On the Crystal Structure of K2Cu5Cl8(OH)4·2H2O

Single crystals of K₂Cu₅Cl₈(OH)₄·2H₂O were grown using hydrothermal techniques. The compound is monoclinic with a = 11.6424(11), b = 6.5639(4), c = 11.7710(10)Å, β = 91.09(1)°, V = 899.4(2)ų, space group P2₁/c, Z = 2. The crystal structure was determined using single crystal X‐ray diffraction data and refined to a residual of R(|F|) = 0.025 for 1208 independent observed reflections with I > 2σ(I). Two out of three crystallographically independent Cu atoms are coordinated to four near hydroxyl groups or chlorine atoms and two more distant Cl atoms, giving an octahedrally Jahn‐Teller distorted (4+2)‐configuration. For the remaining third copper cation a square‐planar coordination can be found. Edge‐sharing of the octahedra results in the formation of kagome‐type sheets parallel to (100). The octahedral layers are decorated on both sides by planar [Cu(OH)₂Cl₂]‐units around the third Cu atom. The K atoms are located between adjacent sheets and are surrounded by six Cl atoms as well as two water molecules. The coordination polyhedra about the K‐atoms can be described as distorted bicapped trigonal prisms. Additional linkage is provided by intra‐ as well as inter‐layer hydrogen bonds (O—H···Cl, O—H···O).     

Direct Syntheses of Bis(tetraphenylphosphonium) and Bis(ethyltriphenylphosphonium) Hexabromo‐diselenates(II), [PPh4]2[Se2Br6] and [PEtPh3]2[Se2Br6]. The Crystal Structure of [PEtPh3]2[Se2Br6]

Brown crystals of [PPh₄]₂[Se₂Br₆] ( 1 ) and [PEtPh₃]₂[Se₂Br₆] ( 2 ) were obtained when selenium and bromine reacted in acetonitrile solution in the presence of tetraphenylphosphonium bromide and ethyltriphenylphosphonium bromide, respectively. The crystal structure of 2 has been determined by X‐ray methods and refined to R = 0.0420 for 4161 reflections. The crystals are monoclinic, space group P2₁/n with Z = 2 and a = 13.055(3) Å, b = 12.628(3) Å, c = 13.530(3) Å, β = 92.40(3)° (293(2) K). In the solid state structure of 2 the dinuclear hexabromo‐diselenate(II) anion is centrosymmetric and consists of two distorted almost square‐planar SeBr₄ units sharing a common edge through two bridging Br atoms. The terminal Se^II–Br bond distances are found to be 2.419(1) and 2.445(1) Å, the bridging μBr–Se^II bond distances 2.901(1) and 2.802(1) Å.     

Synthesis,Crystal Structure,and Magnetic Properties of {[Cu(phen)]2(C4H2O4)2} · 4.5H2O with C4H4O4 = Maleic Acid

Reaction of CuCl₂ · 2H₂O, phenanthroline, maleic acid and NaOH in CH₃OH/H₂O (1:1 v/v) at pH = 7.0 yielded blue {[Cu(phen)]₂(C₄H₂O₄)₂} · 4.5H₂O, which crystallizes in the monoclinic space group C2/c (no. 15) with cell dimensions: a = 18.127(2)Å, b = 12.482(2)Å, c = 14.602(2)Å, β = 103.43(1)°, U = 3213.5(8)ų, Z = 4. The crystal structure consists of the centrosymmetric dinuclear {[Cu(phen)]₂(C₄H₂O₄)₂} complex molecules and hydrogen bonded H₂O molecules. The Cu atoms are each square‐pyramidally coordinated by two N atoms of one phen ligand and three carboxyl O atoms of two maleato ligands with one carboxyl O atom at the apical position (d(Cu‐N) = 2.008, 2.012Å, equatorial d(Cu‐O) = 1.933, 1.969Å, axial d(Cu‐O) = 2.306Å). Two square‐pyramids are condensed via two apical carboxyl O atoms with a relatively larger Cu···Cu separation of 3.346(1)Å. The dinuclear complex molecules are assembled via the intermolecular π—π stacking interactions into 1D ribbons. Crossover of the resulting ribbons via interribbon π—π stacking interactions forms a 3D network with the tunnels occupied by H₂O molecules. The title complex behaves paramagnetically between 5—300 K, following the Curie‐Weiss law _χm(T—θ) = 0.435 cm³ · mol^—1 · K with θ = 1.59 K.     

Crystal Structure of a Cadmium Iodate Monohydrate: Cd(IO3)2·H2O

Single crystals of Cd(IO₃)₂·H₂O are obtained by slow evaporation of aqueous solutions of CdCl₂ and KIO₃. This compound crystallizes in the triclinic space group P1¯ [a = 7.119(2), b = 7.952(2), c = 6.646(2)Å, α = 102.17(2)°, β = 114.13(2)°, γ = 66.78(4)°]. The structure consists in Cd — (μ2‐O)₂ — Cd dimers with a metal — metal distance of 3.74Å. These dimers are connected through two iodate bridges resulting in layers parallel to the (010) plane. The 3D linkage is ensured by I1 — O1 long bonds (2.775Å).     

Single Crystal Growth and Crystal Structure of Anhydrous Mercury(I) Nitrate,Hg2(NO3)2

Polycrystalline anhydrous Hg₂(NO₃)₂ was prepared by drying Hg₂(NO₃)₂·2H₂O over concentrated sulphuric acid. Evaporation of a concentrated and slightly acidified mercury(I) nitrate solution to which the same volumetric amount of pyridine was added, led to the growth of colourless rod‐like single crystals of Hg₂(NO₃)₂. Besides the title compound, crystals of hydrous Hg₂(NO₃)₂·2H₂O and the basic (Hg₂)₂(OH)(NO₃)₃ were formed as by‐products after a crystallization period of about 2 to 4 days at room temperature. The crystal structure was determined from two single crystal diffractometer data sets collected at —100°C and at room temperature: space group P2₁, Z = 4, —100°C [room temperature]: a = 6.2051(10) [6.2038(7)]Å, b = 8.3444(14) [8.3875(10)]Å, c = 11.7028(1) [11.7620(14)]Å, ß = 93.564(3) [93.415(2)]°, 3018 [3202] structure factors, 182 [182] parameters, R[Fμ² > 2σ(Fμ²)] = 0.0266 [0.0313]. The structure is built up of two crystallographically inequivalent Hg₂²⁺ dumbbells and four NO₃^— groups which form molecular [O₂N‐O‐Hg‐Hg‐O‐NO₂] units with short Hg‐O bonds. Via long Hg‐O bonds to adjacent nitrate groups the crystal packing is achieved. The Hg‐Hg distances with an average of d(Hg‐Hg) = 2.5072Å are in the typical range for mercurous oxo compounds. The oxygen coordination around the mercury dumbbells is asymmetric with four and six oxygen atoms as ligands for the two mercury atoms of each dumbbell. The nitrate groups deviate slightly from the geometry of an equilateral triangle with an average distance of d(N‐O) = 1.255Å.     

Synthesis and Crystal Structure of Bis(tetraethylammonium) Octabromo‐triselenate(II)‐{dibromodiselenate(I)}, [NEt4]2[Se3Br8(Se2Br2)], the Salt of a Mixed‐valence Bromoselenate(II,I) Anion

The brown crystals of [NEt₄]₂[Se₃Br₈(Se₂Br₂)] ( 1 ) were obtained when selenium and bromine reacted in the solution of acetonitrile in the presence of tetraethylammonium bromide. The crystal structure of 1 has been determined by the X‐ray methods and refined to R = 0.0308 for 10433 reflections. The crystals are monoclinic, space group P2₁ with Z = 2 and a = 12.0393(3) Å, b = 11.8746(3) Å, c = 13.1946(3) Å, β = 96.561(1)° (123 K). In the solid state structure the anion of 1 is built up of Se₃Br₈ unit which consists of a triangular arrangement of three planar SeBr₄ units sharing a common edge through two μ₃‐bridging Br atoms, and one Se₂Br₂ molecule which is linked to one of μ₃‐bridging Br atoms. The three Se^II atoms form a triangle which is almost perpendicular to the planes given by three SeBr₄ moieties. The contact between the μ₃Br and the Se^I atom of the Se₂Br₂ molecule is 3.1711(8) Å and can be interpreted as a bond of the donor‐acceptor type with the μ₃Br as donor and the Se₂Br₂ molecule as acceptor. The terminal Se^II‐Br and μ₃Br‐Se^II bond lengths are in the ranges 2.3537(7)–2.4737(7) Å and 2.7628(7)–3.1701(7) Å, respectively. The bond lengths in coordinated Se₂Br₂ molecule are: Se^I‐Se^I = 2.2636(9) Å, Se^I‐Br = 2.3387(11) and 2.3936(8) Å.     

Synthetic mansfieldite,AlAsO4·2H2O

Hydro­thermally prepared mansfieldite, AlAsO₄·2H₂O (aluminium arsenate dihydrate), contains a vertex‐sharing three‐dimensional network of cis‐AlO₄(H₂O)₂ octahedra and AsO₄ tetrahedra [d_av(Al—O) = 1.907 (2) Å, d_av(As—O) = 1.685 (2) Å and θ_av(Al—O—As) = 134.5 (1)°].     

Synthesis and Structure of the New Compound La2O(CN2)2 Possessing an Interchanged Anion Proportion Compared to the Parent La2O2(CN2). Synthese und Kristallstruktur der neuen Verbindung La2O(CN2)2 mit einem vertauschten Anionenverhältnis gegenüber der Bezugsverbindung La2O2(CN2)

La₂O(CN₂)₂ was synthesized from a 1:1:2 molar reaction mixture of LaCl₃, LaOCl, and Li₂(CN₂) at 650 °C. Well developed single crystals were grown from a LiCl‐KCl flux. The crystal structure was refined as monoclinic (space group C2/c, Z = 2, a = 13.530(2) Å, b = 6.250(1) Å, c = 6.1017(9) Å, β = 104.81(2)°) from single crystal X‐ray diffraction data. The La³⁺ and (CN₂)^2— ions in the crystal structure of La₂O(CN₂)₂ can be compared to Fe³⁺ and S₂^2— ions in the cubic pyrite structure, being arranged like in a distorted NaCl type structure with their centers of gravity. In addition, the O^2— ions in La₂O(CN₂)₂ are occupying 1/4 of the tetrahedral voids formed by the arrangement of metal ions.     

Single Crystal Growth and Crystal Structure of Mercurous Diarsenate(V), (Hg2)2(As2O7)

Polycrystalline mercurous diarsenate(V), (Hg₂)₂(As₂O₇), was prepared by a redox‐reaction between stoichiometric amounts of HgO and As₂O₃. Canary yellow single crystals were obtained by subsequent chemical transport reactions using HgCl₂ as transport agent [550 → 500 °C, 5 d, sealed and evacuated silica ampoules]. The crystal structure (orthorhombic, Pnma, Z = 4, a = 9.9803(8), b = 12.2039(10), c = 7.2374(6)Å) is composed of two crystallographically independent Hgequation/tex2gif-stack-1.gif dumbbells (d¯(Hg—Hg) = 2.5133Å) with a symmetric oxygen coordination sphere, and a diarsenate group with a staggered conformation and a bent bridging angle As—O—As = 121.0(7)°. The building units are arranged in a layer‐like assembly parallel to (010) and are connected via common oxygen atoms to form a three‐dimensional network.     

Synthesis and Crystal Structure of Bis(tetraphenylphosphonium) Hexabromo‐diselenate(II)‐bis{dibromodiselenate(I)}, [PPh4]2[Se2Br6(Se2Br2)2], the Salt of a Mixed‐valence Bromoselenate(II,I) Anion

The Red crystals of [PPh₄]₂[Se₂Br₆(Se₂Br₂)₂] ( 1 ) were obtained when selenium and bromine reacted in the solution of acetonitrile in the presence of tetraphenylphosphonium bromide. The crystal structure of 1 has been determined by X‐ray diffraction and refined to R = 0.0201 for 4024 reflections. The crystals are triclinic, space group with Z = 2 and a = 11.2757(4) Å, b = 12.3347(5) Å, c = 12.4948(5) Å, α = 113.152(4)°, β = 114.745(4)°, γ = 91.208(3)° (120(2) K). In the solid state the anion of 1 is built up of the Se₂Br₆ core and two Se₂Br₂ molecules each of which is linked to one of the trans‐positioned terminal Br_t atoms of the Se₂Br₆ core. The central Se₂Br₆ part consists of a nearly planar arrangement of two planar SeBr₄ units sharing a common edge through two μ₂‐bridging Br atoms. The contact between the Br_t and the Se^I atom of the Se₂Br₂ molecule is 3.0872(5) Å and can be interpreted as a bond of the donor‐acceptor type with the Br_t as donor and the Se₂Br₂ molecule as acceptor. The terminal Se^II–Br and μ₂Br–Se^II bond lengths are 2.3654(4), 2.6699(5) Å and 2.5482(5), 3.0265(5) Å, respectively. The bond lengths in the coordinated Se₂Br₂ molecule are: Se^I–Se^I = 2.2686(5) Å, Se^I–Br = 2.3779(5) and 2.3810(5) Å.     

Potassium gallium hydrogenphosphate fluoride,K2Ga[H(HPO4)2]F2

Hydrothermally synthesized dipotassium gallium {hydrogen bis[hydrogenphosphate(V)]} difluoride, K₂Ga[H(HPO₄)₂]F₂, is isotypic with K₂Fe[H(HPO₄)₂]F₂. The main features of the structure are ([Ga{H(HPO₄)₂}F₂]²⁻)_n columns consisting of centrosymmetric Ga(F₂O₄) octahedra [average Ga—O = 1.966 (3) Å and Ga—F = 1.9076 (6) Å] stacked above two HPO₄ tetrahedra [average P—O = 1.54 (2) Å] sharing two O‐atom vertices. The charge‐balancing seven‐coordinate K⁺ cations [average K—O,F = 2.76 (2) Å] lie in the intercolumn space, stabilizing a three‐dimensional structure. Strong [O...O = 2.4184 (11) Å] and medium [O...F = 2.6151 (10) Å] hydrogen bonds further reinforce the connections between adjacent columns.     

Crystal Structure of the Ordered Double Perovskite,Sr2NiTeO6

The crystal structure of the ordered double perovskite Sr₂MnTeO₆ has been refined at ambient temperature from high resolution neutron and X‐ray powder diffraction data in the monoclinic space group I 1 2/m 1 with a = 5.6166(1) Å, b = 5.5807(1) Å, c = 7.8797(1) Å and β = 90.048(2)°. The structure is the result of out‐of‐phase (–) rotations of virtually undistorted NiO₆ and TeO₆ octahedra in the (0 – –) sense about two of the axes of the ideal cubic perovskite. Electron diffraction measurements have been used to confirm the proposed space group and structure.     

Preparation and Crystal Structure of the Strontium Aluminium Fluoride Sr5Al2F16

Single crystals of Sr₅Al₂F₁₆ crystallize in colourless translucent plates and have been prepared by solid state synthesis, starting from stoichiometric mixtures of the binary fluorides. The crystal structure has been determined and refined from single crystal diffractometer data (orthorhombic, space group Ccca (no. 68), a = 7.4488(4) Å, b = 12.4714(7) Å, c = 14.1411(8) Å, V = 1313.67(13) ų, Z = 4, R[F ² > 2σ(F ²)] = 0.025; wR2(F ² all) = 0.056, 971 structure factors, 56 parameters) and can be derived from a slightly distorted c.c.p. arrangement where 7/8 of the c.c.p. positions are occupied by the metal atoms. The main features of the structure are AlF₆ octahedra and SrF₈ polyhedra with mean distances d(Al–F) = 1.791 Å and d(Sr–F) = 2.531 Å, respectively.     

Synthesis,Crystal Structure and Properties of Li2Cu5(PO4)4

Li₂Cu^II₅(PO₄)₄ has been obtained by various reactions starting from copper or Cu₂O. Crystallization was achieved using I₂ as oxidant and mineralizer. The new orthophosphate crystallizes in space group P$\bar{1}$ , Z = 2, with a = 6.0502(3) Å, b = 9.2359(4) Å, c = 11.4317(5) Å, α = 75.584(2)°, β = 80.260(2)°, γ = 74.178(2)°, at 293 K. Its structure has been determined from X‐ray single‐crystal data and refined to R₁ = 0.022{wR₂ = 0.058 for 4633 unique reflections with F_o > 4σ (F_o)}. From magnetic measurements μ_eff = 1.51 μ_B/Cu and θ_P = –37.4 K have been determined. The Vis/NIR spectrum of aqua‐green Li₂Cu₅(PO₄)₄ shows a single broad band centered around $\bar{1}$ = 12000 cm^–1. Magnetic behavior and spectrum are discussed within the angular overlap model.     

SYNTHESIS OF A DINUCLEAR YLID COMPLEX DERIVED FROM P(OPh)3: CRYSTAL STRUCTURES OF [Cp2Fe2(CO)2(μ-CO) (μ-CHP(OPh)3)+][BF4 −] AND [Cp2Fe2(CO)2 (μ-CO)(μ-CHPPh3)+][BF4 −]

Abstract

[Cp₂Fe₂(CO)₂(μ-CO)(μ-CHP(OPh)₃)⁺][BF^? ₄] crystallizes in the centrosymmetric monoclinic space group P2₁/n with a = 12.553(7) Å, b = 16.572(11) Å, c = 15.112(8) Å, β = 100.00(4)°, V = 3096(3) ų and D(calcd.) = 1.579 g/cm³ for Z = 4. The structure was refined to R(F) = 5.83% for 1972 reflections above 4σ(F). The cation contains two CpFe(CO) fragments linked via an iron—iron bond (Fe(1)—Fe(2) = 2.544(3)Å), a bridging carbonyl ligand (Fe(1)—C(4) = 1.918(1) Å, Fe(2)—C(4) = 1.946(12)Å) and a bridging CHP(OPh)₃ ligand (Fe(1)—C(1) = 1.980(9)Å, Fe(2)—C(1) = 1.989(8)Å). Distances within the μ-CHP(OPh)₃ moiety include a rather short carbon—phosphorus bond [C(1)—P(1) = 1.680(10)Å] and P—O bond lengths of 1.550(7)–1.579(6)Å. The crystal is stabilized by a network of F…H—C interactions involving the BF^? ₄ anion.

[Cp₂Fe₂(CO)₂(μ-CO)(μ-CHPPh₃)⁺][BF^? ₄], which differs from the previous compound only in having a μ-CHPPh₃ (rather than μ-CHP(OPh)₃) ligand, crystallizes in the centrosymmetric monoclinic space group P2₁/c with a = 11.248(5)Å, b = 13.855(5)Å, c = 18.920(7)Å, β = 96.25(3)°, V = 2931(2)ų and D(calcd.) = 1.559 g/cm³ for Z = 4. This structure was refined to R(F) = 4.66% for 1985 reflections above 4σ(F). Bond lengths within the dinuclear cation here include Fe(1)-Fe(2) = 2.529(2)Å, Fe(1)—C(3) = 1.904(9) Å and Fe(2)—C(3) = 1.911(8) Å (for the bridging CO ligand) and Fe(1)—C(1P) = 1.995(6) Å and Fe(2)—C(1P) = 1.981(7) Å (for the bridging CHPPh₃ ligand). Distances within the μ-CHPPh₃ ligand include a longer carbon—phosphorus bond [C(1P)—P(1) = 1.768(6)Å] and P(1)—C(phenyl) = 1.797(7)–1.815(8) Å.     

Syntheses,and Crystal Structures of Indium Complexes with η2‐Piperidinyldithiocarbamate and η2‐Pyridine‐2‐Thionate Containing Ligands: Structures of [In(η2‐S2CNC5H10)3] and [In(η2‐pyS)3]

The η²‐thio‐indium complexes [In(η²‐thio)₃] (thio = S₂CNC₅H₁₀, 2 ; SNC₄H₄, (pyridine‐2‐thionate, pyS, 3 ) and [In(η²‐pyS)₂(η²‐acac)], 4 , (acac: acetylacetonate) are prepared by reacting the tris(η²‐acac)indium complex [In(η²‐acac)₃], 1 with HS₂CNC₅H₁₀, pySH, and pySH with ratios of 1:3, 1:3, and 1:2 in dichloromethane at room temperature, respectively. All of these complexes are identified by spectroscopic methods and complexes 2 and 3 are determined by single‐crystal X‐ray diffraction. Crystal data for 2 : space group, C2/c with a = 13.5489(8) Å, b = 12.1821(7) Å, c = 16.0893(10) Å, β = 101.654(1)°, V = 2600.9(3) ų, and Z = 4. The structure was refined to R = 0.033 and Rw = 0.086; Crystal data for 3 : space group, P2₁ with a = 8.8064 (6) Å, b = 11.7047 (8) Å, c = 9.4046 (7) Å, β = 114.78 (1)°, V = 880.13(11) ų, and Z = 2. The structure was refined to R = 0.030 and Rw = 0.061. The geometry around the metal atom of the two complexes is a trigonal prismatic coordination. The piperidinyldithiocarbamate and pyridine‐2‐thionate ligands, respectively, coordinate to the indium metal center through the two sulfur atoms and one sulfur and one nitrogen atoms, respectively. The short C‐N bond length in the range of 1.322(4)–1.381(6) Å in 2 and C‐S bond length in the range of 1.715(2)–1.753(6) Å in 2 and 3 , respectively, indicate considerable partial double bond character.     

Crystal Structure and Thermal Behaviour of the Mixed‐Valent Basic Mercury Nitrate HgI2(OH)(NO3)·HgIIO

Single crystals of the hitherto unknown compound Hg₂(OH)(NO₃)·HgO were obtained unintentionally during hydrothermal phase formation experiments in the system Ag—Hg— As—O. Hg₂(OH)(NO₃)·HgO (orthorhombic, Pbca, Z = 8, a = 6.4352(8), b = 11.3609(14), c = 15.958(2) Å, 1693 structure factors, 83 parameters, R1[F² > 2σ(F²)] = 0.0431) adopts a new structure type and is composed of two types of mercury‐oxygen zig‐zag‐chains running perpendicular to each other and of intermediate nitrate groups. One type of chains runs parallel [010] and consists of (Hg—Hg—OH) units with a typical Hg—Hg distance of 2.5143(10) Å for the mercury dumbbell, whereas the other type of chains runs parallel [100] and is made up of (O—Hg—O) units with short Hg—O distances of about 2.02Å. Both types of chains are concatenated by a common O atom with a slightly longer Hg—O distance of 2.25Å. The three‐dimensional assembly is completed by nitrate groups whose O atoms show Hg—O distances > 2.80Å. Weak hydrogen bonding between the OH group and one oxygen atom belonging to the nitrate group stabilizes this arrangement. Hg₂(OH)(NO₃)·HgO decomposes above 200 °C to HgO.     

Synthetic and structural chemistry of hexacobalt cluster compounds II. Preparation and structure of Co6(μ-S)8 (Ph2PCH2P(O)Ph2)6

Co₄(μ₃-S)₈(Ph₂PCH₂sP(O)Ph₂)₆, MW = 3012.5, space group R3 , has the hexagonal parameters, a = 26.764 (10), c = 16.979 (10) Å, V = 10532.8 ų, Z = 3. Mo Ka radiation, λ = 0.71069 Å, Dc = 1.425 g/cm³, μ = 9.94 cm^?3, F(000) = 4650, R = 0.073 and Rw = 0.077 for 1965 observed unique reflections with I > 3σ (I). The molecular structure consists of a distorted octahedral Co₄—core. The Co—Co and Co—S distances fall in the range of 2.805—2.838 and 2.213—2.253 Å, respectively.     

The Crystal Structure of MnF3 Revisited

We correct the crystal structure of MnF₃, of which the space group was reported as monoclinic C2/c (no. 15) with a = 8.9202, b = 5.0472, c = 13.4748 Å, β = 92.64°, V = 606.02 ų, Z = 12, mS48, T not given, likely 298 K. In the structure model proposed here, we use a unit cell of one third of the former volume. The ruby red crystals of MnF₃ were synthesized by a high-pressure/high-temperature method, where MnF₄ was used as a starting material. As determined on a single crystal, MnF₃ crystallizes in the monoclinic space group I2/a (no. 15) with a = 5.4964(11), b = 5.0084(10), c = 7.2411(14) Å, β = 93.00(3)°, V = 199.06(7) ų, Z = 4, mS16, T = 183(2) K. The crystal structure of MnF₃ is related by a direct group-subgroup transition to the VF₃ structure-type. We performed quantum chemical calculations on the crystal structure to allow the assignment of bands of the obtained vibrational spectra.     

A Novel Ruthenium(III) and Lithium Complex: Synthesis,Crystal Structure,and Magnetic Properties

A novel complex [Li₃{μ‐(H₂O)₆}(H₂O)₆]·[RuCl₆] has been synthesized and was characterized by single‐crystal X‐ray diffraction. The compound crystallizes in rhombohedral space group R3¯c, with the unit cell parameters a = b = 9.948(2)Å, c = 33.376(14)Å, γ = 120°, V = 2860.5(15)ų, Z = 6, D_c = 1.918 Mg m^—3, μ = 1.703 mm^—1, R = 0.0244, wR = 0.0478. The compound consists of a cation, which contains three lithium ions linked by six bridged water molecules, and an anion, which contains a ruthenium(III) ion. The whole complex can be described as a three‐dimensional structure linked by hydrogen bonds between cation and anion. The magnetic properties of the complex have been investigated. The IR, UV‐vis and EPR spectra are studied.