supplementary materials


HTML versionpdf versioncif file3d viewstructure factorssupplementary materialsCIF check reportsimilar papers buy article online

hk2320 scheme

Acta Cryst. (2007). E63, o3935    [ doi:10.1107/S1600536807042110 ]

5-(4-Fluorophenyl)-2,6-dioxo-2,3,6,7,8,9-hexahydro-1H,5H-imidazo[1,2-a]quinoline-4-carbonitrile

Q. Zhuang, C. Li, Q. Shao and B. Jiang

Abstract top

In the molecule of the title compound, C18H14FN3O2, the imidazole and dihydropyridine rings are nearly coplanar with a dihedral angle of 2.46 (3)°, while the cyclohexene ring has an envelope conformation. The benzene ring is oriented with respect to the coplanar ring system at a dihedral angle of 81.45 (2)°. In the crystal structure, intermolecular N-H...N hydrogen bonds link the molecules into dimers.

Comment top

1,4-Dihydropyridines (1,4-DHPs) are well known compounds because of their pharmacological profiles as calcium channel modulators (Stout & Meyers, 1982). With a 1,4-DHPs parent nucleus, imidazo[1,2-a]quinoline belongs to a class of compounds which are special not only because of their interesting chemical and physical properties, but also due to their immense utility in the pharmaceutical industries. The discovery of imidazo[1,2-a]quinoline including imidazo[1,2-a]- pyridine moiety, as new potential pharmacological molecules, may be of great significance. It is well established that the chemical modifications on the imidazo[1,2-a]pyridine skeletons may bring remarkable changes of biological activity (Gueiffier et al., 1996; Elhakmaoui et al., 1994). We report herein the crystal structure of the title compound, (I).

In the molecule of the title compound, (I), (Fig. 1) the bond lengths and angles are generally within normal ranges (Allen et al., 1987).

Ring A (C1—C6) is not planar, having total puckering amplitude, QT, of 0.488 (3) Å, [φ = −64.74 (3)°, θ = 117.65 (3)°] (Cremer & Pople, 1975), and adopts an envelope conformation with atom C3 displaced by −0.663 (3) Å from the plane of the other ring atoms. Rings B (N1/C1/C6—C9), C (N1/N2/C9—C11) and D (C13—C18) are, of course, planar and rings B and D are also nearly coplanar with a dihedral angle of 2.46 (3)°. Ring D is oriented with respect to the coplanar ring system at a dihedral angle of 81.45 (2)°.

In the crystal structure, the intermolecular N—H···N hydrogen bonds (Table 1) link the molecules into dimers (Fig. 2), in which they seem to be effective in the stabilization of the structure.

Related literature top

For related literature, see: Stout & Meyers (1982); Gueiffier et al. (1996); Elhakmaoui et al. (1994). For general background, see: Cremer & Pople (1975). For bond-length data, see: Allen et al. (1987).

Experimental top

The title compound, (I), was prepared by the reaction of 4-fluorobenzaldehyde (124 mg, 1 mmol), 2-(3-oxocyclohex-1-enylamino)acetic acid (169 mg, 1 mmol) with malononitrile (66 mg, 1 mmol) in solvent of ethylene glycol (2.0 ml) at 393 K under microwave irradiation (maximum power 200 W, initial power 100 W) for 5 min. Single crystals suitable for X-ray analysis were obtained from an ethanol solution (95%) by slow evaporation (yield; 284 mg, 88%, m.p. 559–560 K).

Refinement top

H atoms were positioned geometrically with N—H = 0.86 Å (for NH) and C—H = 0.93, 0.98 and 0.97 Å for aromatic, methine and methylene H atoms, respectively, and constrained to ride on their parent atoms, with Uiso(H) = 1.2Ueq(C,N).

Computing details top

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT (Bruker, 1999); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1999); software used to prepare material for publication: SHELXTL (Bruker, 1999).

Figures top
[Figure 1] Fig. 1. The molecular structure of the title molecule, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.
[Figure 2] Fig. 2. A packing diagram for (I). Hydrogen bonds are shown as dashed lines.
5-(4-Fluorophenyl)-2,6-dioxo-2,3,6,7,8,9-hexahydro-1H,5H- imidazo[1,2-a]quinoline-4-carbonitrile top
Crystal data top
C18H14FN3O2F000 = 672
Mr = 323.32Dx = 1.412 Mg m−3
Monoclinic, P21/cMelting point: 559-560 K
Hall symbol: -P 2ybcMo Kα radiation
λ = 0.71073 Å
a = 10.781 (3) ÅCell parameters from 1113 reflections
b = 14.937 (4) Åθ = 2.4–21.3º
c = 9.839 (3) ŵ = 0.10 mm−1
β = 106.270 (5)ºT = 298 (2) K
V = 1521.0 (7) Å3Block, colourless
Z = 40.36 × 0.33 × 0.19 mm
Data collection top
Bruker CCD area-detector
diffractometer		2678 independent reflections
Radiation source: fine-focus sealed tube1368 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.058
T = 298(2) Kθmax = 25.0º
φ and ω scansθmin = 2.0º
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −12→12
Tmin = 0.964, Tmax = 0.981k = −17→17
7885 measured reflectionsl = −11→11
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.047H-atom parameters constrained
wR(F2) = 0.112  w = 1/[σ2(Fo2) + (0.0328P)2 + 0.3811P]
where P = (Fo2 + 2Fc2)/3
S = 1.01(Δ/σ)max < 0.001
2678 reflectionsΔρmax = 0.17 e Å−3
217 parametersΔρmin = −0.17 e Å−3
Primary atom site location: structure-invariant direct methodsExtinction correction: none
Crystal data top
C18H14FN3O2V = 1521.0 (7) Å3
Mr = 323.32Z = 4
Monoclinic, P21/cMo Kα
a = 10.781 (3) ŵ = 0.10 mm−1
b = 14.937 (4) ÅT = 298 (2) K
c = 9.839 (3) Å0.36 × 0.33 × 0.19 mm
β = 106.270 (5)º
Data collection top
Bruker CCD area-detector
diffractometer		2678 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		1368 reflections with I > 2σ(I)
Tmin = 0.964, Tmax = 0.981Rint = 0.058
7885 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.047217 parameters
wR(F2) = 0.112H-atom parameters constrained
S = 1.01Δρmax = 0.17 e Å−3
2678 reflectionsΔρmin = −0.17 e Å−3
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 > 2sigma(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
F10.9987 (2)−0.14960 (16)0.7379 (2)0.1056 (8)
N10.6362 (2)0.12725 (14)0.1016 (2)0.0360 (6)
N20.7956 (2)0.13795 (15)0.0009 (2)0.0395 (6)
H20.86210.1239−0.02660.047*
N30.9607 (3)−0.08486 (18)0.0697 (3)0.0617 (8)
O10.48004 (19)−0.12894 (13)0.2715 (2)0.0531 (6)
O20.7643 (2)0.28153 (14)−0.0880 (2)0.0619 (6)
C10.5553 (2)0.08620 (19)0.1683 (3)0.0339 (7)
C20.4489 (3)0.14201 (18)0.1931 (3)0.0414 (8)
H2A0.37640.14260.10840.050*
H2B0.47870.20310.21370.050*
C30.4061 (3)0.10459 (19)0.3161 (3)0.0489 (8)
H3A0.47490.11210.40330.059*
H3B0.33120.13740.32510.059*
C40.3728 (3)0.00648 (19)0.2935 (3)0.0464 (8)
H4A0.3567−0.01760.37850.056*
H4B0.29400.00040.21690.056*
C50.4778 (3)−0.0473 (2)0.2589 (3)0.0385 (7)
C60.5737 (3)−0.00083 (18)0.2071 (3)0.0328 (7)
C70.6892 (3)−0.05532 (17)0.1965 (3)0.0334 (7)
H70.6569−0.11040.14450.040*
C80.7650 (3)−0.00414 (18)0.1131 (3)0.0346 (7)
C90.7373 (3)0.08079 (18)0.0738 (3)0.0341 (7)
C100.7359 (3)0.2201 (2)−0.0233 (3)0.0419 (8)
C110.6280 (3)0.21783 (17)0.0460 (3)0.0425 (8)
H11A0.64140.26180.12130.051*
H11B0.54500.2286−0.02230.051*
C120.8730 (3)−0.04756 (19)0.0866 (3)0.0418 (8)
C130.7743 (3)−0.08156 (19)0.3424 (3)0.0355 (7)
C140.8134 (3)−0.0171 (2)0.4468 (3)0.0450 (8)
H140.78810.04210.42680.054*
C150.8894 (3)−0.0398 (3)0.5800 (3)0.0555 (9)
H150.91540.00350.65030.067*
C160.9252 (3)−0.1262 (3)0.6059 (4)0.0638 (10)
C170.8917 (3)−0.1908 (3)0.5061 (4)0.0716 (11)
H170.9197−0.24940.52650.086*
C180.8151 (3)−0.1678 (2)0.3734 (4)0.0554 (9)
H180.7907−0.21170.30390.066*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
F10.0817 (15)0.149 (2)0.0675 (14)0.0011 (15)−0.0098 (12)0.0457 (15)
N10.0427 (15)0.0250 (13)0.0445 (14)0.0032 (12)0.0189 (12)0.0039 (11)
N20.0443 (15)0.0360 (15)0.0431 (15)0.0017 (12)0.0200 (12)0.0053 (12)
N30.066 (2)0.0445 (17)0.089 (2)0.0114 (15)0.0466 (17)0.0115 (16)
O10.0565 (14)0.0360 (13)0.0746 (16)−0.0037 (11)0.0311 (12)0.0067 (12)
O20.0741 (16)0.0412 (14)0.0792 (16)−0.0040 (12)0.0361 (13)0.0171 (12)
C10.0312 (16)0.0373 (19)0.0341 (17)−0.0034 (14)0.0104 (14)−0.0040 (14)
C20.0454 (19)0.0345 (18)0.0479 (18)0.0059 (15)0.0191 (15)0.0012 (15)
C30.056 (2)0.045 (2)0.055 (2)0.0035 (16)0.0294 (17)−0.0027 (16)
C40.0434 (19)0.048 (2)0.053 (2)0.0015 (16)0.0234 (16)0.0006 (16)
C50.0411 (19)0.0371 (19)0.0381 (17)−0.0010 (16)0.0126 (14)0.0020 (15)
C60.0383 (17)0.0283 (17)0.0341 (16)−0.0029 (14)0.0143 (13)−0.0023 (14)
C70.0407 (17)0.0215 (15)0.0401 (17)−0.0001 (13)0.0148 (14)0.0011 (13)
C80.0379 (17)0.0302 (18)0.0401 (17)0.0022 (14)0.0181 (14)0.0029 (14)
C90.0386 (17)0.0331 (18)0.0338 (16)−0.0011 (14)0.0153 (14)0.0002 (14)
C100.049 (2)0.0305 (18)0.0471 (19)−0.0030 (16)0.0150 (16)0.0051 (15)
C110.056 (2)0.0264 (17)0.0498 (18)0.0045 (15)0.0221 (16)0.0050 (14)
C120.051 (2)0.0280 (17)0.0518 (19)−0.0019 (16)0.0232 (16)0.0047 (15)
C130.0349 (17)0.0298 (17)0.0450 (18)0.0016 (14)0.0165 (14)0.0066 (15)
C140.0413 (19)0.046 (2)0.047 (2)0.0040 (15)0.0130 (16)0.0029 (16)
C150.045 (2)0.077 (3)0.046 (2)−0.0005 (19)0.0137 (17)−0.0024 (19)
C160.045 (2)0.089 (3)0.052 (2)−0.002 (2)0.0055 (18)0.024 (2)
C170.069 (3)0.053 (3)0.082 (3)0.011 (2)0.004 (2)0.031 (2)
C180.060 (2)0.034 (2)0.067 (2)0.0042 (17)0.0087 (19)0.0070 (17)
Geometric parameters (Å, °) top
F1—C161.363 (4)C5—C61.451 (4)
N1—C11.374 (3)C6—C71.516 (3)
N1—C91.383 (3)C7—C81.517 (3)
N1—C111.453 (3)C7—C131.522 (4)
N2—C91.375 (3)C7—H70.9800
N2—C101.375 (3)C8—C91.335 (3)
N2—H20.8600C8—C121.420 (4)
N3—C121.149 (3)C10—C111.504 (4)
O1—C51.225 (3)C11—H11A0.9700
O2—C101.204 (3)C11—H11B0.9700
C1—C61.354 (4)C13—C181.368 (4)
C1—C21.492 (3)C13—C141.384 (4)
C2—C31.518 (4)C14—C151.379 (4)
C2—H2A0.9700C14—H140.9300
C2—H2B0.9700C15—C161.351 (5)
C3—C41.510 (4)C15—H150.9300
C3—H3A0.9700C16—C171.352 (5)
C3—H3B0.9700C17—C181.378 (4)
C4—C51.502 (4)C17—H170.9300
C4—H4A0.9700C18—H180.9300
C4—H4B0.9700
C1—N1—C9120.8 (2)C8—C7—H7107.9
C1—N1—C11128.0 (2)C13—C7—H7107.9
C9—N1—C11111.2 (2)C9—C8—C12120.6 (3)
C9—N2—C10112.6 (2)C9—C8—C7121.7 (2)
C9—N2—H2123.7C12—C8—C7117.6 (2)
C10—N2—H2123.7C8—C9—N2130.1 (3)
C6—C1—N1120.1 (2)C8—C9—N1122.9 (2)
C6—C1—C2123.3 (2)N2—C9—N1107.0 (2)
N1—C1—C2116.7 (2)O2—C10—N2126.5 (3)
C1—C2—C3110.1 (2)O2—C10—C11126.9 (3)
C1—C2—H2A109.6N2—C10—C11106.6 (2)
C3—C2—H2A109.6N1—C11—C10102.6 (2)
C1—C2—H2B109.6N1—C11—H11A111.2
C3—C2—H2B109.6C10—C11—H11A111.2
H2A—C2—H2B108.1N1—C11—H11B111.2
C4—C3—C2110.6 (2)C10—C11—H11B111.2
C4—C3—H3A109.5H11A—C11—H11B109.2
C2—C3—H3A109.5N3—C12—C8177.3 (3)
C4—C3—H3B109.5C18—C13—C14118.5 (3)
C2—C3—H3B109.5C18—C13—C7121.6 (3)
H3A—C3—H3B108.1C14—C13—C7119.9 (2)
C5—C4—C3112.9 (2)C15—C14—C13120.8 (3)
C5—C4—H4A109.0C15—C14—H14119.6
C3—C4—H4A109.0C13—C14—H14119.6
C5—C4—H4B109.0C16—C15—C14118.4 (3)
C3—C4—H4B109.0C16—C15—H15120.8
H4A—C4—H4B107.8C14—C15—H15120.8
O1—C5—C6121.1 (3)C15—C16—C17122.7 (3)
O1—C5—C4120.3 (3)C15—C16—F1119.0 (4)
C6—C5—C4118.7 (3)C17—C16—F1118.3 (4)
C1—C6—C5119.8 (3)C16—C17—C18118.5 (3)
C1—C6—C7123.7 (2)C16—C17—H17120.7
C5—C6—C7116.6 (2)C18—C17—H17120.7
C6—C7—C8110.1 (2)C13—C18—C17121.0 (3)
C6—C7—C13111.3 (2)C13—C18—H18119.5
C8—C7—C13111.5 (2)C17—C18—H18119.5
C6—C7—H7107.9
C9—N1—C1—C6−0.3 (4)C7—C8—C9—N1−2.2 (4)
C11—N1—C1—C6176.6 (3)C10—N2—C9—C8178.1 (3)
C9—N1—C1—C2−179.8 (2)C10—N2—C9—N1−1.1 (3)
C11—N1—C1—C2−3.0 (4)C1—N1—C9—C8−2.2 (4)
C6—C1—C2—C324.5 (4)C11—N1—C9—C8−179.6 (3)
N1—C1—C2—C3−156.0 (2)C1—N1—C9—N2177.0 (2)
C1—C2—C3—C4−53.2 (3)C11—N1—C9—N2−0.3 (3)
C2—C3—C4—C551.4 (3)C9—N2—C10—O2−177.6 (3)
C3—C4—C5—O1162.2 (3)C9—N2—C10—C112.0 (3)
C3—C4—C5—C6−19.4 (4)C1—N1—C11—C10−175.7 (2)
N1—C1—C6—C5−171.3 (2)C9—N1—C11—C101.4 (3)
C2—C1—C6—C58.3 (4)O2—C10—C11—N1177.6 (3)
N1—C1—C6—C77.2 (4)N2—C10—C11—N1−2.0 (3)
C2—C1—C6—C7−173.3 (2)C9—C8—C12—N3153 (7)
O1—C5—C6—C1167.3 (3)C7—C8—C12—N3−23 (7)
C4—C5—C6—C1−11.1 (4)C6—C7—C13—C18130.9 (3)
O1—C5—C6—C7−11.2 (4)C8—C7—C13—C18−105.8 (3)
C4—C5—C6—C7170.3 (2)C6—C7—C13—C14−49.9 (3)
C1—C6—C7—C8−10.3 (4)C8—C7—C13—C1473.4 (3)
C5—C6—C7—C8168.2 (2)C18—C13—C14—C15−1.4 (4)
C1—C6—C7—C13113.9 (3)C7—C13—C14—C15179.4 (2)
C5—C6—C7—C13−67.7 (3)C13—C14—C15—C160.3 (4)
C6—C7—C8—C97.7 (4)C14—C15—C16—C171.3 (5)
C13—C7—C8—C9−116.4 (3)C14—C15—C16—F1−179.0 (2)
C6—C7—C8—C12−176.8 (2)C15—C16—C17—C18−1.7 (5)
C13—C7—C8—C1259.2 (3)F1—C16—C17—C18178.6 (3)
C12—C8—C9—N23.4 (5)C14—C13—C18—C171.0 (4)
C7—C8—C9—N2178.8 (3)C7—C13—C18—C17−179.8 (3)
C12—C8—C9—N1−177.6 (2)C16—C17—C18—C130.5 (5)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N2—H2···N3i0.862.153.006 (4)173
Symmetry codes: (i) −x+2, −y, −z.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N2—H2···N3i0.862.153.006 (4)173
Symmetry codes: (i) −x+2, −y, −z.
Acknowledgements top

We are grateful the National Science Foundation of China (grant No. 20672090), the Natural Science Foundation of Jiangsu Province (grant No. BK 2006033) and the Six Kinds of Professional Elite Foundation of Jiangsu Province (grant No. 06-A-039), for financial support.

references
References top

Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, S1–19.

Bruker (1998). SMART. Bruker AXS Inc., Madison, Wisconsin, USA.

Bruker (1999). SAINT and SHELXTL. Bruker AXS Inc., Madison, Wisconsin, USA.

Cremer, D. & Pople, J. A. (1975). J. Am. Chem. Soc. 97, 1354–1358.

Elhakmaoui, A., Gueiffier, A., Milhavet, J.-C., Blache, Y., Chavignon, O., Teulade, J.-C., Snoeck, R., Andrei, G. & De Clercq, E. (1994). Bioorg. Med. Chem. Lett. 4, 1937–1940.

Gueiffier, A., Lhassani, M., Elhakmaoui, A., Snoeck, R., Andrei, G., Chavignon, O., Teulade, J.-C., Kerbal, A., Essassi, E. M., Debouzy, J.-C., Witvrouw, M., Blache, Y., Balzarini, J., De Clercq, E. & Chapat, J.-P. (1996). J. Med. Chem. 39, 2856–2859.

Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.

Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany.

Stout, D. M. & Meyers, A. I. (1982). Chem. Rev. 82, 223–243.