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In the title hydrated mol­ecular salt, C12H14N2S22+·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 inter­actions [centroid–centroid separation = 3.730 (3) Å] are also observed.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536813015742/hb7089sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536813015742/hb7089Isup2.hkl
Contains datablock I

cml

Chemical Markup Language (CML) file https://doi.org/10.1107/S1600536813015742/hb7089Isup3.cml
Supplementary material

CCDC reference: 961817

Key indicators

  • Single-crystal X-ray study
  • T = 150 K
  • Mean [sigma](C-C) = 0.008 Å
  • R factor = 0.063
  • wR factor = 0.134
  • Data-to-parameter ratio = 18.4

checkCIF/PLATON results

No syntax errors found



Alert level B PLAT029_ALERT_3_B _diffrn_measured_fraction_theta_full Low ....... 0.951
Alert level C PLAT340_ALERT_3_C Low Bond Precision on C-C Bonds ............... 0.0076 Ang. PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd. # 1 C12 H14 N2 S2 PLAT906_ALERT_3_C Large K value in the Analysis of Variance ...... 2.198 PLAT910_ALERT_3_C Missing # of FCF Reflections Below Th(Min) ..... 2 PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L= 0.600 81 PLAT915_ALERT_3_C Low Friedel Pair Coverage ...................... 67 %
Alert level G PLAT002_ALERT_2_G Number of Distance or Angle Restraints on AtSite 6 PLAT005_ALERT_5_G No _iucr_refine_instructions_details in the CIF ? Do ! PLAT007_ALERT_5_G Note: Number of Unrefined Donor-H Atoms ........ 6 PLAT790_ALERT_4_G Centre of Gravity not Within Unit Cell: Resd. # 3 Cl PLAT790_ALERT_4_G Centre of Gravity not Within Unit Cell: Resd. # 4 H2 O PLAT790_ALERT_4_G Centre of Gravity not Within Unit Cell: Resd. # 5 H2 O PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints ....... 6 PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L= 0.600 91
0 ALERT level A = Most likely a serious problem - resolve or explain 1 ALERT level B = A potentially serious problem, consider carefully 6 ALERT level C = Check. Ensure it is not caused by an omission or oversight 8 ALERT level G = General information/check it is not something unexpected 0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 1 ALERT type 2 Indicator that the structure model may be wrong or deficient 7 ALERT type 3 Indicator that the structure quality may be low 5 ALERT type 4 Improvement, methodology, query or suggestion 2 ALERT type 5 Informative message, check

Comment top

As part of our ongoing studies on the synthesis, structures and biological activity of organometallic complexes based in sulfur (Benmebarek et al. 2012 and Benmebarek et al. 2013), we have synthesized and determined the crystal structure of the title compound (I), (Fig. 1). In the cation the S—S bond length is 2.061 (2)°, indicating the single bond character similar to that found in 4,4'-diaminophenyldisulfide (Tang et al., 2011; Goh et al. 2010). In the diprotoned 2,2'-dithiodianiline moiety, the dihedral angle between the benzene rings is 9.03 (17)°; different to that found in [67.82 (9)°] 1,2-Bis(2-nitrophenyl)disulfane (Song & Fan, 2009) and [39.9 (2)°]4,4'- diaminophenyldisulfide (Tang et al., 2011). The crystal packing can be described as alternating layers parallel to (100) plane, wich are linked toghether by N—H···Cl and N—H···O interactions involving molecule of water and anions chloride. O—H···Cl hydrogen bond and ππ stacking are observed.

Related literature top

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 top

2-Aminobenzenethiol (0.1 mmol) was added to concentrated HCl (2 ml) and transfered into a 23 ml teflon-lined stainless steel autoclave and heated at 120° C for 3 days. Then the autoclave was cooled to room temperature at 10°/h. Colourless prisms were collected, washed with ethanol and dried in air at room temperature.

Refinement top

Approximate positions for all H atoms were first obtained from the difference electron density map. However, the H atoms were situated into idealized positions and the H-atoms have been refined within the riding atom approximation. The applied constraints were as follow: Caryl—Haryl = 0.93 Å and Nammonium—Hammonium = 0.89 Å. Uiso(Haryl) = 1.2Ueq(Caryl). Uiso(Hammonium) = 1.5Ueq(Cammonium). Except for H1W, H2W, H3W and H4W (of water molecule) were located in a difference Fourier map and refined isotropically with Uiso(H) = 1.5Ueq(O).

Structure description top

As part of our ongoing studies on the synthesis, structures and biological activity of organometallic complexes based in sulfur (Benmebarek et al. 2012 and Benmebarek et al. 2013), we have synthesized and determined the crystal structure of the title compound (I), (Fig. 1). In the cation the S—S bond length is 2.061 (2)°, indicating the single bond character similar to that found in 4,4'-diaminophenyldisulfide (Tang et al., 2011; Goh et al. 2010). In the diprotoned 2,2'-dithiodianiline moiety, the dihedral angle between the benzene rings is 9.03 (17)°; different to that found in [67.82 (9)°] 1,2-Bis(2-nitrophenyl)disulfane (Song & Fan, 2009) and [39.9 (2)°]4,4'- diaminophenyldisulfide (Tang et al., 2011). The crystal packing can be described as alternating layers parallel to (100) plane, wich are linked toghether by N—H···Cl and N—H···O interactions involving molecule of water and anions chloride. O—H···Cl hydrogen bond and ππ stacking are observed.

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).

Computing details top

Data collection: APEX2 (Bruker, 2011); cell refinement: SAINT (Bruker, 2011); data reduction: SAINT (Bruker, 2011); 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).

Figures top
[Figure 1] Fig. 1. The molecular structure of (I) with displacement ellipsoids drawn at the 50% probability level.
[Figure 2] Fig. 2. Diagram packing of (I) viwed via c axis showing hydrogen bonding in alterning layers.
2,2'-(Disulfanediyl)dianilinium dichloride dihydrate top
Crystal data top
C12H14N2S22+·2Cl·2H2OF(000) = 744
Mr = 357.32Dx = 1.4 Mg m3
Orthorhombic, Pna21Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2c -2nCell parameters from 2698 reflections
a = 17.826 (7) Åθ = 2.3–28.5°
b = 13.358 (5) ŵ = 0.63 mm1
c = 7.120 (3) ÅT = 150 K
V = 1695.4 (12) Å3Prism, colourless
Z = 40.16 × 0.13 × 0.11 mm
Data collection top
Bruker APEXII CCD
diffractometer
2409 reflections with I > 2σ(I)
Radiation source: sealed tubeRint = 0.097
Graphite monochromatorθmax = 28.8°, θmin = 2.8°
φ and ω scansh = 2423
10760 measured reflectionsk = 1818
3584 independent reflectionsl = 98
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.063H 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 reflectionsΔρmax = 0.58 e Å3
195 parametersΔρmin = 0.47 e Å3
6 restraintsAbsolute structure: Flack (1983), 1369 Friedel pairs
Primary atom site location: structure-invariant direct methodsAbsolute structure parameter: 0.12 (12)
Crystal data top
C12H14N2S22+·2Cl·2H2OV = 1695.4 (12) Å3
Mr = 357.32Z = 4
Orthorhombic, Pna21Mo Kα radiation
a = 17.826 (7) ŵ = 0.63 mm1
b = 13.358 (5) ÅT = 150 K
c = 7.120 (3) Å0.16 × 0.13 × 0.11 mm
Data collection top
Bruker APEXII CCD
diffractometer
2409 reflections with I > 2σ(I)
10760 measured reflectionsRint = 0.097
3584 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.063H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.134Δρmax = 0.58 e Å3
S = 1.05Δρmin = 0.47 e Å3
3584 reflectionsAbsolute structure: Flack (1983), 1369 Friedel pairs
195 parametersAbsolute structure parameter: 0.12 (12)
6 restraints
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
xyzUiso*/Ueq
Cl20.98060 (6)0.10914 (8)1.19390 (17)0.0269 (3)
S10.86675 (9)0.10667 (11)1.3286 (2)0.0412 (4)
Cl10.99242 (8)0.36455 (10)0.7389 (2)0.0411 (4)
S20.85864 (8)0.15845 (11)1.0567 (2)0.0395 (4)
O2W0.9096 (2)0.1819 (3)1.5764 (6)0.0381 (10)
H3W0.935 (3)0.233 (3)1.609 (9)0.057*
H4W0.937 (3)0.150 (4)1.497 (7)0.057*
N20.8933 (2)0.0331 (3)0.8354 (6)0.0267 (9)
H2A0.89910.08310.75420.04*
H2B0.92080.0190.79890.04*
H2C0.90820.05280.94890.04*
C210.7911 (3)0.0781 (4)0.9473 (8)0.0286 (12)
O1W1.0599 (3)0.4223 (3)1.3483 (6)0.0534 (12)
H1W1.043 (4)0.476 (3)1.302 (9)0.08*
H2W1.039 (4)0.406 (4)1.453 (6)0.08*
N10.9146 (2)0.2839 (3)1.5749 (6)0.0282 (10)
H1A0.92420.32841.66470.042*
H1B0.93880.22711.59960.042*
H1C0.92980.30791.46470.042*
C260.8140 (2)0.0039 (3)0.8427 (7)0.0218 (10)
C140.7102 (3)0.3103 (4)1.6647 (8)0.0317 (12)
H140.67820.35091.73420.038*
C120.7275 (3)0.1730 (4)1.4523 (8)0.0332 (13)
H120.70730.12121.38110.04*
C250.7627 (3)0.0625 (3)0.7478 (8)0.0272 (11)
H250.77870.11680.67680.033*
C150.7858 (3)0.3249 (3)1.6726 (7)0.0268 (11)
H150.80550.37531.74820.032*
C110.8050 (3)0.1876 (3)1.4566 (7)0.0255 (11)
C230.6638 (3)0.0391 (4)0.8641 (8)0.0395 (14)
H230.61280.05260.87410.047*
C240.6876 (3)0.0396 (4)0.7590 (8)0.0345 (12)
H240.65280.07840.69430.041*
C160.8335 (3)0.2645 (3)1.5676 (7)0.0237 (10)
C130.6811 (3)0.2350 (4)1.5534 (8)0.0381 (13)
H130.62940.22621.54680.046*
C220.7156 (3)0.1002 (4)0.9572 (8)0.0354 (13)
H220.69920.15541.02550.043*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl20.0198 (5)0.0332 (6)0.0276 (7)0.0025 (5)0.0034 (6)0.0026 (5)
S10.0445 (9)0.0428 (7)0.0364 (8)0.0186 (7)0.0119 (8)0.0133 (6)
Cl10.0422 (8)0.0424 (7)0.0388 (9)0.0023 (5)0.0125 (7)0.0027 (6)
S20.0429 (8)0.0445 (7)0.0310 (8)0.0133 (6)0.0111 (8)0.0111 (6)
O2W0.040 (2)0.043 (2)0.031 (3)0.0078 (17)0.002 (2)0.0002 (18)
N20.029 (2)0.030 (2)0.021 (2)0.0051 (16)0.001 (2)0.0027 (17)
C210.034 (3)0.032 (3)0.019 (3)0.001 (2)0.004 (3)0.007 (2)
O1W0.072 (3)0.051 (3)0.038 (3)0.019 (2)0.003 (3)0.003 (2)
N10.030 (2)0.030 (2)0.025 (3)0.0031 (17)0.000 (2)0.0016 (18)
C260.022 (2)0.028 (2)0.015 (3)0.0005 (18)0.003 (2)0.0089 (19)
C140.028 (3)0.044 (3)0.023 (3)0.007 (2)0.002 (3)0.004 (2)
C120.038 (3)0.035 (3)0.027 (3)0.004 (2)0.002 (3)0.006 (2)
C250.030 (3)0.030 (2)0.021 (3)0.005 (2)0.003 (3)0.006 (2)
C150.033 (3)0.026 (2)0.021 (3)0.0076 (19)0.000 (3)0.0043 (19)
C110.030 (3)0.028 (2)0.019 (3)0.008 (2)0.002 (2)0.006 (2)
C230.026 (3)0.062 (4)0.030 (4)0.006 (3)0.002 (3)0.015 (3)
C240.027 (3)0.046 (3)0.030 (3)0.005 (2)0.008 (3)0.008 (2)
C160.024 (2)0.027 (2)0.020 (3)0.0046 (18)0.001 (2)0.010 (2)
C130.024 (3)0.052 (3)0.038 (4)0.000 (2)0.009 (3)0.017 (3)
C220.030 (3)0.049 (3)0.028 (3)0.008 (3)0.005 (3)0.003 (2)
Geometric parameters (Å, º) top
S1—C111.792 (5)C14—C151.364 (6)
S1—S22.061 (2)C14—C131.380 (8)
S2—C211.791 (5)C14—H140.93
O2W—H3W0.86 (2)C12—C131.375 (8)
O2W—H4W0.86 (2)C12—C111.396 (7)
N2—C261.468 (6)C12—H120.93
N2—H2A0.89C25—C241.375 (7)
N2—H2B0.89C25—H250.93
N2—H2C0.89C15—C161.391 (7)
C21—C221.380 (7)C15—H150.93
C21—C261.386 (7)C11—C161.391 (7)
O1W—H1W0.852 (19)C23—C241.358 (8)
O1W—H2W0.858 (19)C23—C221.399 (8)
N1—C161.469 (6)C23—H230.93
N1—H1A0.89C24—H240.93
N1—H1B0.89C13—H130.93
N1—H1C0.89C22—H220.93
C26—C251.380 (7)
C11—S1—S2103.43 (17)C13—C12—H12120
C21—S2—S1104.74 (18)C11—C12—H12120
H3W—O2W—H4W106 (6)C24—C25—C26119.4 (5)
C26—N2—H2A109.5C24—C25—H25120.3
C26—N2—H2B109.5C26—C25—H25120.3
H2A—N2—H2B109.5C14—C15—C16119.9 (5)
C26—N2—H2C109.5C14—C15—H15120
H2A—N2—H2C109.5C16—C15—H15120
H2B—N2—H2C109.5C16—C11—C12118.5 (4)
C22—C21—C26118.9 (5)C16—C11—S1120.7 (4)
C22—C21—S2120.3 (4)C12—C11—S1120.8 (4)
C26—C21—S2120.6 (4)C24—C23—C22120.4 (5)
H1W—O1W—H2W114 (3)C24—C23—H23119.8
C16—N1—H1A109.5C22—C23—H23119.8
C16—N1—H1B109.5C23—C24—C25120.5 (5)
H1A—N1—H1B109.5C23—C24—H24119.7
C16—N1—H1C109.5C25—C24—H24119.7
H1A—N1—H1C109.5C15—C16—C11120.7 (4)
H1B—N1—H1C109.5C15—C16—N1118.7 (4)
C25—C26—C21121.0 (4)C11—C16—N1120.6 (4)
C25—C26—N2118.1 (4)C12—C13—C14120.9 (5)
C21—C26—N2120.8 (4)C12—C13—H13119.5
C15—C14—C13120.0 (5)C14—C13—H13119.5
C15—C14—H14120C21—C22—C23119.6 (5)
C13—C14—H14120C21—C22—H22120.2
C13—C12—C11120.0 (5)C23—C22—H22120.2
C11—S1—S2—C2196.8 (2)C22—C23—C24—C252.1 (8)
S1—S2—C21—C2287.5 (5)C26—C25—C24—C230.7 (8)
S1—S2—C21—C2696.2 (4)C14—C15—C16—C111.2 (7)
C22—C21—C26—C250.7 (8)C14—C15—C16—N1178.3 (4)
S2—C21—C26—C25175.7 (4)C12—C11—C16—C150.3 (7)
C22—C21—C26—N2177.1 (4)S1—C11—C16—C15177.5 (4)
S2—C21—C26—N26.5 (6)C12—C11—C16—N1179.1 (4)
C21—C26—C25—C240.7 (7)S1—C11—C16—N13.0 (6)
N2—C26—C25—C24177.1 (5)C11—C12—C13—C142.1 (8)
C13—C14—C15—C160.4 (7)C15—C14—C13—C121.2 (8)
C13—C12—C11—C161.3 (7)C26—C21—C22—C230.8 (8)
C13—C12—C11—S1179.1 (4)S2—C21—C22—C23177.2 (4)
S2—S1—C11—C16103.3 (4)C24—C23—C22—C212.2 (9)
S2—S1—C11—C1278.8 (4)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···O1Wi0.891.832.723 (6)178
N1—H1B···Cl2i0.892.243.108 (4)166
N1—H1C···Cl1i0.892.253.103 (4)160
N2—H2A···O2Wii0.891.842.727 (6)177
N2—H2B···Cl2iii0.892.263.111 (4)160
N2—H2C···Cl20.892.303.157 (4)163
O2W—H4W···Cl20.86 (5)2.36 (5)3.157 (5)155 (5)
O2W—H3W···Cl1iv0.85 (5)2.23 (5)3.078 (4)171 (6)
O1W—H1W···Cl1v0.85 (5)2.27 (5)3.096 (5)167 (5)
O1W—H2W···Cl1iv0.86 (5)2.27 (5)3.127 (5)176 (7)
Symmetry codes: (i) x+2, y, z+1/2; (ii) x, y, z1; (iii) x+2, y, z1/2; (iv) x, y, z+1; (v) x+2, y+1, z+1/2.

Experimental details

Crystal data
Chemical formulaC12H14N2S22+·2Cl·2H2O
Mr357.32
Crystal system, space groupOrthorhombic, Pna21
Temperature (K)150
a, b, c (Å)17.826 (7), 13.358 (5), 7.120 (3)
V3)1695.4 (12)
Z4
Radiation typeMo Kα
µ (mm1)0.63
Crystal size (mm)0.16 × 0.13 × 0.11
Data collection
DiffractometerBruker APEXII CCD
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
10760, 3584, 2409
Rint0.097
(sin θ/λ)max1)0.678
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.063, 0.134, 1.05
No. of reflections3584
No. of parameters195
No. of restraints6
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.58, 0.47
Absolute structureFlack (1983), 1369 Friedel pairs
Absolute structure parameter0.12 (12)

Computer programs: APEX2 (Bruker, 2011), SAINT (Bruker, 2011), SIR2002 (Burla et al., 2005), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 2012) and DIAMOND (Brandenburg & Berndt, 2001), WinGX (Farrugia, 2012).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···O1Wi0.891.832.723 (6)178
N1—H1B···Cl2i0.892.243.108 (4)166
N1—H1C···Cl1i0.892.253.103 (4)160
N2—H2A···O2Wii0.891.842.727 (6)177
N2—H2B···Cl2iii0.892.263.111 (4)160
N2—H2C···Cl20.892.303.157 (4)163
O2W—H4W···Cl20.86 (5)2.36 (5)3.157 (5)155 (5)
O2W—H3W···Cl1iv0.85 (5)2.23 (5)3.078 (4)171 (6)
O1W—H1W···Cl1v0.85 (5)2.27 (5)3.096 (5)167 (5)
O1W—H2W···Cl1iv0.86 (5)2.27 (5)3.127 (5)176 (7)
Symmetry codes: (i) x+2, y, z+1/2; (ii) x, y, z1; (iii) x+2, y, z1/2; (iv) x, y, z+1; (v) x+2, y+1, z+1/2.
 

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