2-Amino-4-(4-chloro­phen­yl)-5,6-dihydro­benzo[h]quinoline-3-carbonitrile–3-amino-1-(4-chloro­phen­yl)-9,10-dihydro­phenanthrene-2,4-dicarbonitrile (1/4)

Abdullah M Asiri; Abdulrahman O Al-Youbi; Hassan M Faidallah; Seik Weng Ng

doi:10.1107/S1600536811040529

. 2011 Oct 8;67(Pt 11):o2874. doi: 10.1107/S1600536811040529

2-Amino-4-(4-chlorophenyl)-5,6-dihydrobenzo[h]quinoline-3-carbonitrile–3-amino-1-(4-chlorophenyl)-9,10-dihydrophenanthrene-2,4-dicarbonitrile (1/4)

Abdullah M Asiri ^a,^b, Abdulrahman O Al-Youbi ^a, Hassan M Faidallah ^a, Seik Weng Ng ^c,^a,^*

PMCID: PMC3247609 PMID: 22219914

Abstract

The asymmetric unit of the 1:4 title co-crystal of 2-amino-4-(4-chlorophenyl)-5,6-dihydrobenzo[h]quinoline-3-carbonitrile and 3-amino-1-(4-chlorophenyl)-9,10-dihydrophenanthrene-2,4-dicarbonitrile, 0.2C₂₀H₁₄ClN₃·0.8C₂₂H₁₄ClN₃, has the atoms of the fused-ring system and those of the amino, cyano and chlorophenyl substitutents overlapped. The fused-ring system is buckled owing to the ethylene linkage in the central ring. There are two independent overlapped molecules in the asymmetric unit. In one independent molecule, the two flanking aromatic rings are twisted by 24.4 (1)° and the ring of the chlorophenyl substituent is twisted by 87.3 (1)° relative to the amino- and cyano-bearing aromatic ring. In the second molecule, the respective dihedral angles are 26.1 (1) and 57.8 (1)°. The two independent molecules are linked by N—H⋯N hydrogen bonds into dimers.

Related literature

For similar co-crystals, see: Asiri et al. (2011a ▶,b ▶).

Experimental

Crystal data

0.2C₂₀H₁₄ClN₃·0.8C₂₂H₁₄ClN₃
M _r = 351.01
Monoclinic,
a = 19.2576 (7) Å
b = 9.5103 (2) Å
c = 20.2266 (7) Å
β = 114.018 (4)°
V = 3383.7 (2) Å³
Z = 8
Cu Kα radiation
μ = 2.06 mm⁻¹
T = 100 K
0.30 × 0.20 × 0.10 mm

Data collection

Agilent SuperNova Dual diffractometer with an Atlas detector
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2010 ▶) T _min = 0.577, T _max = 0.821
12442 measured reflections
6686 independent reflections
6272 reflections with I > 2σ(I)
R _int = 0.032

Refinement

R[F ² > 2σ(F ²)] = 0.051
wR(F ²) = 0.130
S = 1.05
6686 reflections
471 parameters
H-atom parameters constrained
Δρ_max = 0.44 e Å⁻³
Δρ_min = −0.65 e Å⁻³

Data collection: CrysAlis PRO (Agilent, 2010 ▶); cell refinement: 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: X-SEED (Barbour, 2001 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536811040529/zs2147sup1.cif

e-67-o2874-sup1.cif^{(29.2KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811040529/zs2147Isup2.hkl

e-67-o2874-Isup2.hkl^{(327.2KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536811040529/zs2147Isup3.cml

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
N2—H21⋯N4	0.88	2.14	2.931 (3)	149
N5—H52⋯N3	0.88	2.33	3.136 (3)	152

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Acknowledgments

We thank King Abdulaziz University and the University of Malaya for supporting this study.

supplementary crystallographic information

Comment

2-Amino-5,6-dihydro-4-phenyl-benzoquinoline-3-carbonitrile is synthesized from the reaction of the α-substituted cinnamonitrile, C₆H₅CH═C(CN)₂, with α-tetralone in a reaction that is catalyzed by ammonium acetate. The synthesis when conducted under microwave irradiation leads to an improved yield. In previous studies, we obtained instead di-carbonitrile substituted dihydrophenanthrenes (3-amino-1-(4-methoxyphenyl)-9,10-dihydrophenanthrene-2,4-dicarbonitrile and 3-amino-1-(2H-1,3-benzodioxol-5-yl)- 9,10-dihydrophenanthrene-2,4-dicarbonitrile) with 4-methoxybenzaldehyde and piperonaldehyde in syntheses that differed slightly from the reported ones as we used substituted benzaldehydes, α-tetralone and ethyl cyanoacetate along with a molar excess of ammonium acetate.

In this study, the reaction of 4-chlorobenzaldehyde, α-tetralone and ethyl cyanoacetate yielded the co-crystal of the title compound 2-amino-4-(4-chlorophenyl)-5,6-dihydrobenzoquinoline-3-carbonitrile (C₂₀H₁₄N₃Cl) and 3-amino-1-(4-chlorophenyl)-9,10-dihydrophenanthrene-2,4-dicarbonitrile (C₂₂H₁₄N₃Cl) with the components present in a 1: 4 molar ratio (Scheme I). The fused-ring system is buckled owing to the ethylene linkage in the central ring, the two flanking aromatic rings being twisted by 24.4 (1)°. Relative to the amino- and cyano-bearing aromatic ring, the benzene ring is twisted by 87.3 (1)° in one independent overlapped molecule. For the second molecule, the respective dihedral angles are 26.1 (1) ° and 57.8 (1) ° (Fig. 1 and Fig. 2). Two molecules are linked by an N—H···N hydrogen bonds (Table 1) to generate dimers.

Experimental

A mixture of 4-chlorobenzaldehyde (1.41 g,10 mmol), α-tetralone (1.46 g, 10 mmol), ethyl cyanoacetate (1.13 g, 10 mmol) and ammonium acetate (6.16 g, 80 mmol) in absolute ethanol (50 ml) was refluxed for 6 h. The mixture was allowed to cool and the precipitate that formed was filtered, washed with water, dried and recrystallized from DMF.