1,3-Bis(2,3,5,6-tetra­fluoro-4-iodo­phen­oxy)-2,2-bis­[(2,3,5,6-tetra­fluoro-4-iodo­phen­oxy)meth­yl]propane

Gabriella Cavallo; Pierangelo Metrangolo; Tullio Pilati; Giuseppe Resnati; Giancarlo Terraneo; Maurizio Ursini

doi:10.1107/S1600536813007605

. 2013 Mar 23;69(Pt 4):o579–o580. doi: 10.1107/S1600536813007605

1,3-Bis(2,3,5,6-tetrafluoro-4-iodophenoxy)-2,2-bis[(2,3,5,6-tetrafluoro-4-iodophenoxy)methyl]propane

Gabriella Cavallo ^a, Pierangelo Metrangolo ^a, Tullio Pilati ^a, Giuseppe Resnati ^a, Giancarlo Terraneo ^a,^*, Maurizio Ursini ^a

PMCID: PMC3629626 PMID: 23634113

Abstract

In the crystal structure of the title compound, C₂₉H₈F₁₆I₄O₄, short I⋯I and I⋯F contacts, which can be understood as halogen bonds (XBs), represent the strongest intermolecular interactions, consistent with the presence of I and F atoms, and the absence of H atoms, at the periphery of the molecule. In addition, π–π stacking interactions between tetrafluoroiodophenyl (TFIP) groups and five short F⋯F interactions are present.

Related literature

The title compound is a robust halogen-bonding (XB) donor tecton in supramolecular chemistry. For background to XB-based crystal engeneering, see: Guido et al. (2004 ▶, 2005 ▶); Lucassen et al. (2007 ▶); Metrangolo et al. (2007 ▶). For the synthesis, see: Caronna et al. (2004 ▶). For a description of the Cambridge Structural Database, see: Allen (2002 ▶).

Experimental

Crystal data

C₂₉H₈F₁₆I₄O₄
M _r = 1231.95
Monoclinic,
a = 7.9716 (9) Å
b = 20.665 (3) Å
c = 20.194 (4) Å
β = 92.745 (12)°
V = 3322.8 (9) Å³
Z = 4
Mo Kα radiation
μ = 3.88 mm⁻¹
T = 90 K
0.34 × 0.06 × 0.04 mm

Data collection

Bruker APEX 2000 CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 1998 ▶) T _min = 0.742, T _max = 1.000
39668 measured reflections
9728 independent reflections
7975 reflections with I > 2σ(I)
R _int = 0.042

Refinement

R[F ² > 2σ(F ²)] = 0.038
wR(F ²) = 0.093
S = 1.04
9728 reflections
510 parameters
28 restraints
All H-atom parameters refined
Δρ_max = 2.08 e Å⁻³
Δρ_min = −0.54 e Å⁻³

Data collection: SMART (Bruker, 1998 ▶); cell refinement: SAINT (Bruker, 1998 ▶); data reduction: SAINT; program(s) used to solve structure: SIR2002 (Burla et al., 2003 ▶); program(s) used to refine structure: SHELXL2012 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ▶) and Mercury (Macrae et al., 2006 ▶); software used to prepare material for publication: SHELXL2012.

Supplementary Material

Click here for additional data file.^{(37KB, cif)}

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536813007605/lh5584sup1.cif

e-69-0o579-sup1.cif^{(37KB, cif)}

Click here for additional data file.^{(532.8KB, hkl)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813007605/lh5584Isup2.hkl

e-69-0o579-Isup2.hkl^{(532.8KB, hkl)}

Click here for additional data file.^{(10.9KB, cml)}

Supplementary material file. DOI: 10.1107/S1600536813007605/lh5584Isup3.cml

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

Table 1. Halogen bonds and C—F⋯F—C and π–π short interactions (Å, °).

The distances between the CNTRn of the four TFIP groups showing π–π interactions are also reported (CNTRn is the centroid of the benzene group linking the In iodine atom).

C—X⋯Y(—C)	X⋯Y	C—X⋯Y	X⋯Y—C
C5—I1⋯I3ⁱ	3.7838 (6)	169.59 (11)
C12—I2⋯F15ⁱⁱ	3.323 (3)	174.72 (11)
C19—I3⋯F2ⁱⁱⁱ	3.176 (3)	162.73 (11)
C26—I4⋯F6^iv	3.240 (3)	136.47 (11)
C3—F1⋯(F12—C21)^v	2.610 (3)	162.3 (2)	165.1 (3)
C4—F2⋯(F4—C7)^v	2.790 (4)	150.2 (2)	149.5 (3)
C17—F9⋯(F11—C20)^v	2.771 (4)	151.1 (2)	150.6 (3)
C10—F5⋯(F7—C13)^v	2.679 (3)	158.8 (2)	157.2 (3)
C25—F14⋯(F16—C28)^vi	2.821 (3)	147.6 (2)	149.2 (3)
CNTR1⋯CNTR4ⁱ	3.643 (6)
C3⋯C27ⁱ	3.334 (5)
C16⋯C11^vii	3.317 (5)
C18⋯C9^vii	3.307 (5)
F9⋯C13^vii	3.156 (5)
CNTR2⋯CNTR3^vii	3.648 (6)

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) ; (iv) ; (v) ; (vi) ; (vii) .

Acknowledgments

GC, PM, GR and GT thank the Fondazione Cariplo (projects 2009–2550 and 2010–1351) for financial support.

supplementary crystallographic information

Comment

The title compound is a flexible molecule synthesized and utilized for halogen bonding (XB) based crystal engeneering (Guido et al., 2004, 2005; Metrangolo et al., 2007). Here we present the structure of the pure compound which is characterized by the presence of I···I and I···F XBs, short F···F contacts and π—π stacking interactions between couples of TFIP pendants. The C—I···F short contancts are particularly interesting as they show C—I···F angles consistent with bona fide XBs. The shortest C—I···F contanct is 3.176 (3) Å (see Table 1) and only few shorter distances are found in the Cambridge Structural Database (Version 5.33; Allen, 2002), the shortest being in WEXVUR (2.962 Å, Lucassen et al., 2007). The molecular symmetry is approximately C₂; the torsion angles C0—C1—O1—C2, C0—C8—O2—C9, C0—C15—O3—C16, C0—C22—O4—C23 are 120.9 (3), -162.0 (3), 118.0 (4) and -164.4 (3) °, respectively. Pertinent geometric data are listed in Table 1. The TFIP1 and TFIP3, the phenyl rings bearing I1 and I3, are nearly coplanar and anti-parallel; TFIP2 and TFIP4, the phenyl rings bearing I2 and I4, are not coplanar, but nearly parallel. This conformation favours the formation of π···π interactions between the couples TFIP1/TFIP4 and TFIP2/TFIP3. Supplementary Table A reports the main interactions of the structure. Figure 2 shows the crystal packing.

Experimental

The synthesis of the compound was reported by Caronna et al., (2004). Crystals for X-ray analysis were obtained via isothermal evaporation of a chloroform solution.