Sodium 5-amino-1,3,4-thia­diazole-2-thiol­ate dihydrate

Wu, J.; Wang, Y.; Yi, G.; Luo, S.

doi:10.1107/S1600536809051897

metal-organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 66| Part 1| January 2010| Page m20

doi:10.1107/S1600536809051897

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Sodium 5-amino-1,3,4-thiadiazole-2-thiolate dihydrate

Jiayi Wu,^a Yifeng Wang,^a Guo Yi ^a and Shuping Luo ^a ^*

^aState Key Laboratory Breeding Base of Green Chemistry-Synthesis Technology, Zhejiang University of Technology, Hangzhou, 310014, People's Republic of China
^*Correspondence e-mail: jiayiwu1984@163.com

(Received 5 November 2009; accepted 2 December 2009; online 4 December 2009)

There are two 5-amino-1,3,4-thiadiazole-2(3H)-thiolate anions in the asymmetric unit of the title compound, Na⁺·C₂H₂N₃S₂⁻·2H₂O, which are almost perpendicular to each other [dihedral angle = 84.64 (6)°]. The two Na⁺ cations are in distorted fourfold coordinations by O atoms of the water molecules. The crystal structure is stabilized by N—H⋯S, O—H⋯N and O—H⋯S hydrogen bonds.

Related literature

For use of 5-amino-1,3,4-thiadiazole-2(3〈i〉H〈/i〉)-thione derivatives as intermediates for pharmaceuticals, see: John & Gilmer (1960 ); John (1962 ); For related structures, see: Downie et al. (1971 ); Deng et al. (2005 ); Ma et al. (2007 ).

Experimental

Crystal data

Na⁺·C₂H₂N₃S₂⁻·2H₂O
M_r = 191.21
Monoclinic, P 2₁ /c
a = 8.7810 (3) Å
b = 20.0593 (5) Å
c = 8.4351 (3) Å
β = 91.026 (1)°
V = 1485.53 (8) Å³
Z = 8
Mo Kα radiation
μ = 0.72 mm⁻¹
T = 296 K
0.38 × 0.28 × 0.17 mm

Data collection

Rigaku R-AXIS RAPID diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ) T_min = 0.758, T_max = 0.885
14264 measured reflections
3376 independent reflections
2974 reflections with I > 2σ(I)
R_int = 0.026

Refinement

R[F² > 2σ(F²)] = 0.026
wR(F²) = 0.059
S = 1.00
3376 reflections
182 parameters
H-atom parameters constrained
Δρ_max = 0.30 e Å⁻³
Δρ_min = −0.32 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2A—H104⋯N3B	0.85	1.99	2.8113 (18)	161
O1A—H102⋯S1B	0.87	2.39	3.2563 (14)	172
O2B—H201⋯S1Bⁱ	0.86	2.45	3.2962 (12)	169
O2B—H202⋯N2Bⁱⁱ	0.86	1.95	2.8024 (18)	170
N1A—H1A2⋯S1Bⁱⁱⁱ	0.86	2.57	3.4081 (16)	165
N1B—H1B2⋯S1A^iv	0.86	2.43	3.2589 (17)	161
Symmetry codes: (i) x, y, z+1; (ii) -x+1, -y+1, -z+1; (iii) $[x, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ ; (iv) $[x-1, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ .

Data collection: PROCESS-AUTO (Rigaku/MSC, 2006 ); cell refinement: PROCESS-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2007 ); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809051897/pk2208sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809051897/pk2208Isup2.hkl

checkCIF report

Comment top

Interest in the study of 5-amino-1,3,4-thiadiazole-2(3H)-thione derivatives stems from their use as intermediates of pharmaceuticals (John et al., 1960; John, 1962). Nonetheless, there are few articles that describe this kind of crystal structure (Downie et al., 1972; Deng et al., 2005; Ma et al., 2007). As part of our studies of agrochemicals, the title compound 5-amino-2-thione-1,3,4-thiadiazole sodium dihydrate has been synthesized, and its crystal structure is reported in this article. The complex is located across an inversion centre, and is bridged by two symmetry equivalent water molecules Na—O (bridge) distances of 2.3776 (14) Å and 2.5141 (15) Å and an Na—O—Na bond angle of 98.99 (3)°. It has two 5-amino-1,3,4-thiadiazole-2(3H)-thione molecules in the asymmetric unit that are almost perpendicular to each other [dihedral angle = 84.64 (6)°]. The structure is stabilized by N—H···S, O—H···N and O—H···S hydrogen bonds.

Related literature top

For use of 5-amino-1,3,4-thiadiazole-2(3〈i〉H〈/i〉)-thione derivatives as intermediates for pharmaceuticals, see: John et al. (1960); John (1962); For related structures, see: Downie et al. (1971); Deng et al. (2005); Ma et al. (2007).

Experimental top

5-amino-1,3,4-thiadiazole-2(3H)-thione(0.1 mmol) and sodium hydroxide (0.1 mmol) were dissolved in water (10 ml) and stirred for 3 h. The water was then removed under reduced pressure. Single crystals were obtained by slow evaporation of a methanol solution at room temperature.

Computing details top

Data collection: PROCESS-AUTO (Rigaku/MSC, 2006); cell refinement: PROCESS-AUTO (Rigaku/MSC, 2006); data reduction: CrystalStructure (Rigaku/MSC, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top

	Fig. 1. The asymmetric unit of the title compound with the atomic labeling scheme. Displacement ellipsoids are drawn at the 40% probability level.
	Fig. 2. A partial packing diagram of title compound.

Sodium 5-amino-1,3,4-thiadiazole-2-thiolate dihydrate top

Crystal data top

Na⁺·C₂H₂N₃S₂⁻·2H₂O	F(000) = 784
M_r = 191.21	D_x = 1.710 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 11555 reflections
a = 8.7810 (3) Å	θ = 3.0–27.4°
b = 20.0593 (5) Å	µ = 0.72 mm⁻¹
c = 8.4351 (3) Å	T = 296 K
β = 91.026 (1)°	Block, colorless
V = 1485.53 (8) Å³	0.38 × 0.28 × 0.17 mm
Z = 8

Data collection top

Rigaku R-AXIS RAPID diffractometer	3376 independent reflections
Radiation source: rolling anode	2974 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.026
Detector resolution: 10.00 pixels mm^-1	θ_max = 27.4°, θ_min = 3.1°
ω scans	h = −11→11
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	k = −25→25
T_min = 0.758, T_max = 0.885	l = −10→10
14264 measured reflections

Refinement top

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)] = 0.026	H-atom parameters constrained
wR(F²) = 0.059	w = 1/[σ²(F_o²) + (0.014P)² + 1.P] where P = (F_o² + 2F_c²)/3
S = 1.00	(Δ/σ)_max = 0.001
3376 reflections	Δρ_max = 0.30 e Å⁻³
182 parameters	Δρ_min = −0.32 e Å⁻³
0 restraints	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0516 (12)

Crystal data top

Na⁺·C₂H₂N₃S₂⁻·2H₂O	V = 1485.53 (8) Å³
M_r = 191.21	Z = 8
Monoclinic, P2₁/c	Mo Kα radiation
a = 8.7810 (3) Å	µ = 0.72 mm⁻¹
b = 20.0593 (5) Å	T = 296 K
c = 8.4351 (3) Å	0.38 × 0.28 × 0.17 mm
β = 91.026 (1)°

Data collection top

Rigaku R-AXIS RAPID diffractometer	3376 independent reflections
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	2974 reflections with I > 2σ(I)
T_min = 0.758, T_max = 0.885	R_int = 0.026
14264 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.026	0 restraints
wR(F²) = 0.059	H-atom parameters constrained
S = 1.00	Δρ_max = 0.30 e Å⁻³
3376 reflections	Δρ_min = −0.32 e Å⁻³
182 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 > 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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
S2B	0.46866 (5)	0.720405 (18)	0.04494 (5)	0.03114 (11)
S2A	0.97675 (5)	0.708164 (18)	0.53837 (5)	0.03013 (10)
S1B	0.71560 (5)	0.66512 (2)	−0.16488 (6)	0.03952 (12)
S1A	1.23359 (5)	0.65778 (2)	0.75020 (5)	0.03794 (12)
Na1B	0.71086 (8)	0.49937 (4)	0.47238 (8)	0.04359 (19)
Na1A	0.98033 (7)	0.50450 (3)	0.20940 (8)	0.03560 (16)
O2A	0.70915 (13)	0.49947 (6)	0.18979 (14)	0.0359 (3)
H104	0.6554	0.5221	0.1237	0.054*
H103	0.6897	0.4585	0.1699	0.054*
O1A	0.99706 (15)	0.58368 (6)	0.00068 (15)	0.0446 (3)
H101	1.0720	0.6080	−0.0267	0.067*
H102	0.9227	0.6081	−0.0358	0.067*
O2B	0.75550 (13)	0.50610 (6)	0.74664 (14)	0.0347 (3)
H204	0.5182	0.6062	0.4294	0.052*
H203	0.5156	0.6066	0.5812	0.052*
N2B	0.41175 (17)	0.60144 (7)	0.13535 (18)	0.0379 (3)
N2A	0.93910 (16)	0.58939 (6)	0.43221 (16)	0.0320 (3)
N3B	0.53241 (16)	0.59605 (7)	0.03004 (17)	0.0356 (3)
O1B	0.50110 (17)	0.57964 (7)	0.50136 (16)	0.0540 (4)
H201	0.7328	0.5460	0.7754	0.081*
H202	0.6964	0.4767	0.7880	0.081*
N3A	1.05908 (15)	0.58553 (6)	0.54520 (15)	0.0307 (3)
C2A	0.88628 (18)	0.65001 (7)	0.41696 (18)	0.0278 (3)
N1A	0.76956 (18)	0.66682 (7)	0.31696 (18)	0.0426 (4)
H1A1	0.7261	0.6368	0.2592	0.051*
H1A2	0.7391	0.7075	0.3114	0.051*
C1B	0.57417 (17)	0.65311 (7)	−0.02914 (18)	0.0277 (3)
C2B	0.36620 (18)	0.66293 (8)	0.15350 (18)	0.0304 (3)
N1B	0.24845 (18)	0.67989 (8)	0.2467 (2)	0.0479 (4)
H1B1	0.2000	0.6496	0.2972	0.057*
H1B2	0.2221	0.7210	0.2554	0.057*
C1A	1.09218 (17)	0.64295 (7)	0.61080 (17)	0.0262 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S2B	0.0345 (2)	0.02059 (18)	0.0384 (2)	−0.00051 (15)	0.00191 (16)	0.00096 (15)
S2A	0.0354 (2)	0.02064 (18)	0.0342 (2)	0.00192 (15)	−0.00284 (16)	−0.00291 (15)
S1B	0.0396 (2)	0.0309 (2)	0.0485 (3)	0.00355 (17)	0.01226 (19)	0.00579 (18)
S1A	0.0416 (2)	0.0306 (2)	0.0411 (2)	−0.00624 (17)	−0.01399 (18)	0.00242 (17)
Na1B	0.0385 (4)	0.0584 (5)	0.0339 (4)	0.0037 (3)	0.0013 (3)	0.0044 (3)
Na1A	0.0322 (3)	0.0395 (4)	0.0351 (3)	0.0030 (3)	0.0002 (3)	−0.0019 (3)
O2A	0.0390 (6)	0.0304 (6)	0.0380 (6)	0.0020 (5)	−0.0086 (5)	−0.0004 (5)
O1A	0.0437 (7)	0.0404 (7)	0.0497 (7)	−0.0024 (6)	0.0003 (6)	0.0079 (6)
O2B	0.0352 (6)	0.0321 (6)	0.0370 (6)	−0.0011 (5)	0.0036 (5)	0.0002 (5)
N2B	0.0408 (8)	0.0264 (7)	0.0467 (8)	0.0025 (6)	0.0098 (6)	0.0080 (6)
N2A	0.0395 (7)	0.0238 (6)	0.0323 (7)	0.0009 (6)	−0.0083 (6)	−0.0022 (5)
N3B	0.0383 (8)	0.0251 (7)	0.0437 (8)	0.0045 (6)	0.0069 (6)	0.0060 (6)
O1B	0.0642 (9)	0.0502 (8)	0.0478 (8)	0.0032 (7)	0.0073 (7)	0.0103 (6)
N3A	0.0358 (7)	0.0230 (6)	0.0330 (7)	0.0014 (5)	−0.0071 (6)	−0.0008 (5)
C2A	0.0318 (8)	0.0251 (7)	0.0266 (7)	−0.0002 (6)	−0.0001 (6)	−0.0010 (6)
N1A	0.0486 (9)	0.0313 (7)	0.0473 (9)	0.0050 (6)	−0.0182 (7)	−0.0007 (6)
C1B	0.0284 (7)	0.0240 (7)	0.0304 (7)	0.0020 (6)	−0.0050 (6)	0.0014 (6)
C2B	0.0325 (8)	0.0278 (8)	0.0308 (8)	−0.0020 (6)	−0.0017 (6)	0.0029 (6)
N1B	0.0521 (10)	0.0336 (8)	0.0588 (10)	0.0017 (7)	0.0236 (8)	0.0014 (7)
C1A	0.0296 (7)	0.0233 (7)	0.0257 (7)	−0.0010 (6)	0.0020 (6)	0.0029 (6)

Geometric parameters (Å, º) top

S2B—C2B	1.7340 (16)	O2B—Na1Aⁱⁱ	2.3521 (13)
S2B—C1B	1.7583 (15)	O2B—H201	0.8609
S2A—C2A	1.7354 (15)	O2B—H202	0.8632
S2A—C1A	1.7578 (15)	N2B—C2B	1.306 (2)
S1B—C1B	1.7211 (16)	N2B—N3B	1.3989 (19)
S1A—C1A	1.7207 (16)	N2A—C2A	1.3071 (19)
Na1B—O2B	2.3433 (13)	N2A—N3A	1.4100 (18)
Na1B—O2A	2.3835 (13)	N3B—C1B	1.304 (2)
Na1B—O1Bⁱ	2.4576 (17)	O1B—Na1Bⁱ	2.4576 (17)
Na1B—O1B	2.4619 (16)	O1B—H204	0.8227
Na1B—Na1A	3.2739 (10)	O1B—H203	0.8710
Na1A—O2Bⁱⁱ	2.3521 (13)	N3A—C1A	1.3082 (19)
Na1A—O1A	2.3776 (14)	N3A—Na1Bⁱⁱ	2.6485 (15)
Na1A—O2A	2.3862 (14)	N3A—Na1Aⁱⁱ	2.7735 (15)
Na1A—O1Aⁱⁱⁱ	2.5141 (15)	C2A—N1A	1.358 (2)
O2A—H104	0.8538	N1A—H1A1	0.8600
O2A—H103	0.8559	N1A—H1A2	0.8600
O1A—Na1Aⁱⁱⁱ	2.5141 (15)	C2B—N1B	1.354 (2)
O1A—H101	0.8545	N1B—H1B1	0.8600
O1A—H102	0.8684	N1B—H1B2	0.8600

C2B—S2B—C1B	87.65 (8)	Na1B—Na1A—Na1Aⁱⁱⁱ	139.01 (3)
C2A—S2A—C1A	87.70 (7)	O2Bⁱⁱ—Na1A—Na1Bⁱⁱ	36.27 (3)
O2B—Na1B—O2A	170.14 (5)	O1A—Na1A—Na1Bⁱⁱ	119.10 (4)
O2B—Na1B—O1Bⁱ	93.54 (5)	O2A—Na1A—Na1Bⁱⁱ	138.61 (4)
O2A—Na1B—O1Bⁱ	95.71 (5)	O1Aⁱⁱⁱ—Na1A—Na1Bⁱⁱ	114.91 (4)
O2B—Na1B—O1B	88.66 (5)	N2A—Na1A—Na1Bⁱⁱ	66.59 (3)
O2A—Na1B—O1B	96.17 (5)	N3Aⁱⁱ—Na1A—Na1Bⁱⁱ	63.54 (3)
O1Bⁱ—Na1B—O1B	81.01 (6)	Na1B—Na1A—Na1Bⁱⁱ	92.07 (2)
O2B—Na1B—N3Aⁱⁱ	88.74 (5)	Na1Aⁱⁱⁱ—Na1A—Na1Bⁱⁱ	128.47 (3)
O2A—Na1B—N3Aⁱⁱ	86.31 (5)	Na1B—O2A—Na1A	86.69 (4)
O1Bⁱ—Na1B—N3Aⁱⁱ	99.79 (5)	Na1B—O2A—H104	130.3
O1B—Na1B—N3Aⁱⁱ	177.32 (5)	Na1A—O2A—H104	124.2
O2B—Na1B—N2A	88.52 (5)	Na1B—O2A—H103	101.1
O2A—Na1B—N2A	82.33 (4)	Na1A—O2A—H103	104.4
O1Bⁱ—Na1B—N2A	177.48 (5)	H104—O2A—H103	106.1
O1B—Na1B—N2A	97.60 (5)	Na1A—O1A—Na1Aⁱⁱⁱ	93.36 (5)
N3Aⁱⁱ—Na1B—N2A	81.70 (5)	Na1A—O1A—H101	129.8
O2B—Na1B—Na1A	123.85 (4)	Na1Aⁱⁱⁱ—O1A—H101	98.1
O2A—Na1B—Na1A	46.69 (3)	Na1A—O1A—H102	125.7
O1Bⁱ—Na1B—Na1A	129.72 (5)	Na1Aⁱⁱⁱ—O1A—H102	102.5
O1B—Na1B—Na1A	126.71 (4)	H101—O1A—H102	99.2
N3Aⁱⁱ—Na1B—Na1A	54.62 (3)	Na1B—O2B—Na1Aⁱⁱ	107.31 (5)
N2A—Na1B—Na1A	49.64 (3)	Na1B—O2B—H201	107.3
O2B—Na1B—Na1Bⁱ	91.44 (4)	Na1Aⁱⁱ—O2B—H201	105.8
O2A—Na1B—Na1Bⁱ	97.82 (4)	Na1B—O2B—H202	105.6
O1Bⁱ—Na1B—Na1Bⁱ	40.55 (4)	Na1Aⁱⁱ—O2B—H202	118.2
O1B—Na1B—Na1Bⁱ	40.46 (4)	H201—O2B—H202	112.2
N3Aⁱⁱ—Na1B—Na1Bⁱ	140.27 (5)	C2B—N2B—N3B	112.60 (13)
N2A—Na1B—Na1Bⁱ	138.02 (5)	C2A—N2A—N3A	112.15 (12)
Na1A—Na1B—Na1Bⁱ	144.42 (3)	C2A—N2A—Na1A	126.84 (10)
O2B—Na1B—Na1Aⁱⁱ	36.43 (3)	N3A—N2A—Na1A	110.19 (9)
O2A—Na1B—Na1Aⁱⁱ	134.54 (4)	C2A—N2A—Na1B	111.62 (10)
O1Bⁱ—Na1B—Na1Aⁱⁱ	117.21 (4)	N3A—N2A—Na1B	114.97 (9)
O1B—Na1B—Na1Aⁱⁱ	118.11 (4)	Na1A—N2A—Na1B	76.41 (4)
N3Aⁱⁱ—Na1B—Na1Aⁱⁱ	59.24 (3)	C1B—N3B—N2B	113.37 (13)
N2A—Na1B—Na1Aⁱⁱ	65.29 (3)	Na1Bⁱ—O1B—Na1B	98.99 (6)
Na1A—Na1B—Na1Aⁱⁱ	87.93 (2)	Na1Bⁱ—O1B—H204	129.2
Na1Bⁱ—Na1B—Na1Aⁱⁱ	127.63 (3)	Na1B—O1B—H204	101.7
O2Bⁱⁱ—Na1A—O1A	95.93 (5)	Na1Bⁱ—O1B—H203	115.5
O2Bⁱⁱ—Na1A—O2A	170.82 (5)	Na1B—O1B—H203	112.5
O1A—Na1A—O2A	92.97 (5)	H204—O1B—H203	98.3
O2Bⁱⁱ—Na1A—O1Aⁱⁱⁱ	87.56 (5)	C1A—N3A—N2A	113.29 (12)
O1A—Na1A—O1Aⁱⁱⁱ	86.64 (5)	C1A—N3A—Na1Bⁱⁱ	115.21 (10)
O2A—Na1A—O1Aⁱⁱⁱ	90.73 (5)	N2A—N3A—Na1Bⁱⁱ	123.97 (9)
O2Bⁱⁱ—Na1A—N2A	95.52 (5)	C1A—N3A—Na1Aⁱⁱ	106.70 (10)
O1A—Na1A—N2A	96.34 (5)	N2A—N3A—Na1Aⁱⁱ	116.01 (9)
O2A—Na1A—N2A	85.71 (5)	Na1Bⁱⁱ—N3A—Na1Aⁱⁱ	74.25 (4)
O1Aⁱⁱⁱ—Na1A—N2A	175.46 (5)	N2A—C2A—N1A	123.68 (14)
O2Bⁱⁱ—Na1A—N3Aⁱⁱ	87.67 (4)	N2A—C2A—S2A	114.17 (11)
O1A—Na1A—N3Aⁱⁱ	176.24 (5)	N1A—C2A—S2A	122.15 (12)
O2A—Na1A—N3Aⁱⁱ	83.48 (4)	C2A—N1A—H1A1	120.0
O1Aⁱⁱⁱ—Na1A—N3Aⁱⁱ	94.61 (4)	C2A—N1A—H1A2	120.0
N2A—Na1A—N3Aⁱⁱ	82.20 (4)	H1A1—N1A—H1A2	120.0
O2Bⁱⁱ—Na1A—Na1B	127.81 (4)	N3B—C1B—S1B	126.07 (12)
O1A—Na1A—Na1B	125.29 (4)	N3B—C1B—S2B	112.60 (12)
O2A—Na1A—Na1B	46.62 (3)	S1B—C1B—S2B	121.34 (9)
O1Aⁱⁱⁱ—Na1A—Na1B	121.51 (4)	N2B—C2B—N1B	122.96 (15)
N2A—Na1A—Na1B	53.95 (4)	N2B—C2B—S2B	113.76 (12)
N3Aⁱⁱ—Na1A—Na1B	51.13 (3)	N1B—C2B—S2B	123.27 (13)
O2Bⁱⁱ—Na1A—Na1Aⁱⁱⁱ	92.23 (4)	C2B—N1B—H1B1	120.0
O1A—Na1A—Na1Aⁱⁱⁱ	44.83 (4)	C2B—N1B—H1B2	120.0
O2A—Na1A—Na1Aⁱⁱⁱ	92.49 (4)	H1B1—N1B—H1B2	120.0
O1Aⁱⁱⁱ—Na1A—Na1Aⁱⁱⁱ	41.81 (3)	N3A—C1A—S1A	126.40 (12)
N2A—Na1A—Na1Aⁱⁱⁱ	141.05 (5)	N3A—C1A—S2A	112.69 (11)
N3Aⁱⁱ—Na1A—Na1Aⁱⁱⁱ	136.32 (4)	S1A—C1A—S2A	120.89 (9)

O2B—Na1B—Na1A—O2Bⁱⁱ	13.17 (9)	Na1A—Na1B—O2B—Na1Aⁱⁱ	−10.87 (7)
O2A—Na1B—Na1A—O2Bⁱⁱ	−170.38 (7)	Na1Bⁱ—Na1B—O2B—Na1Aⁱⁱ	173.99 (4)
O1Bⁱ—Na1B—Na1A—O2Bⁱⁱ	−117.66 (7)	O2Bⁱⁱ—Na1A—N2A—C2A	119.25 (13)
O1B—Na1B—Na1A—O2Bⁱⁱ	130.87 (7)	O1A—Na1A—N2A—C2A	22.63 (14)
N3Aⁱⁱ—Na1B—Na1A—O2Bⁱⁱ	−46.25 (6)	O2A—Na1A—N2A—C2A	−69.88 (14)
N2A—Na1B—Na1A—O2Bⁱⁱ	65.53 (6)	N3Aⁱⁱ—Na1A—N2A—C2A	−153.88 (14)
Na1Bⁱ—Na1B—Na1A—O2Bⁱⁱ	−175.20 (6)	Na1B—Na1A—N2A—C2A	−107.01 (14)
Na1Aⁱⁱ—Na1B—Na1A—O2Bⁱⁱ	6.74 (5)	Na1Aⁱⁱⁱ—Na1A—N2A—C2A	18.77 (17)
O2B—Na1B—Na1A—O1A	−122.01 (6)	Na1Bⁱⁱ—Na1A—N2A—C2A	141.65 (14)
O2A—Na1B—Na1A—O1A	54.43 (6)	O2Bⁱⁱ—Na1A—N2A—N3A	−21.79 (10)
O1Bⁱ—Na1B—Na1A—O1A	107.16 (7)	O1A—Na1A—N2A—N3A	−118.40 (10)
O1B—Na1B—Na1A—O1A	−4.31 (8)	O2A—Na1A—N2A—N3A	149.09 (10)
N3Aⁱⁱ—Na1B—Na1A—O1A	178.56 (6)	N3Aⁱⁱ—Na1A—N2A—N3A	65.09 (10)
N2A—Na1B—Na1A—O1A	−69.65 (6)	Na1B—Na1A—N2A—N3A	111.96 (10)
Na1Bⁱ—Na1B—Na1A—O1A	49.61 (9)	Na1Aⁱⁱⁱ—Na1A—N2A—N3A	−122.26 (9)
Na1Aⁱⁱ—Na1B—Na1A—O1A	−128.44 (5)	Na1Bⁱⁱ—Na1A—N2A—N3A	0.61 (8)
O2B—Na1B—Na1A—O2A	−176.45 (7)	O2Bⁱⁱ—Na1A—N2A—Na1B	−133.74 (4)
O1Bⁱ—Na1B—Na1A—O2A	52.73 (7)	O1A—Na1A—N2A—Na1B	129.64 (4)
O1B—Na1B—Na1A—O2A	−58.74 (7)	O2A—Na1A—N2A—Na1B	37.13 (4)
N3Aⁱⁱ—Na1B—Na1A—O2A	124.13 (6)	N3Aⁱⁱ—Na1A—N2A—Na1B	−46.86 (4)
N2A—Na1B—Na1A—O2A	−124.09 (6)	Na1Aⁱⁱⁱ—Na1A—N2A—Na1B	125.78 (6)
Na1Bⁱ—Na1B—Na1A—O2A	−4.82 (7)	Na1Bⁱⁱ—Na1A—N2A—Na1B	−111.34 (3)
Na1Aⁱⁱ—Na1B—Na1A—O2A	177.12 (5)	O2B—Na1B—N2A—C2A	−96.54 (11)
O2B—Na1B—Na1A—O1Aⁱⁱⁱ	127.53 (6)	O2A—Na1B—N2A—C2A	87.15 (11)
O2A—Na1B—Na1A—O1Aⁱⁱⁱ	−56.03 (6)	O1B—Na1B—N2A—C2A	−8.10 (11)
O1Bⁱ—Na1B—Na1A—O1Aⁱⁱⁱ	−3.30 (8)	N3Aⁱⁱ—Na1B—N2A—C2A	174.51 (11)
O1B—Na1B—Na1A—O1Aⁱⁱⁱ	−114.77 (7)	Na1A—Na1B—N2A—C2A	124.59 (11)
N3Aⁱⁱ—Na1B—Na1A—O1Aⁱⁱⁱ	68.10 (6)	Na1Bⁱ—Na1B—N2A—C2A	−6.04 (14)
N2A—Na1B—Na1A—O1Aⁱⁱⁱ	179.89 (6)	Na1Aⁱⁱ—Na1B—N2A—C2A	−125.60 (11)
Na1Bⁱ—Na1B—Na1A—O1Aⁱⁱⁱ	−60.85 (8)	O2B—Na1B—N2A—N3A	32.66 (10)
Na1Aⁱⁱ—Na1B—Na1A—O1Aⁱⁱⁱ	121.10 (5)	O2A—Na1B—N2A—N3A	−143.65 (10)
O2B—Na1B—Na1A—N2A	−52.36 (6)	O1B—Na1B—N2A—N3A	121.10 (10)
O2A—Na1B—Na1A—N2A	124.09 (6)	N3Aⁱⁱ—Na1B—N2A—N3A	−56.29 (11)
O1Bⁱ—Na1B—Na1A—N2A	176.81 (7)	Na1A—Na1B—N2A—N3A	−106.21 (10)
O1B—Na1B—Na1A—N2A	65.34 (7)	Na1Bⁱ—Na1B—N2A—N3A	123.16 (10)
N3Aⁱⁱ—Na1B—Na1A—N2A	−111.79 (5)	Na1Aⁱⁱ—Na1B—N2A—N3A	3.60 (9)
Na1Bⁱ—Na1B—Na1A—N2A	119.27 (8)	O2B—Na1B—N2A—Na1A	138.86 (4)
Na1Aⁱⁱ—Na1B—Na1A—N2A	−58.79 (4)	O2A—Na1B—N2A—Na1A	−37.45 (4)
O2B—Na1B—Na1A—N3Aⁱⁱ	59.43 (6)	O1B—Na1B—N2A—Na1A	−132.69 (5)
O2A—Na1B—Na1A—N3Aⁱⁱ	−124.13 (6)	N3Aⁱⁱ—Na1B—N2A—Na1A	49.92 (4)
O1Bⁱ—Na1B—Na1A—N3Aⁱⁱ	−71.40 (6)	Na1Bⁱ—Na1B—N2A—Na1A	−130.63 (6)
O1B—Na1B—Na1A—N3Aⁱⁱ	177.13 (7)	Na1Aⁱⁱ—Na1B—N2A—Na1A	109.80 (3)
N2A—Na1B—Na1A—N3Aⁱⁱ	111.79 (5)	C2B—N2B—N3B—C1B	−0.4 (2)
Na1Bⁱ—Na1B—Na1A—N3Aⁱⁱ	−128.95 (8)	O2B—Na1B—O1B—Na1Bⁱ	−93.80 (5)
Na1Aⁱⁱ—Na1B—Na1A—N3Aⁱⁱ	52.99 (4)	O2A—Na1B—O1B—Na1Bⁱ	94.83 (5)
O2B—Na1B—Na1A—Na1Aⁱⁱⁱ	178.67 (5)	O1Bⁱ—Na1B—O1B—Na1Bⁱ	0.0
O2A—Na1B—Na1A—Na1Aⁱⁱⁱ	−4.89 (6)	N2A—Na1B—O1B—Na1Bⁱ	177.88 (5)
O1Bⁱ—Na1B—Na1A—Na1Aⁱⁱⁱ	47.84 (8)	Na1A—Na1B—O1B—Na1Bⁱ	133.56 (5)
O1B—Na1B—Na1A—Na1Aⁱⁱⁱ	−63.63 (8)	Na1Aⁱⁱ—Na1B—O1B—Na1Bⁱ	−116.13 (5)
N3Aⁱⁱ—Na1B—Na1A—Na1Aⁱⁱⁱ	119.24 (6)	C2A—N2A—N3A—C1A	0.06 (19)
N2A—Na1B—Na1A—Na1Aⁱⁱⁱ	−128.97 (7)	Na1A—N2A—N3A—C1A	147.14 (11)
Na1Bⁱ—Na1B—Na1A—Na1Aⁱⁱⁱ	−9.71 (10)	Na1B—N2A—N3A—C1A	−128.88 (11)
Na1Aⁱⁱ—Na1B—Na1A—Na1Aⁱⁱⁱ	172.24 (6)	C2A—N2A—N3A—Na1Bⁱⁱ	−148.06 (11)
O2B—Na1B—Na1A—Na1Bⁱⁱ	6.43 (4)	Na1A—N2A—N3A—Na1Bⁱⁱ	−0.97 (13)
O2A—Na1B—Na1A—Na1Bⁱⁱ	−177.12 (5)	Na1B—N2A—N3A—Na1Bⁱⁱ	83.01 (11)
O1Bⁱ—Na1B—Na1A—Na1Bⁱⁱ	−124.39 (6)	C2A—N2A—N3A—Na1Aⁱⁱ	123.98 (12)
O1B—Na1B—Na1A—Na1Bⁱⁱ	124.14 (6)	Na1A—N2A—N3A—Na1Aⁱⁱ	−88.94 (9)
N3Aⁱⁱ—Na1B—Na1A—Na1Bⁱⁱ	−52.99 (4)	Na1B—N2A—N3A—Na1Aⁱⁱ	−4.96 (12)
N2A—Na1B—Na1A—Na1Bⁱⁱ	58.79 (4)	N3A—N2A—C2A—N1A	−179.29 (15)
Na1Bⁱ—Na1B—Na1A—Na1Bⁱⁱ	178.06 (7)	Na1A—N2A—C2A—N1A	40.3 (2)
Na1Aⁱⁱ—Na1B—Na1A—Na1Bⁱⁱ	0.0	Na1B—N2A—C2A—N1A	−48.62 (19)
O1Bⁱ—Na1B—O2A—Na1A	−142.04 (5)	N3A—N2A—C2A—S2A	−0.11 (17)
O1B—Na1B—O2A—Na1A	136.43 (5)	Na1A—N2A—C2A—S2A	−140.52 (9)
N3Aⁱⁱ—Na1B—O2A—Na1A	−42.56 (4)	Na1B—N2A—C2A—S2A	130.56 (8)
N2A—Na1B—O2A—Na1A	39.55 (4)	C1A—S2A—C2A—N2A	0.09 (13)
Na1Bⁱ—Na1B—O2A—Na1A	177.17 (4)	C1A—S2A—C2A—N1A	179.29 (15)
Na1Aⁱⁱ—Na1B—O2A—Na1A	−4.04 (7)	N2B—N3B—C1B—S1B	−178.64 (12)
O1A—Na1A—O2A—Na1B	−138.33 (5)	N2B—N3B—C1B—S2B	1.37 (18)
O1Aⁱⁱⁱ—Na1A—O2A—Na1B	135.00 (4)	C2B—S2B—C1B—N3B	−1.48 (13)
N2A—Na1A—O2A—Na1B	−42.18 (4)	C2B—S2B—C1B—S1B	178.53 (10)
N3Aⁱⁱ—Na1A—O2A—Na1B	40.44 (4)	N3B—N2B—C2B—N1B	178.31 (16)
Na1Aⁱⁱⁱ—Na1A—O2A—Na1B	176.79 (4)	N3B—N2B—C2B—S2B	−0.78 (19)
Na1Bⁱⁱ—Na1A—O2A—Na1B	4.35 (7)	C1B—S2B—C2B—N2B	1.26 (13)
O2Bⁱⁱ—Na1A—O1A—Na1Aⁱⁱⁱ	87.19 (5)	C1B—S2B—C2B—N1B	−177.82 (16)
O2A—Na1A—O1A—Na1Aⁱⁱⁱ	−90.55 (5)	N2A—N3A—C1A—S1A	−178.68 (11)
O1Aⁱⁱⁱ—Na1A—O1A—Na1Aⁱⁱⁱ	0.0	Na1Bⁱⁱ—N3A—C1A—S1A	−27.64 (17)
N2A—Na1A—O1A—Na1Aⁱⁱⁱ	−176.56 (5)	Na1Aⁱⁱ—N3A—C1A—S1A	52.46 (15)
Na1B—Na1A—O1A—Na1Aⁱⁱⁱ	−126.85 (5)	N2A—N3A—C1A—S2A	0.01 (17)
Na1Bⁱⁱ—Na1A—O1A—Na1Aⁱⁱⁱ	116.75 (4)	Na1Bⁱⁱ—N3A—C1A—S2A	151.06 (7)
O1Bⁱ—Na1B—O2B—Na1Aⁱⁱ	133.46 (6)	Na1Aⁱⁱ—N3A—C1A—S2A	−128.85 (8)
O1B—Na1B—O2B—Na1Aⁱⁱ	−145.64 (5)	C2A—S2A—C1A—N3A	−0.06 (12)
N3Aⁱⁱ—Na1B—O2B—Na1Aⁱⁱ	33.73 (5)	C2A—S2A—C1A—S1A	178.72 (10)
N2A—Na1B—O2B—Na1Aⁱⁱ	−48.00 (5)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2A—H104···N3B	0.85	1.99	2.8113 (18)	161
O1A—H102···S1B	0.87	2.39	3.2563 (14)	172
O2B—H201···S1B^iv	0.86	2.45	3.2962 (12)	169
O2B—H202···N2Bⁱ	0.86	1.95	2.8024 (18)	170
N1A—H1A2···S1B^v	0.86	2.57	3.4081 (16)	165
N1B—H1B2···S1A^vi	0.86	2.43	3.2589 (17)	161

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

Experimental details

Crystal data
Chemical formula	Na⁺·C₂H₂N₃S₂⁻·2H₂O
M_r	191.21
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	296
a, b, c (Å)	8.7810 (3), 20.0593 (5), 8.4351 (3)
β (°)	91.026 (1)
V (Å³)	1485.53 (8)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.72
Crystal size (mm)	0.38 × 0.28 × 0.17

Data collection
Diffractometer	Rigaku R-AXIS RAPID diffractometer
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995)
T_min, T_max	0.758, 0.885
No. of measured, independent and observed [I > 2σ(I)] reflections	14264, 3376, 2974
R_int	0.026
(sin θ/λ)_max (Å⁻¹)	0.648

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.026, 0.059, 1.00
No. of reflections	3376
No. of parameters	182
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.30, −0.32

Computer programs: PROCESS-AUTO (Rigaku/MSC, 2006), CrystalStructure (Rigaku/MSC, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2A—H104···N3B	0.85	1.99	2.8113 (18)	160.8
O1A—H102···S1B	0.87	2.39	3.2563 (14)	172.4
O2B—H201···S1Bⁱ	0.86	2.45	3.2962 (12)	168.9
O2B—H202···N2Bⁱⁱ	0.86	1.95	2.8024 (18)	169.5
N1A—H1A2···S1Bⁱⁱⁱ	0.86	2.57	3.4081 (16)	164.6
N1B—H1B2···S1A^iv	0.86	2.43	3.2589 (17)	160.9

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

References

Deng, Q.-J., Yao, M.-X. & Zeng, M.-H. (2005). Acta Cryst. E61, o2239–o2240. Web of Science CSD CrossRef IUCr Journals Google Scholar
Downie, T. C., Harrison, W., Raper, E. S. & Hepworth, M. A. (1971). Acta Cryst. B61, 1584–1590. Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838. CrossRef CAS IUCr Journals Google Scholar
Higashi, T. (1995). ABSCOR. Rigaku Corporation, Tokyo, Japan. Google Scholar
John, S. (1962). US Patent 3033901. Google Scholar
John, S. & Gilmer, T. W. (1960). US Patent 2966495. Google Scholar
Ma, C., Sun, J., Zheng, R. & Wang, D. (2007). Organomet. Chem. 692, 4029–4042. CrossRef CAS Google Scholar
Rigaku/MSC (2006). PROCESS-AUTO. Rigaku/MSC, The Woodlands, Texas, USA. Google Scholar
Rigaku/MSC. (2007). CrystalStructure. Rigaku/MSC, The Woodlands, Texas, USA. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar

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Volume 66| Part 1| January 2010| Page m20

doi:10.1107/S1600536809051897

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