Bis(benzimidazolium) naphthalene-1,5-disulfonate trihydrate

Wang, Z.-L.; Jin, L.-Y.; Wei, L.-H.

doi:10.1107/S1600536808005916

organic compounds

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ISSN: 2056-9890

Volume 64| Part 4| April 2008| Page o674

doi:10.1107/S1600536808005916

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Bis(benzimidazolium) naphthalene-1,5-disulfonate trihydrate

Zi-Liang Wang,^a ^* Lin-Yu Jin ^b and Lin-Heng Wei ^c

^aInstitute of Molecular and Crystal Engineering, College of Chemistry and Chemical Engineering, Henan University, Kaifeng 475001, People's Republic of China, ^bCollege of Chemistry and Chemical Engineering, Henan University, Kaifeng 475001, People's Republic of China, and ^cCollege of the Environment and Planning, Henan University, Kaifeng 475001, People's Republic of China
^*Correspondence e-mail: zlwang@henu.edu.cn

(Received 10 February 2008; accepted 3 March 2008; online 5 March 2008)

The title compound, 2C₇H₇N₂⁺·C₁₀H₆O₆S₂²⁻·3H₂O, consists of two crystallographically independent benzimidazolium cations, two independent naphthalene-1,5-disulfonate dianions (both generated by inversion) and three water molecules. These components construct an infinite three-dimensional framework in the crystal structure via O—H⋯O and N—H⋯O hydrogen bonds.

Related literature

For related literature, see: Wang & Wei (2007 ).

Experimental

Crystal data

2C₇H₇N₂⁺·C₁₀H₆O₆S₂²⁻·3H₂O
M_r = 578.61
Triclinic, $[P \overline 1]$
a = 8.372 (4) Å
b = 9.889 (5) Å
c = 17.044 (8) Å
α = 80.914 (8)°
β = 87.557 (9)°
γ = 73.641 (8)°
V = 1337.0 (11) Å³
Z = 2
Mo Kα radiation
μ = 0.26 mm⁻¹
T = 296 (2) K
0.15 × 0.12 × 0.04 mm

Data collection

Bruker SMART APEX CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2001 ) T_min = 0.962, T_max = 0.990
6891 measured reflections
4670 independent reflections
3494 reflections with I > 2σ(I)
R_int = 0.020

Refinement

R[F² > 2σ(F²)] = 0.043
wR(F²) = 0.110
S = 1.06
4670 reflections
392 parameters
37 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.30 e Å⁻³
Δρ_min = −0.33 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O7ⁱ	0.898 (10)	1.820 (12)	2.708 (3)	170 (3)
N2—H2A⋯O4ⁱⁱ	0.887 (18)	1.885 (19)	2.762 (3)	170 (3)
N3—H3A⋯O3ⁱⁱⁱ	0.895 (10)	1.937 (12)	2.812 (3)	166 (2)
N4—H4A⋯O8^iv	0.899 (10)	1.883 (11)	2.771 (3)	169 (2)
O7—H7B⋯O5^v	0.852 (10)	2.169 (19)	2.839 (3)	135 (2)
O8—H8A⋯O2^vi	0.844 (10)	1.982 (10)	2.826 (3)	178 (3)
O7—H7A⋯O1	0.853 (10)	1.999 (12)	2.823 (3)	162 (3)
O8—H8B⋯O6	0.847 (10)	1.963 (10)	2.809 (3)	176 (3)
O9—H9B⋯O1^iv	0.863 (10)	2.157 (18)	2.970 (3)	157 (3)
Symmetry codes: (i) x, y-1, z+1; (ii) x+1, y, z+1; (iii) x-1, y, z; (iv) -x+1, -y+1, -z+1; (v) x, y+1, z; (vi) x, y-1, z.

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.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808005916/hb2700sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808005916/hb2700Isup2.hkl

checkCIF report

Comment top

This work continues our previous synthetic and structural studies of supramolecular interactions in aromatic molecular salts and adducts (Wang & Wei, 2007). Herein we report the structure of the title salt, (I).

The title compound (I) contains two independent benzimidazolium cations, two naphthalene-1,5-disulfonate dianions and three water molecules (Fig. 1). Each of the dianions occupies a special position on an inversion centre. Therefore, the asymmetric unit of the crystal structure is composed of two half naphthalene-1,5-disulfonate dianions, two benzimidazolium cations and three water molecules.

These ions and molecules are finally organized into an infinite three-dimensional framework through N—H···O and O—H···O hydrogen bonds (Fig. 2 and Table 1).

Related literature top

For related literature, see: Wang & Wei (2007).

Experimental top

A 5-ml ethanol solution of benzimidazole (1.00 mmol, 0.118 g) was added to an aqueous solution (25 ml) of naphthalene-1,5-disulfonic acid (0.50 mmol, 0.15 g). The mixture was stirred for 10 minutes at 373 K. The solution was filtered, and the filtrate was allowed to stand at room temperature. After several days, colourless blocks of (I) were recovered.

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, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: PLATON (Spek, 2003).

Figures top

	Fig. 1. The molecular structure of (I). Displacement ellipsoids for non-H atoms are drawn at the 30% probability level. Hydrogen bonds are shown as dashed lines. Unlabeled atoms in the C8 anion are related to labeled atoms by (1 - x, 1 - y, 1 - z). Unlabeled atoms in the C20 anion are related to labeled atoms by (1 - x, 1 - y, -z).
	Fig. 2. The crystal packing of (I). Hydrogen bonds are shown as dashed lines. For clarity, H atoms not involved in hydrogen bonds are omitted.

Bis(benzimidazolium) naphthalene-1,5-disulfonate trihydrate top

Crystal data top

2C₇H₇N₂⁺·C₁₀H₆O₆S₂²⁻·3H₂O	Z = 2
M_r = 578.61	F(000) = 604
Triclinic, P1	D_x = 1.437 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.372 (4) Å	Cell parameters from 3010 reflections
b = 9.889 (5) Å	θ = 2.5–28.2°
c = 17.044 (8) Å	µ = 0.26 mm⁻¹
α = 80.914 (8)°	T = 296 K
β = 87.557 (9)°	Block, colourless
γ = 73.641 (8)°	0.15 × 0.12 × 0.04 mm
V = 1337.0 (11) Å³

Data collection top

Bruker SMART APEX CCD diffractometer	4670 independent reflections
Radiation source: fine-focus sealed tube	3494 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.020
ω scans	θ_max = 25.0°, θ_min = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −9→6
T_min = 0.962, T_max = 0.990	k = −11→10
6891 measured reflections	l = −20→20

Refinement top

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)] = 0.043	Hydrogen site location: difmap and geom
wR(F²) = 0.110	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ²(F_o²) + (0.0559P)² + 0.0198P] where P = (F_o² + 2F_c²)/3
4670 reflections	(Δ/σ)_max < 0.001
392 parameters	Δρ_max = 0.30 e Å⁻³
37 restraints	Δρ_min = −0.33 e Å⁻³

Crystal data top

2C₇H₇N₂⁺·C₁₀H₆O₆S₂²⁻·3H₂O	γ = 73.641 (8)°
M_r = 578.61	V = 1337.0 (11) Å³
Triclinic, P1	Z = 2
a = 8.372 (4) Å	Mo Kα radiation
b = 9.889 (5) Å	µ = 0.26 mm⁻¹
c = 17.044 (8) Å	T = 296 K
α = 80.914 (8)°	0.15 × 0.12 × 0.04 mm
β = 87.557 (9)°

Data collection top

Bruker SMART APEX CCD diffractometer	4670 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2001)	3494 reflections with I > 2σ(I)
T_min = 0.962, T_max = 0.990	R_int = 0.020
6891 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.043	37 restraints
wR(F²) = 0.110	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	Δρ_max = 0.30 e Å⁻³
4670 reflections	Δρ_min = −0.33 e Å⁻³
392 parameters

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 > 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) top

	x	y	z	U_iso*/U_eq
S1	0.75176 (8)	0.65881 (6)	0.37087 (4)	0.04129 (19)
S2	0.39100 (7)	0.25493 (6)	0.14588 (3)	0.03710 (17)
N1	0.8368 (3)	0.0653 (2)	1.09595 (14)	0.0502 (6)
H1A	0.794 (4)	−0.007 (2)	1.1155 (19)	0.098 (12)*
N2	0.9885 (3)	0.2131 (2)	1.08427 (15)	0.0505 (6)
H2A	1.065 (3)	0.253 (3)	1.0965 (18)	0.082 (11)*
N3	0.0749 (3)	0.7339 (2)	0.48285 (14)	0.0460 (5)
H3A	0.032 (3)	0.670 (2)	0.4660 (15)	0.063 (9)*
N4	0.1689 (3)	0.8418 (2)	0.56460 (12)	0.0432 (5)
H4A	0.192 (3)	0.865 (3)	0.6108 (9)	0.056 (8)*
O1	0.7659 (2)	0.65613 (18)	0.28505 (10)	0.0554 (5)
O2	0.6945 (2)	0.80262 (17)	0.39064 (11)	0.0571 (5)
O3	0.9056 (2)	0.57458 (17)	0.41288 (10)	0.0473 (4)
O4	0.21223 (19)	0.33257 (17)	0.14166 (10)	0.0457 (4)
O5	0.4281 (2)	0.13448 (16)	0.10230 (10)	0.0490 (5)
O6	0.4518 (2)	0.21705 (18)	0.22760 (10)	0.0545 (5)
O7	0.6702 (3)	0.8721 (2)	0.15255 (12)	0.0636 (6)
H7A	0.695 (3)	0.822 (3)	0.1982 (9)	0.072 (5)*
H7B	0.575 (2)	0.928 (3)	0.1601 (16)	0.096 (14)*
O8	0.7493 (3)	0.0547 (2)	0.30528 (12)	0.0573 (5)
H8A	0.733 (3)	−0.0213 (17)	0.3299 (15)	0.067 (5)*
H8B	0.657 (2)	0.102 (3)	0.283 (2)	0.130 (17)*
O9	0.0253 (4)	0.6345 (3)	0.73328 (16)	0.0971 (8)
H9A	−0.066 (2)	0.618 (3)	0.719 (2)	0.081 (5)*
H9B	0.089 (3)	0.5484 (16)	0.743 (2)	0.101 (6)*
C1	0.9359 (3)	0.1177 (3)	1.13375 (17)	0.0546 (7)
H1	0.9641	0.0912	1.1873	0.065*
C2	0.8228 (3)	0.1305 (2)	1.01695 (16)	0.0421 (6)
C3	0.7326 (3)	0.1173 (3)	0.95341 (18)	0.0548 (7)
H3	0.6675	0.0541	0.9585	0.066*
C4	0.7446 (4)	0.2034 (3)	0.88195 (18)	0.0619 (8)
H4	0.6861	0.1975	0.8380	0.074*
C5	0.8424 (4)	0.2990 (3)	0.87418 (18)	0.0626 (8)
H5	0.8468	0.3547	0.8252	0.075*
C6	0.9320 (3)	0.3128 (3)	0.93678 (17)	0.0532 (7)
H6	0.9967	0.3763	0.9314	0.064*
C7	0.9205 (3)	0.2262 (2)	1.00908 (16)	0.0428 (6)
C8	0.4007 (3)	0.4475 (3)	0.37232 (15)	0.0514 (7)
H8	0.3477	0.4186	0.3338	0.062*
C9	0.5171 (3)	0.5243 (3)	0.34934 (15)	0.0455 (6)
H9	0.5410	0.5452	0.2957	0.055*
C10	0.5963 (3)	0.5689 (2)	0.40503 (13)	0.0360 (5)
C11	0.5595 (3)	0.5398 (2)	0.48859 (13)	0.0348 (5)
C12	0.6357 (3)	0.5851 (3)	0.54888 (14)	0.0442 (6)
H12	0.7114	0.6378	0.5346	0.053*
C13	0.0892 (3)	0.7450 (3)	0.55844 (16)	0.0478 (7)
H13	0.0493	0.6927	0.6011	0.057*
C14	0.1487 (3)	0.8290 (2)	0.43592 (14)	0.0392 (6)
C15	0.1657 (3)	0.8615 (3)	0.35337 (16)	0.0541 (7)
H15	0.1264	0.8154	0.3181	0.065*
C16	0.2444 (4)	0.9660 (3)	0.32755 (17)	0.0620 (8)
H16	0.2584	0.9907	0.2733	0.074*
C17	0.3036 (3)	1.0360 (3)	0.38033 (18)	0.0578 (8)
H17	0.3552	1.1060	0.3601	0.069*
C18	0.2877 (3)	1.0043 (3)	0.46113 (16)	0.0477 (6)
H18	0.3274	1.0507	0.4960	0.057*
C19	0.2086 (3)	0.8982 (2)	0.48839 (14)	0.0369 (6)
C20	0.6767 (3)	0.5287 (2)	0.11047 (14)	0.0394 (6)
H20	0.7486	0.5548	0.1414	0.047*
C21	0.6018 (3)	0.4208 (2)	0.14309 (13)	0.0357 (5)
H21	0.6249	0.3764	0.1953	0.043*
C22	0.4946 (3)	0.3809 (2)	0.09785 (13)	0.0308 (5)
C23	0.4614 (3)	0.4453 (2)	0.01605 (12)	0.0288 (5)
C24	0.3560 (3)	0.4050 (2)	−0.03388 (13)	0.0353 (5)
H24	0.3084	0.3323	−0.0139	0.042*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0484 (4)	0.0338 (3)	0.0428 (4)	−0.0151 (3)	−0.0003 (3)	−0.0022 (3)
S2	0.0385 (4)	0.0360 (3)	0.0376 (3)	−0.0162 (3)	0.0002 (3)	0.0027 (3)
N1	0.0443 (13)	0.0410 (13)	0.0639 (16)	−0.0139 (11)	0.0030 (11)	−0.0011 (11)
N2	0.0383 (13)	0.0498 (14)	0.0660 (16)	−0.0161 (11)	−0.0060 (11)	−0.0082 (12)
N3	0.0469 (13)	0.0372 (12)	0.0571 (15)	−0.0157 (10)	−0.0011 (11)	−0.0087 (11)
N4	0.0488 (13)	0.0396 (12)	0.0397 (13)	−0.0117 (10)	−0.0042 (10)	−0.0018 (10)
O1	0.0689 (13)	0.0589 (12)	0.0399 (10)	−0.0246 (10)	0.0042 (9)	−0.0003 (9)
O2	0.0714 (13)	0.0312 (9)	0.0693 (13)	−0.0159 (9)	0.0042 (10)	−0.0072 (9)
O3	0.0444 (10)	0.0422 (10)	0.0567 (11)	−0.0170 (8)	−0.0044 (8)	−0.0020 (8)
O4	0.0346 (10)	0.0478 (10)	0.0541 (11)	−0.0140 (8)	0.0058 (8)	−0.0033 (8)
O5	0.0555 (11)	0.0317 (9)	0.0634 (12)	−0.0180 (8)	0.0009 (9)	−0.0069 (8)
O6	0.0642 (12)	0.0609 (12)	0.0395 (10)	−0.0306 (10)	−0.0067 (9)	0.0153 (8)
O7	0.0655 (15)	0.0497 (13)	0.0740 (15)	−0.0202 (12)	−0.0078 (11)	0.0045 (10)
O8	0.0676 (14)	0.0493 (12)	0.0582 (13)	−0.0246 (11)	−0.0130 (11)	0.0009 (10)
O9	0.109 (2)	0.0876 (17)	0.0720 (16)	0.0001 (16)	0.0210 (16)	−0.0007 (14)
C1	0.0467 (17)	0.0544 (17)	0.0579 (18)	−0.0094 (14)	−0.0031 (14)	−0.0022 (14)
C2	0.0341 (14)	0.0358 (14)	0.0562 (17)	−0.0083 (11)	0.0035 (12)	−0.0099 (12)
C3	0.0445 (16)	0.0523 (17)	0.074 (2)	−0.0178 (13)	0.0072 (14)	−0.0234 (15)
C4	0.0578 (19)	0.069 (2)	0.061 (2)	−0.0145 (16)	−0.0041 (15)	−0.0214 (16)
C5	0.065 (2)	0.0580 (19)	0.0579 (19)	−0.0107 (16)	0.0059 (16)	−0.0032 (15)
C6	0.0507 (17)	0.0434 (15)	0.0679 (19)	−0.0184 (13)	0.0076 (15)	−0.0078 (14)
C7	0.0331 (14)	0.0369 (14)	0.0585 (17)	−0.0084 (11)	0.0032 (12)	−0.0112 (12)
C8	0.0587 (17)	0.0617 (17)	0.0434 (16)	−0.0275 (15)	−0.0076 (13)	−0.0147 (13)
C9	0.0541 (16)	0.0511 (15)	0.0341 (13)	−0.0175 (13)	−0.0024 (12)	−0.0087 (12)
C10	0.0384 (14)	0.0325 (12)	0.0363 (13)	−0.0083 (10)	−0.0013 (11)	−0.0054 (10)
C11	0.0360 (13)	0.0296 (12)	0.0400 (13)	−0.0095 (10)	−0.0027 (10)	−0.0074 (10)
C12	0.0474 (15)	0.0487 (15)	0.0441 (15)	−0.0229 (13)	−0.0004 (12)	−0.0118 (12)
C13	0.0498 (16)	0.0364 (14)	0.0532 (17)	−0.0104 (12)	0.0041 (13)	0.0014 (12)
C14	0.0350 (13)	0.0358 (13)	0.0450 (15)	−0.0080 (11)	0.0009 (11)	−0.0047 (11)
C15	0.0566 (18)	0.0572 (17)	0.0471 (16)	−0.0108 (14)	−0.0004 (13)	−0.0130 (13)
C16	0.067 (2)	0.068 (2)	0.0452 (17)	−0.0154 (17)	0.0105 (15)	−0.0002 (15)
C17	0.0546 (18)	0.0537 (17)	0.0628 (19)	−0.0193 (15)	0.0120 (15)	0.0027 (15)
C18	0.0410 (15)	0.0443 (15)	0.0606 (18)	−0.0165 (12)	0.0006 (13)	−0.0074 (13)
C19	0.0326 (13)	0.0336 (13)	0.0413 (14)	−0.0058 (11)	−0.0028 (11)	−0.0020 (11)
C20	0.0410 (14)	0.0432 (14)	0.0399 (14)	−0.0193 (12)	−0.0071 (11)	−0.0076 (11)
C21	0.0407 (14)	0.0372 (13)	0.0294 (12)	−0.0121 (11)	−0.0022 (10)	−0.0030 (10)
C22	0.0314 (12)	0.0278 (12)	0.0329 (12)	−0.0079 (10)	0.0016 (10)	−0.0045 (9)
C23	0.0276 (12)	0.0273 (12)	0.0319 (12)	−0.0078 (9)	0.0037 (10)	−0.0062 (10)
C24	0.0381 (13)	0.0343 (13)	0.0379 (13)	−0.0185 (11)	−0.0001 (10)	−0.0030 (10)

Geometric parameters (Å, º) top

S1—O2	1.4558 (18)	C5—H5	0.9300
S1—O1	1.4663 (19)	C6—C7	1.402 (4)
S1—O3	1.4665 (18)	C6—H6	0.9300
S1—C10	1.802 (2)	C8—C12ⁱ	1.373 (3)
S2—O5	1.4555 (18)	C8—C9	1.404 (3)
S2—O6	1.4586 (18)	C8—H8	0.9300
S2—O4	1.4761 (18)	C9—C10	1.373 (3)
S2—C22	1.789 (2)	C9—H9	0.9300
N1—C1	1.329 (3)	C10—C11	1.445 (3)
N1—C2	1.393 (3)	C11—C12	1.423 (3)
N1—H1A	0.898 (10)	C11—C11ⁱ	1.442 (4)
N2—C1	1.322 (3)	C12—C8ⁱ	1.373 (3)
N2—C7	1.397 (3)	C12—H12	0.9300
N2—H2A	0.887 (18)	C13—H13	0.9300
N3—C13	1.323 (3)	C14—C19	1.394 (3)
N3—C14	1.398 (3)	C14—C15	1.403 (3)
N3—H3A	0.895 (10)	C15—C16	1.382 (4)
N4—C13	1.330 (3)	C15—H15	0.9300
N4—C19	1.396 (3)	C16—C17	1.401 (4)
N4—H4A	0.899 (10)	C16—H16	0.9300
O7—H7A	0.853 (10)	C17—C18	1.373 (4)
O7—H7B	0.852 (10)	C17—H17	0.9300
O8—H8A	0.844 (10)	C18—C19	1.402 (3)
O8—H8B	0.847 (10)	C18—H18	0.9300
O9—H9A	0.871 (10)	C20—C24ⁱⁱ	1.367 (3)
O9—H9B	0.863 (10)	C20—C21	1.414 (3)
C1—H1	0.9300	C20—H20	0.9300
C2—C3	1.389 (4)	C21—C22	1.382 (3)
C2—C7	1.403 (3)	C21—H21	0.9300
C3—C4	1.389 (4)	C22—C23	1.442 (3)
C3—H3	0.9300	C23—C24	1.425 (3)
C4—C5	1.403 (4)	C23—C23ⁱⁱ	1.436 (4)
C4—H4	0.9300	C24—C20ⁱⁱ	1.367 (3)
C5—C6	1.375 (4)	C24—H24	0.9300

O2—S1—O1	113.02 (11)	C9—C8—H8	119.7
O2—S1—O3	112.36 (11)	C10—C9—C8	120.8 (2)
O1—S1—O3	111.76 (11)	C10—C9—H9	119.6
O2—S1—C10	107.58 (11)	C8—C9—H9	119.6
O1—S1—C10	105.71 (11)	C9—C10—C11	120.7 (2)
O3—S1—C10	105.83 (10)	C9—C10—S1	117.92 (18)
O5—S2—O6	113.58 (11)	C11—C10—S1	121.33 (17)
O5—S2—O4	111.49 (10)	C12—C11—C11ⁱ	118.8 (3)
O6—S2—O4	111.78 (11)	C12—C11—C10	123.3 (2)
O5—S2—C22	108.32 (10)	C11ⁱ—C11—C10	117.9 (3)
O6—S2—C22	106.06 (10)	C8ⁱ—C12—C11	121.2 (2)
O4—S2—C22	105.02 (10)	C8ⁱ—C12—H12	119.4
C1—N1—C2	108.7 (2)	C11—C12—H12	119.4
C1—N1—H1A	127 (2)	N3—C13—N4	110.2 (2)
C2—N1—H1A	124 (2)	N3—C13—H13	124.9
C1—N2—C7	109.1 (2)	N4—C13—H13	124.9
C1—N2—H2A	124 (2)	C19—C14—N3	106.2 (2)
C7—N2—H2A	126 (2)	C19—C14—C15	121.6 (2)
C13—N3—C14	108.8 (2)	N3—C14—C15	132.2 (2)
C13—N3—H3A	124.4 (18)	C16—C15—C14	116.0 (3)
C14—N3—H3A	126.6 (18)	C16—C15—H15	122.0
C13—N4—C19	108.6 (2)	C14—C15—H15	122.0
C13—N4—H4A	124.5 (17)	C15—C16—C17	122.3 (3)
C19—N4—H4A	126.9 (17)	C15—C16—H16	118.9
H7A—O7—H7B	103.0 (15)	C17—C16—H16	118.9
H8A—O8—H8B	105.6 (15)	C18—C17—C16	121.9 (3)
H9A—O9—H9B	100.1 (14)	C18—C17—H17	119.1
N2—C1—N1	110.2 (3)	C16—C17—H17	119.1
N2—C1—H1	124.9	C17—C18—C19	116.6 (3)
N1—C1—H1	124.9	C17—C18—H18	121.7
C3—C2—N1	132.0 (2)	C19—C18—H18	121.7
C3—C2—C7	121.6 (2)	C14—C19—N4	106.3 (2)
N1—C2—C7	106.4 (2)	C14—C19—C18	121.6 (2)
C4—C3—C2	116.5 (3)	N4—C19—C18	132.1 (2)
C4—C3—H3	121.8	C24ⁱⁱ—C20—C21	120.5 (2)
C2—C3—H3	121.8	C24ⁱⁱ—C20—H20	119.7
C3—C4—C5	121.9 (3)	C21—C20—H20	119.7
C3—C4—H4	119.1	C22—C21—C20	120.4 (2)
C5—C4—H4	119.1	C22—C21—H21	119.8
C6—C5—C4	122.0 (3)	C20—C21—H21	119.8
C6—C5—H5	119.0	C21—C22—C23	120.6 (2)
C4—C5—H5	119.0	C21—C22—S2	117.66 (17)
C5—C6—C7	116.4 (3)	C23—C22—S2	121.65 (16)
C5—C6—H6	121.8	C24—C23—C23ⁱⁱ	118.9 (2)
C7—C6—H6	121.8	C24—C23—C22	122.86 (19)
N2—C7—C6	132.7 (2)	C23ⁱⁱ—C23—C22	118.2 (2)
N2—C7—C2	105.7 (2)	C20ⁱⁱ—C24—C23	121.3 (2)
C6—C7—C2	121.6 (3)	C20ⁱⁱ—C24—H24	119.3
C12ⁱ—C8—C9	120.6 (2)	C23—C24—H24	119.3
C12ⁱ—C8—H8	119.7

Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+1, −y+1, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O7ⁱⁱⁱ	0.90 (1)	1.82 (1)	2.708 (3)	170 (3)
N2—H2A···O4^iv	0.89 (2)	1.89 (2)	2.762 (3)	170 (3)
N3—H3A···O3^v	0.90 (1)	1.94 (1)	2.812 (3)	166 (2)
N4—H4A···O8ⁱ	0.90 (1)	1.88 (1)	2.771 (3)	169 (2)
O7—H7B···O5^vi	0.85 (1)	2.17 (2)	2.839 (3)	135 (2)
O8—H8A···O2^vii	0.84 (1)	1.98 (1)	2.826 (3)	178 (3)
O7—H7A···O1	0.85 (1)	2.00 (1)	2.823 (3)	162 (3)
O8—H8B···O6	0.85 (1)	1.96 (1)	2.809 (3)	176 (3)
O9—H9B···O1ⁱ	0.86 (1)	2.16 (2)	2.970 (3)	157 (3)

Symmetry codes: (i) −x+1, −y+1, −z+1; (iii) x, y−1, z+1; (iv) x+1, y, z+1; (v) x−1, y, z; (vi) x, y+1, z; (vii) x, y−1, z.

Experimental details

Crystal data
Chemical formula	2C₇H₇N₂⁺·C₁₀H₆O₆S₂²⁻·3H₂O
M_r	578.61
Crystal system, space group	Triclinic, P1
Temperature (K)	296
a, b, c (Å)	8.372 (4), 9.889 (5), 17.044 (8)
α, β, γ (°)	80.914 (8), 87.557 (9), 73.641 (8)
V (Å³)	1337.0 (11)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.26
Crystal size (mm)	0.15 × 0.12 × 0.04

Data collection
Diffractometer	Bruker SMART APEX CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2001)
T_min, T_max	0.962, 0.990
No. of measured, independent and observed [I > 2σ(I)] reflections	6891, 4670, 3494
R_int	0.020
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.043, 0.110, 1.06
No. of reflections	4670
No. of parameters	392
No. of restraints	37
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.30, −0.33

Computer programs: SMART (Bruker, 2001), SAINT-Plus (Bruker, 2001), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2003).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O7ⁱ	0.898 (10)	1.820 (12)	2.708 (3)	170 (3)
N2—H2A···O4ⁱⁱ	0.887 (18)	1.885 (19)	2.762 (3)	170 (3)
N3—H3A···O3ⁱⁱⁱ	0.895 (10)	1.937 (12)	2.812 (3)	166 (2)
N4—H4A···O8^iv	0.899 (10)	1.883 (11)	2.771 (3)	169 (2)
O7—H7B···O5^v	0.852 (10)	2.169 (19)	2.839 (3)	135 (2)
O8—H8A···O2^vi	0.844 (10)	1.982 (10)	2.826 (3)	178 (3)
O7—H7A···O1	0.853 (10)	1.999 (12)	2.823 (3)	162 (3)
O8—H8B···O6	0.847 (10)	1.963 (10)	2.809 (3)	176 (3)
O9—H9B···O1^iv	0.863 (10)	2.157 (18)	2.970 (3)	157 (3)

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

References

Bruker (2001). SAINT-Plus, SMART and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2003). J. Appl. Cryst. 36, 7–13. Web of Science CrossRef CAS IUCr Journals Google Scholar
Wang, Z.-L. & Wei, L.-H. (2007). Acta Cryst. E63, o1448–o1449. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar