2,2'-Bi-1,3,4-thia-diazole-5,5'-diamine tetra-hydrate.

In the title compound, C(4)H(4)N(6)S(2)·4H(2)O, the complete organic mol-ecule is generated by crystallographic twofold symmetry and the dihedral angle between the aromatic rings is 10.24 (3)°. In the crystal, inter-molecular N-H⋯N, N-H⋯O, O-H⋯N and O-H⋯O hydrogen bonds and aromatic π-π stacking inter-actions [centroid-centroid separations = 3.530 (3) and 3.600 (3) Å] are observed.

Related literature

For background to the pharmacutical properties of thia­dia­zo­les, see: Chapleo et al. (1986 ▶; 1987 ▶); Stillings et al. (1986 ▶); Clerici et al. (2001 ▶). For their tribological behavior, see: Zhu et al. (2009 ▶) and for their pesticidal activity, see: Fan et al. (2010 ▶).

Experimental

Crystal data

C4H4N6S2·4H2O

M = 272.32

Monoclinic,

a = 19.977 (6) Å

b = 6.678 (2) Å

c = 9.328 (3) Å

β = 112.514 (6)°

V = 1149.7 (6) Å3

Z = 4

Mo Kα radiation

μ = 0.48 mm−1

T = 293 K

0.29 × 0.06 × 0.03 mm

Data collection

Bruker APEX CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2003 ▶) T min = 0.659, T max = 1.000

5047 measured reflections

1015 independent reflections

902 reflections with I > 2σ(I)

R int = 0.040

Refinement

R[F 2 > 2σ(F 2)] = 0.034

wR(F 2) = 0.091

S = 1.12

1015 reflections

91 parameters

6 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.36 e Å−3

Δρmin = −0.29 e Å−3

Data collection: SMART (Bruker, 1998 ▶); cell refinement: SAINT (Bruker, 2003 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: Mercury (Macrae et al., 2008 ▶); software used to prepare material for publication: Mercury.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S160053681002996X/hb5580sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S160053681002996X/hb5580Isup2.hkl

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

C4H4N6S2·4H2O	F(000) = 568
Mr = 272.32	Dx = 1.573 Mg m−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 1375 reflections
a = 19.977 (6) Å	θ = 2.2–27.5°
b = 6.678 (2) Å	µ = 0.48 mm−1
c = 9.328 (3) Å	T = 293 K
β = 112.514 (6)°	Rod, colourless
V = 1149.7 (6) Å3	0.29 × 0.06 × 0.03 mm
Z = 4

Bruker APEX CCD diffractometer	1015 independent reflections
Radiation source: fine-focus sealed tube	902 reflections with I > 2σ(I)
graphite	Rint = 0.040
Frames, each covering 0.3 ° in ω scans	θmax = 25.0°, θmin = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 2003)	h = −23→23
Tmin = 0.659, Tmax = 1.000	k = −7→7
5047 measured reflections	l = −11→11

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)] = 0.034	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.091	H atoms treated by a mixture of independent and constrained refinement
S = 1.12	w = 1/[σ2(Fo2) + (0.046P)2 + 0.8924P] where P = (Fo2 + 2Fc2)/3
1015 reflections	(Δ/σ)max < 0.001
91 parameters	Δρmax = 0.36 e Å−3
6 restraints	Δρmin = −0.29 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 > 2σ(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	0.40277 (3)	0.22880 (9)	0.80732 (6)	0.0302 (2)
C1	0.49090 (11)	0.2498 (3)	0.8184 (2)	0.0254 (5)
C2	0.43905 (11)	0.2386 (3)	1.0092 (2)	0.0250 (5)
N1	0.53913 (9)	0.2631 (2)	0.9582 (2)	0.0275 (4)
N2	0.51008 (10)	0.2557 (3)	1.0700 (2)	0.0278 (4)
N3	0.39755 (11)	0.2341 (3)	1.0925 (2)	0.0346 (5)
H3A	0.3518 (10)	0.196 (4)	1.049 (3)	0.042*
H3B	0.4198 (14)	0.236 (4)	1.194 (2)	0.042*
O1	0.30903 (9)	0.3504 (3)	0.3923 (2)	0.0468 (5)
H1A	0.3539 (10)	0.338 (5)	0.434 (3)	0.056*
H1B	0.2881 (16)	0.242 (3)	0.391 (4)	0.056*
O2	0.25880 (9)	1.0305 (3)	0.9186 (2)	0.0451 (5)
H2A	0.2393 (14)	0.997 (5)	0.977 (3)	0.054*
H2B	0.2376 (14)	1.067 (4)	0.827 (2)	0.054*

	U11	U22	U33	U12	U13	U23
S1	0.0234 (3)	0.0449 (4)	0.0199 (3)	0.0004 (2)	0.0057 (2)	−0.0007 (2)
C1	0.0253 (11)	0.0284 (11)	0.0227 (11)	0.0003 (8)	0.0096 (9)	0.0001 (8)
C2	0.0270 (11)	0.0256 (11)	0.0206 (11)	0.0016 (8)	0.0071 (9)	−0.0001 (8)
N1	0.0273 (10)	0.0324 (10)	0.0230 (10)	0.0002 (7)	0.0100 (8)	0.0004 (7)
N2	0.0269 (9)	0.0364 (11)	0.0203 (9)	0.0005 (7)	0.0093 (8)	0.0002 (7)
N3	0.0275 (10)	0.0542 (13)	0.0232 (10)	−0.0021 (8)	0.0109 (9)	−0.0003 (9)
O1	0.0292 (9)	0.0543 (12)	0.0501 (11)	−0.0052 (8)	0.0076 (8)	0.0054 (9)
O2	0.0356 (10)	0.0546 (11)	0.0420 (11)	−0.0013 (8)	0.0113 (8)	0.0006 (9)

S1—C1	1.729 (2)	N3—H3A	0.882 (17)
S1—C2	1.741 (2)	N3—H3B	0.875 (17)
C1—N1	1.294 (3)	O1—H1A	0.834 (18)
C1—C1i	1.455 (4)	O1—H1B	0.833 (17)
C2—N2	1.316 (3)	O2—H2A	0.815 (17)
C2—N3	1.337 (3)	O2—H2B	0.834 (17)
N1—N2	1.375 (3)
C1—S1—C2	86.53 (10)	C2—N2—N1	111.99 (17)
C1—S1—C2	86.53 (10)	C2—N2—N1	111.99 (17)
N1—C1—C1i	122.9 (2)	C2—N3—H3A	120.2 (17)
N1—C1—S1	114.49 (16)	C2—N3—H3A	120.2 (17)
C1i—C1—S1	122.6 (2)	C2—N3—H3B	117.0 (19)
N2—C2—N3	123.9 (2)	C2—N3—H3B	117.0 (19)
N2—C2—S1	113.78 (16)	H3A—N3—H3B	121 (3)
N3—C2—S1	122.30 (17)	H1A—O1—H1B	111 (3)
C1—N1—N2	113.20 (17)	H2A—O2—H2B	126 (3)
C2—S1—C1—N1	−0.35 (15)	C1i—C1—N1—N2	−178.63 (10)
C2—S1—C1—N1	−0.35 (15)	S1—C1—N1—N2	0.6 (2)
C2—S1—C1—C1i	178.91 (8)	N3—C2—N2—N1	−178.00 (19)
C2—S1—C1—C1i	178.91 (8)	S1—C2—N2—N1	0.4 (2)
C1—S1—C2—N2	−0.02 (16)	C1—N1—N2—C2	−0.6 (2)
C1—S1—C2—N3	178.36 (19)	C1—N1—N2—C2	−0.6 (2)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3A···O2ii	0.88 (2)	2.11 (2)	2.953 (3)	161 (2)
N3—H3B···N2iii	0.88 (2)	2.12 (2)	2.981 (3)	170 (3)
O1—H1A···N1i	0.83 (2)	2.05 (2)	2.872 (3)	171 (3)
O1—H1B···O2iv	0.83 (2)	1.96 (2)	2.780 (3)	168 (3)
O2—H2A···O1v	0.82 (2)	2.07 (2)	2.867 (3)	167 (3)
O2—H2B···O1vi	0.83 (2)	1.97 (2)	2.806 (3)	178 (3)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3A⋯O2i	0.88 (2)	2.11 (2)	2.953 (3)	161 (2)
N3—H3B⋯N2ii	0.88 (2)	2.12 (2)	2.981 (3)	170 (3)
O1—H1A⋯N1iii	0.83 (2)	2.05 (2)	2.872 (3)	171 (3)
O1—H1B⋯O2iv	0.83 (2)	1.96 (2)	2.780 (3)	168 (3)
O2—H2A⋯O1v	0.82 (2)	2.07 (2)	2.867 (3)	167 (3)
O2—H2B⋯O1vi	0.83 (2)	1.97 (2)	2.806 (3)	178 (3)

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