1,1′-[Imidazolidine-1,3-diylbis(methyl­ene)]bis­(1H-benzotriazole)

Augusto Rivera; Diego Quiroga; Jaime Ríos-Motta; Karla Fejfarová; Michal Dušek

doi:10.1107/S1600536812000232

. 2012 Jan 11;68(Pt 2):o312–o313. doi: 10.1107/S1600536812000232

1,1′-[Imidazolidine-1,3-diylbis(methylene)]bis(1H-benzotriazole)

Augusto Rivera ^a,^*, Diego Quiroga ^a, Jaime Ríos-Motta ^a, Karla Fejfarová ^b, Michal Dušek ^b

PMCID: PMC3275003 PMID: 22346948

Abstract

In the title compound, C₁₇H₁₈N₈, the imidazolidine ring adopts an envelope conformation with the substituents at the N atoms in trans positions with respect to the central ring. The dihedral angle between the two benzotriazole rings is 71.65 (10)°. In the crystal, non-classical C—H⋯N interactions link the molecules into helical chains along the b axis. The crystal packing is further stabilized by weak C—H⋯π interactions.

Related literature

For related structures, see: Rivera et al. (2011a ▶,b ▶). For the synthesis of the title compound, see: Rivera et al. (2004 ▶); Katriztky et al. (1990 ▶). For ring conformations, see Cremer & Pople (1975 ▶). For bond-length data, see: Allen et al. (1987 ▶). For the anomeric effect, see: Dabbagh et al. (2002 ▶); Selámbaron et al. (2001 ▶); Zefirov & Shekhtman (1971 ▶); Hendrickson (1961 ▶).

Experimental

Crystal data

C₁₇H₁₈N₈
M _r = 334.4
Monoclinic,
a = 11.8609 (6) Å
b = 4.6429 (2) Å
c = 14.4712 (8) Å
β = 93.053 (4)°
V = 795.78 (7) Å³
Z = 2
Cu Kα radiation
μ = 0.74 mm⁻¹
T = 120 K
0.43 × 0.18 × 0.10 mm

Data collection

Agilent Xcalibur diffractometer with an Atlas (Gemini ultra Cu) detector
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2010 ▶) T _min = 0.378, T _max = 1
10081 measured reflections
1609 independent reflections
1541 reflections with I > 3σ(I)
R _int = 0.030

Refinement

R[F ² > 2σ(F ²)] = 0.027
wR(F ²) = 0.073
S = 1.52
1609 reflections
226 parameters
H-atom parameters constrained
Δρ_max = 0.09 e Å⁻³
Δρ_min = −0.11 e Å⁻³

Data collection: CrysAlis PRO (Agilent, 2010 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SIR2002 (Burla et al., 2003 ▶); program(s) used to refine structure: JANA2006 (Petříček et al., 2006 ▶); molecular graphics: DIAMOND (Brandenburg & Putz, 2005 ▶); software used to prepare material for publication: JANA2006.

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812000232/bt5768sup1.cif

e-68-0o312-sup1.cif^{(19.1KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812000232/bt5768Isup2.hkl

e-68-0o312-Isup2.hkl^{(62.1KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536812000232/bt5768Isup3.cml

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

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

Cg3 is the centroid of the N6/N7/N8/C13/C12 aromatic ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C17—H17⋯N5ⁱ	0.96	2.60	3.552 (2)	173
C11—H11b⋯Cg3ⁱⁱ	0.96	2.86	3.394 (2)	116

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

Acknowledgments

We acknowledge the Dirección de Investigaciones, Sede Bogotá (DIB) de la Universidad Nacional de Colombia, for financial support of this work, as well as the Institutional research plan No. AVOZ10100521 of the Institute of Physics and the Praemium Academiae project of the Academy of Sciences of the Czech Republic. DQ acknowledges the Vicerrectoría Académica de la Universidad Nacional de Colombia for a fellowship.

supplementary crystallographic information

Comment

The anomeric effect is a stereoelectronic effect observed in various heterocyclic compounds and some acyclic structures with a great deal of importance due its implications on the molecular structure, conformational properties and reactivity of organic compounds (Zefirov & Shekhtman, 1971; Selámbaron, et al., 2001; Dabbagh, et al., 2002). Our investigations on the synthesis and structural studies of heterocyclic compounds have evidenced the occurrence of a n(N)→σ* (C—N) electron delocalization (Rivera et al., 2011a, 2011b). In this article, we discussed the crystal structure of the title compound, which can be synthetized by a three component condensation between ethylenediamine, formaldehyde and benzotriazole (Katriztky et al., 1990) or using a novel methodology involving a Mannich type reaction between the aminal cage 1,3,6,8-tetrazatricyclo[4.4.1.1^3,8]dodecane and benzotriazole (Rivera et al., 2004). By recrystallization from ethanol we obtained suitable crystals for X-rays analysis.

The molecular structure and atom-numbering scheme for (I) are shown in Fig. 1. The anomeric effect is evidenced by the C—N bond lengths, which are longer as C11—N6 [1.484 (2) Å] and shorter as N2—C11 [1.433 (2) Å] than the expected bond length of 1.469 Å (Allen et al., 1987). Moreover, this effect is confirmed by the bond angles around N2 with a Σα = 339.43 (13) which are distorted from a normal tetrahedral geometry in a five-membered ring (Hendrickson, 1961), whereas for N1 the bond lenghts and angles are within normal ranges. These results are in a good agreement with the crystal structures of related structures (Rivera et al., 2011a, 2011b).

The imidazolidine ring adopts an envelope conformation on C1 as seen in the puckering parameters Q(2) = 0.3953 (17) Å and φ2 = 40.3 (2) ° (Cremer & Pople, 1975), with endocyclic bond angles between 103.06 (13) ° and 106.55 (13) °. The geometry of the N—C—C—N moiety is close to the planar in a syn-periplanar conformation evidenced by the N2—C2—C3—N1 torsion angle [3.05 (17) °]. The benzotriazolylmethyl substituents are arranged trans respect the imidazolidine ring, which is preferred because the nitrogen lone pairs are oriented anti-axial to avoid repulsion electronic repulsions. The benzotriazole rings makes an angle of 38.47 (10) ° and 78.88 (10) ° with the mean plane of imidazolidine ring. The dihedral angle between the two benzotriazole rings is 71.65 (10) °. Chains of molecules in the title compound are linked along the b direction by non-classical intermolecular hydrogen bonds C17—H17···N5 interactions [2.60 Å] which link neighboring molecules. The crystal packing is further stabilized by weak C—H···π interactions.

Experimental

For the originally reported synthesis, see: Rivera et al. (2004). Single crystals of the title compound (I) were grown from ethanol by recrystallization.