3-(1,2,2-Tri­iodo­ethen­yl)benzoic acid

Szell, P.M.J.; Gabidullin, B.; Bryce, D.L.

doi:10.1107/S2414314618002584

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 3| Part 2| February 2018| x180258

https://doi.org/10.1107/S2414314618002584

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3-(1,2,2-Triiodoethenyl)benzoic acid

Patrick M.J. Szell,^a Bulat Gabidullin ^a and David L. Bryce ^a ^*

^aDepartment of Chemistry and Biomolecular Sciences & CCRI, University of Ottawa, 10 Marie Curie Private, Ottawa, Ontario K1N 6N5, Canada
^*Correspondence e-mail: david.bryce@uottawa.ca

Edited by A. J. Lough, University of Toronto, Canada (Received 5 February 2018; accepted 12 February 2018; online 20 February 2018)

The title compound, C₉H₅I₃O₂, has a layered structure exhibiting O—H⋯O hydrogen bonds, as well as C—I⋯C and C—I⋯O halogen bonding. The C atoms of the ethenyl group are disordered over two sets of sites with refined occupancies of 0.545 (18) and 0.455 (18).

Keywords: crystal structure; halogen bonding; hydrogen bonding.

CCDC reference: 1823657

Structure description

Upon analyzing the crystals obtained from recrystallizing 3-iodoethynylbenzoic acid from acetonitrile, a trace quantity of 3-(1,2,2-triiodoethenyl)benzoic acid (Fig. 1) was observed. The crystal structure of 3-(1,2,2-triiodoethenyl)benzoic acid has a disordered ethenyl group, with the disorder akin to that reported for 1,2,2-triiodovinylbenzene (Berger et al., 2016 ). While the iodine atoms' coordinates are well ordered, the carbon atoms occupy two sets of sites.

Figure 1
The molecular structure of 3-(1,2,2-triiodoethenyl)benzoic acid, with displacement ellipsoids drawn at the 50% probability level.

In the crystal, the carboxylic acid group interacts with the carboxylic acid group from an adjacent molecule via O—H⋯O hydrogen bonds (see Table 1), forming inversion dimers. One of the iodine atoms participates in a C—I⋯O halogen bond [d_I⋯O = 3.174 (6) Å, θ_C—I⋯O = 159.3 (6)° for C9—I2⋯O2, 161.3 (4)° for C9′—I2⋯O2] and a second iodine atom participates in a halogen bond (Table 2) to the carbon atom on the benzene ring [d_I⋯C = 3.511 (7) Å, θ_C—I⋯C = 165.0 (5)° for C9′—I1⋯C4 and 164.5 (6)° for C8—I1⋯C4]. As a result of the disorder of the carbon atoms and the dependence of the halogen-bond angle on the position of the carbon atoms, two sets of bond angles can be obtained from the crystal structure. Sheets of inversion dimers are stacked to give the crystal of 3-(1,2,2-triiodoethenyl)benzoic acid. Overall, as shown in Fig. 2, the structure is convoluted as a result of co-present hydrogen and halogen bonds, in addition to disorder.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯O2ⁱ	0.82 (7)	1.83 (8)	2.614 (7)	159 (9)
Symmetry code: (i) -x+2, -y+1, -z+2.

Table 2
Halogen-bond geometry (Å, °)

C—I⋯X	I⋯X	C—I⋯X
C9—I2⋯O2ⁱ	3.174 (6)	159.3 (6)
C9′—I2⋯O2ⁱ	3.174 (6)	161.3 (4)
C8—I1⋯C4ⁱⁱ	3.511 (7)	164.5 (6)
C9′—I1⋯C4ⁱⁱ	3.511 (7)	165.0 (5)
Symmetry codes: (i) − $[{1\over 2}]$ + x, $[{1\over 2}]$ − y, − $[{1\over 2}]$ + z, (ii) 1 − x, 1 − y, 1 − z.

Figure 2
The crystal packing of 3-(1,2,2-triiodoethenyl)benzoic acid, showing O—H⋯O hydrogen bonds and the C—I⋯O and C—I⋯C halogen bonds as dashed lines. The disorder positions in the ethenyl group are also indicated.

Synthesis and crystallization

Crystals of 3-(1,2,2-triiodoethenyl)benzoic acid were obtained as a trace impurity during the recrystallization of 3-iodoethynylbenzoic acid from acetonitrile. The synthesis of 3-iodoethynylbenzoic acid has been reported elsewhere (Szell et al., 2018 ).

Refinement

Crystal data, data collection, and structure refinement details are summarized in Table 3. The triiodoethenyl fragment is disordered over two positions with a 0.545 (18): 0.455 (18) occupancy ratio. It was refined using restraints applied to the atomic displacement parameters, bond distances and angles [RIGU, SAME in SHELXL (Sheldrick, 2015b )]. No additional restraints or constraints were applied.

Table 3
Experimental details

Crystal data
Chemical formula	C₉H₅I₃O₂
M_r	525.83
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	200
a, b, c (Å)	4.7121 (9), 18.752 (4), 13.856 (3)
β (°)	92.379 (5)
V (Å³)	1223.3 (4)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	7.64
Crystal size (mm)	0.48 × 0.16 × 0.06

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2004 )
T_min, T_max	0.485, 0.746
No. of measured, independent and observed [I > 2σ(I)] reflections	9164, 3033, 1539
R_int	0.065
(sin θ/λ)_max (Å⁻¹)	0.670

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.040, 0.078, 0.99
No. of reflections	3033
No. of parameters	159
No. of restraints	97
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	1.14, −1.11
Computer programs: APEX2 and SAINT (Bruker, 2009 ), SHELXT (Sheldrick, 2015a ), SHELXL2014 (Sheldrick, 2015b) and WinGX (Farrugia, 2012 ), Mercury (Macrae et al., 2008 ), PLATON (Spek, 2009 ) and CIFTAB (Sheldrick, 1997 ).

Structural data

CCDC reference: 1823657

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2414314618002584/lh4031sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314618002584/lh4031Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314618002584/lh4031Isup3.cdx

Supporting information file. DOI: https://doi.org/10.1107/S2414314618002584/lh4031Isup4.cml

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: APEX2 (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b) and WinGX (Farrugia, 2012); molecular graphics: Mercury (Macrae et al., 2008) and PLATON (Spek, 2009); software used to prepare material for publication: CIFTAB (Sheldrick, 1997).

3-(1,2,2-Triiodoethenyl)benzoic acid top

Crystal data top

C₉H₅I₃O₂	F(000) = 936
M_r = 525.83	D_x = 2.855 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
a = 4.7121 (9) Å	Cell parameters from 2073 reflections
b = 18.752 (4) Å	θ = 2.6–27.2°
c = 13.856 (3) Å	µ = 7.64 mm⁻¹
β = 92.379 (5)°	T = 200 K
V = 1223.3 (4) Å³	Prism, colourless
Z = 4	0.48 × 0.16 × 0.06 mm

Data collection top

Bruker APEXII CCD diffractometer	1539 reflections with I > 2σ(I)
φ and ω scans	R_int = 0.065
Absorption correction: multi-scan (SADABS; Bruker, 2004)	θ_max = 28.4°, θ_min = 1.8°
T_min = 0.485, T_max = 0.746	h = −6→6
9164 measured reflections	k = −24→24
3033 independent reflections	l = −18→18

Refinement top

Refinement on F²	97 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.040	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.078	w = 1/[σ²(F_o²) + (0.0238P)² + 0.1535P] where P = (F_o² + 2F_c²)/3
S = 0.99	(Δ/σ)_max = 0.001
3033 reflections	Δρ_max = 1.14 e Å⁻³
159 parameters	Δρ_min = −1.10 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.

Refinement. The hydrogen atom bonded to the oxygen atom was located in the difference Fourier map and refined freely while the remaining hydrogen atoms were placed in idealized positions.

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
I1	0.47571 (12)	0.38729 (3)	0.47397 (4)	0.04455 (17)
I2	0.23490 (14)	0.21161 (3)	0.51879 (4)	0.0605 (2)
I3	0.07423 (13)	0.26225 (3)	0.75867 (4)	0.05472 (19)
O1	0.7327 (13)	0.5516 (3)	0.9400 (4)	0.0463 (16)
O2	0.8689 (11)	0.4380 (3)	0.9237 (4)	0.0427 (14)
C1	0.7188 (16)	0.4891 (4)	0.8996 (5)	0.0317 (18)
C2	0.5060 (15)	0.4839 (4)	0.8176 (5)	0.0316 (18)
C3	0.3394 (15)	0.5406 (4)	0.7888 (5)	0.0364 (19)
H3	0.357931	0.584600	0.822475	0.044*
C4	0.1446 (15)	0.5348 (4)	0.7116 (5)	0.037 (2)
H4	0.028550	0.574332	0.692924	0.045*
C5	0.1209 (16)	0.4713 (5)	0.6623 (6)	0.046 (2)
H5	−0.032421	0.464049	0.616701	0.055*
C7	0.4797 (16)	0.4205 (4)	0.7676 (6)	0.047 (2)
H7	0.568537	0.378584	0.792825	0.057*
C6	0.321 (6)	0.4178 (10)	0.6791 (17)	0.038 (6)	0.455 (18)
C8	0.318 (4)	0.3591 (11)	0.6082 (13)	0.032 (4)	0.455 (18)
C9	0.237 (4)	0.2952 (12)	0.6235 (14)	0.032 (4)	0.455 (18)
C6'	0.259 (5)	0.4101 (8)	0.6977 (15)	0.040 (6)	0.545 (18)
C8'	0.228 (3)	0.3326 (9)	0.6600 (12)	0.033 (4)	0.545 (18)
C9'	0.284 (3)	0.3147 (9)	0.5707 (12)	0.030 (4)	0.545 (18)
H1	0.881 (17)	0.550 (4)	0.973 (6)	0.06 (3)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
I1	0.0602 (4)	0.0418 (3)	0.0321 (3)	−0.0075 (3)	0.0067 (3)	0.0011 (3)
I2	0.0916 (5)	0.0355 (3)	0.0558 (4)	−0.0137 (3)	0.0181 (3)	−0.0144 (3)
I3	0.0790 (5)	0.0431 (4)	0.0438 (3)	−0.0026 (3)	0.0223 (3)	0.0041 (3)
O1	0.050 (4)	0.037 (4)	0.051 (4)	0.002 (3)	−0.014 (3)	−0.010 (3)
O2	0.050 (4)	0.030 (3)	0.048 (3)	0.003 (3)	−0.008 (3)	−0.002 (3)
C1	0.038 (5)	0.027 (5)	0.030 (4)	−0.005 (4)	0.002 (4)	−0.007 (4)
C2	0.033 (5)	0.032 (5)	0.030 (4)	−0.002 (4)	0.003 (4)	0.001 (4)
C3	0.045 (5)	0.033 (5)	0.031 (4)	−0.003 (4)	0.007 (4)	−0.006 (4)
C4	0.041 (5)	0.032 (5)	0.038 (5)	0.008 (4)	−0.005 (4)	0.004 (4)
C5	0.031 (5)	0.060 (5)	0.046 (5)	0.003 (4)	−0.001 (4)	−0.013 (4)
C7	0.043 (5)	0.031 (5)	0.067 (6)	0.009 (4)	−0.014 (4)	−0.015 (4)
C6	0.012 (11)	0.054 (9)	0.049 (8)	−0.007 (8)	0.008 (8)	−0.017 (8)
C8	0.034 (11)	0.036 (7)	0.024 (7)	0.000 (7)	−0.009 (7)	0.003 (5)
C9	0.039 (11)	0.037 (8)	0.021 (9)	0.002 (8)	0.006 (9)	0.002 (6)
C6'	0.019 (11)	0.047 (6)	0.054 (10)	0.002 (6)	0.004 (9)	−0.023 (6)
C8'	0.041 (9)	0.031 (7)	0.028 (7)	0.002 (7)	−0.002 (6)	−0.001 (5)
C9'	0.033 (9)	0.030 (7)	0.027 (7)	−0.010 (7)	−0.007 (6)	−0.003 (6)

Geometric parameters (Å, º) top

I1—C8	2.098 (19)	C3—H3	0.9500
I1—C9'	2.137 (16)	C4—C5	1.375 (10)
I2—C9'	2.072 (16)	C4—H4	0.9500
I2—C9	2.14 (2)	C5—C6	1.391 (15)
I3—C8'	2.054 (17)	C5—C6'	1.398 (14)
I3—C9	2.14 (2)	C5—H5	0.9500
O1—C1	1.299 (8)	C7—C6'	1.406 (14)
O1—H1	0.82 (7)	C7—C6	1.410 (15)
O2—C1	1.229 (8)	C7—H7	0.9500
C1—C2	1.488 (9)	C6—C8	1.48 (2)
C2—C3	1.371 (9)	C8—C9	1.28 (3)
C2—C7	1.379 (9)	C6'—C8'	1.55 (2)
C3—C4	1.385 (9)	C8'—C9'	1.32 (3)

C1—O1—H1	103 (6)	C6—C7—H7	120.0
O2—C1—O1	124.6 (7)	C5—C6—C7	116.8 (13)
O2—C1—C2	121.2 (7)	C5—C6—C8	116.1 (11)
O1—C1—C2	114.1 (7)	C7—C6—C8	126.6 (12)
C3—C2—C7	119.0 (7)	C9—C8—C6	126 (2)
C3—C2—C1	122.1 (7)	C9—C8—I1	120.2 (17)
C7—C2—C1	118.9 (7)	C6—C8—I1	114.1 (17)
C2—C3—C4	121.2 (7)	C8—C9—I2	124.6 (17)
C2—C3—H3	119.4	C8—C9—I3	122.4 (17)
C4—C3—H3	119.4	I2—C9—I3	112.9 (10)
C5—C4—C3	119.3 (7)	C5—C6'—C7	116.6 (12)
C5—C4—H4	120.4	C5—C6'—C8'	128.1 (11)
C3—C4—H4	120.4	C7—C6'—C8'	114.7 (10)
C4—C5—C6	120.1 (9)	C9'—C8'—C6'	122.4 (17)
C4—C5—C6'	120.7 (9)	C9'—C8'—I3	123.4 (14)
C4—C5—H5	119.9	C6'—C8'—I3	114.1 (13)
C6—C5—H5	119.9	C8'—C9'—I2	122.7 (14)
C2—C7—C6'	120.9 (8)	C8'—C9'—I1	122.1 (13)
C2—C7—C6	120.1 (9)	I2—C9'—I1	114.9 (8)
C2—C7—H7	120.0

O2—C1—C2—C3	−179.1 (7)	C5—C6—C8—I1	72 (3)
O1—C1—C2—C3	−0.6 (10)	C7—C6—C8—I1	−116 (3)
O2—C1—C2—C7	−0.4 (11)	C6—C8—C9—I2	179.8 (13)
O1—C1—C2—C7	178.1 (7)	I1—C8—C9—I2	−2 (2)
C7—C2—C3—C4	0.7 (11)	C6—C8—C9—I3	2 (3)
C1—C2—C3—C4	179.4 (6)	I1—C8—C9—I3	179.9 (8)
C2—C3—C4—C5	−0.8 (11)	C4—C5—C6'—C7	−18 (3)
C3—C4—C5—C6	−11 (2)	C4—C5—C6'—C8'	171.7 (18)
C3—C4—C5—C6'	9.6 (18)	C2—C7—C6'—C5	17 (3)
C3—C2—C7—C6'	−9.3 (18)	C2—C7—C6'—C8'	−170.5 (13)
C1—C2—C7—C6'	172.0 (16)	C5—C6'—C8'—C9'	59 (3)
C3—C2—C7—C6	11 (2)	C7—C6'—C8'—C9'	−112 (2)
C1—C2—C7—C6	−168.0 (18)	C5—C6'—C8'—I3	−118 (2)
C4—C5—C6—C7	21 (3)	C7—C6'—C8'—I3	71 (2)
C4—C5—C6—C8	−166.2 (17)	C6'—C8'—C9'—I2	−178.6 (11)
C2—C7—C6—C5	−22 (3)	I3—C8'—C9'—I2	−2 (2)
C2—C7—C6—C8	167 (2)	C6'—C8'—C9'—I1	9 (2)
C5—C6—C8—C9	−109 (3)	I3—C8'—C9'—I1	−174.8 (7)
C7—C6—C8—C9	62 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O2ⁱ	0.82 (7)	1.83 (8)	2.614 (7)	159 (9)

Symmetry code: (i) −x+2, −y+1, −z+2.

Halogen-bond geometry (Å, °) top

C—I···X	I···X	C—I···X
C9—I2···O2ⁱ	3.174 (6)	159.3 (6)
C9'—I2···O2ⁱ	3.174 (6)	161.3 (4)
C8—I1···C4ⁱⁱ	3.511 (7)	164.5 (6)
C9'—I1···C4ⁱⁱ	3.511 (7)	165.0 (5)

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

Funding information

Funding for this research was provided by: Natural Sciences and Engineering Research Council of Canada .

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