Sodium piperidine-1-carbodithio­ate dihydrate

Mafud, A.C.; Gambardella, M.T.P.

doi:10.1107/S1600536811022604

metal-organic compounds

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ISSN: 2056-9890

Volume 67| Part 7| July 2011| Page m942

doi:10.1107/S1600536811022604

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Sodium piperidine-1-carbodithioate dihydrate

Ana C. Mafud ^a ^* and Maria Teresa P. Gambardella ^a

^aInstituto de Química de São Carlos, Universidade de São Paulo, Av. Trabalhador Sãocarlense 400, Caixa Postal 780, 13560-970, São Carlos, SP, Brazil
^*Correspondence e-mail: mafud@iqsc.usp.br

(Received 8 June 2011; accepted 10 June 2011; online 18 June 2011)

The asymmetric unit of the title compound, Na⁺·C₆H₁₀NS₂⁻·2H₂O, is composed of a sodium cation, a piperidinedithiocarbamate anion which exhibits positional disorder, and two lattice water molecules. The atoms of the piperidine ring are divided over two sites with occupancy factors of 0.554 (6) and 0.446 (6). In the crystal, the sodium cation (coordination number of 6) and the piperidinedithiocarbamate anion are linked, forming an infinite two-dimensional network extending parallel to (001). O—H⋯S hydrogen bonds, involving the lattice water molecules, also aid in stabilizing the crystal sructure.

Related literature

For the crystal structures of similar compounds, see: Oskarsson et al. (1979 ); Albertsson et al. (1980 ); Ymén (1982 ); Mafud & Gambardella (2011 ). For puckering parameters, see: Cremer & Pople (1975 ).

Experimental

Crystal data

Na⁺·C₆H₁₀NS₂⁻·2H₂O
M_r = 219.29
Monoclinic, P 2₁ /a
a = 12.241 (5) Å
b = 5.909 (5) Å
c = 14.690 (5) Å
β = 95.519 (5)°
V = 1057.6 (11) Å³
Z = 4
Mo Kα radiation
μ = 0.51 mm⁻¹
T = 290 K
0.02 × 0.02 × 0.02 mm

Data collection

Nonius KappaCCD diffractometer
7553 measured reflections
1863 independent reflections
1482 reflections with I > 2σ(I)
R_int = 0.145

Refinement

R[F² > 2σ(F²)] = 0.054
wR(F²) = 0.152
S = 1.02
1863 reflections
176 parameters
6 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.33 e Å⁻³
Δρ_min = −0.36 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H11O⋯S2ⁱ	0.84 (2)	2.39 (2)	3.214 (2)	167 (3)
O1—H12O⋯S1ⁱⁱ	0.85 (2)	2.49 (2)	3.322 (3)	167 (3)
O2—H21O⋯S2ⁱⁱ	0.83 (2)	2.48 (2)	3.283 (2)	163 (3)
O2—H22O⋯S1ⁱⁱⁱ	0.86 (2)	2.46 (2)	3.313 (2)	174 (3)
Symmetry codes: (i) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, z]$ ; (ii) $[x-{\script{1\over 2}}, -y-{\script{1\over 2}}, z]$ ; (iii) x, y-1, z.

Data collection: COLLECT (Nonius, 1998 ); cell refinement: SCALEPACK (Otwinowski & Minor, 1997 ); data reduction: DENZO (Otwinowski & Minor, 1997) and SCALEPACK; program(s) used to solve structure: SIR92 (Altomare et al., 1994 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ) and Mercury (Macrae et al., 2006 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ) and publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811022604/su2283sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811022604/su2283Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811022604/su2283Isup3.cml

checkCIF report

Comment top

The title compound is compossed of a piperidinedithiocarbamate anion, a sodium cation, and two lattice water molecules (Fig. 1). The crystal structures of similar compounds, for example sodium 1-pyrrolidinecarbodithioate dihydrate, has been reported on previously (Oskarsson et al., 1979; Albertsson et al., 1980; Ymén, 1982). The crystal structure of ammonium piperidine-1-carbodithioate dihydrate has been descibed by our group recently (Mafud & Gambardella, 2011).

The atoms of the piperidine ring are disordered, occupying two positions (A = C2',C3',C4',C5',N1' and B = C2,C3,C4,C5,N1) with occupancies of 0.554 (6)/0.446 (6). Both of these six-membered rings have a chair conformation, with puckering parameters, Q = 0.552 (13) Å, θ = 180.0 (13) °, ϕ2 = 128 (25) °, for ring A, and Q = 0.577 (15) Å, θ = 0.0 (15) °, ϕ2 = 313 (27) °, for ring B (Cremer & Pople, 1975).

The sodium atoms are coordinated to two sulfur atoms [Na1···S1 3.0649 (15) Å and Na1···S1ⁱ 2.9644 (15) Å; symmetry code: (i) -x+3/2, y-1/2, -z+1] and four oxygens [Na1···O2 2.360 (3) Å, Na1···O1 2.385 (2) Å, Na1···O1ⁱⁱ 2.416 (3) Å, Na1···O2ⁱⁱⁱ 2.515 (2) Å; symmetry codes: (ii) -x+1, -y, -z+1; (iii) -x+1, -y-1, -z+1], with a bi-pyramidal reversed geometry. This configuration generates close packed layers which remain cohesive in crystal stacking by van der Waals interactions. The distances of these contacts are slightly less than the sum of the van der Waals radii.

In the crystal O-H···S hydrogen bonds, involving the lattice water molecules, aid in stabilizing the crystal structure (Table 1). The crystal packing gives rise to a supramolecular structure, whose infinite two-dimensional network, with base vectors: #1 = [0 1 0], #2 = [1 0 0], grows parallel to (001), as shown in Fig. 2.

Related literature top

For the crystal structures of similar compounds, see: Oskarsson et al. (1979); Albertsson et al. (1980); Ymén (1982); Mafud & Gambardella (2011). For puckering parameters, see: Cremer & Pople (1975).

Experimental top

The title compound was prepared by slow addition of 0.1 mol of CS₂ to a cold solution containing 0.2 mol of piperidine and a stoichiometric amount of sodium hydroxide in ethanol/water 1:1 (v/v). The reaction mixture was placed in the freezer for 12 h and then filtered through a Büchner funnel, washed with cold ether and the product recrystallized in an ethanol water mixture 1:1 (v/v). Colourless single crystals, suitable for X-ray diffraction analysis, were obtained. On heating they sublimed and decomposed.

Computing details top

Data collection: COLLECT (Nonius, 1998); cell refinement: SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO and SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) and Mercury (Macrae et al., 2006); software used to prepare material for publication: WinGX (Farrugia, 1999) and publCIF (Westrip, 2010).

Figures top

	Fig. 1. Perspective view of asymmetric unit of the molecular structure of the title compound, with the numbering scheme and displacement ellipsoids drawn at the 50% probability level. The two components (A = C2',C3',C4',C5',N1' and B = C2,C3,C4,C5,N1) of the disordered piperidine ring are shown.
	Fig. 2. A view along the b-axis of the crystal packing of the title compound. Only the minor (B) component of the disordered piperidine ring is shown. The O-H···S hydrogen bonds are shown as dashed cyan lines and the C-bound H atoms have been omitted for clarity.

Sodium piperidine-1-carbodithioate dihydrate top

Crystal data top

Na⁺·C₆H₁₀NS₂⁻·2H₂O	F(000) = 464
M_r = 219.29	D_x = 1.377 Mg m⁻³
Monoclinic, P2₁/a	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yab	Cell parameters from 24030 reflections
a = 12.241 (5) Å	θ = 2.9–26.7°
b = 5.909 (5) Å	µ = 0.51 mm⁻¹
c = 14.690 (5) Å	T = 290 K
β = 95.519 (5)°	Prism, colourless
V = 1057.6 (11) Å³	0.02 × 0.02 × 0.02 mm
Z = 4

Data collection top

Nonius KappaCCD diffractometer	1482 reflections with I > 2σ(I)
Radiation source: Enraf Nonius FR590	R_int = 0.145
Graphite monochromator	θ_max = 25.1°, θ_min = 3.3°
Detector resolution: 9 pixels mm^-1	h = −14→14
CCD rotation images, thick slices scans	k = −7→6
7553 measured reflections	l = −17→16
1863 independent reflections

Refinement top

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)] = 0.054	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.152	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	w = 1/[σ²(F_o²) + (0.0964P)²] where P = (F_o² + 2F_c²)/3
1863 reflections	(Δ/σ)_max < 0.001
176 parameters	Δρ_max = 0.33 e Å⁻³
6 restraints	Δρ_min = −0.36 e Å⁻³

Crystal data top

Na⁺·C₆H₁₀NS₂⁻·2H₂O	V = 1057.6 (11) Å³
M_r = 219.29	Z = 4
Monoclinic, P2₁/a	Mo Kα radiation
a = 12.241 (5) Å	µ = 0.51 mm⁻¹
b = 5.909 (5) Å	T = 290 K
c = 14.690 (5) Å	0.02 × 0.02 × 0.02 mm
β = 95.519 (5)°

Data collection top

Nonius KappaCCD diffractometer	1482 reflections with I > 2σ(I)
7553 measured reflections	R_int = 0.145
1863 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.054	6 restraints
wR(F²) = 0.152	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	Δρ_max = 0.33 e Å⁻³
1863 reflections	Δρ_min = −0.36 e Å⁻³
176 parameters

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
S1	0.74854 (5)	0.03097 (13)	0.39216 (4)	0.0481 (3)
S2	0.86593 (6)	0.24242 (13)	0.24400 (5)	0.0577 (3)
Na1	0.57813 (8)	−0.24210 (16)	0.48568 (8)	0.0509 (4)
O1	0.41274 (14)	−0.0826 (4)	0.41396 (13)	0.0542 (5)
H11O	0.403 (3)	−0.012 (5)	0.3644 (17)	0.081*
H12O	0.369 (2)	−0.194 (4)	0.418 (2)	0.081*
O2	0.55132 (14)	−0.5918 (4)	0.40928 (13)	0.0533 (5)
H21O	0.509 (2)	−0.604 (6)	0.3618 (16)	0.08*
H22O	0.604 (2)	−0.687 (5)	0.409 (2)	0.08*
C1	0.7694 (2)	0.0599 (5)	0.27824 (18)	0.0551 (7)
N1	0.6797 (6)	0.0084 (12)	0.2149 (4)	0.0541 (16)	0.446 (6)
C2	0.6746 (8)	0.0673 (16)	0.1177 (5)	0.081 (3)	0.446 (6)
H2A	0.73	0.1807	0.1092	0.097*	0.446 (6)
H2B	0.6034	0.1336	0.0991	0.097*	0.446 (6)
C3	0.6917 (19)	−0.128 (5)	0.0585 (18)	0.095 (8)	0.446 (6)
H3A	0.7657	−0.1862	0.0716	0.114*	0.446 (6)
H3B	0.6818	−0.0832	−0.0053	0.114*	0.446 (6)
C4	0.6069 (10)	−0.314 (3)	0.0773 (10)	0.079 (4)	0.446 (6)
H4A	0.5339	−0.2616	0.0555	0.095*	0.446 (6)
H4B	0.6218	−0.449	0.043	0.095*	0.446 (6)
C5	0.6089 (7)	−0.3753 (16)	0.1787 (6)	0.076 (2)	0.446 (6)
H5A	0.5505	−0.4818	0.1877	0.091*	0.446 (6)
H5B	0.6784	−0.4451	0.1998	0.091*	0.446 (6)
C6	0.5931 (7)	−0.1592 (18)	0.2320 (6)	0.067 (2)	0.446 (6)
H6A	0.5213	−0.0958	0.2135	0.08*	0.446 (6)
H6B	0.5969	−0.1932	0.2969	0.08*	0.446 (6)
N1'	0.7338 (4)	−0.1085 (10)	0.2187 (3)	0.0516 (13)	0.554 (6)
C2'	0.7582 (5)	−0.1213 (13)	0.1240 (4)	0.0677 (19)	0.554 (6)
H2'1	0.7906	−0.267	0.1125	0.081*	0.554 (6)
H2'2	0.8103	−0.0042	0.1119	0.081*	0.554 (6)
C3'	0.6545 (14)	−0.091 (5)	0.0626 (11)	0.095 (6)	0.554 (6)
H3'1	0.6717	−0.1086	−0.0002	0.115*	0.554 (6)
H3'2	0.6291	0.0629	0.0693	0.115*	0.554 (6)
C4'	0.5616 (9)	−0.249 (3)	0.0778 (10)	0.111 (5)	0.554 (6)
H4'1	0.5798	−0.4026	0.0616	0.133*	0.554 (6)
H4'2	0.4954	−0.2037	0.0407	0.133*	0.554 (6)
C5'	0.5447 (6)	−0.2350 (14)	0.1783 (6)	0.082 (2)	0.554 (6)
H5'1	0.5157	−0.0869	0.1912	0.098*	0.554 (6)
H5'2	0.4909	−0.3471	0.1922	0.098*	0.554 (6)
C6'	0.6494 (6)	−0.2736 (13)	0.2392 (4)	0.0629 (18)	0.554 (6)
H6'1	0.6349	−0.2592	0.3027	0.075*	0.554 (6)
H6'2	0.6759	−0.4258	0.2299	0.075*	0.554 (6)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0420 (4)	0.0551 (5)	0.0476 (4)	0.0008 (3)	0.0057 (3)	−0.0027 (3)
S2	0.0586 (5)	0.0585 (6)	0.0565 (5)	−0.0121 (3)	0.0090 (3)	0.0002 (3)
Na1	0.0465 (6)	0.0453 (8)	0.0609 (7)	0.0002 (4)	0.0053 (5)	−0.0005 (5)
O1	0.0534 (11)	0.0470 (13)	0.0608 (12)	−0.0039 (9)	−0.0015 (9)	0.0059 (10)
O2	0.0502 (10)	0.0497 (13)	0.0597 (12)	0.0060 (9)	0.0033 (8)	−0.0031 (10)
C1	0.0574 (15)	0.056 (2)	0.0512 (15)	−0.0111 (13)	0.0027 (12)	−0.0035 (14)
N1	0.062 (4)	0.052 (4)	0.047 (3)	−0.008 (3)	−0.001 (3)	0.000 (2)
C2	0.108 (6)	0.080 (7)	0.051 (4)	−0.026 (5)	−0.008 (4)	0.007 (4)
C3	0.104 (14)	0.107 (13)	0.079 (10)	−0.051 (11)	0.044 (10)	−0.030 (8)
C4	0.077 (8)	0.090 (9)	0.070 (6)	−0.033 (7)	0.003 (6)	−0.028 (7)
C5	0.070 (5)	0.070 (6)	0.088 (6)	−0.017 (5)	0.014 (4)	0.000 (5)
C6	0.053 (4)	0.086 (7)	0.061 (4)	−0.022 (5)	0.010 (4)	−0.010 (5)
N1'	0.052 (3)	0.056 (3)	0.047 (2)	−0.011 (2)	0.0082 (18)	−0.007 (2)
C2'	0.071 (4)	0.084 (5)	0.050 (3)	−0.020 (3)	0.016 (3)	−0.018 (3)
C3'	0.105 (12)	0.130 (13)	0.049 (6)	−0.041 (9)	−0.004 (7)	0.016 (7)
C4'	0.082 (8)	0.148 (14)	0.096 (7)	−0.042 (7)	−0.030 (6)	0.037 (7)
C5'	0.061 (4)	0.077 (6)	0.107 (6)	−0.020 (4)	0.007 (4)	−0.002 (4)
C6'	0.066 (4)	0.060 (5)	0.061 (4)	−0.027 (3)	0.000 (3)	−0.009 (3)

Geometric parameters (Å, º) top

S1—C1	1.726 (3)	C3—H3A	0.97
S1—Na1ⁱ	2.9644 (15)	C3—H3B	0.97
S1—Na1	3.0649 (15)	C4—C5	1.530 (18)
S2—C1	1.710 (3)	C4—H4A	0.97
Na1—O2	2.360 (3)	C4—H4B	0.97
Na1—O1	2.385 (2)	C5—C6	1.521 (14)
Na1—O1ⁱⁱ	2.416 (3)	C5—H5A	0.97
Na1—O2ⁱⁱⁱ	2.515 (2)	C5—H5B	0.97
Na1—S1^iv	2.9644 (15)	C6—H6A	0.97
Na1—Na1ⁱⁱ	3.490 (3)	C6—H6B	0.97
Na1—Na1ⁱⁱⁱ	3.644 (3)	N1'—C2'	1.452 (6)
Na1—H12O	2.67 (3)	N1'—C6'	1.473 (7)
O1—Na1ⁱⁱ	2.416 (3)	C2'—C3'	1.495 (19)
O1—H11O	0.839 (17)	C2'—H2'1	0.97
O1—H12O	0.852 (17)	C2'—H2'2	0.97
O2—Na1ⁱⁱⁱ	2.515 (2)	C3'—C4'	1.50 (3)
O2—H21O	0.834 (17)	C3'—H3'1	0.97
O2—H22O	0.856 (17)	C3'—H3'2	0.97
C1—N1'	1.368 (5)	C4'—C5'	1.512 (17)
C1—N1	1.403 (6)	C4'—H4'1	0.97
N1—C2	1.465 (9)	C4'—H4'2	0.97
N1—C6	1.489 (10)	C5'—C6'	1.507 (11)
C2—C3	1.47 (3)	C5'—H5'1	0.97
C2—H2A	0.97	C5'—H5'2	0.97
C2—H2B	0.97	C6'—H6'1	0.97
C3—C4	1.55 (3)	C6'—H6'2	0.97

C1—S1—Na1ⁱ	112.20 (10)	C3—C2—H2A	108.9
C1—S1—Na1	131.13 (10)	N1—C2—H2B	108.9
Na1ⁱ—S1—Na1	116.43 (4)	C3—C2—H2B	108.9
O2—Na1—O1	93.59 (8)	H2A—C2—H2B	107.8
O2—Na1—O1ⁱⁱ	169.15 (8)	C2—C3—C4	108.3 (14)
O1—Na1—O1ⁱⁱ	86.75 (8)	C2—C3—H3A	110
O2—Na1—O2ⁱⁱⁱ	83.29 (8)	C4—C3—H3A	110
O1—Na1—O2ⁱⁱⁱ	82.36 (7)	C2—C3—H3B	110
O1ⁱⁱ—Na1—O2ⁱⁱⁱ	86.01 (8)	C4—C3—H3B	110
O2—Na1—S1^iv	87.16 (7)	H3A—C3—H3B	108.4
O1—Na1—S1^iv	166.91 (6)	C5—C4—C3	113.1 (13)
O1ⁱⁱ—Na1—S1^iv	90.09 (7)	C5—C4—H4A	109
O2ⁱⁱⁱ—Na1—S1^iv	84.76 (6)	C3—C4—H4A	109
O2—Na1—S1	108.51 (7)	C5—C4—H4B	109
O1—Na1—S1	100.34 (7)	C3—C4—H4B	109
O1ⁱⁱ—Na1—S1	82.06 (7)	H4A—C4—H4B	107.8
O2ⁱⁱⁱ—Na1—S1	167.57 (6)	C6—C5—C4	108.2 (9)
S1^iv—Na1—S1	91.78 (4)	C6—C5—H5A	110.1
O2—Na1—Na1ⁱⁱ	136.28 (8)	C4—C5—H5A	110.1
O1—Na1—Na1ⁱⁱ	43.73 (6)	C6—C5—H5B	110.1
O1ⁱⁱ—Na1—Na1ⁱⁱ	43.02 (5)	C4—C5—H5B	110.1
O2ⁱⁱⁱ—Na1—Na1ⁱⁱ	82.00 (7)	H5A—C5—H5B	108.4
S1^iv—Na1—Na1ⁱⁱ	131.81 (6)	N1—C6—C5	110.1 (6)
S1—Na1—Na1ⁱⁱ	91.55 (6)	N1—C6—H6A	109.6
O2—Na1—Na1ⁱⁱⁱ	43.27 (6)	C5—C6—H6A	109.6
O1—Na1—Na1ⁱⁱⁱ	87.06 (7)	N1—C6—H6B	109.6
O1ⁱⁱ—Na1—Na1ⁱⁱⁱ	126.00 (8)	C5—C6—H6B	109.6
O2ⁱⁱⁱ—Na1—Na1ⁱⁱⁱ	40.02 (5)	H6A—C6—H6B	108.2
S1^iv—Na1—Na1ⁱⁱⁱ	84.54 (5)	C1—N1'—C2'	124.6 (4)
S1—Na1—Na1ⁱⁱⁱ	151.58 (5)	C1—N1'—C6'	122.6 (4)
Na1ⁱⁱ—Na1—Na1ⁱⁱⁱ	111.83 (7)	C2'—N1'—C6'	111.9 (5)
O2—Na1—H12O	80.3 (6)	N1'—C2'—C3'	109.4 (7)
O1—Na1—H12O	18.4 (4)	N1'—C2'—H2'1	109.8
O1ⁱⁱ—Na1—H12O	97.4 (7)	C3'—C2'—H2'1	109.8
O2ⁱⁱⁱ—Na1—H12O	68.4 (5)	N1'—C2'—H2'2	109.8
S1^iv—Na1—H12O	151.4 (5)	C3'—C2'—H2'2	109.8
S1—Na1—H12O	116.5 (5)	H2'1—C2'—H2'2	108.2
Na1ⁱⁱ—Na1—H12O	56.0 (6)	C2'—C3'—C4'	116.5 (14)
Na1ⁱⁱⁱ—Na1—H12O	68.7 (4)	C2'—C3'—H3'1	108.2
Na1—O1—Na1ⁱⁱ	93.25 (8)	C4'—C3'—H3'1	108.2
Na1—O1—H11O	129 (2)	C2'—C3'—H3'2	108.2
Na1ⁱⁱ—O1—H11O	97 (3)	C4'—C3'—H3'2	108.2
Na1—O1—H12O	100 (2)	H3'1—C3'—H3'2	107.3
Na1ⁱⁱ—O1—H12O	124 (2)	C3'—C4'—C5'	106.7 (11)
H11O—O1—H12O	114 (3)	C3'—C4'—H4'1	110.4
Na1—O2—Na1ⁱⁱⁱ	96.71 (8)	C5'—C4'—H4'1	110.4
Na1—O2—H21O	121 (3)	C3'—C4'—H4'2	110.4
Na1ⁱⁱⁱ—O2—H21O	96 (2)	C5'—C4'—H4'2	110.4
Na1—O2—H22O	121 (2)	H4'1—C4'—H4'2	108.6
Na1ⁱⁱⁱ—O2—H22O	106 (2)	C6'—C5'—C4'	112.5 (7)
H21O—O2—H22O	111 (2)	C6'—C5'—H5'1	109.1
N1'—C1—N1	40.3 (3)	C4'—C5'—H5'1	109.1
N1'—C1—S2	117.2 (3)	C6'—C5'—H5'2	109.1
N1—C1—S2	117.4 (3)	C4'—C5'—H5'2	109.1
N1'—C1—S1	118.6 (3)	H5'1—C5'—H5'2	107.8
N1—C1—S1	116.2 (3)	N1'—C6'—C5'	110.6 (5)
S2—C1—S1	121.25 (16)	N1'—C6'—H6'1	109.5
C1—N1—C2	123.5 (5)	C5'—C6'—H6'1	109.5
C1—N1—C6	123.9 (6)	N1'—C6'—H6'2	109.5
C2—N1—C6	111.0 (6)	C5'—C6'—H6'2	109.5
N1—C2—C3	113.2 (13)	H6'1—C6'—H6'2	108.1
N1—C2—H2A	108.9

C1—S1—Na1—O2	38.84 (16)	Na1ⁱ—S1—C1—S2	−10.8 (2)
Na1ⁱ—S1—Na1—O2	−135.11 (7)	Na1—S1—C1—S2	175.08 (10)
C1—S1—Na1—O1	−58.52 (16)	N1'—C1—N1—C2	−89.0 (9)
Na1ⁱ—S1—Na1—O1	127.53 (7)	S2—C1—N1—C2	11.7 (9)
C1—S1—Na1—O1ⁱⁱ	−143.72 (15)	S1—C1—N1—C2	166.8 (6)
Na1ⁱ—S1—Na1—O1ⁱⁱ	42.34 (6)	N1'—C1—N1—C6	75.0 (8)
C1—S1—Na1—O2ⁱⁱⁱ	−160.0 (3)	S2—C1—N1—C6	175.6 (6)
Na1ⁱ—S1—Na1—O2ⁱⁱⁱ	26.0 (3)	S1—C1—N1—C6	−29.3 (9)
C1—S1—Na1—S1^iv	126.44 (14)	C1—N1—C2—C3	104.9 (12)
Na1ⁱ—S1—Na1—S1^iv	−47.50 (6)	C6—N1—C2—C3	−60.8 (14)
C1—S1—Na1—Na1ⁱⁱ	−101.64 (15)	N1—C2—C3—C4	55 (2)
Na1ⁱ—S1—Na1—Na1ⁱⁱ	84.41 (5)	C2—C3—C4—C5	−53 (2)
C1—S1—Na1—Na1ⁱⁱⁱ	44.63 (19)	C3—C4—C5—C6	54.8 (15)
Na1ⁱ—S1—Na1—Na1ⁱⁱⁱ	−129.32 (11)	C1—N1—C6—C5	−105.1 (9)
O2—Na1—O1—Na1ⁱⁱ	169.13 (8)	C2—N1—C6—C5	60.6 (11)
O1ⁱⁱ—Na1—O1—Na1ⁱⁱ	0	C4—C5—C6—N1	−57.2 (11)
O2ⁱⁱⁱ—Na1—O1—Na1ⁱⁱ	86.40 (8)	N1—C1—N1'—C2'	90.7 (8)
S1^iv—Na1—O1—Na1ⁱⁱ	76.2 (3)	S2—C1—N1'—C2'	−10.6 (7)
S1—Na1—O1—Na1ⁱⁱ	−81.31 (7)	S1—C1—N1'—C2'	−171.6 (4)
Na1ⁱⁱⁱ—Na1—O1—Na1ⁱⁱ	126.33 (8)	N1—C1—N1'—C6'	−77.5 (6)
O1—Na1—O2—Na1ⁱⁱⁱ	−81.86 (8)	S2—C1—N1'—C6'	−178.7 (4)
O1ⁱⁱ—Na1—O2—Na1ⁱⁱⁱ	9.6 (5)	S1—C1—N1'—C6'	20.2 (7)
O2ⁱⁱⁱ—Na1—O2—Na1ⁱⁱⁱ	0	C1—N1'—C2'—C3'	−113.5 (12)
S1^iv—Na1—O2—Na1ⁱⁱⁱ	85.05 (6)	C6'—N1'—C2'—C3'	55.7 (13)
S1—Na1—O2—Na1ⁱⁱⁱ	175.98 (6)	N1'—C2'—C3'—C4'	−55 (2)
Na1ⁱⁱ—Na1—O2—Na1ⁱⁱⁱ	−70.99 (11)	C2'—C3'—C4'—C5'	52.4 (19)
Na1ⁱ—S1—C1—N1'	149.5 (3)	C3'—C4'—C5'—C6'	−52.4 (15)
Na1—S1—C1—N1'	−24.6 (4)	C1—N1'—C6'—C5'	110.7 (7)
Na1ⁱ—S1—C1—N1	−164.9 (4)	C2'—N1'—C6'—C5'	−58.7 (9)
Na1—S1—C1—N1	21.0 (5)	C4'—C5'—C6'—N1'	57.7 (11)

Symmetry codes: (i) −x+3/2, y+1/2, −z+1; (ii) −x+1, −y, −z+1; (iii) −x+1, −y−1, −z+1; (iv) −x+3/2, y−1/2, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H11O···S2^v	0.84 (2)	2.39 (2)	3.214 (2)	167 (3)
O1—H12O···S1^vi	0.85 (2)	2.49 (2)	3.322 (3)	167 (3)
O2—H21O···S2^vi	0.83 (2)	2.48 (2)	3.283 (2)	163 (3)
O2—H22O···S1^vii	0.86 (2)	2.46 (2)	3.313 (2)	174 (3)

Symmetry codes: (v) x−1/2, −y+1/2, z; (vi) x−1/2, −y−1/2, z; (vii) x, y−1, z.

Experimental details

Crystal data
Chemical formula	Na⁺·C₆H₁₀NS₂⁻·2H₂O
M_r	219.29
Crystal system, space group	Monoclinic, P2₁/a
Temperature (K)	290
a, b, c (Å)	12.241 (5), 5.909 (5), 14.690 (5)
β (°)	95.519 (5)
V (Å³)	1057.6 (11)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.51
Crystal size (mm)	0.02 × 0.02 × 0.02

Data collection
Diffractometer	Nonius KappaCCD diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	7553, 1863, 1482
R_int	0.145
(sin θ/λ)_max (Å⁻¹)	0.597

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.054, 0.152, 1.02
No. of reflections	1863
No. of parameters	176
No. of restraints	6
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.33, −0.36

Computer programs: COLLECT (Nonius, 1998), DENZO and SCALEPACK (Otwinowski & Minor, 1997), SIR92 (Altomare et al., 1994), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997) and Mercury (Macrae et al., 2006), WinGX (Farrugia, 1999) and publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H11O···S2ⁱ	0.839 (17)	2.390 (18)	3.214 (2)	167 (3)
O1—H12O···S1ⁱⁱ	0.852 (17)	2.49 (2)	3.322 (3)	167 (3)
O2—H21O···S2ⁱⁱ	0.834 (17)	2.48 (2)	3.283 (2)	163 (3)
O2—H22O···S1ⁱⁱⁱ	0.856 (17)	2.461 (18)	3.313 (2)	174 (3)

Symmetry codes: (i) x−1/2, −y+1/2, z; (ii) x−1/2, −y−1/2, z; (iii) x, y−1, z.

Acknowledgements

We are grateful to the Instituto de Química de São Carlos and the Universidade de São Paulo for supporting this study.

References

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