Trilithium thio­arsenate octa­hydrate

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.

Key indicators

• Single-crystal X-ray study
• T = 297 K
• Mean [sigma](As-S) = 0.001 Å
• R factor = 0.028
• wR factor = 0.057
• Data-to-parameter ratio = 22.1

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT906_ALERT_3_C Large K value in the Analysis of Variance ......      3.471
PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L=  0.600          9
PLAT975_ALERT_2_C Positive Residual Density at 0.86A from O7     .       0.60 eA-3

Alert level G
FORMU01_ALERT_1_G  There is a discrepancy between the atom counts in the
            _chemical_formula_sum and _chemical_formula_moiety. This is
            usually due to the moiety formula being in the wrong format.
            Atom count from _chemical_formula_sum:   H16 As1 Li3 O8 S4
            Atom count from _chemical_formula_moiety:H2 As1 Li3 O1 S4.8
PLAT005_ALERT_5_G No _iucr_refine_instructions_details  in the CIF          ?
PLAT007_ALERT_5_G Note: Number of Unrefined D-H Atoms ............         16
PLAT042_ALERT_1_G Calc. and Reported MoietyFormula Strings  Differ          ?
PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L=  0.600          5

   0 ALERT level A = Most likely a serious problem - resolve or explain
   0 ALERT level B = A potentially serious problem, consider carefully
   3 ALERT level C = Check. Ensure it is not caused by an omission or oversight
   5 ALERT level G = General information/check it is not something unexpected

   2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   1 ALERT type 2 Indicator that the structure model may be wrong or deficient
   2 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion
   2 ALERT type 5 Informative message, check

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S1. Comment

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

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).

S2. Experimental

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).

S3. Refinement

All water molecules were idealized to have O—H = 0.80 Å and H—O—H = 105.0° and were then refined as rigid groups using AFIX 6 of SHELXL97 (Sheldrick, 2008). A common U_iso for the two H-atoms of each water molecule was used and refined.

Computing details

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

	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

Crystal data

Li3AsS4·8H2O	F(000) = 744
Mr = 368.11	Dx = 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) Å^3	0.30 × 0.27 × 0.25 mm
Z = 4

Data collection

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

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.028	H-atom parameters constrained
wR(F^2) = 0.057	w = 1/[σ^2(Fo^2) + (0.0179P)^2 + 0.5909P] where P = (Fo^2 + 2Fc^2)/3
S = 1.05	(Δ/σ)max = 0.001
4001 reflections	Δρmax = 0.61 e Å^−3
181 parameters	Δρmin = −0.36 e Å^−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0081 (3)

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
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 (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

Li1—O2	2.130 (2)	As1—S1^iii	2.1711 (6)
Li1—O2^i	2.130 (2)	As1—S1	2.1711 (6)
Li1—O1	2.203 (2)	As2—S4^iv	2.1574 (6)
Li1—O1^i	2.203 (2)	As2—S4	2.1574 (6)
Li1—O3	2.274 (2)	As2—S3	2.1677 (6)
Li1—O3^i	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—O4^ii	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—O1^ii	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—S2^iii	2.1482 (6)	O8—H8A	0.80
As1—S2	2.1482 (6)	O8—H8B	0.80
O2—Li1—O2^i	180.0	S4—As2—S3	112.69 (2)
O2—Li1—O1^i	92.91 (6)	S4^iv—As2—S3^iv	112.69 (2)
O2^i—Li1—O1^i	87.09 (6)	S4—As2—S3^iv	106.15 (2)
O2—Li1—O1	87.09 (6)	S3—As2—S3^iv	109.40 (3)
O2^i—Li1—O1	92.91 (6)	Li3—O1—Li1	122.93 (10)
O1^i—Li1—O1	180.0	Li3—O1—H1A	102.7
O2—Li1—O3^i	98.16 (6)	Li1—O1—H1A	115.8
O2^i—Li1—O3^i	81.84 (6)	Li3—O1—H1B	106.3
O1^i—Li1—O3^i	90.41 (6)	Li1—O1—H1B	102.6
O1—Li1—O3^i	89.59 (6)	H1A—O1—H1B	105.0
O2—Li1—O3	81.84 (6)	Li2—O2—Li1	95.65 (13)
O2^i—Li1—O3	98.16 (6)	Li2—O2—H2A	99.3
O1^i—Li1—O3	89.59 (6)	Li1—O2—H2A	120.5
O1—Li1—O3	90.41 (6)	Li2—O2—H2B	134.3
O3^i—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
O4^ii—Li3—O4	114.7 (3)	Li2—O5—H5A	111.0
O4^ii—Li3—O1	110.23 (7)	Li4—O5—H5B	120.8
O4—Li3—O1	109.58 (7)	Li2—O5—H5B	130.7
O4^ii—Li3—O1^ii	109.58 (7)	H5A—O5—H5B	105.0
O4—Li3—O1^ii	110.23 (7)	Li4—O6—Li2	78.26 (19)
O1—Li3—O1^ii	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
S2^iii—As1—S2	109.21 (3)	Li2—O7—H7A	128.0
S2^iii—As1—S1^iii	111.42 (2)	Li4—O7—H7B	107.4
S2—As1—S1^iii	109.04 (2)	Li2—O7—H7B	117.9
S2^iii—As1—S1	109.04 (2)	H7A—O7—H7B	105.0
S2—As1—S1	111.42 (2)	Li4—O8—H8A	109.9
S1^iii—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)

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···S4^i	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···S1^iii	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···S3^iii	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.