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

Abdullah M Asiri; Hassan M Faidallah; Khalid A Alamry; Seik Weng Ng; Edward R T Tiekink

doi:10.1107/S1600536812011129

. 2012 Mar 21;68(Pt 4):o1118–o1119. doi: 10.1107/S1600536812011129

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

Abdullah M Asiri ^a,^b,^‡, Hassan M Faidallah ^a, Khalid A Alamry ^a, Seik Weng Ng ^c,^a, Edward R T Tiekink ^c,^*

PMCID: PMC3344065 PMID: 22589974

Abstract

In the title compound, C₂₄H₁₉N₃O₂, the partially saturated ring adopts a distorted half-chair conformation with the methylene-C atom closest to the aminobenzene ring lying 0.664 (3) Å out of the plane defined by the five remaining atoms (r.m.s. deviation = 0.1429 Å. The dihedral angle [32.01 (10)°] between the benzene rings on either side of this ring indicates a significant fold in this part of the molecule. The dimethoxy-substituted benzene ring is almost orthogonal to the benzene ring to which it is attached [dihedral angle = 72.03 (9)°]. The molecule has been observed previously as the major component of a 1:19 co-crystal with 2-amino-4-(3,4-dimethoxyphenyl)-5,6-dihydrobenzo[ha]quinoline-3-carbonitrile [Asiri et al. (2011). Acta Cryst. E67, o2873–o2873]. Supramolecular chains with base vector [201] are formed in the crystal structure via N—H⋯O hydrogen bonds between the amino H atoms of one molecule interacting with the methoxy O atoms of a neighbouring molecule. The chains are linked into a three-dimensional architecture by C—H⋯π interactions.

Related literature

For background to the biological activity of related phenanthrene compounds, see: Wang et al. (2010 ▶); Rostom et al. (2011 ▶). For related structures, see: Asiri et al. (2011a ▶,b ▶); Al-Youbi et al. (2012 ▶).

Experimental

Crystal data

C₂₄H₁₉N₃O₂
M _r = 381.42
Monoclinic,
a = 8.9360 (7) Å
b = 14.5007 (11) Å
c = 14.8074 (11) Å
β = 103.471 (8)°
V = 1865.9 (2) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 100 K
0.20 × 0.15 × 0.10 mm

Data collection

Agilent SuperNova Dual diffractometer with an Atlas detector
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011 ▶) T _min = 0.983, T _max = 0.991
8105 measured reflections
4272 independent reflections
2851 reflections with I > 2σ(I)
R _int = 0.037

Refinement

R[F ² > 2σ(F ²)] = 0.055
wR(F ²) = 0.136
S = 1.03
4272 reflections
270 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.25 e Å⁻³
Δρ_min = −0.23 e Å⁻³

Data collection: CrysAlis PRO (Agilent, 2011 ▶); 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: ORTEP-3 (Farrugia, 1997 ▶) and DIAMOND (Brandenburg, 2006 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812011129/sj5212sup1.cif

e-68-o1118-sup1.cif^{(21.1KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812011129/sj5212Isup2.hkl

e-68-o1118-Isup2.hkl^{(209.3KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536812011129/sj5212Isup3.cml

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

Cg1 and Cg2 are the centroids of the C1–C6 and C17–C22 rings, respectively.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H1⋯O1ⁱ	0.95 (2)	2.23 (2)	2.921 (2)	129 (2)
N2—H2⋯O2ⁱ	0.90 (3)	2.28 (3)	2.984 (2)	135 (2)
C24—H24B⋯Cg1ⁱⁱ	0.98	2.78	3.538 (2)	135
C7—H7A⋯Cg4ⁱⁱⁱ	0.99	2.92	3.792 (2)	147

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

Acknowledgments

The authors are grateful to the Center of Excellence for Advanced Materials Research and the Chemistry Department at King Abdulaziz University for providing the research facilities. We also thank the Ministry of Higher Education (Malaysia) for funding structural studies through the High-Impact Research scheme (UM.C/HIR/MOHE/SC/12).

supplementary crystallographic information

Comment

The X-ray crystallographic investigation of the title compound, 3-amino-1-(3,4-dimethoxyphenyl)-9,10-dihydrophenanthrene-2,4-dicarbonitrile (I), was motivated by reports of the biological activity of related compounds (Wang et al., 2010; Rostom et al., 2011) and allied crystal structure investigations (Asiri et al., 2011a; Al-Youbi et al., 2012). The molecule of (I) has been observed previously in its 1/19 co-crystal with 2-amino-4-(3,4-dimethoxyphenyl)-5,6-dihydrobenzo[ha]quinoline-3-carbonitrile (Asiri et al., 2011b).

In (I), Fig. 1, the partially saturated ring adopts a distorted twisted half chair conformation with the C2 atom lying 0.664 (3) Å out of the plane defined by the five remaining atoms [r.m.s. deviation = 0.1429 Å; maximum deviations = 0.1733 (11) Å for the C9 atom and -0.2097 (14) Å for the C10 atom]. The dihedral angle between the benzene rings on either side of this ring = 32.01 (10)°, indicating a significant fold in this part of the molecule. The dimethoxy-substituted benzene ring is almost normal to the plane of the benzene ring to which it is attached, forming a dihedral angle of 72.03 (9)° The O1-and O2-methoxy substituents are each slightly twisted out of the plane of the benzene ring to which they are attached as seen in the values of the C23—O1—C19—C18 and C24—O2—C20—C21 torsion angles of -13.7 (3) and -5.0 (3)°, respectively; they lie to opposite sides of the plane through the benzene ting.

The most prominent feature in the crystal packing is the formation of N—H···O hydrogen bonds whereby the amino-H atoms are connected to the two methoxy-O atoms of a neighbouring molecule leading to a seven-membered {···HNH···OC₂O} synthon linked into twisted supramolecular chains, Fig. 2 and Table 1; the base vector is along [2 0 1]. Clearly, the presence of two oxygen atoms in (I), is sufficient to disrupt the normally formed N—H···N hydrogen bonds between centrosymmetrically related molecules leading to to 12-membered {···HNC₃N}₂ synthons (Asiri et al., 2011a; Asiri et al., 2011b). Supramolecular chains are sustained in a three-dimensional architecture by C—H···π interactions, Fig. 3 and Table 1.

Experimental

A mixture of 3,4-dimethoxybenzaldehyde (1.66 g, 0.01 mmol), 1-tetralone (1.46 g, 0.01 mmol), malononitrile (0.66 g, 0.01 mmol) and ammonium acetate (6.2 g, 0.08 mmol) in absolute ethanol (50 ml) was refluxed for 6 h. The reaction mixture was allowed to cool. The precipitate that formed was filtered, washed with water, dried and recrystallized from ethanol. Yield: 69%, M. pt. 533–535 K.