3-Amino-1-(4-bromo­phen­yl)-9,10-dihydro­phenanthrene-2,4-dicarbonitrile

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

doi:10.1107/S1600536811038517

. 2011 Sep 30;67(Pt 10):o2745. doi: 10.1107/S1600536811038517

3-Amino-1-(4-bromophenyl)-9,10-dihydrophenanthrene-2,4-dicarbonitrile

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

PMCID: PMC3201339 PMID: 22058805

Abstract

In the title compound, C₂₂H₁₄BrN₃, the fused-ring system is buckled owing to the ethylene linkage in the central ring; the two flanking aromatic rings are twisted by 25.9 (1) ° with respect to each other. The phenyl ring is twisted by 77.0 (1)° relative to the amino- and cyano-bearing aromatic ring. In the crystal, adjacent molecules are linked by two N–H⋯N hydrogen bonds, generating a zigzag chain along [101].

Related literature

For two related compounds, see: Asiri et al. (2011a ▶,b ▶).

Experimental

Crystal data

C₂₂H₁₄BrN₃
M _r = 400.27
Monoclinic,
a = 13.7683 (5) Å
b = 16.2557 (3) Å
c = 9.7945 (4) Å
β = 127.546 (6)°
V = 1738.07 (17) Å³
Z = 4
Cu Kα radiation
μ = 3.29 mm⁻¹
T = 100 K
0.20 × 0.20 × 0.20 mm

Data collection

Agilent SuperNova Dual diffractometer with Atlas detector
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2010 ▶) T _min = 0.559, T _max = 0.559
2976 measured reflections
2195 independent reflections
2187 reflections with I > 2σ(I)
R _int = 0.012

Refinement

R[F ² > 2σ(F ²)] = 0.021
wR(F ²) = 0.056
S = 1.08
2195 reflections
243 parameters
2 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.22 e Å⁻³
Δρ_min = −0.61 e Å⁻³
Absolute structure: Flack (Flack, 1983 ▶), 482 Friedel pairs
Flack parameter: −0.024 (14)

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/S1600536811038517/bt5646sup1.cif

e-67-o2745-sup1.cif^{(19.2KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811038517/bt5646Isup2.hkl

e-67-o2745-Isup2.hkl^{(107.9KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536811038517/bt5646Isup3.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⋯N1ⁱ	0.93 (3)	2.23 (3)	3.097 (3)	155 (3)
N2—H2⋯N3ⁱⁱ	0.88 (4)	2.54 (4)	3.307 (3)	147 (3)

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Symmetry codes: (i) Inline graphic ; (ii) .

Acknowledgments

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

supplementary crystallographic information

Comment

2-Amino-4-aryl-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. 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 (Asiri et al., 2011a; 2011b). The use of 4-bromobenzaldehyde furnishes the corresponding 4-bromophenyl analog (Scheme I, Fig. 1). The fused-ring system is buckled owing to the ethylene linkage in the central ring; the two flanking aromatic rings are twisted by 25.9 (1) °. Relative to the amino- and cyano-bearing aromatic ring, the phenyl ring is twisted by 77.0 (1) °. Adjacent molecules are linked by two N–H···N hydrogen bonds to generate a chain along [1 0 1] (Table 1).

Experimental

4-Bromobenzaldehyde (1.85 g,10 mmol), 1-tetralone (1.46 g, 10 mmol), malononitrile (0.66 g, 10 mmol) and ammonium acetate (6.2 g, 80 mmol) in absolute ethanol (50 ml) were heated for 6 h. The mixture was allowed to cool, and the precipitate was collected, washed with water, dried and then recrystallized from ethanol; m.p. 517–518.