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Acta Cryst. (2011). E67, o380-o381    [ doi:10.1107/S1600536810052839 ]

1,1'-[4-(2,4-Dichlorophenyl)-2,6-dimethyl-1,4-dihydropyridine-3,5-diyl]diethanone

J. K. Sundar, B. P. Reddy, V. Vijayakumar, S. Natarajan, J. Suresh and P. L. N. Lakshman

Abstract top

In the title compound, C17H17Cl2NO2, the central 1,4-dihydropyridine ring adopts a flattened-boat conformation. The ethanone substituents of the dihydropyridine ring at positions 3 and 5 have synperiplanar (cis) or antiperiplanar (trans) conformations with respect to the adjacent C=C bonds in the dihydropyridine ring. The 2,4-dichlorophenyl ring is almost planar [r.m.s. deviation = 0.0045 (1) Å] and almost perpendicular [89.27 (3)°] to the mean plane of the dihydropyridine ring. In the crystal, an N-H...O hydrogen bond links molecules into a zigzag chain along the ac diagonal. C-H...Cl contacts form centrosymmetric dimers and additional weak C-H...O contacts further consolidate the packing.

Comment top

1,4-Dihydropyridine derivatives have yielded many drugs which act as calcium channel agonists or antagonists (Rose, 1989, 1990) and various bioactive compounds such as vasodilator, antiatherosclerotic, antitumor, geroprotective, heptaprotective and antidiabetic agents (Salehi & Guo, 2004). Triggle and co-workers (Triggle et al., 1980; Janis & Triggle, 1984; Langs & Triggle, 1985) have identified some important structural requirements for biological activity. We have studied the crystal structure of 1,1'-[4-(2,4-dichlorophenyl)-2,6-dimethyl-1,4-dihydropyridine- 3,5-diyl]diethanone.

In the title compound (I)(Fig. 1), C17H17Cl2NO2, the central 1, 4-dihydropyridine ring adopts a flattened boat conformation. The ethanone substituents of the dihydropyridine ring at positions 3 and 5 have different (cis/trans) configurations with respect to the double bonds in the pyridine ring. Each group is oriented in a synperiplanar (cis) or antiperiplanar (trans) conformation with respect to the adjacent C═ C in the dihydropyridine ring, which is evident from the torsion angles of C6—C5—C11—O2 [31.44 (40)°] and C2—C3—C9—O1 [172.43 (20)°], respectively.

The methyl groups attached at C2 and C6 positions of the pyridine ring adopt equatorial orientation as can be seen from the torsion angles [C7—C6—N1—C2] 165.54 (20)° and [C8—C2—N1—C6] -164.62 (20)°. The 2,4-dichlorophenyl ring is planar and almost perpendicular to the mean plane of the dihydropyridine ring with the plane angle: 89.27 (3)°. This close to perpendicular orientation of the dichlorophenyl ring to the dihydropyridine ring can be ascribed to the greater steric hinderance with the two ethanone groups at C3 and C5. Atom N1(x,y,z) of the pyridine ring make a intermolecular hydrogen bond with the atom O1(-1/2 + x, 1/2 + y, -1/2 + z), leading to a zigzag chain running along the diagonal of the ac - plane (Fig. 2). C17—H17···Cl2 contacts form centrosymmetric dimers and additional weak C—H···O contacts further stabilise the structure, Table 1.

Related literature top

For background to the pharmaceutical applications of 1,4-dihydropyridine derivatives, see: Rose (1989, 1990); Salehi & Guo (2004). For structure–activity relationships among 1,4-dihydropyridines, see: Triggle et al. (1980); Janis & Triggle (1984); Langs & Triggle (1985).

Experimental top

2,4,dicholrobenzaldehyde (10 mmol), acetylacetone (20 mmol) and ammonium acetate (10 mmol) in ethanol were heated on a steam bath until the color of the solution changed to reddish-orange. The mixture was cooled in ice to yield a solid product, which was extracted using diethylether. The purity of the crude product was checked through TLC and recrystallized from acetone/ether 1:1 [yield: 60%, m.p. 218–220°C].

Refinement top

H atoms were placed at calculated positions and allowed to ride on their carrier atoms with C—H = 0.93–0.97 Å, and Uiso = 1.2Ueq(C) for CH2 and CH groups and Uiso = 1.5Ueq(C) for CH3 group. The N-bound H atom is located in a difference Fourier map and its positional parameters were refined.

Computing details top

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994); cell refinement: CAD-4 EXPRESS (Enraf–Nonius, 1994); data reduction: XCAD4 (Harms & Wocadlo, 1996); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The molecular structure of (I), showing 40% probability displacement ellipsoids and the atom-numbering scheme.
[Figure 2] Fig. 2. Packing of the crystal structre (I), viewed down the a axis. Hydrogen bonds are shown as dashed lines.
1,1'-[4-(2,4-Dichlorophenyl)-2,6-dimethyl-1,4-dihydropyridine-3,5- diyl]diethanone top
Crystal data top
C17H17Cl2NO2F(000) = 704
Mr = 338.22Dx = 1.405 Mg m−3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 25 reflections
a = 10.307 (4) Åθ = 2–25°
b = 13.745 (3) ŵ = 0.41 mm−1
c = 11.312 (2) ÅT = 293 K
β = 93.80 (2)°Block, colourless
V = 1599.0 (8) Å30.23 × 0.21 × 0.18 mm
Z = 4
Data collection top
Nonius MACH3
diffractometer		2265 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.014
graphiteθmax = 25.0°, θmin = 2.3°
ω–2θ scansh = 0→12
Absorption correction: ψ scan
(North et al., 1968)		k = −1→16
Tmin = 0.910, Tmax = 0.929l = −13→13
3247 measured reflections3 standard reflections every 60 min
2811 independent reflections intensity decay: none
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.032Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.096H atoms treated by a mixture of independent and constrained refinement
S = 1.05 w = 1/[σ2(Fo2) + (0.0451P)2 + 0.6776P]
where P = (Fo2 + 2Fc2)/3
2811 reflections(Δ/σ)max < 0.001
207 parametersΔρmax = 0.21 e Å−3
0 restraintsΔρmin = −0.21 e Å−3
Crystal data top
C17H17Cl2NO2V = 1599.0 (8) Å3
Mr = 338.22Z = 4
Monoclinic, P21/nMo Kα radiation
a = 10.307 (4) ŵ = 0.41 mm−1
b = 13.745 (3) ÅT = 293 K
c = 11.312 (2) Å0.23 × 0.21 × 0.18 mm
β = 93.80 (2)°
Data collection top
Nonius MACH3
diffractometer		2265 reflections with I > 2σ(I)
Absorption correction: ψ scan
(North et al., 1968)		Rint = 0.014
Tmin = 0.910, Tmax = 0.929θmax = 25.0°
3247 measured reflections3 standard reflections every 60 min
2811 independent reflections intensity decay: none
Refinement top
R[F2 > 2σ(F2)] = 0.032H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.096Δρmax = 0.21 e Å−3
S = 1.05Δρmin = −0.21 e Å−3
2811 reflectionsAbsolute structure: ?
207 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
Special details top

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.

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
C20.09331 (17)0.23909 (14)0.35680 (16)0.0368 (4)
C30.21210 (16)0.23609 (13)0.41766 (15)0.0333 (4)
C40.32545 (16)0.18638 (13)0.36213 (15)0.0325 (4)
H40.37700.15170.42470.039*
C50.27979 (18)0.11313 (13)0.26722 (15)0.0371 (4)
C60.16077 (19)0.12296 (14)0.21010 (16)0.0405 (4)
C70.1058 (2)0.06292 (16)0.1077 (2)0.0573 (6)
H7A0.01300.07060.09980.069*
H7B0.1267−0.00430.12160.069*
H7C0.14240.08410.03620.069*
C8−0.02898 (18)0.28757 (18)0.3917 (2)0.0536 (6)
H8A−0.09610.27970.32950.064*
H8B−0.01280.35560.40500.064*
H8C−0.05620.25840.46310.064*
C90.24581 (18)0.28036 (14)0.53385 (16)0.0388 (4)
C100.1592 (2)0.34902 (17)0.59460 (18)0.0538 (6)
H10A0.20280.37110.66730.065*
H10B0.08030.31620.61140.065*
H10C0.13900.40380.54400.065*
C110.3678 (2)0.03428 (15)0.23582 (19)0.0485 (5)
C120.4571 (3)−0.00851 (18)0.3312 (2)0.0695 (7)
H12A0.4768−0.07450.31140.083*
H12B0.4159−0.00720.40490.083*
H12C0.53600.02870.33890.083*
C130.41271 (16)0.26267 (13)0.30834 (15)0.0313 (4)
C140.54362 (16)0.27779 (13)0.34248 (15)0.0348 (4)
C150.61739 (18)0.34868 (15)0.29079 (17)0.0422 (5)
H150.70410.35800.31660.051*
C160.56114 (19)0.40453 (15)0.20163 (17)0.0446 (5)
C170.4322 (2)0.39221 (15)0.16311 (17)0.0457 (5)
H170.39430.43020.10220.055*
C180.36099 (18)0.32216 (14)0.21721 (16)0.0394 (4)
H180.27400.31420.19160.047*
Cl10.62411 (4)0.20669 (4)0.45204 (5)0.05059 (17)
Cl20.65383 (6)0.49418 (5)0.13777 (6)0.0727 (2)
N10.07592 (16)0.19087 (13)0.25047 (15)0.0438 (4)
O10.35315 (14)0.26245 (14)0.58271 (14)0.0638 (5)
O20.3688 (2)0.00154 (15)0.13564 (16)0.0885 (7)
H10.006 (2)0.1959 (17)0.213 (2)0.053 (7)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C20.0286 (9)0.0424 (10)0.0386 (10)−0.0049 (8)−0.0028 (7)0.0092 (8)
C30.0286 (9)0.0395 (10)0.0314 (9)−0.0029 (7)−0.0007 (7)0.0038 (7)
C40.0304 (9)0.0363 (9)0.0297 (9)−0.0005 (7)−0.0065 (7)0.0013 (7)
C50.0417 (10)0.0348 (10)0.0339 (9)−0.0050 (8)−0.0049 (8)0.0011 (8)
C60.0483 (11)0.0366 (10)0.0351 (10)−0.0091 (9)−0.0095 (8)0.0048 (8)
C70.0707 (15)0.0496 (13)0.0480 (12)−0.0153 (11)−0.0231 (11)−0.0001 (10)
C80.0283 (10)0.0693 (15)0.0624 (13)0.0005 (10)−0.0016 (9)0.0081 (11)
C90.0347 (10)0.0472 (11)0.0345 (9)−0.0049 (8)0.0019 (8)0.0016 (8)
C100.0600 (13)0.0636 (14)0.0379 (11)0.0095 (11)0.0043 (9)−0.0027 (10)
C110.0546 (12)0.0396 (11)0.0503 (12)−0.0021 (9)−0.0034 (9)−0.0076 (9)
C120.0770 (17)0.0506 (14)0.0778 (17)0.0214 (12)−0.0178 (14)−0.0106 (12)
C130.0282 (9)0.0359 (9)0.0295 (8)0.0005 (7)−0.0009 (7)−0.0063 (7)
C140.0294 (9)0.0392 (10)0.0351 (9)0.0036 (7)−0.0025 (7)−0.0043 (8)
C150.0290 (9)0.0505 (12)0.0469 (11)−0.0040 (8)0.0010 (8)−0.0042 (9)
C160.0454 (11)0.0459 (11)0.0431 (11)−0.0097 (9)0.0076 (9)−0.0009 (9)
C170.0492 (11)0.0492 (12)0.0377 (10)−0.0045 (9)−0.0051 (9)0.0058 (9)
C180.0333 (9)0.0474 (11)0.0365 (10)−0.0038 (8)−0.0060 (8)−0.0003 (8)
Cl10.0328 (3)0.0580 (3)0.0589 (3)0.0034 (2)−0.0119 (2)0.0099 (2)
Cl20.0696 (4)0.0779 (5)0.0706 (4)−0.0307 (3)0.0044 (3)0.0198 (3)
N10.0329 (9)0.0529 (10)0.0431 (9)−0.0060 (7)−0.0163 (7)0.0043 (8)
O10.0408 (8)0.0997 (13)0.0485 (9)0.0097 (8)−0.0152 (7)−0.0258 (9)
O20.1091 (16)0.0922 (15)0.0621 (11)0.0329 (12)−0.0095 (10)−0.0350 (10)
Geometric parameters (Å, °) top
C2—C31.365 (2)C10—H10A0.9600
C2—N11.375 (3)C10—H10B0.9600
C2—C81.502 (3)C10—H10C0.9600
C3—C91.469 (3)C11—O21.220 (3)
C3—C41.524 (2)C11—C121.492 (3)
C4—C51.524 (2)C12—H12A0.9600
C4—C131.533 (2)C12—H12B0.9600
C4—H40.9800C12—H12C0.9600
C5—C61.355 (3)C13—C181.394 (3)
C5—C111.472 (3)C13—C141.394 (2)
C6—N11.378 (3)C14—C151.389 (3)
C6—C71.503 (3)C14—Cl11.7444 (18)
C7—H7A0.9600C15—C161.366 (3)
C7—H7B0.9600C15—H150.9300
C7—H7C0.9600C16—C171.382 (3)
C8—H8A0.9600C16—Cl21.745 (2)
C8—H8B0.9600C17—C181.378 (3)
C8—H8C0.9600C17—H170.9300
C9—O11.228 (2)C18—H180.9300
C9—C101.497 (3)N1—H10.81 (2)
C3—C2—N1119.17 (17)H10A—C10—H10B109.5
C3—C2—C8128.40 (18)C9—C10—H10C109.5
N1—C2—C8112.41 (16)H10A—C10—H10C109.5
C2—C3—C9126.14 (17)H10B—C10—H10C109.5
C2—C3—C4119.48 (16)O2—C11—C5122.6 (2)
C9—C3—C4114.33 (15)O2—C11—C12118.9 (2)
C5—C4—C3112.16 (14)C5—C11—C12118.43 (18)
C5—C4—C13109.52 (14)C11—C12—H12A109.5
C3—C4—C13110.04 (14)C11—C12—H12B109.5
C5—C4—H4108.3H12A—C12—H12B109.5
C3—C4—H4108.3C11—C12—H12C109.5
C13—C4—H4108.3H12A—C12—H12C109.5
C6—C5—C11120.76 (17)H12B—C12—H12C109.5
C6—C5—C4119.86 (17)C18—C13—C14115.67 (16)
C11—C5—C4119.35 (16)C18—C13—C4119.28 (15)
C5—C6—N1118.96 (17)C14—C13—C4125.05 (16)
C5—C6—C7126.61 (19)C15—C14—C13122.33 (17)
N1—C6—C7114.35 (18)C15—C14—Cl1116.38 (13)
C6—C7—H7A109.5C13—C14—Cl1121.28 (14)
C6—C7—H7B109.5C16—C15—C14119.20 (17)
H7A—C7—H7B109.5C16—C15—H15120.4
C6—C7—H7C109.5C14—C15—H15120.4
H7A—C7—H7C109.5C15—C16—C17121.10 (18)
H7B—C7—H7C109.5C15—C16—Cl2119.04 (15)
C2—C8—H8A109.5C17—C16—Cl2119.85 (16)
C2—C8—H8B109.5C18—C17—C16118.35 (18)
H8A—C8—H8B109.5C18—C17—H17120.8
C2—C8—H8C109.5C16—C17—H17120.8
H8A—C8—H8C109.5C17—C18—C13123.34 (17)
H8B—C8—H8C109.5C17—C18—H18118.3
O1—C9—C3118.17 (17)C13—C18—H18118.3
O1—C9—C10117.81 (17)C2—N1—C6124.61 (16)
C3—C9—C10123.98 (17)C2—N1—H1118.2 (16)
C9—C10—H10A109.5C6—N1—H1116.5 (16)
C9—C10—H10B109.5
N1—C2—C3—C9−177.66 (17)C4—C5—C11—C1234.8 (3)
C8—C2—C3—C90.5 (3)C5—C4—C13—C1862.3 (2)
N1—C2—C3—C44.8 (3)C3—C4—C13—C18−61.4 (2)
C8—C2—C3—C4−177.01 (18)C5—C4—C13—C14−116.97 (18)
C2—C3—C4—C5−22.3 (2)C3—C4—C13—C14119.30 (18)
C9—C3—C4—C5159.92 (15)C18—C13—C14—C151.2 (3)
C2—C3—C4—C1399.89 (18)C4—C13—C14—C15−179.54 (16)
C9—C3—C4—C13−77.89 (18)C18—C13—C14—Cl1−177.96 (13)
C3—C4—C5—C624.6 (2)C4—C13—C14—Cl11.3 (2)
C13—C4—C5—C6−97.9 (2)C13—C14—C15—C16−1.4 (3)
C3—C4—C5—C11−157.55 (16)Cl1—C14—C15—C16177.78 (15)
C13—C4—C5—C1180.0 (2)C14—C15—C16—C170.6 (3)
C11—C5—C6—N1173.01 (18)C14—C15—C16—Cl2179.48 (15)
C4—C5—C6—N1−9.1 (3)C15—C16—C17—C180.2 (3)
C11—C5—C6—C7−3.6 (3)Cl2—C16—C17—C18−178.61 (16)
C4—C5—C6—C7174.23 (18)C16—C17—C18—C13−0.4 (3)
C2—C3—C9—O1172.37 (19)C14—C13—C18—C17−0.3 (3)
C4—C3—C9—O1−10.0 (3)C4—C13—C18—C17−179.59 (18)
C2—C3—C9—C10−10.0 (3)C3—C2—N1—C613.8 (3)
C4—C3—C9—C10167.64 (18)C8—C2—N1—C6−164.67 (18)
C6—C5—C11—O231.2 (3)C5—C6—N1—C2−11.5 (3)
C4—C5—C11—O2−146.6 (2)C7—C6—N1—C2165.50 (18)
C6—C5—C11—C12−147.4 (2)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1···O1i0.81 (2)2.16 (2)2.951 (2)163 (2)
C8—H8B···O2ii0.962.563.397 (3)147
C10—H10C···O2ii0.962.433.341 (3)158
C4—H4···Cl10.982.653.190 (2)115
C17—H17···Cl2iii0.93 (1)2.92 (1)3.796 (2)158 (1)
Symmetry codes: (i) x−1/2, −y+1/2, z−1/2; (ii) −x+1/2, y+1/2, −z+1/2; (iii) −x+1, −y+1, −z.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1···O1i0.81 (2)2.16 (2)2.951 (2)163 (2)
C8—H8B···O2ii0.962.563.397 (3)147
C10—H10C···O2ii0.962.433.341 (3)158
C4—H4···Cl10.982.653.190 (2)115
C17—H17···Cl2iii0.93 (1)2.92 (1)3.796 (2)158 (1)
Symmetry codes: (i) x−1/2, −y+1/2, z−1/2; (ii) −x+1/2, y+1/2, −z+1/2; (iii) −x+1, −y+1, −z.
Acknowledgements top

JK thanks the UGC for the RFSMS fellowship. SN thanks the CSIR for funding provided under the Emeritus Scientist Scheme. VV is grateful to the DST–India for funding through the Young Scientist Scheme (Fast Track Proposal).

references
References top

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