3,3′-(p-Phenyl­enedimethyl­ene)di­imidazol-1-ium bis­(3-carb­oxy-4-hydroxy­benzene­sulfonate) dihydrate

Yong-Li Peng; Li-Hui Jia

doi:10.1107/S1600536809002086

. 2009 Jan 23;65(Pt 2):o365. doi: 10.1107/S1600536809002086

3,3′-(p-Phenylenedimethylene)diimidazol-1-ium bis(3-carboxy-4-hydroxybenzenesulfonate) dihydrate

Yong-Li Peng ^a, Li-Hui Jia ^a,^*

PMCID: PMC2968313 PMID: 21581963

Abstract

In the title compound, C₁₄H₁₆N₄ ²⁺·2C₇H₅O₆S⁻·2H₂O, the 3,3′-(p-phenylenedimethylene)diimidazol-1-ium dication lies on a crystallographic inversion center. In the crystal structure, dications, anions and solvent water molecules are linked via O—H⋯O, N—H⋯O and C—H⋯O hydrogen bonds, and C—H⋯π interactions, forming a three-dimensional network containing R ₂ ²(4), R ₂ ⁴(12), R ₄ ⁴(22), R ₈ ¹⁰(32) and R ₁₂ ¹⁴(66) ring motifs.

Related literature

For information on hydrogen-bond graph-set motifs, see: Bernstein et al. (1995 ▶). For the synthesis and crystal structure of 1,4-bis(imidazol-1-ylmethyl)benzene, see: Hoskins et al. (1997 ▶). For related crystal structures, see: Meng et al. (2007 ▶, 2008 ▶); Muthiah et al. (2003 ▶); Smith et al. (2004 ▶, 2005a ▶,b ▶,c ▶).

Experimental

Crystal data

C₁₄H₁₆N₄ ²⁺·2C₇H₅O₆S⁻·2H₂O
M _r = 710.68
Triclinic,
a = 7.9975 (6) Å
b = 8.8060 (7) Å
c = 11.2419 (8) Å
α = 90.784 (1)°
β = 96.656 (1)°
γ = 97.342 (1)°
V = 779.61 (10) Å³
Z = 1
Mo Kα radiation
μ = 0.25 mm⁻¹
T = 292 (2) K
0.20 × 0.10 × 0.10 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1997 ▶) T _min = 0.942, T _max = 0.976
8434 measured reflections
3168 independent reflections
2524 reflections with I > 2σ(I)
R _int = 0.024

Refinement

R[F ² > 2σ(F ²)] = 0.050
wR(F ²) = 0.142
S = 1.12
3168 reflections
232 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.34 e Å⁻³
Δρ_min = −0.24 e Å⁻³

Data collection: SMART (Bruker, 2001 ▶); cell refinement: SAINT-Plus (Bruker, 2001 ▶); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: PLATON (Spek, 2003 ▶); software used to prepare material for publication: PLATON.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809002086/lh2757sup1.cif

e-65-0o365-sup1.cif^{(19.4KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809002086/lh2757Isup2.hkl

e-65-0o365-Isup2.hkl^{(155.4KB, hkl)}

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

Cg1 is the centroid of atoms N1/N2/C12–C14.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯O7ⁱ	0.93 (4)	1.68 (4)	2.593 (3)	168 (3)
O3—H3A⋯O2	0.87 (2)	2.038 (19)	2.591 (3)	121 (3)
O3—H3A⋯O3ⁱⁱ	0.87 (2)	2.46 (2)	2.883 (4)	111 (2)
O7—H7B⋯O4ⁱⁱⁱ	0.81 (4)	1.93 (4)	2.741 (3)	173 (4)
O7—H7A⋯O5	0.88 (4)	1.93 (4)	2.799 (3)	172 (4)
N1—H1A⋯O6	0.79 (3)	1.95 (3)	2.707 (3)	160 (3)
C4—H4⋯O6^iv	0.93	2.51	3.411 (4)	164
C12—H12⋯O2^v	0.93	2.22	3.035 (3)	146
C14—H14⋯O6^vi	0.93	2.52	3.219 (4)	132
C3—H3⋯Cg1^vii	0.93	2.97 (1)	3.889 (3)	170

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) ; (iv) ; (v) ; (vi) ; (vii) .

supplementary crystallographic information

Comment

5-Sulfosaliyclic acid (5-H₂SSA), a strong organic acid (pK_a1=2.6), can easily release its sulfonic hydrogen atom to a nitrogen-containing Lewis bases (Muthiah et al., 2003; Smith et al., 2004, 2005a, 2005b, 2005c; Meng et al., 2007; Meng et al., 2008), forming organic salts in most cases. In this paper, we report the crystal structure of the title compound, C₁₄H₁₆N₄.2(C₇H₅O₆S).2(H₂O) (I) , which was obtained by crystallization of the 95% methanol solution of 5-H₂SSA and 1,4-Bis(imidazol-1-ylmethyl)benzene) (bix) (molar ratio 2:1) at room temperature.

In (I), the asymmetric unit consists of one half bix²⁺ dication, one complete 5-HSSA^- anion and one water molecule (see Fig. 1 for symmetry complete formula unit). Similar to some analogs (Meng et al., 2007, 2008), the hydrogen atom was transferred from the sulfonic group to the imidazole nitrogen atom, forming an 1:2 organic salt (cation to anion). The hydroxyl O3 atom forms an intramolecular S(6) and an intermolecular R₂²(4) ring, resulting in a 5-HSSA^- dimer (Bernstein, et al., 1995). The carboxyl O1 atom is only hydrogen-bonded to a water molecule at (x, y, z - 1). The plane defined by sulfonic O4/O5/O6 atoms makes a dihedral angle of 88.7 (1)° with the C1—C6 plane, with the distances of each oxygen atom away from the benzene-plane being 0.211 (1), 1.126 (1) and 1.237 (1) Å, respectively, which is slightly different from those recently reported by Meng, et al., 2007, 2008. In the bix²⁺ dication, there is an crystallogrphic inversion centre at the centre of gravity of the benzene ring.

In the crystal structure of (I), the ionic components are linked by a cooperative action of N—H···O, O—H···O and C—H···O hydrogen bonds into a continuous three-dimensional network which is further consolidated by a C—H···π interaction (Table 1). In more detail, the supramolecular structure in (I) can be analyzed in terms of three substructures. First, by utilizing three intermolecular O1—H1···O7ⁱ [symmetry code: (i) x, y, z - 1], O7—H7A···O5 and O7—H7B···O4ⁱⁱ [symmetry code: (ii) 1 - x, 1 - y, 1 - z] hydrogen bonds, the 5-HSSA^- anions and water molecules are linked into a one-dimensional tape structure running parallel to the [001] direction (Fig.2) in which alternating R₂⁴(12) and R₄⁴(20) (Bernstein, et al., 1995) hydrogen-bonded rings are formed. Secondly, these adjacent one-dimensional tapes are further joined together by the hydroxylic R₂²(4) hydrogen-bonded ring, resulting in a two-dimensional wrinkled sheet running parallel to the (110) plane. In addition to, the intramolecular S(6) and intermolecular R₂²(4) hydrogen-bonded rings, another R₈¹⁰(32) hydrogen-bond motif is formed in the sheet (Fig.2). These sheets are joined by means of the N1—H1A···O6 hydrogen bond, forming a three-dimensional network (Fig.3) in which larger R₁₂¹⁴(66) hydrogen-bonded rings are observed. Further analysis (using the program PLATON [Spek, 2003]) shows that these three-dimensional networks are strengthened by C—H···O hydrogen bonds and weak C—H···π interactions (Table 1).

Experimental

1,4-Bis(imidazol-1-ylmethyl)benzene) (bix) was prepared according to a literature method (Hoskins et al., 1997). 1:2 molar amounts of bix (47.6 mg, 0.2 mmol) and 5-sulfosalicylic acid dihydrate (101.6 mg, 0.4 mmol) were dissolved in 95% methanol (20 ml). The mixture was stirred for 30 min at ambient temperature and then filtered. The resulting colourless solution was kept in air for one week. Block colourless crystals of (I) suitable for single-crystal X-ray diffraction analysis were grown at the bottom of the vessel by slow evaporation of the solution (yield 86.4 mg, 60.8%, based on a 1:2 salt).