Polymorphism of a widely used building block for halogen-bonded assemblies: 1,3,5-tri­fluoro-2,4,6-tri­iodo­benzene

Raffo, P.A.; Suárez, S.; Fantoni, A.C.; Baggio, R.; Cukiernik, F.D.

doi:10.1107/S2053229617011007

Polymorphism of a widely used building block for halogen-bonded assemblies: 1,3,5-trifluoro-2,4,6-triiodobenzene

P. A. Raffo, S. Suárez, A. C. Fantoni, R. Baggio and F. D. Cukiernik

After reporting the structure of a new polymorph of 1,3,5-trifluoro-2,4,6-triiodobenzene (denoted BzF3I3), C₆F₃I₃, (I), which crystallized in the space group P2₁/c, we perform a comparative analysis with the already reported P2₁/n polymorph, (II) [Reddy et al. (2006). Chem. Eur. J. 12, 2222–2234]. In polymorph (II), type-II I

I halogen bonds and I

π interactions connect molecules in such a way that a three-dimensional structure is formed; however, the way in which molecules are connected in polymorph (I), through type-II I

I halogen bonds and π–π interactions, gives rise to an exfoldable lamellar structure, which looks less tightly bound than that of (II). In agreement with this structural observation, both the melting point and the melting enthalpy of (I) are lower than those of (II).

Keywords: additive-induced polymorphism; atoms in molecules (AIM); crystal structure; halogen bonding; noncovalent interactions; melting point; cohesion energy.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S2053229617011007/uk3135sup1.cif Contains datablocks I, global
	Structure factor file (CIF format) https://doi.org/10.1107/S2053229617011007/uk3135Isup2.hkl Contains datablock I
	Portable Document Format (PDF) file https://doi.org/10.1107/S2053229617011007/uk3135sup3.pdf Cohesion energies and additional figures

CCDC reference: 1564695

Computing details top

Data collection: CrysAlis PRO (Oxford Diffraction, 2009); cell refinement: CrysAlis PRO (Oxford Diffraction, 2009); data reduction: CrysAlis PRO (Oxford Diffraction, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97, PLATON (Spek, 2009).

1,3,5-Trifluoro-2,4,6-triiodobenzene top

Crystal data top

C₆F₃I₃	F(000) = 888
M_r = 509.76	D_x = 3.391 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 9.3455 (9) Å	Cell parameters from 1826 reflections
b = 13.1854 (10) Å	θ = 4.0–25.5°
c = 9.2185 (8) Å	µ = 9.38 mm⁻¹
β = 118.466 (11)°	T = 295 K
V = 998.61 (18) Å³	Plates, light_brown
Z = 4	0.35 × 0.30 × 0.12 mm

Data collection top

CCD Oxford Diffraction Xcalibur, Eos, Gemini diffractometer	1610 reflections with I > 2σ(I)
Radiation source: Enhance (Mo) X-ray Source	R_int = 0.075
thick slices scans	θ_max = 29.3°, θ_min = 4.0°
Absorption correction: multi-scan CrysAlisPro (Oxford Diffraction, 2009)	h = −12→12
T_min = 0.12, T_max = 0.42	k = −17→17
7952 measured reflections	l = −11→11
2404 independent reflections

Refinement top

Refinement on F²	109 parameters
Least-squares matrix: full	0 restraints
R[F² > 2σ(F²)] = 0.054	w = 1/[σ²(F_o²) + (0.0769P)² + 0.0712P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.165	(Δ/σ)_max < 0.001
S = 1.06	Δρ_max = 1.26 e Å⁻³
2404 reflections	Δρ_min = −1.89 e Å⁻³

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
F1	0.3706 (9)	0.8880 (5)	0.1550 (8)	0.0477 (17)
F3	0.5120 (9)	0.8418 (5)	0.7112 (8)	0.0454 (16)
F5	0.9181 (8)	0.9031 (6)	0.5590 (8)	0.0468 (17)
I2	0.19358 (10)	0.83570 (7)	0.36597 (10)	0.0513 (3)
I4	0.89656 (9)	0.86728 (6)	0.88692 (8)	0.0414 (3)
I6	0.71380 (11)	0.92451 (7)	0.17247 (9)	0.0504 (3)
C1	0.4848 (13)	0.8838 (7)	0.3127 (12)	0.030 (2)
C2	0.4352 (13)	0.8629 (7)	0.4307 (13)	0.031 (2)
C3	0.5582 (15)	0.8611 (7)	0.5956 (13)	0.033 (2)
C4	0.7199 (13)	0.8721 (7)	0.6403 (11)	0.029 (2)
C5	0.7587 (15)	0.8916 (7)	0.5171 (13)	0.034 (2)
C6	0.6472 (15)	0.8977 (9)	0.3549 (13)	0.037 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
F1	0.034 (4)	0.069 (5)	0.033 (3)	0.000 (3)	0.011 (3)	0.008 (3)
F3	0.046 (4)	0.061 (4)	0.035 (3)	0.001 (3)	0.024 (3)	0.008 (3)
F5	0.028 (4)	0.078 (5)	0.036 (3)	−0.005 (3)	0.017 (3)	−0.002 (3)
I2	0.0323 (5)	0.0693 (6)	0.0482 (5)	−0.0118 (4)	0.0159 (4)	0.0070 (4)
I4	0.0357 (5)	0.0575 (5)	0.0285 (4)	0.0021 (4)	0.0133 (4)	−0.0048 (3)
I6	0.0451 (6)	0.0762 (6)	0.0369 (5)	0.0089 (4)	0.0252 (4)	0.0140 (4)
C1	0.025 (6)	0.029 (5)	0.022 (5)	0.006 (5)	0.001 (4)	0.004 (4)
C2	0.024 (5)	0.037 (5)	0.029 (5)	−0.003 (5)	0.009 (5)	0.006 (4)
C3	0.038 (6)	0.036 (6)	0.031 (5)	0.005 (5)	0.021 (5)	0.003 (4)
C4	0.030 (6)	0.032 (5)	0.021 (5)	0.000 (5)	0.008 (4)	0.002 (4)
C5	0.038 (6)	0.027 (5)	0.039 (6)	0.001 (5)	0.020 (5)	−0.007 (4)
C6	0.038 (7)	0.050 (6)	0.025 (5)	−0.011 (5)	0.017 (5)	−0.006 (4)

Geometric parameters (Å, º) top

F1—C1	1.333 (11)	C1—C2	1.398 (14)
F3—C3	1.351 (11)	C1—C6	1.387 (15)
F5—C5	1.358 (14)	C2—C3	1.402 (14)
I2—C2	2.074 (11)	C3—C4	1.371 (15)
I4—C4	2.079 (10)	C4—C5	1.371 (14)
I6—C6	2.083 (10)	C5—C6	1.358 (15)

F1—C1—C2	117.8 (10)	C5—C4—C3	117.4 (10)
F1—C1—C6	120.1 (9)	C5—C4—I4	121.7 (8)
C2—C1—C6	122.1 (9)	C3—C4—I4	120.8 (7)
C1—C2—C3	116.3 (10)	C6—C5—C4	123.8 (11)
C1—C2—I2	122.0 (8)	C6—C5—F5	118.0 (9)
C3—C2—I2	121.8 (7)	C4—C5—F5	118.2 (10)
F3—C3—C4	120.2 (10)	C5—C6—C1	117.6 (9)
F3—C3—C2	117.0 (10)	C5—C6—I6	122.1 (9)
C4—C3—C2	122.7 (9)	C1—C6—I6	120.3 (8)

Experimental details for (I) and (II). top

	(I)	(II)
	This work	Reddy et al. (2006)
Chemical formula	C₆F₃I₃	C₆F₃I₃
M_r, F(000)	509.76, 888	509.76, 888
Crystal system	Monoclinic	Monoclinic
Space group	P2₁/c	P2₁/n
Z	4	4
Temperature (K)	295	298
a, b, c (Å)	9.3455 (9), 13.1854 (10), 9.2185 (8)	13.937 (4), 4.7919 (15), 15.488 (5)
β (°)	118.466 (11)	107.486 (3)
V (Å³)	998.61 (18)	986.6 (5)
Calculated density (Mg m^-1)	3.391	3.432
Radiation type	Mo Kα, 0.7103 Å	Mo Kα, 0.7103 Å
µ (mm^-1)	9.38	9.49
Crystal shape, colour	Plate, light brown	Plate, colourless
Crystal size (mm)	0.35 × 0.30 × 0.12	*
Diffractometer	Oxford Diffraction	Bruker–Nonius SMART APEX CCD
Absorption correction	Multi-scan	Multi-scan
T_min, T_max	0.12, 0.42	*
Total, independent and observed reflections	7952, 2404, 1610	5283, 1923, 1642
R_int	0.075	0.0241
θ range (°)	3.98, 29.33	1.73, 26.03
R[F² > 2σ(F²)], wR(F²), S	0.054, 0.165, 1.06	0.032, 0.080, 1.05
No. of reflections	2404	1923
No. of parameters	109	109
Δρ_max, Δρ_min (e Å^-3)	1.26, -1.88	*

Note: (*) information not available in the original publication.

π–π interaction for (I) top

Code	Type	Cg···Cg	Cg···Cg (Å)	da (°)	d/perp (Å)	Shift (Å)	100*ρ(r_CP) (a.u.)	100*∇²ρ(r_CP) (a.u.)
#1	A–A	Cg1···Cg1ⁱ	3.859 (7)	0.0 (5)	3.531 (4)	1.557	0.40	0.13

Notes: da is the dihedral angle between planes; d/perp is the perpendicular distances of Cg to the opposite plane; Shift is the parallel shift between planes; r_CP is the position of the critical point. Type code: A–A = linking faces type A.

Symmetry code: (i) -x+1, -y+2, -z+1.

C—X···π interactions for (I) (X = F, I) top

Code	Type	C—X···Cg	X···Cg (Å)	X/perp (Å)	X···Cg/perp (°)	C—X/perp (°)	100*ρ(r_CP) (a.u.)	100*∇²ρ(r_CP) (a.u.)
#2	B–B	C6—I6···Cg1ⁱⁱ	4.308 (3)	3.797 (3)	28.1 (2)	69.8 (2)	0.50	0.14
#3	B–B	C3—F3···Cg1ⁱⁱⁱ	3.663 (6)	3.109 (7)	30.8 (2)	111.3 (3)	0.49	0.20

Notes: X/perp is the perpendicular distances of X to the plane; X···Cg/perp is the angle between the X···Cg vector and the plane normal; C—X/perp is the angle between the C—X vector and the plane normal; r_CP is the position of the critical point. Type code: B–B = linking faces type B.

Symmetry codes: (ii) x, -y+3/2, z-1/2; (iii) x, -y+3/2, z+1/2.

C—X···X'—C' interactions for (I) (X = F, I) top

Code	Type	C—X···(X—C)'	X···X' (Å)	<C—X···X'> (°)	<X···X'—C'> (°)	100*ρ(r_CP) (a.u.)	100*∇²ρ(r_CP) (a.u.)
#4	X	C4—I4···(I6—C6)^iv	3.8341 (15)	111.3 (3)	157.4 (3)	0.93	0.22
#5	B–B	C2—I2···(I4—C4)^v	3.9264 (14)	143.3 (3)	100.3 (3)	0.86	0.20
#6	A–A	C4—I4···(I4—C4)^vi	4.0610 (12)	118.1 (3)	118.1 (3)	0.73	0.17
#7	X	C2—I2···(I4—C4)^vii	3.9617 (11)	113.0 (3)	176.6 (3)	0.70	0.18
#8	X	C2—I2···(I6—C6)^viii	4.1271 (15)	152.3 (4)	106.5 (4)	0.42	0.11
#9	B–B	C2—I2···(F1—C1)ⁱⁱⁱ	3.7852 (13)	83.2 (4)	126.1 (4)	0.38	0.12
#10	B–B	C4—I4···(F5—C5)ⁱⁱⁱ	3.8683 (14)	109.6 (3)	86.9 (3)	0.36	0.12

Notes: <C—X···X'> is the angle between the C—X and X···X' vectors; <X···X'—C'> is the angle between the X···X' and X'—C' vectors; r_CP is the position of the critical point. Type codes: X = interplane, A–A = linking faces type A and B–B = linking faces type B.

Symmetry codes: (iii) x, -y+3/2, z+1/2; (iv) x, y, z+1; (v) x-1, -y+3/2, z-1/2; (vi) -x+2, -y+2, -z+2; (vii) x-1, y, z-1; (viii) x-1, y, z.

C—X···π bonds for (II) (X = F, I) top

Code	Type	C—X···Cg	X···Cg (Å)	X/perp (Å)	X···Cg/perp (°)	C—X/perp (°)	100*ρ(r_CP) (a.u.)	100\*υ008711²ρ(r_CP) (a.u.)
#1	X	C2—I2···Cg1ⁱ	3.728 (3)	3.642	12.29	83.1 (2)	0.69	0.21
#2	X	C5—F5···Cg1ⁱⁱ	3.663 (6)	3.575	12.66	82.7 (4)	0.48	0.19

Notes: X/perp is the perpendicular distances of X to the plane; X···Cg/perp is the angle between the X···Cg vector and the plane normal; C—X/perp is the angle between the C—X vector and the plane normal; r_CP: position of the critical point. Type code: X = intra-column. Symmetry codes: (i) x, y+1, z; (ii) x, y-1, z.

C—X···X'—C' bonds for (II) (X = F, I) top

Code	Type	C—X···(X—C)'	X···X'	<C—X···X'> (°)	<X···X'—C'> (°)	100*ρ(r_CP) (a.u.)	100*∇²ρ(r_CP) (a.u.)
#3	Y	C2—I2···(I2—C2)ⁱⁱⁱ	3.774 (2)	171.1 (2)	100.7 (2)	1.02	0.24
#4	Z	C4—I4···(I6—C6)^iv	3.957 (2)	80.5 (5)	146.8 (5)	0.80	0.19
#5	Z	C6—I6···(I6—C6)^v	4.101 (2)	138.4 (2)	138.4 (2)	0.57	0.14
#6	Z	C2—I2···(I4—C4)^vi	4.241 (5)	126.9 (4)	123.2 (4)	0.55	0.13
#7	X	C1—F1···(I6—C6)ⁱ	3.656 (5)	87.3 (4)	90.4 (4)	0.53	0.17
#8	Z	C3—F3···(F3—C3)^vii	2.851 (8)	157.4 (5)	157.4 (5)	0.52	0.28
#9	Z	C1—F1···(I4—C4)^vii	3.584 (5)	145.5 (4)	126.1 (4)	0.49	0.17
#10	Z	C5—F5···(I6—C6)^viii	3.530 (5)	167.3 (4)	74.2 (4)	0.41	0.13
#11	Z	C3—F3···(I4—C4)^vi	3.979 (6)	111.9 (5)	79.0 (5)	0.35	0.11
#12	Z	C2—I2···(I4—C4)^vii	4.044 (2)	105.6 (2)	157.5 (2)	0.24	0.06

Notes: <C—X···X'> is the angle between the C—X and X···X' vectors; <X···X'—C'> is the angle between the X···X' and X'—C' vectors; r_CP is the position of the critical point. Type codes: X = intra-column, Y = intra-bicolumn and Z = inter-bicolumn.

Symmetry codes: (iii) -x-1/2, y-1/2, -z+1/2; (iv) -x+1/2, y+1/2, -z+1/2; (v) -x, -y-1, -z; (vi) -x, -y, -z+1; (vii) x-1/2, -y+1/2, z-1/2; (viii) -x+1/2, y-1/2, -z+1/2.

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Polymorphism of a widely used building block for halogen-bonded assemblies: 1,3,5-tri­fluoro-2,4,6-tri­iodo­benzene

Supporting information

Polymorphism of a widely used building block for halogen-bonded assemblies: 1,3,5-trifluoro-2,4,6-triiodobenzene