2-Amino-4-(3,4-dimeth­oxy­phen­yl)-5,6-dihydro­benzo[h]quinoline-3-carbo­nitrile–3-amino-1-(3,4-dimeth­oxy­phen­yl)-9,10-dihydro­phenanthrene-2,4-dicarbonitrile (1/19)

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

doi:10.1107/S1600536811040517

. 2011 Oct 8;67(Pt 11):o2873. doi: 10.1107/S1600536811040517

2-Amino-4-(3,4-dimethoxyphenyl)-5,6-dihydrobenzo[h]quinoline-3-carbonitrile–3-amino-1-(3,4-dimethoxyphenyl)-9,10-dihydrophenanthrene-2,4-dicarbonitrile (1/19)

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

PMCID: PMC3247608 PMID: 22219913

Abstract

The asymmetric unit of the 1:19 title co-crystal of 2-amino-4-(3,4-dimethoxyphenyl)-5,6-dihydrobenzo[h]quinoline-3-carbonitrile and 3-amino-1-(3,4-dimethoxyphenyl)-9,10-dihydrophenanthrene-2,4-dicarbonitrile, 0.05C₂₂H₁₉N₃O₂·0.95C₂₄H₁₉N₃O₂, has the atoms of the fused-ring system and those of the amino, cyano and dimethoxyphenyl substitutents overlapped. The fused-ring system is buckled owing to the ethylene linkage in the central ring with the two flanking aromatic rings being twisted by 31.9 (1)°. The ring of the dimethoxyphenyl substituent is twisted by 72.4 (1)° relative to the amino- and cyano-bearing aromatic ring. In the crystal, molecules are linked by duplex amine N—H⋯O(methoxy) hydrogen bonds in a cyclic association [graph-set R ₂ ²(7)], generating a helical chain structure extending along [201].

Related literature

For a similar co-crystal, see: Asiri et al. (2011 ▶). For graph-set analysis, see: Etter et al. (1990 ▶).

Experimental

Crystal data

0.05C₂₂H₁₉N₃O₂·0.95C₂₄H₁₉N₃O₂
M _r = 380.22
Monoclinic,
a = 8.9347 (3) Å
b = 14.4915 (5) Å
c = 14.7818 (6) Å
β = 103.446 (4)°
V = 1861.45 (12) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 100 K
0.30 × 0.25 × 0.20 mm

Data collection

Agilent SuperNova Dual diffractometer with an Atlas detector
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2010 ▶) T _min = 0.974, T _max = 0.983
9240 measured reflections
4160 independent reflections
3146 reflections with I > 2σ(I)
R _int = 0.031

Refinement

R[F ² > 2σ(F ²)] = 0.049
wR(F ²) = 0.124
S = 1.04
4160 reflections
270 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.30 e Å⁻³
Δρ_min = −0.24 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/S1600536811040517/zs2146sup1.cif

e-67-o2873-sup1.cif^{(18.2KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811040517/zs2146Isup2.hkl

e-67-o2873-Isup2.hkl^{(203.9KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536811040517/zs2146Isup3.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
N3—H1⋯O1ⁱ	0.95 (2)	2.24 (2)	2.927 (2)	129 (2)
N3—H2⋯O2ⁱ	0.92 (2)	2.25 (2)	2.987 (2)	136 (2)

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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-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 3,4-dimethoxybenzaldehyde, α-tetralone and ethyl cyanoacetate yielded the co-crystal of 2-amino-4-(3,4-dimethoxyphenyl)-5,6-dihydrobenzoquinoline-3-carbonitrile (C₂₂H₁₉N₃O₂) and 3-amino-1-(3,4-dimethoxyphenyl)-9,10-dihydrophenanthrene-2,4-dicarbonitrile (C₂₄H₁₉N₃O₂) with the components present in a 1: 19 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 31.9 (1) °. Relative to the amino- and cyano-bearing aromatic ring, the benzene ring is twisted by 72.4 (1) ° (Figs. 1 and 2). Molecules are linked by duplex amine N–H···O (methoxy) hydrogen bonds (Table 1) in a cyclic association [graph set R²₂(7) (Etter et al., 1990)], generating a helical chain structure extending along [2 0 1].

Experimental

A mixture of 3,4-dimethoxybenzaldehyde (1.66 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.