N-(4-Methyl-piperazin-4-ium-1-yl)dithio-carbamate sesquihydrate.

In the crystal structure of the title compound, C(6)H(13)N(3)S(2)·1.5H(2)O, weak N-H⋯S inter-actions between the zwitterionic mol-ecules are observed, leading to an extensively folded layered arrangement parallel to (100). There are three crystallographically independent water mol-ecules in the asymmetric unit, which are disordered and only half occupied.

Related literature

For the synthesis and structures of a series of −S2CNR-type zwitterionic dithio­carbamic acids, see: Schramm et al. (1984 ▶) for R = C3H6NH+(Me)2; Kokkou et al. (1988 ▶) for R = C3H6NH+(Et)2 and R=C2H4NH+(Et)2; Stergioudis et al. (1989 ▶) for R=C2H4NH+(Me)2; Yamin et al. (2002 ▶) for R=C2H4NH3 +. For structures of dithio­carbamates incorporating a hydrazine-based skeleton, see: Braibanti et al. (1969 ▶); Mattes & Füsser (1984 ▶); Kiel et al. (1985 ▶). For the synthesis of dithio­carba­mates, see: Coucouvanis (1979 ▶); Hogarth (2005 ▶); Eul et al. (1987 ▶); Hulanicki (1967 ▶); Ivanov et al. (1999 ▶). For a description of the Cambridge Structural Database, see: Allen (2002 ▶).

Experimental

Crystal data

C6H13N3S2·1.5H2O

M = 218.34

Monoclinic,

a = 23.3560 (18) Å

b = 6.8191 (3) Å

c = 15.7067 (10) Å

β = 119.920 (9)°

V = 2168.2 (2) Å3

Z = 8

Mo Kα radiation

μ = 0.46 mm−1

T = 120 K

0.48 × 0.23 × 0.21 mm

Data collection

Kuma KM-4-CCD Sapphire2 diffractometer

Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2008 ▶) T min = 0.952, T max = 1

3755 measured reflections

2024 independent reflections

1674 reflections with I > 2σ(I)

R int = 0.021

Refinement

R[F 2 > 2σ(F 2)] = 0.041

wR(F 2) = 0.113

S = 1.08

2024 reflections

140 parameters

5 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.60 e Å−3

Δρmin = −0.21 e Å−3

Data collection: CrysAlis PRO (Oxford Diffraction, 2008 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia,1997 ▶) and Mercury (Macrae et al., 2006 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812020521/nc2276sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812020521/nc2276Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536812020521/nc2276Isup3.cml

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

C6H13N3S2·1.5H2O	F(000) = 936
Mr = 218.34	Dx = 1.338 Mg m−3
Monoclinic, C2/c	Melting point: 402 K
Hall symbol: -C 2yc	Mo Kα radiation, λ = 0.71073 Å
a = 23.3560 (18) Å	Cell parameters from 2050 reflections
b = 6.8191 (3) Å	θ = 2.6–28.7°
c = 15.7067 (10) Å	µ = 0.46 mm−1
β = 119.920 (9)°	T = 120 K
V = 2168.2 (2) Å3	Block, colourless
Z = 8	0.48 × 0.23 × 0.21 mm

Kuma KM-4-CCD Sapphire2 diffractometer	2024 independent reflections
Radiation source: fine-focus sealed tube	1674 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.021
Detector resolution: 8.1883 pixels mm-1	θmax = 25.5°, θmin = 2.7°
ω scans	h = −18→28
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2008)	k = −8→7
Tmin = 0.952, Tmax = 1	l = −19→11
3755 measured reflections

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)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.113	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	w = 1/[σ2(Fo2) + (0.0755P)2] where P = (Fo2 + 2Fc2)/3
2024 reflections	(Δ/σ)max = 0.001
140 parameters	Δρmax = 0.60 e Å−3
5 restraints	Δρmin = −0.21 e Å−3

Experimental. Absorption correction: CrysAlis PRO (Oxford Diffraction, 2008). Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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	Occ. (<1)
S1	0.11286 (3)	0.40172 (9)	1.02811 (4)	0.0315 (2)
S2	0.21612 (3)	0.71645 (9)	1.10583 (4)	0.0325 (2)
N1	0.18466 (9)	0.5160 (3)	0.94834 (12)	0.0253 (4)
H1N	0.2097 (12)	0.592 (4)	0.9456 (16)	0.030*
N2	0.14708 (9)	0.3938 (3)	0.86627 (11)	0.0228 (4)
N3	0.10268 (9)	0.2586 (3)	0.67082 (12)	0.0219 (4)
H3N	0.1226 (12)	0.321 (4)	0.6552 (17)	0.026*
C1	0.17032 (10)	0.5395 (3)	1.02061 (13)	0.0237 (5)
C2	0.19188 (11)	0.2838 (3)	0.84347 (14)	0.0262 (5)
H2A	0.2237	0.2077	0.9017	0.031*
H2B	0.2172	0.3759	0.8260	0.031*
C3	0.15206 (11)	0.1465 (3)	0.75862 (14)	0.0267 (5)
H3A	0.1820	0.0742	0.7422	0.032*
H3B	0.1289	0.0497	0.7777	0.032*
C4	0.06052 (11)	0.3844 (3)	0.69519 (14)	0.0267 (5)
H4A	0.0324	0.3003	0.7107	0.032*
H4B	0.0312	0.4664	0.6377	0.032*
C5	0.10291 (10)	0.5152 (3)	0.78231 (13)	0.0237 (5)
H5A	0.1291	0.6054	0.7657	0.028*
H5B	0.0744	0.5950	0.7989	0.028*
C6	0.06125 (13)	0.1260 (4)	0.58698 (16)	0.0375 (6)
H6A	0.0899	0.0443	0.5725	0.056*
H6B	0.0321	0.2046	0.5290	0.056*
H6C	0.0345	0.0420	0.6042	0.056*
O1	0.1228 (2)	0.9907 (5)	0.9238 (3)	0.0331 (8)	0.50
H1A	0.1408	0.9093	0.9682	0.050*	0.50
H1B	0.1038	1.0904	0.9270	0.050*	0.50
O2	−0.00204 (19)	0.8579 (6)	0.8020 (3)	0.0426 (8)	0.50
H2C	−0.027 (3)	0.891 (10)	0.742 (2)	0.064*	0.50
H2D	0.0350 (19)	0.920 (9)	0.834 (4)	0.064*	0.50
O3	−0.0827 (2)	0.9861 (6)	0.6047 (3)	0.0323 (8)	0.50
H3C	−0.1054	0.8903	0.5705	0.048*	0.50
H3D	−0.1127	1.0731	0.5844	0.048*	0.50

	U11	U22	U33	U12	U13	U23
S1	0.0393 (4)	0.0359 (3)	0.0276 (3)	−0.0079 (3)	0.0229 (3)	−0.0077 (2)
S2	0.0284 (3)	0.0499 (4)	0.0237 (3)	−0.0104 (3)	0.0164 (2)	−0.0164 (2)
N1	0.0264 (9)	0.0334 (11)	0.0183 (8)	−0.0050 (9)	0.0127 (7)	−0.0060 (7)
N2	0.0284 (9)	0.0253 (9)	0.0162 (8)	0.0016 (8)	0.0123 (7)	−0.0031 (6)
N3	0.0251 (10)	0.0253 (9)	0.0183 (8)	−0.0077 (8)	0.0130 (7)	−0.0053 (7)
C1	0.0226 (11)	0.0309 (11)	0.0170 (9)	0.0063 (9)	0.0094 (8)	0.0007 (8)
C2	0.0302 (12)	0.0306 (11)	0.0176 (9)	0.0090 (10)	0.0117 (9)	0.0012 (8)
C3	0.0385 (13)	0.0234 (10)	0.0258 (10)	0.0027 (10)	0.0217 (10)	0.0003 (9)
C4	0.0221 (11)	0.0350 (12)	0.0240 (10)	0.0003 (10)	0.0123 (9)	−0.0060 (9)
C5	0.0242 (10)	0.0247 (11)	0.0206 (10)	0.0033 (9)	0.0101 (8)	−0.0027 (8)
C6	0.0364 (13)	0.0467 (15)	0.0334 (12)	−0.0175 (12)	0.0204 (11)	−0.0225 (11)
O1	0.053 (2)	0.0193 (16)	0.0324 (19)	−0.001 (2)	0.025 (2)	−0.0003 (14)
O2	0.035 (2)	0.040 (2)	0.048 (2)	−0.0038 (17)	0.0176 (18)	−0.0047 (17)
O3	0.040 (2)	0.0276 (18)	0.0301 (19)	0.005 (2)	0.0184 (18)	0.0021 (14)

S1—C1	1.690 (2)	C4—C5	1.516 (3)
S2—C1	1.721 (2)	C4—H4A	0.9900
N1—C1	1.344 (2)	C4—H4B	0.9900
N1—N2	1.413 (2)	C5—H5A	0.9900
N1—H1N	0.80 (3)	C5—H5B	0.9900
N2—C5	1.460 (2)	C6—H6A	0.9800
N2—C2	1.470 (3)	C6—H6B	0.9800
N3—C6	1.489 (3)	C6—H6C	0.9800
N3—C4	1.492 (3)	O1—O2	2.724 (5)
N3—C3	1.493 (3)	O1—H1A	0.8236
N3—H3N	0.76 (2)	O1—H1B	0.8269
C2—C3	1.510 (3)	O2—O3	2.845 (5)
C2—H2A	0.9900	O2—H2C	0.86 (2)
C2—H2B	0.9900	O2—H2D	0.86 (2)
C3—H3A	0.9900	O3—H3C	0.8435
C3—H3B	0.9900	O3—H3D	0.8498
C1—N1—N2	122.54 (18)	N3—C4—H4A	109.5
C1—N1—H1N	117.8 (17)	C5—C4—H4A	109.5
N2—N1—H1N	118.1 (17)	N3—C4—H4B	109.5
N1—N2—C5	109.09 (16)	C5—C4—H4B	109.5
N1—N2—C2	109.24 (16)	H4A—C4—H4B	108.1
C5—N2—C2	109.73 (14)	N2—C5—C4	109.32 (17)
C6—N3—C4	110.78 (17)	N2—C5—H5A	109.8
C6—N3—C3	111.58 (18)	C4—C5—H5A	109.8
C4—N3—C3	111.21 (15)	N2—C5—H5B	109.8
C6—N3—H3N	106.9 (18)	C4—C5—H5B	109.8
C4—N3—H3N	110.4 (19)	H5A—C5—H5B	108.3
C3—N3—H3N	105.7 (19)	N3—C6—H6A	109.5
N1—C1—S1	122.25 (16)	N3—C6—H6B	109.5
N1—C1—S2	114.87 (16)	H6A—C6—H6B	109.5
S1—C1—S2	122.86 (11)	N3—C6—H6C	109.5
N2—C2—C3	109.37 (18)	H6A—C6—H6C	109.5
N2—C2—H2A	109.8	H6B—C6—H6C	109.5
C3—C2—H2A	109.8	O2—O1—H1A	106.6
N2—C2—H2B	109.8	O2—O1—H1B	84.1
C3—C2—H2B	109.8	H1A—O1—H1B	124.5
H2A—C2—H2B	108.2	O1—O2—O3	123.96 (18)
N3—C3—C2	110.47 (17)	O1—O2—H2C	126 (4)
N3—C3—H3A	109.6	O3—O2—H2D	114 (4)
C2—C3—H3A	109.6	H2C—O2—H2D	116 (6)
N3—C3—H3B	109.6	O2—O3—H3C	108.7
C2—C3—H3B	109.6	O2—O3—H3D	126.7
H3A—C3—H3B	108.1	H3C—O3—H3D	99.4
N3—C4—C5	110.62 (17)
C1—N1—N2—C5	101.4 (2)	C4—N3—C3—C2	−53.9 (2)
C1—N1—N2—C2	−138.6 (2)	N2—C2—C3—N3	58.0 (2)
N2—N1—C1—S1	8.7 (3)	C6—N3—C4—C5	178.46 (17)
N2—N1—C1—S2	−172.63 (15)	C3—N3—C4—C5	53.8 (2)
N1—N2—C2—C3	177.53 (16)	N1—N2—C5—C4	−177.72 (15)
C5—N2—C2—C3	−62.9 (2)	C2—N2—C5—C4	62.6 (2)
C6—N3—C3—C2	−178.18 (17)	N3—C4—C5—N2	−57.9 (2)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···S2i	0.80 (3)	2.60 (3)	3.375 (2)	164 (2)
N3—H3N···S1ii	0.76 (2)	2.67 (2)	3.3131 (18)	143 (2)
N3—H3N···S2ii	0.76 (2)	2.67 (2)	3.2846 (18)	140 (2)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N⋯S2i	0.80 (3)	2.60 (3)	3.375 (2)	164 (2)
N3—H3N⋯S1ii	0.76 (2)	2.67 (2)	3.3131 (18)	143 (2)
N3—H3N⋯S2ii	0.76 (2)	2.67 (2)	3.2846 (18)	140 (2)

Symmetry codes: (i) ; (ii) .