2,4-Dichloro-1-[1-(2,4-dichloro­benz­yl­oxy)eth­yl]benzene

Jerry P Jasinski; Ray J Butcher; C S Chidan Kumar; H S Yathirajan; B Narayana

doi:10.1107/S1600536809053422

. 2009 Dec 16;66(Pt 1):o165–o166. doi: 10.1107/S1600536809053422

2,4-Dichloro-1-[1-(2,4-dichlorobenzyloxy)ethyl]benzene

Jerry P Jasinski ^a,^*, Ray J Butcher ^b, C S Chidan Kumar ^c, H S Yathirajan ^c, B Narayana ^d

PMCID: PMC2980264 PMID: 21580052

Abstract

In the title compound, C₁₅H₁₂Cl₄O, the dihedral angle between the least-squares planes of the two benzene rings is 82.6 (9)°. The dihedral angles between the COC mean plane of the oxy group and the two benzene rings are 84.3 (5) and 10.8 (5)°. In the crystal, two weak π–π interactions [centroid–centroid distances = 3.9989 (8) and 3.7912 (8) Å] and a C—H⋯π interaction are observed.

Related literature

For related structures, see: Yan et al. (2007 ▶); Cui et al. (2005 ▶); Moratti et al. (2007 ▶); Kotila et al. (1996 ▶). For compounds related to bis-lactim ethers of cyclic dipeptides, see: Bolte et al. (1999 ▶). For catalytic transfer hydrogenolysis of benzyl ethers, see: Brigas et al. (1999 ▶). For details of theoretical calculations, see: Becke (1988 ▶, 1993 ▶); Frisch et al. (2004 ▶); Hehre et al. (1986 ▶); Lee et al. (1988 ▶); Schmidt & Polik (2007 ▶). For a description of the Cambridge Structural Database, see: Allen (2002 ▶).

Experimental

Crystal data

C₁₅H₁₂Cl₄O
M _r = 350.05
Triclinic,
a = 9.3755 (4) Å
b = 9.9229 (4) Å
c = 9.9667 (4) Å
α = 62.313 (3)°
β = 70.246 (4)°
γ = 71.467 (4)°
V = 758.22 (5) Å³
Z = 2
Mo Kα radiation
μ = 0.77 mm⁻¹
T = 200 K
0.47 × 0.42 × 0.27 mm

Data collection

Oxford Diffraction Gemini diffractometer
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2007 ▶) T _min = 0.638, T _max = 0.812
10547 measured reflections
4961 independent reflections
3334 reflections with I > 2σ(I)
R _int = 0.015

Refinement

R[F ² > 2σ(F ²)] = 0.031
wR(F ²) = 0.086
S = 1.02
4961 reflections
182 parameters
H-atom parameters constrained
Δρ_max = 0.34 e Å⁻³
Δρ_min = −0.25 e Å⁻³

Data collection: CrysAlis PRO (Oxford Diffraction, 2007 ▶); 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: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809053422/is2502sup1.cif

e-66-0o165-sup1.cif^{(17.9KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809053422/is2502Isup2.hkl

e-66-0o165-Isup2.hkl^{(243KB, 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
C12—H12A⋯Cg1ⁱ	0.95	2.97	3.8888 (15)	162

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Symmetry code: (i) Inline graphic . Cg1 is the centroid of the C1–C6 ring.

Acknowledgments

CSC thanks the University of Mysore for use of their research facilities. RJB acknowledges the NSF MRI program (grant No. CHE-0619278) for funds to purchase an X-ray diffractometer.

supplementary crystallographic information

Comment

Ether is a class of chemical compounds which contain an ether group — an oxygen atom connected to two (substituted) alkyl or aryl groups — of general formula R–O–R'. Ethers, with their characteristic solvation abilities, excel as inert reaction media in numerous synthetic procedures. However, in practice this usefulness is often tempered by an unfortunate proclivity to facile air oxidation at ambient temperatures which leads to peroxide formation. The structures of the few related compounds viz., 4-(benzyloxy)-2-fluorobenzonitrile (Yan et al., 2007), 2-benzyloxy-3-nitropyridine (Cui et al., 2005), 2,6-bis[2-(4-benzyloxyphenyl)ethyl]biphenyl (Moratti et al., 2007), 3-tert-butyl-4-methyl-2-phenyl-3-(trimethylsilyloxy)oxetane and 2-(2-benzyloxyphenyl)-3-tert-butyl-3-(trimethylsilyloxy)oxetane (Kotila et al., 1996), bis-lactim ethers of cyclic dipeptides: Compounds derived from cyclo(Gly-L-Val) (Bolte et al., 1999) and 5-benzyloxy-1-phenyltetrazole: catalytic transfer hydrogenolysis of benzyl ethers (Brigas et al., 1999) are already reported. In view of the importance of ethers, the synthesis and crystal structure of the title compound, (I), is reported.

In the title compound, C₁₅H₁₂Cl₄O, (I), the dihedral angle between the least squares planes of the two benzene rings is 82.6 (9)° (Fig.1). The angle between the mean planes of the oxy group and the two benzene rings is 84.3 (5)° and 10.8 (5)°, respectively. Each of the two dichloro benzene rings are stacked diagonally along the (011) plane (Fig. 2). While no classic hydrogen bonds are found, weak π–π [Cg1···Cg1 = 3.9989 (8) Å; 1 - x, 2 - y, 1 - z and Cg2···Cg2 = 3.7912 (8) Å; 2 - x, 1 - y, 2 - z] and C–H···π [C12–H12A···Cg1; Table 1] intermolecular interactions are observed. Bond length and bond angles are within normal ranges (Allen, 2002).

Following geometry optimization using AM1 with MOPAC (Schmidt & Polik, 2007) and density functional theory (DFT) theoretical calculations (Schmidt & Polik, 2007) at the B3LYP/6–31G(d) level (Becke, 1988, 1993; Lee et al., 1988; Hehre et al., 1986) with the Gaussian03 program package (Frisch at al., 2004), the dihedral angle between the least squares planes of the two benzene rings becomes 83.6 (3)° (AM1) or 85.9 (6)° (DFT). The angles between the mean planes of the oxy group and the two benzene rings become 86.4 (2) and 3.5 (6)° (AM1) or 88.6 (5) and 5.5 (3)° (DFT), respectively. It is clear that the weak π–π and C—H···π intermolecular interactions do influence crystal packing stability.

Experimental

A mixture of 1-(2,4-dichlorophenyl)ethanol (0.01 mol, 1.91 g) and 2,4-dichloro-1-(chloromethyl)benzene (0.01 mol, 1.95 g) in 30 ml dry acetone was refluxed over water bath for 6 h (Fig. 3). The crude compound was filtered and recrystallized from ethyl acetate (m.p. 449–451 K). Composition for C₁₅H₁₂Cl₄O: C 51.39 (51.46), H 3.42 (3.46).