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.     

Na12Ge17: A Compound with the Zintl Anions [Ge4]4— and [Ge9]4— — Synthesis,Crystal Structure,and Raman Spectrum

Na₁₂Ge₁₇ is prepared from the elements at 1025 K in sealed niobium ampoules. The crystal structure reinvestigation reveals a doubling of the unit cell (space group:P2₁/c; a = 22.117(3)Å, b = 12.803(3)Å, c = 41.557(6)Å, β = 91.31(2)°, Z = 16; Pearson code: mP464), furthermore, weak superstructure reflections indicate an even larger C‐centred monoclinic cell. The characteristic structural units are the isolated cluster anions [Ge₉]^4— and [Ge₄]^4— in ratio 1:2, respectively. The crystal structure represents a hierarchical cluster replacement structure of the hexagonal Laves phase MgZn₂ in which the Mg and Zn atoms are replaced by the Ge₉ and Ge₄ units, respectively. The Raman spectrum of Na₁₂Ge₁₇ exhibits the characteristic breathing modes of the constituent cluster anions at ν = 274 cm^—1 ([Ge₉]^4—) and ν = 222 cm^—1 ([Ge₄]^4—) which may be used for identification of these clusters in solid phases and in solutions. Raman spectra further prove that Na₁₂Ge₁₇ is partial soluble both in ethylenediamine and liquid ammonia. The solution and the solid extract contain solely [Ge₉]^4—. The remaining insoluble residue is Na₄Ge₄. By heating the solvate Na₄Ge₉(NH₃)_n releases NH₃ and decomposes irreversibly at 742 K, yielding Na₁₂Ge₁₇ and Ge.     

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.     

Polymorphism of [Zn(2,2′‐bipy)(H2PO4)2]2

Two polymorphs of a zero‐dimensional (molecular) zinc phosphate with the formula [Zn(2,2′‐bipy)(H₂PO₄)₂]₂ have been synthesized by a mild hydrothermal route and their crystal structures were determined by single crystal X‐ray diffraction (triclinic, space group (No. 2), Z = 2, α‐form: a = 8.664(1), b = 8.849(2), c = 10.113(2) Å, α = 97.37(2)°, β = 100.54(2)°, γ = 100.98(2)°, V = 737.5(3) ų; β‐form: a = 7.5446(15), b = 10.450(2), c = 10.750(2) Å, α = 67.32(3)°, β = 81.67(3)°, γ = 69.29(3)°, V = 731.4(3) ų). Both structures consist of distorted trigonal‐bipyramidal ZnO₃N₂ units condensed with PO₂(OH)₂ tetrahedra through common vertices giving rise to dimers [Zn(2,2′‐bipy)(H₂PO₄)₂]₂. The structures are stabilized by extensive inter‐ and intramolecular hydrogen bond interactions. Both modifications display subtle differences in their packing originating from the hydrogen bond interactions as well as π…π interactions between the organic ligands.     

Von kleinen Bausteinen zu neuen Poly‐alkoxo‐oxometallat‐Derivaten: Synthese und Strukturaufklärung von K4[VIV12O12(OCH3)16(C4O4)6], Cs10[VIV24O24(OCH3)32(C4O4)12][VIV8O8(OCH3)16(C2O4)] und M2[VIV8O8(OCH3)16(VIVOF4)] (M = [N(nBu)4] bzw. [NEt4])

>From Small Fragments to New Poly‐alkoxo‐oxo‐metalate Derivatives: Syntheses and Crystal Structures of K₄[V^IV₁₂O₁₂(OCH₃)₁₆(C₄O₄)₆], Cs₁₀[V^IV₂₄O₂₄(OCH₃)₃₂(C₄O₄)₁₂][V^IV₈O₈(OCH₃)₁₆(C₂O₄)], and M₂[V^IV₈O₈(OCH₃)₁₆(V^IVOF₄)] (M = [N(nBu)₄] or [NEt₄]) By solvothermal reaction of ortho‐vanadicacid ester [VO(OMe)₃] with squaric acid and potassium or caesium hydroxide the compounds K₄[V^IV₁₂O₁₂(OCH₃)₁₆(C₄O₄)₆] ( 2 ) and Cs₁₀[V^IV₂₄O₂₄(OCH₃)₃₂(C₄O₄)₁₂][V^IV₈O₈(OCH₃)₁₆(C₂O₄)] ( 3 ) could be syntesized. With tetra‐n‐butyl‐ or tetra‐n‐ethylammonium fluoride [N(nBu)₄]₂[V^IV₈O₈(OCH₃)₁₆(V^IVOF₄)] ( 4 ) and [N(Et)₄]₂[V^IV₈O₈(OCH₃)₁₆(V^IVOF₄)] ( 5 ) could be isolated. In 2 and 3 the corners of a tetrahedron or cube resp. are occupied by {(VO)₃(OMe)₄} groups and connected along the edges of the tetrahedron resp. cube by six or twelve resp. squarato‐groups. The octanuclear anions in the compounds 3 , 4 , and 5 are assumedly built up by fragments of the ortho‐vanadicacid ester [VO(OMe)₃]. Around the anions C₂O₄^2— or VOF₄^— these oligormeric chains are closed to a ring . Crystal data: 2 , tetragonal, P4₃, a = 18.166(3)Å, c = 29.165(7)Å, V = 9625(3)ų, Z = 4, d_c = 1.469 gcm^—3; 3 , orthorhombic, Pbca, a = 29.493(5)Å, b = 25.564(4)Å, c = 31.076Å, V = 23430(6)ų, Z = 4, d_c = 1.892 gcm^—3; 4 , monoclinic, P2₁/n, a = 9.528(1)Å, b = 23.021(2)Å, c = 19.303(2)Å, β = 92.570(2)°, V = 4229.8(5)ų, Z = 2, d_c = 1.391 gcm^—3; 5 , monoclinic, P2₁/n, a = 16.451(2)Å, b = 8.806(1)Å, c = 23.812(1)Å, β = 102.423(2)°, V = 3368.7(6)ų, Z = 2, d_c = 1.534 gcm^—3.     

Li4Ca3Si2N6 and Li4Sr3Si2N6 – Quaternary Lithium Nitridosilicates with Isolated [Si2N6]10– Ions

The isotypic nitridosilicates Li₄Ca₃Si₂N₆ and Li₄Sr₃Si₂N₆ were synthesized by reaction of strontium or calcium with Si(NH)₂ and additional excess of Li₃N in weld shut tantalum ampoules. The crystal structure, which has been solved by single‐crystal X‐ray diffraction (Li₄Sr₃Si₂N₆: C2/m, Z = 2, a = 6.1268(12), b = 9.6866(19), c = 6.2200(12) Å, β = 90.24(3)°, wR₂ = 0.0903) is made up from isolated [Si₂N₆]^10– ions and is isotypic to Li₄Sr₃Ge₂N₆. The bonding angels and distances within the edge‐sharing [Si₂N₆]^10– double‐tetrahedra are strongly dependent on the lewis acidity of the counterions. This finding is discussed in relation to the compounds Ca₅Si₂N₆ and Ba₅Si₂N₆, which also exhibit isolated [Si₂N₆]^10– ions.     

Dimers and Chains of Hydrogen bonded [HS2O7]– Anions in the Crystal Structures of M[HS2O7] (M = K, [NH4], [NO], Rb,Cs)

The reactions of KCl, [NH₄]₂[SO₄], Rb₂[CO₃], and Cs₂[CO₃] with fuming sulfuric acid (65 % SO₃) yielded colorless and moisture sensitive crystals of K[HS₂O₇] (monoclinic, P2₁/c (no. 14), Z = 4, a = 716.67(3) pm, b = 1043.57(4) pm, c = 828.78(3) pm, β = 107.884(1)°, V = 589.89(4) × 10⁶ pm³), [NH₄][HS₂O₇] (monoclinic, P2₁/c (no. 14), Z = 4, a = 729.29(1) pm, b = 1079.73(1) pm, c = 843.26(1) pm, β = 106.397(1)°, V = 637.01(1) × 10⁶ pm³), Rb[HS₂O₇] (monoclinic, P2₁/c (no. 14), Z = 4, a = 724.49(2) pm, b = 1073.19(3) pm, c = 852.01(3) pm, β = 106.534(1)°, V = 635.06(3) × 10⁶ pm³), and Cs[HS₂O₇] (triclinic, P$\bar{1}$ (no. 2), Z = 2, a = 537.61(3) pm, b = 784.71(4) pm, c = 867.93(4) pm, α = 94.214(2)°, β = 103.138(2)°, γ = 105.814(2)°, V = 339.47(3) × 10⁶ pm³). Colorless crystals of [NO][HS₂O₇] (monoclinic, P2₁/c (no. 14), Z = 4, a = 739.90(4) pm, b = 1048.00(5) pm, c = 830.97(4) pm, β = 106.985(2)°, V = 106.985(2) × 10⁶ pm³) were obtained as a side product from the reaction of [NH₄]₂[Rh(NO₂)₄] with oleum (65 % SO₃) in the ionic liquid [BMIm][OTf]. The crystal structures of K[HS₂O₇], [NH₄][HS₂O₇], [NO][HS₂O₇], and Rb[HS₂O₇] show the [HS₂O₇]^– ions linked into dimers by strong hydrogen bonds. Contrastingly, in the crystal structure of Cs[HS₂O₇] the [HS₂O₇]^– ions are connected to infinite chains. Raman spectra were recorded for M[HS₂O₇] (M = K, Rb, Cs).     

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 ).     

Sr5Ge2N6 – A Nitridogermanate with Edge‐sharing Double Tetrahedra

The new nitridogermanate Sr₅Ge₂N₆ was obtained as a coarsely crystalline product by Na‐flux technique employing a reaction of Sr, Na, NaN₃ and GeO₂ in weld shut tantalum‐tubes at temperatures up to 760 °C. The crystal structure was determined by single‐crystal X‐ray methods: (Sr₅Ge₂N₆, space group C2/c (no. 15), a = 1040.8(2), b = 652.08(13), c = 1356.5(3) pm, β = 100.29(3)°, V = 905.8(3)·10⁶ pm³, Z = 4, 1240 observed reflections, 61 parameters, R1 = 0.031). In the solid, there are edge‐sharing [Ge₂N₆]¹⁰⁻ double tetrahedra surrounded by Sr²⁺ ions. Sr₅Ge₂N₆ was found to be isotypic with Ca₅Si₂N₆.     

LaPt2Ge2 und EuPt2Ge2 – Neubestimmung der Kristallstrukturen

LaPt₂Ge₂ and EuPt₂Ge₂ – Revision of the Crystal Structures LaPt₂Ge₂ was rechecked by single crystal X‐ray methods resulting in space group P2₁/c (in place of P2₁) and the lattice constants a = 9.953(3), b = 4.439(1), c = 8.879Å, β = 90.62(4)°, and Z = 4. In contrast to previous reports the cell volume had to be doubled. The same is true for EuPt₂Ge₂ (a = 9.731(1), b = 4.446(1), c = 8.823(1) Å, β = 91.26(1)°). The crystal structures correspond to a monoclinic variant of the tetragonal CaBe₂Ge₂ type, whereas the distortion can be described as different rotations of the coordination polyhedra around the La and Eu atoms, respectively. It is most likely that the compounds APt₂Ge₂ with A = Ca, Y, La‐Dy undergo phase transitions at higher temperatures forming then the undistorted CaBe₂Ge₂ type, space group P4/nmm. This was confirmed for SmPt₂Ge₂ (a = 4.292(1), c = 9.980(1) Å; Z = 2) and might also be the case for APt₂Ge₂ with A = Ca, Nd, Sm, Eu, and Gd.     

The Sodium Antimony Telluridogermanate(III) Na9Sb[Ge2Te6]2

Systematic studies in the quaternary system Na/Ge/Sb/Te yielded the new compound Na₉Sb[Ge₂Te₆]₂. Its crystal structure is isotypic to Na₉Sb[Ge₂Se₆]₂ (space group C2/c with a = 9.541(2), b = 26.253(7), c = 7.5820(18) Å and β = 122.233(15)°, Z = 2). The structure is characterized by Ge–Ge dumbbells that are octahedrally coordinated by Te, forming ethane‐like [Ge₂Te₆]^6– anions. Cation sites are occupied by Na⁺ as well as shared by Na⁺ and Sb³⁺. Na₉Sb[Ge₂Te₆]₂ is formally obtained from the reaction of one equivalent Na₈[Ge₄Te₁₀] and one equivalent NaSbTe₂. In contrast to members of the metastable solid solution series (NaSbTe₂)_1–x(GeTe)_x, Na₉Sb[Ge₂Te₆]₂ is a thermodynamically stable compound. It is a semiconductor with a bandgap of 1.51 eV.     

Two New Quaternary Thiophosphates with Pseudo One‐dimensional Structures: Syntheses and Crystal Structures of Cs3Sm[PS4]2 and Rb3Sm[PS4]2

The new thiophosphates Rb₃Sm[PS₄]₂ and Cs₃Sm[PS₄]₂ were obtained as pale yellow needles using an in‐situ formed thiophosphate flux. Rb₃Sm[PS₄]₂ crystallizes in the space group P2₁ with a = 9.7061(19) Å, b = 6.7517(14) Å, c = 11.395(2) Å, β = 90.63(3)°, (Z = 2); Cs₃Sm[PS₄]₂ in space group P2₁/n with a = 15.311(3) Å, b = 6.8762(14) Å, c = 15.352(3) Å, β = 99.49(3)°, (Z = 4). The crystal structures are characterized by the formation of complex anionic chains, which run along the [010] direction in both structures. One of the two independent thiophosphate groups connects three Sm³⁺ cations to form an infinite zigzag like arrangement, while the other acts as a terminal ligand to one Sm³⁺ions. Such a μ₃ or face‐grafting coordination mode of a [PS₄]³⁻ anion is not very common. The Sm³⁺ ions are in bicapped trigonal prismatic chalcogen coordination. The average Sm–S distances within the trigonal prisms are close to 2.88Å, while the bonds to the capping atoms are distinctly longer. The chains are chiral yet their symmetry is close to 2₁/m. In contrast to the rubidium compound, Cs₃Sm[PS₄]₂ contains both enantiomorphs. In both structures the chains are arranged as a distorted hexagonal rod packing.     

Li4Sr2[Cr2N6]: Ein Hexanitridodichromat(V)

Li₄Sr₂[Cr₂N₆]: A Hexanitridodichromate(V) The quaternary hexanitridodichromate(V) Li₄Sr₂[Cr₂N₆] was obtained by reaction of the metals with flowing nitrogen at 900 °C as black‐shining crystals with a platy habit. The crystal structure was determined by X‐ray single crystal methods (orthorhombic, Pbca; a = 914.0 pm, b = 735.4 pm, c = 1053.6 pm; Z = 4). The compound contains isolated complex anions [Cr₂N₆]^8— consisting of two tetrahedra CrN₄ sharing a common edge. The distance Cr—Cr in the complex anion is 249.7 pm. The analysis of the Electron Localization Function (ELF) indicates bonding interactions Cr—Cr. Strontium is in a sixfold (distorted octahedral), Lithium in a distorted tetrahedral ([3+1]) coordination by nitrogen. According to measurements of the magnetic susceptibility the compound is diamagnetic.     

The Phase Diagram of the System [Ph4P]Br/BiBr3. Synthesis,Crystal Structure,Thermal Behaviour,and Vibrational Spectra of [Ph4P]3[Bi2Br9] · CH3COCH3 and two Modifications of [Ph4P]4[Bi6Br22]

The phase diagram of the system [Ph₄P]Br/BiBr₃ was investigated with the aid of DSC, TG and temperature dependent X‐ray powder diffraction measurements. By varying the reaction conditions, stoichiometry and crystallisation conditions of the reaction between BiBr₃ and [Ph₄P]Br four polynuclear bromobismuthates are formed. We report here the crystal structure of the solvation product [Ph₄P]₃[Bi₂Br₉] · CH₃COCH₃, which crystallises with monoclinic symmetry in the S. G. P2₁/n No. 14, a = 12.341(1), b = 32.005(3), c = 19.929(3) Å, β = 99.75(2)°, V = 7758(7) ų, Z = 4 and the crystal structures of two modifications of the compound [Ph₄P]₄[Bi₆Br₂₂]. The α‐form, crystallises with triclinic symmetry in the S. G. P1 No. 2, a = 13.507(4) Å, b = 14.434(4) Å, c = 17.709(5) Å, α = 81.34(2)°, β = 72.42(2)°, γ = 72.53(2)°, V = 3132.7(1) ų, Z = 2. The high‐temperature β‐form, crystallises with triclinic symmetry in the S. G. P1 No. 2, a = 13.893(4) Å, b = 14.267(3) Å, c = 16.580(3), α = 100.13(2)°, β = 96.56(2)°, γ = 110.01(2)°, V = 2985.5(1) ų, Z = 2. Lattice parameters of [Ph₄P]₄[Bi₈Br₂₈] are also given. The thermal behaviour of the compounds and in addition the vibrational spectra of [Ph₄P]₃[Bi₂Br₉] · CH₃COCH₃ are presented and discussed.     

Syntheses,Crystal Structures,and Thermal Behavior of Co(phen)(HL)2 and [Co2(phen)2(H2O)4L2]·H2O with H2L = Pimelic Acid

Two Co^II complexes, Co(phen)(HL)₂ ( 1 ) and [Co₂(phen)₂(H₂O)₄L₂]·H₂O ( 2 ) (H₂L = HOOC‐(CH₂)₅‐COOH), were synthesized and structurally characterized on the basis of single crystal X‐ray diffraction data. In complex 1 the Co atoms are tetrahedrally coordinated by two N atoms of one phen ligand and two O atoms of different hydrogenpimelato ligands. Through π—π stacking interactions between carboxyl group and phen ligand, the complex molecules are assembled into 1D columnar chains, which are connected by intermolecular hydrogen bonds. Complex 2 consists of the centrosymmetric dinuclear [Co₂(phen)₂(H₂O)₄L₂] molecules and hydrogen bonded H₂O molecules. The Co atoms are each octahedrally surrounded by two N atoms of one phen ligand and four O atoms from two bis‐monodentate pimelato ligands and two H₂O molecules at the trans positions. The results about thermal analyses, which were performed in flowing N₂ atmosphere, on both complexes were discussed. Crystal data: ( 1 ) C2/c (no. 15), a = 13.491(1)Å, b = 9.828(1)Å, c = 19.392(2)Å, β = 100.648(1)°, U = 2526.9(4)ų, Z = 4; ( 2 ) P1 (no. 2), a = 11.558(1)Å, b = 11.947(3)Å, c = 15.211(1)Å, α = 86.17(1)°, β = 75.55(1)°, γ = 69.95(1)°, U = 1910.3(3)ų, Z = 2.     

Crystal Structure and Thermal Behaviour of K2[CrF5·H2O]

K₂[CrF₅·H₂O] is monoclinic: a = 9.6835(3) Å, b = 7.7359(2) Å, c = 7.9564(3) Å, β = 95.94(1)°, Z = 4, space group C2/c (n^o 15). Its crystal structure was solved from its X‐ray powder pattern recorded on a powder diffractometer, using for the refinement the Rietveld method. It is built up from isolated octahedral [CrF₅·OH₂]^2? anions separated by potassium cations. The dehydration of K₂[CrF₅·H₂O] leads to anhydrous orthorhombic K₂CrF₅: a = 7.334(2) Å, b = 12.804(4) Å, c = 20.151(5) Å, Z = 16, space group Pbcn (n^o 60), isostructural with K₂FeF₅.     

M[B(CN)4]2: Zwei neue Tetracyanoborate mit zweiwertigen Kationen (M = Zn,Cu)

M[B(CN)₄]₂: Two new Tetracyanoborate Compounds with divalent Cations (M = Zn, Cu) The reaction of ZnO or CuO with [H₃O][B(CN)₄] in aqueous solution yielded single crystals of Zn[B(CN)₄]₂ and Cu[B(CN)₄]₂, respectively. The compounds were characterized by single‐crystal X‐ray diffraction. Zn[B(CN)₄]₂ ( (no. 164), a = b = 7.5092(9) Å, c = 6.0159(6) Å, Z = 1) crystallizes isotypic with Hg[B(CN)₄]₂. The structure of Cu[B(CN)₄]₂ (C2/m (no. 12), a = 13.185(3) Å, b = 7.2919(9) Å, c = 6.029(1) Å, β = 93.02(2)°, Z = 2) can be considered as a super‐structure, resulting from Jahn‐Teller distortion of the Cu²⁺ ions. Magnetic measurements were performed for the copper compound. Vibrational spectra and thermal stabilities were compared with the known mercury(II) tetracyanoborate.     

Molecular structure of 5-[(triphenyl-phosphoranylidene)hydrazono]-exo-3-azatricyclo[5.2.1.02.6]decane-4-one

The molecular structure of 5-[(triphenylphosphoranylidene)hydrazono]-exo-3-azatricyclo[5.2.1.0^2.6]decane-4-one is determined. The C₂₇H₂₆N₃OP compound crystallizes in the space group P?1: a = 9.2163(9) Å, b = 11.1102(11) Å, c = 11.9397(12) Å, α = 74.284(2)°, β = 78.532(2)°, γ = 72.004(2)°.     

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)].     

Synthesis and Structural Characterization of the Helical Coordination Polymers [Co(phen)(oba)(H2O)2] and [Cd3(phen)3(oba)2(Hoba)2(H2O)2] (phen = 1, 10‐phenanthroline; oba = 4, 4′‐oxybis(benzoate)

Two coordination polymers, [Co(phen)(oba)(H₂O)₂] ( 1 ) and [Cd₃(phen)₃(oba)₂(Hoba)₂(H₂O)₂] ( 2 ) (oba = 4, 4′‐oxybis(benzoate), phen = 1, 10‐phenanthroline) have been synthesized under hydrothermal conditions. Complex 1 crystallizes in monoclinic, P2₁/n, a = 7.543(6), b = 33.05(2), c = 9.902(5)Å, β = 103.69(2)°, V = 2398(3)ų, Z = 4; 2 in monoclinic, P2/n, a = 15.11(1), b = 10.069(8), c = 28.02(2)Å, β = 101.83(1)°, V = 4174(5)ų, Z = 2. X‐ray single‐crystal diffraction investigations shows that the complexes 1 and 2 consist of helical chains, which are further assembled into layers and networks via supramolecular interactions such as π—π stacking interactions and hydrogen bonds, respectively. The results indicate that the coordination environment is one of the most important factors for assembly of single‐stranded helical chains into double‐stranded helical chains via supramolecular interactions.