1,3-Bis(carboxy­meth­yl)imidazolium triiodide 1-carboxyl­atomethyl-3-carboxy­methyl­imidazolium

Miao, J.; Hu, C.; Chen, H.; Yuan, G.; Nie, Y.

doi:10.1107/S1600536809025239

organic compounds

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doi:10.1107/S1600536809025239

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1,3-Bis(carboxymethyl)imidazolium triiodide 1-carboxylatomethyl-3-carboxymethylimidazolium

Jinling Miao,^a ^* Chunhua Hu,^b Haiyan Chen,^a Guizhen Yuan ^a and Yong Nie ^a

^aSchool of Chemistry and Chemical Engineering, University of Jinan, Jinan 250022, People's Republic of China, and ^bDepartment of Chemistry, New York University, 100 Washington Square East, New York, NY 10003-6688, USA
^*Correspondence e-mail: chm_miaojl@ujn.edu.cn

(Received 24 June 2009; accepted 30 June 2009; online 4 July 2009)

In the title compound, C₇H₉N₂O₄⁺·I₃⁻·C₇H₈N₂O₄, the two imidazolium units are hydrogen bonded through the carboxyl groups. The units are further linked via intermolecular O—H⋯O hydrogen bonding, resulting in a one-dimensional ladder-type structure. As a result, the two carboxy groups of each imidazolium unit adopt a cis configuration with respect to the imidazolium ring.

Related literature

For the preparation of 1,3-bis(carboxymethyl)imidazole, see: Kratochvíl et al. (1988 ); Fei et al. (2004 ); Barczynski et al. (2008 ). For its structure, see: Kratochvíl et al. (1988).

Experimental

Crystal data

C₇H₉N₂O₄⁺·I₃⁻·C₇H₈N₂O₄
M_r = 750.02
Monoclinic, C 2/c
a = 22.260 (3) Å
b = 10.1973 (17) Å
c = 10.1077 (17) Å
β = 92.209 (2)°
V = 2292.7 (6) Å³
Z = 4
Mo Kα radiation
μ = 4.14 mm⁻¹
T = 298 K
0.49 × 0.44 × 0.40 mm

Data collection

Bruker SMART 1000 CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2001 ) T_min = 0.237, T_max = 0.289 (expected range = 0.157–0.191)
6257 measured reflections
2248 independent reflections
1702 reflections with I > 2σ(I)
R_int = 0.031

Refinement

R[F² > 2σ(F²)] = 0.031
wR(F²) = 0.112
S = 1.03
2248 reflections
140 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.84 e Å⁻³
Δρ_min = −0.99 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H3O⋯O1ⁱ	0.81 (8)	1.80 (8)	2.591 (6)	166 (9)
O2—H2O⋯O2ⁱⁱ	1.224 (4)	1.224 (4)	2.449 (6)	179 (9)
Symmetry codes: (i) x, y+1, z; (ii) $[-x+1, y, -z+{\script{1\over 2}}]$ .

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809025239/bt2982sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809025239/bt2982Isup2.hkl

checkCIF report

Comment top

1,3-bis(carboxymethyl)imidazole was first prepared by the condensation reaction of formaldehyde, glyoxal and glycine (Kratochvĺ et al., 1988). Recently its synthesis by the reaction of alkyl haloacetate with imidazole has been reported (Fei et al., 2004; Barczynski et al., 2008). We have found that the reaction of imidazole with chloroacetic acid in the presence of NaOH as a base produces colorless 1,3-bis(carboxymethyl)imidazole, while the same reaction with iodoacetic acid affords the red title compound.

As shown in Fig. 1, two imidazolium units are hydrogen bonded through the carboxy groups. The presence of an I₃^- anion accounts for the neutral nature of the whole structure. The bond lengths of C4—O1 and C4—O2 are 1.231 (6), 1.259 (6) Å (table 1), respectively, which are between those for a C—O single bond and a C═O double bond. The C—N bond lengths on the rings are found to be within 1.316 (6)–1.384 (6) Å (Table 1), which are between those for a C—N single bond and a C═N double bond, suggesting charge delocalization on the planar imidazolium rings. The two imidazolium units are extended by intermolecular hydrogen bonding (O3-H3O—O1i, [i = x, y+1, z], 2.591 (6) Å) to generate a one-dimensional ladder-type structure along the c axis (Fig. 2). As a result of the hydrogen bonding, the two carboxy groups of each imidazolium unit adopt a cis configuration, while in the structure of 1,3-bis(carboxymethyl)imidazole (Kratochvĺ et al., 1988) a trans configuration has been found.

Related literature top

For the preparation of 1,3-bis(carboxymethyl)imidazole, see: Kratochvíl et al. (1988); Fei et al. (2004); Barczynski et al. (2008). For its structure, see: Kratochvíl et al. (1988).

Experimental top

To a solution of iodoacetic acid (9.314 g, 0.05 mol) in distilled water (25 ml), an aqueous solution (25 ml) of NaOH (2.020 g, 0.05 mol) was added, and followed by the addition of imidazole (2.020 g, 0.03 mol). The resulting colorless solution was heated to reflux during which the color gradually changed to yellow. The pH was adjusted using saturated NaOH solution once per 20 min., keeping in the range of 8–9, till no obvious change observed. The mixture was further refluxed for 30 min. and cooled, acidified with hydrochloric acid till pH 2–3, to give an orange-red solution. After 5 days, deep red crystals (yield 11.5% based on iodoacetic acid) were formed over evaporation. IR (KBr): v = 3437, 3117, 1720, 1665, 1350, 1239, 890 cm ^-1.

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure, with atom labels and 25% probability thermal ellipsoids.
	Fig. 2. The crystal packing diagram viewed along the c axis (only one layer shown), showing the hydrogen bonds as dotted lines; iodine atoms have been omitted for clarity

1,3-Bis(carboxymethyl)imidazolium triiodide 1-carboxylatomethyl-3-carboxymethylimidazolium top

Crystal data top

C₇H₉N₂O₄⁺·I₃⁻·C₇H₈N₂O₄	F(000) = 1408
M_r = 750.02	D_x = 2.173 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 22.260 (3) Å	Cell parameters from 2974 reflections
b = 10.1973 (17) Å	θ = 3.0–27.2°
c = 10.1077 (17) Å	µ = 4.14 mm⁻¹
β = 92.209 (2)°	T = 298 K
V = 2292.7 (6) Å³	Plate, red
Z = 4	0.49 × 0.44 × 0.40 mm

Data collection top

Bruker SMART 1000 CCD area-detector diffractometer	2248 independent reflections
Radiation source: fine-focus sealed tube	1702 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.031
ϕ and ω scans	θ_max = 26.0°, θ_min = 1.8°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −18→27
T_min = 0.237, T_max = 0.289	k = −11→12
6257 measured reflections	l = −9→12

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.031	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.112	w = 1/[σ²(F_o²) + (0.0655P)² + 3.4411P] where P = (F_o² + 2F_c²)/3
S = 1.03	(Δ/σ)_max < 0.001
2248 reflections	Δρ_max = 0.84 e Å⁻³
140 parameters	Δρ_min = −0.99 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0032 (2)

Crystal data top

C₇H₉N₂O₄⁺·I₃⁻·C₇H₈N₂O₄	V = 2292.7 (6) Å³
M_r = 750.02	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 22.260 (3) Å	µ = 4.14 mm⁻¹
b = 10.1973 (17) Å	T = 298 K
c = 10.1077 (17) Å	0.49 × 0.44 × 0.40 mm
β = 92.209 (2)°

Data collection top

Bruker SMART 1000 CCD area-detector diffractometer	2248 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2001)	1702 reflections with I > 2σ(I)
T_min = 0.237, T_max = 0.289	R_int = 0.031
6257 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.031	0 restraints
wR(F²) = 0.112	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	Δρ_max = 0.84 e Å⁻³
2248 reflections	Δρ_min = −0.99 e Å⁻³
140 parameters

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

	x	y	z	U_iso*/U_eq
O1	0.46232 (19)	−0.1010 (4)	0.1047 (4)	0.0471 (10)
O2	0.45813 (18)	0.1069 (4)	0.1678 (4)	0.0467 (10)
O3	0.4311 (2)	0.7258 (4)	−0.0724 (5)	0.0608 (13)
O4	0.4461 (2)	0.5756 (4)	0.0836 (4)	0.0533 (11)
N1	0.38543 (17)	0.1836 (4)	−0.0301 (4)	0.0331 (9)
N2	0.38902 (19)	0.3887 (4)	−0.0756 (4)	0.0337 (9)
C1	0.4130 (2)	0.2736 (5)	−0.0999 (5)	0.0349 (11)
H1	0.4441	0.2581	−0.1566	0.042*
C2	0.3446 (2)	0.3728 (5)	0.0145 (6)	0.0415 (12)
H2	0.3207	0.4385	0.0487	0.050*
C3	0.3423 (3)	0.2448 (5)	0.0434 (6)	0.0431 (13)
H3	0.3167	0.2047	0.1016	0.052*
C4	0.4439 (2)	0.0124 (5)	0.0929 (5)	0.0357 (11)
C5	0.4008 (2)	0.0437 (5)	−0.0226 (5)	0.0362 (11)
H5A	0.4189	0.0175	−0.1043	0.043*
H5B	0.3643	−0.0069	−0.0140	0.043*
C6	0.4295 (2)	0.6072 (5)	−0.0261 (5)	0.0365 (11)
C7	0.4056 (3)	0.5151 (5)	−0.1311 (5)	0.0381 (12)
H7A	0.3706	0.5541	−0.1757	0.046*
H7B	0.4359	0.5019	−0.1962	0.046*
I1	0.228024 (19)	0.42974 (5)	0.27861 (4)	0.0609 (2)
I2	0.2500	0.2500	0.5000	0.0519 (2)
H2O	0.5000	0.106 (9)	0.2500	0.08 (3)*
H3O	0.435 (4)	0.780 (7)	−0.014 (9)	0.07 (2)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.054 (2)	0.037 (2)	0.049 (2)	0.0015 (17)	−0.0163 (19)	−0.0009 (17)
O2	0.052 (2)	0.044 (2)	0.042 (2)	0.0067 (17)	−0.0205 (18)	−0.0129 (17)
O3	0.094 (4)	0.038 (2)	0.048 (3)	−0.016 (2)	−0.026 (2)	0.009 (2)
O4	0.078 (3)	0.051 (2)	0.030 (2)	−0.0123 (19)	−0.014 (2)	0.0074 (17)
N1	0.030 (2)	0.035 (2)	0.034 (2)	0.0008 (17)	−0.0065 (17)	−0.0041 (18)
N2	0.038 (2)	0.040 (2)	0.023 (2)	−0.0028 (18)	−0.0028 (17)	−0.0004 (17)
C1	0.034 (3)	0.040 (3)	0.031 (3)	0.002 (2)	0.001 (2)	−0.005 (2)
C2	0.036 (3)	0.046 (3)	0.043 (3)	0.003 (2)	0.010 (2)	0.000 (2)
C3	0.038 (3)	0.049 (3)	0.044 (3)	−0.002 (2)	0.012 (2)	0.000 (2)
C4	0.032 (3)	0.042 (3)	0.033 (3)	−0.005 (2)	−0.004 (2)	−0.001 (2)
C5	0.035 (3)	0.035 (3)	0.038 (3)	0.000 (2)	−0.010 (2)	−0.005 (2)
C6	0.036 (3)	0.044 (3)	0.030 (3)	−0.001 (2)	−0.001 (2)	0.006 (2)
C7	0.050 (3)	0.038 (3)	0.025 (2)	−0.003 (2)	−0.004 (2)	0.002 (2)
I1	0.0478 (3)	0.0875 (4)	0.0468 (3)	0.0116 (2)	−0.00472 (19)	−0.0100 (2)
I2	0.0379 (3)	0.0668 (4)	0.0508 (4)	0.0012 (2)	−0.0021 (2)	−0.0218 (3)

Geometric parameters (Å, º) top

O1—C4	1.231 (6)	C1—H1	0.9300
O2—C4	1.259 (6)	C2—C3	1.339 (7)
O2—H2O	1.224 (4)	C2—H2	0.9300
O3—C6	1.297 (6)	C3—H3	0.9300
O3—H3O	0.81 (8)	C4—C5	1.516 (7)
O4—C6	1.199 (7)	C5—H5A	0.9700
N1—C1	1.323 (6)	C5—H5B	0.9700
N1—C3	1.384 (6)	C6—C7	1.500 (7)
N1—C5	1.467 (6)	C7—H7A	0.9700
N2—C1	1.316 (6)	C7—H7B	0.9700
N2—C2	1.380 (6)	I1—I2	2.9192 (6)
N2—C7	1.459 (6)	I2—I1ⁱ	2.9192 (6)

C4—O2—H2O	125 (4)	O1—C4—C5	118.1 (5)
C6—O3—H3O	112 (6)	O2—C4—C5	116.0 (5)
C1—N1—C3	108.5 (4)	N1—C5—C4	112.6 (4)
C1—N1—C5	126.2 (4)	N1—C5—H5A	109.1
C3—N1—C5	125.1 (4)	C4—C5—H5A	109.1
C1—N2—C2	108.9 (4)	N1—C5—H5B	109.1
C1—N2—C7	127.3 (4)	C4—C5—H5B	109.1
C2—N2—C7	123.7 (4)	H5A—C5—H5B	107.8
N2—C1—N1	108.7 (4)	O4—C6—O3	124.9 (5)
N2—C1—H1	125.7	O4—C6—C7	125.0 (5)
N1—C1—H1	125.7	O3—C6—C7	110.0 (5)
C3—C2—N2	107.0 (4)	N2—C7—C6	111.7 (4)
C3—C2—H2	126.5	N2—C7—H7A	109.3
N2—C2—H2	126.5	C6—C7—H7A	109.3
C2—C3—N1	106.9 (5)	N2—C7—H7B	109.3
C2—C3—H3	126.6	C6—C7—H7B	109.3
N1—C3—H3	126.6	H7A—C7—H7B	107.9
O1—C4—O2	125.8 (5)	I1ⁱ—I2—I1	180.0

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3O···O1ⁱⁱ	0.81 (8)	1.80 (8)	2.591 (6)	166 (9)
O2—H2O···O2ⁱⁱⁱ	1.22 (1)	1.22 (1)	2.449 (6)	179 (9)

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

Experimental details

Crystal data
Chemical formula	C₇H₉N₂O₄⁺·I₃⁻·C₇H₈N₂O₄
M_r	750.02
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	298
a, b, c (Å)	22.260 (3), 10.1973 (17), 10.1077 (17)
β (°)	92.209 (2)
V (Å³)	2292.7 (6)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	4.14
Crystal size (mm)	0.49 × 0.44 × 0.40

Data collection
Diffractometer	Bruker SMART 1000 CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2001)
T_min, T_max	0.237, 0.289
No. of measured, independent and observed [I > 2σ(I)] reflections	6257, 2248, 1702
R_int	0.031
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.031, 0.112, 1.03
No. of reflections	2248
No. of parameters	140
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.84, −0.99

Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2001), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3O···O1ⁱ	0.81 (8)	1.80 (8)	2.591 (6)	166 (9)
O2—H2O···O2ⁱⁱ	1.224 (4)	1.224 (4)	2.449 (6)	179 (9)

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

Acknowledgements

The authors thank the University of Jinan (B0604) for support of this work.

References

Barczynski, P., Komasa, A., Ratajczak-Sitarz, M., Katrusiak, A., Huczynski, A. & Brzezinski, B. (2008). J. Mol. Struct., 876, 170–176. Web of Science CrossRef CAS Google Scholar
Bruker (2001). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Fei, Z. F., Zhao, D. B., Geldbach, T. J., Scopelliti, R. & Dyson, P. J. (2004). Chem. Eur. J. 10, 4886–4893. Web of Science CSD CrossRef PubMed CAS Google Scholar
Kratochvíl, B., Ondráček, J., Velíšek, J. & Hašek, J. (1988). Acta Cryst. C44, 1579–1582. CSD CrossRef Web of Science IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar

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doi:10.1107/S1600536809025239

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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

1,3-Bis(carb­oxy­meth­yl)imidazolium triiodide 1-carboxyl­ato­methyl-3-carb­oxy­methyl­imidazolium

Related literature

Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

organic compounds

1,3-Bis(carboxymethyl)imidazolium triiodide 1-carboxylatomethyl-3-carboxymethylimidazolium