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

Augusto Rivera; Luz Stella Nerio; Jaime Ríos-Motta; Monika Kučeráková; Michal Dušek

doi:10.1107/S1600536812040329

. 2012 Sep 29;68(Pt 10):o3043–o3044. doi: 10.1107/S1600536812040329

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

Augusto Rivera ^a,^*, Luz Stella Nerio ^a, Jaime Ríos-Motta ^a, Monika Kučeráková ^b, Michal Dušek ^b

PMCID: PMC3470394 PMID: 23125807

Abstract

In the title compound, C₁₇H₁₈F₂N₂O₂, the imidazolidine ring system exists in a twist conformation. The mean plane through this ring system forms dihedral angles of 80.8 (8)° and 66.2 (13)°, with the benzene rings. The dihedral angle between the benzene rings is 52.0 (14)°. Two intramolecular O—H⋯N hydrogen bonds each generate S(6) ring motifs. In the crystal, weak C—H⋯O hydrogen bonds form dimers, which are connected by further C—H⋯O interactions.

Related literature

For related structures, see: Rivera et al. (2011 ▶, 2012 ▶). For the preparation of the title compound, see: Rivera et al. (1993 ▶). For standard bond lengths, see: Allen et al. (1987 ▶). For ring conformations, see Cremer & Pople (1975 ▶). For hydrogen-bond graph-set nomenclature, see: Bernstein et al. (1995 ▶). For the involvement of organo halides in hydrogen bonds, see: Rathore et al. (2011 ▶); Steiner (2002 ▶); Chopra & Guru Row (2005 ▶). For the extinction correction used, see: Becker & Coppens (1974 ▶).

Experimental

Crystal data

C₁₇H₁₈F₂N₂O₂
M _r = 320.3
Monoclinic,
a = 9.5952 (2) Å
b = 9.7018 (2) Å
c = 16.2065 (3) Å
β = 99.4807 (17)°
V = 1488.07 (5) Å³
Z = 4
Cu Kα radiation
μ = 0.94 mm⁻¹
T = 120 K
0.35 × 0.22 × 0.21 mm

Data collection

Agilent Xcalibur (Atlas, Gemini ultra) diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2010 ▶) T _min = 0.123, T _max = 1
35554 measured reflections
2669 independent reflections
2452 reflections with I > 3σ(I)
R _int = 0.025

Refinement

R[F ² > 2σ(F ²)] = 0.031
wR(F ²) = 0.108
S = 2.21
2669 reflections
215 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.19 e Å⁻³
Δρ_min = −0.17 e Å⁻³

Data collection: CrysAlis PRO (Agilent, 2010 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SUPERFLIP (Palatinus & Chapuis, 2007 ▶); 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/S1600536812040329/sj5264sup1.cif

e-68-o3043-sup1.cif^{(85.7KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812040329/sj5264Isup2.hkl

e-68-o3043-Isup2.hkl^{(110.4KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536812040329/sj5264Isup3.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—H1⋯N2	0.937 (16)	1.756 (16)	2.6413 (12)	156.2 (14)
O2—H2⋯N1	0.903 (16)	1.821 (15)	2.6579 (12)	153.2 (13)
C11—H1c11⋯O1ⁱ	0.96	2.44	3.4001 (13)	174.43
C17—H2c17⋯O1ⁱⁱ	0.96	2.55	3.4837 (13)	166

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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 Praemium Academiae project of the Academy of Sciences of the Czech Republic. LSN thanks COLCIENCIAS for a fellowship.

supplementary crystallographic information

Comment

Among the various types of intermolecular interactions, the hydrogen bond is, without doubt, the most important one. Organic halide compounds have attracted much attention due to the role of weak intermolecular C—H···X interactions in supramolecular assembly (Rathore et al. 2011, Steiner 2002). In recent literature, the importance of interactions involving fluorine as possible tools in crystal engineering has been explored in greater detail (Chopra & Guru Row, 2005). With the purpose to understand its effects in Mannich bases, we turn our attention to title compound (I) because fluorine is also able to form non-classical intermolecular C–H···F hydrogen bonds. In this study, we describe the crystal structure of the title compound, 4,4'-difluoro-2,2'-[imidazolidine-1,3-diylbis(methylene)]diphenol.

The molecular structure and atom-numbering scheme for (I) are shown in Fig. 1. The bond lengths (Allen et al., 1987) and angles of (I) are within normal ranges and are comparable to those related structures (Rivera et al., 2011, 2012). As observed in related structures (Rivera et al., 2011, 2012). The imidazoline ring adopts a twist conformation, Q2 = 0.4008 (13) Å and φ2 = 51.81 (18)° (Cremer & Pople, 1975), with a twist about the N2 —C14 bond. In order to reduce steric congestion, the benzene rings have different orientations with respect to the central imidazolidine ring. Thus, one p-fluoro-substituted benzene ring (C1/C2/C5/C10/C6/C17)is approximately orthogonal to the mean plane of the imidazolidine ring defined by N1, C13 and C9, making a dihedral angle of 80.82 (79)°, whereas the other ring (C3/C4/C7/C13/C16/C12) forms a dihedral angle of 66.18 (130)°. The dihedral angle between the benzene rings is 52.04 (136)°. There are two intramolecular hydrogen bonds between the phenolic hydroxyl groups and the nitrogen atoms with graph-set motif S(6) (Bernstein et al., 1995).

The results demonstrate, that not only the packing in (I) is governed by weak C—H···O hydrogen bonds (Table 1), resulting in a hydrogen bonded dimer, which is connected by further C—H···O interactions, but also that fluorine does not participate in any intermolecular interactions. Similarly, in ortho-F and ortho-Cl substituted analogs (Rivera et al., 2012, 2011), the halogen fails to participate in any non-bonded interaction.

Experimental

For the originally reported synthesis of the title compound, see: Rivera et al. (1993). Crystals suitable for X-ray diffraction were obtained from chloroform with a few drops of MeOH upon slow evaporation of the solvents over 3 days at room temperature.