10-(4-Chloro­phen­yl)-9-(4-fluoro­phen­yl)-3,3,6,6-tetra­methyl-3,4,6,7,9,10-hexa­hydro­acridine-1,8(2H,5H)-dione

Ling-Ling Zhao; Da Teng

doi:10.1107/S1600536808025695

. 2008 Aug 16;64(Pt 9):o1772–o1773. doi: 10.1107/S1600536808025695

10-(4-Chlorophenyl)-9-(4-fluorophenyl)-3,3,6,6-tetramethyl-3,4,6,7,9,10-hexahydroacridine-1,8(2H,5H)-dione

Ling-Ling Zhao ^a,^*, Da Teng ^a

PMCID: PMC2960627 PMID: 21201754

Abstract

The title compound, C₂₉H₂₉ClFNO₂, was synthesized by the reaction of 4-fluorobenzaldehyde, 5,5-dimethylcyclohexane-1,3-dione and 3-(4-chlorophenylamino)-5,5-dimethylcyclohex-2-enone in an ionic liquid (1-butyl-3-methylimidazolium bromide). X-ray analysis reveals that the 1,4-dihydropyridine ring adopts a boat conformation, while each of the attached partially saturated six-membered rings adopts a half-chair conformation. The structure is stabilized by weak C—H⋯O and C—H⋯F hydrogen bonds. The molecule has approximate mirror symmetry; the largest deviation from this symmetry concerns the fluoro- and chlorophenyl rings.

Related literature

For related literature, see: Dzierzbicka et al. (2001 ▶); Hutchins et al. (2003 ▶); Kamal et al. (2004 ▶); Li et al. (2003 ▶); Petříček et al. (2000 ▶); Srivastava & Nizamuddin (2004 ▶); Wang et al. (2002 ▶, 2003 ▶).

Experimental

Crystal data

C₂₉H₂₉ClFNO₂
M _r = 477.98
Monoclinic,
a = 12.0985 (12) Å
b = 10.9001 (10) Å
c = 19.4724 (18) Å
β = 101.231 (3)°
V = 2518.7 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.18 mm⁻¹
T = 113 (2) K
0.32 × 0.20 × 0.18 mm

Data collection

Rigaku Saturn diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 1999 ▶) T _min = 0.943, T _max = 0.967
30908 measured reflections
6016 independent reflections
5436 reflections with I > 2σ(I)
R _int = 0.040

Refinement

R[F ² > 2σ(F ²)] = 0.055
wR(F ²) = 0.137
S = 1.10
6016 reflections
312 parameters
H-atom parameters constrained
Δρ_max = 0.42 e Å⁻³
Δρ_min = −0.45 e Å⁻³

Data collection: CrystalClear (Rigaku, 1999 ▶); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: CrystalStructure (Rigaku/MSC, 2003 ▶).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808025695/fb2102sup1.cif

e-64-o1772-sup1.cif^{(25.4KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808025695/fb2102Isup2.hkl

e-64-o1772-Isup2.hkl^{(294.5KB, 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
C16—H16C⋯O2ⁱ	0.98	2.45	3.359 (2)	153
C11—H11⋯O2ⁱⁱ	0.95	2.37	3.286 (2)	160
C10—H10⋯O1ⁱⁱⁱ	0.95	2.55	3.474 (2)	165
C16—H16A⋯O1^iv	0.98	2.59	3.528 (2)	159
C17—H17A⋯F1^v	0.98	2.45	3.373 (2)	157

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) ; (iv) ; (v) .

Acknowledgments

The authors are grateful to the Natural Science Foundation of Xuzhou Normal University (grant Nos. 06AXL10 and 06PYL04) and to the Natural Science Foundation of the Education Committee of Jiangsu Province (grant No. 04KJB150139) for financial support.

supplementary crystallographic information

Comment

Acridine derivatives are well-known compounds because of their pharmacological profile as anticancer agents (Hutchins et al., 2003) and potential DNA-binding agents (Kamal et al., 2004). Acridine derivatives have also been reported to possess antitumor activity (Dzierzbicka et al., 2001) as well as fungicidal activity (Srivastava & Nizamuddin, 2004). Here we report the crystal structure of 10-(4-chlorophenyl)-9-(4-fluorophenyl)-3,4,6,7-tetrahydro-3,3,6,6- tetramethylacridine-1,8(2H,5H,9H,10H)-dione.

The X-ray crystal structure determination indicates that the central 1,4-dihydropyridine ring C1/C2···N1 is slightly distorted and adopts the boat conformation. The atoms C1, C2, C4 and C5 are coplanar, with C3 and N1 deviating from the plane by 0.286 (3) and 0.109 (2) Å, respectively. The similar distortions have been observed in the structures of 3,3,6,6-tetramethyl-9-(4-chlorophenyl)-10-(4-methylphenyl)- 1,2,3,4,5,6,7,8,9,10-decahydroacridine-1,8-dione [0.192 (3) and 0.091 (3) Å for C13 and N, respectively; Wang et al., 2003) and 3,3,6,6-tetramethyl-9-(3,4-methylenedioxylphenyl)-1,2,3,4,5,6,7,8,9,10- decahydroacridine-1,8-dione [0.313 (7) and 0.107 (7) Å for C7 and N1, respectively; Li et al., 2003).

The two outer six-membered rings of the acridine group adopt half-chair conformations; the atoms C13 and C19 deviate from the mean planes defined by C1, C2, C14, C15, C12 and C4, C5, C18, C20, C21 by 0.657 (2) and 0.668 (2) Å, respectively. A similar conformation has been found in the structure of 7,7-dimethyl-2-amino-3-cyano-4-(3,4-methylenedioxylphenyl)-5-oxo-5,6,7,8- tetrahydro-4H-benzo-[b]-pyran (Wang et al., 2002).

The 4-fluorophenyl ring is nearly perpendicular to the plane defined by the atoms C1—C2—C4—C5, forming a dihedral angle of 87.9 (1)°. The molecule has an approximate mirror symmetry. For example, the atoms C14 and C20 of the acridine groups are deviated by about 0.25Å. (The calculation has been carried out with the help of JANA2000 (Petříček et al., 2000). The largest deviation from this symmetry concerns the fluoro- and the chlorophenyl rings whose planes contain 9.3 (1)°.

The weak hydrogen bonds of C—H···O and C—H···F are listed in Table 1. The weak intermolecular hydrogen bonds of C—H···O and C—H···F link the molecules (Fig. 2).

Experimental

The title compound was prepared by the reaction of 4-fluorobenzaldehyde (2 mmol, 0.248 g), 5,5-dimethyl-1,3-cyclohexanedione (2 mmol, 0.280 g) and 3-(4-chlorophenylamino)-5,5-dimethylcyclohex-2-enone (2 mmol, 0.498 g) in the ionic liquid of [Bmim]Br (1-butyl-3-methylimidazolium bromide) (10 ml) at 353 K. After the reaction had completed (monitored by TLC, about 6 h), the reactants were cooled to room temperature. The generated yellow solid was filtered off, and washed with small amount of water. The block crystals (about 0.2 mm in length, width and height respectively) suitable for X-ray diffraction were obtained by slow evaporation from ethanol solution. M.p. 583–585 K.