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

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

doi:10.1107/S1600536811040505

. 2011 Oct 8;67(Pt 11):o2872. doi: 10.1107/S1600536811040505

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

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

PMCID: PMC3247607 PMID: 22219912

Abstract

The asymmetric unit of the 5:3 title co-crystal of 2-amino-4-phenyl-5,6-dihydrobenzo[h]quinoline-3-carbonitrile and 3-amino-1-phenyl-9,10-dihydrophenanthrene-2,4-dicarbonitrile, 0.625C₂₀H₁₅N₃.0.375C₂₂H₁₅N₃, has the atoms of the fused-ring system and those of the amino, cyano and phenyl substitutents overlapped. The fused-ring system is buckled owing to the ethylene linkage in the central ring, the two flanking aromatic rings being twisted by 20.1 (1)°. This ethylene portion is disordered over two positions in a 1:1 ratio. The phenyl ring is twisted by 69.5 (1)° relative to the amino- and cyano-bearing aromatic ring. In the crystal, two molecules are linked by an N—H⋯N hydrogen bond, generating a a helical chain along [010].

Related literature

For the synthesis, see: Aly et al. (1991 ▶); Paul et al. (1998 ▶). For related structures, see: Asiri et al. (2011a ▶,b ▶).

Experimental

Crystal data

0.625C₂₀H₁₅N₃·0.375C₂₂H₁₅N₃
M _r = 306.36
Orthorhombic,
a = 6.9611 (2) Å
b = 12.6093 (2) Å
c = 17.4933 (3) Å
V = 1535.47 (6) Å³
Z = 4
Cu Kα radiation
μ = 0.62 mm⁻¹
T = 100 K
0.30 × 0.20 × 0.02 mm

Data collection

Agilent SuperNova Dual diffractometer with an Atlas detector
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2010 ▶) T _min = 0.835, T _max = 0.988
6293 measured reflections
1794 independent reflections
1707 reflections with I > 2σ(I)
R _int = 0.018

Refinement

R[F ² > 2σ(F ²)] = 0.040
wR(F ²) = 0.119
S = 1.05
1794 reflections
240 parameters
24 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.19 e Å⁻³
Δρ_min = −0.23 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/S1600536811040505/zs2145sup1.cif

e-67-o2872-sup1.cif^{(20.6KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811040505/zs2145Isup2.hkl

e-67-o2872-Isup2.hkl^{(88.4KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536811040505/zs2145Isup3.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—H1⋯N3ⁱ	0.88 (1)	2.37 (2)	3.175 (2)	152 (3)

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Symmetry code: (i) Inline graphic .

Acknowledgments

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

supplementary crystallographic information

Comment

2-Amino-4-phenyl-5,6-dihydrobenzoquinoline-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 (Aly et al., 1991). The synthesis when conducted under microwave irradiation leads to an improved yield (Paul et al., 1998). 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 (Asiri et al., 2011a; 2011b).

In this study, the reaction of benzaldehyde, α-tetralone and ethyl cyanoacetate yielded the co-crystal of 2-amino-4-phenyl-5,6-dihydrobenzoquinoline-3-carbonitrile (C₂₀H₁₅N₃) and 3-amino-1-phenyl-9,10-dihydrophenanthrene-2,4-dicarbonitrile (C₂₂H₁₅N₃), with the two components present in a 5: 3 molar ratio (Scheme I). The fused-ring system is buckled owing to the ethylene linkage in the central ring with the two flanking aromatic rings twisted by 20.1 (1)°. Relative to the amino- and cyano-bearing aromatic ring, the phenyl ring is twisted by 69.5 (1) ° (Fig. 1 and Fig. 2). Two molecules are linked by an N—H···N hydrogen bond to generate a helical chain (Table 1 and Fig. 3). The ethylene portion is disordered over two positions in a 1:1 ratio.

Experimental

A mixture of benzaldehyde (1.06 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.