3-(1-Adamantylamino)-3-methyl-1-phenyl­quinoline-2,4(1H,3H)-dione

Niusha Mahmoodi; Marek Nečas; Robert Vícha

doi:10.1107/S1600536809026464

. 2009 Jul 15;65(Pt 8):o1866. doi: 10.1107/S1600536809026464

3-(1-Adamantylamino)-3-methyl-1-phenylquinoline-2,4(1H,3H)-dione

Niusha Mahmoodi ^a, Marek Nečas ^b, Robert Vícha ^a,^*

PMCID: PMC2977340 PMID: 21583562

Abstract

The structure of the title compound, C₂₆H₂₈N₂O₂, contains essentially planar quinoline and benzene rings, the maximum deviations from the best plane being 0.086 (2) and 0.0056 (19) Å, respectively; the dihedral angle between the rings is 82.87 (4)°. The adamantane cage consists of three fused cyclohexane rings in classical chair conformations, with C—C—C angles in the range 107.85 (15)–111.35 (15)°. Enantiomers are linked alternately into chains along the c axis via short N—H⋯O interactions and further C–H⋯π interactions stabilize pairs of enantiomers, forming a two-dimensional network.

Related literature

For the synthesis and biological activity of related compounds, see: Kafka et al. (2002 ▶); Nayyar et al. (2007 ▶). For the properties of adamantane-containing compounds, see: van Bommel et al. (2001 ▶). For a related structure, see: Shishkina et al. (2001 ▶). For background to C—H⋯π interactions, see: Nishio (2004 ▶); Jorgensen & Severance (1990 ▶).

Experimental

Crystal data

C₂₆H₂₈N₂O₂
M _r = 400.50
Monoclinic,
a = 9.9714 (4) Å
b = 24.1041 (11) Å
c = 9.3805 (5) Å
β = 113.111 (5)°
V = 2073.68 (17) Å³
Z = 4
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 120 K
0.30 × 0.30 × 0.20 mm

Data collection

Kuma KM-4 CCD diffractometer
Absorption correction: none
22477 measured reflections
3648 independent reflections
2226 reflections with I > 2σ(I)
R _int = 0.051

Refinement

R[F ² > 2σ(F ²)] = 0.041
wR(F ²) = 0.106
S = 0.88
3648 reflections
272 parameters
H-atom parameters constrained
Δρ_max = 0.53 e Å⁻³
Δρ_min = −0.25 e Å⁻³

Data collection: Xcalibur (Oxford Diffraction, 2006 ▶); cell refinement: Xcalibur; data reduction: Xcalibur; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶) and Mercury (Macrae et al., 2008 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809026464/pk2176sup1.cif

e-65-o1866-sup1.cif^{(24.2KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809026464/pk2176Isup2.hkl

e-65-o1866-Isup2.hkl^{(178.9KB, hkl)}

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O2ⁱ	0.88	2.29	3.125 (2)	158
C25—H25A⋯Cg1ⁱⁱ	0.95	2.91	3.659 (2)	136

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Symmetry code: (i) Inline graphic ; (ii) . Cg1 is the centroid of the C13–C18 ring.

Acknowledgments

Financial support for this work from the Science Foundation of the Czech Republic (grant No. 203/07/03) and by the Czech Ministry of Education (project No. MSM 7088352101) is gratefully acknowledged.

supplementary crystallographic information

Comment

A number of compounds that include the quinoline moiety have well known chemotherapeutical properties. From a pharmacological point of view, two very important and seemingly contradictory properties may be improved when the adamantane substituent is introduced into biologically active compounds. The solubility in aqueous media may be enhanced by complexation of adamantane with β-cyclodextrin and the liphophilic adamantane cage may accelerate permeability through biological membranes (van Bommel et al., 2001). Recently, some quinolines bearing adamantyl substituents have been introduced as promising anti-tuberculosis agents (Nayyar et al., 2007).

The molecule of the title compound (Fig. 1) consists of planar benzene and quinoline rings with maximum deviations from the best plane being 0.0056 (18) Å for C23 and 0.086 (2) Å for C12, respectively. The dihedral angle between quinoline and benzene rings is 82.87 (4)°. The torsion angles describing the alignment of the adamantane and quinoline moiety C12–C11–N1–C1 and C11–N1–C1–C8 are -73.9 (2)° and 16.8 (2)°, respectively. Enantiomers alternate in chains along the c axis, and are linked via N1–H1a···O2 short interactions (Table 1, Fig. 2). Pairs of inverse enantiomers are stabilized by edge-to-face C–H···π interactions with the H···Cg distance being 2.914 (2) Å (Cg is the centroid of C13–C18).

Experimental

The title compound was prepared according to a slightly modified literature procedure of Kafka et al. (2002). Adamantane-1-amine hydrochloride (200 mg, 1.07 mmol) was dissolved in 3 ml of DMF and triethylamine (212 mg, 2.1 mmol) was added dropwise at 273 K. Into this mixture, a solution of N-phenyl-3-chloro-3-methylquinoline-2,4-dione (153 mg, 0.535 mmol) in 3 ml of DMF was added dropwise at 273 K. The resulting solution was stirred for 93 h at room temperature until starting material disappeared (according to TLC). The mixture was poured into crushed ice, extracted several times with diethyl ether, the combined organic portions were dried over sodium sulfate and the crude product was obtained after evaporation of solvent under reduced pressure. The title compound was isolated from complex crude material by column chromatography (silica gel, ethyl acetate:hexane 1:4 v/v) as a pale yellow crystalline powder (53 mg, 25%, mp 449–451 K). The single crystal suitable for X-ray analysis was obtained by spontaneous evaporation from chloroform solution at 298 K.