3,3'-(p-Phenyl-enedimethyl-ene)di-imidazol-1-ium bis-(3-carb-oxy-4-hydroxy-benzene-sulfonate) dihydrate.

In the title compound, C(14)H(16)N(4) (2+)·2C(7)H(5)O(6)S(-)·2H(2)O, the 3,3'-(p-phenyl-enedimethyl-ene)diimidazol-1-ium dication lies on a crystallographic inversion center. In the crystal structure, dications, anions and solvent water mol-ecules are linked via O-H⋯O, N-H⋯O and C-H⋯O hydrogen bonds, and C-H⋯π inter-actions, 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 = 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

Δρmax = 0.34 e Å−3

Δρmin = −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.

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

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

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

C14H16N42+·2C7H5O6S−·2H2O	Z = 1
Mr = 710.68	F(000) = 370
Triclinic, P1	Dx = 1.514 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.9975 (6) Å	Cell parameters from 2637 reflections
b = 8.8060 (7) Å	θ = 2.3–28.0°
c = 11.2419 (8) Å	µ = 0.25 mm−1
α = 90.784 (1)°	T = 292 K
β = 96.656 (1)°	Block, colorless
γ = 97.342 (1)°	0.20 × 0.10 × 0.10 mm
V = 779.61 (10) Å3

Bruker SMART APEX CCD area-detector diffractometer	3168 independent reflections
Radiation source: fine focus sealed Siemens Mo tube	2524 reflections with I > 2σ(I)
graphite	Rint = 0.024
0.3° wide ω exposures scans	θmax = 26.5°, θmin = 1.8°
Absorption correction: multi-scan (SADABS; Sheldrick, 1997)	h = −9→10
Tmin = 0.942, Tmax = 0.976	k = −11→11
8434 measured reflections	l = −12→14

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.050	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.142	H atoms treated by a mixture of independent and constrained refinement
S = 1.12	w = 1/[σ2(Fo2) + (0.0671P)2 + 0.3146P] where P = (Fo2 + 2Fc2)/3
3168 reflections	(Δ/σ)max < 0.001
232 parameters	Δρmax = 0.34 e Å−3
0 restraints	Δρmin = −0.24 e Å−3

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.

	x	y	z	Uiso*/Ueq
C1	0.6276 (3)	0.1488 (3)	0.0830 (2)	0.0345 (5)
C2	0.7379 (3)	0.0442 (3)	0.1231 (2)	0.0411 (6)
C3	0.7390 (4)	−0.0098 (3)	0.2385 (3)	0.0498 (7)
H3	0.8114	−0.0803	0.2645	0.060*
C4	0.6339 (4)	0.0403 (3)	0.3140 (2)	0.0460 (6)
H4	0.6351	0.0032	0.3911	0.055*
C5	0.5250 (3)	0.1465 (3)	0.2763 (2)	0.0341 (5)
C6	0.5211 (3)	0.1995 (3)	0.1617 (2)	0.0333 (5)
H6	0.4474	0.2693	0.1362	0.040*
C7	0.6258 (3)	0.2045 (3)	−0.0404 (2)	0.0367 (6)
C8	−0.0498 (4)	−0.5225 (3)	0.1136 (2)	0.0445 (6)
C9	0.0677 (4)	−0.6056 (3)	0.0730 (2)	0.0501 (7)
H9	0.1143	−0.6774	0.1221	0.060*
C10	−0.1170 (4)	−0.4163 (3)	0.0397 (3)	0.0517 (7)
H10	−0.1963	−0.3591	0.0661	0.062*
C11	−0.1021 (5)	−0.5466 (4)	0.2371 (3)	0.0625 (9)
H11A	−0.2250	−0.5643	0.2315	0.075*
H11B	−0.0586	−0.6370	0.2699	0.075*
C12	0.0904 (4)	−0.3092 (3)	0.3061 (2)	0.0489 (7)
H12	0.1579	−0.3061	0.2439	0.059*
C13	−0.1055 (4)	−0.3780 (3)	0.4208 (2)	0.0474 (7)
H13	−0.1979	−0.4325	0.4511	0.057*
C14	−0.0133 (4)	−0.2505 (3)	0.4685 (3)	0.0513 (7)
H14	−0.0291	−0.1992	0.5384	0.062*
N1	0.1078 (3)	−0.2097 (3)	0.3962 (2)	0.0523 (6)
H1A	0.175 (4)	−0.135 (4)	0.406 (3)	0.063*
N2	−0.0387 (3)	−0.4140 (2)	0.31870 (18)	0.0419 (5)
O1	0.5166 (2)	0.3008 (2)	−0.07003 (16)	0.0477 (5)
H1	0.520 (4)	0.323 (4)	−0.150 (3)	0.072*
O2	0.7193 (2)	0.1627 (2)	−0.10967 (16)	0.0504 (5)
O3	0.8439 (3)	−0.0099 (3)	0.05360 (19)	0.0635 (6)
H3A	0.858 (4)	0.013 (4)	−0.0196 (15)	0.095*
O4	0.3120 (3)	0.3311 (2)	0.32481 (17)	0.0513 (5)
O5	0.5091 (3)	0.2577 (3)	0.48529 (18)	0.0677 (6)
O6	0.2758 (3)	0.0777 (2)	0.4006 (2)	0.0664 (6)
O7	0.5030 (3)	0.3928 (2)	0.71130 (18)	0.0563 (6)
H7A	0.506 (5)	0.342 (4)	0.644 (4)	0.084*
H7B	0.565 (5)	0.471 (5)	0.700 (3)	0.084*
S1	0.39522 (9)	0.20854 (7)	0.37902 (5)	0.0380 (2)

	U11	U22	U33	U12	U13	U23
C1	0.0372 (13)	0.0356 (11)	0.0304 (13)	−0.0014 (10)	0.0101 (10)	0.0005 (9)
C2	0.0420 (15)	0.0447 (13)	0.0394 (14)	0.0077 (11)	0.0145 (12)	0.0024 (11)
C3	0.0516 (17)	0.0541 (15)	0.0497 (17)	0.0238 (13)	0.0114 (13)	0.0118 (13)
C4	0.0571 (17)	0.0473 (14)	0.0346 (14)	0.0080 (12)	0.0068 (12)	0.0105 (11)
C5	0.0408 (14)	0.0367 (12)	0.0239 (11)	−0.0020 (10)	0.0084 (10)	−0.0001 (9)
C6	0.0362 (13)	0.0355 (11)	0.0282 (12)	0.0018 (10)	0.0074 (10)	0.0017 (9)
C7	0.0391 (14)	0.0405 (12)	0.0302 (12)	−0.0023 (11)	0.0115 (11)	0.0009 (10)
C8	0.0486 (16)	0.0490 (14)	0.0329 (14)	−0.0049 (12)	0.0056 (12)	−0.0065 (11)
C9	0.0567 (18)	0.0533 (16)	0.0403 (15)	0.0168 (13)	−0.0047 (13)	0.0036 (12)
C10	0.0493 (17)	0.0607 (17)	0.0476 (17)	0.0155 (14)	0.0082 (13)	−0.0092 (13)
C11	0.083 (2)	0.0612 (18)	0.0376 (16)	−0.0217 (16)	0.0181 (15)	−0.0101 (13)
C12	0.0461 (16)	0.0579 (16)	0.0411 (15)	−0.0069 (13)	0.0142 (13)	−0.0036 (12)
C13	0.0448 (15)	0.0683 (18)	0.0301 (13)	0.0035 (13)	0.0134 (12)	0.0044 (12)
C14	0.0567 (18)	0.0588 (17)	0.0397 (15)	0.0109 (14)	0.0087 (13)	−0.0068 (13)
N1	0.0543 (16)	0.0512 (14)	0.0470 (14)	−0.0095 (11)	0.0055 (12)	−0.0062 (11)
N2	0.0443 (13)	0.0500 (12)	0.0300 (11)	−0.0033 (10)	0.0100 (9)	−0.0018 (9)
O1	0.0577 (12)	0.0605 (11)	0.0293 (10)	0.0153 (9)	0.0142 (9)	0.0116 (8)
O2	0.0561 (12)	0.0623 (11)	0.0374 (10)	0.0087 (9)	0.0237 (9)	0.0049 (9)
O3	0.0681 (14)	0.0761 (14)	0.0585 (14)	0.0311 (12)	0.0333 (12)	0.0130 (11)
O4	0.0595 (12)	0.0561 (11)	0.0436 (11)	0.0171 (9)	0.0170 (9)	0.0094 (9)
O5	0.0763 (15)	0.0925 (16)	0.0349 (11)	0.0276 (13)	−0.0058 (10)	−0.0228 (11)
O6	0.0833 (15)	0.0500 (11)	0.0726 (15)	−0.0035 (10)	0.0506 (13)	0.0020 (10)
O7	0.0863 (17)	0.0511 (12)	0.0309 (10)	0.0033 (11)	0.0104 (10)	0.0057 (9)
S1	0.0512 (4)	0.0382 (3)	0.0258 (3)	0.0028 (3)	0.0128 (3)	0.0011 (2)

C1—C2	1.399 (4)	C10—H10	0.9300
C1—C6	1.403 (3)	C11—N2	1.474 (3)
C1—C7	1.476 (3)	C11—H11A	0.9700
C2—O3	1.343 (3)	C11—H11B	0.9700
C2—C3	1.386 (4)	C12—N1	1.313 (4)
C3—C4	1.368 (4)	C12—N2	1.316 (3)
C3—H3	0.9300	C12—H12	0.9300
C4—C5	1.396 (4)	C13—C14	1.331 (4)
C4—H4	0.9300	C13—N2	1.371 (3)
C5—C6	1.374 (3)	C13—H13	0.9300
C5—S1	1.765 (2)	C14—N1	1.353 (4)
C6—H6	0.9300	C14—H14	0.9300
C7—O2	1.224 (3)	N1—H1A	0.79 (3)
C7—O1	1.313 (3)	O1—H1	0.93 (4)
C8—C9	1.376 (4)	O3—H3A	0.87 (2)
C8—C10	1.378 (4)	O4—S1	1.4444 (19)
C8—C11	1.505 (4)	O5—S1	1.441 (2)
C9—C10i	1.379 (4)	O6—S1	1.442 (2)
C9—H9	0.9300	O7—H7A	0.88 (4)
C10—C9i	1.379 (4)	O7—H7B	0.81 (4)
C2—C1—C6	119.0 (2)	N2—C11—C8	112.1 (2)
C2—C1—C7	119.7 (2)	N2—C11—H11A	109.2
C6—C1—C7	121.3 (2)	C8—C11—H11A	109.2
O3—C2—C3	117.2 (2)	N2—C11—H11B	109.2
O3—C2—C1	122.7 (2)	C8—C11—H11B	109.2
C3—C2—C1	120.1 (2)	H11A—C11—H11B	107.9
C4—C3—C2	120.3 (2)	N1—C12—N2	108.4 (2)
C4—C3—H3	119.9	N1—C12—H12	125.8
C2—C3—H3	119.9	N2—C12—H12	125.8
C3—C4—C5	120.5 (2)	C14—C13—N2	107.2 (2)
C3—C4—H4	119.8	C14—C13—H13	126.4
C5—C4—H4	119.8	N2—C13—H13	126.4
C6—C5—C4	119.8 (2)	C13—C14—N1	107.1 (2)
C6—C5—S1	121.96 (19)	C13—C14—H14	126.5
C4—C5—S1	118.19 (18)	N1—C14—H14	126.5
C5—C6—C1	120.3 (2)	C12—N1—C14	109.2 (2)
C5—C6—H6	119.8	C12—N1—H1A	126 (3)
C1—C6—H6	119.8	C14—N1—H1A	124 (3)
O2—C7—O1	122.8 (2)	C12—N2—C13	108.1 (2)
O2—C7—C1	122.1 (2)	C12—N2—C11	126.2 (2)
O1—C7—C1	115.1 (2)	C13—N2—C11	125.7 (2)
C9—C8—C10	118.8 (2)	C7—O1—H1	108 (2)
C9—C8—C11	120.3 (3)	C2—O3—H3A	128.1 (11)
C10—C8—C11	120.9 (3)	H7A—O7—H7B	100 (4)
C8—C9—C10i	120.7 (3)	O5—S1—O6	111.68 (15)
C8—C9—H9	119.6	O5—S1—O4	112.97 (13)
C10i—C9—H9	119.6	O6—S1—O4	112.13 (13)
C8—C10—C9i	120.5 (3)	O5—S1—C5	105.30 (12)
C8—C10—H10	119.8	O6—S1—C5	106.67 (11)
C9i—C10—H10	119.8	O4—S1—C5	107.55 (11)
C6—C1—C2—O3	−180.0 (2)	C9—C8—C10—C9i	0.2 (5)
C7—C1—C2—O3	−0.3 (4)	C11—C8—C10—C9i	179.6 (3)
C6—C1—C2—C3	1.0 (4)	C9—C8—C11—N2	110.3 (3)
C7—C1—C2—C3	−179.3 (2)	C10—C8—C11—N2	−69.2 (4)
O3—C2—C3—C4	−179.8 (3)	N2—C13—C14—N1	0.0 (3)
C1—C2—C3—C4	−0.8 (4)	N2—C12—N1—C14	−0.3 (4)
C2—C3—C4—C5	−0.3 (4)	C13—C14—N1—C12	0.2 (4)
C3—C4—C5—C6	1.1 (4)	N1—C12—N2—C13	0.3 (3)
C3—C4—C5—S1	−179.0 (2)	N1—C12—N2—C11	179.9 (3)
C4—C5—C6—C1	−0.8 (4)	C14—C13—N2—C12	−0.2 (3)
S1—C5—C6—C1	179.28 (17)	C14—C13—N2—C11	−179.8 (3)
C2—C1—C6—C5	−0.2 (4)	C8—C11—N2—C12	−21.6 (5)
C7—C1—C6—C5	−179.8 (2)	C8—C11—N2—C13	157.9 (3)
C2—C1—C7—O2	−0.5 (4)	C6—C5—S1—O5	−128.2 (2)
C6—C1—C7—O2	179.2 (2)	C4—C5—S1—O5	52.0 (2)
C2—C1—C7—O1	179.2 (2)	C6—C5—S1—O6	113.1 (2)
C6—C1—C7—O1	−1.2 (3)	C4—C5—S1—O6	−66.8 (2)
C10—C8—C9—C10i	−0.2 (5)	C6—C5—S1—O4	−7.4 (2)
C11—C8—C9—C10i	−179.6 (3)	C4—C5—S1—O4	172.70 (19)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O7ii	0.93 (4)	1.68 (4)	2.593 (3)	168 (3)
O3—H3A···O2	0.87 (2)	2.04 (2)	2.591 (3)	121 (3)
O3—H3A···O3iii	0.87 (2)	2.46 (2)	2.883 (4)	111 (2)
O7—H7B···O4iv	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···O6v	0.93	2.51	3.411 (4)	164
C12—H12···O2vi	0.93	2.22	3.035 (3)	146
C14—H14···O6vii	0.93	2.52	3.219 (4)	132
C3—H3···Cg1viii	0.93	2.97 (1)	3.889 (3)	170

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⋯O6iv	0.93	2.51	3.411 (4)	164
C12—H12⋯O2v	0.93	2.22	3.035 (3)	146
C14—H14⋯O6vi	0.93	2.52	3.219 (4)	132
C3—H3⋯Cg1vii	0.93	2.97 (1)	3.889 (3)	170

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