Zur Elektronenstruktur hochsymmetrischer Verbindungen der f‐Elemente. 41 Synthese,Kristall‐, Molekül‐ und Elektronenstruktur eines Bis(cyclohexylisonitril)‐Addukts des Grundkörpers Tris(bis(trimethylsilyl)amido)erbium(III) sowie Elektronenstrukturen ausgewählter Monoaddukte

Electronic Structures of Highly Symmetrical Compounds of f Elements. 41 Synthesis, Crystal, Molecular and Electronic Structure of a Bis(cyclohexylisonitrile) Adduct Derived from the Tris(bis(trimethylsilyl)amido)erbium(III) Moiety and Electronic Structures of Selected Mono Adducts The reaction of tris(bis(trimethylsilyl)amido)erbium(III) (Er(btmsa)₃) with two equivalents of cyclohexylisonitrile yields the corresponding bis adduct [Er(btmsa)₃(CNC₆H₁₁)₂] ( 1 ). Complex 1 crystallizes in the monoclinic space group C2/c with a = 2542.9(11) pm, b = 1208.4(4) pm, c = 1783.0(2) pm, β = 122.39(3)°, V = 4.638(5)·10⁹ pm³, Z = 4 and R = 0.0380. The structure of compound 1 features the five coordinate Er³⁺ central ion in a nearly exact trigonal bipyramidal environment, with three btmsa ligands in the equatorial and the two cyclohexylisonitrile molecules in the axial positions. On the basis of the absorption spectra of bis adduct 1 and the mono(tetrahydrofuran) as well as the mono(triphenylphosphine oxide) adducts [Er(btmsa)₃(THF)] ( 2 ) and [Er(btmsa)₃(OPPh₃)] ( 3 ), respectively, the underlying truncated crystal field (CF) splitting patterns of these compounds could be derived, and simulated by fitting the free parameters of a phenomenological Hamiltonian. Reduced r.m.s. deviations of 13.0 cm^?1 (42 assignments), 16.0 cm^?1 (63 assignments) and 17.5 cm^?1 (55 assignments) could be achieved for compounds 1 , 2 and 3 , respectively. Making use of the phenomenological CF parameters of the fits, the experimentally based non‐relativistic molecular orbital schemes of complexes 1 , 2 and 3 were set up, and compared with that of base‐free Er(btmsa)₃.     

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.     

Carbonylierung von bis(triphenylphosphin)-platin(II)- und -palladium(II)-komplexen in gegenwart von aminen und α-aminosäureestern

The crystal structure of (C₅H₅)₃Pr·CNC₆H₁₁ was determined from single-crystal X-ray diffraction data. The monoclinic unit cell of dimensions a = 8.298(3), b = 21.66(1), c = 11.943(4) Å, and β = 104.98(3)° contains four molecules in general positions of space group P2₁/c. Each molecule is composed of three C₅H₅ rings in a nearly exact trigonal array, η⁵-bonded to the Pr atom at a distance of 2.53 Å to the centroid of each ring, plus a single CNC₆H₁₁ adduct attached to the Pr atom along the trigonal axis at 2.65 Å. The presence of a CN triple bond in the isonitrile moiety and the nearly linear CNC configuration add credence to the previous proposal that there is a pure donor bond from the isonitrile carbon to the metal atom.     

Zur Elektronenstruktur metallorganischer Komplexe der f‐Elemente. 60 [1] Strukturelle,einkristalloptische und magnetooptische Untersuchungen von Trialkylphosphat‐Addukten des Grundkörpers Tris(cyclopentadienyl)lanthanid(III) (Ln = La,Pr) sowie Ergebnisse vergleichender optischer Studien an [Pr(Ind)3(OP(OEt)3)] (Ind = Indenyl)

Electronic Structures of Organometallic Complexes of f Elements. 60 [1] Structural, Single Crystal Optical and Magnetooptical Investigations on Trialkylphosphate Adducts of the Tris(cyclopentadienyl)lanthanide(III) (Ln = La, Pr) Moiety as well as Results of Comparing Optical Studies of [Pr(Ind)₃(OP(OEt)₃)] (Ind = indenyl) [Ln(Cp)₃(OP(OR)₃)] (Cp = η⁵‐cyclopentadienyl; Ln = La, R = Et ( 1 ); Ln = Pr, R = Me ( 2 ); Ln = Pr, R = Et ( 3 )) and [Pr(Ind)₃(OP(OEt)₃)] ( 4 ) have been synthesized and spectroscopically as well as partly structurally (only compounds 1 and 2 ) characterized. On the basis of variable temperature measurements of α absorption spectra of an oriented single crystal, the magnetic circular dichroism spectra of dissolved, and the luminescence spectra of powdered material, a nearly complete crystal field (CF) splitting pattern could be derived for 3 , and simulated by fitting the free parameters of a phenomenological Hamiltonian. The parameters used in the fit allowed the calculation of the global CF strength experienced by the Pr³⁺ central ion, the estimation of the nephelauxetic and relativistic nephelauxetic parameters, as well as the setup of experimentally based non‐relativistic and relativistic molecular orbital schemes in the f range. The optical spectra of compound 4 suggest that two different species exist at low temperatures, thus preventing a successful CF analysis.     

Coordination Chemistry of Sulfonyl Amides. 2 The Crystal Structure of Copper(II) and Silver(I) Complexes of N,N-4-Toluenesulfonyl-2-Pyridylaminato Ligand

Three structures containing the N,N-4-toluenesulfonyl-2-pyridylaminato ligand are presented. The brown crystal of Cu₂L₄ (L =N,N-4-toluenesulfonyl-2-pyridylaminato) was found to crystallize in the monoclinic space group P2,/c with a = 15.762(12), b = 15.552(5), c = 20.505(11) Å, β = 104.14(7)°; V = 4874(5) Å^3;Z = 4; the final R_F = 0.050, R_WF = 0.049 for 5142 observed reflections and 612 variables. The Cu-Cu distance is small, 2.516(2) Å and the complex is diamagnetic at room temperature. The colorless crystal of Ag₂L was found to crystallize in the monoclinic space group P2_t/n with a = 9.620(2), b = 5.625(2), c ? 23.250(3) Å, Å = 94.72(1)°; V = 1254.0(5) ų; Z = 2; the final R_F = 0.027; R_WF = 0.028 for 1929 observed reflections and 164 variables. The Ag-Ag distance is 2.739(1) Å The green crystal of CuL₂ (py)₂was found to crystallize in the monoclinic space group P2₁ with a = 9.366(2), b = 20.615(7), c = 9.862(2) Å,β = 116.73(2)°; V = 1700.5(8) ų; Z = 2; the final R_F = 0.037; R_WF = 0.038 for 1636 observed reflections and 423 variables. A reversible transformation between Cu₂L₄ and CuL₂(py)₂ is reported.     

Crystal Structures and Magnetic Properties of Charge-Transfer Salts: Cobaltocenium Bis(cis 1,2-diphenylethene-1,2-dithiolato)metalates (Metal = Ni,Pd, Pt)

Charge-transfer salts [Co(C₅H₅)₂][M(dpt)₂] (M = Ni and Pt; dpt = cis-1,2-diphenylethene-1,2-dithiolate) were synthesized and crystallographically characterized. [Co(C₅H₅)₂][Ni(dpt)2] crystallizes in the monoclinic space group C2/c with a = 25, 607(3) Å, b = 9.4151(11) Å, c = 14.407(4) Å, β = 101.373(22)°, V = 3405.3(10) Å₃ and Z = 4. [Co(C₅H₅)₂][Pt(dpt)₂] belongs to the triclinic space group $ {\rm P}\bar 1 $ with a = 9.4666(11) Å, b = 13.9869(12) Å, c = 14.2652(9) Å, α = 99.983(6)°, β = 90.034(7)°, γ = 109.751(7)°, V = 1747.2(3) ų and Z = 2. Both structures consist of ··· D⁺A^?D⁺A^?D⁺A^? ··· linear chains with the local C₅ axis of the eclipsed [Co(C₅H₅)₂]⁺ cation parallel to the best MS₄ plane of the [M(dpt)₂]^? anion. Magnetic susceptibility measurements show that χ_M T values of the complexes [Co(C₅H₅)₂][M(dpt)₂] (M = Ni, Pd, and Pt) remain nearly constant in the temperature range 15–300 K, but decrease rapidly with further decreasing of temperature, indicating weak antiferromagnetic interactions at low temperatures.     

Structural and Electron Density Studies on a Chromium(IV)-Oxo Complex [CrIV(O)(TMP)]

The electron density distribution of a chromium(IV)-oxo complex, [Cr^IV(O)(TMP)] (TMP = 5,10,15,20-tetrakis-p-methoxyphenyl porphyrin), is investigated by molecular orbital calculation. The molecular and crystal structure of the compound is studied by x-ray diffraction. It belongs to the space group 1 2, Z = 2, a = 14.979(4) Å, b = 9.752(3), c = 15.605(3) Å, β = 100.97(2)°, V = 2238(1) ų, Mo Kα radiation λ = 0.7107 Å, R = 4.9%, Rw = 3.5% for 3575 observed reflections. Cr is five-coordinated in a square pyramidal fashion with the Cr atom located 0.42 Å toward the oxo-ligand. Deformation density maps are derived from the single point molecular orbital calculation on the basis of HF and DFT(density functional theory) calculations. The accumulation of deformation density along the C-H, C-C, C-N and C-O bonds in the porphyrin ligand is well represented. The asphericity in electron density around the Cr ion is clearly demonstrated. Natural bond orbital analysis (NBO) reveals that the Cr-O_oxo is actually a triple-bond character (σ²π⁴) and the four N of pyrrole serves as a σ-donor to Cr. The Cr-N_pyrrole bond is essentially a dative bond d-Orbital populations of Cr derived from both calculations are in good agreement with each other. Planar d_π-orbital is the most populated, which is in accord with the prediction from crystal field theory. Detail bond characterization of the Cr-L, multiple bond is discussed.     

Konformation und Vernetzung von (CuCN)6‐Ringen in polymeren Cyanocupraten(I) [Cu2(CN)3—] (n = 2, 3)

Conformation and Cross Linking of (CuCN)₆‐Rings in Polymeric Cyanocuprates(I) equation/tex2gif-stack-8.gif [Cu₂(CN)₃^—] (n = 2, 3) The alkaline‐tricyano‐dicuprates(I) Rbequation/tex2gif-stack-9.gif[Cu₂(CN)₃] · H₂O ( 1 ) and Csequation/tex2gif-stack-10.gif[Cu₂(CN)₃] · H₂O ( 2 ) were synthesized by hydrothermal reaction of CuCN and RbCN or CsCN. The dialkylammonium‐tricyano‐dicuprates(I) [NH₂(Me)₂]equation/tex2gif-stack-11.gif[Cu₂(CN)₃] ( 3 ), [NH₂(iPr)₂]equation/tex2gif-stack-12.gif[Cu₂(CN)₃] ( 4 ), [NH₂(Pr)₂]equation/tex2gif-stack-13.gif[Cu₂(CN)₃] ( 5 ) and [NH₂(secBu)₂]equation/tex2gif-stack-14.gif[Cu₂(CN)₃] ( 6 ) were obtained by the reaction of dimethylamine, diisopropylamine, dipropylamine or di‐sec‐butylamine with CuCN and NaCN in the presence of formic acid. The crystal structures of these compounds are built up by (CuCN)₆‐rings with varying conformations, which are connected to layers ( 1 ) or three‐dimensional zeolite type cyanocuprate(I) frameworks, depending on the size and shape of the cations ( 2 to 6 ). Crystal structure data: 1 , monoclinic, P2₁/c, a = 12.021(3)Å, b = 8.396(2)Å, c = 7.483(2)Å, β = 95.853(5)°, V = 751.4(3)ų, Z = 4, d_c = 2.728 gcm^—1, R₁ = 0.036; 2 , orthorhombic, Pbca, a = 8.760(2)Å, b = 6.781(2)Å, c = 27.113(5)Å, V = 1610.5(5)ų, Z = 8, d_c = 2.937 gcm^—1, R₁ = 0.028; 3 , orthorhombic, Pna2₁, a = 13.504(3)Å, b = 7.445(2)Å, c = 8.206(2)Å, V = 825.0(3)ų, Z = 4, d_c = 2.023 gcm^—1, R₁ = 0.022; 4 , orthorhombic, Pbca, a = 12.848(6)Å, b = 13.370(7)Å, c = 13.967(7)Å, V = 2399(2)ų, Z = 8, d_c = 1.702 gcm^—1, R₁ = 0.022; 5 , monoclinic, P2₁/n, a = 8.079(3)Å, b = 14.550(5)Å, c = 11.012(4)Å, β = 99.282(8)°, V = 1277.6(8)ų, Z = 4, d_c = 1.598 gcm^—1, R₁ = 0.039; 6 , monoclinic, P2₁/c, a = 16.215(4)Å, b = 13.977(4)Å, c = 14.176(4)Å, β = 114.555(5)°, V = 2922(2)ų, Z = 8, d_c = 1.525 gcm^—1, R₁ = 0.070.     

Syntheses,Crystal Structures,and Properties of the Novel Thioborates KBa4(BS3)3 and K4Ba11(BS3)8S

Our systematic studies on quaternary thioborates containing both a comparably small alkali metal ion and a large alkaline earth cation lead to the two new crystalline phases KBa₄(BS₃)₃ and K₄Ba₁₁(BS₃)₈S. The former consists of isolated BS₃ units and the corresponding counter‐ions while in the latter BS₃^3– and S^2– anions coexist. In both compounds boron is found in a trigonal‐planar coordination, in the case of K₄Ba₁₁(BS₃)₈S the additional sulfide anions are located inside an octahedron built of six barium cations. The two compounds were prepared in solid state reactions from the metal sulfides, amorphous boron and sulfur. Evacuated carbon coated silica tubes were used as reaction vessels since temperatures up to 870 K were applied. KBa₄(BS₃)₃ crystallizes in the monoclinic space group C 2/c (no. 15) with a = 14.299(6) Å, b = 8.808(3) Å, c = 13.656(5) Å, β = 98.72(4)°, and Z = 4, while for K₄Ba₁₁(BS₃)₈S the trigonal space group R 3 c (no. 167) was found with a = 18.146(3) Å, c = 25.980(7) Å, and Z = 6. X‐ray powder patterns are compared to calculated diffraction data obtained from single crystal X‐ray structure determination, in the case of K₄Ba₁₁(BS₃)₈S vibrational spectra were recorded.     

Transition Metal Halide Salts and Complexes of 2-Aminopyrimidine: Cobalt(II) and Nickel(II) compounds,Crystal Structures of Bis(2-Aminopyrimidinium)MX4 [M = Co,Ni; X = Cl,Br] and 2-Aminopyrimidinium(+2) [NiBr2(H2O)4]Br2

The reaction of MX₂ (M = Co(II), Ni(II); X = Cl, Br) with 2-aminopyrimidine in aqueous acid yields compounds [(2-apmH)₂MX₄], (2-apmH)₂[MX₄], or (2-apmH₂) [MX₂(H₂O)₄]X₂ (2-apmH = 2-aminopyrimidinium; 2-apmH₂ = 2-aminopyrimidinium(2+)). All compounds have been characterized by single crystal X-ray diffraction. The compounds [(2-apmH)₂MX₄] with M = Co, X = Cl (1); M = Ni, X = Cl (3); and M = Ni, X = Br (4) are isomorphous and crystallize as nearly square planar MX₄ units with the 2-apmH cations coordinated in the axial sites through the unprotonated ring nitrogen. (2-ApmH)₂[CoBr₄] (2) crystallizes as the salt with a nearly tetrahedral CuBr₄ ^2- anion. (2-ApmH₂)[NiBr₂(H₂O)₄]Br₂ (5) forms as a cocrystal of the neutral, six-coordinate nickel complex and (2-ampH₂)Br₂, stabilized by extensive hydrogen bonding. Crystal data (1): monoclinic, P2₁/c, a = 7.540(4), b = 12.954(4), c = 7.277(3) Å, β = 110.09(6), V = 667.4(5) ų, Z = 2, D_calc = 1.955 Mg/m³, μ = 2.079 mm^-1, R = 0.0501 for [|I|≥2(I)]. For (2): triclinic, P-1, a = 7.720(2), b = 7.916(2), c = 14.797(3) Å, α = 97.264(3), β = 104.788(3), γ = 105.171(3)°, V = 825.3(3) ų, Z = 2, D_calc = 2.296 Mg/m³, μ = 10.715 mm^-1, R = 0.0308 for [|I|≥2(I)]. For (3): monoclinic, P2₁/c, a = 7.595(3), b = 12.891(4), c = 7.204(3) Å, β = 111.07(3)°, V = 658.2 ų, Z = 2, D_calc = 1.982 Mg/m³, μ = 2.279 mm^-1, R = 0.0552 for [|I|≥2(I)]. For (4): monoclinic, P2₁/c, a = 7.840(2), b = 13.358(4), c = 7.518(2) Å, β = 110.923(3)°, V = 938.6(3) ų, Z = 2, D_calc = 2.577 Mg/m³, μ = 12.18 mm^-1, R = 0.0280 for [|I|≥2(I)]. For (5): orthorhombic, Pnma, a = 16.776(6), b = 11.943(4), c = 7.079(3) Å, V = 1418.2(9) ų, Z = 4, D_calc = 2.564 Mg/m³, μ = 12.639 mm^-1, R = 0.0381 for [|I|≥2σ(I)].     

Synthese,Charakterisierung und Kristallstrukturen von Tetraiodoferraten(III)

Preparation, Characterization, and Crystal Structures of Tetraiodoferrates(III) The extremely air and moisture sensitive tetraiodoferrates MFeI₄ with M = K, Rb and Cs have been synthesized by reaction of Fe, MI and I₂ at 300°C in closed quartz ampoules. The essentially more stable alkylammonium tetraiodoferrates NR₄FeI₄ with R = H, C₂H₅, n-C₃H₇, n-C₄H₉ and n-C₅H₁₁ can be obtained by reaction of Fe, NR₄I and I₂ in nitromethane. The Raman and UV/Vis-spectra of the black compounds show the existence of tetrahedral [FeI₄]^? ions in the structures. The crystal structure of the monoclinic CsFeI₄ (CsTlI₄ type, spgr P2₁/c; a = 7.281(1) Å; b = 17.960(3) Å; c = 8.248(2) Å; β = 107.35(15)°) is built up by tetrahedral [FeI₄]^? ions and CsI₁₁ polyhedra. The crystal structure of the orthorhombic (n-C₅H₁₁)₄NFeI₄ (spgr Pnna; a = 20.143(4) Å; b = 12.683(3) Å; c = 12.577(3) Å) contains tetrahedral [(n-C₅H₁₁)₄N]⁺ ions and [FeI₄]^? ions, respectively.     

Syntheses and Crystal Structures of Three Polymeric Silver(I) Terephthalate Complexes with Organic N‐Donor Ligands: [Ag(pren)]2(tp)·2H2O, [Ag(en)][Ag(μ2‐tp)]·H2O,and [Ag2(μ4‐tp)(apy)2]

Three polymeric silver(I) complexes with terephthalate anions as counterions or ligands, [Ag(pren)]₂(tp)·2H₂O ( 1 ), [Ag(en)][Ag(μ₂‐tp)]·H₂O ( 2 ), and [Ag₂(μ₄‐tp)(apy)₂] ( 3 ) (where pren = 1, 2‐propylenediamine, tp =terephthalate dianion, en = ethylenediamine, and apy = 2‐aminopyridine) were synthesized and characterized by X‐ray single crystal analysis and infrared spectroscopy. 1 crystallizes in the monoclinic space group P2₁1/c with a = 11.3221(5), b = 7.1522(3), c = 14.8128(5)Å, V = 1015.77(7)ų, β = 122.132(2), and Z = 2. 2 crystallizes in the orthorhombic space group Pnma with a = 9.6144(6), b = 11.3465(7), c = 11.4810(7)Å, V = 1252.5(1)ų, and Z = 4. 3 crystallizes in the monoclinic space group P2₁/n with a = 8.2003(5), b = 5.8869(4), c = 18.3769(11)Å, β = 92.593(1), V = 886.2(1)ų, and Z = 4. Terephthalate dianions are not coordinated to the metal atoms in 1 , but act as a μ₂‐bridging ligand in 2 and as a μ₄‐bridging ligand in 3 .     

Thioureato-verbrückte zweikernige Komplexe der Lanthanoide Darstellung und Struktur von [{PhC(NPh)NC(S)NEt2}{Et2NC(S)NH}LnBr(thf)]2 (Ln = Gd,Sm)

Thioureato Brigded Binuclear Complexes of the Lanthanides Synthesis and Crystal Structure of [{PhC(NPh)NC(S)NEt₂}{Et₂NC(S)NH}LnBr(thf)]₂ (Ln = Gd, Sm) The reaction of potassium-N-(diethylaminothiocarbonyl)-N′-phenyl-benzamidinat with LnBr₃ (Ln = Gd, Sm) leads to the formation of the binuclear complexes [{PhC(NPh)NC(S)NEt₂}{Et₂NC(S)N}LnBr(thf)]₂} (Ln = Gd 1 , Sm 2 ). The two bridging thiureatoligands are probably built during the reaction of potassium with the starting ligand. Coordination by one N-(diethylaminothiocarbonyl)-N′-phenylbenzamidinato-ligand, one Br-ion and one THF-ligand leads to square antiprismatic coordination of the lanthanoids. The structures of both compounds were characterized by X-ray analysis ( 1 : P1 (Nr.2), Z = 1, a = 12,006(4) Å, b = 12,245(4) Å, c = 13,612(3) Å, α = 70,55(3)°, β = 68,21(3)°, γ = 81,31(3)° 2 : P1 (Nr.2), Z = 1, a = 11,803(3) Å, b = 12,344(5) Å, c = 12,797(8) Å, α = 103,07(5)°, β = 101,76(3)°, γ = 114,13(3)°)     

Synthesis and Structure of Lithium Cadmium Selenite Hydroxide,LiCd2(SeO3)2(OH)

The new compound LiCd₂(SeO₃)₂(OH) has been hydrothermally synthesized and characterized by single‐crystal X‐ray diffraction and IR spectroscopy. It is built up from a network of edge‐ and vertex‐sharing pyramidal [SeO₃]^2— groups, distorted CdO₆ octahedra, and CdO₇ monocapped trigonal prisms. The cadmium‐centred groups form infinite columns, onto which Se atoms (as [SeO₃]^2— groups) are grafted. Cross‐linking between the columns results in a three‐dimensional framework which encapsulates [100] channels occupied by the tetrahedrally‐coordinated lithium cations. The H atom of the hydroxyl group appears to participate in a weak, bifurcated, hydrogen bond. Crystal data: LiCd₂(SeO₃)₂(OH), M_r = 502.67, monoclinic, P2₁/c (No. 14), a = 5.8184 (3)Å, b = 10.2790 (5)Å, c = 11.5021 (5)Å, β = 90.446(1)°, V = 687.89 (9)ų, Z = 4, R(F) = 0.021, wR(F²) = 0.046.     

Alkoholyse von [Fe2(OtBu)6] als einfacher Weg zu neuen Eisen(III)‐Alkoxo‐Verbindungen: Synthesen und Kristallstrukturen von [Fe2(OtAmyl)6], [Fe5OCl(OiPr)12], [Fe5O(OiPr)13], [Fe5O(OiBu)13], [Fe5O(OCH2CF3)13], [Fe5O(OnPr)13] und [Fe9O3(OnPr)21] · iPrOH

Alcoholysis of [Fe₂(O^tBu)₆] as a Simple Route to New Iron(III)‐Alkoxo Compounds: Synthesis and Crystal Structures of [Fe₂(O^tAmyl)₆], [Fe₅OCl(OⁱPr)₁₂], [Fe₅O(OⁱPr)₁₃], [Fe₅O(OⁱBu)₁₃], [Fe₅O(OCH₂CF₃)₁₃], [Fe₅O(OⁿPr)₁₃], and [Fe₉O₃(OⁿPr)₂₁] · ⁿPrOH New alkoxo‐iron compounds can be synthesized easily by alcoholysis of [Fe₂(O^tBu)₆] ( 1 ). Due to different bulkyness of the alcohols used, three different structure types are formed: [Fe₂(OR)₆], [Fe₅O(OR)₁₃] and [Fe₉O₃(OR)₂₁] · ROH. We report synthesis and crystal structures of the compounds [Fe₅OCl(OⁱPr)₁₂] ( 2 ), [Fe₂(O^tAmyl)₆] ( 3 ), [Fe₅O(OⁱPr)₁₃] ( 4 ), [Fe₅O(OⁱBu)₁₃] ( 5 ), [Fe₅O(OCH₂CF₃)₁₃] ( 6 ), [Fe₉O₃(OⁿPr)₂₁] · ⁿPrOH ( 7 ) and [Fe₅O(OⁿPr)₁₃] ( 8 ). Crystallographic Data: 2 , tetragonal, P 4/n, a = 16.070(5) Å, c = 9.831(5) Å, V = 2539(2) ų, Z = 2, d_c = 1.360 gcm^?3, R₁ = 0.0636; 3 , monoclinic, P 2₁/c, a = 10.591(5) Å, b = 10.654(4) Å, c = 16.740(7) Å, β = 104.87(2)°, V = 1826(2) ų, Z = 2, d_c = 1.154 gcm^?3, R₁ = 0.0756; 4 , triclinic, , a = 20.640(3) Å, b = 21.383(3) Å, c = 21.537(3) Å, α = 82.37(1)°, β = 73.15(1)°, γ = 61.75(1)°, V = 8013(2) ų, Z = 6, d_c = 1.322 gcm^?3, R₁ = 0.0412; 5 , tetragonal, P 4cc, a = 13.612(5) Å, c = 36.853(5) Å, V = 6828(4) ų, Z = 4, d_c = 1.079 gcm^?3, R₁ = 0.0609; 6 , triclinic, , a = 12.039(2) Å, b = 12.673(3) Å, c = 19.600(4) Å, α = 93.60(1)°, β = 97.02(1)°, γ = 117.83(1)°, V = 2600(2) ų, Z = 2, d_c = 2.022 gcm^?3, R₁ = 0.0585; 7 , triclinic, , a = 12.989(3) Å, b = 16.750(4) Å, c = 21.644(5) Å, α = 84.69(1)°, β = 86.20(1)°, γ = 77.68(1)°, V = 4576(2) ų, Z = 2, d_c = 1.344 gcm^?3, R₁ = 0.0778; 8 , triclinic, , a = 12.597(5) Å, b = 12.764(5) Å, c = 16.727(7) Å, α = 91.94(1)°, β = 95.61(1)°, γ = 93.24(2)°, V = 2670(2) ų, Z = 2, d_c = 1.323 gcm^?3, R₁ = 0.0594.     

Mesityl‐phenolato‐vanadium(III)‐Komplexe: Synthese,Struktur und Verhalten

Mesityl‐vanadium(III)‐phenolate Complexes: Synthesis, Structure, and Reactivity Protolysis reactions of [VMes₃(THF)] with ortho‐substituted phenols (2‐iso‐propyl‐(H–IPP), 2‐tert‐butyl(H–TBP), 2,4,6‐trimethylphenol (HOMes) and 2,2′biphenol (H₂–Biphen) yield the partially and fully phenolate substituted complexes [VMes(OAr)₂(THF)₂] (OAr = IPP ( 1 ), TBP ( 2 )), [VMes₂(OMes)(THF)] ( 4 ), [V(OAr)₃(THF)₂] (OAr = TBP ( 3 ), OMes ( 5 )), and [V₂(Biphen)₃(THF)₄] ( 6 ). Treatment of 6 with Li₂Biphen(Et₂O)₄ results in formation of [{Li(OEt₂)}₃V(Biphen)₃] ( 7 ) and with MesLi complexes [{Li(THF)₂}₂VMes(Biphen)₂] · THF ( 8 ) and [{Li(DME)}VMes₂(Biphen)] ( 9 ) are formed. Reacting [VCl₃(THF)₃] with LiOMes in 1 : 1 to 1 : 4 ratios yields the componds [VCl_3–n(OMes)_n(THF)₂] (n = 1 ( 5 b ), 2 ( 5 a ), 3 ( 5 )) and [{Li(DME)₂}V(OMes)₄] ( 5 c ), the latter showing thermochromism due to a complexation/decomplexation equilibrium of the solvated cation. The mixed ligand mesityl phenolate complexes [{Li(DME)_n}{VMes₂(OAr)₂}] (OAr = IPP ( 10 ), TBP ( 11 ), OMes ( 12 ) (n = 2 or 3) and [{Li(DME)₂}{VMes(OMes)₃}] ( 15 ) are obtained by reaction of 1 , 2 , 5 a and 5 with MesLi. With [{Li(DME)₂(THF)}{VMes₃(IPP)}] ( 13 ) a ligand exchange product of 10 was isolated. Addition of LiOMes to [VMes₃(THF)] forming [Li(THF)₄][VMes₃(OMes)] ( 14 ) completes the series of [Li(solv.)_x][VMes_4–n(OMes)_n] (n = 1 to 4) complexes which have been oxidised to their corresponding neutral [VMes_4–n(OMes)_n] derivatives 16 to 19 by reaction with p‐chloranile. They were investigated by epr spectroscopy. The molecular structures of 1 , 3 , 5 , 5 a , 5 a – Br , 7 , 10 and 13 have been determined by X‐ray analysis. In 1 (monoclinic, C2/c, a = 29.566(3) Å, b = 14.562(2) Å, c = 15.313(1) Å, β = 100.21(1)°, Z = 8), 3 (orthorhombic, Pbcn, a = 28.119(5) Å, b = 14.549(3) Å, c = 17.784(4) Å, β = 90.00°, Z = 8), ( 5 ) (triclinic, P1, a = 8.868(1) Å, b = 14.520(3) Å, c = 14.664(3) Å, α = 111.44(1)°, β = 96.33(1)°, γ = 102.86(1)°, Z = 2), 5 a (monoclinic, P2₁/c, a = 20.451(2) Å, b = 8.198(1) Å, c = 15.790(2) Å, β = 103.38(1)°, Z = 4) and 5 a – Br (monoclinic, P2₁/c, a = 21.264(3) Å, b = 8.242(4) Å, c = 15.950(2) Å, β = 109.14(1)°, Z = 4) the vanadium atoms are coordinated trigonal bipyramidal with the THF molecules in the axial positions. The central atom in 7 (trigonal, P3c1, a = 20.500(3) Å, b = 20.500(3) Å, c = 18.658(4) Å, Z = 6) has an octahedral environment. The three Li(OEt₂)⁺ fragments are bound bridging the biphenolate ligands. The structures of 10 (monoclinic, P2₁/c, a = 16.894(3) Å, b = 12.181(2) Å, c = 25.180(3) Å, β = 91.52(1)°, Z = 4) and 13 (orthorhombic, Pna2₁, a = 16.152(4) Å, b = 17.293(6) Å, c = 16.530(7) Å, Z = 4) are characterised by separated ions with tetrahedrally coordinated vanadate(III) anions and the lithium cations being the centres of octahedral and trigonal bipyramidal solvent environments, respectively.     

The Crystal and Molecular Structure of Mercury Fulminate (Knallquecksilber)

A short survey on the fascinating history of mercury fulminate is given. The crystal structure of Hg(CNO)₂ has been determined using single crystal X‐ray diffraction. Mercury fulminate crystallizes in an orthorhombic cell, space group Cmce with a = 5.3549(2), b = 10.4585(5), c = 7.5579(4) Å and Z = 4. The distances and angles in the O‐N≡C‐Hg‐C≡N‐O molecule are Hg‐C 2.029(6) Å, C≡N 1.143(8) Å, N‐O 1.248(6) Å and C‐Hg‐C 180.0(1)°, Hg‐C≡N 169.1(5)°, C≡N‐O 179.7(6)°. Each mercury atom is surrounded by two oxygen atoms from neighbouring Hg(CNO)₂ molecules with a nonbonding distance of Hg···O 2.833(4) Å. The Hg‐C bond lengths in the linear Hg(CNO)₂ molecules are shorter than those in the tetrahedral complex [Hg(CNO)₄]^2?. This refers to a large contribution of the 6s orbital in the Hg‐C bonds of Hg(CNO)₂. The results of the X‐ray powder investigation on Hg(CNO)₂ are also reported.     

Syntheses and Crystal Structures of Copper(II) and Copper(I) dpp Complexes, [Cu(dpp)Br2] and [Cu(dpp)2][CuBr2] (dpp = 2,9‐diphenyl‐1,10‐phenanthroline)

The complexes [Cu(dpp)Br₂] ( 1 ) and [Cu(dpp)₂][CuBr₂] ( 2 ) (dpp = 2,9‐diphenyl‐1,10‐phenanthroline) were synthesized and characterized by single‐crystal X‐ray diffraction methods. Reaction of copper(II) bromide with the dpp ligand in dichloromethane at room temperature afforded 1 , which is a rare example of non‐square planar four‐coordinate copper(II) complexes. Complex 1 crystallizes in the monoclinic space group C2/c with a = 15.352(3), b = 13.192(3), c = 11.358(2) Å, β = 120.61(3)°, V = 1979.6(7) ų, Z = 4, D_calc = 1.865 g cm^?3. The coordination geometry about the copper center is distorted about halfway between square planar and tetrahedral. The Cu‐N distance is 2.032(2) Å and the Cu‐Br distance 2.3521(5) Å. Heating a CH₂Cl₂ or acetone solution of 1 resulted in complex 2 , which consists of a slightly distorted tetrahedral [Cu(dpp)₂]⁺ cation and a linear two‐coordinate [CuBr₂]^? anion. 2 crystallizes in the triclinic space group with a = 10.445(2), b = 11.009(2), c = 18.458(4) Å, α = 104.72(3), β = 94.71(3), γ = 103.50(3)°, V = 1973.3(7) ų, Z = 2, D_calc = 1.602 g cm^?3. The four Cu(1)‐N distances are between 2.042(3) and 2.067(3) Å, the distance of Cu(2)‐Br(1) 2.2268(8) Å, and the disordered Cu(3)‐Br(2) distances are 2.139(7) and 2.237(4) Å, respectively. Complex 2 could also be prepared by directly reacting CuBr with dpp in CH₂Cl₂.     

Benzeneselenolates of Mercury(II). Crystal and Molecular Structures of [Hg(SePh)2] and (Bu4N)[Hg(SePh)3]

The reaction of dibenzenediselenide, (SePh)₂, with mercury in refluxing xylene gives bis(benzeneselenolato)mercury(II), [Hg(SePh)₂], in a good yield. (ⁿBu₄N)[Hg(SePh)₃] is obtained by the reaction of [Hg(SePh)₂] with a solution of [SePh]^– and (ⁿBu₄N)Br in ethanol. The solid state structures of both compounds have been determined by X-ray diffraction. The mercury atom in [Hg(SePh)₂] (space group C2, a = 7.428(2), b = 5.670(1), c = 14.796(4) Å, β = 103.60(1)°) is linearly co-ordinated by two selenium atoms (Hg–Se = 2.471(2) Å, Se–Hg–Se = 178.0(3)°). Additional weak interactions between the metal and selenium atoms of neighbouring molecules (Hg…Se = 3.4–3.6 Å) associate the [Hg(SePh)₂] units to layers. The crystal structure of (ⁿBu₄N)[Hg(SePh)₃] (space group P2₁/c, a = 9.741(1), b = 17.334(1), c = 21.785(1) Å, β = 95.27(5)°) consists of discrete complex anions and (ⁿBu₄N)⁺ counter ions. The coordination geometry of mercury is distorted trigonal-planar with Hg–Se distances ranging between 2.5 and 2.6 Å.     

Synthese,Kristallstruktur und thermischer Abbau von Fluoroaluminaten der Zusammensetzung (NH4)[M(H2O)6][AlF6] (M = Zn,Ni), [Zn(H2O)6][AlF5(H2O)] und (PyH)4[Al2F10] · 4 H2O

Synthesis, Crystal Structure and Thermal Behaviour of Fluoroaluminates of the Composition (NH₄)[M(H₂O)₆](AlF₆) (M = Zn, Ni), [Zn(H₂O)₆][AlF₅(H₂O)], and (PyH)₄[Al₂F₁₀] · 4 H₂O Four new fluoroaluminates were obtained from fluoroacidic solutions of respective metal salts. The compounds of zinc ( I a : P2₁/c, a = 12.688(3), b = 6.554(1), c = 12.697(3) Å, β = 95.21(3)°, V = 1051.5(4) ų, Z = 4) and nickel ( I b : P2₁/c, a = 12.685(3), b = 6.517(1), c = 12.664(2)Å, β = 94.55(2)°, V = 1043.6(4) ų, Z = 4) are isotypic and represent a new structure type consisting of two different cations, NH₄⁺ and [M(H₂O)₆]²⁺ and [AlF₆]^3–‐anions. [Zn(H₂O)₆][AlF₅(H₂O)] ( II : C2/m, a = 10.769(2), b = 13.747(3), c = 6.487(1)Å, β = 100.02(3)°, V = 945.7(3) ų, Z = 4) is characterized by a H₂O/F‐disorder in the [AlF₅(H₂O)]‐octahedra in two trans positions. In (PyH)₄[Al₂F₁₀] · 4 H₂O ( III : Cmc2₁, a = 15.035(3), b = 20.098(4), c = 12.750(4) Å, V = 5364(2) ų, Z = 8), bioctahedral [Al₂F₁₀]^4– anions have been found for the first time. The structures are described and discussed in comparison. The new compounds were used as precursors in order to obtain new AlF₃‐phases. However, the thermal decomposition did not result in the formation of any new metastable AlF₃‐phase. Instead, phase mixtures of either α‐AlF₃ and β‐AlF₃ or AlF₃ and MF₂ were obtained.