2,2-Dimethyl-2,3-dihydro-1H-perimidine

Sarah Maloney; Alexandra M Z Slawin; J Derek Woollins

doi:10.1107/S1600536813000986

. 2013 Jan 19;69(Pt 2):o246. doi: 10.1107/S1600536813000986

2,2-Dimethyl-2,3-dihydro-1H-perimidine

Sarah Maloney ^a, Alexandra M Z Slawin ^a, J Derek Woollins ^a,^*

PMCID: PMC3569779 PMID: 23424525

Abstract

The title compound, C₁₃H₁₄N₂, was obtained from reaction of diaminonaphthalene with acetone. In both independent molecules in the asymmetric unit, the tricyclic perimidine consists of a planar (r.m.s. deviations = 0.0125 and 0.0181 Å) naphthalene ring system and an envelope conformation C₄N₂ ringwith the NCN group hinged with respect to the naphthalene backbone by 36.9 (2) and 41.3 (2)° in the two independent molecules. The methyl substituents are arranged approximately axial and equatorial on the apical C atom. In the crystal, one of the N—H groups of one independent molecule is involved in classical N—H⋯N hydrogen bonding. Short intermolecular (C/N)—H⋯π(arene) interactions, near the short T-shaped limit, link molecules in the absence of strong acceptors.

Related literature

For general background to perimidines and their biological activity, see: Shaabani & Maleki (2008 ▶); Sauer et al. (2006 ▶). For related structures, see: Martinez-Belmonte et al. (2010 ▶).

Experimental

Crystal data

C₁₃H₁₄N₂
M _r = 198.27
Monoclinic,
a = 16.261 (10) Å
b = 7.710 (4) Å
c = 17.483 (10) Å
β = 106.131 (12)°
V = 2105.6 (19) Å³
Z = 8
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 93 K
0.12 × 0.12 × 0.12 mm

Data collection

Rigaku Mercury70 diffractometer
Absorption correction: multi-scan (REQAB; Rigaku, 1998 ▶) T _min = 0.706, T _max = 0.991
12841 measured reflections
3743 independent reflections
2356 reflections with F ² > 2σ(F ²)
R _int = 0.072

Refinement

R[F ² > 2σ(F ²)] = 0.056
wR(F ²) = 0.133
S = 0.96
3743 reflections
287 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.22 e Å⁻³
Δρ_min = −0.24 e Å⁻³

Data collection: CrystalClear-SM Expert (Rigaku, 2009 ▶); cell refinement: CrystalClear-SM Expert; data reduction: CrystalClear-SM Expert; program(s) used to solve structure: SIR2002 (Burla et al., 2003 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: CrystalStructure (Rigaku, 2010 ▶); software used to prepare material for publication: CrystalStructure.

Supplementary Material

Click here for additional data file.^{(40KB, cif)}

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536813000986/gg2107sup1.cif

e-69-0o246-sup1.cif^{(40KB, cif)}

Click here for additional data file.^{(183.5KB, hkl)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813000986/gg2107Isup2.hkl

e-69-0o246-Isup2.hkl^{(183.5KB, hkl)}

Click here for additional data file.^{(4.5KB, cml)}

Supplementary material file. DOI: 10.1107/S1600536813000986/gg2107Isup3.cml

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

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

Cg1, Cg2 and Cg3 are the centroids of the C21–C25/C30, C25–C30 and C5–C10 rings, respectively.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N21—H21N⋯N29ⁱ	0.88 (2)	2.36 (2)	3.229 (4)	170 (2)
N1—H1N⋯Cg1ⁱⁱ	0.93 (3)	2.93 (3)	3.853 (3)	170 (2)
N9—H9N⋯Cg1	0.88 (4)	2.85 (2)	3.703 (3)	164 (2)
C12—H12C⋯Cg2	0.98	2.55	3.521 (3)	172
C26—H26⋯Cg3ⁱⁱⁱ	0.95	2.53	3.456 (3)	164

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

Acknowledgments

We are grateful to EPSRC for support.

supplementary crystallographic information

Comment

The title compound has a planar napthalene backbone with the the nitrogen atoms above this plane in both independent molecules (N1 0.133, N9 0.182, N21 0.155, N290.047 Å) and the carbon in the C4N2 ring being below this plane (C11 - 0.373, C31 - 0.488 Å). The six membered C₄N₂ ring is hinged about the N···N vector with the N1—C11—N9 and C21—C31—N29 planes being inclined by 36.9 and 41.0° respectively to the naphthalene planes.

Experimental

A solution of 1,8-aminonapthalene (1.52 g, 0.01 mol s) and acetone (0.58 g, 0.78 ml, 0.01 mol s) was refluxed in ethanol (50 ml) for 2 h. The solution was then filtered, solvent evaporated to dryness under reduced pressure and recrystallized from boiling ethanol to give translucent crystals (mp x^oC). (0.897 g, 0.0045 mol s, 45%). IR (KBr disc): 3295 ν(N—H), 1596 aromatic C—H, 1016, 646, 552, 477 cm^-1. Raman (solid sample): 1490, 447, 160 cm^-1. δ_H (270.0 MHz, CDCl₃, Me₄Si): 7.24–7.14 (4H, m, H₁, H₂), 6.47–6.44 (2H, dd, H₃), 4.16 (2H, brd s, H₄), 1.49 (6H, s, H₅). δ_C (75.5 MHz, CDCl₃, Me₄Si): 140.4 (2 C, C₄), 127.1 (2 C,C₃), 117.2 (2 C, C₂), 106.1 (2 C, C₁), 64.7 (1 C, C₅), 28.9 (2 C, C₆). MS EI+: m/z 221.05 (M⁺ + Na)⁺ , 199.06 (M⁺ + H)⁺, 182.08 (M⁺ - Me)⁺. Found: C, 78.27; H, 6.93 N, 14.21. C₁₃H₁₄N₂ requires C, 78.75; H, 7.12; N, 14.13%.