1,2,4,5-Tetra­chloro-3,6-di­iodo­benzene benzene monosolvate

Bosch, E.

doi:10.1107/S2414314619009933

organic compounds

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ISSN: 2414-3146

Volume 4| Part 7| July 2019| x190993

https://doi.org/10.1107/S2414314619009933

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1,2,4,5-Tetrachloro-3,6-diiodobenzene benzene monosolvate

Eric Bosch ^a ^*

^aDepartment of Chemistry, Missouri State University, 901 South National Avenue, Springfield MO 65804 , USA
^*Correspondence e-mail: ericbosch@missouristate.edu

Edited by M. Zeller, Purdue University, USA (Received 8 July 2019; accepted 11 July 2019; online 19 July 2019)

The title compound, C₆Cl₄I₂·C₆H₆, crystallizes from benzene solution as cube-shaped crystals in the triclinic space group P $[\overline{1}]$ with Z = 1. The asymmetric unit of the crystal structure contains one half of each molecule. In the crystal, the benzene ring is almost orthogonal to the perhalobenzene ring and the molecules are linked by C—I⋯π interactions, with a close contact between the iodine atom and the benzene ring of 3.412 (1) Å.

Keywords: crystal structure; solvate; C—I⋯π interactions.

CCDC reference: 1940085

Structure description

Halogen bonding, the attractive interaction between the electropositive σ-hole on a bonded halogen, commonly iodine, and a Lewis base, has been widely used in the supramolecular association of multi-component systems (Cavallo et al., 2016 ). With respect to iodobenzene, it has been established that the addition of fluorine atoms to the benzene ring enhances the σ-hole on iodine resulting in stronger attractions between the components (Präsang et al., 2009 ). Surprisingly, the application of iodoperchlorobenzenes had not been reported until we reported that the co-crystallization of 1,2,4,5-tetrachloro-3,6-diiodobenzene with 1,2-dipyridylethene resulted in a halogen-bonded co-crystal in which the alkenes were oriented such that they underwent photo-induced 2 + 2 cycloaddition (Bosch et al., 2019 ). After preparation of 1,2,4,5-tetrachloro-3,6-diiodobenzene, recrystallization from benzene provided clear, colourless cube-shaped crystals that lost lustre and became opaque several hours after removal from the mother liquor. The crystal structure revealed that the cube-shaped crystals represented a 1:1 benzene solvate.

The asymmetric unit comprises one half of the tetrachlorodiodobenzene and one half of the benzene molecule with a dihedral angle between the rings of 85.89 (16)°, as shown in Fig. 1. The closest contact between the tetrachlorodiiodobenzene and the benzene is between the iodine atom and C4 with a distance of 3.434 (2) Å. Indeed the C1—I1⋯C4 bond angle is almost linear at 178.09 (6)°. This interaction is highlighted in the two Hirshfeld surface plots in Fig. 2 (Turner et al., 2017 ). The C—I⋯π interactions form a stepped chain of alternating tetrachlorodiiodobenzene and benzene molecules (Fig. 3) with adjacent tetrachlorodiiodobenzene molecules slip-stacked with a centroid–centroid distance of 5.4399 (10) Å and perpendicular distance between the perhalobenzene planes of 3.6607 (7) Å (Spek, 2015 ).

Figure 1
The asymmetric unit of the title solvate showing the atom-numbering scheme. Displacement ellipsoids of non-hydrogen atoms are drawn at the 50% level while H atoms are shown as circles of arbitrary size. The intermolecular C—I⋯π contact is shown as a dashed line.

Figure 2
Two views of the Hirshfeld surface of the title solvate highlighting the short contact between I1 and C4 with the halobenzene shown as a ball and stick model in (a) and the benzene ring shown as a ball and stick model in (b).

Figure 3
Partial view of the crystal structure of the title solvate showing the stepped chain formed by the C—I⋯π interactions and also showing the offset π-stacking of the 1,4-diiodotetrachlorobenzene molecules.

Synthesis and crystallization

1,2,4,5-Tetrachloro-3,6-diiodobenzene was prepared by the reaction of 1,2,4,5-tetrachlorobenzene with iodine and sodium metaperiodate in concentrated sulfuric acid. Cube-shaped crystals of the title solvate were obtained on recrystallization from benzene solution. Crystallization from mesitylene, chloroform or dichloromethane yielded block-shaped crystals with structures similar to that previously reported (Reddy et al., 2006 ).

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1.

Table 1
Experimental details

Crystal data
Chemical formula	C₆Cl₄I₂·C₆H₆
M_r	545.77
Crystal system, space group	Triclinic, P $[\overline{1}]$
Temperature (K)	100
a, b, c (Å)	5.4399 (4), 6.3599 (4), 11.0232 (8)
α, β, γ (°)	96.702 (1), 92.728 (1), 98.599 (1)
V (Å³)	373.69 (5)
Z	1
Radiation type	Mo Kα
μ (mm⁻¹)	4.90
Crystal size (mm)	0.39 × 0.12 × 0.05

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2014 )
T_min, T_max	0.611, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	4913, 1668, 1634
R_int	0.018
(sin θ/λ)_max (Å⁻¹)	0.644

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.013, 0.032, 1.09
No. of reflections	1668
No. of parameters	82
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.46, −0.39
Computer programs: SMART and SAINT (Bruker, 2014), SHELXT2018 (Sheldrick, 2015a ), SHELXL2018 (Sheldrick, 2015b ) and X-SEED (Barbour, 2001 ).

Structural data

CCDC reference: 1940085

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2414314619009933/zl4031sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314619009933/zl4031Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314619009933/zl4031Isup3.cdx

Supporting information file. DOI: https://doi.org/10.1107/S2414314619009933/zl4031Isup4.cml

checkCIF report

Computing details top

Data collection: SMART (Bruker, 2014); cell refinement: SMART (Bruker, 2014); data reduction: SAINT (Bruker, 2014); program(s) used to solve structure: SHELXT2018 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2018 (Sheldrick, 2015b); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: X-SEED (Barbour, 2001).

1,2,4,5-Tetrachloro-3,6-diiodobenzene benzene monosolvate top

Crystal data top

C₆Cl₄I₂·C₆H₆	Z = 1
M_r = 545.77	F(000) = 252
Triclinic, P1	D_x = 2.425 Mg m⁻³
a = 5.4399 (4) Å	Mo Kα radiation, λ = 0.71073 Å
b = 6.3599 (4) Å	Cell parameters from 4302 reflections
c = 11.0232 (8) Å	θ = 3.3–27.3°
α = 96.702 (1)°	µ = 4.90 mm⁻¹
β = 92.728 (1)°	T = 100 K
γ = 98.599 (1)°	Cut cube, colourless
V = 373.69 (5) Å³	0.39 × 0.12 × 0.05 mm

Data collection top

Bruker APEXII CCD diffractometer	1668 independent reflections
Radiation source: fine-focus sealed tube	1634 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.018
Detector resolution: 8.3660 pixels mm^-1	θ_max = 27.3°, θ_min = 1.9°
phi and ω scans	h = −7→7
Absorption correction: multi-scan (SADABS; Bruker, 2014)	k = −8→8
T_min = 0.611, T_max = 1.000	l = −14→14
4913 measured reflections

Refinement top

Refinement on F²	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.013	H-atom parameters constrained
wR(F²) = 0.032	w = 1/[σ²(F_o²) + (0.0129P)² + 0.2107P] where P = (F_o² + 2F_c²)/3
S = 1.09	(Δ/σ)_max = 0.001
1668 reflections	Δρ_max = 0.46 e Å⁻³
82 parameters	Δρ_min = −0.39 e Å⁻³
0 restraints

Special details top

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

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

	x	y	z	U_iso*/U_eq
I1	0.63204 (2)	0.24241 (2)	0.70975 (2)	0.01586 (5)
Cl1	0.70962 (8)	0.35540 (7)	0.42245 (4)	0.01743 (9)
C1	0.8497 (3)	0.0970 (3)	0.58350 (15)	0.0125 (3)
Cl2	1.04287 (8)	0.14760 (7)	0.24148 (4)	0.01843 (9)
C2	0.8716 (3)	0.1608 (3)	0.46708 (16)	0.0130 (3)
C3	1.0207 (3)	0.0648 (3)	0.38431 (16)	0.0127 (3)
C4	0.2926 (4)	0.4936 (3)	0.92088 (17)	0.0220 (4)
H4	0.150280	0.488464	0.866558	0.026*
C5	0.4738 (4)	0.6732 (3)	0.93667 (18)	0.0216 (4)
H5	0.455940	0.791629	0.893655	0.026*
C6	0.6826 (4)	0.6801 (3)	1.01573 (18)	0.0217 (4)
H6	0.808105	0.803023	1.026540	0.026*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
I1	0.01473 (7)	0.01688 (7)	0.01605 (7)	0.00549 (4)	0.00276 (4)	−0.00209 (4)
Cl1	0.0194 (2)	0.01586 (19)	0.0194 (2)	0.00981 (16)	0.00007 (16)	0.00377 (15)
C1	0.0112 (7)	0.0113 (7)	0.0143 (8)	0.0021 (6)	0.0016 (6)	−0.0017 (6)
Cl2	0.0233 (2)	0.0205 (2)	0.0141 (2)	0.00780 (16)	0.00371 (16)	0.00617 (16)
C2	0.0122 (7)	0.0100 (7)	0.0170 (8)	0.0031 (6)	−0.0016 (6)	0.0017 (6)
C3	0.0129 (8)	0.0132 (8)	0.0117 (7)	0.0014 (6)	−0.0004 (6)	0.0013 (6)
C4	0.0160 (8)	0.0363 (11)	0.0149 (8)	0.0092 (8)	0.0013 (7)	0.0019 (7)
C5	0.0240 (9)	0.0251 (9)	0.0182 (9)	0.0086 (8)	0.0063 (7)	0.0052 (7)
C6	0.0192 (9)	0.0257 (10)	0.0191 (9)	0.0015 (7)	0.0050 (7)	−0.0008 (7)

Geometric parameters (Å, º) top

I1—C1	2.0922 (17)	C4—C5	1.381 (3)
Cl1—C2	1.7254 (17)	C4—C6ⁱⁱ	1.394 (3)
C1—C2	1.396 (2)	C4—H4	0.9500
C1—C3ⁱ	1.400 (2)	C5—C6	1.390 (3)
Cl2—C3	1.7215 (17)	C5—H5	0.9500
C2—C3	1.397 (2)	C6—H6	0.9500

C2—C1—C3ⁱ	118.86 (15)	C5—C4—C6ⁱⁱ	120.31 (18)
C2—C1—I1	121.01 (12)	C5—C4—H4	119.8
C3ⁱ—C1—I1	120.13 (12)	C6ⁱⁱ—C4—H4	119.8
C1—C2—C3	120.44 (15)	C4—C5—C6	119.78 (18)
C1—C2—Cl1	120.37 (13)	C4—C5—H5	120.1
C3—C2—Cl1	119.17 (13)	C6—C5—H5	120.1
C2—C3—C1ⁱ	120.70 (16)	C5—C6—C4ⁱⁱ	119.90 (19)
C2—C3—Cl2	119.10 (13)	C5—C6—H6	120.0
C1ⁱ—C3—Cl2	120.21 (13)	C4ⁱⁱ—C6—H6	120.0

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

Acknowledgements

We thank the Missouri State University Provost Incentive Fund that funded the purchase of the X-ray diffractometer.

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