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Acta Crystallogr Sect E Struct Rep Online. 2009 September 1; 65(Pt 9): o2221–o2222.
Published online 2009 August 22. doi:  10.1107/S1600536809032504
PMCID: PMC2969902

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

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 [triangle]); Thaimattam et al. (1998 [triangle]). For related structures, see: Ren et al. (2004a [triangle],b [triangle], 2007 [triangle], 2009 [triangle]). For imidazole bond lengths, see: Haga et al. (1996 [triangle]); Hammes et al. (2005 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-65-o2221-scheme1.jpg

Experimental

Crystal data

  • C12H14N4·2C6H7NO3S·2H2O
  • M r = 596.70
  • Orthorhombic, An external file that holds a picture, illustration, etc.
Object name is e-65-o2221-efi1.jpg
  • 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 [triangle]) 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
  • Δρmax = 0.45 e Å−3
  • Δρmin = −0.42 e Å−3

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

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

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

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

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

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.

Refinement

H atoms were positioned geometrically, with N-H = O.86 Å (for NH and NH2), O-H = 0.82 Å (for OH) and 0.85 Å (for H2O) and C-H = 0.93 and 0.97 Å for aromatic and methylene H, respectively, and constrained to ride on their parent atoms, with Uiso(H) = xUeq(C,N,O), where x = 1.5 for OH H and x = 1.2 for all other H atoms.

Figures

Fig. 1.
The molecular structure of the title molecule, with the atom-numbering scheme. Hydrogen bond is shown as dashed line [symmetry code ('): 1 - x, 2 - y, 1 - z].
Fig. 2.
A partial packing diagram for the title compound. Hydrogen bonds are shown as dashed lines.

Crystal data

C12H14N4·2C6H7NO3S·2H2OF(000) = 1256
Mr = 596.70Dx = 1.469 Mg m3
Orthorhombic, PbcaMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2abCell parameters from 3721 reflections
a = 13.6306 (11) Åθ = 2.6–26.3°
b = 12.698 (1) ŵ = 0.26 mm1
c = 15.5907 (13) ÅT = 273 K
V = 2698.5 (4) Å3Block, yellow
Z = 40.15 × 0.12 × 0.10 mm

Data collection

Bruker SMART CCD area-detector diffractometer2346 independent reflections
Radiation source: fine-focus sealed tube1856 reflections with I > 2σ(I)
graphiteRint = 0.036
[var phi] and ω scansθmax = 25.1°, θmin = 2.6°
Absorption correction: multi-scan (SADABS; Bruker, 1998)h = −16→15
Tmin = 0.962, Tmax = 0.975k = −15→15
11859 measured reflectionsl = −18→14

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.045All H-atom parameters refined
wR(F2) = 0.140w = 1/[σ2(Fo2) + (0.0724P)2 + 1.4974P] where P = (Fo2 + 2Fc2)/3
S = 1.08(Δ/σ)max < 0.001
2346 reflectionsΔρmax = 0.45 e Å3
182 parametersΔρmin = −0.42 e Å3
0 restraintsExtinction correction: SHELXTL (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0010 (5)

Special details

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 > 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)

xyzUiso*/Ueq
S10.20619 (5)0.82812 (5)0.31074 (4)0.0423 (3)
O10.29197 (15)0.8625 (2)0.26382 (13)0.0688 (7)
O20.1875 (2)0.71668 (16)0.30647 (13)0.0681 (7)
O30.12151 (14)0.88982 (15)0.28322 (11)0.0536 (5)
H3A0.07290.87140.31040.080*
O4−0.06007 (17)0.8498 (2)0.36193 (13)0.0774 (8)
H4A−0.06460.80280.40060.093*
H4B−0.11050.88460.34700.093*
N10.2770 (2)0.9242 (2)0.67696 (14)0.0615 (8)
H1A0.27750.87400.71400.074*
H1B0.28840.98780.69300.074*
N20.51620 (17)0.7721 (2)0.34661 (15)0.0518 (6)
H10.53680.81800.31030.062*
N30.46812 (18)0.70826 (19)0.46926 (16)0.0530 (6)
C10.25816 (19)0.90302 (19)0.59303 (15)0.0384 (6)
C20.2594 (2)0.98296 (19)0.53090 (16)0.0398 (6)
H20.27051.05220.54760.048*
C30.24456 (19)0.96036 (18)0.44548 (15)0.0368 (6)
H30.24701.01410.40500.044*
C40.22603 (17)0.85807 (18)0.41959 (15)0.0327 (5)
C50.22330 (18)0.77832 (18)0.48013 (15)0.0362 (6)
H50.21050.70950.46310.043*
C60.2394 (2)0.80063 (19)0.56551 (15)0.0392 (6)
H60.23780.74630.60550.047*
C70.49343 (18)0.7937 (2)0.42682 (17)0.0441 (7)
C80.4824 (3)0.6141 (3)0.4154 (2)0.0657 (9)
H8A0.42410.57030.41490.079*
H8B0.53770.57260.43510.079*
C90.5021 (3)0.6610 (3)0.3270 (2)0.0604 (8)
H9A0.56040.63070.30130.073*
H9B0.44680.65060.28890.073*
C100.49700 (19)0.8996 (2)0.46426 (16)0.0446 (7)
C110.5064 (2)0.9132 (2)0.55335 (17)0.0513 (7)
H110.51050.85460.58900.062*
C120.4905 (2)0.9878 (2)0.41216 (17)0.0514 (7)
H120.48390.97960.35320.062*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
S10.0514 (5)0.0491 (4)0.0264 (4)−0.0001 (3)0.0007 (3)−0.0023 (3)
O10.0604 (14)0.1066 (17)0.0396 (12)−0.0006 (13)0.0178 (10)0.0025 (11)
O20.114 (2)0.0497 (12)0.0407 (12)−0.0013 (12)−0.0076 (11)−0.0109 (9)
O30.0497 (12)0.0712 (13)0.0399 (10)−0.0024 (10)−0.0102 (9)0.0053 (9)
O40.0590 (14)0.128 (2)0.0449 (13)0.0017 (14)−0.0103 (10)0.0270 (13)
N10.097 (2)0.0549 (15)0.0321 (12)−0.0210 (14)−0.0048 (12)−0.0035 (10)
N20.0504 (14)0.0678 (16)0.0371 (13)−0.0018 (12)0.0070 (11)0.0087 (11)
N30.0438 (14)0.0646 (15)0.0507 (14)−0.0019 (12)0.0108 (11)0.0103 (12)
C10.0396 (14)0.0445 (13)0.0312 (13)−0.0052 (12)0.0007 (11)−0.0021 (10)
C20.0468 (16)0.0335 (12)0.0390 (14)−0.0056 (11)0.0020 (11)−0.0019 (10)
C30.0389 (14)0.0360 (12)0.0356 (13)0.0004 (11)0.0006 (11)0.0053 (10)
C40.0317 (13)0.0359 (12)0.0304 (12)0.0021 (10)0.0005 (10)0.0013 (9)
C50.0457 (15)0.0315 (12)0.0314 (13)−0.0014 (11)−0.0010 (10)−0.0005 (9)
C60.0466 (15)0.0374 (12)0.0335 (13)−0.0011 (12)−0.0016 (12)0.0068 (10)
C70.0290 (14)0.0668 (17)0.0366 (14)0.0049 (13)0.0043 (11)0.0116 (12)
C80.063 (2)0.071 (2)0.063 (2)−0.0182 (17)0.0129 (16)0.0054 (16)
C90.058 (2)0.072 (2)0.0507 (18)−0.0093 (16)0.0045 (15)−0.0012 (15)
C100.0330 (14)0.0646 (17)0.0361 (14)0.0076 (13)0.0063 (11)0.0110 (12)
C110.0509 (17)0.0654 (18)0.0377 (15)0.0104 (14)0.0065 (12)0.0146 (13)
C120.0494 (17)0.0729 (19)0.0318 (14)0.0101 (15)0.0042 (12)0.0094 (13)

Geometric parameters (Å, °)

S1—O21.439 (2)C3—C41.383 (3)
S1—O11.447 (2)C3—H30.9300
S1—O31.460 (2)C4—C51.385 (3)
S1—C41.760 (2)C5—C61.379 (3)
O3—H3A0.8200C5—H50.9300
O4—H4A0.8501C6—H60.9300
O4—H4B0.8501C7—C101.467 (4)
N1—C11.360 (3)C8—C91.525 (4)
N1—H1A0.8600C8—H8A0.9700
N1—H1B0.8600C8—H8B0.9700
N2—C71.317 (3)C9—H9A0.9700
N2—C91.455 (4)C9—H9B0.9700
N2—H10.8600C10—C121.387 (4)
N3—C71.317 (3)C10—C111.405 (4)
N3—C81.474 (4)C11—C12i1.368 (4)
C1—C61.393 (3)C11—H110.9300
C1—C21.403 (3)C12—C11i1.368 (4)
C2—C31.377 (3)C12—H120.9300
C2—H20.9300
O2—S1—O1114.61 (15)C4—C5—H5119.9
O2—S1—O3111.99 (14)C5—C6—C1121.2 (2)
O1—S1—O3109.17 (13)C5—C6—H6119.4
O2—S1—C4106.51 (12)C1—C6—H6119.4
O1—S1—C4107.34 (13)N3—C7—N2111.6 (3)
O3—S1—C4106.79 (11)N3—C7—C10124.3 (2)
S1—O3—H3A109.5N2—C7—C10124.1 (2)
H4A—O4—H4B120.0N3—C8—C9102.8 (3)
C1—N1—H1A120.0N3—C8—H8A111.2
C1—N1—H1B120.0C9—C8—H8A111.2
H1A—N1—H1B120.0N3—C8—H8B111.2
C7—N2—C9111.7 (2)C9—C8—H8B111.2
C7—N2—H1124.2H8A—C8—H8B109.1
C9—N2—H1124.2N2—C9—C8102.3 (2)
C7—N3—C8110.3 (2)N2—C9—H9A111.3
N1—C1—C6121.0 (2)C8—C9—H9A111.3
N1—C1—C2121.2 (2)N2—C9—H9B111.3
C6—C1—C2117.7 (2)C8—C9—H9B111.3
C3—C2—C1121.0 (2)H9A—C9—H9B109.2
C3—C2—H2119.5C12—C10—C11119.0 (3)
C1—C2—H2119.5C12—C10—C7120.4 (2)
C2—C3—C4120.3 (2)C11—C10—C7120.6 (2)
C2—C3—H3119.8C12i—C11—C10120.3 (3)
C4—C3—H3119.8C12i—C11—H11119.9
C3—C4—C5119.5 (2)C10—C11—H11119.9
C3—C4—S1120.81 (18)C11i—C12—C10120.7 (3)
C5—C4—S1119.67 (18)C11i—C12—H12119.7
C6—C5—C4120.2 (2)C10—C12—H12119.7
C6—C5—H5119.9

Symmetry codes: (i) −x+1, −y+2, −z+1.

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
O3—H3A···O40.822.002.809 (3)168
N1—H1A···O2ii0.862.222.960 (3)145
N1—H1B···O3iii0.862.433.200 (3)150
N1—H1B···O1iii0.862.463.170 (4)141
N2—H1···O3iv0.862.072.897 (3)161
O4—H4A···N3v0.852.082.760 (3)136
O4—H4B···O1vi0.852.202.817 (3)130

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: HK2751).

References

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