8,10-Diiodo-2,6-dioxo-4λ3-ioda-3,5-dioxatricyclo­[5.3.1.04,11]undeca-1(11),7,9-triene-9-carb­oxy­lic acid

Sheng, D.; Han, L.; Zhang, Y.; Yang, Y.

doi:10.1107/S1600536812005351

organic compounds

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ISSN: 2056-9890

Volume 68| Part 3| March 2012| Page o706

doi:10.1107/S1600536812005351

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8,10-Diiodo-2,6-dioxo-4λ³-ioda-3,5-dioxatricyclo[5.3.1.0^4,11]undeca-1(11),7,9-triene-9-carboxylic acid

Daopeng Sheng,^a Lu Han,^a Yi Zhang ^a and Yanzhao Yang ^a ^*

^aKey Laboratory for Special Functional Aggregated Materials of the Education Ministry, School of Chemistry and Chemical Engineering, Shandong University, Jinan 250100, People's Republic of China
^*Correspondence e-mail: yzhyang@sdu.edu.cn

(Received 5 January 2012; accepted 7 February 2012; online 17 February 2012)

In the title compound, C₉HI₃O₆·2H₂O, the molecule is located on a twofold axis that gives rise to disorder of the carboxyl group. This disorder is correlated with the disorder of one of the H atoms of the water molecule. The carboxyl group is twisted relative to the attached benzene ring by 75.1 (4)°. The intramolecular I⋯O distance is 2.112 (6) Å. Molecules are linked via O—H⋯O hydrogen bonding, C—I⋯O halogen bonding, with I⋯O distances in the range 3.156 (5)–3.274 (6) Å, and dipolar C=O⋯C=O interactions between the carboxyl and carboxylate groups, with an O⋯C distance of 2.944 (10) Å.

Related literature

For general background to 1,3,5-triiodobenzene derivatives, see: Morin et al. (1987 ); Yu & Watson (1999 ). For information on the related compound 1,3,5-triiodo-2,4,6-trimethylbenzene, see: Bosch & Barnes (2002 ); Boudjada et al. (2001 ); Reddy et al. (2006 ). For the crystal structures of 5-amino-2,4,6-triiodoisophthalic acid monohydrate and 5-amino-2,4,6-triiodoisophthalic acid–4,4′-bipyridine N,N′-dioxide–water (1/1/1), see: Beck & Sheldrick (2008 ); Zhang et al. (2011 ).

Experimental

Crystal data

C₉HI₃O₆·2H₂O
M_r = 621.83
Monoclinic, C 2/c
a = 14.7667 (8) Å
b = 11.9890 (6) Å
c = 9.7419 (5) Å
β = 127.4236 (5)°
V = 1369.68 (12) Å³
Z = 4
Mo Kα radiation
μ = 6.88 mm⁻¹
T = 130 K
0.32 × 0.14 × 0.12 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (APEX2; Bruker, 2007 ) T_min = 0.217, T_max = 0.492
4078 measured reflections
1547 independent reflections
1515 reflections with I > 2σ(I)
R_int = 0.016

Refinement

R[F² > 2σ(F²)] = 0.042
wR(F²) = 0.097
S = 1.23
1547 reflections
93 parameters
H-atom parameters constrained
Δρ_max = 2.36 e Å⁻³
Δρ_min = −2.23 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H3⋯O1W	0.82	2.08	2.772 (9)	142
O1W—H1W⋯O3	0.82	1.98	2.772 (9)	163
O1W—H2W⋯O1Wⁱ	0.82	1.94	2.730 (14)	160
O1W—H3W⋯O1ⁱⁱ	0.82	2.24	3.053 (9)	172
Symmetry codes: (i) -x+1, -y+2, -z+1; (ii) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT; program(s) used to solve structure: SIR97 (Altomare et al., 1999 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ); molecular graphics: DIAMOND (Brandenburg, 1999 ); software used to prepare material for publication: publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536812005351/gk2447sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812005351/gk2447Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812005351/gk2447Isup3.cml

checkCIF report

Comment top

Iodine-based compounds have always been used as contrast agents for X-ray imaging (Morin et al., 1987). The 1,3,5-triiodo-benzene core has been the basis of many contrast agents (Yu & Watson, 1999). In this paper, we present the crystal structure of a new compound based on 1,3,5-triiodobenzene core.

In the title compound the organic molecule is located on a twofold axis what results in disorder of the carboxylic group (Fig. 1). In the crystal structure, there are hydrogen bonds between symmetry related water molecules as well as between the water molecule and the carboxylic group. It indicates that one of the hydrogen atoms of the water molecule has to be disordered and this disorder is evidently correlated with the disorder of the carboxylic group. The hydrogen atom and the oxygen atom forming hydrogen bond between the water molecule and the carboxylic group are either from the water molecule or the carboxylic group. There is also a hydrogen bond between the water molecule and the carboxylate O1 atom. Hydrogen atom involved in this interaction has full occupancy. The dihedral angle between the plane of the carboxyl group and the benzene ring is 75.1 (4)°.

In addition to hydrogen bond, the structure is stabilized by halogen bonding between the I2 atom and the carboxylate group O1 and O2 atoms. There is also a halogen bond between the water molecule and I1 atom (Fig. 2). A dipolar interaction between carboxyl C6—O3 and carboxylate C4 also is observed (C···O 2.95 Å) (Fig. 3).

Related literature top

For general background to 1,3,5-triiodobenzene derivatives, see: Morin et al. (1987); Yu & Watson (1999). For information on the related compound 1,3,5-triiodo-2,4,6-trimethylbenzene, see: Bosch & Barnes (2002); Boudjada et al. (2001); Reddy et al. (2006). For the crystal structures of 5-amino-2,4,6-triiodoisophthalic acid monohydrate and 5-amino-2,4,6-triiodoisophthalic acid–4,4'-bipyridine N,N'-dioxide–water, see: Beck & Sheldrick (2008); Zhang et al. (2011).

Experimental top

A mixture of 1,3,5-triiodo-2,4,6-trimethylbenzene (5 g) and excess of potassium permanganate (80 g) was dissolved in pyridine (60 ml) and heated under reflux for 24 h to produce the title compound (m.p. 573 K, decompose). Crystallization was carried out from a mixture of water and methanol (v/v 1:2). Colorless crystals suitable for X-ray single-crystal diffraction were obtained by slow evaporation method.

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: APEX2 (Bruker, 2007); data reduction: APEX2 (Bruker, 2007); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 1999); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

	Fig. 1. Molecular structure of the title compound. Displacement ellipsoids are drawn at the 50% probability level. Symmetry code: (i) 1 - x, y, 1.5 + z.
	Fig. 2. Partial view of the crystal structure. Molecules are linked by O—H···O (green dashed lines) and O—H···I hydrogen bonds (purple dashed lines).
	Fig. 3. Packing of the title compound, hydrogen atoms are omitted for clarity. Hydrogen bonds (green), halogen bonds (purple) and dipolar interaction (blue) are shown as dashed lines.

8,10-diiodo-2,6-dioxo-4λ³-ioda-3,5-dioxatricyclo[5.3.1.0^4,11]undeca- 1(11),7,9-triene-9-carboxylic acid top

Crystal data top

C₉HI₃O₆·2H₂O	F(000) = 1128
M_r = 621.83	D_x = 3.016 Mg m⁻³
Monoclinic, C2/c	Melting point: 573 K
Hall symbol: -C 2yc	Mo Kα radiation, λ = 0.71069 Å
a = 14.7667 (8) Å	Cell parameters from 3350 reflections
b = 11.9890 (6) Å	θ = 2.4–27.4°
c = 9.7419 (5) Å	µ = 6.88 mm⁻¹
β = 127.4236 (5)°	T = 130 K
V = 1369.68 (12) Å³	Prism, colourless
Z = 4	0.32 × 0.14 × 0.12 mm

Data collection top

Bruker APEXII CCD area-detector diffractometer	1547 independent reflections
Radiation source: fine-focus sealed tube	1515 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.016
ϕ and ω scans	θ_max = 27.4°, θ_min = 2.4°
Absorption correction: multi-scan (APEX2; Bruker, 2007)	h = −10→19
T_min = 0.217, T_max = 0.492	k = −14→15
4078 measured reflections	l = −12→12

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.042	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.097	H-atom parameters constrained
S = 1.23	w = 1/[σ²(F_o²) + (0.0157P)² + 40.7765P] where P = (F_o² + 2F_c²)/3
1547 reflections	(Δ/σ)_max < 0.001
93 parameters	Δρ_max = 2.36 e Å⁻³
0 restraints	Δρ_min = −2.23 e Å⁻³

Crystal data top

C₉HI₃O₆·2H₂O	V = 1369.68 (12) Å³
M_r = 621.83	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 14.7667 (8) Å	µ = 6.88 mm⁻¹
b = 11.9890 (6) Å	T = 130 K
c = 9.7419 (5) Å	0.32 × 0.14 × 0.12 mm
β = 127.4236 (5)°

Data collection top

Bruker APEXII CCD area-detector diffractometer	1547 independent reflections
Absorption correction: multi-scan (APEX2; Bruker, 2007)	1515 reflections with I > 2σ(I)
T_min = 0.217, T_max = 0.492	R_int = 0.016
4078 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.042	0 restraints
wR(F²) = 0.097	H-atom parameters constrained
S = 1.23	w = 1/[σ²(F_o²) + (0.0157P)² + 40.7765P] where P = (F_o² + 2F_c²)/3
1547 reflections	Δρ_max = 2.36 e Å⁻³
93 parameters	Δρ_min = −2.23 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. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
C1	0.5000	0.3381 (8)	0.7500	0.0216 (19)
C2	0.4147 (5)	0.3903 (6)	0.5979 (8)	0.0207 (13)
C3	0.4155 (6)	0.5066 (6)	0.5979 (9)	0.0249 (14)
C4	0.3340 (6)	0.3120 (6)	0.4528 (9)	0.0248 (14)
C5	0.5000	0.5629 (8)	0.7500	0.0222 (19)
C6	0.5000	0.6916 (8)	0.7500	0.027 (2)
I1	0.5000	0.16946 (5)	0.7500	0.02526 (18)
I2	0.29502 (5)	0.59994 (5)	0.37929 (8)	0.0469 (2)
O1	0.2532 (5)	0.3419 (5)	0.3093 (7)	0.0386 (14)
O2	0.3559 (5)	0.2049 (5)	0.4946 (7)	0.0313 (12)
O3	0.5338 (6)	0.7375 (5)	0.6751 (9)	0.0474 (16)
H3	0.5308	0.8054	0.6818	0.071*	0.50
O1W	0.4370 (6)	0.9449 (6)	0.5383 (9)	0.0494 (16)
H1W	0.4763	0.8910	0.5958	0.074*	0.50
H2W	0.4756	0.9896	0.5303	0.074*	0.50
H3W	0.3831	0.9240	0.4416	0.074*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.021 (4)	0.019 (4)	0.021 (5)	0.000	0.011 (4)	0.000
C2	0.017 (3)	0.024 (3)	0.012 (3)	0.000 (2)	0.004 (2)	−0.001 (2)
C3	0.021 (3)	0.030 (4)	0.017 (3)	0.005 (3)	0.008 (3)	0.004 (3)
C4	0.021 (3)	0.031 (4)	0.015 (3)	−0.002 (3)	0.007 (3)	−0.003 (3)
C5	0.026 (5)	0.018 (4)	0.029 (5)	0.000	0.020 (4)	0.000
C6	0.039 (6)	0.012 (4)	0.035 (6)	0.000	0.025 (5)	0.000
I1	0.0282 (3)	0.0169 (3)	0.0269 (3)	0.000	0.0148 (3)	0.000
I2	0.0427 (4)	0.0392 (3)	0.0341 (3)	0.0125 (2)	0.0104 (3)	0.0160 (2)
O1	0.031 (3)	0.042 (3)	0.019 (3)	0.000 (3)	0.003 (2)	−0.004 (2)
O2	0.030 (3)	0.029 (3)	0.024 (3)	−0.008 (2)	0.011 (2)	−0.008 (2)
O3	0.074 (5)	0.028 (3)	0.069 (5)	0.000 (3)	0.058 (4)	0.005 (3)
O1W	0.050 (4)	0.044 (4)	0.048 (4)	−0.008 (3)	0.026 (3)	−0.002 (3)

Geometric parameters (Å, º) top

C1—C2ⁱ	1.380 (8)	C5—C3ⁱ	1.400 (8)
C1—I1	2.022 (9)	C5—C6	1.543 (13)
C2—C3	1.394 (10)	C6—O3	1.237 (7)
C2—C4	1.501 (9)	I1—O2	2.113 (5)
C3—C5	1.400 (8)	O3—H3	0.8200
C3—I2	2.085 (7)	O1W—H1W	0.8201
C4—O1	1.216 (9)	O1W—H2W	0.8200
C4—O2	1.326 (9)	O1W—H3W	0.8201

C4···O3ⁱⁱ	2.944 (10)	I2···O2^iv	3.156 (5)
I1···O1Wⁱⁱⁱ	3.173 (7)	I2···O1^iv	3.274 (6)

C2ⁱ—C1—C2	126.1 (9)	C3—C5—C3ⁱ	122.3 (9)
C2ⁱ—C1—I1	117.0 (5)	C3—C5—C6	118.8 (5)
C2—C1—I1	117.0 (5)	O3ⁱ—C6—O3	127.1 (10)
C1—C2—C3	116.8 (6)	O3—C6—C5	116.5 (5)
C1—C2—C4	114.3 (6)	C1—I1—O2	78.38 (15)
C3—C2—C4	128.9 (6)	O2ⁱ—I1—O2	156.8 (3)
C2—C3—C5	119.0 (7)	C4—O2—I1	116.1 (4)
C2—C3—I2	122.3 (5)	C6—O3—H3	109.5
C5—C3—I2	118.7 (6)	H1W—O1W—H2W	109.6
O1—C4—O2	121.6 (7)	H1W—O1W—H3W	109.5
O1—C4—C2	124.1 (7)	H2W—O1W—H3W	109.6
O2—C4—C2	114.2 (6)

C2ⁱ—C1—C2—C3	0.5 (5)	I2—C3—C5—C3ⁱ	−179.6 (5)
I1—C1—C2—C3	−179.5 (5)	C2—C3—C5—C6	−179.5 (5)
C2ⁱ—C1—C2—C4	179.7 (6)	I2—C3—C5—C6	0.4 (5)
I1—C1—C2—C4	−0.3 (6)	C3—C5—C6—O3ⁱ	105.1 (5)
C1—C2—C3—C5	−0.9 (9)	C3—C5—C6—O3	−74.9 (5)
C4—C2—C3—C5	180.0 (6)	C3ⁱ—C5—C6—O3	105.1 (5)
C1—C2—C3—I2	179.1 (4)	C2ⁱ—C1—I1—O2	179.6 (4)
C4—C2—C3—I2	0.1 (11)	C2—C1—I1—O2	−0.4 (4)
C1—C2—C4—O1	179.7 (7)	O1—C4—O2—I1	180.0 (6)
C3—C2—C4—O1	−1.3 (13)	C2—C4—O2—I1	−1.5 (8)
C1—C2—C4—O2	1.2 (9)	C1—I1—O2—C4	1.1 (5)
C3—C2—C4—O2	−179.7 (7)	O2ⁱ—I1—O2—C4	1.1 (5)
C2—C3—C5—C3ⁱ	0.5 (5)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3···O1W	0.82	2.08	2.772 (9)	142
O1W—H1W···O3	0.82	1.98	2.772 (9)	163
O1W—H2W···O1W^v	0.82	1.94	2.730 (14)	160
O1W—H3W···O1^iv	0.82	2.24	3.053 (9)	172

Symmetry codes: (iv) −x+1/2, y+1/2, −z+1/2; (v) −x+1, −y+2, −z+1.

Experimental details

Crystal data
Chemical formula	C₉HI₃O₆·2H₂O
M_r	621.83
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	130
a, b, c (Å)	14.7667 (8), 11.9890 (6), 9.7419 (5)
β (°)	127.4236 (5)
V (Å³)	1369.68 (12)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	6.88
Crystal size (mm)	0.32 × 0.14 × 0.12

Data collection
Diffractometer	Bruker APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (APEX2; Bruker, 2007)
T_min, T_max	0.217, 0.492
No. of measured, independent and observed [I > 2σ(I)] reflections	4078, 1547, 1515
R_int	0.016
(sin θ/λ)_max (Å⁻¹)	0.647

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.042, 0.097, 1.23
No. of reflections	1547
No. of parameters	93
H-atom treatment	H-atom parameters constrained
	w = 1/[σ²(F_o²) + (0.0157P)² + 40.7765P] where P = (F_o² + 2F_c²)/3
Δρ_max, Δρ_min (e Å⁻³)	2.36, −2.23

Computer programs: APEX2 (Bruker, 2007), SIR97 (Altomare et al., 1999), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg, 1999), publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3···O1W	0.82	2.08	2.772 (9)	142
O1W—H1W···O3	0.82	1.98	2.772 (9)	163
O1W—H2W···O1Wⁱ	0.82	1.94	2.730 (14)	160
O1W—H3W···O1ⁱⁱ	0.82	2.24	3.053 (9)	172

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

Acknowledgements

The authors acknowledge financial support for this work from the National Natural Science Foundation of China (grant Nos. 20876089 and 21076115), the Natural Science Foundation of Shandong Province (grant No. ZR2010BM019) and the 973 Project of China (grant No. 2011CB935901).

References

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