2,2'-(Disulfanedi-yl)dianilinium dichloride dihydrate.

In the title hydrated mol-ecular salt, C12H14N2S2 (2+)·2Cl(-)·2H2O, the dihedral angle between the benzene rings in the dication is 9.03 (17)° and the C-S-S-C torsion angle is 96.8 (2)°. The crystal packing can be described as alternating organic and anionic water layers lying parallel to (100), which are linked by N-H⋯Cl and N-H⋯O hydrogen bonds. O-H⋯Cl hydrogen bonds and aromatic π-π stacking inter-actions [centroid-centroid separation = 3.730 (3) Å] are also observed.

Related literature

For related structures and background to di­sulfides, see: Benmebarek et al. (2012 ▶, 2013 ▶). For related structures, see: Tang et al. (2011 ▶); Goh et al. (2010 ▶); Song & Fan (2009 ▶).

Experimental

Crystal data

C12H14N2S2 2+·2Cl−·2H2O

M = 357.32

Orthorhombic,

a = 17.826 (7) Å

b = 13.358 (5) Å

c = 7.120 (3) Å

V = 1695.4 (12) Å3

Z = 4

Mo Kα radiation

μ = 0.63 mm−1

T = 150 K

0.16 × 0.13 × 0.11 mm

Data collection

Bruker APEXII CCD diffractometer

10760 measured reflections

3584 independent reflections

2409 reflections with I > 2σ(I)

R int = 0.097

Refinement

R[F 2 > 2σ(F 2)] = 0.063

wR(F 2) = 0.134

S = 1.05

3584 reflections

195 parameters

6 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.58 e Å−3

Δρmin = −0.47 e Å−3

Absolute structure: Flack (1983 ▶), 1369 Friedel pairs

Flack parameter: −0.12 (12)

Data collection: APEX2 (Bruker, 2011 ▶); cell refinement: SAINT (Bruker, 2011 ▶); data reduction: SAINT; program(s) used to solve structure: SIR2002 (Burla et al., 2005 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ▶) and DIAMOND (Brandenburg & Berndt, 2001 ▶); software used to prepare material for publication: WinGX (Farrugia, 2012 ▶).

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536813015742/hb7089sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813015742/hb7089Isup2.hkl

Click here for additional data file.

Supplementary material file. DOI: 10.1107/S1600536813015742/hb7089Isup3.cml

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

C12H14N2S22+·2Cl−·2H2O	F(000) = 744
Mr = 357.32	Dx = 1.4 Mg m−3
Orthorhombic, Pna21	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2c -2n	Cell parameters from 2698 reflections
a = 17.826 (7) Å	θ = 2.3–28.5°
b = 13.358 (5) Å	µ = 0.63 mm−1
c = 7.120 (3) Å	T = 150 K
V = 1695.4 (12) Å3	Prism, colourless
Z = 4	0.16 × 0.13 × 0.11 mm

Bruker APEXII CCD diffractometer	2409 reflections with I > 2σ(I)
Radiation source: sealed tube	Rint = 0.097
Graphite monochromator	θmax = 28.8°, θmin = 2.8°
φ and ω scans	h = −24→23
10760 measured reflections	k = −18→18
3584 independent reflections	l = −9→8

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.063	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.134	w = 1/[σ2(Fo2) + (0.0595P)2] where P = (Fo2 + 2Fc2)/3
S = 1.05	(Δ/σ)max < 0.001
3584 reflections	Δρmax = 0.58 e Å−3
195 parameters	Δρmin = −0.47 e Å−3
6 restraints	Absolute structure: Flack (1983), 1369 Friedel pairs
Primary atom site location: structure-invariant direct methods	Flack parameter: −0.12 (12)

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
Cl2	0.98060 (6)	0.10914 (8)	1.19390 (17)	0.0269 (3)
S1	0.86675 (9)	−0.10667 (11)	1.3286 (2)	0.0412 (4)
Cl1	0.99242 (8)	0.36455 (10)	0.7389 (2)	0.0411 (4)
S2	0.85864 (8)	−0.15845 (11)	1.0567 (2)	0.0395 (4)
O2W	0.9096 (2)	0.1819 (3)	1.5764 (6)	0.0381 (10)
H3W	0.935 (3)	0.233 (3)	1.609 (9)	0.057*
H4W	0.937 (3)	0.150 (4)	1.497 (7)	0.057*
N2	0.8933 (2)	0.0331 (3)	0.8354 (6)	0.0267 (9)
H2A	0.8991	0.0831	0.7542	0.04*
H2B	0.9208	−0.019	0.7989	0.04*
H2C	0.9082	0.0528	0.9489	0.04*
C21	0.7911 (3)	−0.0781 (4)	0.9473 (8)	0.0286 (12)
O1W	1.0599 (3)	0.4223 (3)	1.3483 (6)	0.0534 (12)
H1W	1.043 (4)	0.476 (3)	1.302 (9)	0.08*
H2W	1.039 (4)	0.406 (4)	1.453 (6)	0.08*
N1	0.9146 (2)	−0.2839 (3)	1.5749 (6)	0.0282 (10)
H1A	0.9242	−0.3284	1.6647	0.042*
H1B	0.9388	−0.2271	1.5996	0.042*
H1C	0.9298	−0.3079	1.4647	0.042*
C26	0.8140 (2)	0.0039 (3)	0.8427 (7)	0.0218 (10)
C14	0.7102 (3)	−0.3103 (4)	1.6647 (8)	0.0317 (12)
H14	0.6782	−0.3509	1.7342	0.038*
C12	0.7275 (3)	−0.1730 (4)	1.4523 (8)	0.0332 (13)
H12	0.7073	−0.1212	1.3811	0.04*
C25	0.7627 (3)	0.0625 (3)	0.7478 (8)	0.0272 (11)
H25	0.7787	0.1168	0.6768	0.033*
C15	0.7858 (3)	−0.3249 (3)	1.6726 (7)	0.0268 (11)
H15	0.8055	−0.3753	1.7482	0.032*
C11	0.8050 (3)	−0.1876 (3)	1.4566 (7)	0.0255 (11)
C23	0.6638 (3)	−0.0391 (4)	0.8641 (8)	0.0395 (14)
H23	0.6128	−0.0526	0.8741	0.047*
C24	0.6876 (3)	0.0396 (4)	0.7590 (8)	0.0345 (12)
H24	0.6528	0.0784	0.6943	0.041*
C16	0.8335 (3)	−0.2645 (3)	1.5676 (7)	0.0237 (10)
C13	0.6811 (3)	−0.2350 (4)	1.5534 (8)	0.0381 (13)
H13	0.6294	−0.2262	1.5468	0.046*
C22	0.7156 (3)	−0.1002 (4)	0.9572 (8)	0.0354 (13)
H22	0.6992	−0.1554	1.0255	0.043*

	U11	U22	U33	U12	U13	U23
Cl2	0.0198 (5)	0.0332 (6)	0.0276 (7)	−0.0025 (5)	−0.0034 (6)	0.0026 (5)
S1	0.0445 (9)	0.0428 (7)	0.0364 (8)	−0.0186 (7)	−0.0119 (8)	0.0133 (6)
Cl1	0.0422 (8)	0.0424 (7)	0.0388 (9)	−0.0023 (5)	−0.0125 (7)	0.0027 (6)
S2	0.0429 (8)	0.0445 (7)	0.0310 (8)	0.0133 (6)	0.0111 (8)	0.0111 (6)
O2W	0.040 (2)	0.043 (2)	0.031 (3)	−0.0078 (17)	−0.002 (2)	0.0002 (18)
N2	0.029 (2)	0.030 (2)	0.021 (2)	0.0051 (16)	−0.001 (2)	−0.0027 (17)
C21	0.034 (3)	0.032 (3)	0.019 (3)	0.001 (2)	0.004 (3)	−0.007 (2)
O1W	0.072 (3)	0.051 (3)	0.038 (3)	0.019 (2)	0.003 (3)	−0.003 (2)
N1	0.030 (2)	0.030 (2)	0.025 (3)	−0.0031 (17)	0.000 (2)	−0.0016 (18)
C26	0.022 (2)	0.028 (2)	0.015 (3)	0.0005 (18)	0.003 (2)	−0.0089 (19)
C14	0.028 (3)	0.044 (3)	0.023 (3)	−0.007 (2)	0.002 (3)	−0.004 (2)
C12	0.038 (3)	0.035 (3)	0.027 (3)	0.004 (2)	−0.002 (3)	−0.006 (2)
C25	0.030 (3)	0.030 (2)	0.021 (3)	0.005 (2)	−0.003 (3)	−0.006 (2)
C15	0.033 (3)	0.026 (2)	0.021 (3)	−0.0076 (19)	0.000 (3)	−0.0043 (19)
C11	0.030 (3)	0.028 (2)	0.019 (3)	−0.008 (2)	0.002 (2)	−0.006 (2)
C23	0.026 (3)	0.062 (4)	0.030 (4)	−0.006 (3)	0.002 (3)	−0.015 (3)
C24	0.027 (3)	0.046 (3)	0.030 (3)	0.005 (2)	−0.008 (3)	−0.008 (2)
C16	0.024 (2)	0.027 (2)	0.020 (3)	−0.0046 (18)	0.001 (2)	−0.010 (2)
C13	0.024 (3)	0.052 (3)	0.038 (4)	0.000 (2)	0.009 (3)	−0.017 (3)
C22	0.030 (3)	0.049 (3)	0.028 (3)	−0.008 (3)	0.005 (3)	−0.003 (2)

S1—C11	1.792 (5)	C14—C15	1.364 (6)
S1—S2	2.061 (2)	C14—C13	1.380 (8)
S2—C21	1.791 (5)	C14—H14	0.93
O2W—H3W	0.86 (2)	C12—C13	1.375 (8)
O2W—H4W	0.86 (2)	C12—C11	1.396 (7)
N2—C26	1.468 (6)	C12—H12	0.93
N2—H2A	0.89	C25—C24	1.375 (7)
N2—H2B	0.89	C25—H25	0.93
N2—H2C	0.89	C15—C16	1.391 (7)
C21—C22	1.380 (7)	C15—H15	0.93
C21—C26	1.386 (7)	C11—C16	1.391 (7)
O1W—H1W	0.852 (19)	C23—C24	1.358 (8)
O1W—H2W	0.858 (19)	C23—C22	1.399 (8)
N1—C16	1.469 (6)	C23—H23	0.93
N1—H1A	0.89	C24—H24	0.93
N1—H1B	0.89	C13—H13	0.93
N1—H1C	0.89	C22—H22	0.93
C26—C25	1.380 (7)
C11—S1—S2	103.43 (17)	C13—C12—H12	120
C21—S2—S1	104.74 (18)	C11—C12—H12	120
H3W—O2W—H4W	106 (6)	C24—C25—C26	119.4 (5)
C26—N2—H2A	109.5	C24—C25—H25	120.3
C26—N2—H2B	109.5	C26—C25—H25	120.3
H2A—N2—H2B	109.5	C14—C15—C16	119.9 (5)
C26—N2—H2C	109.5	C14—C15—H15	120
H2A—N2—H2C	109.5	C16—C15—H15	120
H2B—N2—H2C	109.5	C16—C11—C12	118.5 (4)
C22—C21—C26	118.9 (5)	C16—C11—S1	120.7 (4)
C22—C21—S2	120.3 (4)	C12—C11—S1	120.8 (4)
C26—C21—S2	120.6 (4)	C24—C23—C22	120.4 (5)
H1W—O1W—H2W	114 (3)	C24—C23—H23	119.8
C16—N1—H1A	109.5	C22—C23—H23	119.8
C16—N1—H1B	109.5	C23—C24—C25	120.5 (5)
H1A—N1—H1B	109.5	C23—C24—H24	119.7
C16—N1—H1C	109.5	C25—C24—H24	119.7
H1A—N1—H1C	109.5	C15—C16—C11	120.7 (4)
H1B—N1—H1C	109.5	C15—C16—N1	118.7 (4)
C25—C26—C21	121.0 (4)	C11—C16—N1	120.6 (4)
C25—C26—N2	118.1 (4)	C12—C13—C14	120.9 (5)
C21—C26—N2	120.8 (4)	C12—C13—H13	119.5
C15—C14—C13	120.0 (5)	C14—C13—H13	119.5
C15—C14—H14	120	C21—C22—C23	119.6 (5)
C13—C14—H14	120	C21—C22—H22	120.2
C13—C12—C11	120.0 (5)	C23—C22—H22	120.2
C11—S1—S2—C21	96.8 (2)	C22—C23—C24—C25	−2.1 (8)
S1—S2—C21—C22	−87.5 (5)	C26—C25—C24—C23	0.7 (8)
S1—S2—C21—C26	96.2 (4)	C14—C15—C16—C11	1.2 (7)
C22—C21—C26—C25	−0.7 (8)	C14—C15—C16—N1	−178.3 (4)
S2—C21—C26—C25	175.7 (4)	C12—C11—C16—C15	−0.3 (7)
C22—C21—C26—N2	177.1 (4)	S1—C11—C16—C15	177.5 (4)
S2—C21—C26—N2	−6.5 (6)	C12—C11—C16—N1	179.1 (4)
C21—C26—C25—C24	0.7 (7)	S1—C11—C16—N1	−3.0 (6)
N2—C26—C25—C24	−177.1 (5)	C11—C12—C13—C14	2.1 (8)
C13—C14—C15—C16	−0.4 (7)	C15—C14—C13—C12	−1.2 (8)
C13—C12—C11—C16	−1.3 (7)	C26—C21—C22—C23	−0.8 (8)
C13—C12—C11—S1	−179.1 (4)	S2—C21—C22—C23	−177.2 (4)
S2—S1—C11—C16	103.3 (4)	C24—C23—C22—C21	2.2 (9)
S2—S1—C11—C12	−78.8 (4)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O1Wi	0.89	1.83	2.723 (6)	178
N1—H1B···Cl2i	0.89	2.24	3.108 (4)	166
N1—H1C···Cl1i	0.89	2.25	3.103 (4)	160
N2—H2A···O2Wii	0.89	1.84	2.727 (6)	177
N2—H2B···Cl2iii	0.89	2.26	3.111 (4)	160
N2—H2C···Cl2	0.89	2.30	3.157 (4)	163
O2W—H4W···Cl2	0.86 (5)	2.36 (5)	3.157 (5)	155 (5)
O2W—H3W···Cl1iv	0.85 (5)	2.23 (5)	3.078 (4)	171 (6)
O1W—H1W···Cl1v	0.85 (5)	2.27 (5)	3.096 (5)	167 (5)
O1W—H2W···Cl1iv	0.86 (5)	2.27 (5)	3.127 (5)	176 (7)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O1W i	0.89	1.83	2.723 (6)	178
N1—H1B⋯Cl2i	0.89	2.24	3.108 (4)	166
N1—H1C⋯Cl1i	0.89	2.25	3.103 (4)	160
N2—H2A⋯O2W ii	0.89	1.84	2.727 (6)	177
N2—H2B⋯Cl2iii	0.89	2.26	3.111 (4)	160
N2—H2C⋯Cl2	0.89	2.30	3.157 (4)	163
O2W—H4W⋯Cl2	0.86 (5)	2.36 (5)	3.157 (5)	155 (5)
O2W—H3W⋯Cl1iv	0.85 (5)	2.23 (5)	3.078 (4)	171 (6)
O1W—H1W⋯Cl1v	0.85 (5)	2.27 (5)	3.096 (5)	167 (5)
O1W—H2W⋯Cl1iv	0.86 (5)	2.27 (5)	3.127 (5)	176 (7)

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