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In the mol­ecule of the title compound, C23H26ClNO2, 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

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801005189/bt6029sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536801005189/bt6029Isup2.hkl
Contains datablock I

CCDC reference: 165639

Key indicators

  • Single-crystal X-ray study
  • T = 293 K
  • Mean [sigma](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

Comment top

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.

Experimental top

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 (CO), 1603 (N—CO). 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).

Refinement top

The methyl groups were allowed to rotate about their local threefold axis.

Computing details top

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).

Figures top
[Figure 1] Fig. 1. View of the title compound shown with 30% probability ellipsoids.
[Figure 2] Fig. 2. Packing diagram of the title compound.
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
C23H26ClNO2Dx = 1.193 Mg m3
Mr = 383.90Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pna21Cell parameters from 1922 reflections
a = 14.125 (3) Åθ = 2.0–25.0°
b = 14.118 (3) ŵ = 0.20 mm1
c = 10.719 (2) ÅT = 293 K
V = 2137.5 (7) Å3Prism, yellow
Z = 40.35 × 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 tubeRint = 0.000
Graphite monochromatorθmax = 25.0°, θmin = 2.0°
ω scansh = 016
1983 measured reflectionsk = 160
1983 independent reflectionsl = 012
Refinement top
Refinement on F2Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: fullH 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 = 1.03Δρmax = 0.34 e Å3
1983 reflectionsΔρmin = 0.32 e Å3
248 parametersExtinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
1 restraintExtinction coefficient: none
Primary atom site location: structure-invariant direct methodsAbsolute structure: Flack (1983)
Secondary atom site location: difference Fourier mapAbsolute structure parameter: 0.2 (2)
Crystal data top
C23H26ClNO2V = 2137.5 (7) Å3
Mr = 383.90Z = 4
Orthorhombic, Pna21Mo Kα radiation
a = 14.125 (3) ŵ = 0.20 mm1
b = 14.118 (3) ÅT = 293 K
c = 10.719 (2) Å0.35 × 0.30 × 0.15 mm
Data collection top
Bruker CCD
diffractometer
1361 reflections with I > 2σ(I)
1983 measured reflectionsRint = 0.000
1983 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.051H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.208Δρmax = 0.34 e Å3
S = 1.03Δρmin = 0.32 e Å3
1983 reflectionsAbsolute structure: Flack (1983)
248 parametersAbsolute 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
xyzUiso*/Ueq
Cl10.19784 (19)0.1389 (2)0.9628 (2)0.1191 (12)
O10.3780 (4)0.5131 (3)0.6853 (5)0.0683 (14)
O20.2317 (3)0.2663 (3)0.3833 (5)0.0629 (13)
N10.5554 (3)0.3006 (3)0.4412 (6)0.0525 (14)
H1A0.61120.28080.42260.063*
C10.4562 (5)0.4831 (5)0.6499 (6)0.0514 (16)
C20.5476 (5)0.5274 (5)0.6934 (7)0.066 (2)
H2A0.56870.49440.76770.079*
H2B0.53530.59270.71640.079*
C30.6271 (5)0.5257 (5)0.5977 (6)0.0549 (16)
C40.6387 (4)0.4260 (5)0.5504 (8)0.0570 (18)
H4A0.67220.38940.61300.068*
H4B0.67790.42750.47610.068*
C50.5472 (4)0.3759 (4)0.5195 (6)0.0448 (14)
C60.4622 (4)0.4019 (4)0.5649 (6)0.0436 (14)
C70.3718 (4)0.3501 (4)0.5316 (6)0.0471 (14)
H7A0.32580.39690.50170.057*
C80.3911 (4)0.2809 (4)0.4267 (5)0.0417 (13)
C90.4812 (4)0.2562 (4)0.3920 (6)0.0472 (14)
C100.5027 (5)0.1841 (5)0.2929 (7)0.0590 (17)
H10A0.55980.15010.31580.071*
H10B0.51480.21670.21490.071*
C110.4225 (5)0.1130 (5)0.2736 (7)0.0573 (17)
C120.3301 (5)0.1689 (5)0.2601 (7)0.0572 (17)
H12A0.33110.20190.18080.069*
H12B0.27780.12440.25790.069*
C130.3118 (4)0.2390 (4)0.3606 (6)0.0470 (14)
C140.7206 (6)0.5582 (6)0.6536 (9)0.085 (3)
H14A0.73510.52020.72540.127*
H14B0.71570.62340.67790.127*
H14C0.77000.55130.59270.127*
C150.6006 (6)0.5926 (6)0.4908 (8)0.075 (2)
H15A0.53740.57890.46320.113*
H15B0.64400.58390.42280.113*
H15C0.60390.65700.51940.113*
C160.4413 (7)0.0569 (7)0.1536 (9)0.094 (3)
H16A0.39370.00900.14390.141*
H16B0.50250.02760.15850.141*
H16C0.43950.09910.08340.141*
C170.4167 (7)0.0448 (5)0.3804 (9)0.083 (2)
H17A0.40800.07930.45680.124*
H17B0.47420.00870.38500.124*
H17C0.36410.00270.36800.124*
C180.3290 (4)0.2992 (5)0.6415 (6)0.0491 (15)
C190.3798 (5)0.2290 (5)0.7038 (7)0.0643 (19)
H19A0.44150.21490.67970.077*
C200.3377 (6)0.1798 (7)0.8031 (8)0.079 (2)
H20A0.37090.13160.84280.095*
C210.2483 (7)0.2022 (7)0.8418 (7)0.082 (3)
C220.1990 (6)0.2749 (7)0.7848 (9)0.083 (3)
H22A0.13980.29270.81450.100*
C230.2383 (5)0.3212 (6)0.6832 (9)0.073 (2)
H23A0.20340.36770.64230.088*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl10.128 (2)0.172 (3)0.0570 (11)0.0749 (19)0.0008 (14)0.0270 (16)
O10.073 (3)0.065 (3)0.067 (3)0.020 (3)0.016 (3)0.008 (3)
O20.043 (2)0.072 (3)0.074 (3)0.004 (2)0.001 (2)0.018 (3)
N10.033 (2)0.052 (3)0.073 (4)0.005 (2)0.004 (3)0.024 (3)
C10.066 (4)0.045 (3)0.043 (3)0.005 (3)0.011 (3)0.001 (3)
C20.086 (5)0.059 (4)0.053 (4)0.006 (4)0.004 (4)0.020 (4)
C30.060 (4)0.052 (3)0.053 (4)0.011 (3)0.006 (3)0.017 (3)
C40.035 (3)0.062 (4)0.075 (5)0.002 (3)0.007 (3)0.020 (4)
C50.037 (3)0.042 (3)0.055 (4)0.008 (2)0.001 (3)0.005 (3)
C60.044 (3)0.044 (3)0.043 (3)0.001 (2)0.004 (3)0.002 (3)
C70.035 (3)0.052 (3)0.055 (4)0.008 (2)0.005 (3)0.005 (3)
C80.040 (3)0.046 (3)0.039 (3)0.002 (2)0.002 (2)0.005 (3)
C90.049 (3)0.044 (3)0.048 (4)0.001 (2)0.002 (3)0.005 (3)
C100.052 (4)0.062 (4)0.063 (4)0.004 (3)0.014 (3)0.012 (4)
C110.065 (4)0.054 (4)0.053 (4)0.014 (3)0.004 (3)0.009 (3)
C120.053 (4)0.065 (4)0.054 (4)0.013 (3)0.016 (3)0.005 (3)
C130.043 (3)0.053 (3)0.045 (3)0.007 (3)0.004 (3)0.016 (3)
C140.085 (5)0.081 (5)0.088 (6)0.015 (4)0.013 (5)0.028 (5)
C150.087 (5)0.068 (5)0.072 (6)0.016 (4)0.005 (5)0.002 (4)
C160.106 (6)0.090 (6)0.087 (6)0.021 (5)0.003 (5)0.040 (6)
C170.106 (6)0.054 (4)0.088 (6)0.003 (4)0.010 (6)0.001 (5)
C180.040 (3)0.056 (4)0.051 (4)0.001 (3)0.001 (3)0.004 (3)
C190.056 (4)0.075 (5)0.062 (4)0.001 (3)0.000 (4)0.015 (4)
C200.082 (6)0.091 (6)0.062 (5)0.019 (5)0.009 (4)0.025 (5)
C210.089 (6)0.102 (6)0.055 (5)0.053 (5)0.003 (4)0.011 (5)
C220.070 (5)0.111 (7)0.068 (5)0.015 (5)0.031 (4)0.006 (5)
C230.050 (4)0.082 (5)0.089 (6)0.005 (4)0.023 (4)0.006 (5)
Geometric parameters (Å, º) top
Cl1—C211.729 (8)C7—C81.515 (8)
O1—C11.242 (8)C8—C91.371 (8)
O2—C131.220 (7)C8—C131.452 (8)
N1—C91.331 (8)C9—C101.502 (9)
N1—C51.359 (8)C10—C111.528 (9)
C1—C61.468 (9)C11—C171.498 (11)
C1—C21.508 (8)C11—C121.532 (10)
C2—C31.521 (10)C11—C161.533 (11)
C3—C41.505 (9)C12—C131.486 (10)
C3—C141.521 (10)C18—C231.392 (9)
C3—C151.531 (11)C18—C191.395 (10)
C4—C51.510 (8)C19—C201.403 (11)
C5—C61.347 (8)C20—C211.366 (13)
C6—C71.514 (8)C21—C221.382 (13)
C7—C181.506 (9)C22—C231.385 (12)
C9—N1—C5123.1 (5)N1—C9—C8120.3 (5)
O1—C1—C6120.5 (6)N1—C9—C10116.1 (5)
O1—C1—C2121.7 (6)C8—C9—C10123.5 (6)
C6—C1—C2117.8 (5)C9—C10—C11113.1 (6)
C1—C2—C3114.7 (6)C17—C11—C12110.9 (7)
C4—C3—C2108.8 (6)C17—C11—C10111.0 (7)
C4—C3—C14108.6 (6)C12—C11—C10107.8 (5)
C2—C3—C14111.8 (6)C17—C11—C16108.6 (6)
C4—C3—C15110.6 (6)C12—C11—C16109.6 (7)
C2—C3—C15108.3 (6)C10—C11—C16108.9 (7)
C14—C3—C15108.7 (6)C13—C12—C11115.0 (5)
C3—C4—C5114.7 (5)O2—C13—C8119.3 (6)
C6—C5—N1120.8 (5)O2—C13—C12121.1 (6)
C6—C5—C4123.8 (5)C8—C13—C12119.4 (5)
N1—C5—C4115.4 (5)C23—C18—C19118.6 (7)
C5—C6—C1119.3 (6)C23—C18—C7121.0 (6)
C5—C6—C7122.4 (5)C19—C18—C7120.5 (6)
C1—C6—C7118.3 (5)C18—C19—C20119.8 (7)
C18—C7—C6112.6 (5)C21—C20—C19120.6 (8)
C18—C7—C8110.2 (5)C20—C21—C22120.2 (7)
C6—C7—C8109.5 (5)C20—C21—Cl1119.3 (8)
C9—C8—C13118.7 (5)C22—C21—Cl1120.5 (8)
C9—C8—C7122.2 (5)C21—C22—C23119.8 (8)
C13—C8—C7119.1 (5)C22—C23—C18121.0 (8)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1a···O2i0.861.882.735 (6)178
Symmetry code: (i) x+1/2, y+1/2, z.

Experimental details

Crystal data
Chemical formulaC23H26ClNO2
Mr383.90
Crystal system, space groupOrthorhombic, Pna21
Temperature (K)293
a, b, c (Å)14.125 (3), 14.118 (3), 10.719 (2)
V3)2137.5 (7)
Z4
Radiation typeMo Kα
µ (mm1)0.20
Crystal size (mm)0.35 × 0.30 × 0.15
Data collection
DiffractometerBruker CCD
diffractometer
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
1983, 1983, 1361
Rint0.000
(sin θ/λ)max1)0.594
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.051, 0.208, 1.03
No. of reflections1983
No. of parameters248
No. of restraints1
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.34, 0.32
Absolute structureFlack (1983)
Absolute structure parameter0.2 (2)

Computer programs: SMART (Bruker, 1998), SMART, SAINT (Bruker, 1998), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 1998).

Selected geometric parameters (Å, º) top
Cl1—C211.729 (8)N1—C91.331 (8)
O1—C11.242 (8)N1—C51.359 (8)
O2—C131.220 (7)
C9—N1—C5123.1 (5)O2—C13—C8119.3 (6)
O1—C1—C6120.5 (6)O2—C13—C12121.1 (6)
O1—C1—C2121.7 (6)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1a···O2i0.8601.8752.735 (6)178.19
Symmetry code: (i) x+1/2, y+1/2, z.
 

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