725	0.123*
H14C	0.0316	−0.0356	0.2848	0.123*
C15	−0.0351 (2)	0.3015 (2)	0.7361 (4)	0.0369 (7)
C16	−0.1226 (2)	0.3322 (2)	0.7727 (4)	0.0419 (8)
H16	−0.1542	0.3685	0.7044	0.050*
C17	−0.1629 (2)	0.3092 (2)	0.9099 (4)	0.0460 (9)
C18	−0.1201 (3)	0.2569 (2)	1.0170 (5)	0.0546 (10)
H18	−0.1490	0.2427	1.1097	0.066*
C19	−0.0322 (3)	0.2262 (3)	0.9813 (5)	0.0601 (11)
H19	−0.0004	0.1910	1.0511	0.072*
C20	0.0087 (2)	0.2476 (2)	0.8422 (5)	0.0502 (9)
H20	0.0673	0.2252	0.8190	0.060*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.087 (2)	0.062 (2)	0.228 (6)	−0.0124 (19)	−0.028 (3)	−0.046 (3)
O2	0.0642 (17)	0.0392 (14)	0.083 (2)	0.0023 (13)	0.0073 (15)	−0.0065 (15)
O3	0.0300 (12)	0.0580 (16)	0.0790 (19)	0.0021 (11)	−0.0004 (12)	−0.0159 (15)
O4	0.0338 (12)	0.0459 (13)	0.0644 (16)	−0.0014 (10)	0.0015 (12)	−0.0158 (14)
O5	0.0625 (19)	0.101 (3)	0.110 (3)	0.0352 (18)	0.019 (2)	0.016 (2)
O6	0.0561 (18)	0.135 (3)	0.074 (2)	−0.0014 (18)	0.0279 (17)	0.000 (2)
N1	0.0281 (14)	0.0587 (19)	0.068 (2)	−0.0061 (13)	−0.0015 (15)	−0.0031 (18)
N2	0.0416 (18)	0.073 (2)	0.067 (2)	0.0013 (17)	0.0097 (19)	−0.015 (2)
C2	0.0425 (19)	0.049 (2)	0.054 (2)	−0.0116 (17)	0.0048 (17)	−0.0018 (19)
C3	0.049 (2)	0.0379 (18)	0.048 (2)	−0.0085 (15)	0.0025 (16)	0.0004 (18)
C4	0.0321 (15)	0.0364 (17)	0.045 (2)	−0.0017 (13)	−0.0004 (15)	0.0027 (16)
C5	0.0315 (15)	0.0398 (18)	0.0403 (18)	−0.0032 (14)	0.0019 (14)	−0.0013 (16)
C6	0.0367 (17)	0.0436 (18)	0.0431 (19)	−0.0029 (15)	0.0063 (16)	0.0014 (17)
C7	0.052 (2)	0.073 (3)	0.087 (3)	−0.023 (2)	0.004 (2)	−0.013 (3)
C8	0.0331 (18)	0.065 (2)	0.066 (3)	0.0045 (17)	0.0018 (18)	−0.006 (2)
C9	0.062 (3)	0.048 (2)	0.078 (3)	−0.015 (2)	0.003 (2)	−0.004 (2)
C10	0.096 (4)	0.042 (2)	0.127 (5)	0.007 (2)	0.005 (4)	−0.013 (3)
C11	0.093 (4)	0.083 (4)	0.212 (8)	0.034 (3)	−0.011 (5)	−0.029 (5)
C12	0.0334 (18)	0.0437 (19)	0.0375 (19)	−0.0017 (14)	0.0036 (15)	0.0023 (16)
C13	0.0411 (18)	0.052 (2)	0.054 (2)	−0.0043 (16)	−0.0014 (17)	−0.0051 (19)
C14	0.077 (3)	0.068 (3)	0.101 (4)	−0.003 (2)	0.012 (3)	−0.034 (3)
C15	0.0321 (16)	0.0349 (18)	0.0438 (19)	−0.0047 (13)	−0.0006 (15)	−0.0064 (16)
C16	0.0373 (17)	0.0407 (19)	0.048 (2)	−0.0030 (15)	−0.0007 (16)	−0.0053 (17)
C17	0.0358 (17)	0.047 (2)	0.055 (2)	−0.0035 (16)	0.0054 (17)	−0.0082 (18)
C18	0.057 (2)	0.059 (2)	0.048 (2)	−0.0073 (19)	0.0095 (19)	0.009 (2)
C19	0.054 (2)	0.070 (3)	0.056 (2)	0.007 (2)	0.006 (2)	0.020 (2)
C20	0.0400 (18)	0.054 (2)	0.056 (2)	0.0049 (16)	0.0040 (18)	0.009 (2)

Geometric parameters (Å, º)

O1—C9	1.190 (5)	C8—H8A	0.9600
O2—C9	1.338 (4)	C8—H8B	0.9600
O2—C10	1.432 (5)	C8—H8C	0.9600
O3—C12	1.212 (4)	C10—C11	1.462 (6)
O4—C12	1.340 (4)	C10—H10A	0.9700
O4—C13	1.445 (4)	C10—H10B	0.9700
O5—N2	1.209 (5)	C11—H11A	0.9600
O6—N2	1.216 (4)	C11—H11B	0.9600
N1—C6	1.377 (4)	C11—H11C	0.9600
N1—C2	1.382 (4)	C13—C14	1.484 (6)
N1—H1	0.8600	C13—H13A	0.9700
N2—C17	1.476 (4)	C13—H13B	0.9700
C2—C3	1.339 (5)	C14—H14A	0.9600
C2—C7	1.507 (5)	C14—H14B	0.9600
C3—C9	1.462 (5)	C14—H14C	0.9600
C3—C4	1.533 (4)	C15—C16	1.377 (4)
C4—C5	1.512 (5)	C15—C20	1.386 (5)
C4—C15	1.530 (5)	C16—C17	1.370 (5)
C4—H4	0.9800	C16—H16	0.9300
C5—C6	1.359 (4)	C17—C18	1.372 (5)
C5—C12	1.462 (4)	C18—C19	1.381 (5)
C6—C8	1.501 (5)	C18—H18	0.9300
C7—H7A	0.9600	C19—C20	1.381 (6)
C7—H7B	0.9600	C19—H19	0.9300
C7—H7C	0.9600	C20—H20	0.9300
C9—O2—C10	117.7 (3)	C11—C10—H10A	109.7
C12—O4—C13	117.6 (2)	O2—C10—H10B	109.7
C6—N1—C2	124.2 (3)	C11—C10—H10B	109.7
C6—N1—H1	117.9	H10A—C10—H10B	108.2
C2—N1—H1	117.9	C10—C11—H11A	109.5
O5—N2—O6	122.9 (4)	C10—C11—H11B	109.5
O5—N2—C17	118.6 (4)	H11A—C11—H11B	109.5
O6—N2—C17	118.5 (4)	C10—C11—H11C	109.5
C3—C2—N1	119.9 (3)	H11A—C11—H11C	109.5
C3—C2—C7	127.2 (3)	H11B—C11—H11C	109.5
N1—C2—C7	112.9 (3)	O3—C12—O4	121.3 (3)
C2—C3—C9	121.3 (3)	O3—C12—C5	122.5 (3)
C2—C3—C4	120.5 (3)	O4—C12—C5	116.2 (3)
C9—C3—C4	118.1 (3)	O4—C13—C14	106.6 (3)
C5—C4—C15	111.7 (3)	O4—C13—H13A	110.4
C5—C4—C3	111.8 (3)	C14—C13—H13A	110.4
C15—C4—C3	109.1 (3)	O4—C13—H13B	110.4
C5—C4—H4	108.0	C14—C13—H13B	110.4
C15—C4—H4	108.0	H13A—C13—H13B	108.6
C3—C4—H4	108.0	C13—C14—H14A	109.5
C6—C5—C12	125.0 (3)	C13—C14—H14B	109.5
C6—C5—C4	121.6 (3)	H14A—C14—H14B	109.5
C12—C5—C4	113.4 (3)	C13—C14—H14C	109.5
C5—C6—N1	118.6 (3)	H14A—C14—H14C	109.5
C5—C6—C8	128.9 (3)	H14B—C14—H14C	109.5
N1—C6—C8	112.5 (3)	C16—C15—C20	117.6 (3)
C2—C7—H7A	109.5	C16—C15—C4	121.5 (3)
C2—C7—H7B	109.5	C20—C15—C4	120.9 (3)
H7A—C7—H7B	109.5	C17—C16—C15	119.9 (3)
C2—C7—H7C	109.5	C17—C16—H16	120.1
H7A—C7—H7C	109.5	C15—C16—H16	120.1
H7B—C7—H7C	109.5	C16—C17—C18	123.3 (3)
C6—C8—H8A	109.5	C16—C17—N2	118.2 (3)
C6—C8—H8B	109.5	C18—C17—N2	118.5 (3)
H8A—C8—H8B	109.5	C17—C18—C19	117.1 (4)
C6—C8—H8C	109.5	C17—C18—H18	121.5
H8A—C8—H8C	109.5	C19—C18—H18	121.5
H8B—C8—H8C	109.5	C18—C19—C20	120.2 (4)
O1—C9—O2	120.7 (4)	C18—C19—H19	119.9
O1—C9—C3	127.3 (4)	C20—C19—H19	119.9
O2—C9—C3	111.9 (3)	C19—C20—C15	121.9 (3)
O2—C10—C11	109.7 (4)	C19—C20—H20	119.1
O2—C10—H10A	109.7	C15—C20—H20	119.1
C6—N1—C2—C3	10.2 (6)	C9—O2—C10—C11	180.0 (5)
C6—N1—C2—C7	−170.2 (4)	C13—O4—C12—O3	−3.8 (5)
N1—C2—C3—C9	−174.9 (4)	C13—O4—C12—C5	175.8 (3)
C7—C2—C3—C9	5.5 (7)	C6—C5—C12—O3	178.8 (4)
N1—C2—C3—C4	6.3 (6)	C4—C5—C12—O3	0.9 (5)
C7—C2—C3—C4	−173.3 (4)	C6—C5—C12—O4	−0.8 (5)
C2—C3—C4—C5	−18.3 (5)	C4—C5—C12—O4	−178.7 (3)
C9—C3—C4—C5	162.9 (4)	C12—O4—C13—C14	177.1 (4)
C2—C3—C4—C15	105.8 (4)	C5—C4—C15—C16	−131.2 (3)
C9—C3—C4—C15	−73.1 (4)	C3—C4—C15—C16	104.7 (3)
C15—C4—C5—C6	−106.2 (4)	C5—C4—C15—C20	50.7 (4)
C3—C4—C5—C6	16.4 (5)	C3—C4—C15—C20	−73.4 (4)
C15—C4—C5—C12	71.8 (4)	C20—C15—C16—C17	0.0 (5)
C3—C4—C5—C12	−165.7 (3)	C4—C15—C16—C17	−178.1 (3)
C12—C5—C6—N1	179.8 (3)	C15—C16—C17—C18	0.8 (5)
C4—C5—C6—N1	−2.5 (5)	C15—C16—C17—N2	−179.6 (3)
C12—C5—C6—C8	−2.0 (6)	O5—N2—C17—C16	−8.1 (5)
C4—C5—C6—C8	175.7 (4)	O6—N2—C17—C16	170.0 (3)
C2—N1—C6—C5	−12.1 (5)	O5—N2—C17—C18	171.6 (4)
C2—N1—C6—C8	169.4 (3)	O6—N2—C17—C18	−10.3 (5)
C10—O2—C9—O1	−0.8 (7)	C16—C17—C18—C19	−0.5 (6)
C10—O2—C9—C3	−179.8 (4)	N2—C17—C18—C19	179.9 (3)
C2—C3—C9—O1	−6.1 (8)	C17—C18—C19—C20	−0.6 (6)
C4—C3—C9—O1	172.7 (5)	C18—C19—C20—C15	1.5 (6)
C2—C3—C9—O2	172.8 (4)	C16—C15—C20—C19	−1.2 (5)
C4—C3—C9—O2	−8.3 (5)	C4—C15—C20—C19	177.0 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O3^i	0.86	2.32	2.982 (4)	134

Symmetry code: (i) x+1/2, −y+1/2, z.

(IV) diethyl-2,6-dimethyl-1,4-dihydro-4-(4-hydroxy-3-methoxyphenyl)- 3,5-pyridine dicarboxylate

Crystal data

C20H25NO6	Dx = 1.270 Mg m^−3
Mr = 375.41	Melting point: 421(2) K
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 1061 reflections
a = 7.5530 (9) Å	θ = 2.9–19.6°
b = 13.5745 (16) Å	µ = 0.09 mm^−1
c = 19.154 (2) Å	T = 294 K
V = 1963.9 (4) Å^3	Plate, colorless
Z = 4	0.26 × 0.20 × 0.14 mm
F(000) = 800

Data collection

Bruker SMART CCD area-detector diffractometer	3775 independent reflections
Radiation source: fine-focus sealed tube	2056 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.044
φ and ω–scans	θmax = 26.0°, θmin = 1.8°
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	h = −9→6
Tmin = 0.938, Tmax = 0.989	k = −15→16
7380 measured reflections	l = −23→16

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.068	H-atom parameters constrained
wR(F^2) = 0.222	w = 1/[σ^2(Fo^2) + (0.1153P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.04	(Δ/σ)max < 0.001
3775 reflections	Δρmax = 0.48 e Å^−3
249 parameters	Δρmin = −0.44 e Å^−3
1 restraint	Absolute structure: Flack H D (1983), Acta Cryst. A39, 876-881
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0 (2)

Special details

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. Weighted least-squares planes through the starred atoms (Nardelli, Musatti, Domiano & Andreetti Ric·Sci.(1965),15(II—A),807). Equation of the plane: m1*X+m2*Y+m3*Z=d Plane 1 m1 = 0.13768(0.00320) m2 = -0.79349(0.00130) m3 = -0.59280(0.00153) D = 0.30923(0.02516) Atom d s d/s (d/s)**2 C2 * -0.0016 0.0048 - 0.340 0.115 C3 * 0.0013 0.0044 0.305 0.093 C5 * -0.0015 0.0047 - 0.322 0.104 C6 * 0.0016 0.0047 0.333 0.111 N1 0.1392 0.0040 34.391 1182.750 C4 0.3247 0.0044 74.456 5543.643 ============ Sum((d/s)**2) for starred atoms 0.423 Chi-squared at 95% for 1 degrees of freedom: 3.84 The group of atoms does not deviate significantly from planarity Plane 2 m1 = 0.10555(0.00227) m2 = -0.86650(0.00109) m3 = -0.48789(0.00196) D = 0.04966(0.01662) Atom d s d/s (d/s)**2 C3 * 0.0192 0.0044 4.411 19.453 C9 * -0.0072 0.0049 - 1.471 2.164 C10 * 0.0604 0.0067 8.975 80.559 O1 * -0.0040 0.0037 - 1.099 1.208 O2 * -0.0253 0.0038 - 6.654 44.275 C11 - 1.2353 0.0073 - 169.400 28696.338 C4 0.2579 0.0044 59.206 3505.322 C2 - 0.0842 0.0048 - 17.479 305.518 C7 - 0.1588 0.0056 - 28.188 794.539 ============ Sum((d/s)**2) for starred atoms 147.659 Chi-squared at 95% for 2 degrees of freedom: 5.99 The group of atoms deviates significantly from planarity Plane 3 m1 = -0.05824(0.00222) m2 = -0.76415(0.00116) m3 = -0.64240(0.00140) D = -0.80907(0.01396) Atom d s d/s (d/s)**2 C5 * -0.0200 0.0047 - 4.270 18.237 C12 * 0.0075 0.0047 1.598 2.554 C13 * -0.0327 0.0053 - 6.149 37.816 O3 * 0.0046 0.0040 1.150 1.323 O4 * 0.0152 0.0033 4.680 21.900 C14 - 0.1543 0.0055 - 28.106 789.953 C4 0.2820 0.0044 64.533 4164.499 C6 - 0.2455 0.0048 - 51.467 2648.865 C8 - 0.4233 0.0052 - 80.639 6502.590 ============ Sum((d/s)**2) for starred atoms 81.829 Chi-squared at 95% for 2 degrees of freedom: 5.99 The group of atoms deviates significantly from planarity Plane 4 m1 = -0.44041(0.00177) m2 = 0.47666(0.00112) m3 = -0.76081(0.00112) D = -1.82518(0.01182) Atom d s d/s (d/s)**2 C4 * -0.0323 0.0043 - 7.450 55.509 C15 * 0.0229 0.0043 5.305 28.140 C16 * 0.0239 0.0047 5.068 25.689 C17 * -0.0035 0.0048 - 0.743 0.552 C18 * -0.0307 0.0048 - 6.439 41.463 C19 * 0.0004 0.0050 0.089 0.008 C20 * 0.0211 0.0048 4.360 19.008 C21 - 0.0936 0.0063 - 14.887 221.627 O5 - 0.0390 0.0038 - 10.263 105.336 O6 - 0.0762 0.0036 - 21.288 453.200 ============ Sum((d/s)**2) for starred atoms 170.370 Chi-squared at 95% for 4 degrees of freedom: 9.49 The group of atoms deviates significantly from planarity Plane 5 m1 = -0.44271(0.00177) m2 = 0.46059(0.00178) m3 = -0.76933(0.00127) D = -1.78748(0.01223) Atom d s d/s (d/s)**2 C15 * -0.0079 0.0043 - 1.847 3.410 C16 * 0.0062 0.0047 1.313 1.723 C17 * 0.0038 0.0048 0.801 0.642 C18 * -0.0107 0.0048 - 2.232 4.980 C19 * 0.0079 0.0050 1.569 2.463 C20 * 0.0032 0.0048 0.664 0.441 C4 - 0.0911 0.0043 - 21.027 442.116 C21 - 0.0844 0.0063 - 13.455 181.048 O5 - 0.0176 0.0038 - 4.611 21.260 O6 - 0.0310 0.0036 - 8.656 74.925 ============ Sum((d/s)**2) for starred atoms 13.659 Chi-squared at 95% for 3 degrees of freedom: 7.81 The group of atoms deviates significantly from planarity Dihedral angles formed by LSQ-planes Plane - plane angle (s.u.) angle (s.u.) 1 2 7.56 (0.14) 172.44 (0.14) 1 3 11.72 (0.21) 168.28 (0.21) 1 4 89.30 (0.13) 90.70 (0.13) 1 5 88.30 (0.15) 91.70 (0.15) 2 3 14.21 (0.15) 165.79 (0.15) 2 4 84.93 (0.12) 95.07 (0.12) 2 5 85.96 (0.15) 94.04 (0.15) 3 4 81.36 (0.12) 98.64 (0.12) 3 5 80.33 (0.12) 99.67 (0.12) 4 5 1.05 (0.12) 178.95 (0.12)

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 (Ų)

	x	y	z	Uiso*/Ueq
O1	1.0379 (6)	−0.0341 (3)	0.1265 (2)	0.0740 (11)
O2	0.7546 (5)	−0.0242 (3)	0.0922 (2)	0.0771 (11)
O3	0.5531 (4)	0.1675 (3)	−0.0956 (2)	0.0712 (11)
O4	0.7311 (4)	0.2470 (2)	−0.16985 (17)	0.0557 (9)
O5	0.4739 (5)	−0.2431 (3)	−0.0882 (2)	0.0697 (11)
O6	0.7330 (5)	−0.3087 (3)	−0.17389 (18)	0.0709 (11)
H6	0.6301	−0.3166	−0.1864	0.106*
N1	1.1645 (5)	0.1301 (3)	−0.0562 (2)	0.0515 (10)
H1	1.2720	0.1379	−0.0699	0.062*
C2	1.1350 (6)	0.0763 (4)	0.0045 (2)	0.0486 (12)
C3	0.9679 (6)	0.0448 (3)	0.0188 (2)	0.0442 (11)
C4	0.8224 (5)	0.0573 (3)	−0.0348 (2)	0.0425 (11)
H4	0.7127	0.0722	−0.0097	0.051*
C5	0.8598 (6)	0.1419 (3)	−0.0830 (3)	0.0435 (11)
C6	1.0306 (6)	0.1718 (3)	−0.0960 (3)	0.0472 (12)
C7	1.2991 (6)	0.0592 (4)	0.0480 (3)	0.0660 (15)
H7A	1.3986	0.0906	0.0261	0.099*
H7B	1.3210	−0.0103	0.0517	0.099*
H7C	1.2819	0.0864	0.0938	0.099*
C8	1.0995 (6)	0.2475 (4)	−0.1478 (3)	0.0646 (15)
H8A	1.0091	0.2620	−0.1815	0.097*
H8B	1.2018	0.2217	−0.1712	0.097*
H8C	1.1312	0.3068	−0.1234	0.097*
C9	0.9289 (8)	−0.0074 (4)	0.0840 (3)	0.0583 (14)
C10	0.6971 (12)	−0.0821 (5)	0.1510 (3)	0.106 (3)
H10A	0.6004	−0.1245	0.1367	0.128*
H10B	0.7939	−0.1237	0.1665	0.128*
C11	0.6397 (13)	−0.0211 (5)	0.2080 (4)	0.138 (4)
H11A	0.7397	0.0129	0.2274	0.207*
H11B	0.5863	−0.0615	0.2433	0.207*
H11C	0.5548	0.0260	0.1914	0.207*
C12	0.7005 (6)	0.1855 (3)	−0.1163 (3)	0.0455 (11)
C13	0.5768 (6)	0.2958 (4)	−0.2016 (3)	0.0593 (14)
H13A	0.5087	0.3299	−0.1661	0.071*
H13B	0.5009	0.2475	−0.2238	0.071*
C14	0.6439 (8)	0.3666 (4)	−0.2538 (3)	0.0709 (16)
H14A	0.7192	0.4138	−0.2312	0.106*
H14B	0.5459	0.4001	−0.2752	0.106*
H14C	0.7100	0.3319	−0.2888	0.106*
C15	0.7937 (6)	−0.0389 (3)	−0.0748 (2)	0.0441 (11)
C16	0.6401 (6)	−0.0945 (3)	−0.0645 (2)	0.0482 (12)
H16	0.5517	−0.0708	−0.0351	0.058*
C17	0.6186 (6)	−0.1833 (4)	−0.0971 (3)	0.0474 (12)
C18	0.7491 (7)	−0.2193 (3)	−0.1410 (2)	0.0508 (12)
C19	0.8993 (7)	−0.1642 (4)	−0.1530 (3)	0.0560 (13)
H19	0.9858	−0.1873	−0.1834	0.067*
C20	0.9214 (7)	−0.0748 (4)	−0.1197 (2)	0.0543 (13)
H20	1.0236	−0.0382	−0.1277	0.065*
C21	0.3422 (7)	−0.2117 (5)	−0.0404 (3)	0.0805 (18)
H21A	0.3928	−0.2065	0.0054	0.121*
H21B	0.2473	−0.2587	−0.0398	0.121*
H21C	0.2974	−0.1486	−0.0546	0.121*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.092 (3)	0.061 (2)	0.069 (2)	0.009 (2)	−0.007 (2)	0.014 (2)
O2	0.067 (3)	0.094 (3)	0.070 (2)	0.009 (2)	0.027 (2)	0.029 (2)
O3	0.0301 (18)	0.089 (3)	0.094 (3)	−0.0022 (18)	0.008 (2)	0.026 (2)
O4	0.0382 (17)	0.063 (2)	0.066 (2)	0.0025 (17)	−0.0003 (17)	0.0100 (19)
O5	0.056 (2)	0.065 (2)	0.088 (3)	−0.0252 (18)	0.018 (2)	−0.012 (2)
O6	0.074 (3)	0.063 (2)	0.076 (2)	−0.012 (2)	0.012 (2)	−0.013 (2)
N1	0.0277 (19)	0.065 (3)	0.062 (2)	−0.0012 (18)	0.006 (2)	0.000 (2)
C2	0.041 (3)	0.053 (3)	0.052 (3)	0.007 (2)	0.001 (2)	−0.006 (3)
C3	0.046 (3)	0.043 (3)	0.044 (2)	−0.003 (2)	0.007 (2)	0.003 (2)
C4	0.032 (2)	0.046 (3)	0.050 (2)	−0.003 (2)	0.006 (2)	−0.002 (2)
C5	0.033 (2)	0.047 (3)	0.051 (3)	−0.003 (2)	0.000 (2)	−0.002 (2)
C6	0.041 (3)	0.051 (3)	0.049 (3)	−0.001 (2)	−0.001 (2)	0.008 (2)
C7	0.049 (3)	0.084 (4)	0.066 (3)	0.007 (3)	−0.002 (3)	−0.009 (3)
C8	0.042 (3)	0.068 (3)	0.084 (4)	−0.005 (3)	0.016 (3)	0.020 (3)
C9	0.079 (4)	0.041 (3)	0.054 (3)	0.011 (3)	0.002 (3)	−0.004 (2)
C10	0.145 (7)	0.084 (4)	0.090 (5)	0.023 (5)	0.046 (5)	0.030 (4)
C11	0.198 (10)	0.111 (6)	0.104 (6)	0.041 (6)	0.064 (7)	0.034 (5)
C12	0.037 (3)	0.044 (3)	0.056 (3)	0.000 (2)	0.005 (2)	−0.001 (3)
C13	0.038 (3)	0.073 (3)	0.067 (3)	0.009 (2)	−0.011 (3)	0.003 (3)
C14	0.066 (4)	0.086 (4)	0.061 (3)	0.013 (3)	−0.009 (3)	0.012 (3)
C15	0.040 (2)	0.049 (3)	0.042 (2)	0.002 (2)	0.002 (2)	0.001 (2)
C16	0.042 (3)	0.049 (3)	0.054 (3)	−0.006 (2)	0.006 (2)	0.003 (3)
C17	0.042 (3)	0.049 (3)	0.051 (3)	−0.011 (2)	0.001 (2)	0.005 (3)
C18	0.056 (3)	0.048 (3)	0.048 (3)	−0.005 (2)	−0.003 (3)	−0.003 (2)
C19	0.051 (3)	0.063 (3)	0.054 (3)	0.000 (3)	0.012 (3)	−0.005 (3)
C20	0.048 (3)	0.061 (3)	0.054 (3)	−0.006 (2)	0.006 (3)	−0.003 (3)
C21	0.051 (3)	0.092 (4)	0.099 (4)	−0.022 (3)	0.020 (4)	−0.006 (4)

Geometric parameters (Å, º)

O1—C9	1.213 (6)	C8—H8B	0.9600
O2—C9	1.345 (7)	C8—H8C	0.9600
O2—C10	1.440 (7)	C10—C11	1.437 (7)
O3—C12	1.208 (5)	C10—H10A	0.9700
O4—C12	1.342 (5)	C10—H10B	0.9700
O4—C13	1.471 (5)	C11—H11A	0.9600
O5—C17	1.372 (5)	C11—H11B	0.9600
O5—C21	1.416 (6)	C11—H11C	0.9600
O6—C18	1.373 (6)	C13—C14	1.476 (7)
O6—H6	0.8200	C13—H13A	0.9700
N1—C6	1.387 (6)	C13—H13B	0.9700
N1—C2	1.391 (6)	C14—H14A	0.9600
N1—H1	0.8600	C14—H14B	0.9600
C2—C3	1.360 (6)	C14—H14C	0.9600
C2—C7	1.511 (6)	C15—C20	1.382 (6)
C3—C9	1.467 (7)	C15—C16	1.398 (6)
C3—C4	1.514 (6)	C16—C17	1.368 (6)
C4—C5	1.500 (6)	C16—H16	0.9300
C4—C15	1.529 (6)	C17—C18	1.384 (7)
C4—H4	0.9800	C18—C19	1.378 (7)
C5—C6	1.375 (6)	C19—C20	1.381 (7)
C5—C12	1.485 (6)	C19—H19	0.9300
C6—C8	1.521 (7)	C20—H20	0.9300
C7—H7A	0.9600	C21—H21A	0.9600
C7—H7B	0.9600	C21—H21B	0.9600
C7—H7C	0.9600	C21—H21C	0.9600
C8—H8A	0.9600
C9—O2—C10	118.6 (5)	C10—C11—H11A	109.5
C12—O4—C13	117.3 (4)	C10—C11—H11B	109.5
C17—O5—C21	117.5 (4)	H11A—C11—H11B	109.5
C18—O6—H6	109.5	C10—C11—H11C	109.5
C6—N1—C2	123.8 (4)	H11A—C11—H11C	109.5
C6—N1—H1	118.1	H11B—C11—H11C	109.5
C2—N1—H1	118.1	O3—C12—O4	122.4 (4)
C3—C2—N1	118.8 (4)	O3—C12—C5	121.7 (4)
C3—C2—C7	127.0 (4)	O4—C12—C5	115.9 (4)
N1—C2—C7	114.2 (4)	O4—C13—C14	107.5 (4)
C2—C3—C9	120.7 (5)	O4—C13—H13A	110.2
C2—C3—C4	120.1 (4)	C14—C13—H13A	110.2
C9—C3—C4	119.1 (4)	O4—C13—H13B	110.2
C5—C4—C3	111.5 (4)	C14—C13—H13B	110.2
C5—C4—C15	111.9 (3)	H13A—C13—H13B	108.5
C3—C4—C15	110.3 (4)	C13—C14—H14A	109.5
C5—C4—H4	107.6	C13—C14—H14B	109.5
C3—C4—H4	107.6	H14A—C14—H14B	109.5
C15—C4—H4	107.6	C13—C14—H14C	109.5
C6—C5—C12	124.4 (4)	H14A—C14—H14C	109.5
C6—C5—C4	120.9 (4)	H14B—C14—H14C	109.5
C12—C5—C4	114.7 (4)	C20—C15—C16	118.5 (4)
C5—C6—N1	117.7 (4)	C20—C15—C4	120.9 (4)
C5—C6—C8	129.7 (4)	C16—C15—C4	120.5 (4)
N1—C6—C8	112.6 (4)	C17—C16—C15	120.6 (4)
C2—C7—H7A	109.5	C17—C16—H16	119.7
C2—C7—H7B	109.5	C15—C16—H16	119.7
H7A—C7—H7B	109.5	C16—C17—O5	124.0 (4)
C2—C7—H7C	109.5	C16—C17—C18	120.2 (4)
H7A—C7—H7C	109.5	O5—C17—C18	115.7 (4)
H7B—C7—H7C	109.5	O6—C18—C19	118.4 (5)
C6—C8—H8A	109.5	O6—C18—C17	121.8 (5)
C6—C8—H8B	109.5	C19—C18—C17	119.8 (4)
H8A—C8—H8B	109.5	C18—C19—C20	120.0 (5)
C6—C8—H8C	109.5	C18—C19—H19	120.0
H8A—C8—H8C	109.5	C20—C19—H19	120.0
H8B—C8—H8C	109.5	C19—C20—C15	120.8 (4)
O1—C9—O2	122.3 (5)	C19—C20—H20	119.6
O1—C9—C3	125.4 (5)	C15—C20—H20	119.6
O2—C9—C3	112.3 (5)	O5—C21—H21A	109.5
C11—C10—O2	111.8 (5)	O5—C21—H21B	109.5
C11—C10—H10A	109.3	H21A—C21—H21B	109.5
O2—C10—H10A	109.3	O5—C21—H21C	109.5
C11—C10—H10B	109.3	H21A—C21—H21C	109.5
O2—C10—H10B	109.3	H21B—C21—H21C	109.5
H10A—C10—H10B	107.9
C6—N1—C2—C3	14.2 (7)	C13—O4—C12—O3	2.3 (6)
C6—N1—C2—C7	−166.0 (4)	C13—O4—C12—C5	−176.7 (4)
N1—C2—C3—C9	−176.6 (4)	C6—C5—C12—O3	−168.5 (5)
C7—C2—C3—C9	3.5 (7)	C4—C5—C12—O3	14.1 (6)
N1—C2—C3—C4	7.5 (7)	C6—C5—C12—O4	10.6 (7)
C7—C2—C3—C4	−172.3 (4)	C4—C5—C12—O4	−166.9 (4)
C2—C3—C4—C5	−26.1 (6)	C12—O4—C13—C14	174.3 (4)
C9—C3—C4—C5	158.0 (4)	C5—C4—C15—C20	56.8 (5)
C2—C3—C4—C15	98.9 (5)	C3—C4—C15—C20	−68.0 (5)
C9—C3—C4—C15	−77.0 (5)	C5—C4—C15—C16	−125.7 (4)
C3—C4—C5—C6	26.7 (6)	C3—C4—C15—C16	109.6 (5)
C15—C4—C5—C6	−97.4 (5)	C20—C15—C16—C17	1.3 (7)
C3—C4—C5—C12	−155.8 (4)	C4—C15—C16—C17	−176.3 (4)
C15—C4—C5—C12	80.1 (5)	C15—C16—C17—O5	178.3 (4)
C12—C5—C6—N1	174.3 (4)	C15—C16—C17—C18	−0.1 (7)
C4—C5—C6—N1	−8.4 (7)	C21—O5—C17—C16	−2.1 (7)
C12—C5—C6—C8	−4.3 (8)	C21—O5—C17—C18	176.3 (4)
C4—C5—C6—C8	173.0 (5)	C16—C17—C18—O6	179.1 (4)
C2—N1—C6—C5	−13.7 (7)	O5—C17—C18—O6	0.7 (7)
C2—N1—C6—C8	165.1 (4)	C16—C17—C18—C19	−1.5 (7)
C10—O2—C9—O1	−4.6 (8)	O5—C17—C18—C19	−180.0 (5)
C10—O2—C9—C3	174.9 (4)	O6—C18—C19—C20	−178.8 (5)
C2—C3—C9—O1	−6.6 (7)	C17—C18—C19—C20	1.8 (7)
C4—C3—C9—O1	169.3 (5)	C18—C19—C20—C15	−0.6 (7)
C2—C3—C9—O2	173.9 (4)	C16—C15—C20—C19	−1.0 (7)
C4—C3—C9—O2	−10.2 (6)	C4—C15—C20—C19	176.6 (4)
C9—O2—C10—C11	97.7 (8)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O3^i	0.86	2.22	3.073 (5)	174

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

(I) diethyl 4-(4-methoxyphenyl)-2,6-dimethyl-1,4-dihydropyridine- 3,5-dicarboxylate

Crystal data

C20H25NO5	F(000) = 768
Mr = 359.41	Dx = 1.236 Mg m^−3
Monoclinic, P21/n	Melting point: 431 K
Hall symbol: -P 2yn	Mo Kα radiation, λ = 0.71073 Å
a = 9.7834 (7) Å	Cell parameters from 2948 reflections
b = 7.4749 (5) Å	θ = 2.4–21.6°
c = 26.6788 (18) Å	µ = 0.09 mm^−1
β = 98.171 (1)°	T = 294 K
V = 1931.2 (2) Å^3	Block, yellow
Z = 4	0.19 × 0.15 × 0.11 mm

Data collection

Bruker SMART CCD area-detector diffractometer	3778 independent reflections
Radiation source: fine-focus sealed tube	2680 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.035
φ and ω–scans	θmax = 26.0°, θmin = 2.1°
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	h = −11→12
Tmin = 0.949, Tmax = 0.994	k = −9→9
14550 measured reflections	l = −31→32

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)] = 0.053	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.149	H-atom parameters constrained
S = 1.05	w = 1/[σ^2(Fo^2) + (0.0716P)^2 + 0.4618P] where P = (Fo^2 + 2Fc^2)/3
3778 reflections	(Δ/σ)max = 0.024
245 parameters	Δρmax = 0.41 e Å^−3
2 restraints	Δρmin = −0.30 e Å^−3

Special details

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. Weighted least-squares planes through the starred atoms (Nardelli, Musatti, Domiano & Andreetti Ric·Sci.(1965),15(II—A),807). Equation of the plane: m1*X+m2*Y+m3*Z=d Plane 1 m1 = 0.73377(0.00055) m2 = -0.15956(0.00147) m3 = -0.66039(0.00074) D = -18.24943(0.01717) Atom d s d/s (d/s)**2 C2 * 0.0000 0.0021 - 0.022 0.000 C3 * 0.0000 0.0019 0.020 0.000 C5 * 0.0000 0.0019 - 0.020 0.000 C6 * 0.0000 0.0020 0.021 0.000 N1 0.1645 0.0017 97.312 9469.663 C4 0.3570 0.0019 186.242 34686.051 ============ Sum((d/s)**2) for starred atoms 0.002 Chi-squared at 95% for 1 degrees of freedom: 3.84 The group of atoms does not deviate significantly from planarity Plane 2 m1 = 0.63507(0.00074) m2 = -0.13547(0.00103) m3 = -0.76048(0.00058) D = -20.33992(0.01019) Atom d s d/s (d/s)**2 C3 * 0.0209 0.0019 11.010 121.210 C9 * -0.0063 0.0021 - 2.952 8.712 C10 * 0.0689 0.0030 23.124 534.739 O1 * -0.0070 0.0018 - 3.860 14.902 O2 * -0.0253 0.0016 - 15.944 254.200 C11D 0.4824 0.0119 40.524 1642.159 C4 0.2741 0.0019 144.262 20811.404 C2 - 0.0786 0.0021 - 37.504 1406.583 C7 - 0.1841 0.0024 - 76.307 5822.793 ============ Sum((d/s)**2) for starred atoms 933.763 Chi-squared at 95% for 2 degrees of freedom: 5.99 The group of atoms deviates significantly from planarity Plane 3 m1 = 0.81652(0.00048) m2 = 0.04085(0.00102) m3 = -0.57587(0.00066) D = -15.94291(0.01684) Atom d s d/s (d/s)**2 C5 * -0.0293 0.0019 - 15.171 230.166 C12 * 0.0037 0.0020 1.866 3.481 C13 * -0.0721 0.0026 - 28.026 785.479 O3 * 0.0102 0.0017 5.937 35.253 O4 * 0.0390 0.0016 23.648 559.211 C14 - 0.1996 0.0036 - 55.995 3135.490 C4 0.2080 0.0019 107.549 11566.726 C6 - 0.2334 0.0020 - 116.676 13613.297 C8 - 0.3284 0.0024 - 135.587 18383.736 ============ Sum((d/s)**2) for starred atoms 1613.591 Chi-squared at 95% for 2 degrees of freedom: 5.99 The group of atoms deviates significantly from planarity Plane 4 m1 = -0.51759(0.00062) m2 = -0.70111(0.00063) m3 = -0.49046(0.00058) D = -11.80001(0.01234) Atom d s d/s (d/s)**2 C4 * 0.0350 0.0019 18.864 355.833 C15 * -0.0252 0.0019 - 13.546 183.485 C16 * -0.0278 0.0021 - 13.514 182.629 C17 * 0.0086 0.0022 4.006 16.045 C18 * 0.0256 0.0020 12.820 164.356 C19 * 0.0053 0.0021 2.513 6.315 C20 * -0.0221 0.0020 - 11.315 128.034 O5 0.0624 0.0016 38.662 1494.765 C21 0.1263 0.0030 41.796 1746.868 ============ Sum((d/s)**2) for starred atoms 1036.697 Chi-squared at 95% for 4 degrees of freedom: 9.49 The group of atoms deviates significantly from planarity Plane 5 m1 = -0.53023(0.00071) m2 = -0.70174(0.00062) m3 = -0.47583(0.00072) D = -11.48032(0.01547) Atom d s d/s (d/s)**2 C15 * 0.0079 0.0019 4.236 17.942 C16 * -0.0083 0.0021 - 4.046 16.368 C17 * 0.0013 0.0022 0.610 0.372 C18 * 0.0043 0.0020 2.138 4.572 C19 * -0.0030 0.0021 - 1.457 2.122 C20 * -0.0037 0.0020 - 1.899 3.607 C4 0.0976 0.0019 52.515 2757.817 O5 0.0146 0.0016 9.033 81.594 C21 0.0643 0.0030 21.234 450.863 ============ Sum((d/s)**2) for starred atoms 44.983 Chi-squared at 95% for 3 degrees of freedom: 7.81 The group of atoms deviates significantly from planarity Plane 6 m1 = -0.53128(0.00108) m2 = -0.71566(0.00130) m3 = -0.45341(0.00134) D = -11.03797(0.02544) Atom d s d/s (d/s)**2 O5 * -0.0049 0.0016 - 3.050 9.304 C21 * 0.0082 0.0030 2.709 7.336 C18 * 0.0080 0.0020 3.975 15.802 C17 * -0.0046 0.0022 - 2.138 4.571 C19 0.0361 0.0021 17.266 298.127 ============ Sum((d/s)**2) for starred atoms 37.013 Chi-squared at 95% for 1 degrees of freedom: 3.84 The group of atoms deviates significantly from planarity Dihedral angles formed by LSQ-planes Plane - plane angle (s.u.) angle (s.u.) 1 2 8.18 (0.06) 171.82 (0.06) 1 3 13.36 (0.09) 166.64 (0.09) 1 4 86.79 (0.07) 93.21 (0.07) 1 5 87.87 (0.07) 92.13 (0.07) 1 6 88.64 (0.09) 91.36 (0.09) 2 3 18.02 (0.06) 161.98 (0.06) 2 4 81.99 (0.06) 98.01 (0.06) 2 5 83.10 (0.06) 96.90 (0.06) 2 6 84.01 (0.09) 95.99 (0.09) 3 4 80.28 (0.06) 99.72 (0.06) 3 5 79.19 (0.06) 100.81 (0.06) 3 6 78.35 (0.08) 101.65 (0.08) 4 5 1.11 (0.05) 178.89 (0.05) 4 6 2.41 (0.09) 177.59 (0.09) 5 6 1.51 (0.08) 178.49 (0.08)

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 (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
C21	0.4091 (3)	0.3358 (4)	0.71364 (10)	0.0794 (9)
H21A	0.3166	0.3081	0.6985	0.119*
H21B	0.4711	0.3178	0.6892	0.119*
H21C	0.4137	0.4582	0.7246	0.119*
O4	0.37089 (17)	0.29250 (18)	1.03564 (6)	0.0536 (4)
O3	0.23954 (18)	0.47303 (18)	0.98290 (6)	0.0592 (5)
C4	0.1281 (2)	0.1945 (2)	0.91880 (7)	0.0361 (4)
H4	0.0789	0.3078	0.9209	0.043*
O5	0.44753 (16)	0.2223 (2)	0.75587 (6)	0.0576 (4)
N1	0.16423 (18)	−0.1453 (2)	0.96119 (6)	0.0450 (4)
H1	0.1929	−0.2531	0.9669	0.054*
O2	−0.12075 (16)	0.2576 (2)	0.86053 (6)	0.0623 (5)
C12	0.2744 (2)	0.3223 (2)	0.99596 (7)	0.0391 (5)
C15	0.2162 (2)	0.2105 (2)	0.87603 (7)	0.0358 (4)
C3	0.0206 (2)	0.0462 (3)	0.90704 (7)	0.0382 (5)
C20	0.3317 (2)	0.1024 (3)	0.87409 (7)	0.0410 (5)
H20	0.3591	0.0236	0.9006	0.049*
C5	0.2164 (2)	0.1614 (2)	0.96974 (7)	0.0363 (5)
C2	0.0474 (2)	−0.1193 (3)	0.92633 (8)	0.0409 (5)
C18	0.3673 (2)	0.2265 (3)	0.79415 (7)	0.0413 (5)
C6	0.2376 (2)	−0.0089 (2)	0.98734 (7)	0.0386 (5)
C16	0.1812 (2)	0.3285 (3)	0.83612 (8)	0.0442 (5)
H16	0.1063	0.4047	0.8368	0.053*
C19	0.4064 (2)	0.1092 (3)	0.83391 (8)	0.0445 (5)
H19	0.4828	0.0354	0.8335	0.053*
C17	0.2542 (2)	0.3366 (3)	0.79530 (8)	0.0470 (5)
H17	0.2273	0.4157	0.7688	0.056*
C9	−0.1059 (2)	0.0828 (3)	0.87167 (8)	0.0476 (5)
O1	−0.19019 (18)	−0.0272 (3)	0.85336 (7)	0.0753 (6)
C8	0.3325 (3)	−0.0732 (3)	1.03287 (8)	0.0539 (6)
H8A	0.4251	−0.0797	1.0250	0.081*
H8B	0.3038	−0.1897	1.0423	0.081*
H8C	0.3295	0.0085	1.0604	0.081*
C7	−0.0365 (3)	−0.2872 (3)	0.91539 (9)	0.0578 (6)
H7A	−0.1315	−0.2561	0.9050	0.087*
H7B	−0.0291	−0.3595	0.9454	0.087*
H7C	−0.0025	−0.3530	0.8888	0.087*
C13	0.4210 (3)	0.4459 (3)	1.06615 (9)	0.0600 (7)
H13A	0.3442	0.5122	1.0763	0.072*
H13B	0.4727	0.5251	1.0470	0.072*
C14	0.5108 (4)	0.3775 (4)	1.11113 (12)	0.1002 (12)
H14A	0.4581	0.3010	1.1301	0.150*
H14B	0.5469	0.4761	1.1320	0.150*
H14C	0.5856	0.3109	1.1006	0.150*
C10	−0.2360 (3)	0.3044 (5)	0.82239 (11)	0.0880 (10)
H10A	−0.2807	0.4122	0.8322	0.106*	0.638 (5)
H10B	−0.3034	0.2085	0.8184	0.106*	0.638 (5)
H10C	−0.2440	0.2147	0.7959	0.106*	0.362 (5)
H10D	−0.3202	0.3005	0.8377	0.106*	0.362 (5)
C11	−0.1779 (6)	0.3346 (11)	0.77309 (18)	0.124 (2)	0.638 (5)
H11A	−0.1024	0.4175	0.7788	0.186*	0.638 (5)
H11B	−0.2488	0.3824	0.7481	0.186*	0.638 (5)
H11C	−0.1459	0.2229	0.7613	0.186*	0.638 (5)
C11D	−0.2252 (12)	0.4843 (12)	0.7989 (5)	0.124 (2)	0.362 (5)
H11D	−0.2094	0.5734	0.8250	0.186*	0.362 (5)
H11E	−0.3094	0.5107	0.7771	0.186*	0.362 (5)
H11F	−0.1496	0.4845	0.7795	0.186*	0.362 (5)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C21	0.093 (2)	0.097 (2)	0.0541 (16)	0.0150 (17)	0.0295 (15)	0.0322 (15)
O4	0.0692 (11)	0.0362 (8)	0.0488 (9)	−0.0035 (7)	−0.0137 (8)	−0.0027 (6)
O3	0.0825 (12)	0.0304 (8)	0.0590 (10)	−0.0012 (7)	−0.0100 (9)	0.0029 (7)
C4	0.0413 (11)	0.0309 (9)	0.0357 (10)	0.0028 (8)	0.0043 (9)	0.0005 (8)
O5	0.0564 (10)	0.0729 (11)	0.0464 (9)	0.0073 (8)	0.0170 (8)	0.0158 (8)
N1	0.0543 (11)	0.0288 (8)	0.0508 (11)	0.0013 (7)	0.0036 (9)	0.0001 (7)
O2	0.0476 (10)	0.0667 (11)	0.0680 (11)	0.0060 (8)	−0.0080 (8)	0.0123 (8)
C12	0.0484 (12)	0.0342 (10)	0.0351 (11)	−0.0021 (9)	0.0074 (9)	0.0013 (8)
C15	0.0382 (11)	0.0347 (10)	0.0331 (10)	−0.0039 (8)	0.0005 (8)	0.0002 (8)
C3	0.0381 (11)	0.0426 (11)	0.0350 (11)	−0.0026 (9)	0.0088 (9)	−0.0047 (9)
C20	0.0445 (12)	0.0416 (11)	0.0359 (11)	0.0027 (9)	0.0026 (9)	0.0076 (9)
C5	0.0434 (11)	0.0321 (9)	0.0337 (10)	0.0003 (8)	0.0065 (9)	0.0006 (8)
C2	0.0434 (12)	0.0401 (11)	0.0413 (11)	−0.0042 (9)	0.0130 (10)	−0.0069 (9)
C18	0.0395 (11)	0.0487 (11)	0.0357 (11)	−0.0059 (9)	0.0052 (9)	0.0040 (9)
C6	0.0470 (12)	0.0345 (10)	0.0344 (11)	−0.0003 (9)	0.0065 (9)	−0.0015 (8)
C16	0.0430 (12)	0.0433 (11)	0.0457 (12)	0.0073 (9)	0.0042 (10)	0.0100 (9)
C19	0.0401 (12)	0.0484 (12)	0.0450 (12)	0.0073 (9)	0.0060 (10)	0.0068 (9)
C17	0.0484 (13)	0.0526 (12)	0.0392 (12)	0.0047 (10)	0.0034 (10)	0.0161 (10)
C9	0.0413 (12)	0.0604 (14)	0.0421 (12)	0.0004 (11)	0.0094 (10)	−0.0045 (10)
O1	0.0589 (11)	0.0805 (13)	0.0795 (13)	−0.0130 (9)	−0.0151 (10)	−0.0107 (10)
C8	0.0723 (16)	0.0377 (11)	0.0487 (13)	0.0020 (10)	−0.0019 (12)	0.0077 (10)
C7	0.0606 (15)	0.0467 (12)	0.0680 (16)	−0.0144 (11)	0.0156 (13)	−0.0094 (11)
C13	0.0789 (17)	0.0399 (12)	0.0556 (14)	−0.0095 (11)	−0.0095 (13)	−0.0062 (10)
C14	0.123 (3)	0.0705 (19)	0.088 (2)	0.0047 (18)	−0.049 (2)	−0.0209 (16)
C10	0.0632 (18)	0.112 (2)	0.080 (2)	0.0229 (17)	−0.0204 (16)	0.0129 (18)
C11	0.099 (4)	0.159 (6)	0.098 (4)	−0.023 (4)	−0.039 (3)	0.059 (4)
C11D	0.099 (4)	0.159 (6)	0.098 (4)	−0.023 (4)	−0.039 (3)	0.059 (4)

Geometric parameters (Å, º)

C21—O5	1.418 (3)	C16—C17	1.386 (3)
C21—H21A	0.9600	C16—H16	0.9300
C21—H21B	0.9600	C19—H19	0.9300
C21—H21C	0.9600	C17—H17	0.9300
O4—C12	1.333 (2)	C9—O1	1.217 (3)
O4—C13	1.451 (2)	C8—H8A	0.9600
O3—C12	1.214 (2)	C8—H8B	0.9600
C4—C5	1.523 (3)	C8—H8C	0.9600
C4—C15	1.530 (3)	C7—H7A	0.9600
C4—C3	1.530 (3)	C7—H7B	0.9600
C4—H4	0.9800	C7—H7C	0.9600
O5—C18	1.374 (2)	C13—C14	1.474 (4)
N1—C6	1.378 (2)	C13—H13A	0.9700
N1—C2	1.381 (3)	C13—H13B	0.9700
N1—H1	0.8600	C14—H14A	0.9600
O2—C9	1.344 (3)	C14—H14B	0.9600
O2—C10	1.450 (3)	C14—H14C	0.9600
C12—C5	1.464 (3)	C10—C11D	1.494 (5)
C15—C16	1.388 (3)	C10—C11	1.522 (4)
C15—C20	1.395 (3)	C10—H10A	0.9700
C3—C2	1.351 (3)	C10—H10B	0.9700
C3—C9	1.471 (3)	C10—H10C	0.9700
C20—C19	1.382 (3)	C10—H10D	0.9700
C20—H20	0.9300	C11—H11A	0.9600
C5—C6	1.363 (3)	C11—H11B	0.9600
C2—C7	1.506 (3)	C11—H11C	0.9600
C18—C17	1.382 (3)	C11D—H11D	0.9600
C18—C19	1.388 (3)	C11D—H11E	0.9600
C6—C8	1.499 (3)	C11D—H11F	0.9600
O5—C21—H21A	109.5	C6—C8—H8A	109.5
O5—C21—H21B	109.5	C6—C8—H8B	109.5
H21A—C21—H21B	109.5	H8A—C8—H8B	109.5
O5—C21—H21C	109.5	C6—C8—H8C	109.5
H21A—C21—H21C	109.5	H8A—C8—H8C	109.5
H21B—C21—H21C	109.5	H8B—C8—H8C	109.5
C12—O4—C13	117.28 (16)	C2—C7—H7A	109.5
C5—C4—C15	111.71 (16)	C2—C7—H7B	109.5
C5—C4—C3	110.59 (15)	H7A—C7—H7B	109.5
C15—C4—C3	110.35 (15)	C2—C7—H7C	109.5
C5—C4—H4	108.0	H7A—C7—H7C	109.5
C15—C4—H4	108.0	H7B—C7—H7C	109.5
C3—C4—H4	108.0	O4—C13—C14	107.30 (19)
C18—O5—C21	117.50 (18)	O4—C13—H13A	110.3
C6—N1—C2	123.97 (16)	C14—C13—H13A	110.3
C6—N1—H1	118.0	O4—C13—H13B	110.3
C2—N1—H1	118.0	C14—C13—H13B	110.3
C9—O2—C10	116.0 (2)	H13A—C13—H13B	108.5
O3—C12—O4	121.43 (18)	C13—C14—H14A	109.5
O3—C12—C5	123.42 (19)	C13—C14—H14B	109.5
O4—C12—C5	115.15 (16)	H14A—C14—H14B	109.5
C16—C15—C20	116.91 (18)	C13—C14—H14C	109.5
C16—C15—C4	121.19 (17)	H14A—C14—H14C	109.5
C20—C15—C4	121.84 (17)	H14B—C14—H14C	109.5
C2—C3—C9	120.99 (19)	C11D—C10—O2	114.6 (5)
C2—C3—C4	119.64 (18)	C11D—C10—C11	56.4 (5)
C9—C3—C4	119.20 (18)	O2—C10—C11	107.1 (3)
C19—C20—C15	121.87 (18)	C11D—C10—H10A	55.0
C19—C20—H20	119.1	O2—C10—H10A	110.3
C15—C20—H20	119.1	C11—C10—H10A	110.3
C6—C5—C12	124.93 (18)	C11D—C10—H10B	135.1
C6—C5—C4	119.89 (17)	O2—C10—H10B	110.3
C12—C5—C4	115.17 (16)	C11—C10—H10B	110.3
C3—C2—N1	118.88 (18)	H10A—C10—H10B	108.6
C3—C2—C7	128.2 (2)	C11D—C10—H10C	108.6
N1—C2—C7	112.93 (18)	O2—C10—H10C	108.6
O5—C18—C17	125.02 (18)	C11—C10—H10C	58.2
O5—C18—C19	115.39 (18)	H10A—C10—H10C	141.1
C17—C18—C19	119.59 (19)	H10B—C10—H10C	55.0
C5—C6—N1	118.27 (17)	C11D—C10—H10D	108.6
C5—C6—C8	128.73 (18)	O2—C10—H10D	108.6
N1—C6—C8	113.01 (17)	C11—C10—H10D	144.3
C17—C16—C15	122.11 (19)	H10A—C10—H10D	58.0
C17—C16—H16	118.9	H10B—C10—H10D	54.5
C15—C16—H16	118.9	H10C—C10—H10D	107.6
C20—C19—C18	119.82 (19)	C10—C11—H11A	109.5
C20—C19—H19	120.1	C10—C11—H11B	109.5
C18—C19—H19	120.1	C10—C11—H11C	109.5
C18—C17—C16	119.68 (18)	C10—C11D—H11D	109.5
C18—C17—H17	120.2	C10—C11D—H11E	109.5
C16—C17—H17	120.2	H11D—C11D—H11E	109.5
O1—C9—O2	121.5 (2)	C10—C11D—H11F	109.5
O1—C9—C3	126.3 (2)	H11D—C11D—H11F	109.5
O2—C9—C3	112.18 (19)	H11E—C11D—H11F	109.5
C13—O4—C12—O3	7.0 (3)	C21—O5—C18—C17	−1.9 (3)
C13—O4—C12—C5	−173.55 (19)	C21—O5—C18—C19	178.1 (2)
C5—C4—C15—C16	−143.99 (18)	C12—C5—C6—N1	173.06 (18)
C3—C4—C15—C16	92.5 (2)	C4—C5—C6—N1	−7.9 (3)
C5—C4—C15—C20	38.8 (2)	C12—C5—C6—C8	−6.7 (4)
C3—C4—C15—C20	−84.7 (2)	C4—C5—C6—C8	172.31 (19)
C5—C4—C3—C2	−28.2 (2)	C2—N1—C6—C5	−16.7 (3)
C15—C4—C3—C2	95.9 (2)	C2—N1—C6—C8	163.07 (19)
C5—C4—C3—C9	156.50 (17)	C20—C15—C16—C17	1.8 (3)
C15—C4—C3—C9	−79.4 (2)	C4—C15—C16—C17	−175.58 (18)
C16—C15—C20—C19	−1.3 (3)	C15—C20—C19—C18	0.2 (3)
C4—C15—C20—C19	176.01 (18)	O5—C18—C19—C20	−179.52 (18)
O3—C12—C5—C6	−169.9 (2)	C17—C18—C19—C20	0.5 (3)
O4—C12—C5—C6	10.7 (3)	O5—C18—C17—C16	179.95 (19)
O3—C12—C5—C4	11.0 (3)	C19—C18—C17—C16	0.0 (3)
O4—C12—C5—C4	−168.40 (16)	C15—C16—C17—C18	−1.1 (3)
C15—C4—C5—C6	−95.0 (2)	C10—O2—C9—O1	−5.1 (3)
C3—C4—C5—C6	28.3 (2)	C10—O2—C9—C3	174.6 (2)
C15—C4—C5—C12	84.1 (2)	C2—C3—C9—O1	−6.3 (3)
C3—C4—C5—C12	−152.60 (17)	C4—C3—C9—O1	168.9 (2)
C9—C3—C2—N1	−177.03 (17)	C2—C3—C9—O2	173.98 (18)
C4—C3—C2—N1	7.7 (3)	C4—C3—C9—O2	−10.8 (3)
C9—C3—C2—C7	2.0 (3)	C12—O4—C13—C14	172.2 (2)
C4—C3—C2—C7	−173.23 (19)	C9—O2—C10—C11D	−161.3 (7)
C6—N1—C2—C3	16.9 (3)	C9—O2—C10—C11	−101.0 (4)
C6—N1—C2—C7	−162.32 (18)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O3^i	0.86	2.13	2.983 (2)	173

Symmetry code: (i) x, y−1, z.

(III) 3, 5-diacetyl-2, 6-dimethyl -1, 4 dihydro-4-(3-nitrophenyl)-3, 5-pyridine

Crystal data

C17H18N2O4	F(000) = 664
Mr = 314.33	Dx = 1.353 Mg m^−3
Monoclinic, P21/n	Melting point: 483 K
Hall symbol: -P 2yn	Mo Kα radiation, λ = 0.71073 Å
a = 8.8420 (7) Å	Cell parameters from 1601 reflections
b = 16.0785 (14) Å	θ = 2.3–19.1°
c = 11.2188 (10) Å	µ = 0.10 mm^−1
β = 104.606 (2)°	T = 294 K
V = 1543.4 (2) Å^3	Needle, pale yellow
Z = 4	0.25 × 0.18 × 0.11 mm

Data collection

Bruker SMART CCD area-detector diffractometer	3025 independent reflections
Radiation source: fine-focus sealed tube	2030 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.050
φ and ω–scans	θmax = 26.0°, θmin = 2.3°
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	h = −10→9
Tmin = 0.908, Tmax = 0.986	k = −19→19
11818 measured reflections	l = −13→13

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)] = 0.065	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.126	H-atom parameters constrained
S = 1.11	w = 1/[σ^2(Fo^2) + (0.0354P)^2 + 0.421P] where P = (Fo^2 + 2Fc^2)/3
3025 reflections	(Δ/σ)max < 0.001
212 parameters	Δρmax = 0.17 e Å^−3
0 restraints	Δρmin = −0.17 e Å^−3

Special details

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. Weighted least-squares planes through the starred atoms (Nardelli, Musatti, Domiano & Andreetti Ric·Sci.(1965),15(II—A),807). Equation of the plane: m1*X+m2*Y+m3*Z=d Plane 1 m1 = 0.87379(0.00058) m2 = -0.48113(0.00094) m3 = -0.07075(0.00176) D = 1.89972(0.01121) Atom d s d/s (d/s)**2 C2 * 0.0084 0.0025 3.367 11.335 C3 * -0.0071 0.0023 - 3.042 9.252 C5 * 0.0076 0.0024 3.142 9.875 C6 * -0.0085 0.0025 - 3.389 11.484 N1 0.1412 0.0021 67.573 4566.087 C4 0.3261 0.0024 135.494 18358.529 ============ Sum((d/s)**2) for starred atoms 41.946 Chi-squared at 95% for 1 degrees of freedom: 3.84 The group of atoms deviates significantly from planarity Plane 2 m1 = -0.74291(0.00091) m2 = 0.66679(0.00100) m3 = -0.05897(0.00143) D = -1.11306(0.00619) Atom d s d/s (d/s)**2 C3 * 0.0025 0.0023 1.092 1.192 C9 * -0.0089 0.0025 - 3.558 12.656 C10 * 0.0037 0.0029 1.290 1.663 O1 * 0.0017 0.0018 0.945 0.894 C4 0.0288 0.0024 12.167 148.024 C2 - 0.0420 0.0025 - 16.905 285.763 ============ Sum((d/s)**2) for starred atoms 16.405 Chi-squared at 95% for 1 degrees of freedom: 3.84 The group of atoms deviates significantly from planarity Plane 3 m1 = 0.92828(0.00061) m2 = -0.33419(0.00155) m3 = -0.16312(0.00134) D = 2.79785(0.01296) Atom d s d/s (d/s)**2 C5 * 0.0017 0.0024 0.717 0.515 C11 * -0.0067 0.0027 - 2.475 6.124 C12 * 0.0032 0.0034 0.966 0.933 O2 * 0.0015 0.0021 0.711 0.505 C4 0.1092 0.0024 45.050 2029.545 C6 - 0.0559 0.0025 - 22.154 490.789 ============ Sum((d/s)**2) for starred atoms 8.077 Chi-squared at 95% for 1 degrees of freedom: 3.84 The group of atoms deviates significantly from planarity Plane 4 m1 = 0.49406(0.00071) m2 = 0.84245(0.00038) m3 = -0.21488(0.00099) D = 5.42882(0.00469) Atom d s d/s (d/s)**2 C4 * 0.0111 0.0023 4.809 23.131 C13 * -0.0090 0.0023 - 3.926 15.411 C14 * -0.0038 0.0025 - 1.531 2.344 C15 * -0.0021 0.0025 - 0.826 0.683 C16 * 0.0111 0.0027 4.096 16.780 C17 * 0.0044 0.0028 1.562 2.441 C18 * -0.0101 0.0026 - 3.913 15.313 N2 - 0.0485 0.0028 - 17.299 299.243 O3 - 0.1793 0.0027 - 66.941 4481.142 O4 0.0270 0.0026 10.226 104.580 ============ Sum((d/s)**2) for starred atoms 76.103 Chi-squared at 95% for 4 degrees of freedom: 9.49 The group of atoms deviates significantly from planarity Plane 5 m1 = 0.48909(0.00103) m2 = 0.84594(0.00060) m3 = -0.21255(0.00111) D = 5.40243(0.00651) Atom d s d/s (d/s)**2 C13 * 0.0017 0.0023 0.732 0.536 C14 * 0.0023 0.0025 0.912 0.832 C15 * -0.0050 0.0025 - 1.978 3.911 C16 * 0.0036 0.0027 1.341 1.799 C17 * 0.0015 0.0028 0.547 0.300 C18 * -0.0040 0.0026 - 1.545 2.388 C4 0.0317 0.0023 13.801 190.462 N2 - 0.0562 0.0028 - 20.093 403.732 O3 - 0.1829 0.0027 - 68.337 4669.910 O4 0.0114 0.0026 4.302 18.510 ============ Sum((d/s)**2) for starred atoms 9.766 Chi-squared at 95% for 3 degrees of freedom: 7.81 The group of atoms deviates significantly from planarity Plane 6 m1 = 0.40886(0.00149) m2 = 0.87414(0.00073) m3 = -0.26213(0.00147) D = 4.89338(0.00937) Atom d s d/s (d/s)**2 N2 * 0.0050 0.0027 1.839 3.384 O3 * -0.0017 0.0026 - 0.634 0.401 O4 * -0.0017 0.0026 - 0.633 0.400 C15 * -0.0012 0.0025 - 0.476 0.227 C14 0.0902 0.0025 36.717 1348.155 C16 - 0.1269 0.0027 - 47.205 2228.329 ============ Sum((d/s)**2) for starred atoms 4.412 Chi-squared at 95% for 1 degrees of freedom: 3.84 The group of atoms deviates significantly from planarity Dihedral angles formed by LSQ-planes Plane - plane angle (s.u.) angle (s.u.) 1 2 15.03 (0.09) 164.97 (0.09) 1 3 10.44 (0.10) 169.56 (0.10) 1 4 87.62 (0.06) 92.38 (0.06) 1 5 87.97 (0.08) 92.03 (0.08) 1 6 87.43 (0.09) 92.57 (0.09) 2 3 25.47 (0.10) 154.53 (0.10) 2 4 78.03 (0.07) 101.97 (0.07) 2 5 77.69 (0.08) 102.31 (0.08) 2 6 72.87 (0.10) 107.13 (0.10) 3 4 77.75 (0.09) 102.25 (0.09) 3 5 78.11 (0.10) 101.89 (0.10) 3 6 82.52 (0.12) 97.48 (0.12) 4 5 0.37 (0.07) 179.63 (0.07) 4 6 5.87 (0.10) 174.13 (0.10) 5 6 5.64 (0.10) 174.36 (0.10) ====================================================================

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 (Ų)

	x	y	z	Uiso*/Ueq
O1	0.4112 (2)	0.12566 (11)	0.16606 (15)	0.0564 (5)
O2	0.5779 (2)	0.36297 (11)	−0.00143 (16)	0.0659 (6)
O3	0.6369 (3)	0.12095 (16)	−0.22215 (19)	0.0897 (8)
O4	0.8667 (3)	0.06884 (16)	−0.1976 (2)	0.0985 (8)
N1	0.7526 (2)	0.31151 (13)	0.42101 (17)	0.0442 (5)
H1	0.8169	0.3220	0.4908	0.053*
N2	0.7685 (4)	0.10566 (16)	−0.1587 (2)	0.0658 (7)
C2	0.6619 (3)	0.24154 (15)	0.4126 (2)	0.0402 (6)
C3	0.5843 (3)	0.21367 (14)	0.2991 (2)	0.0363 (6)
C4	0.6194 (3)	0.25303 (14)	0.1858 (2)	0.0360 (6)
H4	0.5212	0.2546	0.1214	0.043*
C5	0.6768 (3)	0.34194 (14)	0.2089 (2)	0.0362 (6)
C6	0.7481 (3)	0.36661 (15)	0.3249 (2)	0.0399 (6)
C7	0.6660 (3)	0.20488 (17)	0.5371 (2)	0.0554 (7)
H7A	0.5622	0.2039	0.5489	0.083*
H7B	0.7321	0.2382	0.6003	0.083*
H7C	0.7063	0.1492	0.5415	0.083*
C8	0.8227 (3)	0.44876 (17)	0.3697 (2)	0.0592 (8)
H8A	0.9047	0.4603	0.3299	0.089*
H8B	0.8656	0.4464	0.4572	0.089*
H8C	0.7455	0.4920	0.3505	0.089*
C9	0.4705 (3)	0.14626 (15)	0.2741 (2)	0.0415 (6)
C10	0.4149 (3)	0.10003 (18)	0.3718 (2)	0.0583 (8)
H10A	0.3481	0.0550	0.3347	0.087*
H10B	0.3577	0.1373	0.4112	0.087*
H10C	0.5033	0.0783	0.4319	0.087*
C11	0.6493 (3)	0.39327 (15)	0.0967 (2)	0.0445 (6)
C12	0.7071 (4)	0.48069 (17)	0.0954 (3)	0.0714 (9)
H12A	0.6862	0.5002	0.0120	0.107*
H12B	0.8176	0.4822	0.1320	0.107*
H12C	0.6545	0.5157	0.1415	0.107*
C13	0.7352 (3)	0.20074 (14)	0.1369 (2)	0.0356 (6)
C14	0.7014 (3)	0.17810 (15)	0.0138 (2)	0.0415 (6)
H14	0.6073	0.1938	−0.0398	0.050*
C15	0.8090 (3)	0.13189 (15)	−0.0284 (2)	0.0448 (6)
C16	0.9500 (3)	0.10816 (16)	0.0470 (3)	0.0559 (7)
H16	1.0214	0.0777	0.0165	0.067*
C17	0.9828 (3)	0.13075 (17)	0.1692 (3)	0.0568 (8)
H17	1.0774	0.1152	0.2223	0.068*
C18	0.8766 (3)	0.17614 (16)	0.2135 (2)	0.0461 (6)
H18	0.9003	0.1905	0.2965	0.055*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0661 (13)	0.0555 (12)	0.0409 (11)	−0.0167 (10)	0.0010 (9)	0.0038 (8)
O2	0.0956 (16)	0.0526 (12)	0.0409 (11)	−0.0044 (11)	0.0010 (10)	0.0094 (9)
O3	0.114 (2)	0.112 (2)	0.0429 (13)	0.0063 (17)	0.0195 (13)	−0.0081 (13)
O4	0.125 (2)	0.1047 (19)	0.0852 (17)	0.0079 (17)	0.0618 (16)	−0.0292 (14)
N1	0.0480 (13)	0.0464 (13)	0.0338 (11)	−0.0020 (11)	0.0022 (9)	−0.0009 (9)
N2	0.096 (2)	0.0589 (17)	0.0523 (16)	−0.0068 (16)	0.0374 (16)	−0.0055 (13)
C2	0.0425 (15)	0.0439 (15)	0.0359 (14)	0.0035 (12)	0.0125 (11)	0.0024 (11)
C3	0.0369 (14)	0.0395 (14)	0.0330 (12)	0.0047 (11)	0.0095 (10)	0.0040 (10)
C4	0.0362 (13)	0.0383 (13)	0.0311 (12)	0.0011 (11)	0.0044 (10)	0.0034 (10)
C5	0.0384 (14)	0.0359 (13)	0.0345 (13)	0.0049 (11)	0.0096 (10)	0.0012 (10)
C6	0.0398 (14)	0.0385 (14)	0.0417 (14)	0.0057 (11)	0.0108 (11)	−0.0007 (11)
C7	0.0681 (19)	0.0609 (18)	0.0358 (14)	−0.0034 (15)	0.0106 (13)	0.0020 (13)
C8	0.072 (2)	0.0476 (17)	0.0541 (16)	−0.0052 (15)	0.0086 (15)	−0.0087 (13)
C9	0.0409 (15)	0.0438 (15)	0.0388 (14)	0.0055 (12)	0.0084 (11)	0.0062 (12)
C10	0.0551 (18)	0.0672 (19)	0.0529 (17)	−0.0136 (15)	0.0143 (14)	0.0102 (14)
C11	0.0486 (16)	0.0414 (15)	0.0435 (15)	0.0074 (13)	0.0116 (12)	0.0033 (12)
C12	0.103 (3)	0.0469 (18)	0.0615 (19)	−0.0067 (17)	0.0160 (18)	0.0099 (15)
C13	0.0415 (14)	0.0302 (13)	0.0361 (13)	−0.0035 (11)	0.0114 (11)	0.0035 (10)
C14	0.0492 (16)	0.0393 (14)	0.0370 (14)	−0.0019 (12)	0.0128 (12)	0.0050 (11)
C15	0.0596 (18)	0.0370 (14)	0.0452 (15)	−0.0060 (13)	0.0267 (14)	−0.0020 (12)
C16	0.0516 (18)	0.0461 (16)	0.079 (2)	−0.0010 (14)	0.0326 (16)	−0.0067 (15)
C17	0.0434 (16)	0.0546 (18)	0.070 (2)	0.0047 (14)	0.0102 (14)	−0.0037 (15)
C18	0.0436 (15)	0.0472 (15)	0.0446 (15)	0.0011 (13)	0.0057 (12)	−0.0026 (12)

Geometric parameters (Å, º)

O1—C9	1.238 (3)	C8—H8A	0.9600
O2—C11	1.224 (3)	C8—H8B	0.9600
O3—N2	1.226 (3)	C8—H8C	0.9600
O4—N2	1.219 (3)	C9—C10	1.506 (3)
N1—C2	1.371 (3)	C10—H10A	0.9600
N1—C6	1.388 (3)	C10—H10B	0.9600
N1—H1	0.8600	C10—H10C	0.9600
N2—C15	1.476 (3)	C11—C12	1.497 (4)
C2—C3	1.361 (3)	C12—H12A	0.9600
C2—C7	1.508 (3)	C12—H12B	0.9600
C3—C9	1.458 (3)	C12—H12C	0.9600
C3—C4	1.520 (3)	C13—C18	1.384 (3)
C4—C5	1.517 (3)	C13—C14	1.387 (3)
C4—C13	1.529 (3)	C14—C15	1.382 (3)
C4—H4	0.9800	C14—H14	0.9300
C5—C6	1.354 (3)	C15—C16	1.373 (4)
C5—C11	1.473 (3)	C16—C17	1.376 (4)
C6—C8	1.505 (3)	C16—H16	0.9300
C7—H7A	0.9600	C17—C18	1.377 (3)
C7—H7B	0.9600	C17—H17	0.9300
C7—H7C	0.9600	C18—H18	0.9300
C2—N1—C6	124.6 (2)	O1—C9—C3	119.3 (2)
C2—N1—H1	117.7	O1—C9—C10	116.4 (2)
C6—N1—H1	117.7	C3—C9—C10	124.3 (2)
O4—N2—O3	123.1 (3)	C9—C10—H10A	109.5
O4—N2—C15	118.5 (3)	C9—C10—H10B	109.5
O3—N2—C15	118.4 (3)	H10A—C10—H10B	109.5
C3—C2—N1	118.9 (2)	C9—C10—H10C	109.5
C3—C2—C7	128.8 (2)	H10A—C10—H10C	109.5
N1—C2—C7	112.3 (2)	H10B—C10—H10C	109.5
C2—C3—C9	125.9 (2)	O2—C11—C5	118.8 (2)
C2—C3—C4	119.0 (2)	O2—C11—C12	117.7 (2)
C9—C3—C4	115.1 (2)	C5—C11—C12	123.4 (2)
C5—C4—C3	112.33 (19)	C11—C12—H12A	109.5
C5—C4—C13	110.70 (19)	C11—C12—H12B	109.5
C3—C4—C13	111.53 (18)	H12A—C12—H12B	109.5
C5—C4—H4	107.3	C11—C12—H12C	109.5
C3—C4—H4	107.3	H12A—C12—H12C	109.5
C13—C4—H4	107.3	H12B—C12—H12C	109.5
C6—C5—C11	126.4 (2)	C18—C13—C14	118.5 (2)
C6—C5—C4	119.6 (2)	C18—C13—C4	121.1 (2)
C11—C5—C4	114.0 (2)	C14—C13—C4	120.4 (2)
C5—C6—N1	118.3 (2)	C15—C14—C13	119.3 (2)
C5—C6—C8	129.5 (2)	C15—C14—H14	120.4
N1—C6—C8	112.1 (2)	C13—C14—H14	120.4
C2—C7—H7A	109.5	C16—C15—C14	122.3 (2)
C2—C7—H7B	109.5	C16—C15—N2	119.2 (3)
H7A—C7—H7B	109.5	C14—C15—N2	118.5 (3)
C2—C7—H7C	109.5	C15—C16—C17	118.1 (3)
H7A—C7—H7C	109.5	C15—C16—H16	121.0
H7B—C7—H7C	109.5	C17—C16—H16	121.0
C6—C8—H8A	109.5	C16—C17—C18	120.5 (3)
C6—C8—H8B	109.5	C16—C17—H17	119.7
H8A—C8—H8B	109.5	C18—C17—H17	119.7
C6—C8—H8C	109.5	C17—C18—C13	121.2 (2)
H8A—C8—H8C	109.5	C17—C18—H18	119.4
H8B—C8—H8C	109.5	C13—C18—H18	119.4
C6—N1—C2—C3	13.8 (4)	C4—C3—C9—C10	−178.2 (2)
C6—N1—C2—C7	−167.2 (2)	C6—C5—C11—O2	−177.4 (2)
N1—C2—C3—C9	−172.9 (2)	C4—C5—C11—O2	3.7 (3)
C7—C2—C3—C9	8.3 (4)	C6—C5—C11—C12	3.9 (4)
N1—C2—C3—C4	8.9 (3)	C4—C5—C11—C12	−175.0 (2)
C7—C2—C3—C4	−169.9 (2)	C5—C4—C13—C18	73.3 (3)
C2—C3—C4—C5	−26.9 (3)	C3—C4—C13—C18	−52.5 (3)
C9—C3—C4—C5	154.7 (2)	C5—C4—C13—C14	−105.6 (2)
C2—C3—C4—C13	98.1 (2)	C3—C4—C13—C14	128.6 (2)
C9—C3—C4—C13	−80.3 (2)	C18—C13—C14—C15	0.1 (3)
C3—C4—C5—C6	25.5 (3)	C4—C13—C14—C15	179.0 (2)
C13—C4—C5—C6	−99.9 (2)	C13—C14—C15—C16	−0.8 (4)
C3—C4—C5—C11	−155.4 (2)	C13—C14—C15—N2	177.7 (2)
C13—C4—C5—C11	79.2 (2)	O4—N2—C15—C16	−5.4 (4)
C11—C5—C6—N1	174.9 (2)	O3—N2—C15—C16	173.6 (3)
C4—C5—C6—N1	−6.2 (3)	O4—N2—C15—C14	176.0 (2)
C11—C5—C6—C8	−2.9 (4)	O3—N2—C15—C14	−4.9 (4)
C4—C5—C6—C8	176.0 (2)	C14—C15—C16—C17	0.9 (4)
C2—N1—C6—C5	−15.3 (4)	N2—C15—C16—C17	−177.6 (2)
C2—N1—C6—C8	162.9 (2)	C15—C16—C17—C18	−0.2 (4)
C2—C3—C9—O1	−178.2 (2)	C16—C17—C18—C13	−0.4 (4)
C4—C3—C9—O1	0.1 (3)	C14—C13—C18—C17	0.5 (4)
C2—C3—C9—C10	3.5 (4)	C4—C13—C18—C17	−178.4 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1^i	0.86	2.11	2.933 (3)	160
C18—H18···O2^i	0.93	2.56	3.305 (3)	137

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