3-Amino-1-(2H-1,3-benzodioxol-5-yl)-9,10-dihydro­phenanthrene-2,4-dicarbonitrile

Abdullah M Asiri; Abdulrahman O Al-Youbi; Hassan M Faidallah; Seik Weng Ng; Edward R T Tiekink

doi:10.1107/S1600536811033563

. 2011 Aug 27;67(Pt 9):o2438. doi: 10.1107/S1600536811033563

3-Amino-1-(2H-1,3-benzodioxol-5-yl)-9,10-dihydrophenanthrene-2,4-dicarbonitrile

Abdullah M Asiri ^a,^b,^‡, Abdulrahman O Al-Youbi ^a, Hassan M Faidallah ^a, Seik Weng Ng ^c, Edward R T Tiekink ^c,^*

PMCID: PMC3200934 PMID: 22059011

Abstract

In the title compound, C₂₃H₁₅N₃O₂, significant deviations from planarity are evidenced in the values of the dihedral angles formed between the amino-benzene ring and the benzene rings of the 1,3-benzodioxole [65.38 (12)°] and 1,2-dihydronaphthalene [26.27 (14)°] residues; the dioxole ring has an envelope conformation with the methylene-C being the flap atom. The amino-H atoms form hydrogen bonds to one of the dioxole-O atoms and to one of the cyano-N atoms to generate a two-dimensional array with a zigzag topology that stacks along the ( Inline graphic 0 2) plane.

Related literature

For background to the biological activity of related compounds, see: Aly et al. (1991 ▶); Al-Saadi et al. (2005 ▶); Rostom et al. (2011 ▶). For ring conformational analysis, see: Cremer & Pople (1975 ▶).

Experimental

Crystal data

C₂₃H₁₅N₃O₂
M _r = 365.38
Monoclinic,
a = 8.9280 (6) Å
b = 22.4518 (13) Å
c = 8.9473 (6) Å
β = 109.058 (7)°
V = 1695.18 (19) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 100 K
0.25 × 0.25 × 0.05 mm

Data collection

Agilent Technologies SuperNova Dual diffractometer with Atlas detector
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2010 ▶) T _min = 0.776, T _max = 1.000
9604 measured reflections
3775 independent reflections
2570 reflections with I > 2σ(I)
R _int = 0.042

Refinement

R[F ² > 2σ(F ²)] = 0.065
wR(F ²) = 0.167
S = 1.02
3775 reflections
261 parameters
2 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.65 e Å⁻³
Δρ_min = −0.30 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: 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/S1600536811033563/om2463sup1.cif

e-67-o2438-sup1.cif^{(21.3KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811033563/om2463Isup2.hkl

e-67-o2438-Isup2.hkl^{(185.1KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536811033563/om2463Isup3.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⋯O1ⁱ	0.88 (1)	2.40 (2)	3.231 (3)	157 (3)
N2—H2⋯N1ⁱⁱ	0.88 (1)	2.37 (2)	3.188 (3)	156 (3)

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

Acknowledgments

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

supplementary crystallographic information

Comment

The study of the title compound (I) was motivated by recent reports of the biological activity of related compounds (Aly et al., 1991; Al-Saadi et al., 2005; Rostom et al., 2011).

With respect to the amino-benzene ring, the benzene rings of the 1,3-benzodioxole and 1,2-dihydronaphthalene residues form dihedral angles of 65.38 (12) and 26.27 (14) °, respectively, indicating non-planarity in the molecule. The five-membered dioxole ring has an envelope conformation with the methylene-C23 atom being the flap atom. The Cremer & Pople (1975) parameters defining the five-membered ring are q₂ = 0.182 (3) Å and φ₂ = 324.8 (9) Å. In the 1,2-dihydronaphthalene residue, the cyclohexa-1,3-diene ring has a distorted half-chair conformation as defined by the following parameters (Cremer & Pople, 1975): q₂ = 0.503 (3) Å, φ₂ = 265.5 (3) °, q₃ = -0.189 (3) Å, and puckering amplitude Q = 0.537 (3) Å.

In the crystal structure, supramolecular arrays with zigzag topology and running parallel to the (1 0 2) plane are formed through N—H···O(dioxole) and N—H···N(cyano) hydrogen bonding Table 1 and Fig. 2.

Experimental

A mixture of the piperonaldehyde (1.5 g,10 mmol), 1-tetralone (1.46 g, 10 mmol), ethyl cyanoacetate (1.1 g, 10 mmol) and ammonium acetate (6.2 g, 80 mmol) in absolute ethanol (50 ml) was refluxed for 6 h. The reaction mixture was allowed to cool and the precipitate that formed was filtered, washed with water, dried and recrystallized from DMF; M.pt.: 549–551 K.