3-Amino-1-methyl-9,10-dihydro­phenanthrene-2,4-dicarbonitrile

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

doi:10.1107/S1600536811035008

. 2011 Sep 14;67(Pt 10):o2569. doi: 10.1107/S1600536811035008

3-Amino-1-methyl-9,10-dihydrophenanthrene-2,4-dicarbonitrile

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

PMCID: PMC3201274 PMID: 22065653

Abstract

The asymmetric unit of the title compound, C₁₇H₁₃N₃, contains two independent molecules, which are non-planar as they are buckled owing to the ethylene portion. The dihedral angle between the benzene rings is 26.4 (1)° in one molecule and 32.9 (1)° in the other. In the crystal, the molecules are disposed about a false inversion center, and are linked by two N—H⋯N hydrogen bonds, generating a dimer. The dimers are linked by further N—H⋯N hydrogen bonds, resulting in a chain that runs along the longest axis of the orthorhombic unit cell.

Related literature

For the synthesis of dihydrophenanthrenes, see: Dellagreca et al. (2000 ▶); Ram & Goel (1997 ▶).

Experimental

Crystal data

C₁₇H₁₃N₃
M _r = 259.30
Orthorhombic,
a = 26.8587 (7) Å
b = 8.8158 (2) Å
c = 11.2035 (3) Å
V = 2652.78 (12) Å³
Z = 8
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 = 0.836, T _max = 0.988
10819 measured reflections
2800 independent reflections
2621 reflections with I > 2σ(I)
R _int = 0.033

Refinement

R[F ² > 2σ(F ²)] = 0.034
wR(F ²) = 0.091
S = 1.09
2800 reflections
379 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.16 e Å⁻³
Δρ_min = −0.20 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/S1600536811035008/xu5310sup1.cif

e-67-o2569-sup1.cif^{(25.4KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811035008/xu5310Isup2.hkl

e-67-o2569-Isup2.hkl^{(137.5KB, 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
N2—H21⋯N4	0.91 (4)	2.15 (4)	3.007 (3)	156 (3)
N2—H22⋯N6ⁱ	0.91 (3)	2.38 (3)	3.265 (3)	164 (2)
N5—H51⋯N1ⁱⁱ	0.91 (4)	2.12 (4)	3.012 (3)	168 (3)
N5—H52⋯N3	0.91 (3)	2.41 (3)	3.283 (3)	161 (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

As the dihydrophenanthrene skeleton is a principal component of a number of pharmaceutical products, there is a large collection of reserach on the synthesis of dihydrophenanthrene compounds. This skeleton is known to mimic natural products, which is yet another source of bioactive compounds (Dellagreca et al., 2000). In this study, we have used 1-tetralone, acetaldehyde, and malonitrile to synthesize the skeleton; an early study reported the use of 1-tetralone to condense with 2H-pyran-2-ones to furnish this skeleton (Ram & Goel, 1997). The title molecule, C₁₇H₁₃N₃ (Scheme I), is non-planar as the molecule it is buckled owing to the ethylene portion; the dihedral angle between the aromatic rings is 26.4 (1) ° in one independent molecule and 32.9 (1) ° in the other. The molecules are disposed about a false inversion center, and are linked by two N–H···N hydrogen bonds to generate a dimer (Fig. 1). The dimers are linked by N–H···N hydrogen bonds to result in a linear chain (Table 1).

Experimental

Acetaldehyde (0.44 g,10 mmol), 1-tetralone (1.46 g, 10 mmol), malononitrile (0.66 g, 10 mmol) and ammonium acetate(6.20 g, 80 mmol) in absolute ethanol (50 ml) were heated for 6 houyrs. The mixture was allowed to cool, and the solid was collected, washed with water, dried and then recrystallized from ethanol to yield light brown crystals, m.p. 457–459 K.