(Diamino-methyl-idene)sulfonium chloride-thio-urea (3/2).

The asymetric unit of the title salt, 3CH(5)N(2)S(+)·3Cl(-)·2CH(4)N(2)S, contains two mol-ecules of thio-urea, three (diamino-methyl-idene)sulfonium cations and three chloride anions. The crystal packing is stabilized by N-H⋯Cl, N-H⋯S, S-H⋯Cl and S-H⋯S hydrogen bonds, forming a three-dimensional network.

Related literature

For applications of thio­urea salts, see: Xing et al. (1987 ▶); Velsko et al. (1990 ▶).

Experimental

Crystal data

3CH5N2S+·3Cl−·2CH4N2S

M = 489.98

Monoclinic,

a = 16.3469 (6) Å

b = 8.9579 (3) Å

c = 16.1505 (5) Å

β = 109.105 (2)°

V = 2234.72 (13) Å3

Z = 4

Mo Kα radiation

μ = 0.89 mm−1

T = 100 K

0.45 × 0.32 × 0.29 mm

Data collection

Bruker APEXII CCD detector diffractometer

25994 measured reflections

4885 independent reflections

4190 reflections with I > 2σ(I)

R int = 0.036

Refinement

R[F 2 > 2σ(F 2)] = 0.026

wR(F 2) = 0.068

S = 1.06

4885 reflections

300 parameters

15 restraints

All H-atom parameters refined

Δρmax = 0.45 e Å−3

Δρmin = −0.39 e Å−3

Data collection: APEX2 (Bruker, 2005 ▶); cell refinement: SAINT (Bruker, 2005 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: PLATON (Spek, 2009 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536811052809/bt5746sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811052809/bt5746Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536811052809/bt5746Isup3.cml

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

3CH5N2S+·3Cl−·2CH4N2S	F(000) = 1016
Mr = 489.98	Dx = 1.456 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 257 reflections
a = 16.3469 (6) Å	θ = 1.9–26.7°
b = 8.9579 (3) Å	µ = 0.89 mm−1
c = 16.1505 (5) Å	T = 100 K
β = 109.105 (2)°	Prism, colourless
V = 2234.72 (13) Å3	0.45 × 0.32 × 0.29 mm
Z = 4

Bruker APEXII CCD detector diffractometer	4190 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.036
graphite	θmax = 27.0°, θmin = 1.3°
ω and φ scans	h = −19→20
25994 measured reflections	k = −11→11
4885 independent reflections	l = −20→20

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)] = 0.026	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.068	All H-atom parameters refined
S = 1.06	w = 1/[σ2(Fo2) + (0.030P)2 + 0.6051P] where P = (Fo2 + 2Fc2)/3
4885 reflections	(Δ/σ)max = 0.001
300 parameters	Δρmax = 0.45 e Å−3
15 restraints	Δρmin = −0.39 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
C1	0.38413 (9)	0.58264 (16)	0.27012 (9)	0.0213 (3)
C2	0.25156 (10)	0.52767 (18)	0.50586 (9)	0.0248 (3)
C3	0.11263 (10)	0.86257 (17)	0.22690 (10)	0.0243 (3)
C4	0.07611 (10)	0.32825 (17)	0.03972 (10)	0.0256 (3)
C5	0.56391 (11)	0.66084 (17)	0.01498 (10)	0.0274 (3)
Cl1	0.36083 (2)	0.16969 (4)	0.21733 (2)	0.02368 (9)
Cl2	0.14816 (2)	0.26513 (4)	0.30590 (2)	0.02530 (9)
Cl3	0.25954 (3)	0.95922 (5)	0.52321 (3)	0.03198 (10)
H10N	0.1886 (13)	1.0337 (17)	0.2623 (13)	0.049 (6)*
H11N	−0.0063 (10)	0.887 (2)	0.2194 (12)	0.039 (5)*
H12N	0.0483 (13)	1.0283 (18)	0.2478 (13)	0.047 (6)*
H13N	0.1429 (12)	0.326 (2)	0.1616 (10)	0.038 (5)*
H14N	0.1828 (11)	0.408 (2)	0.1057 (12)	0.039 (5)*
H15N	0.0337 (12)	0.357 (2)	−0.0832 (11)	0.045 (6)*
H16N	0.1202 (11)	0.429 (2)	−0.0372 (12)	0.039 (5)*
H17N	0.6669 (11)	0.561 (2)	0.0740 (13)	0.044 (6)*
H18N	0.6263 (13)	0.628 (2)	0.1350 (11)	0.045 (6)*
H19N	0.6042 (11)	0.582 (2)	−0.0693 (12)	0.042 (6)*
H1N	0.2689 (14)	0.552 (2)	0.2609 (13)	0.048 (6)*
H20N	0.5209 (13)	0.667 (2)	−0.1093 (12)	0.035 (5)*
H2N	0.3116 (12)	0.413 (2)	0.2562 (12)	0.034 (5)*
H2S	0.1772 (14)	0.501 (2)	0.3670 (14)	0.063 (7)*
H3N	0.4498 (11)	0.418 (2)	0.2606 (11)	0.028 (5)*
H4N	0.5001 (12)	0.556 (2)	0.2727 (12)	0.033 (5)*
H4S	−0.0549 (15)	0.234 (2)	−0.0260 (15)	0.065 (7)*
H5N	0.2310 (11)	0.331 (2)	0.4620 (10)	0.033 (5)*
H5S	0.4337 (15)	0.768 (2)	−0.0474 (15)	0.068 (7)*
H6N	0.2823 (13)	0.341 (2)	0.5582 (11)	0.052 (6)*
H7N	0.2821 (12)	0.7027 (17)	0.5739 (12)	0.036 (5)*
H8N	0.3128 (12)	0.567 (2)	0.6237 (10)	0.042 (6)*
H9N	0.2319 (10)	0.890 (2)	0.2464 (12)	0.038 (5)*
N1	0.31308 (10)	0.50667 (17)	0.26422 (10)	0.0286 (3)
N10	0.62646 (10)	0.61272 (18)	0.08312 (9)	0.0349 (3)
N2	0.45314 (10)	0.50807 (17)	0.26805 (10)	0.0295 (3)
N3	0.25464 (10)	0.38179 (17)	0.50862 (10)	0.0341 (3)
N4	0.28862 (11)	0.60913 (18)	0.57553 (10)	0.0362 (4)
N5	0.18693 (10)	0.93523 (17)	0.24771 (11)	0.0355 (3)
N6	0.04351 (10)	0.93486 (16)	0.23118 (10)	0.0320 (3)
N7	0.14216 (10)	0.35255 (17)	0.11049 (9)	0.0307 (3)
N8	0.07441 (10)	0.37960 (17)	−0.03649 (9)	0.0307 (3)
N9	0.56308 (10)	0.63381 (18)	−0.06456 (9)	0.0317 (3)
S1	0.38657 (3)	0.77282 (4)	0.28160 (3)	0.02625 (10)
S2	0.19881 (3)	0.62081 (5)	0.40844 (3)	0.03084 (11)
S3	0.10697 (3)	0.67952 (4)	0.19506 (3)	0.02933 (10)
S4	−0.00958 (3)	0.22533 (6)	0.05196 (4)	0.04788 (14)
S5	0.48080 (3)	0.76310 (6)	0.03389 (3)	0.04573 (13)

	U11	U22	U33	U12	U13	U23
C1	0.0220 (8)	0.0232 (7)	0.0164 (7)	0.0000 (6)	0.0031 (6)	−0.0008 (5)
C2	0.0248 (8)	0.0286 (8)	0.0211 (8)	0.0015 (6)	0.0077 (6)	0.0016 (6)
C3	0.0261 (8)	0.0229 (7)	0.0215 (7)	0.0010 (6)	0.0045 (6)	0.0007 (6)
C4	0.0254 (8)	0.0247 (8)	0.0275 (8)	−0.0002 (6)	0.0099 (7)	−0.0041 (6)
C5	0.0271 (9)	0.0276 (8)	0.0276 (8)	−0.0040 (7)	0.0093 (7)	−0.0006 (6)
Cl1	0.0267 (2)	0.02205 (18)	0.02225 (18)	−0.00058 (14)	0.00803 (15)	−0.00263 (13)
Cl2	0.0296 (2)	0.02340 (18)	0.02352 (19)	−0.00071 (15)	0.00952 (16)	−0.00253 (14)
Cl3	0.0266 (2)	0.0341 (2)	0.0364 (2)	0.00110 (16)	0.01196 (17)	−0.00136 (17)
N1	0.0235 (8)	0.0219 (7)	0.0418 (8)	−0.0027 (6)	0.0126 (6)	−0.0068 (6)
N10	0.0344 (9)	0.0496 (9)	0.0197 (7)	0.0044 (7)	0.0076 (6)	0.0011 (6)
N2	0.0250 (8)	0.0211 (7)	0.0433 (9)	−0.0008 (6)	0.0122 (6)	−0.0021 (6)
N3	0.0438 (10)	0.0277 (8)	0.0246 (8)	0.0012 (7)	0.0027 (7)	0.0029 (6)
N4	0.0482 (10)	0.0320 (8)	0.0220 (7)	−0.0004 (7)	0.0027 (7)	−0.0004 (6)
N5	0.0243 (8)	0.0257 (7)	0.0560 (10)	−0.0006 (6)	0.0124 (7)	−0.0089 (7)
N6	0.0255 (8)	0.0237 (7)	0.0463 (9)	0.0012 (6)	0.0113 (7)	−0.0020 (6)
N7	0.0317 (8)	0.0394 (8)	0.0207 (7)	−0.0071 (7)	0.0082 (6)	−0.0012 (6)
N8	0.0270 (8)	0.0418 (8)	0.0218 (7)	−0.0056 (7)	0.0060 (6)	−0.0018 (6)
N9	0.0287 (8)	0.0426 (9)	0.0212 (7)	0.0079 (7)	0.0047 (6)	0.0034 (6)
S1	0.0223 (2)	0.01955 (19)	0.0319 (2)	−0.00003 (15)	0.00212 (16)	−0.00217 (15)
S2	0.0373 (2)	0.0297 (2)	0.0220 (2)	0.00586 (17)	0.00489 (17)	0.00139 (16)
S3	0.0255 (2)	0.02236 (19)	0.0326 (2)	0.00159 (15)	−0.00071 (17)	−0.00544 (16)
S4	0.0410 (3)	0.0524 (3)	0.0473 (3)	−0.0191 (2)	0.0104 (2)	0.0089 (2)
S5	0.0439 (3)	0.0502 (3)	0.0446 (3)	0.0125 (2)	0.0165 (2)	−0.0067 (2)

C1—N1	1.322 (2)	N4—H8N	0.841 (15)
C1—N2	1.321 (2)	N5—H10N	0.911 (15)
C2—N4	1.311 (2)	N5—H9N	0.847 (14)
C2—N3	1.308 (2)	N6—H11N	0.884 (14)
C3—N6	1.324 (2)	N6—H12N	0.875 (15)
C3—N5	1.321 (2)	N7—H14N	0.851 (14)
C4—N7	1.308 (2)	N7—H13N	0.855 (14)
C4—N8	1.306 (2)	N8—H16N	0.873 (14)
C5—N10	1.306 (2)	N8—H15N	0.851 (15)
C5—N9	1.303 (2)	N9—H19N	0.840 (15)
N1—H1N	0.81 (2)	N9—H20N	0.87 (2)
N1—H2N	0.84 (2)	S1—C1	1.7127 (15)
N10—H18N	0.850 (15)	S2—H2S	1.25 (2)
N10—H17N	0.857 (15)	S2—C2	1.7398 (15)
N2—H4N	0.861 (19)	S3—C3	1.7120 (16)
N2—H3N	0.811 (19)	S4—H4S	1.24 (2)
N3—H6N	0.862 (15)	S4—C4	1.7414 (16)
N3—H5N	0.855 (14)	S5—H5S	1.29 (2)
N4—H7N	0.844 (15)	S5—C5	1.7464 (17)
C2—S2—H2S	92.4 (10)	C1—N2—H3N	119.1 (13)
C5—S5—H5S	94.6 (10)	C1—N2—H4N	119.4 (12)
C4—S4—H4S	94.9 (10)	H3N—N2—H4N	121.4 (18)
N2—C1—N1	118.37 (15)	C3—N5—H9N	119.5 (13)
N2—C1—S1	121.06 (12)	C3—N5—H10N	119.3 (13)
N1—C1—S1	120.56 (12)	H9N—N5—H10N	121.2 (18)
N8—C4—N7	121.45 (15)	C4—N7—H13N	123.0 (13)
N8—C4—S4	121.58 (13)	C4—N7—H14N	117.6 (13)
N7—C4—S4	116.97 (12)	H13N—N7—H14N	118.9 (18)
N9—C5—N10	121.48 (16)	C1—N1—H2N	120.1 (12)
N9—C5—S5	120.81 (13)	C1—N1—H1N	119.4 (15)
N10—C5—S5	117.71 (13)	H2N—N1—H1N	119.9 (19)
N5—C3—N6	118.38 (15)	C5—N9—H20N	120.2 (12)
N5—C3—S3	120.21 (12)	C5—N9—H19N	116.2 (13)
N6—C3—S3	121.41 (13)	H20N—N9—H19N	123.6 (18)
N3—C2—N4	121.66 (15)	C3—N6—H12N	119.5 (14)
N3—C2—S2	120.80 (12)	C3—N6—H11N	119.5 (12)
N4—C2—S2	117.53 (13)	H12N—N6—H11N	120.9 (18)
C2—N3—H5N	119.8 (13)	C5—N10—H17N	117.8 (13)
C2—N3—H6N	117.5 (14)	C5—N10—H18N	121.4 (14)
H5N—N3—H6N	123 (2)	H17N—N10—H18N	120.7 (19)
C2—N4—H8N	119.2 (14)	C4—N8—H15N	121.5 (14)
C2—N4—H7N	120.5 (13)	C4—N8—H16N	115.9 (13)
H8N—N4—H7N	119.7 (19)	H15N—N8—H16N	122.2 (18)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···S3	0.82 (2)	2.76 (2)	3.5403 (17)	161.9 (18)
N1—H2N···Cl1	0.848 (18)	2.474 (18)	3.2683 (16)	156.2 (18)
N10—H17N···Cl3i	0.86 (2)	2.44 (2)	3.2261 (17)	152 (2)
N10—H18N···Cl1ii	0.85 (2)	2.35 (2)	3.2019 (14)	175 (2)
N2—H3N···Cl1	0.815 (18)	2.624 (18)	3.3656 (16)	152.0 (17)
N2—H4N···Cl1ii	0.86 (2)	2.45 (2)	3.3060 (17)	174.5 (17)
N3—H5N···Cl2	0.86 (2)	2.51 (2)	3.3333 (16)	161 (2)
N3—H6N···Cl1iii	0.86 (2)	2.47 (2)	3.2799 (16)	157 (2)
N4—H7N···Cl3	0.84 (2)	2.43 (2)	3.2422 (17)	163 (2)
N4—H8N···Cl1iii	0.84 (2)	2.57 (2)	3.3327 (16)	151 (2)
N4—H8N···S1iv	0.84 (2)	2.83 (2)	3.3571 (16)	123 (2)
N5—H9N···S1	0.85 (2)	2.62 (2)	3.4493 (18)	166 (2)
N5—H10N···Cl2v	0.91 (2)	2.35 (2)	3.2262 (16)	161 (2)
N6—H11N···Cl2vi	0.88 (2)	2.47 (2)	3.3555 (17)	176 (1)
N6—H12N···Cl2v	0.88 (2)	2.65 (2)	3.4328 (15)	149 (2)
N7—H13N···Cl2	0.86 (2)	2.37 (2)	3.2219 (15)	177 (1)
N7—H14N···Cl3vii	0.85 (2)	2.42 (2)	3.2066 (17)	154 (2)
N8—H15N···S3viii	0.85 (2)	2.44 (2)	3.2649 (16)	164 (2)
N8—H16N···Cl3vii	0.87 (2)	2.38 (2)	3.2036 (17)	156 (2)
N9—H19N···Cl3i	0.84 (2)	2.38 (2)	3.1674 (17)	157 (2)
N9—H20N···S1vii	0.872 (19)	2.38 (2)	3.2412 (16)	167.7 (19)
S2—H2S···Cl2	1.253 (19)	2.315 (19)	3.5612 (6)	172.9 (14)
S4—H4S···S3viii	1.24 (2)	2.69 (2)	3.8755 (8)	159.2 (15)
S5—H5S···S1vii	1.29 (2)	2.64 (2)	3.8691 (7)	159.3 (16)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N⋯S3	0.82 (2)	2.76 (2)	3.5403 (17)	161.9 (18)
N1—H2N⋯Cl1	0.848 (18)	2.474 (18)	3.2683 (16)	156.2 (18)
N10—H17N⋯Cl3i	0.86 (2)	2.45 (2)	3.2261 (17)	152 (2)
N10—H18N⋯Cl1ii	0.85 (2)	2.35 (2)	3.2019 (14)	175 (2)
N2—H3N⋯Cl1	0.815 (18)	2.624 (18)	3.3656 (16)	152.0 (17)
N2—H4N⋯Cl1ii	0.86 (2)	2.45 (2)	3.3060 (17)	174.5 (17)
N3—H5N⋯Cl2	0.86 (2)	2.51 (2)	3.3333 (16)	161 (2)
N3—H6N⋯Cl1iii	0.86 (2)	2.47 (2)	3.2799 (16)	157 (2)
N4—H7N⋯Cl3	0.84 (2)	2.43 (2)	3.2422 (17)	163 (2)
N4—H8N⋯Cl1iii	0.84 (2)	2.57 (2)	3.3327 (16)	151 (2)
N4—H8N⋯S1iv	0.84 (2)	2.83 (2)	3.3571 (16)	123 (2)
N5—H9N⋯S1	0.85 (2)	2.62 (2)	3.4493 (18)	166 (2)
N5—H10N⋯Cl2v	0.91 (2)	2.35 (2)	3.2262 (16)	161 (2)
N6—H11N⋯Cl2vi	0.88 (2)	2.47 (2)	3.3555 (17)	176 (1)
N6—H12N⋯Cl2v	0.88 (2)	2.65 (2)	3.4328 (15)	149 (2)
N7—H13N⋯Cl2	0.86 (2)	2.37 (2)	3.2219 (15)	177 (1)
N7—H14N⋯Cl3vii	0.85 (2)	2.42 (2)	3.2066 (17)	154 (2)
N8—H15N⋯S3viii	0.85 (2)	2.44 (2)	3.2649 (16)	164 (2)
N8—H16N⋯Cl3vii	0.87 (2)	2.39 (2)	3.2036 (17)	156 (2)
N9—H19N⋯Cl3i	0.84 (2)	2.38 (2)	3.1674 (17)	157 (2)
N9—H20N⋯S1vii	0.872 (19)	2.38 (2)	3.2412 (16)	167.7 (19)
S2—H2S⋯Cl2	1.253 (19)	2.315 (19)	3.5612 (6)	172.9 (14)
S4—H4S⋯S3viii	1.24 (2)	2.69 (2)	3.8755 (8)	159.2 (15)
S5—H5S⋯S1vii	1.29 (2)	2.64 (2)	3.8691 (7)	159.3 (16)

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