inorganic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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ISSN: 2056-9890

Trilithium thio­arsenate octa­hydrate

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[Mereiter, K., Preisinger, A. & Guth, H. (1979). Acta Cryst. B35, 19-25.], 1982[Mereiter, K., Preisinger, A., Baumgartner, O., Heger, G., Mikenda, W. & Steidl, H. (1982). Acta Cryst. B38, 401-408.], 1983[Mereiter, K., Preisinger, A. & Zellner, A. (1983). Inorg. Chim. Acta, 72, 67-73.]); Krebs et al. (1990[Krebs, B., Huerter, H. U., Enax, J. & Froehlich, R. (1990). Z. Anorg. Allg. Chem. 581, 141-152.]); Krebs & Jacobsen (1976[Krebs, B. & Jacobsen, H. J. (1976). Z. Anorg. Allg. Chem. 421, 97-104.]); Krebs & Huerter (1980[Krebs, B. & Huerter, H. U. (1980). Z. Anorg. Allg. Chem. 462, 143-151.]); Schiwy et al. (1973[Schiwy, W., Pohl, S. & Krebs, B. (1973). Z. Anorg. Allg. Chem. 402, 77-86.]); Melullis & Dehnen (2007[Melullis, M. & Dehnen, S. (2007). Z. Anorg. Allg. Chem. 633, 2159-2167.]), Ruzin et al. (2006[Ruzin, E., Kracke, A. & Dehnen, S. (2006). Z. Anorg. Allg. Chem. 632, 1018-1026.], 2008[Ruzin, E., Jakobi, S. & Dehnen, S. (2008). Z. Anorg. Allg. Chem. 634, 995-1001.]). For the prototype compound Schlippe's Salt, Na3SbS4·9H2O, see: Schlippe (1821[Schlippe, K. (1821). Versuche ueber das Schwefelspiessglanznatron und den Goldschwefel. In Schweiggers Journal für Chemie und Physik. XXXIII, 1821, S. 320-323.]). For the synthesis of the title compound and early crystallographic data, see: Rémy & Bachet (1968[Rémy, F. & Bachet, B. (1968). Bull. Soc. Chim. Fr. pp. 3568-3569.]). For the synthesis and crystal structure of Ba3(AsS4)2·7H2O as a precursor of the title compound, see: Mereiter & Preisinger (1992[Mereiter, K. & Preisinger, A. (1992). Acta Cryst. C48, 984-987.]). For the crystal structure of Na2S·9H2O, see: Preisinger et al. (1982[Preisinger, A., Mereiter, K., Baumgartner, O., Heger, G., Mikenda, W. & Steidl, H. (1982). Inorg. Chim. Acta, 57, 237-246.]). For a review on O—H⋯S hydrogen bonds in salt hydrates, see: Mikenda et al. (1989[Mikenda, W., Mereiter, K. & Preisinger, A. (1989). Inorg. Chim. Acta, 161, 21-28.]).

Experimental

Crystal data
  • Li3AsS4·8H2O

  • Mr = 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 Tmin = 0.51, Tmax = 0.54

  • 5729 measured reflections

  • 4001 independent reflections

  • 2913 reflections with I > 2σ(I)

  • Rint = 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

  • Δρmax = 0.61 e Å−3

  • Δρmin = −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 DA 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⋯S3iv 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⋯S3v 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⋯S4iv 0.80 2.54 3.307 (2) 162
O7—H7A⋯S1vi 0.80 2.49 3.244 (2) 157
O7—H7B⋯S3 0.80 2.58 3.333 (2) 157
O8—H8A⋯S2vii 0.80 2.50 3.253 (2) 157
O8—H8B⋯S3vi 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[Hornstra, J. & Vossers, H. (1973). Philips Tech. Rev. 33, 61-73.]); cell refinement: LLSQ (Mereiter, 1992[Mereiter (1992). LLSQ and PWD. Vienna University of Technology, Austria.]); data reduction: PWD (Mereiter, 1992[Mereiter (1992). LLSQ and PWD. Vienna University of Technology, Austria.]); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: Mercury (Macrae et al., 2006[Macrae, C. F., Edgington, P. R., McCabe, P., Pidcock, E., Shields, G. P., Taylor, R., Towler, M. & van de Streek, J. (2006). J. Appl. Cryst. 39, 453-457.]) and DIAMOND (Brandenburg, 2012[Brandenburg, K. (2012). DIAMOND. Crystal Impact GbR, Bonn, Germany.]); software used to prepare material for publication: SHELXL97 and publCIF (Westrip, 2010[Westrip, S. P. (2010). J. Appl. Cryst. 43, 920-925.]).

Supporting information


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 = S2-, Se2-, Te2-, 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 AsS43- 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 AsS43- 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 AsS43- 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).

Refinement top

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 Uiso for the two H-atoms of each water molecule was used and refined.

Structure description 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 = S2-, Se2-, Te2-, 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 AsS43- 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 AsS43- 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 AsS43- 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).

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
[Figure 1] 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.
[Figure 2] 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.
[Figure 3] 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.
[Figure 4] 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
Li3AsS4·8H2OF(000) = 744
Mr = 368.11Dx = 1.778 Mg m3
Monoclinic, P2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ycCell parameters from 34 reflections
a = 10.036 (2) Åθ = 9.1–26.2°
b = 10.064 (2) ŵ = 3.09 mm1
c = 14.264 (3) ÅT = 297 K
β = 107.30 (1)°Oval, colourless
V = 1375.5 (5) Å30.30 × 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 tubeRint = 0.026
Graphite monochromatorθmax = 30.0°, θmin = 2.0°
ω–2θ scansh = 1413
Absorption correction: for a sphere
µR = 0.45
k = 1414
Tmin = 0.51, Tmax = 0.54l = 020
5729 measured reflections3 standard reflections every 60 min
4001 independent reflections intensity decay: 2.0%
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.028H-atom parameters constrained
wR(F2) = 0.057 w = 1/[σ2(Fo2) + (0.0179P)2 + 0.5909P]
where P = (Fo2 + 2Fc2)/3
S = 1.05(Δ/σ)max = 0.001
4001 reflectionsΔρmax = 0.61 e Å3
181 parametersΔρmin = 0.36 e Å3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0081 (3)
Crystal data top
Li3AsS4·8H2OV = 1375.5 (5) Å3
Mr = 368.11Z = 4
Monoclinic, P2/cMo Kα radiation
a = 10.036 (2) ŵ = 3.09 mm1
b = 10.064 (2) ÅT = 297 K
c = 14.264 (3) Å0.30 × 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
Rint = 0.026
Tmin = 0.51, Tmax = 0.543 standard reflections every 60 min
5729 measured reflections intensity decay: 2.0%
4001 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0280 restraints
wR(F2) = 0.057H-atom parameters constrained
S = 1.05Δρmax = 0.61 e Å3
4001 reflectionsΔρmin = 0.36 e Å3
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
xyzUiso*/Ueq
Li10.50000.50000.50000.0393 (13)
Li20.2821 (4)0.7213 (4)0.5102 (4)0.0443 (10)
Li30.50000.5984 (5)0.75000.0311 (11)
Li40.0724 (5)0.8832 (5)0.4126 (5)0.0610 (14)
As10.00000.40273 (3)0.25000.01865 (8)
As20.50000.91402 (2)0.25000.01887 (8)
S10.12581 (5)0.53147 (5)0.31185 (4)0.02508 (11)
S20.13565 (5)0.27910 (5)0.36066 (4)0.02849 (12)
S30.37068 (5)1.03848 (5)0.31147 (4)0.02615 (12)
S40.64151 (6)0.79087 (5)0.35891 (4)0.02873 (12)
O10.55849 (15)0.47247 (15)0.66032 (12)0.0297 (3)
H1A0.64000.46290.68740.054 (6)*
H1B0.52390.40230.66550.054 (6)*
O20.28906 (17)0.51048 (16)0.50233 (12)0.0330 (3)
H2A0.26930.49230.55120.068 (8)*
H2B0.24940.45640.46270.068 (8)*
O30.48739 (17)0.72351 (17)0.51911 (12)0.0359 (4)
H3A0.52330.76960.56540.077 (8)*
H3B0.52110.74660.47750.077 (8)*
O40.33730 (16)0.70514 (14)0.67279 (12)0.0303 (3)
H4A0.27030.66890.68040.051 (6)*
H4B0.34230.77450.70100.051 (6)*
O50.05507 (17)0.72354 (16)0.48637 (12)0.0344 (4)
H5A0.01670.67000.44590.059 (7)*
H5B0.01100.72470.52480.059 (7)*
O60.2558 (2)0.9454 (2)0.49965 (14)0.0486 (5)
H6A0.29390.97200.46140.107 (11)*
H6B0.26801.00220.54060.107 (11)*
O70.1906 (2)0.7739 (2)0.34519 (16)0.0535 (5)
H7A0.15170.72560.30090.112 (12)*
H7B0.23290.82510.32200.112 (12)*
O80.05671 (19)1.0198 (2)0.36351 (18)0.0573 (6)
H8A0.01901.08060.34550.102 (11)*
H8B0.12881.01000.32100.102 (11)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Li10.035 (3)0.041 (3)0.041 (3)0.003 (3)0.010 (2)0.012 (3)
Li20.035 (2)0.038 (2)0.059 (3)0.0012 (18)0.013 (2)0.001 (2)
Li30.029 (3)0.030 (3)0.032 (3)0.0000.006 (2)0.000
Li40.049 (3)0.046 (2)0.086 (4)0.005 (2)0.017 (3)0.018 (3)
As10.01756 (13)0.01845 (13)0.01937 (15)0.0000.00463 (11)0.000
As20.02138 (14)0.01735 (13)0.01920 (15)0.0000.00807 (11)0.000
S10.0240 (2)0.0256 (2)0.0277 (3)0.00128 (18)0.0108 (2)0.0028 (2)
S20.0273 (3)0.0254 (2)0.0287 (3)0.0044 (2)0.0022 (2)0.0044 (2)
S30.0294 (3)0.0243 (2)0.0287 (3)0.00180 (19)0.0148 (2)0.0032 (2)
S40.0294 (3)0.0266 (2)0.0286 (3)0.0047 (2)0.0063 (2)0.0071 (2)
O10.0293 (8)0.0294 (7)0.0276 (8)0.0006 (6)0.0042 (6)0.0006 (6)
O20.0358 (8)0.0319 (8)0.0293 (8)0.0075 (7)0.0066 (7)0.0028 (7)
O30.0358 (9)0.0438 (9)0.0290 (9)0.0110 (7)0.0110 (7)0.0023 (8)
O40.0314 (8)0.0250 (7)0.0365 (9)0.0023 (6)0.0130 (7)0.0017 (6)
O50.0385 (9)0.0360 (8)0.0311 (9)0.0074 (7)0.0140 (7)0.0056 (7)
O60.0590 (12)0.0413 (9)0.0406 (11)0.0078 (9)0.0076 (10)0.0058 (9)
O70.0693 (14)0.0463 (11)0.0568 (13)0.0217 (10)0.0367 (11)0.0157 (10)
O80.0377 (10)0.0424 (11)0.0836 (16)0.0008 (9)0.0052 (10)0.0137 (11)
Geometric parameters (Å, º) top
Li1—O22.130 (2)As1—S1iii2.1711 (6)
Li1—O2i2.130 (2)As1—S12.1711 (6)
Li1—O12.203 (2)As2—S4iv2.1574 (6)
Li1—O1i2.203 (2)As2—S42.1574 (6)
Li1—O32.274 (2)As2—S32.1677 (6)
Li1—O3i2.274 (2)As2—S3iv2.1677 (6)
Li2—O32.026 (4)O1—H1A0.80
Li2—O22.127 (5)O1—H1B0.80
Li2—O52.202 (4)O2—H2A0.80
Li2—O42.225 (5)O2—H2B0.80
Li2—O62.271 (5)O3—H3A0.80
Li2—O72.319 (5)O3—H3B0.80
Li3—O4ii1.991 (3)O4—H4A0.80
Li3—O41.991 (3)O4—H4B0.80
Li3—O12.009 (4)O5—H5A0.80
Li3—O1ii2.009 (4)O5—H5B0.80
Li4—O81.876 (5)O6—H6A0.80
Li4—O51.957 (5)O6—H6B0.80
Li4—O61.990 (6)O7—H7A0.80
Li4—O72.054 (6)O7—H7B0.80
As1—S2iii2.1482 (6)O8—H8A0.80
As1—S22.1482 (6)O8—H8B0.80
O2—Li1—O2i180.0S4—As2—S3112.69 (2)
O2—Li1—O1i92.91 (6)S4iv—As2—S3iv112.69 (2)
O2i—Li1—O1i87.09 (6)S4—As2—S3iv106.15 (2)
O2—Li1—O187.09 (6)S3—As2—S3iv109.40 (3)
O2i—Li1—O192.91 (6)Li3—O1—Li1122.93 (10)
O1i—Li1—O1180.0Li3—O1—H1A102.7
O2—Li1—O3i98.16 (6)Li1—O1—H1A115.8
O2i—Li1—O3i81.84 (6)Li3—O1—H1B106.3
O1i—Li1—O3i90.41 (6)Li1—O1—H1B102.6
O1—Li1—O3i89.59 (6)H1A—O1—H1B105.0
O2—Li1—O381.84 (6)Li2—O2—Li195.65 (13)
O2i—Li1—O398.16 (6)Li2—O2—H2A99.3
O1i—Li1—O389.59 (6)Li1—O2—H2A120.5
O1—Li1—O390.41 (6)Li2—O2—H2B134.3
O3i—Li1—O3180.0Li1—O2—H2B104.1
O3—Li2—O288.03 (18)H2A—O2—H2B105.0
O3—Li2—O5174.8 (3)Li2—O3—Li194.22 (14)
O2—Li2—O592.89 (17)Li2—O3—H3A105.0
O3—Li2—O490.12 (18)Li1—O3—H3A130.2
O2—Li2—O488.84 (18)Li2—O3—H3B127.1
O5—Li2—O494.98 (19)Li1—O3—H3B98.5
O3—Li2—O695.14 (18)H3A—O3—H3B105.0
O2—Li2—O6172.9 (3)Li3—O4—Li2121.68 (14)
O5—Li2—O683.40 (16)Li3—O4—H4A105.3
O4—Li2—O697.45 (19)Li2—O4—H4A102.5
O3—Li2—O798.6 (2)Li3—O4—H4B105.9
O2—Li2—O7100.6 (2)Li2—O4—H4B114.8
O5—Li2—O776.20 (15)H4A—O4—H4B105.0
O4—Li2—O7167.3 (2)Li4—O5—Li280.7 (2)
O6—Li2—O772.74 (15)Li4—O5—H5A105.4
O4ii—Li3—O4114.7 (3)Li2—O5—H5A111.0
O4ii—Li3—O1110.23 (7)Li4—O5—H5B120.8
O4—Li3—O1109.58 (7)Li2—O5—H5B130.7
O4ii—Li3—O1ii109.58 (7)H5A—O5—H5B105.0
O4—Li3—O1ii110.23 (7)Li4—O6—Li278.26 (19)
O1—Li3—O1ii101.7 (2)Li4—O6—H6A102.8
O8—Li4—O5129.8 (3)Li2—O6—H6A107.9
O8—Li4—O6114.2 (3)Li4—O6—H6B126.3
O5—Li4—O697.9 (3)Li2—O6—H6B132.2
O8—Li4—O7130.4 (3)H6A—O6—H6B105.0
O5—Li4—O788.2 (2)Li4—O7—Li275.9 (2)
O6—Li4—O784.6 (2)Li4—O7—H7A118.8
S2iii—As1—S2109.21 (3)Li2—O7—H7A128.0
S2iii—As1—S1iii111.42 (2)Li4—O7—H7B107.4
S2—As1—S1iii109.04 (2)Li2—O7—H7B117.9
S2iii—As1—S1109.04 (2)H7A—O7—H7B105.0
S2—As1—S1111.42 (2)Li4—O8—H8A109.9
S1iii—As1—S1106.72 (3)Li4—O8—H8B124.1
S4iv—As2—S4109.87 (4)H8A—O8—H8B105.0
S4iv—As2—S3106.15 (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···AD—HH···AD···AD—H···A
O1—H1A···S1v0.802.493.262 (2)163
O1—H1B···S4i0.802.513.287 (2)163
O2—H2A···S1vi0.802.763.531 (2)162
O2—H2B···S20.802.373.167 (2)173
O3—H3A···S3vii0.802.613.400 (2)168
O3—H3B···S40.802.393.190 (2)173
O4—H4A···S1vi0.802.513.240 (2)153
O4—H4B···S3viii0.802.423.207 (2)170
O5—H5A···S10.802.453.247 (2)172
O5—H5B···S2vi0.802.503.303 (2)177
O6—H6A···S30.802.573.354 (2)168
O6—H6B···S4vii0.802.543.307 (2)162
O7—H7A···S1iii0.802.493.244 (2)157
O7—H7B···S30.802.583.333 (2)157
O8—H8A···S2ix0.802.503.253 (2)157
O8—H8B···S3iii0.802.613.394 (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 formulaLi3AsS4·8H2O
Mr368.11
Crystal system, space groupMonoclinic, P2/c
Temperature (K)297
a, b, c (Å)10.036 (2), 10.064 (2), 14.264 (3)
β (°) 107.30 (1)
V3)1375.5 (5)
Z4
Radiation typeMo Kα
µ (mm1)3.09
Crystal size (mm)0.30 × 0.27 × 0.25
Data collection
DiffractometerPhilips PW1100 four-circle
Absorption correctionFor a sphere
µR = 0.45
Tmin, Tmax0.51, 0.54
No. of measured, independent and
observed [I > 2σ(I)] reflections
5729, 4001, 2913
Rint0.026
(sin θ/λ)max1)0.704
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.028, 0.057, 1.05
No. of reflections4001
No. of parameters181
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)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—O22.130 (2)Li3—O12.009 (4)
Li1—O12.203 (2)Li4—O81.876 (5)
Li1—O32.274 (2)Li4—O51.957 (5)
Li2—O32.026 (4)Li4—O61.990 (6)
Li2—O22.127 (5)Li4—O72.054 (6)
Li2—O52.202 (4)As1—S22.1482 (6)
Li2—O42.225 (5)As1—S12.1711 (6)
Li2—O62.271 (5)As2—S42.1574 (6)
Li2—O72.319 (5)As2—S32.1677 (6)
Li3—O41.991 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1A···S1i0.802.493.262 (2)162.7
O1—H1B···S4ii0.802.513.287 (2)163.2
O2—H2A···S1iii0.802.763.531 (2)162.3
O2—H2B···S20.802.373.167 (2)173.4
O3—H3A···S3iv0.802.613.400 (2)167.5
O3—H3B···S40.802.393.190 (2)172.5
O4—H4A···S1iii0.802.513.240 (2)153.3
O4—H4B···S3v0.802.423.207 (2)170.2
O5—H5A···S10.802.453.247 (2)171.6
O5—H5B···S2iii0.802.503.303 (2)177.2
O6—H6A···S30.802.573.354 (2)168.0
O6—H6B···S4iv0.802.543.307 (2)161.7
O7—H7A···S1vi0.802.493.244 (2)156.5
O7—H7B···S30.802.583.333 (2)156.9
O8—H8A···S2vii0.802.503.253 (2)157.4
O8—H8B···S3vi0.802.613.394 (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.
 

References

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