9,9-Dimethyl-12-(3-nitro­phen­yl)-7,8,9,10,11,12-hexa­hydro­benz[a]acridin-11-one

Runhong Jia; Juhua Peng; Shujiang Tu

doi:10.1107/S1600536809033935

. 2009 Aug 29;65(Pt 9):o2284. doi: 10.1107/S1600536809033935

9,9-Dimethyl-12-(3-nitrophenyl)-7,8,9,10,11,12-hexahydrobenz[a]acridin-11-one

Runhong Jia ^a, Juhua Peng ^a, Shujiang Tu ^b,^*

PMCID: PMC2969871 PMID: 21577677

Abstract

The title compound, C₂₅H₂₂N₂O₃, was synthesized by the reaction of 3-nitrobenzaldehyde, dimedone and 2-naphthylamine in ethanol. In the molecular structure, the cyclohexenone ring adopts an envelope conformation, whereas the piperidine ring has a boat conformation. The crystal packing is stabilized by intermolecular N—H⋯O hydrogen bonds.

Related literature

For the biological and physical activity of compounds containing the acridine skeleton, see: Wysocka-Skrzela & Ledochowski (1976 ▶); Matsumoto et al. (1983 ▶); Popielarz et al. (1997 ▶). Jia et al. (2007 ▶); Kidwai & Rastogi (2005 ▶); Srividya et al. (1996 ▶). For microwave irradiation in organic synthesis, see: Tu et al. (2002 ▶, 2004 ▶). For related structures, see: Jia et al. (2006 ▶); Wang et al. (2006 ▶); Tu et al. (2006 ▶).

Experimental

Crystal data

C₂₅H₂₂N₂O₃
M _r = 398.45
Monoclinic,
a = 10.264 (7) Å
b = 13.099 (9) Å
c = 15.018 (10) Å
β = 94.403 (10)°
V = 2013 (2) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 298 K
0.17 × 0.16 × 0.10 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 1998 ▶) T _min = 0.985, T _max = 0.991
10293 measured reflections
3541 independent reflections
1401 reflections with I > 2σ(I)
R _int = 0.078

Refinement

R[F ² > 2σ(F ²)] = 0.055
wR(F ²) = 0.185
S = 1.01
3541 reflections
273 parameters
H-atom parameters constrained
Δρ_max = 0.18 e Å⁻³
Δρ_min = −0.19 e Å⁻³

Data collection: SMART (Bruker, 1998 ▶); cell refinement: SAINT (Bruker, 1998 ▶); data reduction: SAINT; 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: SHELXTL.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809033935/zq2005sup1.cif

e-65-o2284-sup1.cif^{(22.2KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809033935/zq2005Isup2.hkl

e-65-o2284-Isup2.hkl^{(173.7KB, 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—H1⋯O1ⁱ	0.86	2.13	2.937 (4)	156

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Symmetry code: (i) Inline graphic .

Acknowledgments

The authors thank the National Science Foundation of China (No. 20672090) and the Natural Science Foundation of Jiangsu Province (No. BK2006033) and the Graduate Foundation of Xuzhou Normal University (No. 08YLB031) for financial support.

supplementary crystallographic information

Comment

A lot of natural and synthetic compounds containing the acridine skeleton display interesting biological and physical activities, such as antimalaria (Wysocka-Skrzela et al. 1976) and antitumor agents (Matsumoto et al. 1983), and multihydroacridineone derivatives have been reported to have high fluorescence efficiency and can be used as fluorescent molecular probes for monitoring of polymerization process (Popielarz et al. 1997). They are also increasingly receiving attention due to their likeness in properties with those of 1,4-dihydropyridines, which have similarities in structure to the biologically important compounds such as NADH and NADPH (Srividya et al. 1996). As a consequence, the interest of organic chemists in the synthesis or structure modifications of acridinedione derivatives remains high. Microwave irradiation is a very useful technique in organic synthesis (Tu et al. 2002). It is a simple, timesaving, high yielding, and environmentally friendly process. We have already reported the synthesis of heterocyclic compounds under microwave irradiation (Tu et al. 2004). M. Kidwai and S. Rastogi have reported the synthesis of polyhydroacridinones without additional fused benzene rings (Kidwai et al. 2005). The efficiency of microwave irradiation in promoting organic reaction and the success of its application in heterocyclic synthesis (Jia et al. 2007) has rapidly gained in popularity. Therefore design and synthesis of these compounds has been challenging. For these reasons, the synthesis of compounds containing cyanopyridine derivatives is strongly desired. In this paper we report the crystal structure of the title compound (I).

In the crystal structure, the dihedral angle between the C1/C6/C8/C17/N1 plane and the C20—C25 benzene ring is 83.5 (8)° (Fig. 1). The dihedral angle between the C1/C6/C8/C17/N1 plane and the C8/C9/C14/C15/C16/C17 plane is 5.8 (5)°. The dihedral angle between the C1/C6/C8/C17/N1 plane and the C1/C2/C4/C5/C6 plane is 11.4 (4)°, indicating that they are almost parallel. The distance between atom C3 and the mean plane C4/C5/C6/C1/C2 is 0.594 (6) Å, showing that the cyclohexenone ring adopts an envelope conformation. The newly formed piperidine ring has a boat conformation with the atoms N1 and C7 deviating from the plane C1/C6/C17/C8 by 0.098 (5) and 0.184 (6) Å, respectively, on the same direction. One chiral center exists in the title compound at C7. The centrosymmetric space group indicates the presence of equimolar enantiomers (S and R) in the crystal structure. The molecules are connected via N1—H1···O1 hydrogen bonds, forming infinite one-dimensional chains along the b axis (Fig. 2).

Experimental

Compound (I) was prepared by the reaction of 3-nitrobenzaldehyde (1 mmol), dimedone (1 mmol), 2-naphthylamine (1 mmol), in ethanol (2 ml) under microwave irradiation without catalyst. Single crystals of (I) suitable for X-ray diffraction were obtained by slow evaporation of a 95% aqueous ethanol solution (yield 92%; m.p. 567–569 K). IR (cm^-1): 3260, 2928, 1582, 1522, 1494, 1385, 1234, 1155, 1093, 982, 923, 811, 729, 687, 654; ¹H NMR (DMSO-d₆): 0.82 (s, 3H, CH3), 1.06 (s, 3H, CH3), 2.04 (d, 1H, J = 16.0 Hz, CH), 2.25 (d, 1H, J = 16.0 Hz, CH), 2.43 (d, 1H, J = 16.4 Hz, CH), 2.58 (d, 1H, J = 16.4 Hz, CH), 5.97 (s, 1H, CH), 7.48–7.31 (m, 4H, ArH), 7.70 (d, 1H, J = 7.6 Hz, ArH),7.96–7.82 (m, 4H, ArH), 8.07 (s, 1H, ArH), 9.90 (s, 1H, NH).