Trilithium thio­arsenate octa­hydrate

Mereiter, K.

doi:10.1107/S1600536813010921

inorganic compounds

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ISSN: 2056-9890

Volume 69| Part 5| May 2013| Pages i30-i31

https://doi.org/10.1107/S1600536813010921

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Trilithium thioarsenate octahydrate

Kurt Mereiter ^a ^*

^aInstitute of Chemical Technology and Analytics, Vienna University of Technology, Getreidemarkt 9/164SC, A-1060 Vienna, Austria
^*Correspondence e-mail: kurt.mereiter@tuwien.ac.at

(Received 19 April 2013; accepted 22 April 2013; online 27 April 2013)

The title compound, Li₃AsS₄·8H₂O, is built up from infinite cationic [Li₃(H₂O)₈]³⁺ chains which extend along [001] and are cross-linked by isolated tetrahedral AsS₄³⁻ anions via O—H⋯S hydrogen bonds. Two Li and two As atoms lie on special positions with site symmetries -1 (1 × Li) and 2 (1 × Li and 2 × As). The [Li₃(H₂O)₈]³⁺ chain contains four independent Li atoms of which two are in octahedral and two in tetrahedral coordination by water O atoms. An outstanding feature of this chain is a linear group of three edge-sharing LiO₆ octahedra to both ends of which two LiO₄ tetrahedra are attached by face-sharing. Such groups of composition Li₅O₁₆ are linked into branched chains by means of a further LiO₄ tetrahedron sharing vertices with four adjacent LiO₆ octahedra. The Li—O bonds range from 1.876 (5) to 2.054 (6) Å for the LiO₄ tetrahedra and from 2.026 (5) to 2.319 (5) Å for the LiO₆ octahedra. The two independent AsS₄³⁻ anions have As—S bond lengths ranging from 2.1482 (6) to 2.1677 (6) Å [<As—S> = 2.161 (10) Å]. The eight independent water molecules of the structure donate 16 relatively straight O—H⋯S hydrogen bonds to all S atoms of the AsS₄ tetrahedra [<O⋯S> = 3.295 (92) Å]. Seven water molecules are in distorted tetrahedral coordination by two Li and two S; one water molecule has a flat pyramidal coordination by one Li and two S. At variance with related compounds like Schlippe's salt, Na₃SbS₄·9H₂O, there are neither alkali–sulfur bonds nor O—H⋯O hydrogen bonds in the structure.

Related literature

For crystal structures of related chalcogenosalt hydrates based on isolated tetrahedral XY₄ anions, see: Mereiter et al. (1979 , 1982 , 1983 ); Krebs et al. (1990 ); Krebs & Jacobsen (1976 ); Krebs & Huerter (1980 ); Schiwy et al. (1973 ); Melullis & Dehnen (2007 ), Ruzin et al. (2006 , 2008 ). For the prototype compound Schlippe's Salt, Na₃SbS₄·9H₂O, see: Schlippe (1821 ). For the synthesis of the title compound and early crystallographic data, see: Rémy & Bachet (1968 ). For the synthesis and crystal structure of Ba₃(AsS₄)₂·7H₂O as a precursor of the title compound, see: Mereiter & Preisinger (1992 ). For the crystal structure of Na₂S·9H₂O, see: Preisinger et al. (1982 ). For a review on O—H⋯S hydrogen bonds in salt hydrates, see: Mikenda et al. (1989 ).

Experimental

Crystal data

Li₃AsS₄·8H₂O
M_r = 368.11
Monoclinic, P 2/c
a = 10.036 (2) Å
b = 10.064 (2) Å
c = 14.264 (3) Å
β = 107.30 (1)°
V = 1375.5 (5) Å³
Z = 4
Mo Kα radiation
μ = 3.09 mm⁻¹
T = 297 K
0.30 × 0.27 × 0.25 mm

Data collection

Philips PW1100 four-circle diffractometer
Absorption correction: for a sphere μR = 0.45 T_min = 0.51, T_max = 0.54
5729 measured reflections
4001 independent reflections
2913 reflections with I > 2σ(I)
R_int = 0.026
3 standard reflections every 60 min intensity decay: 2.0%

Refinement

R[F² > 2σ(F²)] = 0.028
wR(F²) = 0.057
S = 1.05
4001 reflections
181 parameters
H-atom parameters constrained
Δρ_max = 0.61 e Å⁻³
Δρ_min = −0.36 e Å⁻³

Table 1
Selected bond lengths (Å)

Li1—O2	2.130 (2)
Li1—O1	2.203 (2)
Li1—O3	2.274 (2)
Li2—O3	2.026 (4)
Li2—O2	2.127 (5)
Li2—O5	2.202 (4)
Li2—O4	2.225 (5)
Li2—O6	2.271 (5)
Li2—O7	2.319 (5)
Li3—O4	1.991 (3)
Li3—O1	2.009 (4)
Li4—O8	1.876 (5)
Li4—O5	1.957 (5)
Li4—O6	1.990 (6)
Li4—O7	2.054 (6)
As1—S2	2.1482 (6)
As1—S1	2.1711 (6)
As2—S4	2.1574 (6)
As2—S3	2.1677 (6)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1A⋯S1ⁱ	0.80	2.49	3.262 (2)	163
O1—H1B⋯S4ⁱⁱ	0.80	2.51	3.287 (2)	163
O2—H2A⋯S1ⁱⁱⁱ	0.80	2.76	3.531 (2)	162
O2—H2B⋯S2	0.80	2.37	3.167 (2)	173
O3—H3A⋯S3^iv	0.80	2.61	3.400 (2)	168
O3—H3B⋯S4	0.80	2.39	3.190 (2)	173
O4—H4A⋯S1ⁱⁱⁱ	0.80	2.51	3.240 (2)	153
O4—H4B⋯S3^v	0.80	2.42	3.207 (2)	170
O5—H5A⋯S1	0.80	2.45	3.247 (2)	172
O5—H5B⋯S2ⁱⁱⁱ	0.80	2.50	3.303 (2)	177
O6—H6A⋯S3	0.80	2.57	3.354 (2)	168
O6—H6B⋯S4^iv	0.80	2.54	3.307 (2)	162
O7—H7A⋯S1^vi	0.80	2.49	3.244 (2)	157
O7—H7B⋯S3	0.80	2.58	3.333 (2)	157
O8—H8A⋯S2^vii	0.80	2.50	3.253 (2)	157
O8—H8B⋯S3^vi	0.80	2.61	3.394 (2)	166
Symmetry codes: (i) $[x+1, -y+1, z+{\script{1\over 2}}]$ ; (ii) -x+1, -y+1, -z+1; (iii) -x, -y+1, -z+1; (iv) -x+1, -y+2, -z+1; (v) $[x, -y+2, z+{\script{1\over 2}}]$ ; (vi) $[-x, y, -z+{\script{1\over 2}}]$ ; (vii) x, y+1, z.

Data collection: Philips PW1100 software (Hornstra & Vossers, 1973 ); cell refinement: LLSQ (Mereiter, 1992 ); data reduction: PWD (Mereiter, 1992); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: Mercury (Macrae et al., 2006 ) and DIAMOND (Brandenburg, 2012 ); software used to prepare material for publication: SHELXL97 and publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536813010921/pj2002sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536813010921/pj2002Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S1600536813010921/pj2002Isup3.cml

checkCIF report

Comment top

The title compound, Li₃AsS₄.8H₂O, belongs to a group of alkali chalcogenosalt hydrates with tetrahedral XY₄ anions, X = P(V), As(V), Sb(V), Ge(IV), Sn(IV) and Y = S^2-, Se^2-, Te^2-, of which Schlippe's salt, Na₃SbS₄.9H₂O (Schlippe, 1821; Mereiter et al., 1979) can be considered as the prototype. Other representatives with known crystal structures are Na₃PS₄.8H₂O (Mereiter et al., 1983), Na₃AsS₄.8H₂O (Mereiter et al., 1982), Na₃AsSe₄.9H₂O (Krebs et al., 1990), Na₄SnS₄.14H₂O (Schiwy et al., 1973), Na₄GeSe₄.14H₂O (Krebs & Jacobsen, 1976), Na₄SnSe₄.16H₂O (Krebs & Huerter, 1980), K₄GeSe₄.4H₂O (Melullis & Dehnen, 2007), Rb₄SnTe₄.2H₂O (Ruzin et al., 2006), K₄SnS₄.4H₂O (Ruzin et al., 2008), to mention only some examples.

In context with previous work (Mereiter & Preisinger, 1992) the title compound Li₃AsS₄.8H₂O was prepared and its crystal structure was determined. An early report on the synthesis and crystal data of this compound was given by Rémy & Bachet (1968).

Li₃AsS₄.8H₂O crystallizes in the infrequent centrosymmetric monoclinic space group P2/c (No. 13). The crystal structure contains four independent Li atoms, two independent AsS₄ tetrahedra and eight independent water molecules in the asymmetric unit. Li1 lies on a centre of inversion while Li3, As1, and As2 are located on twofold axes. All other constituents comprising Li2 and Li4, four S, and eight H₂O are in general position. A view of a characteristic part of the crystal structure containing all constituents is shown in Fig. 1. All lithium atoms are exclusively coordinated by the oxygen atoms of the water molecules but not by any sulfur atom. Li1 and Li2 form Li(H₂O)₆ octahedra while Li3 and Li4 form Li(H₂O)₄ tetrahedra. The Li1(H₂O)₆ octahedron shares edges with two adjacent Li2(H₂O)₆ octahedra, and they in turn share faces with two Li4(H₂O)₄ tetrahedra. This gives rise to characteristic polyhedral pentamers Li₅(H₂O)₁₆ which are linked by the Li3(H₂O)₄ tetrahedra via vertex sharing with four adjacent Li(H₂O)₆ octahedra to form infinite branched chains of the composition Li₆(H₂O)₁₆ or Li₃(H₂O)₈ (Figs. 2 and 3). The chains extend along [001] and have the Li₅(H₂O)₁₆ fragments oriented in a criss-cross fashion (Figs. 3 and 4). Embedded between the chains are the tetrahedral AsS₄^3- anions, which are are anchored exclusively by O—H···S type hydrogen bonds donated by the water molecules. The sulfur atoms receive either three (S2, S4) or five (S1, S3) hydrogen bonds so that each AsS₄^3- anion receives 16 hydrogen bonds of which 8 are symmetry redundant. The eight different water molecules of the structure have mainly distorted tetrahedral coordination environments by two Li cations and two S atoms as hydrogen bond acceptors. Only the water molecule H₂O8 differs from this behaviour by being bonded to only one Li and two S atoms within a distorted trigonal pyramidal coordination.

The Li—O bonds range from 2.026 (5) to 2.319 (5) Å for the LiO₆ octahedra and from 1.876 (5) to 2.054 (6) Å for the LiO₄ tetrahedra (Table 1). The mean Li—O bond lengths are 2.202 (65), 2.195 (105), 2.000 (10) and 1.969 (74) Å for Li1 through Li4. The coordination figures of Li1 and Li3 are relatively regular (O—Li—O bond angles for Li1O₆ 81.84 (6)–98.16 (6)° and 180°, for Li3O₄ 101.7 (2)–114.3 (3)°) while those of Li2 and Li4 are notably distorted due to the face-sharing link between them (O—Li—O bond angles for Li2O₆ 72.7 (2)–100.6 (2)° and 167.3 (2)–174.8 (3)°, for Li4O₄ 84.6 (2)–129.8 (2)°; Li2···Li4 = 2.698 (7) Å). The two independent AsS₄^3- anions have As—S bond distances from 2.1482 (6) to 2.1677 (6) Å, <As—S> = 2.161 (10) Å. The two shorter As—S bonds in each tetrahedron are to sulfur atoms receiving three hydrogen bonds (S2, S4) while the longer As—S bonds are to sulfur atoms receiving five hydrogen bonds (S1, S3). The As—S bond lengths and the S—As—S bond angles (106.72 (3)–111.42 (2) and 106.15 (2)–112.69 (2)° for As1 and As2, respectively) show that the two tetrahedra are relatively regular. They agree in their dimensions with related thioarsenates (Mereiter et al., 1982; Mereiter & Preisinger, 1992). The eight independent water molecules of the structure donate 16 relatively straight O—H···S hydrogen bonds to all S atoms of the AsS₄ tetrahedra, O···S = 3.167 (2) – 3.531 (2) Å, <O···S> = 3.295 (92) Å and O—H···S = 153–177° (Table 2; Figs. 2 and 3). These dimensions fit well into the pattern of O—H···S hydrogen bonds in sulfosalt hydrates reported by Mikenda et al. (1989).

The structure of title compound Li₃AsS₄.8H₂O adds a new facet to the very diverse structural chemistry of the chalcogenosalt hydrates with tetrahedral XY₄ anions defined above. The two isochemical relatives of the title compound, Na₃PS₄.8H₂O (Mereiter et al., 1983) and Na₃AsS₄.8H₂O (Mereiter et al., 1982), represent an isostructural pair built up from NaS₂(H₂O)₄, NaS(H₂O)₅ and Na(H₂O)₆ octahedra which form together with the PS₄/AsS₄ tetrahedra undulating layers. The PS₄/AsS₄ tetrahedron is linked with three S atoms to the Na cations. The water molecules are mostly bonded to two Na and donate pairs of O—H···S hydrogen bonds. One water molecule is bonded to only one Na and accepts in compensation an O—H···O hydrogen bond. Schlippe's salt, Na₃SbS₄.9H₂O (Mereiter et al., 1979) and the isostructural selenoarsenate (Krebs et al., 1990) contain per formula unit one water more than the title compound. They are built up from tripledeckers of facesharing octahedra - namely a Na(H₂O)₆ octahedron which shares two opposite faces with a Na(H₂O)₆ and a NaS₃(H₂O)₃ octahedron. The tetrahedral SbS₄ anion is bonded with three S atoms to three tripledeckers and links them into a complicated framework of cubic symmetry. Here again only one S atom is not cation-bonded and the structure contains independent five O—H···S and one O—H···O bonds. The compounds Na₄SnS₄.14H₂O (Schiwy et al., 1973), Na₄GeSe₄.14H₂O (Krebs & Jacobsen, 1976), and Na₄SnSe₄.16H₂O (Krebs & Huerter, 1980) can be seen as variants of the Na-water triple deckers in Schlippe's salt and only in Na₄SnSe₄.16H₂O these triple deckers form Na—H₂O polymers without any Na-chalcogen bonds. Alkali sulfosalts with cations larger than Na – e.g. K₄GeSe₄.4H₂O (Melullis & Dehnen, 2007), Rb₄SnTe₄.2H₂O (Ruzin et al., 2006), or K₄SnS₄.4H₂O (Ruzin et al., 2008) – contain less water per cation and adopt alkali-water structures with higher coordination numbers than 6 for the cation sites and they involve therefore increasingly alkali-chalcogen bonds. Although not a sulfo-salt, Na₂S.9H₂O may be mentioned here for comparison with Li₃AsS₄.8H₂O because it is built up from octahedral chains Na(H₂O)₅ (corner-sharing spiral chains) and Na(H₂O)₄ (edge-sharing spiral chains) held together by isolated sulfide ions via many O—H···S bonds and by some O—H···O bonds (Preisinger et al., 1982).

Related literature top

For crystal structures of related chalcogenosalt hydrates based on isolated tetrahedral XY₄ anions, see: Mereiter et al. (1979, 1982, 1983); Krebs et al. (1990); Krebs & Jacobsen (1976); Krebs & Huerter (1980); Schiwy et al. (1973); Melullis & Dehnen (2007), Ruzin et al. (2006, 2008). For the prototype compound Schlippe's Salt, Na₃SbS₄.9H₂O, see: Schlippe (1821). For the synthesis of the title compound and early crystallographic data, see: Rémy & Bachet (1968). For the synthesis and crystal structure of Ba₃(AsS₄)₂.7H₂O as a precursor of the title compound, see: Mereiter & Preisinger (1992). For the crystal structure of Na₂S.9H₂O, see: Preisinger et al. (1982). For a review on O—H···S hydrogen bonds in salt hydrates, see: Mikenda et al. (1989).

Experimental top

The title compound was prepared by mixing dilute aqueous solutions of Ba₃(AsS₄)₂.7H₂O (Mereiter & Preisinger, 1992) and Li₂SO₄.H₂O in stoichiometric amounts. After removing BaSO₄ by filtration, the solution was preconcentrated in a rotavapor under reduced pressure and then filtered. Crystallization by room temperature evaporation in an exsiccator over conc. H₂SO₄ as desiccant gave the desired Li₃AsS₄.8H₂O in the form of colourless prisms. For structure analysis, a fragment was rounded to an oval by turning it on wet filter paper. Another preparation method for Li₃AsS₄.8H₂O was reported by Rémy & Bachet (1968).

Structure description top

For crystal structures of related chalcogenosalt hydrates based on isolated tetrahedral XY₄ anions, see: Mereiter et al. (1979, 1982, 1983); Krebs et al. (1990); Krebs & Jacobsen (1976); Krebs & Huerter (1980); Schiwy et al. (1973); Melullis & Dehnen (2007), Ruzin et al. (2006, 2008). For the prototype compound Schlippe's Salt, Na₃SbS₄.9H₂O, see: Schlippe (1821). For the synthesis of the title compound and early crystallographic data, see: Rémy & Bachet (1968). For the synthesis and crystal structure of Ba₃(AsS₄)₂.7H₂O as a precursor of the title compound, see: Mereiter & Preisinger (1992). For the crystal structure of Na₂S.9H₂O, see: Preisinger et al. (1982). For a review on O—H···S hydrogen bonds in salt hydrates, see: Mikenda et al. (1989).

Computing details top

Data collection: Philips PW1100 software (Hornstra & Vossers, 1973); cell refinement: LLSQ (Mereiter, 1992); data reduction: PWD (Mereiter, 1992); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: Mercury (Macrae et al., 2006) and DIAMOND (Brandenburg, 2012); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and publCIF (Westrip, 2010).

Figures top

	Fig. 1. A respresentative part of the structure of Li₃AsS₄.8H₂O with displacement ellipsoids for the non-hydrogen atoms drawn at the 50% probability level. Symmetry codes are given on the lower right. Hydrogen bonds in this assembly are shown as dashed lines.
	Fig. 2. A packing diagram of Li₃AsS₄.8H₂O viewed along the b-axis showing also the hydrogen bonds. Only the label numbers are given for As, S, and O atoms.
	Fig. 3. A packing diagram of Li₃AsS₄.8H₂O viewed approximately along to [110] showing also the hydrogen bonds. Only the label numbers are given for As, S, and O atoms.
	Fig. 4. View of the structure of Li₃AsS₄.8H₂O along [001]. H-atoms omitted for clarity. Li3, As1 and As2 lie on twofold axes parallel [010], and Li1 on 1 at x,y,z = 1/2,1/2,1/2.

Trilithium thioarsenate octahydrate top

Crystal data top

Li₃AsS₄·8H₂O	F(000) = 744
M_r = 368.11	D_x = 1.778 Mg m⁻³
Monoclinic, P2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yc	Cell parameters from 34 reflections
a = 10.036 (2) Å	θ = 9.1–26.2°
b = 10.064 (2) Å	µ = 3.09 mm⁻¹
c = 14.264 (3) Å	T = 297 K
β = 107.30 (1)°	Oval, colourless
V = 1375.5 (5) Å³	0.30 × 0.27 × 0.25 mm
Z = 4

Data collection top

Philips PW1100 four-circle diffractometer	2913 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.026
Graphite monochromator	θ_max = 30.0°, θ_min = 2.0°
ω–2θ scans	h = −14→13
Absorption correction: for a sphere µR = 0.45	k = −14→14
T_min = 0.51, T_max = 0.54	l = 0→20
5729 measured reflections	3 standard reflections every 60 min
4001 independent reflections	intensity decay: 2.0%

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)] = 0.028	H-atom parameters constrained
wR(F²) = 0.057	w = 1/[σ²(F_o²) + (0.0179P)² + 0.5909P] where P = (F_o² + 2F_c²)/3
S = 1.05	(Δ/σ)_max = 0.001
4001 reflections	Δρ_max = 0.61 e Å⁻³
181 parameters	Δρ_min = −0.36 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0081 (3)

Crystal data top

Li₃AsS₄·8H₂O	V = 1375.5 (5) Å³
M_r = 368.11	Z = 4
Monoclinic, P2/c	Mo Kα radiation
a = 10.036 (2) Å	µ = 3.09 mm⁻¹
b = 10.064 (2) Å	T = 297 K
c = 14.264 (3) Å	0.30 × 0.27 × 0.25 mm
β = 107.30 (1)°

Data collection top

Philips PW1100 four-circle diffractometer	2913 reflections with I > 2σ(I)
Absorption correction: for a sphere µR = 0.45	R_int = 0.026
T_min = 0.51, T_max = 0.54	3 standard reflections every 60 min
5729 measured reflections	intensity decay: 2.0%
4001 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.028	0 restraints
wR(F²) = 0.057	H-atom parameters constrained
S = 1.05	Δρ_max = 0.61 e Å⁻³
4001 reflections	Δρ_min = −0.36 e Å⁻³
181 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
Li1	0.5000	0.5000	0.5000	0.0393 (13)
Li2	0.2821 (4)	0.7213 (4)	0.5102 (4)	0.0443 (10)
Li3	0.5000	0.5984 (5)	0.7500	0.0311 (11)
Li4	0.0724 (5)	0.8832 (5)	0.4126 (5)	0.0610 (14)
As1	0.0000	0.40273 (3)	0.2500	0.01865 (8)
As2	0.5000	0.91402 (2)	0.2500	0.01887 (8)
S1	−0.12581 (5)	0.53147 (5)	0.31185 (4)	0.02508 (11)
S2	0.13565 (5)	0.27910 (5)	0.36066 (4)	0.02849 (12)
S3	0.37068 (5)	1.03848 (5)	0.31147 (4)	0.02615 (12)
S4	0.64151 (6)	0.79087 (5)	0.35891 (4)	0.02873 (12)
O1	0.55849 (15)	0.47247 (15)	0.66032 (12)	0.0297 (3)
H1A	0.6400	0.4629	0.6874	0.054 (6)*
H1B	0.5239	0.4023	0.6655	0.054 (6)*
O2	0.28906 (17)	0.51048 (16)	0.50233 (12)	0.0330 (3)
H2A	0.2693	0.4923	0.5512	0.068 (8)*
H2B	0.2494	0.4564	0.4627	0.068 (8)*
O3	0.48739 (17)	0.72351 (17)	0.51911 (12)	0.0359 (4)
H3A	0.5233	0.7696	0.5654	0.077 (8)*
H3B	0.5211	0.7466	0.4775	0.077 (8)*
O4	0.33730 (16)	0.70514 (14)	0.67279 (12)	0.0303 (3)
H4A	0.2703	0.6689	0.6804	0.051 (6)*
H4B	0.3423	0.7745	0.7010	0.051 (6)*
O5	0.05507 (17)	0.72354 (16)	0.48637 (12)	0.0344 (4)
H5A	0.0167	0.6700	0.4459	0.059 (7)*
H5B	0.0110	0.7247	0.5248	0.059 (7)*
O6	0.2558 (2)	0.9454 (2)	0.49965 (14)	0.0486 (5)
H6A	0.2939	0.9720	0.4614	0.107 (11)*
H6B	0.2680	1.0022	0.5406	0.107 (11)*
O7	0.1906 (2)	0.7739 (2)	0.34519 (16)	0.0535 (5)
H7A	0.1517	0.7256	0.3009	0.112 (12)*
H7B	0.2329	0.8251	0.3220	0.112 (12)*
O8	−0.05671 (19)	1.0198 (2)	0.36351 (18)	0.0573 (6)
H8A	−0.0190	1.0806	0.3455	0.102 (11)*
H8B	−0.1288	1.0100	0.3210	0.102 (11)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Li1	0.035 (3)	0.041 (3)	0.041 (3)	0.003 (3)	0.010 (2)	0.012 (3)
Li2	0.035 (2)	0.038 (2)	0.059 (3)	0.0012 (18)	0.013 (2)	0.001 (2)
Li3	0.029 (3)	0.030 (3)	0.032 (3)	0.000	0.006 (2)	0.000
Li4	0.049 (3)	0.046 (2)	0.086 (4)	0.005 (2)	0.017 (3)	0.018 (3)
As1	0.01756 (13)	0.01845 (13)	0.01937 (15)	0.000	0.00463 (11)	0.000
As2	0.02138 (14)	0.01735 (13)	0.01920 (15)	0.000	0.00807 (11)	0.000
S1	0.0240 (2)	0.0256 (2)	0.0277 (3)	0.00128 (18)	0.0108 (2)	−0.0028 (2)
S2	0.0273 (3)	0.0254 (2)	0.0287 (3)	0.0044 (2)	0.0022 (2)	0.0044 (2)
S3	0.0294 (3)	0.0243 (2)	0.0287 (3)	0.00180 (19)	0.0148 (2)	−0.0032 (2)
S4	0.0294 (3)	0.0266 (2)	0.0286 (3)	0.0047 (2)	0.0063 (2)	0.0071 (2)
O1	0.0293 (8)	0.0294 (7)	0.0276 (8)	0.0006 (6)	0.0042 (6)	0.0006 (6)
O2	0.0358 (8)	0.0319 (8)	0.0293 (8)	−0.0075 (7)	0.0066 (7)	−0.0028 (7)
O3	0.0358 (9)	0.0438 (9)	0.0290 (9)	−0.0110 (7)	0.0110 (7)	−0.0023 (8)
O4	0.0314 (8)	0.0250 (7)	0.0365 (9)	−0.0023 (6)	0.0130 (7)	−0.0017 (6)
O5	0.0385 (9)	0.0360 (8)	0.0311 (9)	−0.0074 (7)	0.0140 (7)	−0.0056 (7)
O6	0.0590 (12)	0.0413 (9)	0.0406 (11)	−0.0078 (9)	0.0076 (10)	−0.0058 (9)
O7	0.0693 (14)	0.0463 (11)	0.0568 (13)	−0.0217 (10)	0.0367 (11)	−0.0157 (10)
O8	0.0377 (10)	0.0424 (11)	0.0836 (16)	0.0008 (9)	0.0052 (10)	0.0137 (11)

Geometric parameters (Å, º) top

Li1—O2	2.130 (2)	As1—S1ⁱⁱⁱ	2.1711 (6)
Li1—O2ⁱ	2.130 (2)	As1—S1	2.1711 (6)
Li1—O1	2.203 (2)	As2—S4^iv	2.1574 (6)
Li1—O1ⁱ	2.203 (2)	As2—S4	2.1574 (6)
Li1—O3	2.274 (2)	As2—S3	2.1677 (6)
Li1—O3ⁱ	2.274 (2)	As2—S3^iv	2.1677 (6)
Li2—O3	2.026 (4)	O1—H1A	0.80
Li2—O2	2.127 (5)	O1—H1B	0.80
Li2—O5	2.202 (4)	O2—H2A	0.80
Li2—O4	2.225 (5)	O2—H2B	0.80
Li2—O6	2.271 (5)	O3—H3A	0.80
Li2—O7	2.319 (5)	O3—H3B	0.80
Li3—O4ⁱⁱ	1.991 (3)	O4—H4A	0.80
Li3—O4	1.991 (3)	O4—H4B	0.80
Li3—O1	2.009 (4)	O5—H5A	0.80
Li3—O1ⁱⁱ	2.009 (4)	O5—H5B	0.80
Li4—O8	1.876 (5)	O6—H6A	0.80
Li4—O5	1.957 (5)	O6—H6B	0.80
Li4—O6	1.990 (6)	O7—H7A	0.80
Li4—O7	2.054 (6)	O7—H7B	0.80
As1—S2ⁱⁱⁱ	2.1482 (6)	O8—H8A	0.80
As1—S2	2.1482 (6)	O8—H8B	0.80

O2—Li1—O2ⁱ	180.0	S4—As2—S3	112.69 (2)
O2—Li1—O1ⁱ	92.91 (6)	S4^iv—As2—S3^iv	112.69 (2)
O2ⁱ—Li1—O1ⁱ	87.09 (6)	S4—As2—S3^iv	106.15 (2)
O2—Li1—O1	87.09 (6)	S3—As2—S3^iv	109.40 (3)
O2ⁱ—Li1—O1	92.91 (6)	Li3—O1—Li1	122.93 (10)
O1ⁱ—Li1—O1	180.0	Li3—O1—H1A	102.7
O2—Li1—O3ⁱ	98.16 (6)	Li1—O1—H1A	115.8
O2ⁱ—Li1—O3ⁱ	81.84 (6)	Li3—O1—H1B	106.3
O1ⁱ—Li1—O3ⁱ	90.41 (6)	Li1—O1—H1B	102.6
O1—Li1—O3ⁱ	89.59 (6)	H1A—O1—H1B	105.0
O2—Li1—O3	81.84 (6)	Li2—O2—Li1	95.65 (13)
O2ⁱ—Li1—O3	98.16 (6)	Li2—O2—H2A	99.3
O1ⁱ—Li1—O3	89.59 (6)	Li1—O2—H2A	120.5
O1—Li1—O3	90.41 (6)	Li2—O2—H2B	134.3
O3ⁱ—Li1—O3	180.0	Li1—O2—H2B	104.1
O3—Li2—O2	88.03 (18)	H2A—O2—H2B	105.0
O3—Li2—O5	174.8 (3)	Li2—O3—Li1	94.22 (14)
O2—Li2—O5	92.89 (17)	Li2—O3—H3A	105.0
O3—Li2—O4	90.12 (18)	Li1—O3—H3A	130.2
O2—Li2—O4	88.84 (18)	Li2—O3—H3B	127.1
O5—Li2—O4	94.98 (19)	Li1—O3—H3B	98.5
O3—Li2—O6	95.14 (18)	H3A—O3—H3B	105.0
O2—Li2—O6	172.9 (3)	Li3—O4—Li2	121.68 (14)
O5—Li2—O6	83.40 (16)	Li3—O4—H4A	105.3
O4—Li2—O6	97.45 (19)	Li2—O4—H4A	102.5
O3—Li2—O7	98.6 (2)	Li3—O4—H4B	105.9
O2—Li2—O7	100.6 (2)	Li2—O4—H4B	114.8
O5—Li2—O7	76.20 (15)	H4A—O4—H4B	105.0
O4—Li2—O7	167.3 (2)	Li4—O5—Li2	80.7 (2)
O6—Li2—O7	72.74 (15)	Li4—O5—H5A	105.4
O4ⁱⁱ—Li3—O4	114.7 (3)	Li2—O5—H5A	111.0
O4ⁱⁱ—Li3—O1	110.23 (7)	Li4—O5—H5B	120.8
O4—Li3—O1	109.58 (7)	Li2—O5—H5B	130.7
O4ⁱⁱ—Li3—O1ⁱⁱ	109.58 (7)	H5A—O5—H5B	105.0
O4—Li3—O1ⁱⁱ	110.23 (7)	Li4—O6—Li2	78.26 (19)
O1—Li3—O1ⁱⁱ	101.7 (2)	Li4—O6—H6A	102.8
O8—Li4—O5	129.8 (3)	Li2—O6—H6A	107.9
O8—Li4—O6	114.2 (3)	Li4—O6—H6B	126.3
O5—Li4—O6	97.9 (3)	Li2—O6—H6B	132.2
O8—Li4—O7	130.4 (3)	H6A—O6—H6B	105.0
O5—Li4—O7	88.2 (2)	Li4—O7—Li2	75.9 (2)
O6—Li4—O7	84.6 (2)	Li4—O7—H7A	118.8
S2ⁱⁱⁱ—As1—S2	109.21 (3)	Li2—O7—H7A	128.0
S2ⁱⁱⁱ—As1—S1ⁱⁱⁱ	111.42 (2)	Li4—O7—H7B	107.4
S2—As1—S1ⁱⁱⁱ	109.04 (2)	Li2—O7—H7B	117.9
S2ⁱⁱⁱ—As1—S1	109.04 (2)	H7A—O7—H7B	105.0
S2—As1—S1	111.42 (2)	Li4—O8—H8A	109.9
S1ⁱⁱⁱ—As1—S1	106.72 (3)	Li4—O8—H8B	124.1
S4^iv—As2—S4	109.87 (4)	H8A—O8—H8B	105.0
S4^iv—As2—S3	106.15 (2)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···S1^v	0.80	2.49	3.262 (2)	163
O1—H1B···S4ⁱ	0.80	2.51	3.287 (2)	163
O2—H2A···S1^vi	0.80	2.76	3.531 (2)	162
O2—H2B···S2	0.80	2.37	3.167 (2)	173
O3—H3A···S3^vii	0.80	2.61	3.400 (2)	168
O3—H3B···S4	0.80	2.39	3.190 (2)	173
O4—H4A···S1^vi	0.80	2.51	3.240 (2)	153
O4—H4B···S3^viii	0.80	2.42	3.207 (2)	170
O5—H5A···S1	0.80	2.45	3.247 (2)	172
O5—H5B···S2^vi	0.80	2.50	3.303 (2)	177
O6—H6A···S3	0.80	2.57	3.354 (2)	168
O6—H6B···S4^vii	0.80	2.54	3.307 (2)	162
O7—H7A···S1ⁱⁱⁱ	0.80	2.49	3.244 (2)	157
O7—H7B···S3	0.80	2.58	3.333 (2)	157
O8—H8A···S2^ix	0.80	2.50	3.253 (2)	157
O8—H8B···S3ⁱⁱⁱ	0.80	2.61	3.394 (2)	166

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

Experimental details

Crystal data
Chemical formula	Li₃AsS₄·8H₂O
M_r	368.11
Crystal system, space group	Monoclinic, P2/c
Temperature (K)	297
a, b, c (Å)	10.036 (2), 10.064 (2), 14.264 (3)
β (°)	107.30 (1)
V (Å³)	1375.5 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	3.09
Crystal size (mm)	0.30 × 0.27 × 0.25

Data collection
Diffractometer	Philips PW1100 four-circle
Absorption correction	For a sphere µR = 0.45
T_min, T_max	0.51, 0.54
No. of measured, independent and observed [I > 2σ(I)] reflections	5729, 4001, 2913
R_int	0.026
(sin θ/λ)_max (Å⁻¹)	0.704

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.028, 0.057, 1.05
No. of reflections	4001
No. of parameters	181
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.61, −0.36

Computer programs: Philips PW1100 software (Hornstra & Vossers, 1973), LLSQ (Mereiter, 1992), PWD (Mereiter, 1992), SHELXS97 (Sheldrick, 2008), Mercury (Macrae et al., 2006) and DIAMOND (Brandenburg, 2012), SHELXL97 (Sheldrick, 2008) and publCIF (Westrip, 2010).

Selected bond lengths (Å) top

Li1—O2	2.130 (2)	Li3—O1	2.009 (4)
Li1—O1	2.203 (2)	Li4—O8	1.876 (5)
Li1—O3	2.274 (2)	Li4—O5	1.957 (5)
Li2—O3	2.026 (4)	Li4—O6	1.990 (6)
Li2—O2	2.127 (5)	Li4—O7	2.054 (6)
Li2—O5	2.202 (4)	As1—S2	2.1482 (6)
Li2—O4	2.225 (5)	As1—S1	2.1711 (6)
Li2—O6	2.271 (5)	As2—S4	2.1574 (6)
Li2—O7	2.319 (5)	As2—S3	2.1677 (6)
Li3—O4	1.991 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···S1ⁱ	0.80	2.49	3.262 (2)	162.7
O1—H1B···S4ⁱⁱ	0.80	2.51	3.287 (2)	163.2
O2—H2A···S1ⁱⁱⁱ	0.80	2.76	3.531 (2)	162.3
O2—H2B···S2	0.80	2.37	3.167 (2)	173.4
O3—H3A···S3^iv	0.80	2.61	3.400 (2)	167.5
O3—H3B···S4	0.80	2.39	3.190 (2)	172.5
O4—H4A···S1ⁱⁱⁱ	0.80	2.51	3.240 (2)	153.3
O4—H4B···S3^v	0.80	2.42	3.207 (2)	170.2
O5—H5A···S1	0.80	2.45	3.247 (2)	171.6
O5—H5B···S2ⁱⁱⁱ	0.80	2.50	3.303 (2)	177.2
O6—H6A···S3	0.80	2.57	3.354 (2)	168.0
O6—H6B···S4^iv	0.80	2.54	3.307 (2)	161.7
O7—H7A···S1^vi	0.80	2.49	3.244 (2)	156.5
O7—H7B···S3	0.80	2.58	3.333 (2)	156.9
O8—H8A···S2^vii	0.80	2.50	3.253 (2)	157.4
O8—H8B···S3^vi	0.80	2.61	3.394 (2)	166.3

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

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Volume 69| Part 5| May 2013| Pages i30-i31

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