Alkoxo‐Verbindungen des dreiwertigen Eisen: Synthese und Charakterisierung von [Fe2(OtBu)6], [Fe2Cl2(OtBu)4], [Fe2Cl4(OtBu)2] und [N(nBu)4]2[Fe6OCl6(OMe)12]

Alkoxo Compounds of Iron(III): Syntheses and Characterization of [Fe₂(OtBu)₆], [Fe₂Cl₂(OtBu)₄], [Fe₂Cl₄(OtBu)₂] and [N(nBu)₄]₂[Fe₆OCl₆(OMe)₁₂] The reaction of iron(III)chloride in diethylether with sodium tert‐butylat yielded the homoleptic dimeric tert‐‐butoxide Fe₂(OtBu)₆ ( 1 ). The chloro‐derivatives [Fe₂Cl₂(OtBu)₄] ( 2 ), and [Fe₂Cl₄(OtBu)₂] ( 3 ) could be synthesized by ligand exchange between 1 and iron(III)chloride. Each of the molecules 1 , 2 , and 3 consists of two edge‐sharing tetrahedrons, with two tert‐butoxo‐groups as μ₂‐bridging ligands. For the synthesis of the alkoxides 1 , 2 , and 3 diethylether plays an important role. In the first step the dietherate of iron(III)chloride FeCl₃(OEt₂)₂ ( 4 ) is formed. The reaction of iron(III)chloride with tetrabutylammonium methoxide in methanol results in the formation of a tetrabutylammonium methoxo‐chloro‐oxo‐hexairon cluster [N(nBu)₄]₂[Fe₆OCl₆(OMe)₁₂] ( 5 ). Crystal structure data: 1 , triclinic, P1¯, a = 9.882(2) Å, b = 10.523(2) Å, c = 15.972(3) Å, α = 73.986(4)°, β = 88.713(4)°, γ = 87.145(4)°, V = 1594.4(5) ų, Z = 2, d_c = 1.146 gcm^—1, R₁ = 0.044; 2 , monoclinic, P2₁/n, a = 11.134(2) Å, b = 10.141(2) Å, c = 12.152(2) Å und β = 114.157(3)°, V = 1251.8(4) ų, Z = 2, d_c = 1.377 gcm^—1, R₁ = 0.0581; 3 , monoclinic, P2₁/n, a = 6.527(2) Å, b = 11.744(2) Å, c = 10.623(2), β = 96.644(3)°, V = 808.8(2) ų, Z = 2, d_c = 1.641 gcm^—1, R₁ = 0.0174; 4 , orthorhombic, Iba2, a = 23.266(5) Å, b = 9.541(2) Å, c = 12.867(3) Å, V = 2856(2) ų, Z = 8, d_c = 1.444 gcm^—1, R₁ = 0.0208; 5 , trigonal, P3₁, a = 13.945(2) Å, c = 30.011(6) Å, V = 5054(2) ų, Z = 6, d_c = 1.401 gcm^—1; R_c = 0.0494.     

Strukturen von planaren und tetraedrischen TetrafulminatoMetallkomplexen: [N(C3H7)4]2 [Ni(CNO)4], [N(C3H7)4]2 [Pt(CNO)4] und [N(C3H7)4]2 [Zn(CNO)4]

Pseudohalogeno Metal Compounds. LXXVIII. Structures of Planar and Tetrahedral Tetrafulminato Metal Complexes: [N(C₃H₇)₄]₂ [Ni(CNO)₄], [N(C₃H₇)₄]₂ [Pt(CNO)₄], and [N(C₃H₇)₄]₂ [Zn(CNO)₄] The crystals contain the tetrafulminatometallates of an ideal square planar structure ([Ni(CNO)₄]^2–, [Pt(CNO)₄]^2–) with D_4h symmetry at the nickel and platinum atom and a tetrahedron ([Zn(CNO)₄]^2–) with perfect T_d symmetry at the zinc atom and with linear C≡N–O ligands. The metal carbon bonds (Ni–C: 187 pm, Pt–C: 200 pm, Zn–C: 201 pm) of the metal fulminates are very close to those of the corresponding cyano complexes. In the crystals the anions ([Ni(CNO)₄]^2–, [Pt(CNO)₄]^2–, [Zn(CNO)₄]^2–) are separated by the cations ([N(C₃H₇)₄]⁺) which explains the thermal stability of these compounds.     

Crystal and molecular structure of guanidinium hexatungsto-bis(p-aminophenylarsonate) tetrahydrate,[C(NH2)3]4[p-NH3C6H4As)2W6O25]·4H2O

The crystal structure of a new type arylarsonic polytungstate [C(NH₂)₃]₄[p-NH₃C₆H₄As)₂W₆O₂₅]·4H₂O was determined by single-crystal X-ray diffraction analysis. It belongs to triclinic, space group \[ P\bar 1 \], with cell dimensions a = 12.863(3), b = 18.912(3), c = 21.383(4) Å α = 91.14(2)°, β = 93.65(3)°, γ = 92.25(3)°, V = 5185.9 ų, Z = 4, D_c = 2.753 g/cm³. The intensity data were collected on an Enraf-Nonius CAD4 diffractometer with Mo K_α radiation. The positions of all tungsten and arsenic atoms were determined by direct method. The other non-hydrogen atoms were revealed by difference Fourier synthesis. The structure was refined by fullmatrix least-squares procedure to a final R value of 0.070. The crystal structure contains two similar but nonidentical molecules. Two similar anions consist of a ring of six WO₆ octahedra, which are connected with one face-sharing, two corner-sharings and three edge-sharings, and two p-aminophenylarsonic tetrahedra capped above and below the ring. In each WO₆ ring, four tungsten atoms, which are joined with edge-sharing oxygen atoms, are almost coplanar, while the two others, which are joined with face-sharing oxygen atoms, protrude out of the ring towards the same side. The two arsenic atoms in each anion are not equivalent in their bonding manner. In each anion, all non-hydrogen atoms of each organic group are in the same plane. Each molecule contains one anion, four C(NH₂)₃+ cations and four water molecules. There are many hydrogen bonds between cations and anions throughout the whole crystal. The amino groups can accept protons, so that the charge of the resulting anion decreases and [(RAs)₂W₆O₂₅]^4- type complexes are formed.     

Cis-trioxa-tris-β-homobenzene as tridentate ligand : X-ray crystal structure analyses of [Li(C6H6O3)2 PF6] and [Ca(C6H6O3)3H2O(ClO4)2]

In the title complexes the cis-benzenetrioxide acts as tridentate ligand, allowing for octahedral and unusual tetracapped trigonal prismatic coordination (TECTP).     

Solvothermal Synthesis and Crystal Structures of Two Thioantimonate(V) Compounds with the [SbS4]3— Anion Acting as a Monodentate Ligand: [Mn(C6H18N4)(C6H19N4)]SbS4 and [Mn(C6H14N2)3]2[Mn(C6H14N2)2(SbS4)2]·6H2O

The two novel thioantimonate(V) compounds [Mn(C₆H₁₈N₄)(C₆H₁₉N₄)]SbS₄ ( I ) and [Mn(C₆H₁₄N₂)₃][Mn(C₆H₁₄N₂)₂(SbS₄)₂]·6H₂O ( II ) were synthesized under solvothermal conditions by reacting elemental Mn, Sb and S in the stoichiometric ratio in 5 ml tris(2‐aminoethyl)amine (tren) at 140 °C or chxn (trans‐1, 2‐diaminocyclohexane, aqueous solution 50 %) at 130 °C. Compound I crystallises in the triclinic space group P1¯, a = 9.578(2), b = 11.541(2), c = 12.297(2)Å, α = 62.55(1), β = 85.75(1), γ = 89.44(1)°, V = 1202.6(4)ų, Z = 2, and II in the monoclinic space group C2/c, a = 32.611(2), b = 13.680(1), c = 19.997(1)Å, β = 117.237(5)°, V = 7931.7(8)ų, Z = 4. In I the Mn²⁺ cation is surrounded by one tetradentate tren molecule, one protonated tren acting as a monodentate ligand and a monodentate [SbS₄]^3— anion yielding a distorted octahedral environment. In II one unique Mn²⁺ ion is in an octahedral environment of three bidentate chxn molecules and the second independent Mn²⁺ ion is coordinated by two chxn ligands and two monodentate [SbS₄]^3— units leading to a distorted octahedral surrounding. The compounds were investigated and characterized with thermal and spectroscopic methods.     

Two New Modifications of [P(C6H5)4]2[Cu2I4]

Single crystals of two new modifications of [P(C₆H₅)₄]₂[Cu₂I₄] were obtained by reaction of granulated copper with iodine and [P(C₆H₅)₄]I in dry acetone under nitrogen atmosphere. They crystallise monoclinically, space group P2₁/n (No. 14), a = 11.550(6), b = 7.236(2), c = 27.232(13) Å, β = 98.13(3)°, V = 2253(2) ų, and Z = 2 ([P(C₆H₅)₄]₂[Cu₂I₄]-C), and space group Cc (No. 9), a = 17.133(5), b = 15.941(5), c = 18.762 (6) Å, β = 114.02(1)°, V = 4681(3) ų, and Z = 4 ([P(C₆H₅)₄]₂[Cu₂I₄]-D), respectively. In these compounds the [CuI₂]^? anions form dimers di-μ-iodo-diiodocuprate(I), which are either planar ( C ) or folded ( D ).     

Cerium Complex with Four Types of Ligands: (NH4)6[Ce(H2W12O40)(C4H2O4)(NO3)(H2O)3]

A novel polymer (NH₄)₆[Ce(H₂W₁₂O₄₀)(C₄H₂O₄)(NO₃)(H₂O)₃] ( 1 ) has been constructed at room temperature and characterized by single crystal X‐ray structural analyses, elemental analyses, cyclic voltammetry, IR spectrum, and thermogravimetry. X‐ray structural analysis reveals that through the W–Ot′–Ce–Ob–W linkages a one‐dimension infinitely linear chain with alternating cations and anions is formed. 1 represents the first characterized compound that the Ce³⁺ ions are coordinated by four different types of ligands, and maleinate as ligands in constructing LnPOM architecture.     

Interactions with ATP, DNA Cleavage and Anti-tumor Activities of Complexes with Anions [Mo（V）O2（O2CeH4）2]^3-, [Mo（Ⅴ）0.5W（Ⅵ）0.5O2（O2C6H4）2]^2.5- and [W（Ⅵ）O2（O2C6H4）2]^2-

(NH3CH2CH2NH2)3[Mo(Ⅴ)O2(O2C6H4)2] (1), (NH3CH2CH2NH2)2.5[Mo(Ⅴ)o.sW(Ⅵ)o.502(O2C6H4)2] (2) and(NH3CH2CH2NH2)2[VC(Ⅵ)O2(O2C6H4)2] (3) were synthesized, structurally characterized by X-ray diffraction analysis, and studied on their interactions with ATP, their DNA cleavage activities and antitumor properties. The redox state of molybdenum was not changed on going from crystal to aqueous solutions in complexes 1 and 2, while tungsten underwent reduction from W(VI) to W(V) in complexes 2 and 3. ATP promoted the oxidation of both molybdenum and tungsten from M(Ⅴ) to M(Ⅵ) and the hydrolysis of catecholate ligands in solution consisting of ATP and the complexes. Complex 1 possesses fairly good activity to DNA cleavage and against tumor S180 in mice, and is more effective than the control drug cyclophosphamide under the identical conditions. However, complexes 2 and 3 exhibited marginal effectiveness. The effectiveness of anti-tumor of the complexes was related positively to their DNA cleavage activities and their hydrolysis of catecholate ligands.