Syntheses and Characterization of New Copper Complexes with the Heterocyclic Thione,AMTTO. X‐Ray Structures of [Cu(AMTTO)Cl2], [Cu(AMTTO)2]Cl,and [Cu(AMTTO)(PPh3)2Cl] (AMTTO = 4‐Amino‐6‐methyl‐1, 2, 4‐triazine‐3‐thione‐5‐one)

The complexes [Cu(AMTTO)Cl₂] ( 2 ), [Cu(AMTTO)₂]Cl ( 3 ), and [Cu(AMTTO)(PPh₃)₂Cl] ( 4 ) have been prepared and characterized by IR spectroscopy and elemental analyses. Also single‐crystal X‐ray diffraction studies on compound 2 , 3 and 4 revealed that AMTTO acts in 2 as a bidentate ligand via nitrogen and sulfur atoms, in 3 and 4 as a monodentate via sulfur atoms. Complex 3 was already mentioned in literature, but the structure was not described in detail. The molecules in 2 form infinite chains through additional weak Cu—S interactions along [010] indicating the Jahn‐Teller distortion of the d⁹ ion Cu²⁺. The infinite chains are connected by hydrogen bonding along [100]. Crystal data for 2 at —80°C: monoclinic, space group P2₁/m, a = 666.7(1), b = 609.4(1), c = 1132.6(2) pm, b = 95.46(2)°, Z = 2, R₁ = 0.0365; for 3 at —80°C: orthorhombic, space group Pbcn, a = 1291.2(2), b = 1146.5(1), c = 1000.5(1) pm, Z = 4, R₁ = 0.0315; for 4 at —80°C: monoclinic, space group, P2₁/n, a = 879.4(1), b = 1849.3(2), c = 2293.8(3) pm, β = 92.38(1)°, Z = 4, R₁ = 0.0688.     

Pyridin‐Komplexe von Seltenerd‐Trichloriden. Synthese und Kristallstrukturen von [YCl3(Py)4] und [LnCl3(Py)4] · 0,5 Py mit Ln = La und Er

Pyridine Complexes of Rare Earth Element Trichlorides. Syntheses and Crystal Structures of [YCl₃(py)₄] and [LnCl₃(py)₄] · 0.5 py with Ln = La and Er The pyridine complexes [YCl₃(py)₄] ( 1 ), [LaCl₃(py)₄] · 0.5 py ( 2 · 0.5 py), and [ErCl₃(py)₄] · 0.5 py ( 3 · 0.5 py) have been prepared from the diacetone‐alcohol complexes [LnCl₃(DAA)₂] or directly from the metal trichlorides with excess pyridine to give colourless, only sparingly moisture sensitive crystals. They were characterized by IR spectroscopy and by crystal structure determinations. 1 : Space group Pbca, Z = 16, lattice dimensions at –80 °C: a = 1647.4(1), b = 1743.1(1), c = 3190.5(1) pm, R₁ = 0.031. 2 · 0,5 Py: Space group P2₁/n, Z = 4, lattice dimensions at –80 °C: a = 978.9(1), b = 1704.5(1), c = 1589.5(1) pm, β = 103.61(1)°, R₁ = 0.0281. 3 · 0,5 Py: Space group P2₁/n, Z = 4, lattice dimensions at –80 °C: a = 970.1(1), b = 1706.4(1), c = 1566.1(1) pm, β = 103.46(1)°, R₁ = 0.0232. All complexes realize monomeric molecular structures with the metal atom in a distorted pentagonal‐bipyramidal coordination. One of the chlorine atoms and the four pyridine molecules are in the equatorial plane.     

Syntheses and X‐Ray Crystal Structures of New Copper(I) and Silver(I) Complexes containing Thione Ligands

The reaction of [(Ph₃P)₂CuCl]₂ with 4‐amino‐6‐methyl‐1,2,4‐triazine‐thione‐5‐one (AMTTO, 1 ) in methanol and further recrystallization from methanol/acetone solution gives [(C₄H₄N₃SON(=CMe₂)Cu(PPh₃)₂Cl] ( 2 ) as a neutral complex. [(C₄H₄N₃SON(=CMe₂)Ag(PPh₃)₂]NO₃ ( 4 ) can be obtained in excellent yield by the reaction of [(AMTTO)₂Ag]NO₃ ( 3 ) with triphenylphosphane in methanol/acetone. Both complexes were characterized by infrared spectroscopy, elemental analyses as well as by X‐ray diffraction studies. Crystal data for 2 at –80 °C: space group P1 with a = 1233.8(1), b = 1389.7(1), c = 1417.1(1) pm, α = 89.36(1)°; β = 65.10(1)°, γ = 65.95(1)°, Z = 2, R₁ = 0.0582 and for 4 at –80 °C: space group P1, with a = 1193.3(1), b = 1308.5(1), c = 1385.3(1) pm, α = 94.69(1)°, β = 109.14(1)°, γ = 93.42(1)°, Z = 2, R₁ = 0.0716.     

Neue Untersuchungen zum Reaktionsverhalten von Triorganylcyclotriphosphanen. Die Kristallstrukturen von [(PPh3)2Pt(PtBu)3], [(PPh3)2Pd(PtBu)2], [(CO)4Cr{(PiPr)3}2], [RhCl(PPh3)(PtBu)3], [(NiCO)6(μ2-CO)3{(PtBu)2}2] und [(CpFeCO)2(μ-CO)(μ-PHtBu)]+ · [FeCl3(thf)]–

New Research of Reaction Behaviour of Triorganylcyclotriphosphines. The Crystal Structures of [(PPh₃)₂Pt(P^tBu)₃], [(PPh₃)₂Pd(P^tBu)₂], [(CO)₄Cr{(PⁱPr)₃}₂], [RhCl(PPh₃)(P^tBu)₃], [(NiCO)₆(μ₂-CO)₃{(P^tBu)₂}₂], and [(CpFeCO)₂(μ-CO)(μ-PH^tBu)]⁺ · [FeCl₃(thf)]^– By the reaction of triorganylcyclotriphosphines with transition metal complexes single- and polynuclear compounds are formed, in which the cyclophosphines are bonded in different ways to the metal, the ring either preserving structure or under going ring opening. Depending on the reaction conditions the following compounds can be characterized: [(PPh₃)₂Pt(P^tBu)₃] ( 1 ), [(PPh₃)₂Pd(P^tBu)₂] ( 2 ), [(CO)₄Cr{(PⁱPr)₃}₂] ( 3 ), [RhCl(PPh₃)(P^tBu)₃] ( 4 ), [(NiCO)₆(μ₂-CO)₃{(P^tBu)₂}₂] ( 5 ) and [(CpFeCO)₂(μ-CO)(μ-PH^tBu)]⁺ · [FeCl₃(thf)]^– ( 6 ). The structures of 1 – 6 were obtained by X-ray single crystal structure analysis ( 1 : space group P2₁/n (No. 14), Z = 4, a = 1279.6(3) pm, b = 1733.1(4) pm, c = 2079.1(4) pm, β = 90.20(3)°; 2 : space group P2₁/c (No. 14), Z = 4, a = 1053.3(2) pm, b = 2085.2(4) pm, c = 1855.7(4) pm, β = 98.77(3)°; 3 : space group P 1 (No. 2), Z = 2, a = 1022.6(2) pm, b = 1026.4(2) pm, c = 1706.0(3) pm, α = 82.36(3)°, β = 86.10(3)°, γ = 64.40(3)°; 4 : space group P 1 (No. 2), Z = 2, a = 980.2(2) pm, b = 1309.5(3) pm, c = 1573.4(3) pm, α = 99.09(3)°, β = 99.46(3)°, γ= 111.87(3)°; 5 : space group P2₁/c (No. 14), Z = 4, a = 1804.0(5) pm, b = 2261.2(6) pm, c = 1830.1(7) pm, β = 96.99(3)°; 6 : space group P2₁/c (No. 14), Z = 4, a = 943.2(3) pm, b = 2510.6(7) pm, c = 1325.1(6) pm, β = 98.21(3)°).     

[(C2H5)3NH]2Sn3Se7 · 0,25 H2O und [(C3H7)2NH2]4Sn4Se10 · 4 H2O

Synthesis, Structure, and Properties of Some Selenidostannates. II. [(C₂H₅)₃NH]₂Sn₃Se₇ · 0,25 H₂O and [(C₃H₇)₂NH₂]₄Sn₄Se₁₀ · 4 H₂O The new selenidostannate hydrates [(C₂H₅)₃NH]₂Sn₃Se₇ · 0.25 H₂O ( I ) and [(C₃H₇)₂NH₂]₄Sn₄Se₁₀ · 4 H₂O ( II ) were synthesized from an aqueous suspension of triethylammonium (tripropylammonium), tin, selenium I and in addition sulfur II at 130 °C. I crystallizes at ambient temperature in the monoclinic space group P2₁/n (a = 2069,3(4) pm, b = 1396,6(3) pm, c = 2342,8(5) pm, β = 114,68(3)°, Z = 8) and is characterized by two different anions, chains from edge‐sharing [Se₃Se₇]^2– units and nets from trigonal SnSe₅ bipyramids. II crystallizes at ambient temperature in the tetragonal space group I4₁/amd (a = 2150,0(3) pm, c = 1174,4(2) pm, Z = 4) and contains adamantane like [Sn₄Se₁₀]^4–‐cages. The UV‐VIS spectra of the selenidostannates demonstrate that the absorption edges red shift as the dimensionality of the compounds is increased.     

Synthesis,Characterization of a Novel 1,2,4‐Thiotriazine Derivative (CAMTTO), and Copper(I) and Silver(I) Complexes thereof (CAMTTO = {(4‐[(4‐Chlorobenzylidene)‐amino]‐6‐methyl‐3‐thioxo‐[1,2,4]‐triazin‐3,4‐dihydro(2H)‐5‐one)}

The reaction of 4‐amino‐6‐methyl‐1,2,4‐triazin‐thione‐5‐one (H₂AMTTO, 1 ) with 4‐chlorobenzaldhyde led to the corresponding iminic compound {(4‐[(4‐chloro‐benzylidene)‐amino]‐6‐methyl‐3‐thioxo[1,2,4]‐triazin‐3,4‐dihydro(2H)‐5‐one), CAMTTO ( 2 ). Treatment of 2 with copper(I) chloride in chloroform gave the dimeric complex [{(CAMTTO)₂CuCl}₂]·2CHCl₃ ( 3 ). Treatment of 2 with copper(I) chloride and silver(I) nitrate in the presence of the co‐ligand triphenylphophane gave the complexes [(CAMTTO)CuCl(PPh₃)₂] ( 4 ) and [(CAMTTO)Ag(PPh₃)₂]NO₃·2CHCl₃ ( 5 ). All compounds have been characterized by elemental analyses, ¹H NMR spectroscopy, IR spectroscopy, and partly by mass spectrometry and X‐ray diffraction studies. In addition 4 and 5 have been characterized by ³¹P{¹H} NMR spectroscopy. Crystal data for 2 at ?80 °C: monoclinic, space group P2₁/c, a = 1370.3(1), b = 767.8(1), c = 1268.7(1) pm, β = 107.12(1)°, Z = 4, R₁ = 0.0379; for 3 at ?80 °C: monoclinic, space group P2₁/c, a = 1442.6(2), b = 878.8(1), c = 2558.7(3) pm, β = 95.31(1)°, Z = 2, R₁ = 0.0746; for 4 at ?80 °C: triclinic, space group , a = 1287.9(1), b = 1291.7(1), c = 1359.5(1) pm, α = 90.44(1)°, β = 94.81(1)°, γ = 107.54(1)°, Z = 2, R₁ = 0.0359 and for 5 at ?80 °C: triclinic, space group , a = 1060.5(1), b = 1578.2(2), c = 1689.6(2) pm, α = 87.70(1)°, β = 86.66(1)°, γ = 76.84(1)°, Z = 2, R₁ = 0.0487.     

A New Complex as a Dimer of a Silver Ion with AMTTO and Phosphane Ligands. The Crystal Structure of {[(AMTTO)Ag(PPh3)2]NO3}2·0.5CH3OH·0.5H2O

Reaction of 4‐amino‐6‐methyl‐1,2,4‐triazine‐3‐thione‐5‐on (AMTTO) as a bidentate ligand with silver nitrate and triphenyl phosphine as the co‐ligand make the centrosymmetric dimeric complex {[(AMTTO)Ag(PPh₃)₂]NO₃}₂·0.5CH₃OH·0.5H₂O ( 1 ). 1 was characterized by elemental analyses, IR‐ and NMR spectroscopy as well as X‐ray diffraction studies. The silver atom in 1 has distorted tetrahedral coordination. 1 crystallizes in triclinic space group . Crystal data for 1 at −80 °C: a = 1185.8(1), b = 1314.6(1), c = 1385.3(1) pm, α = 97.78(1)°, β = 111.38(1)°, γ = 92.41(1)°, Z = 2, R₁ = 0.0377.     

Synthese und Struktur der Komplexe [(n‐Bu)4N]2[{(THF)Cl4Re≡N}2PdCl2], [Ph4P]2[(THF)Cl4Re≡N‐PdCl(μ‐Cl)]2 und [(n‐Bu)4N]2[Pd3Cl8]

Synthesis and Crystal Structure of the Complexes [(n‐Bu)₄N]₂[{(THF)Cl₄Re≡N}₂PdCl₂], [Ph₄P]₂[(THF)Cl₄Re≡N‐PdCl(μ‐Cl)]₂ and [(n‐Bu)₄N]₂[Pd₃Cl₈] The threenuclear complex [(n‐Bu)₄N]₂[{(THF)Cl₄Re≡N}₂ PdCl₂] ( 1 ) is obtained in THF by the reaction of PdCl₂(NCC₆H₅)₂ with [(n‐Bu)₄N][ReNCl₄] in the molar ration 1:2. It forms orange crystals with the composition 1· THF crystallizing in the monoclinic space group C2/c with a = 2973.3(2); b = 1486.63(7); c = 1662.67(8)pm; β = 120.036(5)° and Z = 4. If the reaction is carried out with PdCl₂ instead of PdCl₂(NCC₆H₅)₂, orange crystals of hitherto unknown [(n‐Bu)₄N]₂[Pd₃Cl₈] ( 3 ) are obtained besides some crystals of 1· THF. 3 crystallizes with the space group P1¯ and a = 1141.50(8), b = 1401.2(1), c = 1665.9(1)pm, α = 67.529(8)°, β = 81.960(9)°, γ = 66.813(8)° and Z = 2. In the centrosymmetric complex anion [{(THF)Cl₄Re≡N}₂PdCl₂]^2— a linear PdCl₂ moiety is connected in trans arrangement with two complex fragments [(THF)Cl₄Re≡N]^— via asymmetric nitrido bridges Re≡N‐Pd. For Pd(II) thereby results a square‐planar coordination PdCl₂N₂. The linear nitrido bridges are characterized by distances Re‐N = 163.8(7)pm and Pd‐N = 194.1(7)pm. The crystal structure of 3 contains two symmetry independent, planar complexes [Pd₃Cl₈]^2— with the symmetry 1¯, in which the Pd atoms are connected by slightly asymmetric chloro bridges. By the reaction of equimolar amounts of [Ph₄P][ReNCl₄] and PdCl₂(NCC₆H₅)₂ in THF brown crystals of the heterometallic complex, [Ph₄P]₂[(THF)Cl₄Re≡N‐PdCl(μ‐Cl)]₂ ( 2 ) result. 2 crystallizes in the monoclinic space group P2₁/n with a = 979.55(9); b = 2221.5(1); c = 1523.1(2)pm; β = 100.33(1)° and Z = 2. In the central unit ClPd(μ‐Cl)₂PdCl of the centrosymmetric anionic complex [(THF)Cl₄Re≡N‐PdCl(μ‐Cl)]₂^2— the coordination of the Pd atoms is completed by two nitrido bridges Re≡N‐Pd to nitrido complex fragments [(THF)Cl₄Re≡N]^— forming a square‐planar arrangement for Pd(II). The distances in the linear nitrido bridges are Re‐N = 163.8(9)pm and Pd‐N = 191.5(9)pm.     

Synthesis,Characterization and Molecular Structure of a New Tetrameric Palladium(II) Complex Containing Schiff‐Bases Derived from AMTTO (AMTTO = 4‐amino‐6‐methyl‐1,2,4‐triazine‐thione‐5‐one)

The reactions of AMTTO = 4‐amino‐6‐methyl‐1,2,4‐triazine‐thione‐5‐one (AMTTO, 1 ) with 2‐hydroxybenzaldehyde (salicylaldehyde) and 4‐hydroxybenzaldehyde in methanol under reflux conditions led to the corresponding Schiff‐bases ( H₂L1 and H₂L2 ). The reaction of H₂L1 with palladium acetate in ethanol and additional recrystallization from toluene gave the tetrameric complex [Pd(L)]₄·2C₇H₈ ( 2 ). All compounds were characterized by infrared spectroscopy, elemental analyses as well as by X‐ray diffraction studies. Crystal data for H₂L1 at ?80 °C: space group P2₁/c with a = 1285.4(1), b = 707.7(1), c = 1348.2(1) pm, β = 109.32(1)°, Z = 4, R₁ = 0.0328, H₂L2 at ?80 °C: space group P4₃2₁2 with a = 762.5(1), b = 762.5(1), c = 4038.9(2) pm, Z = 8, R₁ = 0.025 and for 2 at ?103 °C: space group C2/c with a = 2862.5(6), b = 2847.6(6), c = 1727.8(4) pm, β = 105.18(3)°, Z = 8, R₁ = 0.0704.     

Synthese und Struktur von [(Me2PhP)3Cl2ReN]2ReCl4, [(Me2PhP)3Cl2ReN]2ReCl4 · 2 SbCl3 und [Re(NH)Cl2(PMe2Ph)3][SbCl6]

Synthesis and Structure of [(Me₂PhP)₃Cl₂ReN]₂ReCl₄, [(Me₂PhP)₃Cl₂ReN]₂ReCl₄ · 2 SbCl₃ and [Re(NH)Cl₂(PMe₂Ph)₃][SbCl₆] The reaction of ReNCl₂(PMePh)₃ with SbCl₅ in toluene yields the trinuclear complex [(Me₂PhP)₃Cl₂Re≡N]₂ReCl₄ · 2 SbCl₃ ( 1 · 2 SbCl₃). It forms triclinic crystals with the composition 1 · 2 SbCl₃, as well as monoclinic crystals 1 · 2 SbCl₃ · 4 C₇H₈. The monoclinic crystals with the space group P2₁/c, and a = 1212.3(2), b = 2098.5(4), c = 1827.7(3) pm, β = 95.51(1)°, Z = 2, have been used for a crystal structure determination. In the centrosymmetric complex 1 two complexes ReNCl₂(PMe₂Ph)₃ coordinate with their nitrido ligands a square planar, central unit ReCl₄. The SbCl₃ molecules are coordinated by chlorine bridges to Cl atoms of 1 , and, in addition, connect the complexes 1 with each other. The SbCl₃ free compound 1 is obtained in good yield by the reaction of ReNCl₂(PMePh)₃ with ReCl₄(NCEt)₂. It crystallizes in the triclinic space group P1 with a = 1037.7(3), b = 1153.0(2), c = 1393.8(3) pm, α = 72.31(2)°, β = 74.06(2)°, γ = 67.94(2)°, and Z = 1. The bond lengths of the Re–N triple bonds are 172 pm in 1 and 170 pm in 1 · 2 SbCl₃. By the reaction of ReNCl₂(PMePh)₃ with SbCl₅ in CH₂Cl₂ the solvent is decomposed forming HCl which protonates the nitrido ligand to afford the imido complex [Re(NH)Cl₂(PMe₂Ph)₃][SbCl₆] ( 2 ) crystallizing in the monoclinic space group P2₁/n with a = 1221.4(2), b = 1358.6(2), c = 2177.3(1) pm, β = 92,72(1)° and Z = 4. The Re–N distance in the almost linear unit Re≡N–H is 169,1 pm.     

Phosphaniminato‐Komplexe des Hafniums. Die Kristallstrukturen von [Hf(NPPh3)4] · 3 THF und [Hf(NPPh3)2Cl2(HNPPh3)2]

Phosphoraneiminato Complexes of Hafnium. Crystal Structures of [Hf(NPPh₃)₄] · 3 THF and [Hf(NPPh₃)₂Cl₂(HNPPh₃)₂] The phosphoraneiminato complexes [Hf(NPPh₃)₄] · 3 THF ( 1 · 3 THF) and [Hf(NPPh₃)₂Cl₂(HNPPh₃)₂] ( 2 ) have been prepared as colourless, moisture sensitive single crystals by reactions of hafnium tetrachloride with [CsNPPh₃]₄ · 2 toluene in tetrahydrofurane solutions by application of different ratios of the educts. Both complexes are characterized by IR spectroscopy and X‐ray crystal structure determinations. 1 · 3 THF: space group P 1, Z = 4, lattice dimensions at 193 K: a = 2007.6(1); b = 2064.2(1); c = 2115.9(1) pm; α = 109.193(4)°; β = 111.285(4)°; γ = 96.879(4)°; R₁ = 0.0506. 1 forms monomeric molecules with tetrahedral coordination of the nitrogen‐atoms of the (NPPh₃^–)‐groups towards the Hafnium atom. The HfN distances of 200.9 pm in average correspond with double bonds. 2 : space group P 1, Z = 4, lattice dimensions at 193 K: a = 1444.0(1); b = 1928.1(1); c = 2455.8(2) pm; α = 67.273(8)°; β = 87.445(8)°; γ = 87.082(8)°; R₁ = 0.0312. 2 has a monomeric molecular structure with octahedral coordination of the hafnium atom. The chlorine atoms are in trans position to one another, whereas the nitrogen atoms of the phosphoraneiminato groups (NPPh₃^–) are in trans position towards the nitrogen atoms ot the phosphorane imine molecules (HNPPh₃). The HfN bond lengths of the (NPPh₃^–) groups of 199.7 pm in average correspond with double bonds, whereas the HfN distances of the HNPPh₃ molecules with bond lengths of 230.2 pm in average are of donor‐acceptor type.     

Eine neue Synthese und die Kristallstruktur von Hexaphenyl‐cyclo‐triphosphazen, [NPPh2]3 · THF

A New Synthesis and the Crystal Structure of Hexaphenyl‐cyclo‐triphosphazene, [NPPh₂]₃ · THF [NPPh₂]₃ · THF ( 1 · THF) has been prepared from KNPPh₃ in THF solution in the presence of MoO₃ and 18‐crown‐6. According to the crystal structure determination all structural parameters are similar to known symmetric substituted cyclo‐triphosphazenes. The dihedral angles of the phenyl groups with the “best plane” P₃N₃ lie between 50 and 67°. 1 · THF: Space group P 1, Z = 2, lattice dimensions at –80 °C: a = 1146.5(1), b = 1360.5(1), c = 1382.9(1) pm, α = 108.06(1)°, β = 103.32(1)°, γ = 112.19(1)°, R₁ = 0.0441.     

Synthese und Kristallstrukturen der Nitrido‐Chloro‐Molybdate [Mg(THF)4{NMoCl4(THF)}2] · 4 CH2Cl2 und [Li(12‐Krone‐4)(NMoCl4)]2 · 2 CH2Cl2

Syntheses and Crystal Structures of the Nitrido‐chloro‐molybdates [Mg(THF)₄{NMoCl₄(THF)}₂] · 4 CH₂Cl₂ and [Li(12‐Crown‐4)(NMoCl₄)]₂ · 2 CH₂Cl₂ Both the title compounds as well as [Li(12‐crown‐4)₂]⁺MoNCl₄^– were made from MoNCl₃ and the chlorides MgCl₂ and LiCl, respectively, in dichloromethane suspensions in the presence of tetrahydrofuran and 12‐crown‐4, respectively. They form orange‐red moisture‐sensitive crystals, which were characterized by their IR spectra and partly by crystal structure analyses. [Mg(THF)₄{NMoCl₄(THF)}₂] · 4 CH₂Cl₂ ( 1 ): space group C2/m, Z = 2, lattice dimensions at –50 °C: a = 1736.6(1), b = 1194.8(1), c = 1293.5(2) pm; β = 90.87(1)°; R₁ = 0.037. In 1 the magnesium ion is coordinated octahedrally by the oxygen atoms of the four THF molecules and in trans‐position by the nitrogen atoms of the two [N≡MoCl₄(THF)]^– ions. [Li(12‐crown‐4)(NMoCl₄)]₂ · 2 CH₂Cl₂ ( 2 ): space group P 1, Z = 1, lattice dimensions at –70 °C: a = 930.4(1), b = 957.9(1), c = 1264.6(1) pm; α = 68.91(1)°, β = 81.38(1)°, γ = 63.84(1)°; R₁ = 0.0643. 2 forms a centrosymmetric ion ensemble in the dimeric cation of which, i. e. [Li(12‐crown‐4)]₂²⁺, the lithium ions on the one hand are connected to the four oxygen atoms each of the crown ether molecules in a way not yet known; and in addition, each of the lithium ions enters into a intermolecular Li–O bond with neighboring crown ether molecules under formation of a Li₂O₂ four‐membered ring. The two N≡MoCl₄^– counterions are loosely coordinated to one oxygen atom each of the crown ether molecules with Mo–O distances of 320.2 pm.     

Synthesis,Characterization and Crystal Structure of Dimeric {[(AMTTO)2Ag]NO3}2 (AMTTO = 4‐Amino‐6‐methyl‐1, 2, 4‐triazine‐3(2H)‐thione‐5‐one)

The reaction of 4‐Amino‐6‐methyl‐1, 2, 4‐triazine‐3(2H)‐thione‐5‐one (AMTTO, 1 ) with silver nitrate in methanol led to the dimeric complex {[(AMTTO)₂Ag]NO₃}₂ ( 2 ). 2 was characterized by elemental analyses and IR spectroscopy as well as by X‐ray structure analysis. Crystal data for 2 at ?80 °C: crystal system orthorhombic, space group P2₁2₁2₁ with a = 1043.6(1), b = 1329.6(1), c = 2358.4(1) pm, Z = 8 and R₁ = 0.037. The cation possesses a highly distorted linear coordination sphere in the solid state.     

Synthesis and Crystal Structure of a New Silver(I) Complex

The reaction of 4-amino-6-methyl-1,2,4-triazine-3(2 H)-thione-5-one (AMTTO) with silver(I) nitrate in methanol gives the complex [Ag(AMTTO)₂]NO₃ ( 1 ). 1 was characterized by IR and ¹³C NMR spectroscopy and by an X-ray structure analysis [space group C2/c, Z = 4, lattice dimensions at –80 °C: a = 1306.7(2), b = 1139.0(2), c = 1089.2(1) pm, β = 94.54(1)°, R₁ = 0.0294]. The cation possesses a highly distorted linear coordination sphere in the solid state.     

Über die komplexen Hydroxide des Chroms: Na9[Cr(OH)6]2(OH)3 · 6 H2O und Na4[Cr(OH)6]X · H2O (X = Cl, (S2)1/2) – Synthese,Kristallstruktur und thermisches Verhalten

Complex Hydroxides of Chromium: Na₉[Cr(OH)₆]₂(OH)₃ · 6 H₂O and Na₄[Cr(OH)₆]X · H₂O (X = Cl, (S₂)_1/2) – Synthesis, Crystal Structure, and Thermal Behaviour Green plate‐like crystals of Na₉[Cr(OH)₆]₂(OH)₃ · 6 H₂O (triclinic, P1, a = 872.9(1) pm, b = 1142.0(1) pm, c = 1166.0(1) pm, α = 74.27(1)°, β = 87.54(1)°, γ = 70.69(1)°) are obtained upon slow cooling of a hot saturated solution of Cr^III in conc. NaOH (50 wt%) at room temperature. In the presence of chloride or disulfide the reaction yields green prismatic crystals of Na₄[Cr(OH)₆]Cl · H₂O (monoclinic, C2/c, a = 1138.8(2) pm, b = 1360.4(1) pm, c = 583.20(7) pm, β = 105.9(1)°) or green elongated plates of Na₄[Cr(OH)₆](S₂)_1/2 · H₂O (monoclinic, P2₁/c, a = 580.8(1) pm, b = 1366.5(3) pm, c = 1115.0(2) pm, β = 103.71(2)°), respectively. The latter compounds crystallize in related structures. All compounds can be described as distorted cubic closest packings of the anions and the crystal water molecules with the cations occupying octahedral sites in an ordered way. The thermal decomposition of the compounds was investigated by DSC/TG or DTA/TG and high temperature X‐ray powder diffraction measurements. In all cases the final decomposition product is NaCrO₂.     

Die Kristallstruktur der hydratisierten Cyanokomplexe NMe4MnII[(Mn, Cr)III(CN)6] · 3 H2O und NMe4Cd[MIII(CN)6] · 3 H2O (MIII = Fe,Co): Verwandte des Berliner Blaus

The Crystal Structure of the Hydrated Cyano Complexes NMe₄Mn^II[(Mn, Cr)^III(CN)₆] · 3 H₂O and NMe₄Cd[M^III(CN)₆] · 3 H₂O (M^III = Fe, Co): Compounds Related to Prussian Blue The crystal structures of the isotypic tetragonal compounds (space group I4, Z = 10) NMe₄Mn^II · [(Mn, Cr)^III(CN)₆] · 3 H₂O (a = 1653.2(4), c = 1728.8(6) pm), NMe₄Cd[Fe(CN)₆] · 3 H₂O (a = 1642.7(1), c = 1733.1(1) pm) and NMe₄Cd[Co(CN)₆] · 3 H₂O (a = 1632.1(2), c = 1722.4(3) pm) were determined by X‐rays. They exhibit ⊥ c cyanobridged layers of octahedra [M^III(CN)₆] and [M^IIN₄(OH₂)₂], which punctually are interconnected also || c to yield altogether a spaceous framework. The M^II atoms at the positions linking into the third dimension are only five‐coordinated and form square pyramids [M^IIN₅] with angles N–M^II–N near 104° and distances of Mn–N: 1 × 214, 4 × 219 pm; Cd–N: 1 × 220 resp. 222, 4 × 226 resp. 228 pm. Further details and structural relations within the family of Prussian Blue are reported and discussed.     

Die Kristallstruktur des Diacetonalkohol‐Komplexes [Mn(DAA)3]2+[MnI4]2– · DAA

Crystal Structure of the Diacetone Alcohol Complex [Mn(DAA)₃]²⁺[MnI₄]^2– · DAA The title compound has been prepared from MnI₂ and excess diacetone alcohol (4‐hydroxy‐4‐methyl‐2‐pentanon) to give brown single crystals which were suitable for a crystal structure determination. Space group P2₁/c, Z = 4, lattice dimensions at 157 K: a = 1158.3(1), b = 1806.0(1), c = 1846.5(2) pm, β = 97.421(8)°, R₁ = 0.0381. The structure consists of [Mn(DAA)₃]²⁺ ions with distorted octahedral environment of the manganese atom, tetrahedral [MnI₄]^2– ions and a diacetone alcohol molecule which is connected by two hydrogen bridges with the complex cation.     

Darstellung,Schwingungsspektren und Kristallstrukturen von [(Ph3P)2N]2[(W6Cl)I] · 2 Et2O · 2 CH2Cl2 und [(Ph3P)2N]2[(W6Cl)(NCS)] · 2 CH2Cl2

Synthesis, Crystal Structures, and Vibrational Spectra of [(Ph₃P)₂N]₂[(W₆Cl )I ] · 2 Et₂O · 2 CH₂Cl₂ and [(Ph₃P)₂N]₂[(W₆Cl )(NCS) ] · 2 CH₂Cl₂ By treatment of [(W₆Cl)I]^2– with (SCN)₂ in dichloromethane at –20 °C the hexaisothiocyanato cluster anion [(W₆Cl)(NCS)]^2– is formed. X‐ray structure determinations have been performed on single crystals of [(Ph₃P)₂N]₂[(W₆Cl)I] · 2 CH₂Cl₂ · 2 Et₂O ( 1 ) (triclinic, space group P1, a = 10.324(5), b = 14.908(3), c = 17.734(8) Å, α = 112.78(2)°, β = 99.13(3)°, γ = 92.02(3)°, Z = 1) and [(Ph₃P)₂N]₂[(W₆Cl)(NCS)] · 2 CH₂Cl₂ ( 2 ) (triclinic, space group P1, a = 11.115(2), b = 14.839(2), c = 17.036(3) Å, α = 104.46(1)°, β = 105.75(2)°, γ = 110.59(1)°, Z = 1). The thiocyanate ligands of 2 are bound exclusively via N atoms with W–N bond lengths of 2.091–2.107 Å, W–N–C angles of 173.1–176.9° and N–C–S angles of 178.1–179.3°. The vibrational spectra exhibit characteristic innerligand vibrations at 2067–2045 (ν_CN), 879–867 (ν_CS) and 490–482 (δ_NCS). Based on the molekular parameters of the X‐ray determination of 1 the vibrational spectra of the corresponding (n‐Bu₄N) salt of 1 are assigned by normal coordinate analysis. The valence force constants are f_d(WW) = 1.61, f_d(WI) = 1.23 and f_d(WCl) = 1.10 mdyn/Å.     

Synthese und Kristallstruktur der Übergangsmetalltrimetaphosphimate Zn3[(PO2NH)3]2 · 14 H2O und Co3[(PO2NH)3]2 · 14 H2O

Synthesis and Crystal Structure of the Transition Metal Trimetaphosphimates Zn₃[(PO₂NH)₃]₂ · 14 H₂O and Co₃[(PO₂NH)₃]₂ · 14 H₂O The transition metal trimetaphosphimates Zn₃[(PO₂NH)₃]₂ · 14 H₂O and Co₃[(PO₂NH)₃]₂ · 14 H₂O were obtained by the reaction of an aqueous solution of Na₃(PO₂NH)₃ · 4 H₂O with the respective metal nitrate or halide (molar ratio 1 : 4). The structure of Zn₃[(PO₂NH)₃]₂ · 14 H₂O was solved by single crystal X‐ray methods. The structure of isotypic Co₃[(PO₂NH)₃]₂ · 14 H₂O was refined from X‐ray powder diffraction data using the Rietveld method (Zn₃[(PO₂NH)₃]₂ · 14 H₂O ( 1 ): P 1, a = 743.7(2), b = 955.9(2), c = 980.1(2) pm, α = 102.70(3), β = 90.46(3), and γ = 100.12(3)°, Z = 1; Co₃[(PO₂NH)₃]₂ · 14 H₂O ( 2 ): P 1, a = 746.05(1), b = 957.06(2), c = 988.51(2) pm, α = 102.162(1), β = 90.044(1), and γ = 99.258(1)°, Z = 1). In 1 and 2 the P₃N₃ rings of the trimetaphosphimate ions attain a conformation which can be described as a combination of an ideal boat and an ideal twist conformation. The trimetaphosphimate ions act as bridging ligands. Thus chains of alternating M²⁺ and (PO₂NH)₃^3– ions are formed which are interconnected by additional M²⁺ ions forming electro‐neutral double chains. In the solid these double chains are connected by hydrogen bonds.