2,2′-Dimethyl-2,2′-(m-phenyl­ene­dimethyl­ene)propane­dinitrile

Junmei Zhao; Volker Böhmer; Michael Bolte

doi:10.1107/S1600536809023344

. 2009 Jun 20;65(Pt 7):o1658. doi: 10.1107/S1600536809023344

2,2′-Dimethyl-2,2′-(m-phenylenedimethylene)propanedinitrile

Junmei Zhao ^a, Volker Böhmer ^a, Michael Bolte ^b,^*

PMCID: PMC2969357 PMID: 21582920

Abstract

The title compound, C₁₆H₁₄N₄, features an aromatic ring with two 2,2′-dicyanopropyl residues in positions 1 and 3, which are located above and below the ring plane. The two residues differ in their conformation with respect to the aromatic ring: whereas one of the C_methyl—C—C_methylene—C_aromatic torsion angles is gauche [68.93 (12)°], the other one is fully staggered [177.63 (9)°]. The crystal structure is stabilized by C—H⋯N hydrogen-bonding interactions.

Related literature

Calix[4]arenes, fixed in their cone conformation, offer a platform to attach various ligating functions via amide bonds to their wide or narrow rim, see: Arnaud-Neu et al. (1996 ▶); Barboso et al. (1999 ▶); Casnati et al. (2005 ▶); Danila et al. (2005a ▶,b ▶). Tetranitriles are suitable precursors for the attachment to the narrow rim. The title compound was envisaged as another potential tetranitrile. It is readily available by alkylation of methylmalonodinitrile with 1,3-bis-chloromethylbenzene.

Experimental

Crystal data

C₁₆H₁₄N₄
M _r = 262.31
Monoclinic,
a = 11.6475 (10) Å
b = 13.3751 (13) Å
c = 9.4691 (9) Å
β = 99.020 (7)°
V = 1456.9 (2) Å³
Z = 4
Mo Kα radiation
μ = 0.07 mm⁻¹
T = 173 K
0.47 × 0.24 × 0.22 mm

Data collection

Stoe IPDS-II two-circle diffractometer
Absorption correction: none
8679 measured reflections
2725 independent reflections
2410 reflections with I > 2σ(I)
R _int = 0.038

Refinement

R[F ² > 2σ(F ²)] = 0.037
wR(F ²) = 0.101
S = 1.04
2725 reflections
182 parameters
H-atom parameters constrained
Δρ_max = 0.22 e Å⁻³
Δρ_min = −0.16 e Å⁻³

Data collection: X-AREA (Stoe & Cie, 2001 ▶); cell refinement: X-AREA; data reduction: X-AREA; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: XP in SHELXTL-Plus (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809023344/at2821sup1.cif

e-65-o1658-sup1.cif^{(17.4KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809023344/at2821Isup2.hkl

e-65-o1658-Isup2.hkl^{(133.8KB, 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
C11—H11A⋯N24ⁱ	0.99	2.49	3.4028 (17)	153

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Symmetry code: (i) Inline graphic .

supplementary crystallographic information

Comment

Calix[4]arenes, fixed in their cone conformation, offer a platform to attach various ligating functions via amide bonds to their wide or narrow rim [e.g. CMPO-groups (Arnaud-Neu et al., 1996; Barboso et al., 1999), picolinamides (Casnati et al., 2005)]. Suitable precursors for the attachment to the narrow rim are tetranitriles obtained by O-alkylation with ω-bromoalkyl nitriles, which can be easily reduced to the respective tetraamines (Danila et al., 2005a,b). The title compound, 1,3-bis-(2,2'-dicyano)propyl benzene, (Fig. 1), was envisaged as another potential tetranitrile. It is readily available by alkylation of methylmalonodinitrile with 1,3-bis-chloromethylbenzene.

The title compound features an aromatic ring with two 2,2'-dicyano-propyl residues in positions 1 and 3, which are located above and below the ring plane. The two residues differ in their conformation with respect to the aromatic ring: whereas one of the C_methyl-C-C_methylene-C_aromatic torsion angles is gauche [68.93 (12)\%], the other one is fully staggered [177.63 (9)\%]. The crystal structure is stabilized by C—H···N hydrogen-bonding interactions (Table 1).

Experimental

A solution of methylmalonodinitrile (1.59 g, 13.9 mmol) in dry acetone (10 ml) was added to a suspension of K₂CO₃ (3.95 g, 28.6 mmol) in 20 ml acetone. The mixture was stirred for 30 min. Then 1,3-bischloromethylbenzene (500 mg, 2.86 mmol) and KI (80.5 g) were added and the mixture was stirred 10 h under reflux. The solvent was evaporated to dryness and the residue taken up with CHCl₃ (50 ml), washed with 1 M HCl, (2 x 30 ml), water and brine and dried over MgSO₄. Evaporation of the solvent and purification by column chromatography (hexane/ethylacetate 5:1) gave 530 mg (71%) of 1,3-bis-(2,2'-dicyano)propyl benzene, m.p. 130–131°C; ¹H NMR (400 MHz, CDCl₃): δ / p.p.m.: 1.82 (s, 6H), 3.23 (s, 4H), 7.34 (d, 1H), 7.4–7.5 (m, 3H); MS(FD): m/z 262.3 (100%, M⁺).

Single crystals were obtained by slow evaporation of a solution in hexane/chloroform.