Bis(tetra­methyl­ammonium) thio­sulfate tetra­hydrate

Yang, Y.-X.; Ng, S.W.

doi:10.1107/S1600536811021672

organic compounds

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ISSN: 2056-9890

Volume 67| Part 7| July 2011| Page o1664

doi:10.1107/S1600536811021672

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Bis(tetramethylammonium) thiosulfate tetrahydrate

Yun-Xia Yang ^a and Seik Weng Ng ^b ^*

^aKey Laboratory of Polymer Materials of Gansu Province, Ministry of Education, College of Chemistry and Chemical Engineering, Northwest Normal University, Lanzhou 730070, Gansu, People's Republic of China, and ^bDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
^*Correspondence e-mail: seikweng@um.edu.my

(Received 5 June 2011; accepted 6 June 2011; online 18 June 2011)

The anion of the title salt, 2C₄H₁₂N⁺·S₂O₃²⁻·4H₂O, possesses approximate C_3v symmetry. The water molecules themselves engage in hydrogen bonding, forming a ribbon running along the a axis; adjacent chains are linked to the thiosulfate anions by hydrogen bonds, forming a three-dimensional network. The cavities in the network are occupied by the tetramethylammonium counter ions.

Related literature

For tetraethylammonium thiosulfate dihydrate, see: Leyten et al. (1988 ).

Experimental

Crystal data

2C₄H₁₂N⁺·S₂O₃²⁻·4H₂O
M_r = 332.48
Monoclinic, P 2₁ /n
a = 8.1869 (1) Å
b = 15.4342 (2) Å
c = 14.0867 (2) Å
β = 94.074 (1)°
V = 1775.47 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.33 mm⁻¹
T = 130 K
0.25 × 0.20 × 0.15 mm

Data collection

Bruker SMART APEX diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.923, T_max = 0.953
11725 measured reflections
4080 independent reflections
3531 reflections with I > 2σ(I)
R_int = 0.019

Refinement

R[F² > 2σ(F²)] = 0.045
wR(F²) = 0.127
S = 1.02
4080 reflections
204 parameters
12 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.74 e Å⁻³
Δρ_min = −0.26 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1W—H11⋯O1	0.83 (1)	1.88 (1)	2.706 (3)	174 (3)
O1W—H12⋯O3W	0.84 (2)	1.92 (2)	2.758 (2)	178 (1)
O2W—H21⋯O1W	0.84 (2)	1.86 (2)	2.689 (2)	172 (2)
O2W—H22⋯O4W	0.84 (2)	1.90 (3)	2.736 (2)	173 (3)
O3W—H31⋯O2ⁱ	0.83 (2)	1.93 (2)	2.759 (2)	172 (2)
O3W—H32⋯O2Wⁱⁱ	0.84 (2)	1.88 (2)	2.713 (2)	173 (2)
O4W—H41⋯S2ⁱⁱⁱ	0.83 (2)	2.51 (2)	3.3280 (19)	170 (2)
O4W—H42⋯O3Wⁱⁱⁱ	0.83 (2)	1.93 (2)	2.760 (2)	179 (2)
Symmetry codes: (i) $[-x+{\script{3\over 2}}, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (ii) -x+1, -y+2, -z+1; (iii) x-1, y, z.

Data collection: APEX2 (Bruker, 2007 ); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001 ); software used to prepare material for publication: publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811021672/xu5240sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811021672/xu5240Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811021672/xu5240Isup3.cml

checkCIF report

Comment top

The thiosulfate anion of tetramethylammonium thiosulfate tetrahydrate (Scheme I, Fig. 1) resulted from the decomposition of 1,2-hydrazinedicarbothioamide under basic conditions. The anion of the salt, tetramethylammonium thiosulfate tetrahydrate, possesses approximate C_3v symmetry. The four water molecules themselves engage in hydrogen bonding to form a ribbon running along the a-axis of the monoclinic unit cell; adjacent chains are linked to the thiosulfate anion by hydrogen bonds to form a three-dimensional network. The cavities in the network are occupied by the ammonium counterions. Tetraethylammonium thiosulfate exists as a dihydrate; in this salt, the sulfur-sulfur bond is 2.028 (1) Å (Leyten et al., 1988).

Related literature top

For tetraethylammonium thiosulfate dihydrate, see: Leyten et al. (1988).

Experimental top

1,2-Hydrazinedicarbothioamide (0.25 mmol, 0.038 g) was dissolved in tetramethylammonium hydroxide (25% aqueous solution) in a 1:2 molar ratio. A small quantity of water-ethanol (1:2) was added to dissolve the reactants completely. The mixture was set aside for the growth of colorless crystals, which separated after several days.

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

	Fig. 1. Thermal ellipsoid plot (Barbour, 2001) of 2(CH₃)₄N⁺ S₂O₃^2-.4H₂O at the 70% probability level; hydrogen atoms are drawn as spheres of arbitrary radius.
	Fig. 2. Ribbon motif arising from hydrogen bonds involving water molecules.

Bis(tetramethylammonium) thiosulfate tetrahydrate top

Crystal data top

2C₄H₁₂N⁺·S₂O₃²⁻·4H₂O	F(000) = 728
M_r = 332.48	D_x = 1.244 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 5675 reflections
a = 8.1869 (1) Å	θ = 2.8–27.6°
b = 15.4342 (2) Å	µ = 0.33 mm⁻¹
c = 14.0867 (2) Å	T = 130 K
β = 94.074 (1)°	Block, colorless
V = 1775.47 (4) Å³	0.25 × 0.20 × 0.15 mm
Z = 4

Data collection top

Bruker SMART APEX diffractometer	4080 independent reflections
Radiation source: fine-focus sealed tube	3531 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.019
ω scans	θ_max = 27.6°, θ_min = 2.0°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −10→10
T_min = 0.923, T_max = 0.953	k = −20→20
11725 measured reflections	l = −18→12

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)] = 0.045	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.127	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	w = 1/[σ²(F_o²) + (0.0501P)² + 2.4726P] where P = (F_o² + 2F_c²)/3
4080 reflections	(Δ/σ)_max = 0.001
204 parameters	Δρ_max = 0.74 e Å⁻³
12 restraints	Δρ_min = −0.26 e Å⁻³

Crystal data top

2C₄H₁₂N⁺·S₂O₃²⁻·4H₂O	V = 1775.47 (4) Å³
M_r = 332.48	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 8.1869 (1) Å	µ = 0.33 mm⁻¹
b = 15.4342 (2) Å	T = 130 K
c = 14.0867 (2) Å	0.25 × 0.20 × 0.15 mm
β = 94.074 (1)°

Data collection top

Bruker SMART APEX diffractometer	4080 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	3531 reflections with I > 2σ(I)
T_min = 0.923, T_max = 0.953	R_int = 0.019
11725 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.045	12 restraints
wR(F²) = 0.127	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	Δρ_max = 0.74 e Å⁻³
4080 reflections	Δρ_min = −0.26 e Å⁻³
204 parameters

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

	x	y	z	U_iso*/U_eq
S1	0.69577 (6)	0.66503 (3)	0.67106 (3)	0.02068 (13)
S2	0.83493 (9)	0.67111 (4)	0.56042 (5)	0.04154 (18)
O1	0.5466 (2)	0.71568 (13)	0.64692 (18)	0.0556 (6)
O2	0.6474 (3)	0.57509 (11)	0.68608 (12)	0.0437 (5)
O3	0.7837 (3)	0.70123 (13)	0.75481 (13)	0.0495 (5)
O1W	0.4917 (2)	0.88844 (12)	0.63615 (14)	0.0384 (4)
O2W	0.2208 (2)	0.92082 (12)	0.52239 (12)	0.0346 (4)
O3W	0.7668 (2)	0.99207 (10)	0.64424 (12)	0.0322 (4)
O4W	−0.0083 (2)	0.85939 (12)	0.63760 (13)	0.0353 (4)
N1	0.7309 (2)	0.37242 (11)	0.56622 (11)	0.0223 (3)
N2	1.2319 (2)	0.64015 (13)	0.83568 (12)	0.0277 (4)
C1	0.7226 (3)	0.43773 (15)	0.48818 (16)	0.0361 (5)
H1A	0.7122	0.4958	0.5152	0.054*
H1B	0.6274	0.4257	0.4440	0.054*
H1C	0.8226	0.4346	0.4540	0.054*
C2	0.8740 (3)	0.39114 (17)	0.63428 (16)	0.0344 (5)
H2A	0.8628	0.4494	0.6608	0.052*
H2B	0.9749	0.3880	0.6010	0.052*
H2C	0.8785	0.3484	0.6859	0.052*
C3	0.5774 (3)	0.37662 (15)	0.61729 (16)	0.0301 (5)
H3A	0.5661	0.4346	0.6444	0.045*
H3B	0.5823	0.3335	0.6685	0.045*
H3C	0.4831	0.3645	0.5725	0.045*
C4	0.7481 (3)	0.28336 (14)	0.52585 (16)	0.0309 (5)
H4A	0.6541	0.2711	0.4808	0.046*
H4B	0.7520	0.2407	0.5775	0.046*
H4C	0.8492	0.2800	0.4928	0.046*
C5	1.2059 (4)	0.5696 (2)	0.76359 (19)	0.0487 (7)
H5A	1.2113	0.5132	0.7957	0.073*
H5B	1.2911	0.5727	0.7183	0.073*
H5C	1.0981	0.5766	0.7295	0.073*
C6	1.2232 (3)	0.72610 (19)	0.7873 (2)	0.0452 (7)
H6A	1.1151	0.7332	0.7536	0.068*
H6B	1.3079	0.7295	0.7417	0.068*
H6C	1.2407	0.7721	0.8349	0.068*
C7	1.3963 (3)	0.62940 (17)	0.88745 (16)	0.0337 (5)
H7A	1.4021	0.5728	0.9189	0.051*
H7B	1.4132	0.6753	0.9353	0.051*
H7C	1.4815	0.6331	0.8421	0.051*
C8	1.1031 (3)	0.63532 (18)	0.90535 (17)	0.0374 (5)
H8A	1.1080	0.5786	0.9368	0.056*
H8B	0.9950	0.6431	0.8719	0.056*
H8C	1.1217	0.6811	0.9532	0.056*
H11	0.515 (3)	0.8363 (7)	0.641 (2)	0.036 (8)*
H12	0.576 (2)	0.9191 (13)	0.638 (2)	0.058 (10)*
H21	0.3104 (18)	0.912 (2)	0.5532 (18)	0.046 (8)*
H22	0.145 (2)	0.903 (3)	0.554 (2)	0.085 (14)*
H31	0.791 (4)	1.0218 (15)	0.6926 (11)	0.049 (9)*
H32	0.768 (5)	1.0224 (17)	0.5952 (11)	0.076 (12)*
H41	−0.053 (3)	0.8120 (9)	0.625 (2)	0.053 (9)*
H42	−0.077 (3)	0.8988 (12)	0.640 (2)	0.055 (10)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0216 (2)	0.0191 (2)	0.0214 (2)	−0.00144 (18)	0.00176 (17)	−0.00134 (17)
S2	0.0512 (4)	0.0395 (3)	0.0368 (3)	−0.0140 (3)	0.0236 (3)	−0.0079 (3)
O1	0.0277 (10)	0.0471 (11)	0.0919 (16)	0.0091 (8)	0.0034 (10)	0.0030 (11)
O2	0.0689 (13)	0.0263 (8)	0.0374 (9)	−0.0122 (8)	0.0146 (9)	0.0000 (7)
O3	0.0599 (13)	0.0547 (12)	0.0332 (9)	−0.0133 (10)	−0.0017 (9)	−0.0143 (8)
O1W	0.0280 (9)	0.0380 (10)	0.0478 (10)	−0.0030 (8)	−0.0066 (7)	0.0038 (8)
O2W	0.0292 (9)	0.0409 (9)	0.0332 (8)	−0.0024 (7)	−0.0026 (7)	0.0054 (7)
O3W	0.0383 (9)	0.0256 (8)	0.0327 (8)	−0.0050 (7)	0.0021 (7)	−0.0009 (7)
O4W	0.0325 (9)	0.0321 (9)	0.0413 (9)	−0.0017 (7)	0.0022 (7)	0.0032 (7)
N1	0.0268 (9)	0.0203 (8)	0.0198 (8)	−0.0010 (7)	0.0009 (6)	−0.0012 (6)
N2	0.0214 (9)	0.0385 (10)	0.0233 (8)	0.0043 (8)	0.0016 (7)	0.0029 (7)
C1	0.0504 (15)	0.0282 (11)	0.0295 (11)	−0.0031 (10)	0.0016 (10)	0.0086 (9)
C2	0.0273 (11)	0.0459 (13)	0.0294 (11)	−0.0015 (10)	−0.0028 (9)	−0.0093 (10)
C3	0.0276 (11)	0.0300 (11)	0.0334 (11)	0.0010 (9)	0.0073 (9)	−0.0009 (9)
C4	0.0390 (13)	0.0214 (10)	0.0326 (11)	−0.0012 (9)	0.0045 (9)	−0.0062 (8)
C5	0.0539 (17)	0.0598 (18)	0.0321 (12)	−0.0035 (14)	0.0000 (11)	−0.0122 (12)
C6	0.0370 (14)	0.0514 (16)	0.0482 (15)	0.0112 (12)	0.0110 (11)	0.0238 (13)
C7	0.0226 (11)	0.0459 (13)	0.0321 (11)	0.0077 (10)	−0.0022 (9)	0.0019 (10)
C8	0.0278 (12)	0.0495 (14)	0.0364 (12)	0.0050 (10)	0.0116 (9)	0.0074 (11)

Geometric parameters (Å, º) top

S1—O3	1.4496 (18)	C1—H1C	0.9800
S1—O2	1.4631 (17)	C2—H2A	0.9800
S1—O1	1.4696 (19)	C2—H2B	0.9800
S1—S2	1.9970 (8)	C2—H2C	0.9800
O1W—H11	0.828 (9)	C3—H3A	0.9800
O1W—H12	0.834 (10)	C3—H3B	0.9800
O2W—H21	0.837 (10)	C3—H3C	0.9800
O2W—H22	0.841 (10)	C4—H4A	0.9800
O3W—H31	0.834 (10)	C4—H4B	0.9800
O3W—H32	0.835 (10)	C4—H4C	0.9800
O4W—H41	0.831 (10)	C5—H5A	0.9800
O4W—H42	0.832 (10)	C5—H5B	0.9800
N1—C2	1.488 (3)	C5—H5C	0.9800
N1—C1	1.489 (3)	C6—H6A	0.9800
N1—C3	1.493 (3)	C6—H6B	0.9800
N1—C4	1.498 (3)	C6—H6C	0.9800
N2—C6	1.490 (3)	C7—H7A	0.9800
N2—C8	1.493 (3)	C7—H7B	0.9800
N2—C7	1.494 (3)	C7—H7C	0.9800
N2—C5	1.494 (3)	C8—H8A	0.9800
C1—H1A	0.9800	C8—H8B	0.9800
C1—H1B	0.9800	C8—H8C	0.9800

O3—S1—O2	111.83 (11)	N1—C3—H3B	109.5
O3—S1—O1	109.87 (13)	H3A—C3—H3B	109.5
O2—S1—O1	108.00 (12)	N1—C3—H3C	109.5
O3—S1—S2	109.83 (9)	H3A—C3—H3C	109.5
O2—S1—S2	109.44 (8)	H3B—C3—H3C	109.5
O1—S1—S2	107.78 (10)	N1—C4—H4A	109.5
H11—O1W—H12	111.2 (16)	N1—C4—H4B	109.5
H21—O2W—H22	108.9 (16)	H4A—C4—H4B	109.5
H31—O3W—H32	110.5 (16)	N1—C4—H4C	109.5
H41—O4W—H42	111.3 (16)	H4A—C4—H4C	109.5
C2—N1—C1	109.68 (18)	H4B—C4—H4C	109.5
C2—N1—C3	109.39 (16)	N2—C5—H5A	109.5
C1—N1—C3	109.27 (17)	N2—C5—H5B	109.5
C2—N1—C4	109.40 (17)	H5A—C5—H5B	109.5
C1—N1—C4	109.96 (16)	N2—C5—H5C	109.5
C3—N1—C4	109.11 (17)	H5A—C5—H5C	109.5
C6—N2—C8	109.37 (19)	H5B—C5—H5C	109.5
C6—N2—C7	109.53 (19)	N2—C6—H6A	109.5
C8—N2—C7	109.12 (17)	N2—C6—H6B	109.5
C6—N2—C5	109.8 (2)	H6A—C6—H6B	109.5
C8—N2—C5	109.7 (2)	N2—C6—H6C	109.5
C7—N2—C5	109.33 (19)	H6A—C6—H6C	109.5
N1—C1—H1A	109.5	H6B—C6—H6C	109.5
N1—C1—H1B	109.5	N2—C7—H7A	109.5
H1A—C1—H1B	109.5	N2—C7—H7B	109.5
N1—C1—H1C	109.5	H7A—C7—H7B	109.5
H1A—C1—H1C	109.5	N2—C7—H7C	109.5
H1B—C1—H1C	109.5	H7A—C7—H7C	109.5
N1—C2—H2A	109.5	H7B—C7—H7C	109.5
N1—C2—H2B	109.5	N2—C8—H8A	109.5
H2A—C2—H2B	109.5	N2—C8—H8B	109.5
N1—C2—H2C	109.5	H8A—C8—H8B	109.5
H2A—C2—H2C	109.5	N2—C8—H8C	109.5
H2B—C2—H2C	109.5	H8A—C8—H8C	109.5
N1—C3—H3A	109.5	H8B—C8—H8C	109.5

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H11···O1	0.83 (1)	1.88 (1)	2.706 (3)	174 (3)
O1W—H12···O3W	0.84 (2)	1.92 (2)	2.758 (2)	178 (1)
O2W—H21···O1W	0.84 (2)	1.86 (2)	2.689 (2)	172 (2)
O2W—H22···O4W	0.84 (2)	1.90 (3)	2.736 (2)	173 (3)
O3W—H31···O2ⁱ	0.83 (2)	1.93 (2)	2.759 (2)	172 (2)
O3W—H32···O2Wⁱⁱ	0.84 (2)	1.88 (2)	2.713 (2)	173 (2)
O4W—H41···S2ⁱⁱⁱ	0.83 (2)	2.51 (2)	3.3280 (19)	170 (2)
O4W—H42···O3Wⁱⁱⁱ	0.83 (2)	1.93 (2)	2.760 (2)	179 (2)

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

Experimental details

Crystal data
Chemical formula	2C₄H₁₂N⁺·S₂O₃²⁻·4H₂O
M_r	332.48
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	130
a, b, c (Å)	8.1869 (1), 15.4342 (2), 14.0867 (2)
β (°)	94.074 (1)
V (Å³)	1775.47 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.33
Crystal size (mm)	0.25 × 0.20 × 0.15

Data collection
Diffractometer	Bruker SMART APEX diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.923, 0.953
No. of measured, independent and observed [I > 2σ(I)] reflections	11725, 4080, 3531
R_int	0.019
(sin θ/λ)_max (Å⁻¹)	0.651

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.045, 0.127, 1.02
No. of reflections	4080
No. of parameters	204
No. of restraints	12
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.74, −0.26

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001), publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H11···O1	0.829 (12)	1.881 (11)	2.706 (3)	174 (3)
O1W—H12···O3W	0.836 (18)	1.923 (18)	2.758 (2)	178.4 (14)
O2W—H21···O1W	0.837 (19)	1.86 (2)	2.689 (2)	172 (2)
O2W—H22···O4W	0.84 (2)	1.90 (3)	2.736 (2)	173 (3)
O3W—H31···O2ⁱ	0.833 (19)	1.931 (18)	2.759 (2)	172 (2)
O3W—H32···O2Wⁱⁱ	0.84 (2)	1.882 (19)	2.713 (2)	173 (2)
O4W—H41···S2ⁱⁱⁱ	0.831 (17)	2.506 (18)	3.3280 (19)	170 (2)
O4W—H42···O3Wⁱⁱⁱ	0.83 (2)	1.93 (2)	2.760 (2)	179 (2)

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

Acknowledgements

We thank Northwest Normal University, China, and the University of Malaya for supporting this study.

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