Bis(2-amino-pyridinium) 5,5'-disulfanediylbis(1,3,4-thia-diazole-2-thiol-ate) monohydrate.

In the crystal of the title compound, 2C(5)H(7)N(2) (+)·C(4)N(4)S(6) (2-)·H(2)O, inter-molecular N-H⋯S and N-H⋯N hydrogen bonds link four cations and two dianions into a centrosymmetric cluster. The crystal packing is further consolidated by π-π inter-actions between the five- and six-membered rings of neighbouring clusters [centroid-centroid distances = 3.692 (3), 3.718 (3), 3.660 (3) and 3.696 (3) Å] and via O-H⋯N, O-H⋯S and N-H⋯O hydrogen bonds involving the uncoordinated water mol-ecules.

Related literature

For general background to supra­molecular compounds, see: Rowsell & Yaghi (2005 ▶); Neville et al. (2008 ▶); Huang et al. (2007 ▶); Burchell et al. (2006 ▶). For related structures, see: Jebas et al. (2006 ▶); Jian et al. (2006 ▶); Banerjee et al. (2006 ▶); Moers et al. (2000 ▶).

Experimental

Crystal data

2C5H7N2 +·C4N4S6 2−·H2O

M = 504.71

Monoclinic,

a = 7.3109 (15) Å

b = 14.112 (3) Å

c = 20.930 (4) Å

β = 98.13 (3)°

V = 2137.8 (7) Å3

Z = 4

Mo Kα radiation

μ = 0.67 mm−1

T = 295 K

0.24 × 0.22 × 0.20 mm

Data collection

Enraf–Nonius CAD-4 diffractometer

9377 measured reflections

4911 independent reflections

3931 reflections with I > 2σ(I)

R int = 0.023

3 standard reflections every 100 reflections intensity decay: none

Refinement

R[F 2 > 2σ(F 2)] = 0.048

wR(F 2) = 0.086

S = 1.17

4911 reflections

270 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.55 e Å−3

Δρmin = −0.26 e Å−3

Data collection: CAD-4 Software (Enraf–Nonius, 1989 ▶); cell refinement: CAD-4 Software; data reduction: NRCVAX (Gabe et al., 1989 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811008336/cv5028sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811008336/cv5028Isup2.hkl

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

2C5H7N2+·C4N4S62−·H2O	F(000) = 1040
Mr = 504.71	Dx = 1.568 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 25 reflections
a = 7.3109 (15) Å	θ = 4–14°
b = 14.112 (3) Å	µ = 0.67 mm−1
c = 20.930 (4) Å	T = 295 K
β = 98.13 (3)°	Block, colourless
V = 2137.8 (7) Å3	0.24 × 0.22 × 0.20 mm
Z = 4

Enraf–Nonius CAD-4 diffractometer	Rint = 0.023
Radiation source: fine-focus sealed tube	θmax = 27.5°, θmin = 1.8°
graphite	h = −9→9
ω scans	k = −18→17
9377 measured reflections	l = −27→27
4911 independent reflections	3 standard reflections every 100 reflections
3931 reflections with I > 2σ(I)	intensity decay: none

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)] = 0.048	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.086	H atoms treated by a mixture of independent and constrained refinement
S = 1.17	w = 1/[σ2(Fo2) + (0.0278P)2 + 0.2825P] where P = (Fo2 + 2Fc2)/3
4911 reflections	(Δ/σ)max = 0.001
270 parameters	Δρmax = 0.55 e Å−3
0 restraints	Δρmin = −0.26 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
S1	0.40901 (12)	0.94077 (5)	0.59925 (3)	0.0364 (2)
S2	0.26262 (10)	0.84201 (4)	0.47444 (3)	0.02842 (17)
S3	0.18855 (10)	0.64715 (4)	0.40985 (3)	0.02446 (15)
S4	0.37606 (10)	0.66357 (4)	0.34565 (3)	0.02432 (15)
S5	0.29173 (9)	0.86996 (4)	0.30034 (3)	0.02237 (15)
S6	0.12212 (10)	0.98806 (4)	0.18451 (3)	0.02636 (16)
N1	−0.1312 (3)	0.89557 (15)	0.04470 (11)	0.0380 (6)
H1A	−0.0716	0.9175	0.0800	0.046*
H1B	−0.1810	0.9339	0.0153	0.046*
N2	−0.0676 (3)	0.74324 (14)	0.08195 (10)	0.0251 (5)
H2A	−0.0060	0.7670	0.1163	0.030*
N3	0.6664 (4)	0.84178 (15)	0.72187 (11)	0.0387 (6)
H3A	0.6044	0.8593	0.6858	0.046*
H3B	0.7133	0.8835	0.7493	0.046*
N4	0.6138 (3)	0.68622 (14)	0.69089 (10)	0.0237 (5)
H4A	0.5520	0.7064	0.6555	0.028*
N5	0.4136 (3)	0.75310 (14)	0.57420 (9)	0.0231 (5)
N6	0.3619 (3)	0.68528 (14)	0.52826 (9)	0.0231 (5)
N7	0.1864 (3)	0.72209 (14)	0.23431 (10)	0.0254 (5)
N8	0.1316 (3)	0.79840 (14)	0.19588 (9)	0.0247 (5)
C1	−0.0815 (4)	0.64796 (18)	0.07686 (13)	0.0314 (6)
H1C	−0.0260	0.6098	0.1104	0.038*
C2	−0.1754 (4)	0.60765 (19)	0.02344 (14)	0.0349 (7)
H2B	−0.1856	0.5421	0.0198	0.042*
C3	−0.2571 (4)	0.66701 (19)	−0.02635 (13)	0.0322 (6)
H3C	−0.3223	0.6405	−0.0634	0.039*
C4	−0.2419 (4)	0.76228 (18)	−0.02103 (12)	0.0260 (6)
H4B	−0.2945	0.8010	−0.0546	0.031*
C5	−0.1462 (4)	0.80276 (17)	0.03563 (12)	0.0247 (6)
C6	0.6319 (4)	0.59150 (17)	0.70022 (12)	0.0249 (6)
H6B	0.5793	0.5503	0.6681	0.030*
C7	0.7250 (4)	0.55568 (18)	0.75551 (12)	0.0274 (6)
H7B	0.7364	0.4906	0.7620	0.033*
C8	0.8036 (4)	0.62005 (19)	0.80266 (12)	0.0282 (6)
H8B	0.8678	0.5972	0.8411	0.034*
C9	0.7875 (4)	0.71541 (18)	0.79316 (12)	0.0266 (6)
H9A	0.8410	0.7571	0.8248	0.032*
C10	0.6895 (4)	0.75046 (18)	0.73512 (12)	0.0250 (6)
C11	0.3711 (4)	0.84127 (17)	0.55446 (12)	0.0247 (5)
C12	0.2803 (4)	0.72031 (16)	0.47427 (11)	0.0216 (5)
C13	0.2721 (3)	0.74813 (16)	0.29047 (11)	0.0205 (5)
C14	0.1749 (3)	0.88218 (17)	0.22216 (11)	0.0197 (5)
O1W	0.3564 (3)	0.48901 (14)	0.56202 (10)	0.0342 (5)
H2W1	0.371 (5)	0.542 (3)	0.5504 (17)	0.058 (12)*
H1W1	0.293 (5)	0.498 (2)	0.5915 (18)	0.055 (12)*

	U11	U22	U33	U12	U13	U23
S1	0.0584 (6)	0.0233 (3)	0.0242 (4)	0.0096 (3)	−0.0051 (3)	−0.0068 (3)
S2	0.0413 (4)	0.0220 (3)	0.0193 (3)	0.0082 (3)	−0.0047 (3)	−0.0003 (2)
S3	0.0300 (4)	0.0230 (3)	0.0191 (3)	−0.0054 (3)	−0.0009 (3)	−0.0009 (2)
S4	0.0292 (4)	0.0247 (3)	0.0178 (3)	0.0056 (3)	−0.0008 (3)	0.0005 (2)
S5	0.0259 (4)	0.0225 (3)	0.0169 (3)	−0.0031 (3)	−0.0033 (3)	−0.0015 (2)
S6	0.0318 (4)	0.0221 (3)	0.0233 (3)	−0.0021 (3)	−0.0025 (3)	0.0033 (2)
N1	0.0514 (17)	0.0233 (11)	0.0325 (13)	−0.0013 (11)	−0.0176 (12)	0.0000 (9)
N2	0.0286 (13)	0.0262 (11)	0.0180 (11)	−0.0024 (9)	−0.0053 (9)	−0.0025 (8)
N3	0.0507 (17)	0.0279 (12)	0.0316 (13)	−0.0065 (11)	−0.0146 (12)	−0.0018 (9)
N4	0.0251 (13)	0.0281 (11)	0.0159 (10)	−0.0007 (9)	−0.0035 (9)	−0.0007 (8)
N5	0.0300 (13)	0.0223 (10)	0.0157 (10)	0.0003 (9)	−0.0011 (9)	−0.0004 (8)
N6	0.0275 (13)	0.0221 (10)	0.0187 (11)	−0.0015 (9)	−0.0004 (9)	0.0005 (8)
N7	0.0345 (14)	0.0214 (11)	0.0184 (10)	0.0005 (9)	−0.0030 (10)	−0.0006 (8)
N8	0.0325 (14)	0.0220 (10)	0.0170 (11)	−0.0012 (9)	−0.0052 (9)	−0.0003 (8)
C1	0.0382 (18)	0.0242 (14)	0.0312 (15)	0.0003 (12)	0.0024 (13)	0.0047 (11)
C2	0.0412 (19)	0.0233 (13)	0.0400 (17)	−0.0050 (12)	0.0053 (14)	−0.0069 (11)
C3	0.0278 (16)	0.0399 (16)	0.0282 (14)	−0.0052 (12)	0.0010 (12)	−0.0121 (11)
C4	0.0232 (15)	0.0342 (14)	0.0191 (13)	0.0012 (11)	−0.0023 (11)	−0.0019 (10)
C5	0.0228 (15)	0.0274 (13)	0.0227 (13)	−0.0019 (11)	−0.0012 (11)	−0.0026 (10)
C6	0.0241 (15)	0.0272 (13)	0.0235 (13)	−0.0001 (11)	0.0032 (11)	−0.0044 (10)
C7	0.0249 (15)	0.0290 (13)	0.0286 (14)	0.0047 (11)	0.0050 (12)	0.0023 (11)
C8	0.0204 (14)	0.0443 (16)	0.0200 (13)	0.0036 (12)	0.0031 (11)	0.0049 (11)
C9	0.0226 (15)	0.0355 (15)	0.0203 (13)	−0.0033 (11)	−0.0021 (11)	−0.0044 (10)
C10	0.0232 (15)	0.0266 (13)	0.0248 (13)	−0.0041 (11)	0.0017 (11)	−0.0042 (10)
C11	0.0288 (15)	0.0274 (13)	0.0174 (12)	0.0038 (11)	0.0016 (11)	−0.0008 (10)
C12	0.0247 (14)	0.0212 (12)	0.0180 (12)	−0.0013 (10)	0.0002 (10)	−0.0030 (9)
C13	0.0222 (14)	0.0215 (12)	0.0174 (12)	0.0018 (10)	0.0009 (10)	0.0008 (9)
C14	0.0189 (13)	0.0248 (12)	0.0152 (12)	−0.0007 (10)	0.0013 (10)	0.0005 (9)
O1W	0.0491 (15)	0.0229 (11)	0.0295 (12)	−0.0011 (9)	0.0022 (10)	0.0002 (8)

S1—C11	1.689 (3)	N6—C12	1.299 (3)
S2—C12	1.722 (2)	N7—C13	1.304 (3)
S2—C11	1.749 (3)	N7—N8	1.370 (3)
S3—C12	1.754 (2)	N8—C14	1.324 (3)
S3—S4	2.0638 (11)	C1—C2	1.352 (4)
S4—C13	1.757 (2)	C1—H1C	0.9300
S5—C13	1.735 (2)	C2—C3	1.403 (4)
S5—C14	1.744 (2)	C2—H2B	0.9300
S6—C14	1.708 (2)	C3—C4	1.352 (4)
N1—C5	1.326 (3)	C3—H3C	0.9300
N1—H1A	0.8600	C4—C5	1.410 (3)
N1—H1B	0.8600	C4—H4B	0.9300
N2—C5	1.348 (3)	C6—C7	1.355 (4)
N2—C1	1.351 (3)	C6—H6B	0.9300
N2—H2A	0.8600	C7—C8	1.403 (4)
N3—C10	1.324 (3)	C7—H7B	0.9300
N3—H3A	0.8600	C8—C9	1.363 (4)
N3—H3B	0.8600	C8—H8B	0.9300
N4—C6	1.355 (3)	C9—C10	1.410 (4)
N4—C10	1.356 (3)	C9—H9A	0.9300
N4—H4A	0.8600	O1W—H2W1	0.80 (4)
N5—C11	1.334 (3)	O1W—H1W1	0.83 (4)
N5—N6	1.371 (3)
Cg1···Cg3i	3.692 (3)	Cg2···Cg4iii	3.660 (3)
Cg1···Cg3ii	3.718 (3)	Cg2···Cg4iv	3.696 (3)
C12—S2—C11	88.39 (12)	N1—C5—N2	119.6 (2)
C12—S3—S4	102.56 (9)	N1—C5—C4	122.8 (2)
C13—S4—S3	103.82 (9)	N2—C5—C4	117.6 (2)
C13—S5—C14	88.00 (11)	N4—C6—C7	121.2 (2)
C5—N1—H1A	120.0	N4—C6—H6B	119.4
C5—N1—H1B	120.0	C7—C6—H6B	119.4
H1A—N1—H1B	120.0	C6—C7—C8	117.7 (2)
C5—N2—C1	122.9 (2)	C6—C7—H7B	121.1
C5—N2—H2A	118.5	C8—C7—H7B	121.1
C1—N2—H2A	118.5	C9—C8—C7	121.2 (2)
C10—N3—H3A	120.0	C9—C8—H8B	119.4
C10—N3—H3B	120.0	C7—C8—H8B	119.4
H3A—N3—H3B	120.0	C8—C9—C10	119.7 (2)
C6—N4—C10	122.6 (2)	C8—C9—H9A	120.2
C6—N4—H4A	118.7	C10—C9—H9A	120.2
C10—N4—H4A	118.7	N3—C10—N4	118.7 (2)
C11—N5—N6	113.89 (19)	N3—C10—C9	123.8 (2)
C12—N6—N5	113.05 (19)	N4—C10—C9	117.5 (2)
C13—N7—N8	111.79 (19)	N5—C11—S1	126.22 (19)
C14—N8—N7	115.17 (19)	N5—C11—S2	110.88 (18)
N2—C1—C2	120.5 (3)	S1—C11—S2	122.88 (15)
N2—C1—H1C	119.8	N6—C12—S2	113.78 (18)
C2—C1—H1C	119.8	N6—C12—S3	121.56 (18)
C1—C2—C3	118.4 (2)	S2—C12—S3	124.59 (14)
C1—C2—H2B	120.8	N7—C13—S5	114.06 (17)
C3—C2—H2B	120.8	N7—C13—S4	120.60 (18)
C4—C3—C2	120.7 (3)	S5—C13—S4	125.02 (14)
C4—C3—H3C	119.6	N8—C14—S6	124.38 (18)
C2—C3—H3C	119.6	N8—C14—S5	110.99 (17)
C3—C4—C5	119.8 (2)	S6—C14—S5	124.63 (14)
C3—C4—H4B	120.1	H2W1—O1W—H1W1	102 (3)
C5—C4—H4B	120.1
C12—S3—S4—C13	−98.27 (12)	N6—N5—C11—S2	−0.5 (3)
C11—N5—N6—C12	−0.4 (3)	C12—S2—C11—N5	0.9 (2)
C13—N7—N8—C14	0.1 (3)	C12—S2—C11—S1	−177.71 (19)
C5—N2—C1—C2	0.7 (4)	N5—N6—C12—S2	1.1 (3)
N2—C1—C2—C3	0.2 (4)	N5—N6—C12—S3	−175.97 (18)
C1—C2—C3—C4	0.1 (5)	C11—S2—C12—N6	−1.1 (2)
C2—C3—C4—C5	−1.2 (4)	C11—S2—C12—S3	175.82 (19)
C1—N2—C5—N1	178.1 (3)	S4—S3—C12—N6	−106.0 (2)
C1—N2—C5—C4	−1.9 (4)	S4—S3—C12—S2	77.26 (17)
C3—C4—C5—N1	−177.9 (3)	N8—N7—C13—S5	0.1 (3)
C3—C4—C5—N2	2.1 (4)	N8—N7—C13—S4	−173.73 (18)
C10—N4—C6—C7	1.2 (4)	C14—S5—C13—N7	−0.1 (2)
N4—C6—C7—C8	−0.5 (4)	C14—S5—C13—S4	173.34 (18)
C6—C7—C8—C9	−0.2 (4)	S3—S4—C13—N7	−100.7 (2)
C7—C8—C9—C10	0.3 (4)	S3—S4—C13—S5	86.25 (17)
C6—N4—C10—N3	179.5 (2)	N7—N8—C14—S6	−179.89 (19)
C6—N4—C10—C9	−1.1 (4)	N7—N8—C14—S5	−0.2 (3)
C8—C9—C10—N3	179.7 (3)	C13—S5—C14—N8	0.2 (2)
C8—C9—C10—N4	0.3 (4)	C13—S5—C14—S6	179.88 (18)
N6—N5—C11—S1	178.1 (2)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···S6	0.86	2.63	3.488 (3)	177
N2—H2A···N8	0.86	1.87	2.726 (3)	171
N3—H3A···S1	0.86	2.43	3.273 (3)	166
N4—H4A···N5	0.86	1.97	2.826 (3)	179
O1W—H2W1···N6	0.80 (4)	2.07 (4)	2.860 (3)	169 (4)
N1—H1B···O1Wv	0.86	2.07	2.898 (3)	162
O1W—H1W1···S6iv	0.83 (4)	2.47 (4)	3.294 (3)	175 (3)
N3—H3B···S6vi	0.86	2.49	3.338 (2)	171

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯S6	0.86	2.63	3.488 (3)	177
N2—H2A⋯N8	0.86	1.87	2.726 (3)	171
N3—H3A⋯S1	0.86	2.43	3.273 (3)	166
N4—H4A⋯N5	0.86	1.97	2.826 (3)	179
O1W—H2W1⋯N6	0.80 (4)	2.07 (4)	2.860 (3)	169 (4)
N1—H1B⋯O1Wi	0.86	2.07	2.898 (3)	162
O1W—H1W1⋯S6ii	0.83 (4)	2.47 (4)	3.294 (3)	175 (3)
N3—H3B⋯S6iii	0.86	2.49	3.338 (2)	171

Symmetry codes: (i) ; (ii) ; (iii) .