4,4′-Dichloro-2,2′-[imidazolidine-1,3-diylbis(methylene)]diphenol

Augusto Rivera; John Sadat-Bernal; Jaime Ríos-Motta; Michaela Pojarová; Michal Dušek

doi:10.1107/S1600536811035677

. 2011 Sep 14;67(Pt 10):o2581. doi: 10.1107/S1600536811035677

4,4′-Dichloro-2,2′-[imidazolidine-1,3-diylbis(methylene)]diphenol

Augusto Rivera ^a,^*, John Sadat-Bernal ^a, Jaime Ríos-Motta ^a, Michaela Pojarová ^b, Michal Dušek ^b

PMCID: PMC3201546 PMID: 22065817

Abstract

The imidazolidine ring in the title compound, C₁₇H₁₈Cl₂N₂O₂, adopts a twist conformation. The observed conformation is stabilized by two intramolecular O—H⋯N hydrogen bonds, with both N atoms acting as hydrogen-bond acceptors. The phenyl substituents are aligned at 70.0 (1) and 76.6 (1)° with respect to the best plane through the five atoms of the imidazolidine ring. Weak intermolecular C—H⋯O interactions stabilize the crystal packing.

Related literature

For the preparation of the title compound, see: Rivera et al. (1993 ▶). For synthetic applications of these di-Mannich bases, see: Rivera & Quevedo (2004 ▶); Rivera et al. (2004 ▶). For a closely related structure, see: Rivera et al. (2010 ▶). For puckering parameters, see: Cremer & Pople (1975 ▶). For applications of tetrahydrosalens and heterocalixarenes in medicine and metal-complex catalysis, see: Balsells & Walsh (2000 ▶); Weber et al. (1996 ▶).

Experimental

Crystal data

C₁₇H₁₈Cl₂N₂O₂
M _r = 353.23
Monoclinic,
a = 10.8640 (2) Å
b = 9.6125 (2) Å
c = 16.7242 (4) Å
β = 106.608 (2)°
V = 1673.65 (6) Å³
Z = 4
Cu Kα radiation
μ = 3.58 mm⁻¹
T = 120 K
0.42 × 0.37 × 0.25 mm

Data collection

Oxford Diffraction Xcalibur Atlas Gemini ultra diffractometer
Absorption correction: analytical (CrysAlis PRO; Oxford Diffraction, 2010 ▶) T _min = 0.669, T _max = 0.777
19547 measured reflections
2994 independent reflections
2772 reflections with I > 2σ(I)’
R _int = 0.040

Refinement

R[F ² > 2σ(F ²)] = 0.035
wR(F ²) = 0.101
S = 1.04
2994 reflections
208 parameters
H-atom parameters constrained
Δρ_max = 0.29 e Å⁻³
Δρ_min = −0.30 e Å⁻³

Data collection: CrysAlis PRO (Oxford Diffraction, 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: DIAMOND (Brandenburg & Putz, 2005 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536811035677/bt5631sup1.cif

e-67-o2581-sup1.cif^{(18.6KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811035677/bt5631Isup2.hkl

e-67-o2581-Isup2.hkl^{(147KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536811035677/bt5631Isup3.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
O1—H1O1⋯N1	0.97	1.77	2.6524 (17)	149
O2—H1O2⋯N2	0.96	1.77	2.6515 (17)	150
C4—H4B⋯O2ⁱ	0.97	2.52	3.466 (2)	163
C9—H9⋯O2ⁱⁱ	0.93	2.47	3.395 (2)	172
C11—H11B⋯O1ⁱⁱⁱ	0.97	2.58	3.482 (2)	154

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

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 project Praemium Academiae of the Academy of Science of the Czech Republic. JSB acknowledges the Vicerrectoría Académica de la Universidad Nacional de Colombia for a fellowship.

supplementary crystallographic information

Comment

In connection with our synthetic studies on heterocyclic compounds we earlier synthesized a series of di-Mannich bases named 2,2'-(imidazolidine-1,3-diyldimethanediyl)bis(4-substitutedphenol) by reaction of appropriate phenols with 1,3,6,8-tetraazatricyclo[4.4.1.1^3,8]dodecane (Rivera et al., 1993). They are promising synthetic intermediates for the synthesis of tetrahydrosalens (Rivera, Quevedo, Navarro & Maldonado, 2004) and heterocalixarenes (Rivera & Quevedo, 2004), which find wide use in both medicine and metal-complex catalysis (Balsells & Walsh, 2000; Weber et al. 1996). These Mannich bases are convenient models for studying the nature of hydrogen bonding and weak noncovalent interactions, which play a key role in biological processes and design of complex structures.

We report here the structure of the title compound (I) (Fig. 1), which was prepared according to the previously reported procedure (Rivera et al., 1993) but using the intriguing aminal 1,3,6,8-tetraazatricyclo[4.3.1.1^3,8]undecane. Recrystallization from methanol by slow evaporation over a period of one week affording crystals suitable for X-ray analysis.

The asymmetric unit of (I), Fig 1, contains one independent 2,2'-(imidazolidine-1,3-diylbis(methylene))bis(4-chlorophenol) molecule. Distances and angles are similar to those observed before in the closely related structure 4,4'-dichloro-2,2'-[(3aR,7aR/3aS,7aS)-2,3,3a,4,5,6,7,7a-octahydro-1H-1,3-benzimidazole-1,3-diyl)bis(methylene)]diphenol (Rivera et al., 2010). The imidazolidine ring is in a twist conformation on C1–N2 with Q(2) 0.402 (2) Å and φ 52.7 (2)° (Cremer & Pople, 1975). Its central ring makes an angle of 70.0 (1)° and 76.6 (1)° with the planar phenyl rings (C5—C10) and (C12—C17) respectively. The crystal structure has two intramolecular hydrogen bonds and three C—H···O intermolecular hydrogen bonds (Table 1). The unit cell contains four molecules of the title compound (I), which form pairs of hydrogen bonded dimers (Table 1, Figs. 2). Neighboring pairs of these dimers are orthogonally arranged with respect to each other. Lattice binding is provided principally by C—H···O interactions, shown in Figure 2. The chains, aligned along the c axis, are further linked together via cross-linking weaker C—H···O interactions (Table 1).

Experimental

For the originally reported synthesis, see: Rivera et al. (1993)