Na2B2S5 and Li2B2S5: Two Novel Perthioborates with Planar 1,2,4-Trithia-3,5-Diborolane Rings

For the first time perthioborates with trigonal planar coordination of boron were prepared. Na₂B₂S₅ (Pnma, a = 12.545(2) Å, b = 7.441(1) Å, c = 8.271(1) Å, Z = 4) and Li₂B₂S₅ (Cmcm, a = 15.864(1) Å, b = 6.433(1) Å, c = 6.862(1) Å, Z = 4) were obtained by reaction of the metal sulfides with stoichiometric amounts of boron and an excess of sulfur (effective molar ratio M:B:S = 1:1:4) at 600°C (650°C) and subsequent annealing. The non-isotypic structures contain exactly planar [B₂S₅]^2? groups consisting of five-membered B₂S₃ rings with one additional exocyclic sulfur on each of the boron atoms. The alkaline metal cations are four-coordinate (lithium) and (four + four)-coordinate (sodium) respectively.     

Li5B7S13 und Li9B19S33: Zwei Lithiumthioborate mit neuen hochpolymeren Anionengerüsten

Li₅B₇S₁₃ and Li₉B₁₉S₃₃: Two Lithium Thioborates with Novel Highly Polymeric Anion Networks Li₅B₇S₁₃ (C2/c; a = 17.304(2) Å, b = 21.922(3) Å, c = 12.233(2) Å, β = 134.91(1)°; Z = 8) and Li₉B₁₉S₃₃ (C2/c; a = 23.669(9) Å, b = 14.361(3) Å, c = 12.237(3) Å, β = 103.77(2)°; Z = 4) were prepared by reaction of stoichiometric amounts of lithium sulfide, boron, and sulfur at 750°C (Li₅B₇S₁₃) and 700°C (Li₉B₁₉S₃₃) with subsequent annealing. The crystal structures consist of interpenetrating, polymeric boron sulfur anion networks which are formed by corner-sharing of B₄S₁₀ and B₁₀S₂₀ units (Li₅B₇S₁₃), or B₁₉S₃₆ units (Li₉B₁₉S₃₃). The lithium cations are situated in between with a strong disorder in Li₉B₁₉S₃₃.     

LiBaBS3 und LiBaB3S6: Zwei neue quaternäre Thioborate mit trigonal-planar koordiniertem Bor

LiBaBS₃ and LiBaB₃S₆: Two New Quaternary Thioborates with Trigonally Coordinated Boron LiBaBS₃ (P2₁/c; a = 7.577(2) Å, b = 8.713(2) Å, c = 8.687(2) Å, β = 116.22(2)°; Z = 4) und LiBaB₃S₆ (Cc; a = 15.116(3) Å, b = 8.824(2) Å, c = 8.179(2) Å, β = 117.46(3)°; Z = 4) were prepared by reaction of stoichiometric amounts of the metal sulfides, boron, and sulfur at 750°C. The anionic part of the structure of the orthothioborate LiBaBS₃ consists of isolated planar [BS₃]^3? anions. The crystal structure of the metathioborate LiBaB₃S₆ contains [B₃S₆]^3? anions formed by six-membered B₃S₃ rings with three exocyclic sulfur atoms. The metal cations are situated between the anion units leading to a ninefold sulfur coordination of the barium atoms and to a fivefold (LiBaBS₃) and fourfold (LiBaB₃S₆) coordination of the lithium atoms.     

Na2B2Se7, K2B2S7 und K2B2Se7: Drei Perchalkogenoborate mit neuem polymeren Anionengerüst

Na₂B₂Se₇, K₂B₂S₇, and K₂B₂Se₇: Three Perchalcogenoborates with a Novel Polymeric Anion Network Na₂B₂Se₇ (I 2/a; a = 11.863(4) Å, b = 6.703(2) Å, c = 13.811(6) Å, β = 109.41(2)°; Z = 4), K₂B₂S₇ (I 2/a; a = 11.660(2) Å, β = 6.827(1) Å, c = 12.992(3) Å, β = 106.78(3)°; Z = 4), and K₂B₂Se₇ (I 2/a; a = 12.092(4) Å, b = 7.054(2) Å, c = 13.991(5) Å, β = 107.79(3)°; Z = 4) were prepared by reaction of stoichiometric amounts of sodium selenide (potassium sulfide) with boron and sulfur or of potassium selenide and boron diselenide, respectively, at 600°C with subsequent annealing. The crystal structures consist of polymeric anion chains of composition ([B₂S₇]^2?)_n or ([B₂Se₇]^2?)_n formed by spirocyclically connected five-membered B₂S₃ (B₂Se₃) rings and six-membered B₂S₄ (B₂Se₄) rings. The nine-coordinate alkaline metal cations are situated in between.     

Cs2B2S4 – Ein Salz der dimeren Metathioborsäure

Cs₂B₂S₄ – A Derivative of the Dimeric Metathioboric Acid Cs₂B₂S₄ (structure: I4₁/acd; a = 7.270(1) Å, c = 35.737(7) Å; Z = 8; substructure: I4/mmm; a′ = 5.141(1) Å, c′ = 17.868(4) Å, Z = 2) is prepared by the reaction of cesium sulfide with stoichiometric amounts of boron and sulfur (effective molar ratio M:B:S = 2:2:4) at 600°C and subsequent annealing. The crystal structure contains isolated [B₂S₄]^2? groups consisting of four-membered B₂S₂ rings with two exocyclic sulfur atoms on each of the boron atoms. The cesium cations are nine-coordinate between these rings. The structural feature of two edge-sharing BS₃ groups forming an isolated anion appears for the first time in thioborate chemistry, although it is known as a part of the polymeric network in B₂S₃.     

Sr3(BS3)2 und Sr3(B3S6)2: Zwei neue nicht‐oxidische Chalkogenoborate mit trigonal‐planar koordiniertem Bor

Sr₃(BS₃)₂ and Sr₃(B₃S₆)₂: Two Novel Non‐oxidic Chalcogenoborates with Boron in a Trigonal‐Planar Coordination The thioborates Sr₃(BS₃)₂ and Sr₃(B₃S₆)₂ were prepared from strontium sulfide, amorphous boron and sulfur in solid state reactions at a temperature of 1123 K. In a systematic study on the structural cation influence on this type of ternary compounds, the crystal structures were determined by single crystal X‐ray diffraction. Sr₃(BS₃)₂ crystallizes in the monoclinic spacegroup C2/c (No. 15) with a = 10.187(4) Å, b = 6.610(2) Å, c = 15.411(7) Å, β = 102.24(3)° and Z = 4. The crystal structure of Sr₃(B₃S₆)₂ is trigonal, spacegroup R3¯ (Nr. 148), with a = 8.605(1) Å, c = 21.542(4) Å and Z = 3. Sr₃(BS₃)₂ contains isolated [BS₃]^3— anions with boron in a trigonal‐planar coordination. The strontium cations are found between the layers of orthothioborate anions. Sr₃(B₃S₆)₂ consists of cyclic [B₃S₆]^3— anions and strontium cations, respectively.     

Structure Cristalline du Sulfure d'Étain(II) et de Thallium(I) Tl2Sn2S3

Crystal Structure of Tl₂Sn₂S₃ The compound Tl₂Sn₂S₃ had been prepared from SnS? Tl₂S mixtures. The cell is monoclinic, space group C2/c with a = 13.887(7), b = 7.742(4), c = 7.267(4) Å, β = 105.39(3)° and Z = 4. The structure was solved by the symbolic addition method and refined by least-squares to a final R = 0.086 for the 382 observed reflections. From this structure it is apparent that Tl₂Sn₂S₃ is of defect NaCl type with the thallium and tin atoms distributed over the cation positions, the sulfur atoms and vacancies over the anion positions. Tl and Sn atoms have four bonds to S atoms of 2.81–3.13 Å and 2.68–3.11 Å respectively. The thallium and tin lone pairs of electrons are stereochemically active.     

Darstellung und Kristallstrukturen von Li4−2xSr2+xB10S19 (x ≈ 0,27) und Na6B10S18. Zwei neue Thioborate mit hochpolymeren Makrotetraeder-Netzwerken

Synthesis and Crystal Structures of Li_4?2xSr_2+xB₁₀S₁₉ (x ≈ 0.27) and Na₆B₁₀S₁₈. Two Novel Thioborates with Highly Polymeric Macro-tetrahedral Networks Li_4?2xSr_2+xB₁₀S₁₉ (x ≈ 0.27) and Na₆B₁₀S₁₈ were prepared from the reaction of strontium sulfide and lithium sulfide (sodium sulfide) with boron and sulfur at 700°C in graphitized silica tubes. Li_4?2xSr_2+xB₁₀S₁₉ (x ≈ 0.27) crystallizes in the monoclinic space group P2₁/c with a = 10.919(2) Å, b = 13.590(3) Å, c = 16.423(4) Å, and β = 90.48(2)°, Na₆B₁₀S₁₈ in the tetragonal space group I4₁/acd with a = 14.415(3) Å, c = 26.137(4) Å. Both structures contain supertetrahedral B₁₀S₂₀ units which are linked through tetrahedral corners to form a three-dimensional polymeric network in the case of Na₆B₁₀S₁₈ and one-dimensional chains in the case of Li_4?2xSr_2+xB₁₀S₁₉ (x ≈ 0.27). All boron atoms are in tetrahedral BS₄ coordination (B? S bond lengths vary from 1.879(5) to 1.951(5) Å (1.875(10) to 1.987(9) Å)). The strontium and lithium (sodium) cations are located within large channels formed by the anions.     

Schwermetall-π-Komplexe. X. Synthese und Kristallstruktur von {[(1,3,5-(CH3)3C6H3)2Tl][AlCl4]}2: ein arenstabilisiertes dimeres Thallium(I)-tetrachloroaluminat

π-Complexes of Heavy Metals. X. Synthesis and Crystal Structure of {[(1,3,5-(CH₃)₃C₆H₃)₂Tl][AlCl₄]}₂: an Arene Stabilized Dimeric Thallium(I) Tetrachloroaluminate From a solution of AlCl₃ and TlCl in mesitylene, the bis(arene)thallium complex {[(1,3,5-(CH₃)₃C₆H₃)₂Tl][AlCl₄]}₂ ( 1 ) (space group P2₁/c with a = 19.575(4) Å, b = 12.436(2) Å, c = 19.415(4) Å, β = 101.69(3)° at T = ?90 ± 1°C; Z = 4) will crystallize at low temperature. This compound can be described as a dimeric thallium(I) tetrachloroaluminate with a sceleton similar to that of (TeI₄)₄, shielded by four arenes, in pairs coordinated at the thallium atoms. In the solid state the complete configuration has point group symmetry 1 (C₁). Tl? Cl distances ranging from 3.292(3) to 3.679(3) Å point out an ionic bonding situation between arene₂Tl⁺ and AlCl₄^? fragments. The strengths of the η⁶ like Tl-arene interactions are characterized by distances Tl(1)–C of 3.250 Å and 3.315 Å, and Tl(2)? C of 3.285 Å and 3.328 Å and a temperature of release of all arene molecules of 61°C, which has been determined by differential thermal analysis, to yield pure thallium(I) tetrachloroaluminate.     

The Oxidation of Heterogeneous Tl/Ni/P‐Alloys — Preparation and Crystal Structures of the Thallium Nickel Phosphates TlNi4(PO4)3, Tl4Ni7(PO4)6, and Tl2Ni4(P2O7)(PO4)2

Single crystals of the first anhydrous thallium nickel phosphates were prepared by reaction of heterogeneous Tl/Ni/P alloys with oxygen. TlNi₄(PO₄)₃ (pale‐yellow, orthorhombic, space group Cmc2₁, a = 6.441(2)Å, b = 16.410(4)Å, c = 9.624(2)Å, Z = 4) crystallizes with a structure closely related to that of NaNi₄(PO₄)₃. Tl₄Ni₇(PO₄)₆ (yellow‐brown, monoclinic, space group Cm, a = 10.711(1)Å, b = 14.275(2)Å, c = 6.688(2)Å, β = 103.50(2)°, Z = 8) is isotypic with Na₄Ni₇(PO₄)₆, and Tl₂Ni₄(P₂O₇)(PO₄)₂ (brown, monoclinic, space group C2/c, a = 10.389(2)Å, b = 13.888(16)Å, c = 18.198(3)Å, β = 103.1(2)°, Z = 8) adopts the K₂Ni₄(P₂O₇)(PO₄)₂ structure. Tl₂Ni₄(P₂O₇)(PO₄)₂ could also be prepared in nearly single phase form by reaction of Tl₂CO₃, NiO, and (NH₄)₂HPO₄.     

Syntheses of Halogenated Polyhedral Phosphaboranes: Crystal Structure of conjuncto‐3,3′‐(closo‐1,2‐P2B4Br3)2

Co‐pyrolysis of B₂Br₄ with PBr₃ at 480 °C gave, in addition to the main product closo‐1,2‐P₂B₄Br₄, conjuncto‐3,3′‐(1,2‐P₂B₄Br₃)₂ ( 1 ) and the twelve‐vertex closo‐1,7‐P₂B₁₀Br₁₀ ( 2 ), both in low yields. X‐ray structure determination for 1 [triclinic, space‐group P1 with a = 7.220(2) Å, b = 7.232(2) Å, c = 8.5839(15) Å, α = 97.213(15)°, β = 96.81(2)°, γ = 94.07(2)° and Z = 1] confirmed that 1 adopts a structure consisting of two symmetrically boron–boron linked distorted octahedra with the bridging boron atoms in the 3,3′‐positions and the phosphorus atoms in the 1,2‐positions. The intercluster 2e/2c B–B bond length is 1.61(3) Å. The shortest boron–boron bond within the cluster framework is 1.68(2) Å located between the boron atoms antipodal to the phosphorus atoms. The icosahedral phosphaborane 2 was characterized by ¹¹B‐¹¹B COSY NMR spectroscopy showing cross peaks indicative for the isomer with the phosphorus atoms in 1,7‐positions. Both the X‐ray data of 1 and the NMR spectroscopic data of 1 and 2 give further evidence for the influence of an antipodal effect of heteroatoms to cross‐cage boron atoms and, vice versa, of an additional shielding of the phosphorus atoms caused by B‐Hal substitution at the boron positions trans to phosphorus.     

Darstellung und Kristallstruktur der Addukte [DB-18C6] · CH3CN · CH3CSOH und [DC-18C6](CH3CSOH)2 sowie der salzartigen Verbindungen [Cs(B-15C5)2]CH3CSS und [Cs(DB-18C6)]2S5(DMF)21)

Synthesis and Crystal Structure of the Adducts [DB-18C6] · CH₃CN · CH₃CSOH and [DC-18C6](CH₃CSOH)₂ as well as of the Salt-like Compounds [Cs(B-15C5)₂]CH₃CSS and [Cs(DB-18C6)]₂S₅(DMF)₂¹) The reaction products of crown ethers, cesium, and sulfur in aprotic solvents like acetonitrile and dimethylformamide strongly depend on the reaction conditions. Using CH₃CN as a solvent, sometimes neutral host-guest adducts crystallize only, e.g., [dibenzo-18C6] · CH₃CN · CH₃CSOH (monoclinic, S. G. P2₁/c, Z = 4, a = 9.73(1) Å, b = 22.03(1) Å, c = 11.86(1) Å, β = 91.8(1)°) or [dicyclohexyl-18C6](CH₃CSOH)₂ (monoclinic, S. G. P2₁/n, Z = 2, a = 7.75(1) Å, b = 10.32(1) Å, c = 17.73(1) Å, β = 95.7(1)°). The monothioacetic acid, CH₃CSOH, must be regarded as the first product of the hydrolysis of CH₃CN. Furthermore, another product of this kind of hydrolysis, CH₃CSSH, is obtained too. Therefore, we also obtain the salt-like compound [Cs(benzo-15C5)₂]CH₃CSS (monoclinic, S. G. C2/c, Z = 4, a = 16.05(1) Å, b = 16.73(1) Å, c = 13.11(1) Å, β = 106.3(1)°). If the solvent DMF is used, the pentasulfide [Cs(dibenzo-18C6)]₂S₅(DMF)₂ crystallizes (monoclinic, S. G. P2₁/n, Z = 4, a = 14.79(1) Å, b = 14.24(1) Å, c = 25.74(1) Å, β = 92.7(1°. The S₅^2? anions show the cis-conformation.     

The synthesis and structure of La5Pb3Z,Z  N,O. Interstitial derivatives of a Cr5B3-Type structure

Suitable proportions of La, La₄Pb₃ and La₂O₃ or LaN reacted in pressed pellets at 1050°–1250°C result in high yields of the title compounds. Single crystal X-ray studies of the oxide show it to be an isopointal, interstitial derivative of the Cr₅B₃ structure (I4/mcm, Z = 4, a = 8.6895(2) Å, c = 14.540(1) Å, R/R_w = 3.0/3.5%). Oxygen or nitrogen atoms are bound in (La2)₄ tetrahedra within chains along (0, 1 /2, z). Negligible dimerization of the type characteristic of Cr₅B₃ is indicated by the Pb2? Pb2 separation, 3.550(1) Å. The structure is compared with other related examples.     

Preparation,crystal structure,and magnetic properties of β-Li3TiF6 = LiLi(TiF6)(TiF6)2 – a double fluoride?

Purple colored single crystals of the β-modification of Li₃TiF₆ have been prepared by heating an appropriate mixture of LiF and TiF₃ at 820°C under an argon atmosphere. β-Li₃TiF₆ crystallizes in C2/c with a = 14.452(2) Å, b = 8.798(1) Å, c = 10.113(1) Å and β = 96.30(1)º. The structure is isotypic to β-Li₃VF₆ and contains isolated compressed TiF₆ octahedra (d_Ti–F = 1.91–2.01 Å). Magnetic properties of β-Li₃TiF₆ were studied and discussed. Band structure calculations and calculations of the Madelung part of the lattice energy, MAPLE, were performed to discuss the chemical bonding.     

Hochdrucksynthesen von Carbonaten. V. Carbonatdarstellungen durch Schmelzreaktionen unter hohen CO2-Drücken

High Pressure Syntheses of Carbonates. V. Syntheses of Carbonates by Melt Reactions under High CO₂ Pressure Binary compounds of transition metals react in melts of Tl₂CO₃ under CO₂ pressure from 1 000 to 5 000 bar by giving ternary carbonates. By this the compounds Tl₂Cu(CO₃)₂, TlCr(CO₃)₂, Tl₃Cr(CO₃)₃, and Tl₃V(CO₂)₃ could be prepared. The structure of Tl₂Cu(CO₃)₂ contains Cu₂ groups (a₀ = 7.583 Å, b₀ = 9.799 Å, c₀ = 9.119 Å, β 111.51°, Z = 4, space group P2₁/c Nr. 14). The space group of TlCr(CO₃)₂ is also P2₁/c Nr. 14 (a₀ = 19.917 Å, b₀ = 8.605 Å, c₀ = 19.138 Å, β = 104.79°, Z = 24). The compounds too were characterized by infrared spectroscopy.     

Ag6B10S18: Ein neues Thioborat mit tetraedrischer Koordination des Bors

Ag₆B₁₀S₁₈: A Novel Thioborate with Tetrahedral Coordination of Boron Ag₆B₁₀S₁₈ was prepared as a novel thioborate from the reaction of stoichiometric amounts of Ag₂S, B, and S at 700°C with successive annealing at 580–460°C. The orange-yellow compound crystallizes in the monoclinic space group C2/c with a = 21.663(8), b = 21.639(8), c = 16.572(5) Å, ß = 129.40(4)°, Z = 8, d_x = 2.948 g · cm^?3. According to the complete X-ray crystal structure analysis the anionic part of the Ag₆B₁₀S₁₈ structure contains B₁₀S₂₀ “supertetrahedra” consisting of ten parallel corner-sharing BS₄ tetrahedra; the B₁₀S₂₀ groups are linked through corners to form a layer-like arrangement of (B₁₀S₁₆S_4/2^6?)_n = (B₁₀S₁₈^6?)_n polyantions. The mean B? S bond length is 1.915 Å. The electron densities in the regions of the Ag⁺ ions show a dynamically disordered arrangement which can be described by a distribution of the 6 Ag⁺ ions of the asymmetric unit over 18 partially occupied sites, these structural characteristics making Ag₆B₁₀S₁₈ an Ag⁺ ionic conductor. The i.r. spectrum of the compound shows B? S stretching vibrations at 610, 640, 685, 735, and 760 cm^?1.     

SYNTHESIS AND STRUCTURAL CHARACTERIZATION OF TRIS(DIMETHYLDITHIOCARBAMATE) INDIUM(III), In[S2CN(CH3)2]3

Abstract

The synthesis and structure of the indium dithiocarbamate, In[S₂CN(CH₃)₂]₃·(1/2) 4-mepy (4-mepy=4-methylpyridine), is described. Indium metal was oxidized by tetramethylthiuram disulfide in 4-methylpyridine at 25°C to form a new, homoleptic indium(III) dithiocarbamate in yields exceeding 60%. In[S₂CN(CH₃)₂]₃ exists as a discrete molecule with a distorted-octahedral geometry. The compound crystallizes in the P 1 (No. 2) space group with a=9.282(1)Å, b=10.081(1)Å, c=12.502Å, α=73.91(1)°, β=70.21(1)°, γ=85.84(1)°, Z=2, V(Å)=1057.3(3), R=0.046 and R_w =0.061.     

Cu3SbS3: Zur Kristallstruktur und Polymorphie

Cu₃SbS₃: Crystal Structure and Polymorphism The hitherto unknown crystal structure of β-Cu₃SbS₃ at room temperature could be determined from a twinned crystal. The compound crystallizes in the monoclinic system, space group P2₁/c (No. 14), with a = 7.808(1), b = 10.233(2) and c = 13.268(2) Å, β = 90.31(1)°, V = 1 060.1(2) ų, Z = 8. An Extended-Hückel-Calculation shows weak bonding interactions between copper atoms which are coordinated trigonal planar. At ?9°C a first order phase transition occurs and the crystals disintegrate. The low-temperature modification (γ) crystallizes in the orthorhombic system with a = 7.884(2), b = 10.219(2) and c = 6.623(2) Å, V = 533.6(2) ų (?100°C). At 121°C a phase transition of higher order is observed. The high-temperature polymorph (α) of Cu₃SbS₃ is orthorhombic again. From high-temperature precession photographs the space groups Pnma (No. 62) or Pna2₁ (No. 33) can be derived. The lattice constants at 200°C are a = 7.828(3), b = 10.276(4) and c = 6.604(3) Å, V = 531.2(2) ų.     

Volatile ZnPhen(S2CNEt2)2 and MnPhen(S2CNEt2)2 complexes and the MnZn2Phen3(S2CNEt2)6 phase: Thermal behavior and crystal and molecular structures of two modifications of ZnPhen(S2CNEt2)2

Two crystal modifications, I and II, of the ZnPhen(S₂CNEt₂)₂ complex have been isolated. According to XRD data, the single crystals of I are triclinic with a=9.745(2), b=10.252(2), c=14.331(3) Å, α=99.18(2), β=91.01(2), γ=113.28(2)°, V=1293.2(4) ų, space group P1, Z=2, d_calc=1.401 g/cm³. The crystals of II are monoclinic with a=7.220(6), b=18.095(2), c=19.050(4) Å, β=95.85(2)°, V=2475.8(7) ų, space group C2/c, Z=4, d_calc=1.461 g/cm³. In both modifications, the structure is formed by monomer molecules with a distorted octahedral environment of the zinc atom. All atoms in I are in the general position; in II, the atoms are linked by the twofold rotation axis. It is shown by X-ray phase analysis (XRPA) that the MnPhen(S₂CNEt₂)₂ complexes (III) are isostructural to modification I of the ZnPhen(S₂CNEt₂)₂ complex, which underlies the synthesis of a solid solution of these complexes, MnZn₂Phen₃(S₂CNEt₂)₆ (phase IV). It is found that MPhen(S₂CNEt₂)₂ (M=Zn²⁺, Mn²⁺) and phase IV quantitatively sublime when heated in vacuum. Thermolysis of III in argon yields manganese(II) sulfide of cubic modification; the main product of thermolysis of phase IV is a solid solution of Zn_xMn_1?xS of hexagonal modification.     

Li3BS3 und LiSrBS3: Neue Orthothioborate mit trigonal-planar koordiniertem Bor

Li₃BS₃ and LiSrBS₃: New Orthothioborates with Trigonal Planar Boron Coordination We report on the two new orthothioborates Li₃BS₃ (Pnma; a = 8.144(1) Å, b = 10.063(2) Å, 6.161(1) Å; Z = 4) and LiSrBS₃ (Pnma; a = 7.557(1) Å, b = 9.083(2) Å, c = 7.049(1) Å: Z = 4). The two new phases were prepared by reaction of the metal sulfides, amorphous boron, and sulfur at 700°C. Both compounds contain isolated, planar [BS₃]^3?-anions. The lithium ions have fourfold (Li₃BS₃) and sixfold (LiSrBS₃) sulfur coordination, the strontium ion shows an eightfold sulfur coordination. The two compounds represent new A₃BX₃ resp. AA′BX₃ structure types.