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Acta Cryst. (2007). E63, o4038    [ doi:10.1107/S1600536807043826 ]

Imidazolium 3-carboxy-4-hydroxybenzenesulfonate

D. Yang

Abstract top

The asymmetric unit of the title structure, C3H5N2+·C7H5O6S-, consists of an imidazolium cation and a sulfosalicylate anion connected via an N-H...O hydrogen bond. In the crystal structure, intermolecular hydrogen bonds and [pi]-[pi] stacking interactions [with centroid-centroid distances of 3.655 (2)-4.075 (2) Å] link the molecules into a three-dimensional framework.

Comment top

5-sulfosalicylic acid (5-SSA) is a strong organic acid which can readily release its sulfonic proton when reacting with many Lewis bases. The crystals structures of a series of 5-SSA organic salts have been reported (Smith et al., 2004; Smith et al., 2005a,b; Smith, Wermuth & Healy, 2005; Smith, 2005; Smith et al., 2006; Muthiah et al., 2003; Fan, et al., 2005). More recently, two organic salts formed by 5-SSA and benzimidazole and 4-Methylimidazole have been reported (Wang & Wei, 2007; Hou, 2007). To further the research of analogous 5-SSA-containing organic adducts, we report here the crystal structure of imidazolium 3-carboxy-4-hydroxybenzenesulfonate (abbr. 5-SSA·Im).

The asymmetric unit consists of one imidazolium cation, one sulfosalicylate anion (Fig. 1). The sulfonic hydrogen atom has been transferred to the imine N atom. Unlike the reported analogs (Hou, 2007; Wang & Wei, 2007), in the title structure there are no solvent molecules in the crystal lattice. In the supramolecular structure, by a combination of N–H···O, O–H···O and C–H···O hydrogen bonds and π-π stacking interactions the ions are linked into a three-dimensional framework which can be easily discussed in terms of two types of simple substructures.

Firstly, by means of the series of H-bond interactions listed in table 1, 5-SSA anions and imidazole (abbr. Im) cations are interlinked into a two-dimensional network running parallel to the (101) direction (Fig.2). In addition to H-bonds interactions, the (101) network is consolidated by two intra-network π–π stacking interactions [Cg1···Cg1vii = 4.075 (2) Å and Cg2···Cg2ix = 3.655 (2) Å, symmetry code: (vii) 1 − x, 1 − y, 1 − z; (ix) 1 − x, 2 − y, 1 − z where Cg1 and Cg2 are the centroids of the benzene and imidzole rings.]

Secondly, by the other two symmetry-related π-π stacking interactions between the adjacent network [Cg1···Cg1vi = 3.874 (2) Å and Cg2···Cg2viii = 3.774 (2) Å, symmetry code: (vi) −x, 1 − y, 1 − z; (viii) −x, 2 − y, 1 − z, where Cg1 and Cg2 are the centroids of the benzene and imidzole rings] the adjacent two-dimensional networks are interlinked into a three-dimensional network (Fig.3). It is noteworthy that in the supramolecular structure of the title compound the 5-SSA anions and Im cations are stacked homogeneously, i.e. 5-SSA anions stack only on top of 5-SSA anions, and Im anions stack only on top of Im anion. However, the stacks in the 4-Methyl dihydrate and benzimidazole trihydrate analogs reported by (Hou, 2007; Wang & Wei, 2007) are heterogeneous and homogeneous, respectively. Why and how the cations and water solvent molecules affect the stacking patterns is worthy of further study.

Related literature top

For related literature, see: Fan et al. (2005); Hou (2007); Muthiah et al. (2003); Smith (2005); Smith et al. (2004, 2005a, 2005b); Smith, Wermuth & Healy (2005, 2006); Wang & Wei (2007).

Experimental top

Crystals of the title compound were unexpectedly obtained by mixing equimolar amount of 5-sulfosalicylic acid dihydrate (0.1 mmol, 25.4 mg), imidazole (0.1 mmol, 6.8 mg) and silver nitrate (0.1 mmol, 17.0 mg) in 10 ml water solvent sealed in a 25 ml Teflon-lined autoclave. The mixture was heated to 423 K and maintained for 140 h. After slowly cooling to room temperature with the rate of 10°/h, colorless crystals suitable for single-crystal X-ray diffraction analysis were obtained. The crystals were filtered and washed with distilled water and dried in air (Yield: 40%, 13.0 mg, based on the 1:1 organic salt.)

Refinement top

H atoms bonded to carbon atoms were located at the geometrical positions with C—H=0.93 Å, and Uiso(H) = 1.2Ueq(C). H atoms attached to N and O atoms were located from the difference maps with the N–H and O–H distances refined freely and their Uiso values set 1.5 or 1.2 times of their carrier atoms, respectively.

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT-Plus (Bruker, 2001); data reduction: SAINT-Plus (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: PLATON (Spek, 2003).

Figures top
[Figure 1] Fig. 1. Molecular structure, showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. Hydrogen bonds are shown as dashed lines.
[Figure 2] Fig. 2. Part of the crystal structure, showing the formation of the two-dimensional (101) network fromed by 5-SSA anions and Im anions. Hydrogen bonds and π–π stacking interactions are shown as dashed lines.
[Figure 3] Fig. 3. Part of the crystal structure, showing the formation of the three-dimensional network formed by 5-SSA anions and Im anions. Hydrogen bonds and π–π stacking interactions are shown as dashed lines.
Imidazolium 3-carboxy-4-hydroxybenzenesulfonate top
Crystal data top
C3H5N2+·C7H5O6S–F000 = 592
Mr = 286.26Dx = 1.606 Mg m−3
Monoclinic, P21/nMo Kα radiation
λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 2471 reflections
a = 6.9486 (5) Åθ = 2.2–24.7º
b = 14.5898 (11) ŵ = 0.30 mm−1
c = 12.0504 (9) ÅT = 294 (2) K
β = 104.220 (1)ºBlock, colorless
V = 1184.22 (15) Å30.10 × 0.10 × 0.08 mm
Z = 4
Data collection top
Bruker SMART APEX CCD area-detector
diffractometer		2575 independent reflections
Radiation source: fine focus sealed Siemens Mo tube1805 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.049
T = 294(2) Kθmax = 27.0º
0.3° wide ω exposures scansθmin = 2.2º
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −8→8
Tmin = 0.969, Tmax = 0.971k = −18→18
12957 measured reflectionsl = −15→15
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.057H atoms treated by a mixture of
independent and constrained refinement
wR(F2) = 0.169  w = 1/[σ2(Fo2) + (0.1041P)2]
where P = (Fo2 + 2Fc2)/3
S = 1.07(Δ/σ)max < 0.001
2575 reflectionsΔρmax = 0.65 e Å−3
185 parametersΔρmin = −0.40 e Å−3
Primary atom site location: structure-invariant direct methodsExtinction correction: none
Crystal data top
C3H5N2+·C7H5O6S–V = 1184.22 (15) Å3
Mr = 286.26Z = 4
Monoclinic, P21/nMo Kα
a = 6.9486 (5) ŵ = 0.30 mm−1
b = 14.5898 (11) ÅT = 294 (2) K
c = 12.0504 (9) Å0.10 × 0.10 × 0.08 mm
β = 104.220 (1)º
Data collection top
Bruker SMART APEX CCD area-detector
diffractometer		2575 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		1805 reflections with I > 2σ(I)
Tmin = 0.969, Tmax = 0.971Rint = 0.049
12957 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.057185 parameters
wR(F2) = 0.169H atoms treated by a mixture of
independent and constrained refinement
S = 1.07Δρmax = 0.65 e Å−3
2575 reflectionsΔρmin = −0.40 e Å−3
Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s 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 > 2sigma(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
xyzUiso*/Ueq
C10.2333 (3)0.47417 (16)0.47446 (19)0.0266 (5)
C20.3081 (4)0.49675 (17)0.58992 (19)0.0305 (6)
C30.3199 (4)0.58790 (17)0.6234 (2)0.0339 (6)
H30.36950.60290.70010.041*
C40.2586 (4)0.65660 (17)0.5438 (2)0.0334 (6)
H40.26800.71760.56680.040*
C50.1832 (4)0.63454 (16)0.42953 (19)0.0299 (6)
C60.1715 (4)0.54408 (15)0.39553 (19)0.0285 (6)
H60.12160.52970.31870.034*
C70.2281 (4)0.37808 (16)0.4350 (2)0.0311 (6)
C80.2003 (5)1.0567 (2)0.4116 (3)0.0465 (7)
H80.15351.06630.33330.056*
C90.2919 (4)0.9900 (2)0.5773 (3)0.0513 (8)
H90.31980.94490.63360.062*
C100.3176 (5)1.0799 (2)0.5933 (3)0.0539 (8)
H100.36561.10960.66290.065*
N10.2177 (4)0.97671 (16)0.4640 (2)0.0453 (6)
H1A0.188 (5)0.928 (3)0.422 (3)0.068*
N20.2606 (4)1.11996 (17)0.4891 (2)0.0486 (7)
H2A0.266 (5)1.180 (3)0.477 (3)0.073*
O10.2791 (3)0.31374 (12)0.50053 (15)0.0416 (5)
O20.1645 (3)0.36856 (13)0.32466 (15)0.0464 (6)
H2B0.192 (5)0.319 (3)0.292 (3)0.070*
O30.3731 (3)0.43343 (14)0.67244 (14)0.0444 (6)
H3A0.350 (5)0.385 (3)0.632 (3)0.067*
O40.1132 (4)0.80550 (13)0.38169 (18)0.0608 (7)
O50.2646 (5)0.71675 (13)0.2598 (2)0.0731 (8)
O6−0.0765 (4)0.69516 (18)0.2535 (2)0.0870 (10)
S10.11344 (12)0.72006 (4)0.32363 (5)0.0403 (3)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0296 (14)0.0194 (12)0.0319 (12)−0.0017 (10)0.0096 (10)−0.0019 (9)
C20.0358 (15)0.0234 (12)0.0314 (12)−0.0011 (10)0.0066 (10)0.0029 (9)
C30.0442 (16)0.0252 (13)0.0318 (12)−0.0033 (11)0.0080 (11)−0.0056 (10)
C40.0459 (17)0.0190 (12)0.0353 (12)−0.0037 (11)0.0100 (11)−0.0048 (9)
C50.0375 (15)0.0194 (12)0.0337 (12)−0.0016 (10)0.0103 (11)0.0007 (9)
C60.0388 (15)0.0195 (12)0.0262 (11)−0.0008 (10)0.0057 (10)−0.0007 (8)
C70.0373 (15)0.0212 (12)0.0352 (13)0.0032 (10)0.0099 (11)−0.0005 (9)
C80.059 (2)0.0361 (16)0.0417 (15)−0.0014 (14)0.0069 (14)0.0025 (11)
C90.050 (2)0.0452 (18)0.0535 (17)0.0016 (14)0.0026 (14)0.0190 (14)
C100.058 (2)0.051 (2)0.0468 (16)−0.0051 (16)0.0030 (15)−0.0055 (14)
N10.0522 (16)0.0236 (12)0.0595 (15)−0.0015 (11)0.0125 (12)−0.0062 (10)
N20.0590 (17)0.0211 (12)0.0619 (16)−0.0022 (11)0.0073 (13)0.0006 (10)
O10.0604 (14)0.0190 (9)0.0433 (11)0.0023 (8)0.0088 (9)0.0015 (7)
O20.0721 (15)0.0243 (10)0.0373 (11)0.0076 (9)0.0030 (10)−0.0081 (7)
O30.0688 (15)0.0251 (10)0.0329 (10)0.0013 (9)0.0000 (10)0.0044 (7)
O40.110 (2)0.0157 (9)0.0564 (13)0.0093 (11)0.0199 (13)−0.0023 (8)
O50.136 (2)0.0249 (11)0.0788 (16)0.0221 (12)0.0651 (16)0.0256 (10)
O60.104 (2)0.0504 (16)0.0761 (16)−0.0188 (13)−0.0361 (16)0.0301 (12)
S10.0679 (6)0.0144 (4)0.0370 (4)−0.0005 (3)0.0100 (3)0.0037 (2)
Geometric parameters (Å, °) top
C1—C61.389 (3)C8—N11.318 (4)
C1—C21.400 (3)C8—H80.9300
C1—C71.478 (3)C9—C101.332 (5)
C2—O31.351 (3)C9—N11.350 (4)
C2—C31.386 (3)C9—H90.9300
C3—C41.380 (3)C10—N21.353 (4)
C3—H30.9300C10—H100.9300
C4—C51.386 (3)N1—H1A0.87 (4)
C4—H40.9300N2—H2A0.89 (4)
C5—C61.378 (3)O2—H2B0.87 (4)
C5—S11.765 (2)O3—H3A0.86 (4)
C6—H60.9300O4—S11.4296 (19)
C7—O11.222 (3)O5—S11.447 (3)
C7—O21.301 (3)O6—S11.428 (3)
C8—N21.307 (4)
C6—C1—C2119.0 (2)N2—C8—H8126.1
C6—C1—C7119.8 (2)N1—C8—H8126.1
C2—C1—C7121.1 (2)C10—C9—N1107.0 (3)
O3—C2—C3117.2 (2)C10—C9—H9126.5
O3—C2—C1123.1 (2)N1—C9—H9126.5
C3—C2—C1119.7 (2)C9—C10—N2107.0 (3)
C4—C3—C2120.5 (2)C9—C10—H10126.5
C4—C3—H3119.7N2—C10—H10126.5
C2—C3—H3119.7C8—N1—C9109.0 (3)
C3—C4—C5119.9 (2)C8—N1—H1A118 (2)
C3—C4—H4120.0C9—N1—H1A133 (2)
C5—C4—H4120.0C8—N2—C10109.1 (3)
C6—C5—C4119.9 (2)C8—N2—H2A126 (2)
C6—C5—S1118.44 (17)C10—N2—H2A124 (2)
C4—C5—S1121.59 (19)C7—O2—H2B120 (2)
C5—C6—C1120.9 (2)C2—O3—H3A100 (2)
C5—C6—H6119.5O6—S1—O4113.53 (17)
C1—C6—H6119.5O6—S1—O5111.29 (19)
O1—C7—O2123.4 (2)O4—S1—O5112.18 (14)
O1—C7—C1122.7 (2)O6—S1—C5107.30 (13)
O2—C7—C1113.9 (2)O4—S1—C5107.19 (12)
N2—C8—N1107.9 (3)O5—S1—C5104.74 (12)
C6—C1—C2—O3−179.4 (2)C2—C1—C7—O13.5 (4)
C7—C1—C2—O3−2.3 (4)C6—C1—C7—O20.6 (3)
C6—C1—C2—C3−0.2 (4)C2—C1—C7—O2−176.5 (2)
C7—C1—C2—C3176.9 (2)N1—C9—C10—N2−0.7 (4)
O3—C2—C3—C4179.2 (2)N2—C8—N1—C9−0.4 (4)
C1—C2—C3—C40.0 (4)C10—C9—N1—C80.7 (4)
C2—C3—C4—C50.5 (4)N1—C8—N2—C10−0.1 (4)
C3—C4—C5—C6−0.7 (4)C9—C10—N2—C80.5 (4)
C3—C4—C5—S1−177.1 (2)C6—C5—S1—O650.0 (3)
C4—C5—C6—C10.4 (4)C4—C5—S1—O6−133.5 (3)
S1—C5—C6—C1176.93 (19)C6—C5—S1—O4172.3 (2)
C2—C1—C6—C50.0 (4)C4—C5—S1—O4−11.3 (3)
C7—C1—C6—C5−177.1 (2)C6—C5—S1—O5−68.3 (2)
C6—C1—C7—O1−179.4 (2)C4—C5—S1—O5108.1 (2)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O3—H3A···O10.86 (4)1.85 (4)2.665 (3)158 (3)
N1—H1A···O40.87 (4)1.89 (4)2.720 (3)159 (3)
C8—H8···O3i0.932.393.206 (4)147
C8—H8···O5ii0.932.593.167 (4)121
C4—H4···O40.932.572.930 (3)104
C6—H6···O20.932.372.696 (3)100
C10—H10···O2iii0.932.493.293 (4)144
C9—H9···O6iii0.932.503.419 (4)168
C4—H4···O6iii0.932.583.310 (3)136
O2—H2B···O5iv0.87 (4)1.67 (4)2.536 (3)174 (4)
N2—H2A···O1v0.89 (4)1.97 (4)2.832 (3)162 (3)
Symmetry codes: (i) x−1/2, −y+3/2, z−1/2; (ii) −x+1/2, y+1/2, −z+1/2; (iii) x+1/2, −y+3/2, z+1/2; (iv) −x+1/2, y−1/2, −z+1/2; (v) x, y+1, z.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O3—H3A···O10.86 (4)1.85 (4)2.665 (3)158 (3)
N1—H1A···O40.87 (4)1.89 (4)2.720 (3)159 (3)
C8—H8···O3i0.932.393.206 (4)147
C8—H8···O5ii0.932.593.167 (4)121
C4—H4···O40.932.572.930 (3)104
C6—H6···O20.932.372.696 (3)100
C10—H10···O2iii0.932.493.293 (4)144
C9—H9···O6iii0.932.503.419 (4)168
C4—H4···O6iii0.932.583.310 (3)136
O2—H2B···O5iv0.87 (4)1.67 (4)2.536 (3)174 (4)
N2—H2A···O1v0.89 (4)1.97 (4)2.832 (3)162 (3)
Symmetry codes: (i) x−1/2, −y+3/2, z−1/2; (ii) −x+1/2, y+1/2, −z+1/2; (iii) x+1/2, −y+3/2, z+1/2; (iv) −x+1/2, y−1/2, −z+1/2; (v) x, y+1, z.
Acknowledgements top

The author is grateful to the Key Fundamental Project for financial support.

references
References top

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