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In the molecule of the title compound, C
23H
26ClNO
2, the dihydropyridine plane is approximately bisected by the plane of the orthogonal phenyl ring and the two fused rings are in the same boat main plane. A striking feature of the title compound is seen in the formation of a linear structure through N—H
O hydrogen bonds.
Supporting information
CCDC reference: 165639
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (C-C) = 0.010 Å
- R factor = 0.051
- wR factor = 0.208
- Data-to-parameter ratio = 8.0
checkCIF results
No syntax errors found
ADDSYM reports no extra symmetry
General Notes
REFLT_03
From the CIF: _diffrn_reflns_theta_max 24.96
From the CIF: _reflns_number_total 1983
Count of symmetry unique reflns 1988
Completeness (_total/calc) 99.75%
TEST3: Check Friedels for noncentro structure
Estimate of Friedel pairs measured 0
Fraction of Friedel pairs measured 0.000
Are heavy atom types Z>Si present yes
WARNING: Large fraction of Friedel related reflns may
be needed to determine absolute structure
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).
The methyl groups were allowed to rotate about their local threefold axis.
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).
9-(4-Chlorophenyl)-3,3,6,6-tetramethyl-1,2,3,4,5,6,7,8,9,10-decahydroacridine-
1,8-dione
top
Crystal data top
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 | |
Data collection top
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 top
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) |
Crystal data top
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 |
Data collection top
Bruker CCD diffractometer | 1361 reflections with I > 2σ(I) |
1983 measured reflections | Rint = 0.000 |
1983 independent reflections | |
Refinement top
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 | |
Special details top
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 (Å2) top | 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* | |
Atomic displacement parameters (Å2) top | 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) |
Geometric parameters (Å, º) top
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) |
Hydrogen-bond geometry (Å, º) top
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) |
Selected geometric parameters (Å, º) topCl1—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) | | |
Hydrogen-bond geometry (Å, º) top
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. |
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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.