1,4-Bis(4,5-dihydro-1H-imidazol-2-yl)benzene–4-amino­benzene­sulfonic acid–water (1/2/2)

Shao-Ming Shang; Chun-Xia Ren; Xin Wang; Lu-De Lu; Xu-Jie Yang

doi:10.1107/S1600536809032504

. 2009 Aug 22;65(Pt 9):o2221–o2222. doi: 10.1107/S1600536809032504

1,4-Bis(4,5-dihydro-1H-imidazol-2-yl)benzene–4-aminobenzenesulfonic acid–water (1/2/2)

Shao-Ming Shang ^a, Chun-Xia Ren ^b, Xin Wang ^a,^*, Lu-De Lu ^a, Xu-Jie Yang ^a

PMCID: PMC2969902 PMID: 21577622

Abstract

The asymmetric unit of the title compound, C₁₂H₁₄N₄·2C₆H₇NO₃S·2H₂O, contains one half of a centrosymmetric 1,4-bis(4,5-dihydro-1H-imidazol-2-yl)benzene (bib) molecule, one 4-aminobenzenesulfonic acid molecule and one water molecule. In the bib molecule, the imidazole ring adopts an envelope conformation. The benzene rings of bib and 4-aminobenzenesulfonic acid are oriented at a dihedral angle of 21.89 (4)°. In the crystal structure, intermolecular N—H⋯O, O—H⋯N and O—H⋯O interactions link the molecules into a three-dimensional network. Weak π–π contacts between the benzene and imidazole rings and between the benzene rings [centroid–centroid distances = 3.895 (1) and 3.833 (1) Å, respectively] may further stabilize the structure.

Related literature

For general background, see: Jeffrey (1997 ▶); Thaimattam et al. (1998 ▶). For related structures, see: Ren et al. (2004a ▶,b ▶, 2007 ▶, 2009 ▶). For imidazole bond lengths, see: Haga et al. (1996 ▶); Hammes et al. (2005 ▶).

Experimental

Crystal data

C₁₂H₁₄N₄·2C₆H₇NO₃S·2H₂O
M _r = 596.70
Orthorhombic,
a = 13.6306 (11) Å
b = 12.698 (1) Å
c = 15.5907 (13) Å
V = 2698.5 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.26 mm⁻¹
T = 273 K
0.15 × 0.12 × 0.10 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 1998 ▶) T _min = 0.962, T _max = 0.975
11859 measured reflections
2346 independent reflections
1856 reflections with I > 2σ(I)
R _int = 0.036

Refinement

R[F ² > 2σ(F ²)] = 0.045
wR(F ²) = 0.140
S = 1.08
2346 reflections
182 parameters
All H-atom parameters refined
Δρ_max = 0.45 e Å⁻³
Δρ_min = −0.42 e Å⁻³

Data collection: SMART (Bruker, 1998 ▶); cell refinement: SAINT (Bruker, 1998 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL and PLATON (Spek, 2009 ▶); software used to prepare material for publication: SHELXTL and PLATON.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809032504/hk2751sup1.cif

e-65-o2221-sup1.cif^{(17.8KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809032504/hk2751Isup2.hkl

e-65-o2221-Isup2.hkl^{(115.4KB, hkl)}

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

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H3A⋯O4	0.82	2.00	2.809 (3)	168
N1—H1A⋯O2ⁱ	0.86	2.22	2.960 (3)	145
N1—H1B⋯O3ⁱⁱ	0.86	2.43	3.200 (3)	150
N1—H1B⋯O1ⁱⁱ	0.86	2.46	3.170 (4)	141
N2—H1⋯O3ⁱⁱⁱ	0.86	2.07	2.897 (3)	161
O4—H4A⋯N3^iv	0.85	2.08	2.760 (3)	136
O4—H4B⋯O1^v	0.85	2.20	2.817 (3)	130

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

Acknowledgments

This work was generously supported by the National Natural Science Foundation of China (grant No. 20701016).

supplementary crystallographic information

Comment

Attention has recently focused on the use of supramolecular interactions such as hydrogen bonding and π–π interactions, in addition to coordinate bonds, in the controlled assembly of supramolecular architectures (Jeffrey, 1997). Hydrogen bonds often play a dominant role in crystal engineering because of their combine strength with directionality (Thaimattam et al., 1998). On the other hand, supramolecular systems sustained by soft connections, such as hydrogen bonds, are comparatively more flexible and sensitive to the chemical environment. Consequently hydrogen-bond sustained systems are less designable and remain to be further investigated. We described previously a number of such metal complexes, including imidazole ligand, and have concluded that hydrogen bonding involving this group influences the geometry around the metal atom and the crystallization mechanism (Ren et al., 2004a; Ren et al., 2004b; Ren et al., 2007; Ren et al., 2009). We reported herein the synthesis and crystal structure of the title compound.

The asymmetric unit of the title compound contains one-half of 1,4-bis(4,5-di-hydro-1H-imidazol-2-yl)benzene (bib) ligand, one 4-aminobenzenesulfonic acid (SA) and one water molecules. In bib, the imidazole ring B (N2/N3/C7-C9) adopts envelope conformation with atom C8 displaced by -0.185 (3)Å from the plane of the other ring atoms. Rings A (C1-C6) and C (C10/C11/C12/C10'/C11'/C12') [symmetry code ('): 1 - x, 2 - y, 1 - z] are, of course, planar and they are oriented at a dihedral angle of 21.89 (4)°.

In the crystal structure, intramolecular O-H···O and intermolecular N-H···O, O-H···N and O-H···O interactions (Table 1) link the molecules into a three-dimensional network (Fig. 2), in which they may be effective in the stabilization of the structure. The π–π contacts between the benzene and imidazole rings and between the benzene rings, Cg1—Cg2 and Cg1—Cg3, [where Cg1, Cg2 and Cg3 are centroids of the rings A (C1-C6), B (N2/N3/C7-C9) and C (C10/C11/C12/C10'/C11'/C12'), respectively] may further stabilize the structure, with centroid-centroid distances of 3.895 (1) and 3.833 (1) Å, respectively.

Experimental

For the preparation of 1,4-bis(4,5-dihydro-1H-imidazol-2-yl)benzene, (bib), 1,4-benzenedicarboxylic acid (2.31 g, 13.9 mmol), ethylenediamine (3.70 ml, 50 mmol), ethylenediamine dihydrochloride(6.64 g, 50 mmol) and toluene-p-sulfonic acid (0.208 g, 1.09 mmol) were added to the solvent of ethyleneglycol (20 ml), and the mixture was refluxed for 3 h. About half of the ethylene glycol solvent was then slowly removed by distillation. The residue was dissolved in a mixture of water (40 ml) and concentrated HCl (11 M, 3 ml). The addition of 50% aqueous NaOH gave a yellow precipitate that was purified by recrystallization. The ligand bib was obtained in 83% based on 1,4-benzenedicarboxylic acid (ca 2.50 g). Found: C 66.98; H 6.92; N 26.08%. Calc. for C12H14N4: C 67.27; H 6.59; N 26.15%. Main IR bonds (KBr, cm^-1): 3188m, 2936m, 2866m, 1606 s, 1532 s, 1466 s, 1345m, 1270 s, 1191w, 1080w, 981m, 907w, 767w, 687m. For the preparation of the title compound, to a solution of bib (0.043 g, 0.2 mmol) in MeOH (15 ml), an aqueous solution (5 ml) of SA (0.068 g, 0.4 mmol) was added. The solution was allowed at room temperature in air for 3 d by slow evaporation. Large yellow prismatic crystals were obtained, which were collected by filtration, washed with water and dried in vacuum desiccator over silica gel (0.047 g, 54%). Main IR bonds (KBr,cm^-1): 3424m, 3354m, 3249w, 1655w, 1603m, 1507m, 1119m, 1024 s, 1001m, 698m, 569w.