Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801005189/bt6029sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536801005189/bt6029Isup2.hkl |
CCDC reference: 165639
Compound (I) was prepared by the reaction of 4-chlorobenzaldehyde (2 mmol), dimedone (4 mmol) and ammonium bicarbonate (3 mmol) under microwave irradiation for 4 min. The reaction mixture was cooled and washed with ethanol. The yellow solid obtained was purified by recrystallization from 95% ethanol producing single crystals suitable for X-ray diffraction. Yield: 92%; m.p.: 569–571 K. Analysis calculated for the title compound: C 71.95, H 6.83, N 3.65%; found: C 71.66, H 6.99, N 3.42%. FT—IR data (KBr pellet, cm-1): 3383 (NH), 1623 (C═O), 1603 (N—C═O). 1H NMR (CDCl3, δ, p.p.m.): 0.93 (s, 6H, 2CH3), 1.05 (s, 6H, 2CH3), 2.21–2.25 (m, 8H, 4CH2), 5.06 (s, 1H, CH), 7.12–7.32 (m, 4H, ArH), 7.72 (s, 1H, NH).
Data collection: SMART (Bruker, 1998); cell refinement: SMART; data reduction: SAINT (Bruker, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1998).
Fig. 1. View of the title compound shown with 30% probability ellipsoids. | |
Fig. 2. Packing diagram of the title compound. |
C23H26ClNO2 | Dx = 1.193 Mg m−3 |
Mr = 383.90 | Mo Kα radiation, λ = 0.71073 Å |
Orthorhombic, Pna21 | Cell parameters from 1922 reflections |
a = 14.125 (3) Å | θ = 2.0–25.0° |
b = 14.118 (3) Å | µ = 0.20 mm−1 |
c = 10.719 (2) Å | T = 293 K |
V = 2137.5 (7) Å3 | Prism, yellow |
Z = 4 | 0.35 × 0.30 × 0.15 mm |
F(000) = 816 |
Bruker CCD diffractometer | 1361 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.000 |
Graphite monochromator | θmax = 25.0°, θmin = 2.0° |
ω scans | h = 0→16 |
1983 measured reflections | k = −16→0 |
1983 independent reflections | l = 0→12 |
Refinement on F2 | Hydrogen site location: inferred from neighbouring sites |
Least-squares matrix: full | H atoms treated by a mixture of independent and constrained refinement |
R[F2 > 2σ(F2)] = 0.051 | w = 1/[σ2(Fo2) + (0.1373P)2 + 0.7655P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.208 | (Δ/σ)max < 0.001 |
S = 1.03 | Δρmax = 0.34 e Å−3 |
1983 reflections | Δρmin = −0.32 e Å−3 |
248 parameters | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
1 restraint | Extinction coefficient: none |
Primary atom site location: structure-invariant direct methods | Absolute structure: Flack (1983) |
Secondary atom site location: difference Fourier map | Absolute structure parameter: 0.2 (2) |
C23H26ClNO2 | V = 2137.5 (7) Å3 |
Mr = 383.90 | Z = 4 |
Orthorhombic, Pna21 | Mo Kα radiation |
a = 14.125 (3) Å | µ = 0.20 mm−1 |
b = 14.118 (3) Å | T = 293 K |
c = 10.719 (2) Å | 0.35 × 0.30 × 0.15 mm |
Bruker CCD diffractometer | 1361 reflections with I > 2σ(I) |
1983 measured reflections | Rint = 0.000 |
1983 independent reflections |
R[F2 > 2σ(F2)] = 0.051 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.208 | Δρmax = 0.34 e Å−3 |
S = 1.03 | Δρmin = −0.32 e Å−3 |
1983 reflections | Absolute structure: Flack (1983) |
248 parameters | Absolute structure parameter: 0.2 (2) |
1 restraint |
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 | ||
Cl1 | 0.19784 (19) | 0.1389 (2) | 0.9628 (2) | 0.1191 (12) | |
O1 | 0.3780 (4) | 0.5131 (3) | 0.6853 (5) | 0.0683 (14) | |
O2 | 0.2317 (3) | 0.2663 (3) | 0.3833 (5) | 0.0629 (13) | |
N1 | 0.5554 (3) | 0.3006 (3) | 0.4412 (6) | 0.0525 (14) | |
H1A | 0.6112 | 0.2808 | 0.4226 | 0.063* | |
C1 | 0.4562 (5) | 0.4831 (5) | 0.6499 (6) | 0.0514 (16) | |
C2 | 0.5476 (5) | 0.5274 (5) | 0.6934 (7) | 0.066 (2) | |
H2A | 0.5687 | 0.4944 | 0.7677 | 0.079* | |
H2B | 0.5353 | 0.5927 | 0.7164 | 0.079* | |
C3 | 0.6271 (5) | 0.5257 (5) | 0.5977 (6) | 0.0549 (16) | |
C4 | 0.6387 (4) | 0.4260 (5) | 0.5504 (8) | 0.0570 (18) | |
H4A | 0.6722 | 0.3894 | 0.6130 | 0.068* | |
H4B | 0.6779 | 0.4275 | 0.4761 | 0.068* | |
C5 | 0.5472 (4) | 0.3759 (4) | 0.5195 (6) | 0.0448 (14) | |
C6 | 0.4622 (4) | 0.4019 (4) | 0.5649 (6) | 0.0436 (14) | |
C7 | 0.3718 (4) | 0.3501 (4) | 0.5316 (6) | 0.0471 (14) | |
H7A | 0.3258 | 0.3969 | 0.5017 | 0.057* | |
C8 | 0.3911 (4) | 0.2809 (4) | 0.4267 (5) | 0.0417 (13) | |
C9 | 0.4812 (4) | 0.2562 (4) | 0.3920 (6) | 0.0472 (14) | |
C10 | 0.5027 (5) | 0.1841 (5) | 0.2929 (7) | 0.0590 (17) | |
H10A | 0.5598 | 0.1501 | 0.3158 | 0.071* | |
H10B | 0.5148 | 0.2167 | 0.2149 | 0.071* | |
C11 | 0.4225 (5) | 0.1130 (5) | 0.2736 (7) | 0.0573 (17) | |
C12 | 0.3301 (5) | 0.1689 (5) | 0.2601 (7) | 0.0572 (17) | |
H12A | 0.3311 | 0.2019 | 0.1808 | 0.069* | |
H12B | 0.2778 | 0.1244 | 0.2579 | 0.069* | |
C13 | 0.3118 (4) | 0.2390 (4) | 0.3606 (6) | 0.0470 (14) | |
C14 | 0.7206 (6) | 0.5582 (6) | 0.6536 (9) | 0.085 (3) | |
H14A | 0.7351 | 0.5202 | 0.7254 | 0.127* | |
H14B | 0.7157 | 0.6234 | 0.6779 | 0.127* | |
H14C | 0.7700 | 0.5513 | 0.5927 | 0.127* | |
C15 | 0.6006 (6) | 0.5926 (6) | 0.4908 (8) | 0.075 (2) | |
H15A | 0.5374 | 0.5789 | 0.4632 | 0.113* | |
H15B | 0.6440 | 0.5839 | 0.4228 | 0.113* | |
H15C | 0.6039 | 0.6570 | 0.5194 | 0.113* | |
C16 | 0.4413 (7) | 0.0569 (7) | 0.1536 (9) | 0.094 (3) | |
H16A | 0.3937 | 0.0090 | 0.1439 | 0.141* | |
H16B | 0.5025 | 0.0276 | 0.1585 | 0.141* | |
H16C | 0.4395 | 0.0991 | 0.0834 | 0.141* | |
C17 | 0.4167 (7) | 0.0448 (5) | 0.3804 (9) | 0.083 (2) | |
H17A | 0.4080 | 0.0793 | 0.4568 | 0.124* | |
H17B | 0.4742 | 0.0087 | 0.3850 | 0.124* | |
H17C | 0.3641 | 0.0027 | 0.3680 | 0.124* | |
C18 | 0.3290 (4) | 0.2992 (5) | 0.6415 (6) | 0.0491 (15) | |
C19 | 0.3798 (5) | 0.2290 (5) | 0.7038 (7) | 0.0643 (19) | |
H19A | 0.4415 | 0.2149 | 0.6797 | 0.077* | |
C20 | 0.3377 (6) | 0.1798 (7) | 0.8031 (8) | 0.079 (2) | |
H20A | 0.3709 | 0.1316 | 0.8428 | 0.095* | |
C21 | 0.2483 (7) | 0.2022 (7) | 0.8418 (7) | 0.082 (3) | |
C22 | 0.1990 (6) | 0.2749 (7) | 0.7848 (9) | 0.083 (3) | |
H22A | 0.1398 | 0.2927 | 0.8145 | 0.100* | |
C23 | 0.2383 (5) | 0.3212 (6) | 0.6832 (9) | 0.073 (2) | |
H23A | 0.2034 | 0.3677 | 0.6423 | 0.088* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cl1 | 0.128 (2) | 0.172 (3) | 0.0570 (11) | −0.0749 (19) | 0.0008 (14) | 0.0270 (16) |
O1 | 0.073 (3) | 0.065 (3) | 0.067 (3) | 0.020 (3) | 0.016 (3) | −0.008 (3) |
O2 | 0.043 (2) | 0.072 (3) | 0.074 (3) | −0.004 (2) | 0.001 (2) | 0.018 (3) |
N1 | 0.033 (2) | 0.052 (3) | 0.073 (4) | 0.005 (2) | 0.004 (3) | −0.024 (3) |
C1 | 0.066 (4) | 0.045 (3) | 0.043 (3) | 0.005 (3) | 0.011 (3) | −0.001 (3) |
C2 | 0.086 (5) | 0.059 (4) | 0.053 (4) | −0.006 (4) | 0.004 (4) | −0.020 (4) |
C3 | 0.060 (4) | 0.052 (3) | 0.053 (4) | −0.011 (3) | −0.006 (3) | −0.017 (3) |
C4 | 0.035 (3) | 0.062 (4) | 0.075 (5) | −0.002 (3) | −0.007 (3) | −0.020 (4) |
C5 | 0.037 (3) | 0.042 (3) | 0.055 (4) | 0.008 (2) | 0.001 (3) | −0.005 (3) |
C6 | 0.044 (3) | 0.044 (3) | 0.043 (3) | −0.001 (2) | 0.004 (3) | −0.002 (3) |
C7 | 0.035 (3) | 0.052 (3) | 0.055 (4) | 0.008 (2) | 0.005 (3) | 0.005 (3) |
C8 | 0.040 (3) | 0.046 (3) | 0.039 (3) | −0.002 (2) | −0.002 (2) | 0.005 (3) |
C9 | 0.049 (3) | 0.044 (3) | 0.048 (4) | −0.001 (2) | −0.002 (3) | −0.005 (3) |
C10 | 0.052 (4) | 0.062 (4) | 0.063 (4) | 0.004 (3) | 0.014 (3) | −0.012 (4) |
C11 | 0.065 (4) | 0.054 (4) | 0.053 (4) | −0.014 (3) | −0.004 (3) | −0.009 (3) |
C12 | 0.053 (4) | 0.065 (4) | 0.054 (4) | −0.013 (3) | −0.016 (3) | 0.005 (3) |
C13 | 0.043 (3) | 0.053 (3) | 0.045 (3) | −0.007 (3) | −0.004 (3) | 0.016 (3) |
C14 | 0.085 (5) | 0.081 (5) | 0.088 (6) | −0.015 (4) | −0.013 (5) | −0.028 (5) |
C15 | 0.087 (5) | 0.068 (5) | 0.072 (6) | −0.016 (4) | 0.005 (5) | 0.002 (4) |
C16 | 0.106 (6) | 0.090 (6) | 0.087 (6) | −0.021 (5) | 0.003 (5) | −0.040 (6) |
C17 | 0.106 (6) | 0.054 (4) | 0.088 (6) | −0.003 (4) | −0.010 (6) | 0.001 (5) |
C18 | 0.040 (3) | 0.056 (4) | 0.051 (4) | −0.001 (3) | 0.001 (3) | −0.004 (3) |
C19 | 0.056 (4) | 0.075 (5) | 0.062 (4) | 0.001 (3) | 0.000 (4) | 0.015 (4) |
C20 | 0.082 (6) | 0.091 (6) | 0.062 (5) | −0.019 (5) | −0.009 (4) | 0.025 (5) |
C21 | 0.089 (6) | 0.102 (6) | 0.055 (5) | −0.053 (5) | −0.003 (4) | 0.011 (5) |
C22 | 0.070 (5) | 0.111 (7) | 0.068 (5) | −0.015 (5) | 0.031 (4) | −0.006 (5) |
C23 | 0.050 (4) | 0.082 (5) | 0.089 (6) | 0.005 (4) | 0.023 (4) | 0.006 (5) |
Cl1—C21 | 1.729 (8) | C7—C8 | 1.515 (8) |
O1—C1 | 1.242 (8) | C8—C9 | 1.371 (8) |
O2—C13 | 1.220 (7) | C8—C13 | 1.452 (8) |
N1—C9 | 1.331 (8) | C9—C10 | 1.502 (9) |
N1—C5 | 1.359 (8) | C10—C11 | 1.528 (9) |
C1—C6 | 1.468 (9) | C11—C17 | 1.498 (11) |
C1—C2 | 1.508 (8) | C11—C12 | 1.532 (10) |
C2—C3 | 1.521 (10) | C11—C16 | 1.533 (11) |
C3—C4 | 1.505 (9) | C12—C13 | 1.486 (10) |
C3—C14 | 1.521 (10) | C18—C23 | 1.392 (9) |
C3—C15 | 1.531 (11) | C18—C19 | 1.395 (10) |
C4—C5 | 1.510 (8) | C19—C20 | 1.403 (11) |
C5—C6 | 1.347 (8) | C20—C21 | 1.366 (13) |
C6—C7 | 1.514 (8) | C21—C22 | 1.382 (13) |
C7—C18 | 1.506 (9) | C22—C23 | 1.385 (12) |
C9—N1—C5 | 123.1 (5) | N1—C9—C8 | 120.3 (5) |
O1—C1—C6 | 120.5 (6) | N1—C9—C10 | 116.1 (5) |
O1—C1—C2 | 121.7 (6) | C8—C9—C10 | 123.5 (6) |
C6—C1—C2 | 117.8 (5) | C9—C10—C11 | 113.1 (6) |
C1—C2—C3 | 114.7 (6) | C17—C11—C12 | 110.9 (7) |
C4—C3—C2 | 108.8 (6) | C17—C11—C10 | 111.0 (7) |
C4—C3—C14 | 108.6 (6) | C12—C11—C10 | 107.8 (5) |
C2—C3—C14 | 111.8 (6) | C17—C11—C16 | 108.6 (6) |
C4—C3—C15 | 110.6 (6) | C12—C11—C16 | 109.6 (7) |
C2—C3—C15 | 108.3 (6) | C10—C11—C16 | 108.9 (7) |
C14—C3—C15 | 108.7 (6) | C13—C12—C11 | 115.0 (5) |
C3—C4—C5 | 114.7 (5) | O2—C13—C8 | 119.3 (6) |
C6—C5—N1 | 120.8 (5) | O2—C13—C12 | 121.1 (6) |
C6—C5—C4 | 123.8 (5) | C8—C13—C12 | 119.4 (5) |
N1—C5—C4 | 115.4 (5) | C23—C18—C19 | 118.6 (7) |
C5—C6—C1 | 119.3 (6) | C23—C18—C7 | 121.0 (6) |
C5—C6—C7 | 122.4 (5) | C19—C18—C7 | 120.5 (6) |
C1—C6—C7 | 118.3 (5) | C18—C19—C20 | 119.8 (7) |
C18—C7—C6 | 112.6 (5) | C21—C20—C19 | 120.6 (8) |
C18—C7—C8 | 110.2 (5) | C20—C21—C22 | 120.2 (7) |
C6—C7—C8 | 109.5 (5) | C20—C21—Cl1 | 119.3 (8) |
C9—C8—C13 | 118.7 (5) | C22—C21—Cl1 | 120.5 (8) |
C9—C8—C7 | 122.2 (5) | C21—C22—C23 | 119.8 (8) |
C13—C8—C7 | 119.1 (5) | C22—C23—C18 | 121.0 (8) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1a···O2i | 0.86 | 1.88 | 2.735 (6) | 178 |
Symmetry code: (i) x+1/2, −y+1/2, z. |
Experimental details
Crystal data | |
Chemical formula | C23H26ClNO2 |
Mr | 383.90 |
Crystal system, space group | Orthorhombic, Pna21 |
Temperature (K) | 293 |
a, b, c (Å) | 14.125 (3), 14.118 (3), 10.719 (2) |
V (Å3) | 2137.5 (7) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.20 |
Crystal size (mm) | 0.35 × 0.30 × 0.15 |
Data collection | |
Diffractometer | Bruker CCD diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 1983, 1983, 1361 |
Rint | 0.000 |
(sin θ/λ)max (Å−1) | 0.594 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.051, 0.208, 1.03 |
No. of reflections | 1983 |
No. of parameters | 248 |
No. of restraints | 1 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.34, −0.32 |
Absolute structure | Flack (1983) |
Absolute structure parameter | 0.2 (2) |
Computer programs: SMART (Bruker, 1998), SMART, SAINT (Bruker, 1998), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 1998).
Cl1—C21 | 1.729 (8) | N1—C9 | 1.331 (8) |
O1—C1 | 1.242 (8) | N1—C5 | 1.359 (8) |
O2—C13 | 1.220 (7) | ||
C9—N1—C5 | 123.1 (5) | O2—C13—C8 | 119.3 (6) |
O1—C1—C6 | 120.5 (6) | O2—C13—C12 | 121.1 (6) |
O1—C1—C2 | 121.7 (6) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1a···O2i | 0.860 | 1.875 | 2.735 (6) | 178.19 |
Symmetry code: (i) x+1/2, −y+1/2, z. |
A great deal of work has been directed toward the synthesis of novel derivatives of 1,4-dihydropyridines (1,4-DHP) because they can act as calcium channel antagonists or agonists (Goldmann & Stoltefuss, 1991). Of particular interest is knowing which conformation in 1,4-DHPs gives optimum results and, consequently, the relationship between the conformation and the pharmacological effect. It has been proved that cyclohexanone rings in the 1,4-DHP system lead to compounds with a positive inotropic effect, that is, they promote instead of blocking the entry of calcium to the intracellular space due to conformational changes (Martin et al., 1995). Furthermore, although the crystal structures of many aryl-ring substituent derivatives of 1,4-DHPs having the antagonist activity have been determined by X-ray studies (Fossheim, 1985, 1986; Fossheim et al., 1988), that of the cyclohexanone-ring substituted 1,4-DHP is still unknown. Taking into account the above-mentioned aspects, we report herein the synthesis and crystal structure of a new 1,4-DHP compound with cyclohexanone rings, namely 9-(4-chlorophenyl)-3,3,6,6-tetramethyl-1,2,3,4,5,6,7,8,9,10-decahydroacridine- 1,8-dione, (I).
As in the previously determined structures of 4-aryl-substituted 1,4-DHPs, there exists a flattened-boat conformation in (I) in which the aryl substituent is in a pseudo-axial position, orthogonal to the dihydropyridine plane, as shown in Fig. 1. The dihydropyridine plane is approximately bisected by the plane of the phenyl ring, indicated by the magnitude of the dihedral angle between the two planes, which is 87.2°. The two fused rings are in the same plane, with atoms C3 and C11 displaced from this plane.
The sum of the bond angles around the amino N atom (359.9°) shows that it is essentially sp2 hybridized, which is similar to previous results (Fossheim, 1987). The H atom is thus located only slightly deviated from the plane containing C5, C9 and N1. Fossheim (1987)predicted that for the above reason, the requirement for a strong linear hydrogen bond is best fulfilled when the acceptor atom of the receptor lies approximately in the DHP ring. In this compound, the formation of N—H···O hydrogen bonds links the molecules to form linear chains, as shown in Fig. 2.