The 1:1 co-crystal of triphen­yl(2,3,5,6-tetra­fluoro­benz­yl)phospho­nium bromide and 1,1,2,2-tetra­fluoro-1,2-di­iodo­ethane

Cavallo, G.; Metrangolo, P.; Meyer, F.; Pilati, T.; Resnati, G.; Terraneo, G.

doi:10.1107/S1600536813032522

organic compounds

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ISSN: 2056-9890

Volume 70| Part 1| January 2014| Pages o9-o10

https://doi.org/10.1107/S1600536813032522

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The 1:1 co-crystal of triphenyl(2,3,5,6-tetrafluorobenzyl)phosphonium bromide and 1,1,2,2-tetrafluoro-1,2-diiodoethane

Gabriella Cavallo,^a Pierangelo Metrangolo,^a Franck Meyer,^b Tullio Pilati,^a Giuseppe Resnati ^a and Giancarlo Terraneo ^a ^*

^aNFMLab, Department of Chemistry, Materials and Chemical Engineering, "Giulio Natta", Politecnico di Milano, Via Mancinelli, 7, I-20131 Milano, Italy, and ^bLaboratory of Biopolymers and Supramolecular Nanomaterials, Universitè Libre de Bruxelles (ULB), Campus de la Plaine, Boulevard du Triomphe, B-1050 Bruxelles, Belgium
^*Correspondence e-mail: giancarlo.terraneo@polimi.it

(Received 17 March 2013; accepted 29 November 2013; online 4 December 2013)

The title compound, C₂₅H₁₈F₄P⁺·Br⁻·C₂F₄I₂, is a 1:1 co-crystal of triphenyl(2,3,5,6-tetrafluorobenzyl)phosphonium (TTPB) bromide and 1,1,2,2-tetrafluoro-1,2-diiodoethane (TFDIE). The crystal structure consists of a framework of TTPB cations held together by C—H⋯Br interactions. In this framework, infinite channels along [100] are filled by TFDIE molecules held together in infinite ribbons by short F⋯F [2.863 (2)–2.901 (2)Å] interactions. The structure contains halogen bonds (XB) and hydrogen bonds (HB) in the bromide coordination sphere. TFDIE functions as a monodentate XB donor as only one I atom is linked to the Br⁻ anion and forms a short and directional interaction [I⋯Br⁻ 3.1798 (7) Å and C—I⋯Br⁻ 177.76 (5)°]. The coordination sphere of the bromide anion is completed by two short HBs of about 2.8 Å (for H⋯Br) with the acidic methylene H atoms and two longer HBs of about 3.0 Å with H atoms of the phenyl rings. Surprisingly neither the second iodine atom of TFDIE nor the H atom on the tetrafluorophenyl group make any short contacts.

CCDC reference: 974492

Related literature

For a general discussion on halogen bonds (XBs) involving anionic halogen-bonding acceptors, see: for oxyanions, Abate et al. (2011 ); for chloride and bromide, Abate et al. (2009 ); for iodide, Metrangolo et al. (2008 ). For examples of reliable XB donors in an ionic context, see: Cavallo et al. (2010 ); Metrangolo et al. (2009 ); Logothetis et al. (2004 ). For different supramolecular structures of halogen-bonded (poly)anions, see for: discrete adducts, Gattuso et al. (2007 ); infinite chains, Gattuso et al. (2006 ); comb-like arrays, Biella et al. (2009 ); 'ring and stick' one-dimensional chains, Gattuso et al. (2009 ); two-dimensional layers showing Borromean interpenetration, Liantonio et al. (2006 ). For very short XBs in the presence of HBs, see: Cametti et al. (2012 ); Gattuso et al. (2007). For a description of the Cambridge Structural Database, see: Allen (2002 ). For van der Waals radii, see Bondi (1964 ).

Experimental

Crystal data

C₂₅H₁₈F₄P⁺·Br⁻·C₂F₄I₂
M_r = 859.09
Triclinic, $[P \overline 1]$
a = 9.6451 (10) Å
b = 10.9491 (12) Å
c = 13.8425 (15) Å
α = 78.07 (2)°
β = 79.08 (2)°
γ = 76.76 (2)°
V = 1376.7 (3) Å³
Z = 2
Mo Kα radiation
μ = 3.87 mm⁻¹
T = 90 K
0.26 × 0.14 × 0.10 mm

Data collection

Bruker SMART APEX CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ) T_min = 0.795, T_max = 1.000
21807 measured reflections
10912 independent reflections
9550 reflections with I > 2σ(I)
R_int = 0.021

Refinement

R[F² > 2σ(F²)] = 0.030
wR(F²) = 0.077
S = 1.04
10912 reflections
424 parameters
153 restraints
All H-atom parameters refined
Δρ_max = 1.33 e Å⁻³
Δρ_min = −0.82 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C19—H19A⋯Br1	0.92 (2)	2.80 (2)	3.6866 (19)	163 (2)
C19—H19B⋯Br1ⁱ	0.92 (2)	2.83 (2)	3.7263 (19)	166 (2)
C16—H16⋯Br1ⁱⁱ	0.94 (1)	2.99 (2)	3.910 (2)	168 (2)
C11—H11⋯Br1ⁱⁱⁱ	0.93 (1)	3.03 (2)	3.725 (2)	133 (2)
Symmetry codes: (i) -x+1, -y+1, -z; (ii) x-1, y+1, z; (iii) x-1, y, z.

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); 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.

Supporting information

CCDC reference: 974492

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536813032522/qk2057sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536813032522/qk2057Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S1600536813032522/qk2057Isup3.cml

checkCIF report

Comment top

We have recently reported how oxyanions (Abate et al., 2011) and chloride, bromide, (Abate et al., 2009) or, more commonly, iodide anions (Metrangolo et al., 2008) are effective acceptors of halogen bonds (XB) when interacting with a variety of XB donors, e.g. di- (Cavallo et al., 2010) or tri-haloperfluorocarbons (Metrangolo et al., 2009), haloimidazolium (Cametti et al., 2012) or halopyridinium (Logothetis et al., 2004) derivatives. In particular, naked halide anions were proven to work as particularly versatile XB acceptors and afforded supramolecular (poly)anions with quite different structures, e.g. discrete adducts (Gattuso et al., 2007), infinite one-dimensional chains (Gattuso et al., 2006), comb-like arrays (Biella et al., 2009), 'ring and stick' one-dimensional chains (Gattuso et al., 2009), and two-dimensional layers showing Borromean interpenetration (Liantonio et al., 2006). In most of these structures, halide anions prefer to work as polydentate XB acceptors also when some H atoms in the cation could work as particularly effective hydrogen bond (HB) donor sites. In the present structure (Fig. 1), the bromide anion forms only one XB despite the composition of the system could allow for the bromide to function as a bidentate XB acceptor. Surprisingly, one iodine atom of TFDIE is not involved in any short contact. The positive phosphorus atom and the tetrafluorophenyl residue promote the acidity of the benzylic H atoms and they are both involved in short, probably strong, HBs with bromide anions, the coordination sphere of which is completed by two long, probably weak, HB interactions with H atoms of the non fluorinated phenyl rings (see Table A). A CSD search (CSD version 5.33; Allen (2002)) of C—I···Br^- interactions shows that the I···Br^- distances observed here (I···Br^- 3.1798 (7) Å) is below the lower quartile of the corresponding dataset (48 hits; mean I···Br^- distance: 3.399 Å; minimum I···Br^- distance: 3.093 Å), thus suggesting it is quite strong. The structural packing (Fig. 2) presents some interesting features. The tetrafluoro-1,2-diiodoethane molecules segregate in channels surrounded by cation molecules and do not show any rotational disorder. All the F atoms are engaged in F···F short contacts and produce an infinite ribbon (Fig. 3) which is anchored to the surrounding cations by H···F and C···F short contacts. Table B reports all the short contacts involving diiodoperfluoroethane molecules.

Related literature top

For a general discussion on halogen bonds (XBs) involving anionic halogen-bonding acceptors, see: for oxyanions, Abate et al. (2011); for chloride and bromide, Abate et al. (2009); for iodide, Metrangolo et al. (2008). For examples of reliable XB donors in an ionic context, see: Cavallo et al. (2010); Metrangolo et al. (2009); Logothetis et al. (2004). For different supramolecular structures of halogen-bonded (poly)anions, see: discrete adducts, Gattuso et al. (2007); infinite chains, Gattuso et al. (2006); comb-like arrays, Biella et al. (2009); 'ring and stick' one-dimensional chains, Gattuso et al. (2009); two-dimensional layers showing Borromean interpenetration, Liantonio et al. (2006). For very short XBs in presence of HBs, see: Cametti et al. (2012); Gattuso et al. (2007). For a description of the Cambridge Structural Database, see: Allen (2002). For van der Waals radii, see Bondi (1964).

Experimental top

In order to prepare the complex, a vial containing a CHCl₃ solution of the two starting components (1:1 molar ratio) was sealed in a wide mouth vessel containg vaseline oil. Slow and isothermal CHCl₃ diffusion furnished good quality crystals.

Structure description top

For a general discussion on halogen bonds (XBs) involving anionic halogen-bonding acceptors, see: for oxyanions, Abate et al. (2011); for chloride and bromide, Abate et al. (2009); for iodide, Metrangolo et al. (2008). For examples of reliable XB donors in an ionic context, see: Cavallo et al. (2010); Metrangolo et al. (2009); Logothetis et al. (2004). For different supramolecular structures of halogen-bonded (poly)anions, see: discrete adducts, Gattuso et al. (2007); infinite chains, Gattuso et al. (2006); comb-like arrays, Biella et al. (2009); 'ring and stick' one-dimensional chains, Gattuso et al. (2009); two-dimensional layers showing Borromean interpenetration, Liantonio et al. (2006). For very short XBs in presence of HBs, see: Cametti et al. (2012); Gattuso et al. (2007). For a description of the Cambridge Structural Database, see: Allen (2002). For van der Waals radii, see Bondi (1964).

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT (Bruker, 2005); 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 (Sheldrick, 2008).

Figures top

	Fig. 1. ORTEP view of the asymmetric unit of the title compound showing displacement ellipsoids at the 50% probability level.
	Fig. 2. Mercury ball and stick plot of the complex viewed along a axis, showing the channels were the TFDIE molecules are segregated. Colour code: carbon, grey; hydrogen, light blue, fluorine, yellow; bromine, light brown and iodine, purple.
	Fig. 3. Mercury ball and stick plot of the complex, showing a part of the infinite chain of diiodotetrafluoro ethane molecules. Black dotted lines represent short intermolecular interactions. Colour code as Figure 2.

Triphenyl(2,3,5,6-tetrafluorobenzyl)phosphonium bromide–1,1,2,2-tetrafluoro-1,2-diiodoethane (1/1) top

Crystal data top

C₂₅H₁₈F₄P⁺·Br⁻·C₂F₄I₂	Z = 2
M_r = 859.09	F(000) = 816
Triclinic, P1	D_x = 2.072 Mg m⁻³
a = 9.6451 (10) Å	Mo Kα radiation, λ = 0.71073 Å
b = 10.9491 (12) Å	Cell parameters from 11010 reflections
c = 13.8425 (15) Å	θ = 2.3–34.3°
α = 78.07 (2)°	µ = 3.87 mm⁻¹
β = 79.08 (2)°	T = 90 K
γ = 76.76 (2)°	Prism, colourless
V = 1376.7 (3) Å³	0.26 × 0.14 × 0.10 mm

Data collection top

Bruker SMART APEX CCD diffractometer	9550 reflections with I > 2σ(I)
ω and φ scans	R_int = 0.021
Absorption correction: multi-scan (SADABS; Bruker, 2005)	θ_max = 34.8°, θ_min = 1.9°
T_min = 0.795, T_max = 1.000	h = −15→15
21807 measured reflections	k = −17→17
10912 independent reflections	l = −21→21

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.030	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.077	All H-atom parameters refined
S = 1.04	w = 1/[σ²(F_o²) + (0.0439P)² + 0.1396P] where P = (F_o² + 2F_c²)/3
10912 reflections	(Δ/σ)_max = 0.002
424 parameters	Δρ_max = 1.33 e Å⁻³
153 restraints	Δρ_min = −0.82 e Å⁻³

Crystal data top

C₂₅H₁₈F₄P⁺·Br⁻·C₂F₄I₂	γ = 76.76 (2)°
M_r = 859.09	V = 1376.7 (3) Å³
Triclinic, P1	Z = 2
a = 9.6451 (10) Å	Mo Kα radiation
b = 10.9491 (12) Å	µ = 3.87 mm⁻¹
c = 13.8425 (15) Å	T = 90 K
α = 78.07 (2)°	0.26 × 0.14 × 0.10 mm
β = 79.08 (2)°

Data collection top

Bruker SMART APEX CCD diffractometer	10912 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	9550 reflections with I > 2σ(I)
T_min = 0.795, T_max = 1.000	R_int = 0.021
21807 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.030	153 restraints
wR(F²) = 0.077	All H-atom parameters refined
S = 1.04	Δρ_max = 1.33 e Å⁻³
10912 reflections	Δρ_min = −0.82 e Å⁻³
424 parameters

Special details top

Experimental. OXFORD low temperature device.

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. H atoms were refined by imposing soft restraint (all C—H distances nearly equal, see _iucr_refine_instructions_details)

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
P1	0.22061 (5)	0.62628 (4)	0.20374 (3)	0.01039 (8)
C1	0.23578 (19)	0.57972 (17)	0.33387 (13)	0.0118 (3)
C2	0.1283 (2)	0.63023 (18)	0.40614 (14)	0.0158 (3)
H2	0.054 (2)	0.6956 (19)	0.3883 (19)	0.024 (7)*
C3	0.1375 (2)	0.5875 (2)	0.50599 (15)	0.0193 (4)
H3	0.065 (2)	0.623 (2)	0.5528 (16)	0.020 (7)*
C4	0.2531 (2)	0.4930 (2)	0.53479 (16)	0.0208 (4)
H4	0.264 (3)	0.464 (3)	0.5999 (12)	0.036 (8)*
C5	0.3586 (2)	0.4403 (2)	0.46351 (16)	0.0199 (4)
H5	0.435 (2)	0.3789 (19)	0.4843 (19)	0.021 (7)*
C6	0.3510 (2)	0.48281 (18)	0.36277 (15)	0.0158 (3)
H6	0.420 (2)	0.446 (2)	0.3162 (14)	0.010 (5)*
C7	0.1505 (2)	0.50892 (17)	0.16526 (14)	0.0134 (3)
C8	0.2253 (2)	0.43955 (19)	0.09166 (16)	0.0194 (4)
H8	0.3168 (17)	0.451 (2)	0.0619 (18)	0.019 (6)*
C9	0.1600 (3)	0.3527 (2)	0.06445 (18)	0.0245 (4)
H9	0.208 (3)	0.308 (2)	0.0141 (16)	0.029 (7)*
C10	0.0227 (3)	0.3377 (2)	0.10923 (17)	0.0227 (4)
H10	−0.029 (3)	0.287 (2)	0.090 (2)	0.029 (7)*
C11	−0.0530 (2)	0.4085 (2)	0.18308 (17)	0.0225 (4)
H11	−0.1430 (19)	0.393 (3)	0.215 (2)	0.035 (8)*
C12	0.0113 (2)	0.4928 (2)	0.21135 (16)	0.0188 (4)
H12	−0.043 (3)	0.542 (2)	0.2572 (16)	0.025 (7)*
C13	0.09467 (19)	0.77405 (16)	0.18385 (13)	0.0116 (3)
C14	0.0966 (2)	0.87510 (18)	0.23130 (15)	0.0157 (3)
H14	0.156 (2)	0.867 (2)	0.2793 (15)	0.015 (6)*
C15	0.0025 (2)	0.99060 (18)	0.20884 (16)	0.0170 (4)
H15	−0.001 (3)	1.0570 (19)	0.2419 (18)	0.023 (7)*
C16	−0.0912 (2)	1.00599 (18)	0.14058 (16)	0.0176 (4)
H16	−0.161 (2)	1.0804 (18)	0.130 (2)	0.027 (7)*
C17	−0.0919 (2)	0.90590 (19)	0.09336 (15)	0.0167 (4)
H17	−0.151 (3)	0.917 (3)	0.0462 (18)	0.038 (8)*
C18	0.0017 (2)	0.79030 (18)	0.11510 (14)	0.0140 (3)
H18	0.001 (3)	0.726 (2)	0.081 (2)	0.033 (8)*
C19	0.39365 (19)	0.64217 (17)	0.12875 (14)	0.0124 (3)
H19A	0.452 (2)	0.5643 (16)	0.1463 (18)	0.019 (6)*
H19B	0.374 (3)	0.657 (2)	0.0643 (12)	0.021 (7)*
C20	0.44941 (18)	0.75023 (17)	0.14995 (13)	0.0117 (3)
C21	0.40228 (19)	0.87529 (18)	0.10587 (14)	0.0138 (3)
F1	0.31174 (12)	0.90025 (11)	0.03855 (9)	0.0172 (2)
C22	0.4469 (2)	0.97554 (18)	0.12931 (15)	0.0170 (4)
F2	0.39219 (14)	1.09432 (11)	0.08625 (10)	0.0231 (3)
C23	0.5442 (2)	0.9558 (2)	0.19465 (16)	0.0195 (4)
H23	0.577 (2)	1.0179 (18)	0.2150 (18)	0.015 (6)*
C24	0.5952 (2)	0.8316 (2)	0.23629 (15)	0.0188 (4)
F3	0.69239 (14)	0.80545 (14)	0.29958 (10)	0.0262 (3)
C25	0.5492 (2)	0.73121 (18)	0.21507 (14)	0.0151 (3)
F4	0.60278 (13)	0.61239 (11)	0.25752 (10)	0.0202 (2)
I1	0.68637 (2)	0.17750 (2)	0.35932 (2)	0.01447 (3)
C26	0.7339 (2)	0.07462 (18)	0.50522 (15)	0.0153 (3)
F5	0.85788 (14)	0.09688 (12)	0.52343 (10)	0.0218 (3)
F6	0.62843 (14)	0.11632 (12)	0.57682 (9)	0.0215 (3)
C27	0.7486 (2)	−0.06934 (19)	0.51369 (15)	0.0163 (3)
F7	0.86111 (13)	−0.11245 (12)	0.44721 (9)	0.0208 (2)
F8	0.63051 (13)	−0.09436 (12)	0.49073 (10)	0.0203 (2)
I2	0.78089 (2)	−0.17193 (2)	0.66122 (2)	0.02326 (4)
Br1	0.61475 (2)	0.31789 (2)	0.14415 (2)	0.01496 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
P1	0.01231 (18)	0.00947 (19)	0.00968 (19)	−0.00121 (14)	−0.00371 (15)	−0.00144 (15)
C1	0.0150 (7)	0.0117 (7)	0.0099 (7)	−0.0031 (6)	−0.0044 (6)	−0.0022 (6)
C2	0.0180 (8)	0.0153 (8)	0.0128 (8)	−0.0005 (6)	−0.0035 (6)	−0.0017 (6)
C3	0.0225 (9)	0.0212 (9)	0.0122 (8)	−0.0002 (7)	−0.0022 (7)	−0.0031 (7)
C4	0.0246 (9)	0.0262 (10)	0.0105 (8)	−0.0030 (8)	−0.0049 (7)	−0.0007 (7)
C5	0.0198 (9)	0.0208 (9)	0.0164 (9)	0.0015 (7)	−0.0064 (7)	0.0002 (7)
C6	0.0160 (8)	0.0152 (8)	0.0154 (8)	−0.0004 (6)	−0.0047 (6)	−0.0015 (7)
C7	0.0172 (8)	0.0111 (7)	0.0131 (8)	−0.0030 (6)	−0.0061 (6)	−0.0009 (6)
C8	0.0193 (9)	0.0180 (9)	0.0234 (10)	−0.0006 (7)	−0.0064 (7)	−0.0095 (8)
C9	0.0304 (11)	0.0173 (9)	0.0296 (12)	−0.0007 (8)	−0.0110 (9)	−0.0116 (8)
C10	0.0351 (11)	0.0161 (9)	0.0223 (10)	−0.0113 (8)	−0.0147 (9)	0.0006 (7)
C11	0.0286 (10)	0.0239 (10)	0.0193 (10)	−0.0164 (8)	−0.0057 (8)	0.0014 (8)
C12	0.0229 (9)	0.0200 (9)	0.0160 (9)	−0.0098 (7)	−0.0017 (7)	−0.0033 (7)
C13	0.0127 (7)	0.0096 (7)	0.0117 (8)	−0.0003 (6)	−0.0023 (6)	−0.0011 (6)
C14	0.0161 (8)	0.0136 (8)	0.0167 (9)	−0.0006 (6)	−0.0033 (7)	−0.0029 (7)
C15	0.0184 (8)	0.0115 (8)	0.0192 (9)	−0.0016 (6)	0.0012 (7)	−0.0036 (7)
C16	0.0140 (8)	0.0129 (8)	0.0210 (9)	0.0013 (6)	0.0005 (7)	0.0009 (7)
C17	0.0142 (8)	0.0174 (9)	0.0165 (9)	−0.0002 (6)	−0.0054 (7)	0.0009 (7)
C18	0.0142 (7)	0.0133 (8)	0.0134 (8)	−0.0003 (6)	−0.0040 (6)	−0.0011 (6)
C19	0.0149 (7)	0.0116 (7)	0.0104 (7)	−0.0011 (6)	−0.0039 (6)	−0.0015 (6)
C20	0.0113 (7)	0.0138 (8)	0.0099 (7)	−0.0019 (6)	−0.0015 (6)	−0.0022 (6)
C21	0.0121 (7)	0.0165 (8)	0.0117 (8)	−0.0024 (6)	−0.0011 (6)	−0.0008 (6)
F1	0.0170 (5)	0.0158 (5)	0.0172 (6)	−0.0012 (4)	−0.0066 (4)	0.0020 (4)
C22	0.0186 (8)	0.0122 (8)	0.0184 (9)	−0.0043 (6)	0.0027 (7)	−0.0024 (7)
F2	0.0276 (6)	0.0126 (5)	0.0264 (7)	−0.0040 (5)	0.0006 (5)	−0.0012 (5)
C23	0.0198 (9)	0.0219 (10)	0.0192 (9)	−0.0099 (7)	0.0036 (7)	−0.0082 (8)
C24	0.0171 (8)	0.0295 (11)	0.0132 (8)	−0.0098 (7)	−0.0034 (7)	−0.0047 (7)
F3	0.0260 (7)	0.0381 (8)	0.0212 (7)	−0.0136 (6)	−0.0116 (5)	−0.0045 (6)
C25	0.0146 (8)	0.0176 (8)	0.0125 (8)	−0.0028 (6)	−0.0031 (6)	−0.0002 (6)
F4	0.0214 (6)	0.0188 (6)	0.0208 (6)	−0.0026 (4)	−0.0123 (5)	0.0029 (5)
I1	0.01472 (6)	0.01475 (6)	0.01311 (6)	−0.00167 (4)	−0.00179 (4)	−0.00214 (4)
C26	0.0162 (8)	0.0151 (8)	0.0141 (8)	−0.0015 (6)	−0.0035 (6)	−0.0020 (6)
F5	0.0232 (6)	0.0217 (6)	0.0248 (7)	−0.0083 (5)	−0.0109 (5)	−0.0026 (5)
F6	0.0267 (6)	0.0208 (6)	0.0135 (6)	0.0010 (5)	0.0009 (5)	−0.0046 (5)
C27	0.0141 (8)	0.0183 (9)	0.0162 (9)	−0.0023 (6)	−0.0024 (6)	−0.0030 (7)
F7	0.0197 (6)	0.0216 (6)	0.0192 (6)	0.0011 (5)	−0.0004 (5)	−0.0071 (5)
F8	0.0206 (6)	0.0190 (6)	0.0241 (6)	−0.0073 (4)	−0.0088 (5)	−0.0010 (5)
I2	0.03227 (8)	0.01838 (7)	0.01800 (7)	−0.00200 (5)	−0.00925 (5)	0.00110 (5)
Br1	0.01754 (8)	0.01333 (8)	0.01289 (8)	0.00093 (6)	−0.00445 (6)	−0.00218 (6)

Geometric parameters (Å, º) top

P1—C7	1.7917 (19)	C14—H14	0.935 (14)
P1—C13	1.7920 (18)	C15—C16	1.388 (3)
P1—C1	1.7922 (19)	C15—H15	0.926 (14)
P1—C19	1.8153 (19)	C16—C17	1.389 (3)
C1—C2	1.398 (3)	C16—H16	0.936 (14)
C1—C6	1.405 (2)	C17—C18	1.389 (3)
C2—C3	1.377 (3)	C17—H17	0.920 (14)
C2—H2	0.920 (14)	C18—H18	0.930 (14)
C3—C4	1.394 (3)	C19—C20	1.507 (3)
C3—H3	0.932 (14)	C19—H19A	0.921 (13)
C4—C5	1.389 (3)	C19—H19B	0.920 (14)
C4—H4	0.909 (14)	C20—C21	1.389 (2)
C5—C6	1.386 (3)	C20—C25	1.394 (3)
C5—H5	0.924 (14)	C21—F1	1.341 (2)
C6—H6	0.919 (13)	C21—C22	1.383 (3)
C7—C8	1.388 (3)	C22—F2	1.345 (2)
C7—C12	1.406 (3)	C22—C23	1.376 (3)
C8—C9	1.399 (3)	C23—C24	1.378 (3)
C8—H8	0.925 (14)	C23—H23	0.922 (13)
C9—C10	1.382 (3)	C24—F3	1.346 (2)
C9—H9	0.924 (14)	C24—C25	1.378 (3)
C10—C11	1.402 (3)	C25—F4	1.340 (2)
C10—H10	0.934 (14)	I1—C26	2.175 (2)
C11—C12	1.375 (3)	C26—F6	1.349 (2)
C11—H11	0.931 (14)	C26—F5	1.351 (2)
C12—H12	0.921 (14)	C26—C27	1.532 (3)
C13—C18	1.386 (3)	C27—F8	1.338 (2)
C13—C14	1.404 (3)	C27—F7	1.347 (2)
C14—C15	1.393 (3)	C27—I2	2.159 (2)

C7—P1—C13	107.23 (9)	C16—C15—C14	120.78 (19)
C7—P1—C1	108.81 (9)	C16—C15—H15	119.1 (17)
C13—P1—C1	109.90 (9)	C14—C15—H15	120.0 (17)
C7—P1—C19	109.70 (9)	C15—C16—C17	120.20 (17)
C13—P1—C19	109.68 (9)	C15—C16—H16	120.9 (17)
C1—P1—C19	111.42 (9)	C17—C16—H16	118.6 (17)
C2—C1—C6	120.18 (17)	C16—C17—C18	119.52 (18)
C2—C1—P1	120.78 (14)	C16—C17—H17	120.2 (18)
C6—C1—P1	118.78 (14)	C18—C17—H17	120.3 (18)
C3—C2—C1	119.93 (17)	C13—C18—C17	120.53 (18)
C3—C2—H2	118.9 (17)	C13—C18—H18	121.8 (18)
C1—C2—H2	121.0 (17)	C17—C18—H18	117.7 (18)
C2—C3—C4	119.94 (18)	C20—C19—P1	111.81 (12)
C2—C3—H3	118.5 (16)	C20—C19—H19A	112.2 (16)
C4—C3—H3	121.6 (16)	P1—C19—H19A	103.6 (16)
C5—C4—C3	120.50 (19)	C20—C19—H19B	111.5 (16)
C5—C4—H4	117 (2)	P1—C19—H19B	103.4 (17)
C3—C4—H4	122 (2)	H19A—C19—H19B	114 (2)
C6—C5—C4	120.15 (18)	C21—C20—C25	116.27 (17)
C6—C5—H5	120.9 (16)	C21—C20—C19	121.35 (16)
C4—C5—H5	119.0 (16)	C25—C20—C19	122.37 (16)
C5—C6—C1	119.28 (18)	F1—C21—C22	118.80 (17)
C5—C6—H6	119.5 (15)	F1—C21—C20	119.61 (17)
C1—C6—H6	121.2 (15)	C22—C21—C20	121.59 (18)
C8—C7—C12	120.72 (18)	F2—C22—C23	120.42 (18)
C8—C7—P1	122.82 (15)	F2—C22—C21	118.00 (19)
C12—C7—P1	116.43 (14)	C23—C22—C21	121.58 (18)
C7—C8—C9	118.7 (2)	C22—C23—C24	117.24 (19)
C7—C8—H8	120.0 (15)	C22—C23—H23	126.3 (15)
C9—C8—H8	121.3 (15)	C24—C23—H23	116.5 (15)
C10—C9—C8	120.5 (2)	F3—C24—C25	118.05 (19)
C10—C9—H9	120.5 (18)	F3—C24—C23	120.27 (19)
C8—C9—H9	119.0 (18)	C25—C24—C23	121.68 (19)
C9—C10—C11	120.7 (2)	F4—C25—C24	119.11 (17)
C9—C10—H10	123.8 (17)	F4—C25—C20	119.30 (17)
C11—C10—H10	115.3 (17)	C24—C25—C20	121.58 (18)
C12—C11—C10	119.2 (2)	F6—C26—F5	107.16 (16)
C12—C11—H11	122.0 (17)	F6—C26—C27	109.03 (16)
C10—C11—H11	118.6 (17)	F5—C26—C27	108.36 (15)
C11—C12—C7	120.16 (19)	F6—C26—I1	109.67 (12)
C11—C12—H12	117.5 (17)	F5—C26—I1	110.37 (13)
C7—C12—H12	122.2 (17)	C27—C26—I1	112.11 (14)
C18—C13—C14	120.25 (16)	F8—C27—F7	107.53 (16)
C18—C13—P1	118.75 (14)	F8—C27—C26	109.93 (16)
C14—C13—P1	120.84 (14)	F7—C27—C26	108.98 (16)
C15—C14—C13	118.72 (18)	F8—C27—I2	108.64 (13)
C15—C14—H14	118.8 (15)	F7—C27—I2	108.96 (12)
C13—C14—H14	122.4 (15)	C26—C27—I2	112.67 (14)

C7—P1—C1—C2	−97.32 (17)	C15—C16—C17—C18	0.1 (3)
C13—P1—C1—C2	19.81 (18)	C14—C13—C18—C17	−0.9 (3)
C19—P1—C1—C2	141.60 (16)	P1—C13—C18—C17	−176.34 (15)
C7—P1—C1—C6	76.88 (17)	C16—C17—C18—C13	0.4 (3)
C13—P1—C1—C6	−165.98 (15)	C7—P1—C19—C20	173.43 (12)
C19—P1—C1—C6	−44.20 (18)	C13—P1—C19—C20	55.90 (15)
C6—C1—C2—C3	1.9 (3)	C1—P1—C19—C20	−66.02 (14)
P1—C1—C2—C3	175.99 (16)	P1—C19—C20—C21	−81.71 (19)
C1—C2—C3—C4	−0.7 (3)	P1—C19—C20—C25	97.62 (18)
C2—C3—C4—C5	−0.7 (3)	C25—C20—C21—F1	176.67 (16)
C3—C4—C5—C6	1.0 (3)	C19—C20—C21—F1	−4.0 (3)
C4—C5—C6—C1	0.2 (3)	C25—C20—C21—C22	−3.0 (3)
C2—C1—C6—C5	−1.6 (3)	C19—C20—C21—C22	176.32 (17)
P1—C1—C6—C5	−175.86 (16)	F1—C21—C22—F2	2.8 (3)
C13—P1—C7—C8	121.66 (17)	C20—C21—C22—F2	−177.53 (16)
C1—P1—C7—C8	−119.51 (17)	F1—C21—C22—C23	−177.31 (17)
C19—P1—C7—C8	2.62 (19)	C20—C21—C22—C23	2.4 (3)
C13—P1—C7—C12	−56.18 (17)	F2—C22—C23—C24	179.70 (17)
C1—P1—C7—C12	62.64 (17)	C21—C22—C23—C24	−0.2 (3)
C19—P1—C7—C12	−175.23 (14)	C22—C23—C24—F3	178.92 (18)
C12—C7—C8—C9	−0.3 (3)	C22—C23—C24—C25	−1.1 (3)
P1—C7—C8—C9	−178.07 (16)	F3—C24—C25—F4	−0.2 (3)
C7—C8—C9—C10	0.9 (3)	C23—C24—C25—F4	179.83 (18)
C8—C9—C10—C11	−0.5 (3)	F3—C24—C25—C20	−179.67 (17)
C9—C10—C11—C12	−0.5 (3)	C23—C24—C25—C20	0.4 (3)
C10—C11—C12—C7	1.1 (3)	C21—C20—C25—F4	−177.76 (16)
C8—C7—C12—C11	−0.7 (3)	C19—C20—C25—F4	2.9 (3)
P1—C7—C12—C11	177.23 (16)	C21—C20—C25—C24	1.7 (3)
C7—P1—C13—C18	−22.55 (18)	C19—C20—C25—C24	−177.67 (17)
C1—P1—C13—C18	−140.67 (15)	F6—C26—C27—F8	67.0 (2)
C19—P1—C13—C18	96.51 (16)	F5—C26—C27—F8	−176.66 (14)
C7—P1—C13—C14	162.02 (15)	I1—C26—C27—F8	−54.61 (18)
C1—P1—C13—C14	43.91 (18)	F6—C26—C27—F7	−175.36 (14)
C19—P1—C13—C14	−78.91 (17)	F5—C26—C27—F7	−59.0 (2)
C18—C13—C14—C15	0.8 (3)	I1—C26—C27—F7	63.01 (18)
P1—C13—C14—C15	176.16 (15)	F6—C26—C27—I2	−54.30 (18)
C13—C14—C15—C16	−0.3 (3)	F5—C26—C27—I2	62.02 (17)
C14—C15—C16—C17	−0.2 (3)	I1—C26—C27—I2	−175.94 (7)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C19—H19A···Br1	0.92 (2)	2.80 (2)	3.6866 (19)	163 (2)
C19—H19B···Br1ⁱ	0.92 (2)	2.83 (2)	3.7263 (19)	166 (2)
C16—H16···Br1ⁱⁱ	0.94 (1)	2.99 (2)	3.910 (2)	168 (2)
C11—H11···Br1ⁱⁱⁱ	0.93 (1)	3.03 (2)	3.725 (2)	133 (2)

Symmetry codes: (i) −x+1, −y+1, −z; (ii) x−1, y+1, z; (iii) x−1, y, z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C19—H19A···Br1	0.921 (19)	2.796 (18)	3.6866 (19)	162.8 (19)
C19—H19B···Br1ⁱ	0.921 (18)	2.825 (16)	3.7263 (19)	166 (2)
C16—H16···Br1ⁱⁱ	0.936 (14)	2.991 (15)	3.910 (2)	168 (2)
C11—H11···Br1ⁱⁱⁱ	0.931 (14)	3.025 (15)	3.725 (2)	133 (2)

Symmetry codes: (i) −x+1, −y+1, −z; (ii) x−1, y+1, z; (iii) x−1, y, z.

Table A. Short H···Br contacts. top

	H···Br	C—H···Br
C19—H19A···Br1	2.797 (15)	163 (2)
C19—H19B···Br1ⁱ	2.826 (15)	167 (2)
C16—H16···Br1ⁱⁱ	2.991 (15)	168 (2)
C11—H11···Br1ⁱⁱⁱ	3.025 (15)	133 (2)

Symmetry codes: (i) 1-x, 1-y, -z; (ii) 1+x, -1+y, z; (iii) 1+x, y, z.

Table B. Contacts below the sum of van der Waals radii^a involving TFDIE. top

	F···Z	C—F···Z
C26—F5···F7ⁱ	2.863 (2)	172.27 (12)
C26—F6···F8ⁱⁱ	2.901 (2)	102.90 (11)
C27—F7···F5ⁱ	2.863 (2)	117.40 (11)
C27—F8···F8ⁱⁱ	2.875 (3)	117.65 (12)
C27—F8···F8ⁱⁱ	2.875 (3)	117.65 (12)
C26—F6···C24ⁱⁱⁱ	3.099 (3)	170.23 (12)
C27—F7···H2^iv	2.62 (2)	148.9 (6)

Note: (a) van der Waals radii from Bondi (1964). Symmetry codes: (i) 2-x, -y, 1-z; (ii) 1-x, -y, 1-z; (iii) 1-x, 1-y, 1-z; (iv) 1+x, -1+y, z.

Acknowledgements

GC, PM, GR and GT acknowledge the Fondazione Cariplo (projects 2009–2550 and 2010–1351) and the "5x1000–2011 project" for financial support.

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