Crystal structure of tetra-butyl-ammonium bromide-1,2-di-iodo-3,4,5,6-tetra-fluoro-benzene-di-chloro-methane (2/2/1).

The crystallization of a 1:1 molar solution of 1,2-di-iodo-3,4,5,6-tetra-fluoro-benzene (o-DITFB) and tetra-butyl-ammonium bromide (n-Bu4NBr) from di-chloro-methane yielded pure white crystals of a halogen-bonded compound, C16H36N(+)·Br(-)·C6F4I2·0.5CH2Cl2 or [(n-Bu4NBr)(o-DITFB)]·0.5CH2Cl2. The compound may be described as a quaternary system and may be classified as a salt-cocrystal solvate. The asymmetric unit contains one mol-ecule of solvent, two o-DITFB mol-ecules, two cations (n-Bu4N(+)) and two crystallographically distinct bromide ions [θI ⋯ Br- ⋯ I = 144.18 (1) and 135.35 (1)°]. The bromide ion is a bidentate halogen-bond acceptor which inter-acts with two covalently bonded iodines (i.e. halogen-bond donors), resulting in a one-dimensional polymeric zigzag chain network approximately along the a axis. The observed short contacts and angles are characteristic of the non-covalent inter-action [d C-I⋯Br = 3.1593 (4)-3.2590 (5) Å; θC-I⋯Br = 174.89 (7) and 178.16 (7)°]. It is noted that iodine acts as both a halogen-bond donor and a weak CH hydrogen-bond acceptor, while the bromide ions act as acceptors for weak CH hydrogen bonds and halogen bonds.

Related literature

The halogen-bonding motif of a polymeric anionic zigzag chain has been described for halogen-bonded compounds of phospho­nium halides and di­iodo­perfluoro­benzenes, see: Abate et al. (2009 ▸). For the structure of o-DITFB, see: Viger-Gravel (2014 ▸) and of n-Bu4NBr, see: Elsegood (2011 ▸). The title compound may be classified as a salt–cocrystal solvate, see: Bond (2012 ▸). For weak hydrogen bonds, see: Desiraju & Steiner (1999 ▸).

Experimental

Crystal data

2C16H36N+·2Br−·2C6F4I2·CH2Cl2

M = 1533.38

Triclinic,

a = 13.1654 (3) Å

b = 15.0483 (3) Å

c = 16.2559 (4) Å

α = 66.668 (1)°

β = 84.654 (1)°

γ = 80.842 (1)°

V = 2917.90 (12) Å3

Z = 2

Mo Kα radiation

μ = 3.65 mm−1

T = 200 K

0.24 × 0.24 × 0.12 mm

Data collection

Bruker APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2005 ▸) T min = 0.534, T max = 0.746

42707 measured reflections

14456 independent reflections

12211 reflections with I > 2σ(I)

R int = 0.022

Refinement

R[F 2 > 2σ(F 2)] = 0.024

wR(F 2) = 0.057

S = 1.02

14456 reflections

568 parameters

H-atom parameters constrained

Δρmax = 0.99 e Å−3

Δρmin = −0.99 e Å−3

Data collection: APEX2, Bruker (2005 ▸); cell refinement: APEX2 and SAINT Bruker (2005 ▸); data reduction: SAINT and XPREP Bruker (2005 ▸); program(s) used to solve structure: SHELXS03 (Sheldrick, 2008 ▸); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2015 ▸); molecular graphics: SHELXTL (Sheldrick, 2008 ▸); software used to prepare material for publication: SHELXTL.

Crystal structure: contains datablock(s) I, New_Global_Publ_Block. DOI: 10.1107/S2056989015006593/gw2150sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015006593/gw2150Isup2.hkl

Click here for additional data file.

n 4 o 2 2 . DOI: 10.1107/S2056989015006593/gw2150fig1.tif

Halogen bonding environment of [(n-Bu4NBr)(o-DITFB)]·CH2Cl2, where iodine is in purple, carbon in black, fluorine in green, and bromine in orange.

Click here for additional data file.

a b c x x n 4 o 2 2 b b c n 4 + . DOI: 10.1107/S2056989015006593/gw2150fig2.tif

(a) Detail of crystal structure showing selected weak hydrogen bond contacts to bromide and to iodine. (b, c) 2 x 2 x 2 supercell of [(n-Bu4NBr)(o-DITFB)]·CH2Cl2 viewed along the b axis where in (b) the cation is present and in (c) is absent to clarify the image. Rows of the polymeric bromide anionic chains are separated by n-Bu4N+ cations. Hydrogen atoms are not shown for clarity, iodine is in purple, carbon in black, fluorine in green, bromine in orange, and chlorine in blue.

CCDC reference: 1057419

Additional supporting information: crystallographic information; 3D view; checkCIF report

2C16H36N+·2Br−·2C6F4I2·CH2Cl2	Z = 2
Mr = 1533.38	F(000) = 1492
Triclinic, P1	Dx = 1.745 Mg m−3
a = 13.1654 (3) Å	Mo Kα radiation, λ = 0.71073 Å
b = 15.0483 (3) Å	Cell parameters from 9968 reflections
c = 16.2559 (4) Å	θ = 2.8–28.3°
α = 66.668 (1)°	µ = 3.65 mm−1
β = 84.654 (1)°	T = 200 K
γ = 80.842 (1)°	Block, colourless
V = 2917.90 (12) Å3	0.24 × 0.24 × 0.12 mm

Bruker APEXII CCD diffractometer	12211 reflections with I > 2σ(I)
φ and ω scans	Rint = 0.022
Absorption correction: multi-scan (SADABS; Bruker, 2009)	θmax = 28.4°, θmin = 2.0°
Tmin = 0.534, Tmax = 0.746	h = −17→17
42707 measured reflections	k = −20→20
14456 independent reflections	l = −21→21

Refinement on F2	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.024	H-atom parameters constrained
wR(F2) = 0.057	w = 1/[σ2(Fo2) + (0.0216P)2 + 2.2414P] where P = (Fo2 + 2Fc2)/3
S = 1.02	(Δ/σ)max = 0.002
14456 reflections	Δρmax = 0.99 e Å−3
568 parameters	Δρmin = −0.98 e Å−3

Experimental. Data collection is performed with four batch runs at phi = 0.00 ° (600 frames), at phi = 90.00 ° (600 frames), at phi = 180.00 ° (600 frames), and at phi = 270.00 ° (600 frames). A fifth batch run is collected at phi = 0.00 ° (50 frames) to monitor crystal and diffractometer stability. Frame width = 0.30 ° in omega. Data is merged, corrected for decay (if any), and treated with multi-scan absorption corrections (if required). All symmetry-equivalent reflections are merged for centrosymmetric data. Friedel pairs are not merged for noncentrosymmetric data.

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.

	x	y	z	Uiso*/Ueq
I1	0.24735 (2)	0.72180 (2)	0.14178 (2)	0.04521 (5)
I2	0.01151 (2)	0.59950 (2)	0.19674 (2)	0.03492 (4)
I3	0.70784 (2)	−0.18215 (2)	0.37143 (2)	0.03702 (4)
I4	0.44346 (2)	−0.05201 (2)	0.31053 (2)	0.03407 (4)
Br1	0.28482 (2)	0.88557 (2)	0.21586 (2)	0.04897 (7)
Br2	0.81851 (2)	0.63216 (2)	0.32589 (2)	0.03880 (6)
F1	0.03880 (12)	0.46121 (11)	0.09146 (11)	0.0500 (4)
F2	0.17634 (14)	0.43539 (12)	−0.03182 (12)	0.0566 (4)
F3	0.34622 (15)	0.52720 (15)	−0.07434 (13)	0.0693 (5)
F4	0.37602 (14)	0.64816 (16)	0.00315 (14)	0.0698 (5)
F5	0.42205 (13)	0.12714 (11)	0.36785 (11)	0.0526 (4)
F6	0.55057 (16)	0.19756 (12)	0.43805 (12)	0.0635 (5)
F7	0.74257 (15)	0.10137 (13)	0.48392 (12)	0.0594 (5)
F8	0.80628 (12)	−0.06286 (13)	0.45697 (12)	0.0572 (4)
N1	0.91649 (15)	0.31256 (13)	0.48925 (12)	0.0302 (4)
N2	0.68646 (16)	0.83381 (15)	0.02856 (14)	0.0387 (5)
C1	0.2196 (2)	0.62142 (19)	0.08822 (17)	0.0392 (5)
C2	0.13221 (19)	0.57390 (17)	0.11037 (16)	0.0350 (5)
C3	0.12048 (19)	0.51035 (18)	0.07065 (17)	0.0383 (5)
C4	0.1907 (2)	0.49549 (19)	0.00793 (18)	0.0429 (6)
C5	0.2762 (2)	0.5427 (2)	−0.01434 (19)	0.0483 (6)
C6	0.2901 (2)	0.6044 (2)	0.02608 (19)	0.0468 (6)
C7	0.54822 (19)	−0.00556 (17)	0.37100 (15)	0.0329 (5)
C8	0.64711 (19)	−0.05500 (17)	0.39466 (15)	0.0334 (5)
C9	0.7104 (2)	−0.01755 (19)	0.43258 (18)	0.0408 (6)
C10	0.6785 (2)	0.06638 (19)	0.44735 (17)	0.0438 (6)
C11	0.5823 (2)	0.11516 (18)	0.42431 (17)	0.0437 (6)
C12	0.5173 (2)	0.07841 (17)	0.38746 (16)	0.0385 (5)
C13	0.94820 (19)	0.21590 (16)	0.56604 (16)	0.0336 (5)
H13A	1.0118	0.1833	0.5469	0.040*
H13B	0.8937	0.1738	0.5766	0.040*
C14	0.9674 (2)	0.22143 (17)	0.65406 (17)	0.0369 (5)
H14A	0.9033	0.2498	0.6766	0.044*
H14B	1.0207	0.2644	0.6449	0.044*
C15	1.0030 (2)	0.11948 (17)	0.72286 (17)	0.0389 (5)
H15A	0.9492	0.0770	0.7321	0.047*
H15B	1.0663	0.0910	0.6995	0.047*
C16	1.0244 (2)	0.1222 (2)	0.81190 (19)	0.0517 (7)
H16A	1.0463	0.0557	0.8546	0.077*
H16B	0.9617	0.1500	0.8354	0.077*
H16C	1.0791	0.1626	0.8033	0.077*
C17	0.81947 (19)	0.36712 (16)	0.51409 (16)	0.0339 (5)
H17A	0.8322	0.3769	0.5688	0.041*
H17B	0.8065	0.4325	0.4653	0.041*
C18	0.7229 (2)	0.31889 (19)	0.53080 (19)	0.0430 (6)
H18A	0.7310	0.2568	0.5842	0.052*
H18B	0.7115	0.3038	0.4786	0.052*
C19	0.6312 (2)	0.3865 (2)	0.5458 (2)	0.0548 (7)
H19A	0.6358	0.3885	0.6054	0.066*
H19B	0.6347	0.4533	0.5002	0.066*
C20	0.5300 (2)	0.3569 (2)	0.5408 (3)	0.0623 (8)
H20A	0.4745	0.4035	0.5510	0.093*
H20B	0.5251	0.2915	0.5867	0.093*
H20C	0.5240	0.3564	0.4814	0.093*
C21	0.99919 (19)	0.38009 (17)	0.46600 (16)	0.0351 (5)
H21A	0.9698	0.4457	0.4245	0.042*
H21B	1.0157	0.3861	0.5216	0.042*
C22	1.0985 (2)	0.34942 (19)	0.42390 (18)	0.0403 (6)
H22A	1.1265	0.2818	0.4621	0.048*
H22B	1.0851	0.3508	0.3644	0.048*
C23	1.1766 (2)	0.4183 (2)	0.41343 (18)	0.0458 (6)
H23A	1.1958	0.4106	0.4736	0.055*
H23B	1.1446	0.4865	0.3822	0.055*
C24	1.2730 (3)	0.3988 (3)	0.3611 (3)	0.0737 (10)
H24A	1.3207	0.4447	0.3559	0.111*
H24B	1.2546	0.4074	0.3011	0.111*
H24C	1.3060	0.3318	0.3925	0.111*
C25	0.89861 (19)	0.28809 (17)	0.41017 (15)	0.0336 (5)
H25A	0.9643	0.2562	0.3934	0.040*
H25B	0.8488	0.2402	0.4293	0.040*
C26	0.8586 (2)	0.37464 (19)	0.32801 (17)	0.0445 (6)
H26A	0.9047	0.4255	0.3113	0.053*
H26B	0.7894	0.4028	0.3422	0.053*
C27	0.8526 (3)	0.3456 (2)	0.24908 (19)	0.0537 (7)
H27A	0.8369	0.4056	0.1948	0.064*
H27B	0.9209	0.3127	0.2386	0.064*
C28	0.7739 (4)	0.2797 (3)	0.2609 (2)	0.0872 (14)
H28A	0.7751	0.2644	0.2075	0.131*
H28B	0.7054	0.3123	0.2693	0.131*
H28C	0.7895	0.2191	0.3136	0.131*
C29	0.6285 (2)	0.8347 (2)	−0.04838 (18)	0.0444 (6)
H29A	0.5544	0.8540	−0.0384	0.053*
H29B	0.6514	0.8860	−0.1043	0.053*
C30	0.6398 (2)	0.7404 (2)	−0.06305 (18)	0.0450 (6)
H30A	0.6202	0.6872	−0.0072	0.054*
H30B	0.7124	0.7228	−0.0790	0.054*
C31	0.5710 (2)	0.7528 (2)	−0.13814 (19)	0.0513 (7)
H31A	0.4987	0.7708	−0.1215	0.062*
H31B	0.5903	0.8072	−0.1932	0.062*
C32	0.5780 (3)	0.6617 (3)	−0.1580 (2)	0.0667 (9)
H32A	0.5316	0.6739	−0.2062	0.100*
H32B	0.5582	0.6076	−0.1040	0.100*
H32C	0.6489	0.6447	−0.1768	0.100*
C33	0.80217 (19)	0.81006 (19)	0.01584 (18)	0.0413 (6)
H33A	0.8166	0.7431	0.0168	0.050*
H33B	0.8360	0.8098	0.0678	0.050*
C34	0.8511 (2)	0.8777 (2)	−0.0685 (2)	0.0566 (8)
H34A	0.8227	0.8742	−0.1213	0.068*
H34B	0.8340	0.9457	−0.0723	0.068*
C35	0.9686 (2)	0.8509 (2)	−0.0705 (3)	0.0621 (8)
H35A	0.9985	0.9031	−0.1214	0.075*
H35B	0.9956	0.8485	−0.0146	0.075*
C36	1.0036 (3)	0.7566 (3)	−0.0790 (2)	0.0651 (9)
H36A	1.0789	0.7439	−0.0787	0.098*
H36B	0.9800	0.7591	−0.1355	0.098*
H36C	0.9749	0.7042	−0.0287	0.098*
C37	0.6580 (2)	0.93582 (19)	0.02917 (18)	0.0426 (6)
H37A	0.6677	0.9840	−0.0326	0.051*
H37B	0.5839	0.9442	0.0458	0.051*
C38	0.7171 (2)	0.9601 (2)	0.0910 (2)	0.0497 (7)
H38A	0.7891	0.9661	0.0679	0.060*
H38B	0.7184	0.9069	0.1513	0.060*
C39	0.6675 (2)	1.0547 (2)	0.0975 (2)	0.0508 (7)
H39A	0.6566	1.1049	0.0362	0.061*
H39B	0.5991	1.0451	0.1281	0.061*
C40	0.7296 (3)	1.0921 (3)	0.1474 (3)	0.0656 (9)
H40A	0.6921	1.1525	0.1505	0.098*
H40B	0.7961	1.1053	0.1158	0.098*
H40C	0.7409	1.0429	0.2082	0.098*
C41	0.6578 (2)	0.7557 (2)	0.11715 (17)	0.0447 (6)
H41A	0.6830	0.6911	0.1149	0.054*
H41B	0.6947	0.7609	0.1651	0.054*
C42	0.5454 (2)	0.7588 (3)	0.1429 (2)	0.0557 (8)
H42A	0.5070	0.7522	0.0965	0.067*
H42B	0.5187	0.8224	0.1469	0.067*
C43	0.5291 (3)	0.6755 (3)	0.2335 (2)	0.0658 (9)
H43A	0.5746	0.6788	0.2772	0.079*
H43B	0.4572	0.6863	0.2549	0.079*
C44	0.5493 (4)	0.5770 (3)	0.2329 (3)	0.1005 (15)
H44A	0.5379	0.5288	0.2936	0.151*
H44B	0.6207	0.5647	0.2129	0.151*
H44C	0.5026	0.5717	0.1920	0.151*
C45	0.8462 (3)	0.9249 (3)	0.6717 (3)	0.0774 (11)
H45A	0.8378	0.9523	0.7185	0.093*
H45B	0.7938	0.9625	0.6264	0.093*
Cl1	0.96601 (9)	0.93975 (8)	0.62159 (9)	0.0951 (4)
Cl2	0.82419 (9)	0.80409 (9)	0.71994 (8)	0.0888 (3)

	U11	U22	U33	U12	U13	U23
I1	0.03980 (9)	0.05145 (10)	0.05094 (10)	−0.01695 (7)	0.00179 (7)	−0.02342 (8)
I2	0.03671 (8)	0.03464 (8)	0.03288 (8)	−0.00851 (6)	0.00126 (6)	−0.01166 (6)
I3	0.03450 (8)	0.03702 (8)	0.04262 (9)	−0.00278 (6)	−0.00354 (6)	−0.01896 (7)
I4	0.03396 (8)	0.03321 (7)	0.03537 (8)	−0.00373 (6)	−0.00246 (6)	−0.01365 (6)
Br1	0.04762 (15)	0.04415 (14)	0.05824 (17)	−0.00928 (12)	−0.01439 (13)	−0.01921 (13)
Br2	0.04265 (14)	0.03591 (12)	0.03926 (13)	−0.00107 (10)	−0.00096 (10)	−0.01773 (10)
F1	0.0502 (9)	0.0472 (9)	0.0607 (10)	−0.0161 (7)	0.0022 (8)	−0.0267 (8)
F2	0.0659 (11)	0.0518 (9)	0.0629 (11)	0.0038 (8)	−0.0069 (9)	−0.0369 (9)
F3	0.0623 (12)	0.0857 (14)	0.0656 (12)	−0.0023 (10)	0.0197 (9)	−0.0428 (11)
F4	0.0482 (10)	0.0924 (14)	0.0811 (13)	−0.0296 (10)	0.0273 (9)	−0.0455 (12)
F5	0.0615 (10)	0.0444 (8)	0.0529 (10)	0.0109 (7)	−0.0088 (8)	−0.0251 (7)
F6	0.1002 (15)	0.0406 (9)	0.0601 (11)	−0.0073 (9)	−0.0051 (10)	−0.0307 (8)
F7	0.0777 (12)	0.0600 (10)	0.0569 (10)	−0.0328 (9)	−0.0055 (9)	−0.0305 (9)
F8	0.0427 (9)	0.0709 (11)	0.0721 (12)	−0.0089 (8)	−0.0122 (8)	−0.0397 (10)
N1	0.0384 (11)	0.0249 (8)	0.0298 (10)	−0.0065 (8)	0.0003 (8)	−0.0128 (7)
N2	0.0352 (11)	0.0435 (11)	0.0329 (11)	0.0073 (9)	−0.0077 (8)	−0.0135 (9)
C1	0.0386 (13)	0.0418 (13)	0.0379 (13)	−0.0072 (10)	−0.0002 (10)	−0.0156 (11)
C2	0.0347 (12)	0.0338 (11)	0.0327 (12)	−0.0040 (9)	0.0000 (10)	−0.0094 (10)
C3	0.0371 (13)	0.0334 (12)	0.0420 (14)	−0.0015 (10)	−0.0053 (11)	−0.0126 (10)
C4	0.0492 (15)	0.0374 (13)	0.0424 (14)	0.0044 (11)	−0.0077 (12)	−0.0182 (11)
C5	0.0466 (16)	0.0520 (16)	0.0424 (15)	0.0030 (12)	0.0055 (12)	−0.0194 (13)
C6	0.0385 (14)	0.0522 (16)	0.0479 (16)	−0.0098 (12)	0.0067 (12)	−0.0180 (13)
C7	0.0398 (13)	0.0323 (11)	0.0285 (11)	−0.0077 (10)	0.0013 (9)	−0.0133 (9)
C8	0.0393 (13)	0.0325 (11)	0.0315 (12)	−0.0092 (10)	0.0016 (10)	−0.0148 (9)
C9	0.0413 (14)	0.0446 (14)	0.0391 (13)	−0.0116 (11)	0.0003 (11)	−0.0172 (11)
C10	0.0611 (17)	0.0429 (14)	0.0353 (13)	−0.0238 (13)	0.0012 (12)	−0.0179 (11)
C11	0.0699 (19)	0.0314 (12)	0.0328 (13)	−0.0113 (12)	0.0031 (12)	−0.0151 (10)
C12	0.0497 (15)	0.0326 (12)	0.0309 (12)	−0.0029 (11)	0.0011 (10)	−0.0115 (10)
C13	0.0415 (13)	0.0232 (10)	0.0360 (12)	−0.0028 (9)	−0.0038 (10)	−0.0114 (9)
C14	0.0420 (13)	0.0288 (11)	0.0397 (13)	−0.0023 (10)	−0.0081 (11)	−0.0126 (10)
C15	0.0375 (13)	0.0316 (11)	0.0444 (14)	−0.0035 (10)	−0.0056 (11)	−0.0109 (10)
C16	0.0633 (19)	0.0399 (14)	0.0478 (16)	0.0004 (13)	−0.0224 (14)	−0.0111 (12)
C17	0.0430 (13)	0.0269 (10)	0.0333 (12)	−0.0016 (9)	0.0005 (10)	−0.0146 (9)
C18	0.0451 (15)	0.0359 (12)	0.0485 (15)	−0.0038 (11)	0.0050 (12)	−0.0188 (11)
C19	0.0519 (17)	0.0463 (15)	0.0639 (19)	−0.0016 (13)	0.0139 (14)	−0.0242 (14)
C20	0.0519 (18)	0.0566 (18)	0.076 (2)	0.0023 (14)	0.0054 (16)	−0.0281 (17)
C21	0.0461 (14)	0.0296 (11)	0.0352 (12)	−0.0133 (10)	0.0016 (10)	−0.0161 (10)
C22	0.0419 (14)	0.0409 (13)	0.0433 (14)	−0.0118 (11)	−0.0003 (11)	−0.0194 (11)
C23	0.0490 (16)	0.0524 (15)	0.0399 (14)	−0.0205 (13)	−0.0037 (12)	−0.0166 (12)
C24	0.056 (2)	0.100 (3)	0.074 (2)	−0.034 (2)	0.0123 (17)	−0.038 (2)
C25	0.0423 (13)	0.0328 (11)	0.0325 (12)	−0.0110 (10)	0.0009 (10)	−0.0181 (10)
C26	0.0639 (18)	0.0395 (13)	0.0329 (13)	−0.0169 (12)	−0.0028 (12)	−0.0131 (11)
C27	0.072 (2)	0.0612 (18)	0.0331 (14)	−0.0214 (16)	0.0030 (13)	−0.0207 (13)
C28	0.132 (4)	0.093 (3)	0.053 (2)	−0.062 (3)	−0.013 (2)	−0.026 (2)
C29	0.0418 (14)	0.0528 (15)	0.0347 (13)	0.0069 (12)	−0.0113 (11)	−0.0157 (12)
C30	0.0450 (15)	0.0517 (15)	0.0356 (13)	0.0007 (12)	−0.0046 (11)	−0.0161 (12)
C31	0.0551 (17)	0.0572 (17)	0.0408 (15)	−0.0060 (14)	−0.0102 (13)	−0.0169 (13)
C32	0.075 (2)	0.075 (2)	0.062 (2)	−0.0110 (18)	−0.0065 (17)	−0.0371 (18)
C33	0.0327 (13)	0.0423 (13)	0.0429 (14)	0.0074 (10)	−0.0051 (11)	−0.0140 (11)
C34	0.0508 (17)	0.0497 (16)	0.0546 (18)	0.0076 (13)	0.0063 (14)	−0.0119 (14)
C35	0.0478 (17)	0.0564 (18)	0.076 (2)	−0.0086 (14)	0.0156 (16)	−0.0225 (17)
C36	0.056 (2)	0.068 (2)	0.063 (2)	0.0088 (16)	0.0014 (16)	−0.0234 (17)
C37	0.0373 (13)	0.0464 (14)	0.0414 (14)	0.0091 (11)	−0.0077 (11)	−0.0183 (12)
C38	0.0478 (16)	0.0523 (16)	0.0492 (16)	0.0066 (13)	−0.0120 (13)	−0.0226 (13)
C39	0.0463 (16)	0.0487 (15)	0.0551 (17)	−0.0009 (12)	0.0016 (13)	−0.0206 (13)
C40	0.066 (2)	0.0583 (19)	0.080 (2)	−0.0045 (16)	−0.0077 (18)	−0.0354 (18)
C41	0.0383 (14)	0.0573 (16)	0.0324 (13)	−0.0026 (12)	−0.0042 (10)	−0.0119 (12)
C42	0.0429 (16)	0.074 (2)	0.0429 (16)	−0.0010 (14)	0.0027 (12)	−0.0188 (15)
C43	0.0457 (18)	0.102 (3)	0.0432 (17)	−0.0143 (18)	0.0068 (13)	−0.0208 (18)
C44	0.089 (3)	0.089 (3)	0.095 (3)	−0.019 (2)	0.030 (3)	−0.010 (3)
C45	0.096 (3)	0.073 (2)	0.057 (2)	0.016 (2)	0.0007 (19)	−0.0295 (18)
Cl1	0.0980 (8)	0.0768 (6)	0.1320 (10)	−0.0225 (6)	0.0321 (7)	−0.0670 (7)
Cl2	0.0813 (7)	0.1009 (8)	0.1077 (8)	−0.0284 (6)	0.0117 (6)	−0.0625 (7)

I1—C1	2.109 (3)	C9—C10	1.372 (4)
I2—C2	2.112 (2)	C10—C11	1.362 (4)
I3—C8	2.115 (2)	C11—C12	1.381 (4)
I4—C7	2.112 (2)	C13—C14	1.512 (3)
F1—C3	1.344 (3)	C14—C15	1.528 (3)
F2—C4	1.346 (3)	C15—C16	1.517 (4)
F3—C5	1.342 (3)	C17—C18	1.513 (4)
F4—C6	1.348 (3)	C18—C19	1.517 (4)
F5—C12	1.345 (3)	C19—C20	1.489 (4)
F6—C11	1.341 (3)	C21—C22	1.510 (4)
F7—C10	1.351 (3)	C22—C23	1.526 (3)
F8—C9	1.349 (3)	C23—C24	1.515 (4)
N1—C17	1.517 (3)	C25—C26	1.514 (3)
N1—C13	1.521 (3)	C26—C27	1.522 (4)
N1—C25	1.517 (3)	C27—C28	1.495 (4)
N1—C21	1.527 (3)	C29—C30	1.512 (4)
N2—C33	1.522 (3)	C30—C31	1.522 (4)
N2—C29	1.520 (3)	C31—C32	1.515 (4)
N2—C41	1.516 (3)	C33—C34	1.507 (4)
N2—C37	1.525 (3)	C34—C35	1.537 (4)
C1—C6	1.379 (4)	C35—C36	1.477 (5)
C1—C2	1.395 (3)	C37—C38	1.509 (4)
C2—C3	1.382 (3)	C38—C39	1.508 (4)
C3—C4	1.372 (4)	C39—C40	1.508 (4)
C4—C5	1.371 (4)	C41—C42	1.499 (4)
C5—C6	1.373 (4)	C42—C43	1.534 (4)
C7—C12	1.385 (3)	C43—C44	1.468 (6)
C7—C8	1.398 (3)	C45—Cl2	1.733 (4)
C8—C9	1.383 (3)	C45—Cl1	1.711 (4)
C17—N1—C13	111.15 (18)	F8—C9—C8	121.0 (2)
C17—N1—C25	110.59 (18)	C10—C9—C8	121.7 (3)
C13—N1—C25	106.52 (16)	C11—C10—C9	120.0 (2)
C17—N1—C21	106.23 (17)	C11—C10—F7	119.9 (2)
C13—N1—C21	111.40 (18)	C9—C10—F7	120.1 (3)
C25—N1—C21	111.01 (17)	F6—C11—C10	120.5 (2)
C33—N2—C29	111.5 (2)	F6—C11—C12	120.2 (3)
C33—N2—C41	105.38 (18)	C10—C11—C12	119.3 (2)
C29—N2—C41	111.8 (2)	F5—C12—C7	120.7 (2)
C33—N2—C37	111.4 (2)	F5—C12—C11	117.6 (2)
C29—N2—C37	105.28 (18)	C7—C12—C11	121.7 (2)
C41—N2—C37	111.6 (2)	N1—C13—C14	116.31 (18)
C6—C1—C2	118.5 (2)	C13—C14—C15	110.04 (19)
C6—C1—I1	118.13 (19)	C16—C15—C14	111.6 (2)
C2—C1—I1	123.34 (19)	C18—C17—N1	116.13 (18)
C3—C2—C1	118.9 (2)	C17—C18—C19	109.8 (2)
C3—C2—I2	117.59 (18)	C20—C19—C18	113.7 (3)
C1—C2—I2	123.40 (18)	C22—C21—N1	116.31 (18)
F1—C3—C2	121.0 (2)	C23—C22—C21	110.0 (2)
F1—C3—C4	117.2 (2)	C22—C23—C24	112.3 (3)
C2—C3—C4	121.7 (2)	C26—C25—N1	114.90 (19)
F2—C4—C5	119.9 (2)	C25—C26—C27	111.6 (2)
F2—C4—C3	120.8 (3)	C28—C27—C26	114.6 (3)
C5—C4—C3	119.3 (2)	C30—C29—N2	116.9 (2)
F3—C5—C4	119.8 (3)	C29—C30—C31	109.6 (2)
F3—C5—C6	120.7 (3)	C32—C31—C30	113.3 (3)
C4—C5—C6	119.6 (3)	N2—C33—C34	116.3 (2)
F4—C6—C5	117.6 (3)	C35—C34—C33	111.4 (2)
F4—C6—C1	120.5 (3)	C36—C35—C34	114.1 (3)
C5—C6—C1	121.9 (3)	C38—C37—N2	116.5 (2)
C12—C7—C8	118.6 (2)	C37—C38—C39	110.2 (2)
C12—C7—I4	118.16 (18)	C40—C39—C38	113.8 (3)
C8—C7—I4	123.29 (17)	C42—C41—N2	116.1 (2)
C9—C8—C7	118.7 (2)	C41—C42—C43	109.7 (2)
C9—C8—I3	117.76 (19)	C44—C43—C42	115.3 (3)
C7—C8—I3	123.47 (16)	Cl2—C45—Cl1	113.4 (2)
F8—C9—C10	117.4 (2)
C6—C1—C2—C3	1.2 (4)	F6—C11—C12—F5	−1.1 (4)
I1—C1—C2—C3	179.13 (18)	C10—C11—C12—F5	178.2 (2)
C6—C1—C2—I2	−175.3 (2)	F6—C11—C12—C7	178.9 (2)
I1—C1—C2—I2	2.6 (3)	C10—C11—C12—C7	−1.8 (4)
C1—C2—C3—F1	178.4 (2)	C17—N1—C13—C14	−57.7 (3)
I2—C2—C3—F1	−4.8 (3)	C25—N1—C13—C14	−178.2 (2)
C1—C2—C3—C4	−2.3 (4)	C21—N1—C13—C14	60.6 (3)
I2—C2—C3—C4	174.47 (19)	N1—C13—C14—C15	−177.5 (2)
F1—C3—C4—F2	1.2 (4)	C13—C14—C15—C16	179.3 (2)
C2—C3—C4—F2	−178.1 (2)	C13—N1—C17—C18	−64.7 (3)
F1—C3—C4—C5	−178.9 (2)	C25—N1—C17—C18	53.4 (3)
C2—C3—C4—C5	1.8 (4)	C21—N1—C17—C18	173.9 (2)
F2—C4—C5—F3	−1.4 (4)	N1—C17—C18—C19	−174.5 (2)
C3—C4—C5—F3	178.7 (2)	C17—C18—C19—C20	166.0 (3)
F2—C4—C5—C6	179.6 (2)	C17—N1—C21—C22	−170.0 (2)
C3—C4—C5—C6	−0.3 (4)	C13—N1—C21—C22	68.8 (3)
F3—C5—C6—F4	0.0 (4)	C25—N1—C21—C22	−49.7 (3)
C4—C5—C6—F4	179.0 (3)	N1—C21—C22—C23	−174.3 (2)
F3—C5—C6—C1	−179.8 (3)	C21—C22—C23—C24	−172.9 (3)
C4—C5—C6—C1	−0.8 (4)	C17—N1—C25—C26	54.9 (3)
C2—C1—C6—F4	−179.5 (2)	C13—N1—C25—C26	175.8 (2)
I1—C1—C6—F4	2.4 (4)	C21—N1—C25—C26	−62.8 (3)
C2—C1—C6—C5	0.3 (4)	N1—C25—C26—C27	174.5 (2)
I1—C1—C6—C5	−177.8 (2)	C25—C26—C27—C28	67.3 (4)
C12—C7—C8—C9	−0.7 (3)	C33—N2—C29—C30	61.0 (3)
I4—C7—C8—C9	178.92 (18)	C41—N2—C29—C30	−56.7 (3)
C12—C7—C8—I3	−178.46 (17)	C37—N2—C29—C30	−178.1 (2)
I4—C7—C8—I3	1.2 (3)	N2—C29—C30—C31	176.1 (2)
C7—C8—C9—F8	179.7 (2)	C29—C30—C31—C32	179.5 (3)
I3—C8—C9—F8	−2.5 (3)	C29—N2—C33—C34	58.5 (3)
C7—C8—C9—C10	0.0 (4)	C41—N2—C33—C34	−180.0 (2)
I3—C8—C9—C10	177.9 (2)	C37—N2—C33—C34	−58.8 (3)
F8—C9—C10—C11	−179.8 (2)	N2—C33—C34—C35	175.8 (3)
C8—C9—C10—C11	−0.2 (4)	C33—C34—C35—C36	67.8 (4)
F8—C9—C10—F7	0.8 (4)	C33—N2—C37—C38	−50.4 (3)
C8—C9—C10—F7	−179.5 (2)	C29—N2—C37—C38	−171.4 (2)
C9—C10—C11—F6	−179.7 (2)	C41—N2—C37—C38	67.1 (3)
F7—C10—C11—F6	−0.3 (4)	N2—C37—C38—C39	−169.2 (2)
C9—C10—C11—C12	1.0 (4)	C37—C38—C39—C40	−171.8 (3)
F7—C10—C11—C12	−179.6 (2)	C33—N2—C41—C42	−176.2 (3)
C8—C7—C12—F5	−178.4 (2)	C29—N2—C41—C42	−54.9 (3)
I4—C7—C12—F5	2.0 (3)	C37—N2—C41—C42	62.7 (3)
C8—C7—C12—C11	1.6 (4)	N2—C41—C42—C43	180.0 (3)
I4—C7—C12—C11	−178.04 (19)	C41—C42—C43—C44	−69.2 (4)

Table 1

Contacts below the sum of the van der Waals radii involving DITFB (, )

CXH	XH	CXH
C30F2H30B i	2.6538(15)	120.189(17)
C33F2H33A i	2.8610(19)	170.331(18)
C31F5H31B i	2.6222(17)	140.526(17)
C25F7H25B	2.518(2)	172.421(16)
C45F7H45B ii	2.4890(15)	149.87(3)
C26I2H26A iii	3.0204(3)	115.88(7)

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

Table 2

Halogen-bond geometry (, )

CX Y	X Y	CX Y	Y X Y	Y X Y
C1I1Br1	3.2582(5)	177.15(8)	I1Br1I4	144.180(13)
C2I4Br1iv	3.1593(4)	178.16(7)
C1I2Br2iii	3.2452(4)	176.83(7)	I3Br2I2	134.350(12)
C2I3Br2v	3.2590(5)	174.89(7)

Symmetry codes: (iv) x, 1+y, z; (iii) 1+x, y,z; (v) x, 1+y, z.