Crystal structure of tetra-ethyl-ammonium chloride 3,4,5,6-tetra-fluoro-1,2-di-iodo-benzene.

Equimolar qu-anti-ties of tetra-ethyl-ammonium chloride (Et4NCl) and 3,4,5,6-tetra-fluoro-1,2-di-iodo-benzene (o-DITFB or o-C6F4I2) have been co-crystallized in a solution of di-chloro-methane yielding a pure halogen-bonded compound, 3,4,5,6-tetra-fluoro-1,2-di-iodo-benzene-tetra-ethyl ammonium chloride (2/1), Et4N(+)·Cl(-)·2C6F4I2, in the form of translucent needles. [(Et4NCl)(o-C6F4I2)2] packs in the C2/c space group. The asymmetric unit includes one mol-ecule of DITFB, one Et4N(+) cation located on a twofold rotation axis, and one chloride anion also located on a twofold rotation symmetry axis. This compound has an inter-esting halogen-bonding environment surrounding the halide. Here, the chloride anion acts as a tetra-dentate halogen bond acceptor and forms a distorted square-pyramidal geometry, with I⋯Cl(-)⋯I angles of 80.891 (6) and 78.811 (11)°, where two crystallographically distinct iodine atoms form halogen bonds with the chloride anion. Resulting from that square-pyramidal geometry are short contacts between some of the adjacent F atoms. Along the b axis, the halogen-bonding inter-action results in a polymeric network, producing a sheet in which the two closest chloride ions are 7.8931 (6) Å apart. The Et4N(+) cation alternates in columns with the halide ion. The expected short contacts (shorter than the sum of their van der Waals radii) are observed for the halogen bonds [3.2191 (2) and 3.2968 (2) Å], as well as almost linear angles [170.953 (6) and 173.529 (6)°].

Related literature

The crystal structure of 3,4,5,6-tetra­fluoro-1,2-di­iodo­benzene has been recently published by our group (Viger-Gravel, Leclerc et al., 2014 ▸) and the crystal structure of Et4NCl was reported by Staples (1999 ▸). Reports by Abate et al. (2009 ▸), and our previous work (Viger-Gravel, Leclerc et al., 2014 ▸; Viger-Gravel, Meyer et al., 2014 ▸; Viger-Gravel et al., 2015 ▸) may be consulted for other similar halogen-bonded compounds containing o- or p-DITFB and ammonium halide salts. In these reports, halogen-bonding inter­actions are observed. Abate et al. discuss applications in crystal engineering. The latter reports describe the usefulness of solid-state nuclear magnetic resonance to characterize these types of halogen-bonding environments (Viger-Gravel, Leclerc et al., 2014 ▸; Viger-Gravel, Meyer et al., 2014 ▸).

Experimental

Crystal data

C8H20N+·Cl−·2C6F4I2

M = 969.42

Monoclinic,

a = 7.8930 (6) Å

b = 16.8088 (13) Å

c = 20.9962 (16) Å

β = 97.803 (3)°

V = 2759.8 (4) Å3

Z = 4

Mo Kα radiation

μ = 4.68 mm−1

T = 200 K

0.23 × 0.18 × 0.08 mm

Data collection

Bruker APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2009 ▸) T min = 0.555, T max = 0.746

19329 measured reflections

3445 independent reflections

3260 reflections with I > 2σ(I)

R int = 0.019

Refinement

R[F 2 > 2σ(F 2)] = 0.023

wR(F 2) = 0.070

S = 1.02

3445 reflections

155 parameters

H-atom parameters constrained

Δρmax = 0.31 e Å−3

Δρmin = −1.75 e Å−3

Data collection: APEX2 (Bruker, 2009 ▸); cell refinement: APEX2 and SAINT (Bruker, 2009 ▸); data reduction: SAINT and XPREP (Bruker, 2009 ▸); program(s) used to solve structure: SHELXS97 (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. DOI: 10.1107/S205698901500732X/gw2151sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S205698901500732X/gw2151Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S205698901500732X/gw2151Isup3.cml

Click here for additional data file.

4 o 6 4 2 . DOI: 10.1107/S205698901500732X/gw2151fig1.tif

Halogen-bonding inter­actions in [(Et4NCl)(o-C6F4I2)], where iodine is in purple, carbon in black, fluorine in green, and chloride in blue. Short type I fluorine–fluorine contacts are also shown.

Click here for additional data file.

x x 4 o a a a b ac . DOI: 10.1107/S205698901500732X/gw2151fig2.tif

2 x 2 x 2 supercell of [(Et4NCl)(o-DITFB)] along the a axis in (a). Along the a axis, rows of alternating halogen-bonded complexes and cations are easily observed. In (b) is presented the network formed in the ac plane where the closest anions are 7.8931 Å apart. The color legend used is: iodine in purple, carbon in black, fluorine in green, and chloride in blue.

CCDC reference: 1059313

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

C8H20N+·Cl−·2C6F4I2	F(000) = 1792
Mr = 969.42	Dx = 2.333 Mg m−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 7.8930 (6) Å	Cell parameters from 9886 reflections
b = 16.8088 (13) Å	θ = 2.4–28.3°
c = 20.9962 (16) Å	µ = 4.68 mm−1
β = 97.803 (3)°	T = 200 K
V = 2759.8 (4) Å3	Plate, colourless
Z = 4	0.23 × 0.18 × 0.08 mm

Bruker APEXII CCD diffractometer	3260 reflections with I > 2σ(I)
φ and ω scans	Rint = 0.019
Absorption correction: multi-scan (SADABS; Bruker, 2009)	θmax = 28.3°, θmin = 2.4°
Tmin = 0.555, Tmax = 0.746	h = −10→10
19329 measured reflections	k = −21→22
3445 independent reflections	l = −27→27

Refinement on F2	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.023	H-atom parameters constrained
wR(F2) = 0.070	w = 1/[σ2(Fo2) + (0.0482P)2 + 4.146P] where P = (Fo2 + 2Fc2)/3
S = 1.02	(Δ/σ)max = 0.004
3445 reflections	Δρmax = 0.31 e Å−3
155 parameters	Δρmin = −1.74 e Å−3

Experimental. Data collection is performed with three batch runs at phi = 0.00 ° (650 frames), at phi = 120.00 ° (650 frames), and at phi = 240.00 ° (650 frames). 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	1.20603 (2)	0.23394 (2)	0.64245 (2)	0.03195 (7)
I2	0.73344 (2)	0.23667 (2)	0.65441 (2)	0.03262 (7)
Cl3	0.5000	0.15395 (5)	0.7500	0.03270 (17)
F1	0.57429 (19)	0.34488 (13)	0.54284 (9)	0.0488 (4)
F2	0.6984 (2)	0.43431 (12)	0.45505 (9)	0.0548 (5)
F3	1.0382 (2)	0.43372 (12)	0.44632 (9)	0.0552 (5)
F4	1.2508 (2)	0.34428 (14)	0.52645 (10)	0.0551 (5)
N1	1.0000	0.98253 (15)	0.7500	0.0303 (6)
C1	1.0245 (3)	0.29692 (14)	0.57959 (11)	0.0285 (4)
C2	0.8494 (3)	0.29779 (14)	0.58425 (11)	0.0281 (4)
C3	0.7436 (3)	0.34314 (17)	0.54106 (12)	0.0325 (5)
C4	0.8050 (3)	0.38943 (16)	0.49509 (12)	0.0363 (5)
C5	0.9761 (3)	0.38863 (16)	0.49051 (13)	0.0372 (5)
C6	1.0838 (3)	0.34232 (17)	0.53238 (13)	0.0347 (5)
C7	1.0674 (4)	1.03725 (15)	0.70149 (13)	0.0378 (5)
H7A	0.9725	1.0715	0.6818	0.045*
H7B	1.1558	1.0723	0.7247	0.045*
C8	1.1435 (5)	0.9949 (2)	0.64821 (18)	0.0577 (9)
H8A	1.1831	1.0343	0.6192	0.087*
H8B	1.0564	0.9609	0.6241	0.087*
H8C	1.2403	0.9621	0.6669	0.087*
C9	0.8599 (4)	0.92855 (16)	0.71801 (15)	0.0401 (6)
H9A	0.9077	0.8954	0.6858	0.048*
H9B	0.8246	0.8922	0.7510	0.048*
C10	0.7022 (4)	0.9708 (2)	0.68505 (18)	0.0525 (8)
H10A	0.6191	0.9313	0.6658	0.079*
H10B	0.7344	1.0058	0.6514	0.079*
H10C	0.6511	1.0025	0.7167	0.079*

	U11	U22	U33	U12	U13	U23
I1	0.02594 (10)	0.03161 (11)	0.03700 (11)	0.00044 (5)	−0.00040 (7)	0.00317 (6)
I2	0.02988 (10)	0.03613 (12)	0.03308 (11)	−0.00047 (6)	0.00879 (7)	−0.00037 (6)
Cl3	0.0309 (4)	0.0339 (4)	0.0335 (4)	0.000	0.0050 (3)	0.000
F1	0.0244 (7)	0.0691 (12)	0.0524 (10)	0.0085 (7)	0.0034 (7)	0.0081 (9)
F2	0.0482 (10)	0.0664 (12)	0.0472 (10)	0.0187 (9)	−0.0025 (8)	0.0198 (9)
F3	0.0542 (11)	0.0637 (11)	0.0490 (10)	−0.0016 (9)	0.0122 (8)	0.0254 (9)
F4	0.0261 (8)	0.0771 (13)	0.0631 (12)	−0.0022 (8)	0.0100 (7)	0.0259 (10)
N1	0.0397 (15)	0.0185 (12)	0.0328 (15)	0.000	0.0047 (12)	0.000
C1	0.0250 (10)	0.0298 (11)	0.0297 (11)	−0.0006 (8)	0.0001 (8)	−0.0006 (9)
C2	0.0260 (10)	0.0312 (11)	0.0270 (11)	−0.0016 (9)	0.0033 (8)	−0.0041 (9)
C3	0.0246 (10)	0.0398 (13)	0.0325 (12)	0.0029 (9)	0.0014 (9)	−0.0021 (10)
C4	0.0347 (12)	0.0411 (13)	0.0309 (12)	0.0066 (10)	−0.0030 (9)	0.0037 (11)
C5	0.0383 (13)	0.0404 (13)	0.0330 (13)	−0.0019 (11)	0.0053 (10)	0.0081 (11)
C6	0.0257 (11)	0.0416 (14)	0.0370 (13)	−0.0016 (10)	0.0047 (9)	0.0038 (11)
C7	0.0503 (15)	0.0278 (11)	0.0364 (13)	0.0003 (11)	0.0104 (11)	0.0044 (10)
C8	0.077 (2)	0.0514 (18)	0.0494 (19)	0.0087 (17)	0.0271 (17)	−0.0018 (15)
C9	0.0433 (14)	0.0279 (12)	0.0472 (15)	−0.0045 (10)	−0.0004 (11)	−0.0066 (11)
C10	0.0464 (16)	0.0472 (16)	0.060 (2)	0.0030 (14)	−0.0062 (14)	−0.0076 (15)

I1—C1	2.098 (2)	N1—C7i	1.521 (3)
I2—C2	2.105 (2)	C1—C6	1.382 (3)
F1—C3	1.342 (3)	C1—C2	1.398 (3)
F2—C4	1.339 (3)	C2—C3	1.377 (3)
F3—C5	1.341 (3)	C3—C4	1.378 (4)
F4—C6	1.341 (3)	C4—C5	1.367 (4)
N1—C9i	1.515 (3)	C5—C6	1.378 (4)
N1—C9	1.515 (3)	C7—C8	1.517 (4)
N1—C7	1.521 (3)	C9—C10	1.516 (4)
C9i—N1—C9	106.4 (3)	F1—C3—C4	117.0 (2)
C9i—N1—C7	111.01 (16)	C2—C3—C4	122.3 (2)
C9—N1—C7	111.46 (16)	F2—C4—C5	120.3 (2)
C9i—N1—C7i	111.45 (16)	F2—C4—C3	120.5 (2)
C9—N1—C7i	111.01 (16)	C5—C4—C3	119.2 (2)
C7—N1—C7i	105.6 (3)	F3—C5—C4	120.0 (2)
C6—C1—C2	118.6 (2)	F3—C5—C6	120.6 (2)
C6—C1—I1	117.43 (17)	C4—C5—C6	119.4 (2)
C2—C1—I1	123.94 (18)	F4—C6—C5	117.1 (2)
C3—C2—C1	118.5 (2)	F4—C6—C1	120.9 (2)
C3—C2—I2	116.65 (17)	C5—C6—C1	122.0 (2)
C1—C2—I2	124.86 (18)	C8—C7—N1	114.8 (2)
F1—C3—C2	120.7 (2)	C10—C9—N1	115.3 (2)
C6—C1—C2—C3	0.8 (4)	C3—C4—C5—C6	−0.7 (4)
I1—C1—C2—C3	178.32 (18)	F3—C5—C6—F4	−0.4 (4)
C6—C1—C2—I2	−177.65 (19)	C4—C5—C6—F4	−179.2 (3)
I1—C1—C2—I2	−0.1 (3)	F3—C5—C6—C1	178.2 (3)
C1—C2—C3—F1	178.8 (2)	C4—C5—C6—C1	−0.7 (4)
I2—C2—C3—F1	−2.6 (3)	C2—C1—C6—F4	179.2 (2)
C1—C2—C3—C4	−2.2 (4)	I1—C1—C6—F4	1.4 (4)
I2—C2—C3—C4	176.4 (2)	C2—C1—C6—C5	0.6 (4)
F1—C3—C4—F2	0.8 (4)	I1—C1—C6—C5	−177.1 (2)
C2—C3—C4—F2	−178.2 (2)	C9i—N1—C7—C8	58.5 (3)
F1—C3—C4—C5	−178.8 (3)	C9—N1—C7—C8	−60.0 (3)
C2—C3—C4—C5	2.2 (4)	C7i—N1—C7—C8	179.4 (3)
F2—C4—C5—F3	0.9 (4)	C9i—N1—C9—C10	177.6 (3)
C3—C4—C5—F3	−179.6 (3)	C7—N1—C9—C10	−61.2 (3)
F2—C4—C5—C6	179.7 (3)	C7i—N1—C9—C10	56.2 (3)

Table 1

Halogen-bonded geometry (, )

CX Y	X Y	CX Y	Y X Y	Y X Y
C1I1Cl3i	3.2968(2)	173.529(6)	I1iiCl3I2	80.891(6)
C2I2Cl3	3.2191(2)	170.953(6)	I2Cl3I1iii	78.811(11)

Symmetry codes: (i) x+1, y, z; (ii) 2x, y, z; (iii) 1+x, y, z.

Table 2

Short contacts between hydrogen, DITFB or chloride (, )

CX Z	FZ	CFZ
C3F1F4	2.532(2)	166.944(15)
C3F1F2	2.663(3)	62.0647(13)
C4F2F3	2.713(2)	59.936(12)
C5F3F4	2.671(2)	60.201(13)
C3F1C2	2.364(3)	30.165(12)
C3F1H8B i	2.614(2)	100.233(14)
C4F2H10B ii	2.570(2)	165.27(2)
C10H10CCl3iii	2.936(2)	148.5(2)

Symmetry codes: (i) x , y , z; (ii) x+, y+, z+1; (iii) x+1, y1, z+.