Synthese und Kristallstrukturen von Chlororhenaten(III) mit den zweiwertigen Kationen Ethylendiammonium und Piperazinium:(EnH2)2(Pipzh2)[Re3Cl12]2· 6H2O,und (PipzH2) [Re3Cl12]CI·H2O und (Pipzh2) [Re3Cl11(H2O)]·3H2O

Synthesis and Crystal Structures of Chlororhenates(III) with the Divalent Cations Ethylenediammonium and Piperazinium: (EnH₂)₂(PipzH₂) [Re₃Cl₁₂]₂·6H₂O, (EnH₂) (PipzH₂) [Re₃Cl₁₂]Cl· H₂O, and (PipzH₂) [Re₃Cl₁₁(H₂O)] · 3H₂O The deep red salt (EnH₂)₂(PipzH₂)[Re₃CI₁₂] · 6 H₂O ( 1 ), (EnH₂)(PipzH₂)[Re₃Cl₁₂]CI · H₂O ( 2 ), and (PipzH₂)[Re₃Cl₁₁(H₂O)] · 3H₂O ( 3 ) crystallize upon evaporation from hydrochloride acid solutions of ReCl₃ on addition of ethylenediammonium chloride (EnH₂Cl₂) and/or piperazinium chloride (PipzH₂Cl₂). The crystal structures have been determined from four-circle diffractometer data. 1: monoclinic; a = 1889.63(11), b = 1615.82(8), c = 790.28(4)pm; β = 101.354(5)°; Z = 2; P2₁/n; R = 0.119, R_w = 0.070. 2: triclinic; a = 1330.35(4), b = 1051.14(5), c = 1165.32(6)pm; α = 122.308(4), β = 102.412(3), γ = 92.226(4)°; Z = 2, P1 ; R = 0.092, R_w = 0.059. 3: orthorhombic; a = 971.43(4), b = 1619.51(7), c = 1478.87(6)pm; Z = 4; Pbcm; R = 0.034, R_w = 0.032.     

Synthese,Kristallstruktur und thermischer Abbau von Cs1,5[Re3I3Cl7,5(H2O)1,5]

Synthesis, Crystal Structure and Thermal Behaviour of Cs_1,5[Re₃I₃Cl_7,5(H₂O)_1,5] Dark brown tetrahedra of Cs_1,5[Re₃I₃Cl_7,5(H₂O)_1,5] crystallize on slow cooling of a hot saturated solution of ReI₃ and CsCl in conc. hydrochlorid acid. The crystal structure (cubic, P4 3m (No. 215), a = 1241.06(3)pm, V_m = 287.8(1) cm³mol^?1, Z = 4, R = 0.067, R_w = 0.037) is built up from isolated building units [Re₃I₃Cl_7,5(H₂O)_1,5]^1,5? with statistical distribution of chloride ions and water molecules in the in plane, terminal positions. Consistent with the result based on the X-ray analysis, the IR-spectrum shows one band for the OH stretching frequencies of the water molecules coordinated to the Re₃ triangle at 3240 cm^?1. The anions are arranged in the fashion of a cubic closest packing with the cesium ions occupying all octahedral and one quarter of the tetrahedral interstices. Temperature-dependent Guinier-Simon photographs in connection with DTA/TG investigations reveal that Cs_1,5[Re₃I₃Cl_7,5(H₂O)_1,5] releases water at 190°C accompanied with a structural transition and the dehydration product decomposes at 370°C to Cs₂ReCl_6?xI_x, Re₃I_3+yCl_6?y and rhenium metal.     

Eine Chlorosäure des dreiwertigen Rheniums: Hydroxonium-decachloro-diaqua-trirhenat(III)-pentahydrat,H3O[Re3Cl10(H2O)2] · 5H2O

A Chloroacid of Trivalent Rhenium: Hydroxonium Decachloro Diaqua Trirhenate(III) Pentahydrate, H₃O[Re₃Cl₁₀(H₂O)₂] · 5H₂O . A chloroacid of rhenium(III), H₃O[Re₃Cl₁₀(H₂O)₂] · 5H₂O, was obtained at room temperature from a saturated solution of “ReCl₃ · 2H₂O” with an excess of NaCl in concentrated hydrochloric acid. The crystal structure (tetragonal, P4₁2₁2 (Nr. 92); a = 1 150.9(2) pm; c = 1 592.2(6) pm; Z = 4; R = 0.086; R_w = 0.066) has been determined from four-circle diffractometer data. The structure contains isolated cluster anions, [Re₃ClClCl^i,t (H₂O)]^?, which are enclosed by a cage of water molecules. These building units are connected with each other through a “strong” hydrogen-bonding system.     

Synthesis and crystal structure of tetraethylammonium-μ-trichloro-heptachloro-diaqua-trirhenate(III)-dihydrate,NEt4[Re3Cl10(H2O)2] · 2 H2O

NEt₄[Re₃Cl₁₀(H₂O)₂] · 2 H₂O ( 1 ) was obtained from hydrochloric acid solutions of ReCl₃ and tetraethylammonium chloride, NEt₄Cl, by isothermal evaporation as dark red crystals. 1 crystallizes in the orthorhombic crystal system, space group Pnma, Z = 4, with a = 1838,7(2), b = 1456.9(1), c = 972.08(7) pm, V_m = 391.81(6) cm³ · mol^?l. The crystal structure consists of [Re₃Cl₁₀(H₂O)₂]^? anions that are arranged in the fashion of a hexagonal closest-packing of spheres. These are held together by partially disordered NEt₄⁺ cations and are bound into a hydrogen bonding system with the crystal water.     

[Rb2(H2O)2][Re3(μ-Cl)3Br7(H2O)2]2 · H2O,ein gemischtes Halogenid-Hydrat mit anionischen Dimeren {[Re3(μ-Cl)3Br7(H2O)2]2 · H2O}2−

[Rb₂(H₂O)₂][Re₃(μ-Cl)₃Br₇(H₂O)₂]₂ · H₂O, a Mixed Halide-Hydrate with the Anionic Dimer {[Re₃(μ-Cl)₃Br₇(H₂O)₂]₂ · H₂O}^2? [Rb₂(H₂O)₂][Re₃(μ-Cl)₃Br₇(H₂O)₂]₂ · H₂O crystallizes as dark redbrown single crystals from an hydrobromic-acid solution of ReCl₃ and RbBr at 0°C. An important feature of the crystal structure (monoclinic, C2/c; a = 1494.61(8); b = 835.71(4); c = 3079.96(19) pm; β = 97.801(4)°; V_m = 573.9(4) cm³mol^?1; R = 0.060; R_w = 0.038) is the connection of two anions [Re₃(μ-Cl)₃Br₇(H₂O)₂]^? via a water molecule to dimers, {[Re₃(μ-Cl)₃Br₇(H₂O)₂]₂ · H₂O}^2?. These dimeric units are contained in slabs that are stacked in the [001] direction and held together by Rb⁺ cations and crystal water.     

Reaction of hexanuclear niobium and tantalum halide clusters with mercury(II) halides. II. Semiconducting compounds with [Ta6Cl12]3+ unit

A series of paramagnetic clusters of the composition [(Ta₆Cl₁₂)Cl(H₂O)₅][HgX₄] · 9H₂)O (X = Cl, Br, I) has been prepared by the reaction of [Ta₆Cl₁₂]³⁺ methanol-water solutions with HgX₂ and NaX halides. The structure of [(Ta₆Cl₁₂)Cl(H₂O)₅][HgBr₄] · 9H₂O has been solved by X-ray diffraction in the cubic space group Fd 3m. Crystal data: a = 20.036(2) Å, V = 8043.0(1) ų, Z = 8, R = 0.048 (R_w = 0.051). The structure is composed of an octahedral [(Ta₆Cl₁₂)Cl(H₂O)₅]²⁺ cluster cation, tetrahedral [HgBr₄]²⁻ anion and crystal water molecules. The 2mm symmetry of the octahedron is reduced by the statistical distribution of the five water molecules, O(1), and chlorine, Cl(2), at the terminal coordination sites. Thus, the distances Ta-O(1) and Ta-Cl(2) are averaged to the value of 2.32(2) Å. The Ta-Ta and Ta-Cl(1) bond distances are 2.911(1) Å and 2.440(3) Å, respectively, whereas the Hg-Br bond distance is 2.564(3) Å. The cluster [(Ta₆Cl₁₂)Cl(H₂O)₅][HgBr₄] · 9H₂O is semiconducting with two levels governing conductivity with respective activation energies, E_al = 0.24 eV and E_a2 = 0.17 eV.     

Rhenium trichloride,ReCl3, and its 5/3-hydrate synthesis,crystal structure,and thermal expansion

Single crystals of ReCl₃ were grown by vacuum sublimation and the crystal structure (trigonal, R3 m, a = 1020.62(5), c = 2035.3(2) pm, V_m = 61.430(8) cm³mol^?1) was refined to R = 0.049, R_w = 0.031. From hydrochloric acid solutions of ReCl₃ containing me₄NCl, the hydrete ReCl₃ · 5/3 H₂O is salted out: hexagonal, P6 2_c, a = 944.89(3), c = 1470.07(9) pm, V_m = 114.09(1) cm³ mol^?1. The crystal structure (R = 0.079, R_w = 0.051) contains hexagonally closest-packed [Re₃Cl₉(H₂O)₃] molecules held loosely together by two molecules of crystal water positioned between the clusters in the [00.1] direction thereby forming chains that are shifted against each other by 1/2c. Thermal expansion of ReCl₃, ReCl₃. 5/3 H₂O and RbReCl₄ has been recorded and is discussed in connection with the crystal structures.     

Metallampullen als Mini‐Autoklaven: Synthese und Kristallstrukturen der Ammoniakate [Al(NH3)4Cl2][Al(NH3)2Cl4] und (NH4)2[Al(NH3)4Cl2][Al(NH3)2Cl4]Cl2

Metal Ampoules as Mini‐Autoclaves: Syntheses and Crystal Structures of [Al(NH₃)₄Cl₂][Al(NH₃)₂Cl₄] and (NH₄)₂[Al(NH₃)₄Cl₂][Al(NH₃)₂Cl₄]Cl₂ The salts [Al(NH₃)₄Cl₂]⁺[Al(NH₃)₂Cl₄]^–≡AlCl₃ · 3 NH₃ ( 1 ) and (NH₄⁺)²[Al(NH₃)₄Cl₂]⁺[Al(NH₃)₂Cl₄]^–(Cl^–)₂≡ AlCl₃ · 3 NH₃ · (NH₄)Cl ( 2 ) have been obtained as single crystals during the reactions of aluminum and aluminum trichloride, respectively, with ammonium chloride in sealed Monel metal containers. The crystal structure of 1 was determined again [triclinic, P‐1; a = 574.16(10); b = 655.67(12); c = 954.80(16) pm; α = 86.41(2); β = 87.16(2); γ = 84.89(2)°], that of 2 for the first time [monoclinic, I2/m; a = 657.74(12); b = 1103.01(14); c = 1358.1(3) pm; β = 103.24(2)°].     

Synthese von Oxovanadium(V)‐halogeno‐Komplexen der tripodalen Sauerstoffliganden LR— = [η5‐(C5H5)Co{PR2(O)}3]—, R = OMe,OEt

Syntheses of Oxovanadium(V) Halide Complexes Stabilized with Tripodal Oxygen Ligands L_R^— = [η⁵‐(C₅H₅)Co{PR₂(O)}₃]^—, R = OMe, OEt The sodium salts of the tripodal oxygen ligands L_R^— = [η⁵‐(C₅H₅)Co{PR₂(O)}₃]^— (R = OMe, OEt) react with the oxovanadium halides V(O)F₃ and V(O)Cl₃ to yield deep red compounds of the type [V(O)X₂L_R]. Halide exchange reactions with [V(O)Cl₂L_OMe] und [V(O)F₂L_OMe] aiming at the preparation of the analogous bromide complex [V(O)Br₂L_OMe] led to the isomer [VO(L_OMe)₂][V(O)Br₄]. The crystal structure of [V(O)Cl₂L_OMe] has been determined by single crystal x‐ray diffraction. The compound crystallizes in the monoclinic space group P2₁/n with a = 9.6332(8), b = 15.0312(11) and c = 15.3742(12)Å, β = 100.181(8)°. The coordination around vanadium is distorted octahedral.     

Synthesis,Molecular and Crystal Structure of a Second Rhenium Trichloride Hydrate: [Re3Cl9(H2O)3] · 10 H2O

The decahydrate of [Re₃Cl₉(H₂O)₃] is obtained from aqueous solutions of ReCl₃ at zero to -5°C. The crystal structure (orthorhombic, Pnma, Z = 4; a = 1125.16(3), b = 1 630.30(5), c = 1 378.84(5) pm) has been determined from single-crystal X-ray diffractometer data. The [Re₃Cl₉(H₂O)₃] molecules are stacked in the [0 1 0] direction and the rows of such molecules are separated by the crystal water molecules. Together with the water ligands, these form a rather strong hydrogen bonding system judging from O? O distances (d = 277 pm) alone.     

NH4[Re3Cl10(OH2)2] · 2 H2O: Synthese und Struktur Ein Beispiel für starke N?H …︁ O- und O?H …︁ Cl-Bindungen

NH₄[Re₃Cl₁₀(OH₂)₂] · 2 H₂O: Synthesis and Structure. An Example for “Strong” N? H …? O and O? H …? Cl Hydrogen Bonding The red NH₄[Re₃Cl₁₀(OH₂)₂] · 2 H₂O crystallizes from hydrochloric-acid solutions of ReCl₃ with NH₄Cl. It is tetragonal, P4₁2₁2, No. 92, a = 1157.6, c = 1614.5 pm, Z = 4. The crystal structure contains “isolated” clusters [Re₃Cl₁₀(OH₂)₂]^?. These contain Cl…?H? O? H…?Cl units with “very strong” hydrogen bonds: distances Cl? O are only 286 pm. NH₄⁺ has seven Cl^? as nearest neighbours and, additionally, one H₂O which belongs to a cluster [d(N? O1) = 271 pm] and one crystal water [d(N? O2) = 286 pm].     

Thiocyanate Compounds of [Nb6Cl12]2+: The structure of A4[Nb6Cl12(NCS)6](H2O)4 (A = K,Rb, NH4)

New compounds of the general formula A₄[Nb₆Cl₁₂(NCS)₆](H₂O)₄ (A = K, Rb, NH₄) were synthesized from Nb₆Cl₁₄ and ASCN in aqueous solutions. X-ray structure refinements were performed on single-crystal data of the three compounds. They are isotypic and crystallize with the space group P1 (Z = 1) and the lattice parameters: a = 877.9(3) pm, b = 1176.6(3) pm, c = 1187.0(3) pm, α = 114.29(1)°, β = 98.96(2)°, γ = 100.91(2)° for K₄[Nb₆Cl₁₂(NCS)₆](H₂O)₄ ( 1 ); a = 887.6(3) pm, b = 1184.0(4) pm, c = 1195.4(4) pm, α = 114.95(2)°, β = 98.84(2)°, γ = 101.31(2)° for Rb₄[Nb₆Cl₁₂(NCS)₆](H₂O)₄ ( 2 ) and a = 886.0(4) pm, b = 1181.1(6) pm, c = 1183.9(6) pm, α = 114.49(2)°, β = 99.48(3)°, γ = 101.53(1)° for (NH₄)₄[Nb₆Cl₁₂(NCS)₆](H₂O)₄ ( 3 ). Each centrosymmetric [Nb₆Cl₁₂(NCS)₆]^4? ion of the isotypic compounds contains six terminal thiocyanate groups being bound to the corners of the octahedral niobium cluster through the nitrogen atoms (d_{Nb? N} = 221.5(6)–224.3(6) pm, bond angles Nb? N? C 168.6(5)–176.4(6)°). The [Nb₆Cl₁₂(NCS)₆]^4? ions are linked via A? S and A? Cl interactions with the A cations. Half of the cations occur to be disordered along two crystallographic sites.     

Über die Kristallstrukturen der Cyanokomplexe [Co(NH3)6][Fe(CN)6], [Co(NH3)6]2[Ni(CN)4]3 · 2 H2O und [Cu(en)2][Ni(CN)4]

On the Crystal Structures of the Cyano Complexes [Co(NH₃)₆][Fe(CN)₆], [Co(NH₃)₆]₂[Ni(CN)₄]₃ · 2 H₂O, and [Cu(en)₂][Ni(CN)₄] Of the three title compounds X‐ray structure determinations were performed with single crystals. [Co(NH₃)₆][Fe(CN)₆] (a = 1098.6(6), c = 1084.6(6) pm, R3, Z = 3) crystallizes with the CsCl‐like [Co(NH₃)₆][Co(CN)₆] type structure. [Co(NH₃)₆]₂[Ni(CN)₄]₃ · 2 H₂O (a = 805.7(5), b = 855.7(5), c = 1205.3(7) pm, α = 86.32(3), β = 100.13(3), γ = 90.54(3)°, P1, Z = 1) exhibits a related cation lattice, the one cavity of which is occupied by one anion and 2 H₂O, whereas the other contains two anions parallel to each other with distance Ni…Ni: 423,3 pm. For [Cu(en)₂][Ni(CN)₄] (a = 650.5(3), b = 729.0(3), c = 796.5(4) pm, α = 106.67(2), β = 91.46(3), γ = 106.96(2)°, P1, Z = 1) the results of a structure determination published earlier have been confirmed. The compound is weakly paramagnetic and obeys the Curie‐Weiss law in the range T < 100 K. The distances within the complex ions of the compounds investigated (Co–N: 195.7 and 196.4 pm, Ni–C: 186.4 and 186.9 pm, resp.) and their hydrogen bridge relations are discussed.     

Oxidative Addition von N‐Chlortriphenylphosphanimin an Phosphortrichlorid und Antimontrichlorid. Kristallstrukturen von (Cl3PNPPh3)2[PCl6][ClHCl],[SbCl4(HNPPh3)2][SbCl6] und [Sb(NPPh3)4][SbCl6]

Oxidative Addition of N‐chlorotriphenylphosphoraneimine onto Phosphorus(III) Chloride and Antimony(III) Chloride. Crystal Structures of (Cl₃PNPPh₃)₂[PCl₆][ClHCl], [SbCl₄(HNPPh₃)₂][SbCl₆], and [Sb(NPPh₃)₄][SbCl₆] Phosphorus(III) chloride reacts with N‐chlorotriphenylphosphoraneimine, ClNPPh₃, in CH₂Cl₂ solution strongly exothermically via oxidative addition to give (Cl₃PNPPh₃)₂[PCl₆][ClHCl] ( 1 ). As a by‐product, Ph₃PNP(O)Cl₂ can be obtained, which is formed from PCl₃ and ClNPPh₃ in the presence of POCl₃. In contrast to these results, antimony(III) chloride reacts with ClNPPh₃ in CH₂Cl₂ solution to give a mixture of the phosphoraneimine complex [SbCl₄(HNPPh₃)₂][SbCl₆] ( 2 ) and the phosphoraneiminato complex [Sb(NPPh₃)₄][SbCl₆] ( 3 ). The complexes 1 ‐ 3 were characterized by IR spectroscopy and by single crystal X‐ray determinations. 1 : Space group C2/c, Z = 4, lattice dimensions at 193 K: a = 3282.0(2), b = 798.7(1), c = 1926.1(2) pm, β = 107.96(1)°, R₁ = 0.0302. 1 contains [Cl₃PNPPh₃]⁺ cations with PN bond lengths of 152.5(2) and 160.9(2) pm, and a PNP bond angle of 140.5(1)°. 2 ·CH₂Cl₂: Space group , Z = 2, lattice dimensions at 193 K: a = 1031.2(1), b = 1448.3(2), c = 1811,4(2) pm, α = 70.96(1)°, β = 87.67(1)°, γ = 75.37(1)°, R₁ = 0.0713. 2 ·CH₂Cl₂ contains cations [SbCl₄(HNPPh₃)₂]⁺ with octahedrally coordinated Sb atom and the HNPPh₃ ligand molecules being in trans‐position. Sb–N bond lengths are 207.6(6) and 209.3(6) pm, PN bond lengths 162.3(7) and 160.8(7), which approximately corresponds with double bonds. 3 ·0.5CH₂Cl₂: Space group P4/n, Z = 2, lattice dimensions at 193 K: a = b = 1678.8(1), c = 1244.3(1) pm, R₁ = 0.0618. 3 ·0.5CH₂Cl₂ contains [Sb(NPPh₃)₄]⁺ cations with tetrahedrally coordinated Sb atom and short Sb–N bond lengths of 193.7(6) pm. The PN distances of the phosphoraneiminato ligands, (NPPh₃)^? with 156.5(6) pm, correspond with double bonds, the SbNP bond angles are 130.6(3)°.     

Spektroskopische und kristallographische Charakterisierung von [Cl3PNPCl3][MoOCl4] und die Kristallstruktur von [Cl3PNPCl3][MoCl6]

Spectroscopic and Crystallographic Characterization of [Cl₃PNPCl₃][MoOCl₄] and Crystal Structure of [Cl₃PNPCl₃][MoCl₆] [Cl₃PNPCl₃][MoCl₆] was obtained by reaction of MoCl₅ with [Cl₃PNPCl₃]Cl or [Cl₃PNPCl₃][PCl₆]. Its crystal was determined by X-ray diffraction (R = 0.072 for 889 observed reflexions). Lattice parameters: a = 811.9, b = 2086, c = 1016 pm, β = 101.7°, space group P2₁/c, Z = 4. The [Cl₃PNPCl₃]⁺ ions have a similar structure as in Cl₃PNPCl₃ [PCl₆] with PNP angles of 139°, but the crystal structures of the two compounds are not isotypic. Partial hydrolysis of [Cl₃PNPCl₃][MoCl₆] yields [Cl₃PNPCl₃][MoOCl₄] which forms green, very moisture sensitive crystals. X-ray diffraction patterns of [Cl₃PNPCl₃][MoOCl₄] single crystals exhibit planes of diffuse scattered radiation perpendicular to c^*, which show the presence of a two-dimensional disorder. Additional sharp reflexions correspond to an averaged structure with the lattice parameters a = 1598.4, b = 1141.2 and c = 415.1 pm, Z = 2, space group Pba2. Refinement of the averaged     

Das Lanthan‐Dodekahydro‐closo‐Dodekaborat‐Hydrat [La(H2O)9]2[B12H12]3·15 H2O und sein Oxonium‐Chlorid‐Derivat [La(H2O)9](H3O)Cl2[B12H12]·H2O

The Lanthanum Dodecahydro‐closo‐Dodecaborate Hydrate [La(H₂O)₉]₂[B₁₂H₁₂]₃·15 H₂O and its Oxonium‐Chloride Derivative [La(H₂O)₉](H₃O)Cl₂[B₁₂H₁₂]·H₂O By neutralization of an aqueous solution of the free acid (H₃O)₂[B₁₂H₁₂] with basic La₂O₃ and after isothermic evaporation colourless, face‐rich single crystals of a water‐rich lanthanum(III) dodecahydro‐closo‐dodecaborate hydrate [La(H₂O)₉]₂[B₁₂H₁₂]₃·15 H₂O are isolated. The compound crystallizes in the trigonal system with the centrosymmetric space group (a = 1189.95(2), c = 7313.27(9) pm, c/a = 6.146; Z = 6; measuring temperature: 100 K). The crystal structure of [La(H₂O)₉]₂[B₁₂H₁₂]₃·15 H₂O can be characterized by two of each other independent, one into another posed motives of lattice components. The [B₁₂H₁₂]²⁻ anions (d(B–B) = 177–179 pm; d(B–H) = 105–116 pm) are arranged according to the samarium structure, while the La³⁺ cations are arranged according to the copper structure. The lanthanum cations are coordinated in first sphere by nine oxygen atoms from water molecules in form of a threecapped trigonal prism (d(La–O) = 251–262 pm). A coordinative influence of the [B₁₂H₁₂]²⁻ anions on La³⁺ has not been determined. Since “zeolitic” water of hydratation is also present, obviously the classical H–O^δ–···^+δH–O‐hydrogen bonds play a significant role in the stabilization of the crystal structure. During the conversion of an aqueous solution of (H₃O)₂[B₁₂H₁₂] with lanthanum trichloride an anion‐mixed salt with the composition [La(H₂O)₉](H₃O)Cl₂[B₁₂H₁₂]·H₂O is obtained. The compound crystallizes in the hexagonal system with the non‐centrosymmetric space group (a = 808.84(3), c = 2064.51(8) pm, c/a = 2.552; Z = 2; measuring temperature: 293 K). The crystal structure can be characterized as a layer‐like structure, in which [B₁₂H₁₂]²⁻ anions and H₃O⁺ cations alternate with layers of [La(H₂O)₉]³⁺ cations (d(La–O) = 252–260 pm) and Cl⁻ anions along [001]. The [B₁₂H₁₂]²⁻ (d(B–B) = 176–179 pm; d(B–H) = 104–113 pm) and Cl⁻ anions exhibit no coordinative influence on La³⁺. Hydrogen bonds are formed between the H₃O⁺ cations and [B₁₂H₁₂]²⁻ anions, also between the water molecules of [La(H₂O)₉]³⁺ and Cl⁻ anions, which contribute to the stabilization of the crystal structure.     

Dimethylsulfoxid‐Komplexe von Beryllium(II)‐chlorid. Kristallstrukturen von [Be(OSMe2)4]Cl2, [Be(OSMe2)3(H2O)]Cl2 und [Be(OSMe2)2(H2O)2]Cl2

Dimethylsulfoxide Complexes of Beryllium(II) Chloride. Crystal Structures of [Be(OSMe₂)₄]Cl₂, [Be(OSMe₂)₃(H₂O)]Cl₂ and [Be(OSMe₂)₂(H₂O)₂]Cl₂ Single crystals of the mixed ligand complexes [Be(OSMe₂)₃(H₂O)]Cl₂ ( 2 ) and [Be(OSMe₂)₂(H₂O)₂]Cl₂ ( 3 ) were obtained from saturated solutions of [Be(OSMe₂)₄]Cl₂ ( 1 ) in acetonitrile and dichloromethane, respectively, in the presence of traces of water, while single crystals of 1 were available by reaction of the carbodiphosphorane complex [BeCl₂{C(PPh₃)₂}] with DMSO/toluene solution. All complexes are characterized by X‐ray diffraction and IR spectroscopy. 1 : Space group Pbca, Z = 8, lattice dimensions at 193 K: a = 962.4(1), b = 1888.8(2), c = 2115.8(2) pm, R₁ = 0.0344. 1 consists of [Be(OSMe₂)₄]²⁺ cations with distorted tetrahedral coordination of the oxygen atoms of the DMSO molecules with Be–O distances of 161.9 pm on average, and chloride ions. 2 : Space group , Z = 2, lattice dimensions at 193 K: a = 903.9(2), b = 925.2(3), c = 1121.3(3) pm, α = 93.65(3)°, β = 108.03(3)°, γ = 115.20(3)°, R₁ = 0.0472. 3 : Space group , Z = 2, lattice dimensions at 173 K: a = 788.2(2), b = 801.6(2), c = 1070.7(3) pm, α = 86.66(2)°, β = 83.80(2)°, γ = 71.00(2)°, R₁ = 0.0699. 2 and 3 also form dications with distorted tetrahedral coordination of the Be²⁺ ions by the oxygen atoms of DMSO and water molecules, respectively. The chloride ions are associated by strong hydrogen bonds O–H···Cl to give three‐dimensional networks.     

Synthese,Kristallstruktur und magnetisches Verhalten von (2,4,6‐Trimethylpyridinium)10[ErCl6][ErCl5(H2O)]2Cl3

Preparation, Crystal Structure, and Magnetic Behaviour of (2,4,6‐Trimethylpyridinium)₁₀[ErCl₆][ErCl₅(H₂O)]₂Cl₃ Crystals of the complex chloride (2,4,6‐Trimethylpyridinium)₁₀[ErCl₆][ErCl₅(H₂O)]₂Cl₃ have been prepared by reaction of ErCl₃·6H₂O with 2,4,6‐Trimethylpyridiniumchloride in ethanol solution for the first time. The crystal structure has been determined from single crystal X‐ray diffraction data. The compound crystallizes monoclinically in the space group P2₁/a (Z = 2) with a = 1704.5(3) pm, b = 1696.7(2) pm, c = 1798.5(4) pm and β = 90.76(3)°. The structure contains octahedral building units [ErCl₆]^3— and [ErCl₅(H₂O)]^2—. The octahedra, the organic cations and isolated chloride anions are interconnected via hydrogen bonds forming layers parallel to the ac‐plane (0 1 0). The magnetic behaviour of (2,4,6‐Trimethylpyridinium)₁₀[ErCl₆][ErCl₅(H₂O)]₂Cl₃ has been studied. The magnetic data are interpreted by ligand field calculations applying the angular overlap model.     

Darstellung und Kristallstruktur von (CH3NH3)8[NdCl6][NdCl4(H2O)2]2Cl3

Preparation and Crystal Structure of (CH₃NH₃)₈[NdCl₆][NdCl₄(H₂0)₂]₂Cl₃ (CH₃NH₃)₈[NdCl₆][NdCl₄ (H₂O)₂]₂Cl₃ is for the first time prepared and investigated by X-ray, single crystal work. It crystallizes in the monoclinic system (space group C2/m, Z = 2) with a = 9.358(5), b = 17.424(9), c = 15.360(8) Å, β = 108.30(4)°. The structure contains besides isolated Cl^? ions distorted [NdCl₆]^3? octahedra and [NdCl₄(H₂O)₂]^? chains.     

Selenious Acid as a Ligand: Molecular and Crystal Structure of [Co(H2O)2Cl2(H2SeO3)2]

[Co(H₂O)₂Cl₂(H₂SeO₃)₂] (monoclinic, P2₁/c, Z = 2, a = 519.82(5), b = 1462.6(1), c = 643.09(7) pm, β = 92.51(1)°, R_all = 0.0583) was obtained from CoCl₂ and H₂SeO₃ as purple plate–shaped single crystals. In the compound, the Co²⁺ ions are octahedrally coordinated by two Cl^? ions, two H₂O molecules, and two monodentate H₂SeO₃ molecules, leading to neutral complexes [Co(H₂O)₂Cl₂(H₂SeO₃)₂]. They are connected by hydrogen bonds involving both chlorine and oxygen atoms as acceptor atoms.