organic compounds
2-Amino-7,7-dimethyl-5-oxo-4-[3-(trifluoromethyl)phenyl]-1,4,5,6,7,8-hexahydroquinoline-3-carbonitrile
aX-ray Crystallography Laboratory, Post-Graduate Department of Physics & Electronics, University of Jammu, Jammu Tawi 180 006, India, and bDepartment of Chemistry, Shivaji University, Kolhapur 416 004 (MS), India
*Correspondence e-mail: rkvk.paper11@gmail.com
In the title molecule, C19H18F3N3O, the dihydropyridine and cyclohexene rings both adopt sofa conformations. The five essentially planar atoms of the dihydropyridine ring [maximum deviation = 0.039 (2) Å] form a dihedral angle of 88.19 (8)° with the benzene ring. The F atoms of the trifluoromethyl group were refined as disordered over two sets of sites in a 0.840 (3):0.160 (3) ratio. In the crystal, N—H⋯O and N—H⋯N hydrogen bonds link molecules into a two-dimensional network parallel to (100).
Related literature
For applications of dihydropyridines, see: Mayler et al. (1989); Triggle et al.(1989); Leon et al. (2008). For related structures, see: Jiang et al. (2006); Tu et al. (2005). For ring conformations, see: Duax & Norton (1975).
Experimental
Crystal data
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Refinement
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Data collection: CrysAlis PRO (Oxford Diffraction, 2010); cell CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 2012) and PLATON (Spek, 2009); software used to prepare material for publication: PLATON.
Supporting information
https://doi.org/10.1107/S1600536812050684/lh5570sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536812050684/lh5570Isup2.hkl
Supporting information file. DOI: https://doi.org/10.1107/S1600536812050684/lh5570Isup3.cml
In a 50 ml round bottom flask 5,5-dimethylcyclohexane- 1,3-dione (1 mmol) and ammonium acetate (3.5 mmol) were taken in water (10 ml). The reaction mixture was stirred at 373K for 40 min. Then malononitrile (1 mmol), 3-trifluoro methyl benzaldehyde (1 mmol) were charged, and the mixture was heated at 373K for 30 min. After the completion of reaction (monitored by TLC), the reaction mixture was stirred at RT for 15 min. The separated solid was then filtered off and recrystallized from ethanol to afford pure product as crystals suitable for X-ray diffraction. M.P.: 558–560 K, Yield: 83%.
IR(KBr): 3392, 3335, 3225, 2922, 2180, 1657, 1605, 1478 cm-1. 1H NMR (300 MHz, DMSO-d6): δ 0.87(s, 3H, CH3), 1.00(s, 3H, CH3), 2.15–2.34(dd, 2H, J= 18 Hz, CH2), 2.42–2.49(dd, 2H, J= 17.4 Hz, CH2), 4.42 (s, 1H, CH), 5.89(s, 2H, NH2), 7.38–7.55(m, 4H, Ar—H), 9.09(br s, 1H, NH).
All H atoms were positioned geometrically and were treated as riding on their parent C atoms, with C—H distances of 0.93–0.98 Å, N—H distances of 0.86 and with Uiso(H) = 1.2Ueq(C/N) or 1.5Ueq(methyl C).
The nucleus containing 1,4- dihydropyridine (DHP) nucleus act as a versatile intermediate for the synthesis of several pharmaceuticals together with those of cardiovascular drugs and as a calcium channel modulators, laser dyes and photo initiators (Leon et al., 2008). The design and synthesis of 1,4-dihydropyridines has attracted much attention over the past 30 years due to the calcium antagonist effect they display (Mayler, 1989). The establishment of the pharmacological action as drugs for the treatment of cardiovascular diseases such as angina, hypertension or arrhythmia was mainly based on the structural studies carried out by X-ray diffraction on differently substituted 1,4-dihydropyridines (Triggle et al., 1989). In this paper, we report the
of the title compound, (I).In (I) (Fig.1), all bond lengths and angles are normal and correspond to those observed in related structures (Jiang et al.,2006; Tu et al., 2005). The (N1/C2/C3/C4/C4A/C8A) and (C4A/C5—C8/C8A) rings adopt sofa conformations (ΔCs(C4) = 3.35 & ΔCs (C7) = 6.70) (Duax & Norton, 1975) with atoms C4 and C7 forming the flaps in each ring. The five essentially planar atoms (N1/C2/C3/C4A/C8A) of the dihydropyridine ring (maximum deviation 0.039 (2)Å for C8) form a dihedral angle of 88.19 (8)° with the benzene ring. The F atoms of the trifluoromethyl group are disordered over two sets of sites in a 0.840 (3):0.160 (3) ratio. In the crystal, N—H···O and N—H···N hydrogen bonds (Table 1) link molecules into a two-dimensional network parallel to (100) (Fig. 2).
For applications of dihydropyridines, see: Mayler et al. (1989); Triggle et al.(1989); Leon et al. (2008). For related structures, see: Jiang et al. (2006); Tu et al. (2005). For ring conformations, see: Duax & Norton (1975).
Data collection: CrysAlis PRO (Oxford Diffraction, 2010); cell
CrysAlis PRO (Oxford Diffraction, 2010); data reduction: CrysAlis PRO (Oxford Diffraction, 2010); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 2012) and PLATON (Spek, 2009); software used to prepare material for publication: PLATON (Spek, 2009).C19H18F3N3O | F(000) = 1504 |
Mr = 361.36 | Dx = 1.356 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -C 2yc | Cell parameters from 14640 reflections |
a = 24.2434 (6) Å | θ = 3.4–29.1° |
b = 9.6030 (2) Å | µ = 0.11 mm−1 |
c = 15.2426 (4) Å | T = 293 K |
β = 93.960 (2)° | Block, white |
V = 3540.15 (15) Å3 | 0.3 × 0.2 × 0.2 mm |
Z = 8 |
Oxford Diffraction Xcalibur Sapphire3 diffractometer | 3469 independent reflections |
Radiation source: fine-focus sealed tube | 2462 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.059 |
Detector resolution: 16.1049 pixels mm-1 | θmax = 26.0°, θmin = 3.4° |
ω scans | h = −29→29 |
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010) | k = −11→11 |
Tmin = 0.896, Tmax = 1.000 | l = −18→18 |
42194 measured reflections |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.057 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.143 | H-atom parameters constrained |
S = 1.03 | w = 1/[σ2(Fo2) + (0.0559P)2 + 3.608P] where P = (Fo2 + 2Fc2)/3 |
3469 reflections | (Δ/σ)max = 0.021 |
247 parameters | Δρmax = 0.31 e Å−3 |
6 restraints | Δρmin = −0.39 e Å−3 |
C19H18F3N3O | V = 3540.15 (15) Å3 |
Mr = 361.36 | Z = 8 |
Monoclinic, C2/c | Mo Kα radiation |
a = 24.2434 (6) Å | µ = 0.11 mm−1 |
b = 9.6030 (2) Å | T = 293 K |
c = 15.2426 (4) Å | 0.3 × 0.2 × 0.2 mm |
β = 93.960 (2)° |
Oxford Diffraction Xcalibur Sapphire3 diffractometer | 3469 independent reflections |
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010) | 2462 reflections with I > 2σ(I) |
Tmin = 0.896, Tmax = 1.000 | Rint = 0.059 |
42194 measured reflections |
R[F2 > 2σ(F2)] = 0.057 | 6 restraints |
wR(F2) = 0.143 | H-atom parameters constrained |
S = 1.03 | Δρmax = 0.31 e Å−3 |
3469 reflections | Δρmin = −0.39 e Å−3 |
247 parameters |
Experimental. CrysAlis PRO, Oxford Diffraction Ltd., Version 1.171.34.40 (release 27–08-2010 CrysAlis171. NET) (compiled Aug 27 2010,11:50:40) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm. |
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. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
N1 | 0.08447 (8) | 0.55967 (18) | 1.03562 (11) | 0.0401 (5) | |
H1 | 0.0954 | 0.5379 | 1.0887 | 0.048* | |
O1 | 0.07532 (8) | 0.42797 (18) | 0.73842 (10) | 0.0563 (5) | |
C2 | 0.06002 (9) | 0.6875 (2) | 1.01957 (13) | 0.0362 (5) | |
C3 | 0.04788 (9) | 0.7283 (2) | 0.93483 (13) | 0.0354 (5) | |
C4 | 0.06809 (9) | 0.6491 (2) | 0.85675 (13) | 0.0363 (5) | |
H4 | 0.0374 | 0.6442 | 0.8115 | 0.044* | |
C4A | 0.08252 (9) | 0.5025 (2) | 0.88458 (13) | 0.0350 (5) | |
C5 | 0.08524 (9) | 0.3977 (2) | 0.81668 (14) | 0.0398 (5) | |
C6 | 0.09892 (10) | 0.2509 (2) | 0.84435 (15) | 0.0456 (6) | |
H6A | 0.1167 | 0.2045 | 0.7972 | 0.055* | |
H6B | 0.0648 | 0.2016 | 0.8531 | 0.055* | |
C7 | 0.13683 (10) | 0.2413 (2) | 0.92868 (15) | 0.0423 (5) | |
C8 | 0.10963 (10) | 0.3241 (2) | 0.99962 (14) | 0.0432 (6) | |
H8A | 0.0776 | 0.2732 | 1.0172 | 0.052* | |
H8B | 0.1355 | 0.3325 | 1.0508 | 0.052* | |
C8A | 0.09185 (9) | 0.4663 (2) | 0.96972 (13) | 0.0356 (5) | |
C9 | 0.11521 (10) | 0.7283 (2) | 0.81799 (13) | 0.0396 (5) | |
C10 | 0.16917 (10) | 0.7220 (2) | 0.85492 (14) | 0.0430 (6) | |
H10 | 0.1778 | 0.6633 | 0.9024 | 0.052* | |
C11 | 0.21021 (11) | 0.8024 (3) | 0.82171 (16) | 0.0512 (6) | |
C12 | 0.19821 (14) | 0.8905 (3) | 0.75167 (18) | 0.0651 (8) | |
H12 | 0.2259 | 0.9441 | 0.7293 | 0.078* | |
C13 | 0.14494 (15) | 0.8983 (3) | 0.71519 (18) | 0.0704 (9) | |
H13 | 0.1364 | 0.9585 | 0.6684 | 0.084* | |
C14 | 0.10400 (12) | 0.8170 (3) | 0.74772 (15) | 0.0547 (7) | |
H14 | 0.0682 | 0.8221 | 0.7218 | 0.066* | |
C15 | 0.26709 (13) | 0.7982 (4) | 0.8633 (2) | 0.0745 (9) | |
N16 | 0.04957 (9) | 0.7592 (2) | 1.09228 (12) | 0.0525 (6) | |
H16A | 0.0337 | 0.8392 | 1.0877 | 0.063* | |
H16B | 0.0587 | 0.7251 | 1.1434 | 0.063* | |
C17 | 0.19316 (10) | 0.3023 (3) | 0.91246 (19) | 0.0609 (7) | |
H17A | 0.1884 | 0.3923 | 0.8855 | 0.091* | |
H17B | 0.2119 | 0.2418 | 0.8742 | 0.091* | |
H17C | 0.2147 | 0.3114 | 0.9674 | 0.091* | |
C18 | 0.14324 (13) | 0.0896 (3) | 0.95821 (18) | 0.0643 (8) | |
H18A | 0.1685 | 0.0845 | 1.0095 | 0.096* | |
H18B | 0.1573 | 0.0354 | 0.9118 | 0.096* | |
H18C | 0.1079 | 0.0535 | 0.9719 | 0.096* | |
C19 | 0.01978 (9) | 0.8543 (2) | 0.91716 (13) | 0.0392 (5) | |
N20 | −0.00412 (10) | 0.9548 (2) | 0.89909 (13) | 0.0585 (6) | |
F1 | 0.27627 (11) | 0.8904 (3) | 0.92719 (19) | 0.1116 (10) | 0.840 (3) |
F2 | 0.30660 (11) | 0.8169 (6) | 0.81017 (19) | 0.168 (2) | 0.840 (3) |
F3 | 0.28039 (9) | 0.6777 (3) | 0.9066 (2) | 0.1130 (11) | 0.840 (3) |
F1A | 0.2709 (7) | 0.782 (2) | 0.9463 (6) | 0.1116 (10) | 0.160 (3) |
F2A | 0.2907 (6) | 0.9202 (14) | 0.8416 (11) | 0.168 (2) | 0.160 (3) |
F3A | 0.2932 (6) | 0.7083 (15) | 0.8168 (11) | 0.1130 (11) | 0.160 (3) |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.0578 (12) | 0.0371 (10) | 0.0246 (9) | 0.0141 (9) | −0.0029 (8) | −0.0001 (7) |
O1 | 0.0772 (13) | 0.0577 (11) | 0.0325 (9) | 0.0107 (9) | −0.0065 (8) | −0.0096 (7) |
C2 | 0.0402 (12) | 0.0354 (11) | 0.0329 (11) | 0.0057 (9) | 0.0018 (9) | −0.0005 (9) |
C3 | 0.0388 (12) | 0.0346 (11) | 0.0324 (11) | 0.0072 (9) | −0.0001 (9) | −0.0006 (9) |
C4 | 0.0385 (12) | 0.0411 (12) | 0.0284 (10) | 0.0079 (10) | −0.0046 (9) | −0.0034 (9) |
C4A | 0.0347 (12) | 0.0378 (12) | 0.0321 (11) | 0.0046 (9) | −0.0020 (9) | −0.0037 (9) |
C5 | 0.0368 (12) | 0.0460 (13) | 0.0362 (12) | 0.0014 (10) | −0.0010 (9) | −0.0059 (10) |
C6 | 0.0522 (14) | 0.0408 (13) | 0.0438 (13) | 0.0045 (11) | 0.0032 (11) | −0.0109 (10) |
C7 | 0.0482 (14) | 0.0377 (12) | 0.0412 (12) | 0.0090 (10) | 0.0053 (10) | −0.0007 (10) |
C8 | 0.0546 (14) | 0.0372 (12) | 0.0379 (12) | 0.0058 (11) | 0.0049 (10) | 0.0017 (10) |
C8A | 0.0365 (12) | 0.0364 (11) | 0.0336 (11) | 0.0024 (9) | 0.0008 (9) | −0.0038 (9) |
C9 | 0.0510 (14) | 0.0403 (12) | 0.0276 (10) | 0.0084 (10) | 0.0041 (10) | −0.0023 (9) |
C10 | 0.0489 (14) | 0.0468 (13) | 0.0337 (11) | 0.0060 (11) | 0.0049 (10) | −0.0001 (10) |
C11 | 0.0534 (16) | 0.0567 (15) | 0.0450 (14) | 0.0006 (12) | 0.0157 (12) | −0.0084 (12) |
C12 | 0.078 (2) | 0.0660 (18) | 0.0545 (16) | −0.0052 (16) | 0.0301 (15) | 0.0029 (14) |
C13 | 0.096 (2) | 0.072 (2) | 0.0451 (16) | 0.0086 (18) | 0.0183 (16) | 0.0219 (14) |
C14 | 0.0634 (17) | 0.0645 (17) | 0.0356 (13) | 0.0102 (14) | −0.0001 (12) | 0.0101 (12) |
C15 | 0.0557 (19) | 0.104 (3) | 0.0661 (19) | −0.0103 (18) | 0.0188 (15) | −0.0020 (19) |
N16 | 0.0822 (16) | 0.0441 (11) | 0.0312 (10) | 0.0217 (11) | 0.0048 (10) | 0.0007 (9) |
C17 | 0.0431 (15) | 0.0735 (18) | 0.0662 (17) | 0.0134 (13) | 0.0044 (12) | 0.0091 (15) |
C18 | 0.093 (2) | 0.0416 (14) | 0.0585 (16) | 0.0215 (14) | 0.0101 (15) | −0.0004 (12) |
C19 | 0.0438 (13) | 0.0441 (13) | 0.0289 (11) | 0.0057 (11) | −0.0034 (9) | −0.0044 (9) |
N20 | 0.0766 (16) | 0.0503 (12) | 0.0466 (12) | 0.0247 (12) | −0.0106 (11) | −0.0038 (10) |
F1 | 0.1020 (19) | 0.117 (2) | 0.111 (2) | −0.0025 (18) | −0.0302 (15) | −0.0414 (19) |
F2 | 0.0574 (17) | 0.364 (6) | 0.086 (2) | −0.026 (3) | 0.0359 (14) | 0.015 (3) |
F3 | 0.0607 (15) | 0.105 (2) | 0.169 (3) | 0.0148 (13) | −0.0228 (16) | 0.017 (2) |
F1A | 0.1020 (19) | 0.117 (2) | 0.111 (2) | −0.0025 (18) | −0.0302 (15) | −0.0414 (19) |
F2A | 0.0574 (17) | 0.364 (6) | 0.086 (2) | −0.026 (3) | 0.0359 (14) | 0.015 (3) |
F3A | 0.0607 (15) | 0.105 (2) | 0.169 (3) | 0.0148 (13) | −0.0228 (16) | 0.017 (2) |
N1—C8A | 1.367 (3) | C10—C11 | 1.382 (3) |
N1—C2 | 1.377 (3) | C10—H10 | 0.9300 |
N1—H1 | 0.8600 | C11—C12 | 1.377 (4) |
O1—C5 | 1.235 (3) | C11—C15 | 1.478 (4) |
C2—N16 | 1.344 (3) | C12—C13 | 1.372 (4) |
C2—C3 | 1.362 (3) | C12—H12 | 0.9300 |
C3—C19 | 1.406 (3) | C13—C14 | 1.381 (4) |
C3—C4 | 1.522 (3) | C13—H13 | 0.9300 |
C4—C4A | 1.504 (3) | C14—H14 | 0.9300 |
C4—C9 | 1.525 (3) | C15—F1A | 1.272 (9) |
C4—H4 | 0.9800 | C15—F3A | 1.308 (9) |
C4A—C8A | 1.348 (3) | C15—F2 | 1.309 (3) |
C4A—C5 | 1.449 (3) | C15—F1 | 1.323 (4) |
C5—C6 | 1.503 (3) | C15—F2A | 1.355 (10) |
C6—C7 | 1.530 (3) | C15—F3 | 1.360 (4) |
C6—H6A | 0.9700 | N16—H16A | 0.8600 |
C6—H6B | 0.9700 | N16—H16B | 0.8600 |
C7—C17 | 1.522 (3) | C17—H17A | 0.9600 |
C7—C8 | 1.528 (3) | C17—H17B | 0.9600 |
C7—C18 | 1.529 (3) | C17—H17C | 0.9600 |
C8—C8A | 1.494 (3) | C18—H18A | 0.9600 |
C8—H8A | 0.9700 | C18—H18B | 0.9600 |
C8—H8B | 0.9700 | C18—H18C | 0.9600 |
C9—C14 | 1.381 (3) | C19—N20 | 1.149 (3) |
C9—C10 | 1.389 (3) | ||
C8A—N1—C2 | 122.02 (17) | C11—C10—C9 | 120.6 (2) |
C8A—N1—H1 | 119.0 | C11—C10—H10 | 119.7 |
C2—N1—H1 | 119.0 | C9—C10—H10 | 119.7 |
N16—C2—C3 | 126.42 (19) | C12—C11—C10 | 120.5 (3) |
N16—C2—N1 | 114.42 (18) | C12—C11—C15 | 119.3 (3) |
C3—C2—N1 | 119.14 (18) | C10—C11—C15 | 120.1 (2) |
C2—C3—C19 | 119.98 (19) | C13—C12—C11 | 119.4 (3) |
C2—C3—C4 | 122.51 (18) | C13—C12—H12 | 120.3 |
C19—C3—C4 | 117.28 (18) | C11—C12—H12 | 120.3 |
C4A—C4—C3 | 109.16 (17) | C12—C13—C14 | 120.2 (3) |
C4A—C4—C9 | 114.22 (18) | C12—C13—H13 | 119.9 |
C3—C4—C9 | 110.12 (17) | C14—C13—H13 | 119.9 |
C4A—C4—H4 | 107.7 | C9—C14—C13 | 121.3 (3) |
C3—C4—H4 | 107.7 | C9—C14—H14 | 119.4 |
C9—C4—H4 | 107.7 | C13—C14—H14 | 119.4 |
C8A—C4A—C5 | 119.74 (19) | F1A—C15—F3A | 116.9 (12) |
C8A—C4A—C4 | 122.22 (18) | F1A—C15—F2 | 128.8 (8) |
C5—C4A—C4 | 118.03 (18) | F2—C15—F1 | 105.7 (4) |
O1—C5—C4A | 120.7 (2) | F1A—C15—F2A | 110.3 (11) |
O1—C5—C6 | 121.1 (2) | F3A—C15—F2A | 102.1 (10) |
C4A—C5—C6 | 118.14 (19) | F2—C15—F3 | 104.9 (4) |
C5—C6—C7 | 113.60 (18) | F1—C15—F3 | 101.0 (3) |
C5—C6—H6A | 108.8 | F1A—C15—C11 | 115.6 (8) |
C7—C6—H6A | 108.8 | F3A—C15—C11 | 104.8 (7) |
C5—C6—H6B | 108.8 | F2—C15—C11 | 115.6 (3) |
C7—C6—H6B | 108.8 | F1—C15—C11 | 113.7 (3) |
H6A—C6—H6B | 107.7 | F2A—C15—C11 | 105.7 (8) |
C17—C7—C8 | 110.5 (2) | F3—C15—C11 | 114.5 (3) |
C17—C7—C18 | 109.9 (2) | C2—N16—H16A | 120.0 |
C8—C7—C18 | 109.12 (19) | C2—N16—H16B | 120.0 |
C17—C7—C6 | 109.5 (2) | H16A—N16—H16B | 120.0 |
C8—C7—C6 | 107.43 (18) | C7—C17—H17A | 109.5 |
C18—C7—C6 | 110.3 (2) | C7—C17—H17B | 109.5 |
C8A—C8—C7 | 112.92 (18) | H17A—C17—H17B | 109.5 |
C8A—C8—H8A | 109.0 | C7—C17—H17C | 109.5 |
C7—C8—H8A | 109.0 | H17A—C17—H17C | 109.5 |
C8A—C8—H8B | 109.0 | H17B—C17—H17C | 109.5 |
C7—C8—H8B | 109.0 | C7—C18—H18A | 109.5 |
H8A—C8—H8B | 107.8 | C7—C18—H18B | 109.5 |
C4A—C8A—N1 | 121.11 (19) | H18A—C18—H18B | 109.5 |
C4A—C8A—C8 | 123.73 (19) | C7—C18—H18C | 109.5 |
N1—C8A—C8 | 115.15 (18) | H18A—C18—H18C | 109.5 |
C14—C9—C10 | 118.1 (2) | H18B—C18—H18C | 109.5 |
C14—C9—C4 | 119.7 (2) | N20—C19—C3 | 176.9 (2) |
C10—C9—C4 | 122.06 (19) | ||
C8A—N1—C2—N16 | 172.0 (2) | C2—N1—C8A—C4A | 9.3 (3) |
C8A—N1—C2—C3 | −6.8 (3) | C2—N1—C8A—C8 | −169.6 (2) |
N16—C2—C3—C19 | −2.7 (4) | C7—C8—C8A—C4A | 21.7 (3) |
N1—C2—C3—C19 | 176.0 (2) | C7—C8—C8A—N1 | −159.39 (19) |
N16—C2—C3—C4 | 171.7 (2) | C4A—C4—C9—C14 | 141.8 (2) |
N1—C2—C3—C4 | −9.7 (3) | C3—C4—C9—C14 | −95.0 (2) |
C2—C3—C4—C4A | 21.0 (3) | C4A—C4—C9—C10 | −42.8 (3) |
C19—C3—C4—C4A | −164.59 (19) | C3—C4—C9—C10 | 80.4 (2) |
C2—C3—C4—C9 | −105.2 (2) | C14—C9—C10—C11 | −0.2 (3) |
C19—C3—C4—C9 | 69.3 (2) | C4—C9—C10—C11 | −175.6 (2) |
C3—C4—C4A—C8A | −18.5 (3) | C9—C10—C11—C12 | 0.3 (4) |
C9—C4—C4A—C8A | 105.2 (2) | C9—C10—C11—C15 | 178.0 (2) |
C3—C4—C4A—C5 | 160.28 (18) | C10—C11—C12—C13 | 0.2 (4) |
C9—C4—C4A—C5 | −76.0 (2) | C15—C11—C12—C13 | −177.5 (3) |
C8A—C4A—C5—O1 | 178.0 (2) | C11—C12—C13—C14 | −0.9 (4) |
C4—C4A—C5—O1 | −0.9 (3) | C10—C9—C14—C13 | −0.5 (4) |
C8A—C4A—C5—C6 | −0.4 (3) | C4—C9—C14—C13 | 175.1 (2) |
C4—C4A—C5—C6 | −179.2 (2) | C12—C13—C14—C9 | 1.1 (4) |
O1—C5—C6—C7 | 150.7 (2) | C12—C11—C15—F1A | 143.6 (11) |
C4A—C5—C6—C7 | −31.0 (3) | C10—C11—C15—F1A | −34.2 (11) |
C5—C6—C7—C17 | −65.5 (3) | C12—C11—C15—F3A | −86.1 (9) |
C5—C6—C7—C8 | 54.5 (3) | C10—C11—C15—F3A | 96.1 (9) |
C5—C6—C7—C18 | 173.4 (2) | C12—C11—C15—F2 | −34.1 (5) |
C17—C7—C8—C8A | 70.0 (3) | C10—C11—C15—F2 | 148.1 (4) |
C18—C7—C8—C8A | −169.0 (2) | C12—C11—C15—F1 | 88.4 (4) |
C6—C7—C8—C8A | −49.4 (3) | C10—C11—C15—F1 | −89.3 (4) |
C5—C4A—C8A—N1 | −173.7 (2) | C12—C11—C15—F2A | 21.3 (8) |
C4—C4A—C8A—N1 | 5.1 (3) | C10—C11—C15—F2A | −156.5 (8) |
C5—C4A—C8A—C8 | 5.1 (3) | C12—C11—C15—F3 | −156.2 (3) |
C4—C4A—C8A—C8 | −176.1 (2) | C10—C11—C15—F3 | 26.0 (4) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O1i | 0.86 | 2.39 | 3.117 (2) | 143 |
N16—H16A···N20ii | 0.86 | 2.12 | 2.966 (3) | 168 |
N16—H16B···O1i | 0.86 | 2.08 | 2.897 (2) | 158 |
Symmetry codes: (i) x, −y+1, z+1/2; (ii) −x, −y+2, −z+2. |
Experimental details
Crystal data | |
Chemical formula | C19H18F3N3O |
Mr | 361.36 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 293 |
a, b, c (Å) | 24.2434 (6), 9.6030 (2), 15.2426 (4) |
β (°) | 93.960 (2) |
V (Å3) | 3540.15 (15) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 0.11 |
Crystal size (mm) | 0.3 × 0.2 × 0.2 |
Data collection | |
Diffractometer | Oxford Diffraction Xcalibur Sapphire3 |
Absorption correction | Multi-scan (CrysAlis PRO; Oxford Diffraction, 2010) |
Tmin, Tmax | 0.896, 1.000 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 42194, 3469, 2462 |
Rint | 0.059 |
(sin θ/λ)max (Å−1) | 0.617 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.057, 0.143, 1.03 |
No. of reflections | 3469 |
No. of parameters | 247 |
No. of restraints | 6 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.31, −0.39 |
Computer programs: CrysAlis PRO (Oxford Diffraction, 2010), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 2012) and PLATON (Spek, 2009), PLATON (Spek, 2009).
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O1i | 0.86 | 2.39 | 3.117 (2) | 143 |
N16—H16A···N20ii | 0.86 | 2.12 | 2.966 (3) | 168 |
N16—H16B···O1i | 0.86 | 2.08 | 2.897 (2) | 158 |
Symmetry codes: (i) x, −y+1, z+1/2; (ii) −x, −y+2, −z+2. |
Acknowledgements
RK acknowledges the Department of Science & Technology for access to the single-crystal X-ray diffractometer sanctioned as a National Facility under project No. SR/S2/CMP-47/2003.
References
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The nucleus containing 1,4- dihydropyridine (DHP) nucleus act as a versatile intermediate for the synthesis of several pharmaceuticals together with those of cardiovascular drugs and as a calcium channel modulators, laser dyes and photo initiators (Leon et al., 2008). The design and synthesis of 1,4-dihydropyridines has attracted much attention over the past 30 years due to the calcium antagonist effect they display (Mayler, 1989). The establishment of the pharmacological action as drugs for the treatment of cardiovascular diseases such as angina, hypertension or arrhythmia was mainly based on the structural studies carried out by X-ray diffraction on differently substituted 1,4-dihydropyridines (Triggle et al., 1989). In this paper, we report the crystal structure of the title compound, (I).
In (I) (Fig.1), all bond lengths and angles are normal and correspond to those observed in related structures (Jiang et al.,2006; Tu et al., 2005). The (N1/C2/C3/C4/C4A/C8A) and (C4A/C5—C8/C8A) rings adopt sofa conformations (ΔCs(C4) = 3.35 & ΔCs (C7) = 6.70) (Duax & Norton, 1975) with atoms C4 and C7 forming the flaps in each ring. The five essentially planar atoms (N1/C2/C3/C4A/C8A) of the dihydropyridine ring (maximum deviation 0.039 (2)Å for C8) form a dihedral angle of 88.19 (8)° with the benzene ring. The F atoms of the trifluoromethyl group are disordered over two sets of sites in a 0.840 (3):0.160 (3) ratio. In the crystal, N—H···O and N—H···N hydrogen bonds (Table 1) link molecules into a two-dimensional network parallel to (100) (Fig. 2).