Einkristallzüchtung und Röntgenstrukturanalyse von CoSO4 · Pyrazin · 6 H2O (I) und (CoSO4)2 · Pyrazin · 12 H2O (II)

Crystal Growth and Structure of CoSO₄ · Pyrazine · 6 H₂O (I) and (CoSO₄)₂ · Pyrazine · 12 H₂O (II) Single crystals of μ-pyrazino-bis[pentaquacobalt(II)]-sulfate-dihydrate CoSO₄(pz) · 6 H₂O and Tetraqua-μ-pyrazino-cobalt(II)sulfate-dihydrate (CoSO₄)₂(pz) · 12 H₂O were grown by using gel methods and investigated by X-ray analysis. CoSO₄(pz) · 6 H₂O (I) shows monoclinic symmetry, space group C2/c; a = 1006.4(4) pm, b = 1026.9(4) pm, c = 1261.5(2) pm; β = 104.01(4)°; Z = 4. (CoSO₄)₂(pz) · 12 H₂O (II) shows orthorhombic symmetry, space group Pbam; a = 1262.3(4) pm, b = 1231.3(4) pm, c = 684.1(2) pm; Z = 2. CoSO₄ and Pyrazine crystallize in a polymeric (I) as well as in a dimeric (II) compound. In the polymeric compound the molecules are bonded by pyrazine to form alternating linear chains. The dimer is a dinuclear complex with a bridging pyrazine molecule.     

Die ersten Hydrogencarbonate mit einer trimeren [H2(CO3)3]4−-Baugruppe: Zur Darstellung und Kristallstruktur von Rb4H2(CO3)3 · H2O und K4H2(CO3)3 · 1,5 H2O

The First Hydrogencarbonates with a Trimeric [H₂(CO₃)₃]^4? Group: Preparation and Crystal Structure of Rb₄H₂(CO₃)₃ · H₂O and K₄H₂(CO₃)₃ · 1.5 H₂O Rb₄H₂(CO₃)₃ · H₂O and K₄H₂(CO₃)₃ · 1,5 H₂O were prepared by means of the reaction of (CH₃)₂CO₃ with RbOH resp. KOH in aqueous methanole. Trimer [H₂(CO₃)₃]^4?-anions were found in the crystal structure of Rb₄H₂(CO₃)₃ · H₂O (orthorhombic, Pnma (no. 62), a = 1 218.0(1) pm, b = 1 572.3(6) pm, c = 615.9(1) pm, V_EZ = 1 179.5(5) · 10⁶ pm³, Z = 4, R1(I ≥ 2σ(I)) = 0.027, wR2(I ≥ 2σ(I)) = 0.055). K₄H₂(CO₃)₃ · 1,5 H₂O crystallizes in an OD-structure. The determined superposition structure (orthorhombic, Pbam (no. 55), a = 1 161.8(1) pm, b = 597.0(1) pm, c = 383.85(3) pm, V_EZ = 266.3(1) · 10⁶ pm³, Z = 1, R1(I ≥ 2σ(I)) = 0.035, wR2(I ≥ 2σ(I)) = 0.074) can be derived from the structure of the rubidium compound. The thermal decomposition of the substances is discussed.     

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.     

Komplexe von FeI2 und FeI3 mit Tetramethylharnstoff

Complexes of FeI₂ and FeI₃ with Tetramethylurea [FeI₂(OC(NMe₂)₂)₂] ( 1 , [Fe₂I₄(OC(NMe₂)₂)₂] ( 2 ), and [FeI₃(OC(NMe₂)₂] ( 3 ) were prepared by the reaction of FeI₂ and FeI₂/iodine, respectively, with tetramethylurea. The structures of 1 and 3 were determined from single crystal X-ray diffraction data. 1 crystallizes in the triclinic space group P1 , with a = 809.9(1), b = 923.2(1), c = 1 374.6(1) pm, α = 106.80(1), β = 90.47(1), γ = 101.55(1)°; Z = 2; R = 0.045., 3 : monoclinic, P2₁/c, a = 1 311.4(1), b = 783.3(1), c = 1 409.1(1) pm, β = 97.36(1)°; Z = 4; R = 0.047. 1 and 3 are isolated neutral complexes with distorted tetrahedral coordination of iron. 3 is the first FeI₃-complex with an O-donor ligand. The IR-spectra exhibit strong shifts of n?C = O and n?_asC—N of tetramethylurea especially on coordinating to FeI₃.     

Competitive Coordination of the Uranyl ion by Perchlorate and Water – The Crystal Structures of UO2(ClO4)2·3H2O and UO2(ClO4)2·5H2O and a Redetermination of UO2(ClO4)2·7H2O (Z. Anorg. Allg. Chem. 2003, 629, 1012–1016)

In the article “Competitive Coordination of the Uranyl ion by Perchlorate and Water – The Crystal Structures of UO₂(ClO₄)₂·3H₂O and UO₂(ClO₄)₂·5H₂O and a Redetermination of UO₂(ClO₄)₂·7H₂O” (Z. Anorg. Allg. Chem. 2003 , 629, 1012–1016), some wrong parameters and bond lengths for UO₂(ClO₄)₂·7H₂O were given in table 1 and table 3 The correct parameters are: a = 1449.5(2) pm, b = 921.6(1) pm, c = 1067.5(2) pm, V = 1422.5(4)·10⁶ pm³, ρ = 2.712 g·cm^?3, μ = 119 cm^?1. The corrected bond lengths for this structure are U–O(1) 175.8(5) pm, U–O(2) 239.1(5) pm, U–O(3) 240.8(5), U–O(4) 242.0(7). A cif file with the correct data has been deposited with the ICSD.     

Crystal Structures and Raman Spectra of cis‐[SnCl4(H2O)2]·2H2O,cis‐[SnCl4(H2O)2]·3H2O, [Sn2Cl6(OH)2(H2O)2]·4H2O,and [HL][SnCl5(H2O)]·2.5H2O (L=3‐acetyl‐5‐benzyl‐1‐phenyl‐4, 5‐dihydro‐1, 2, 4‐triazine‐6‐one oxime,C18H18N4O2)

The complexes cis‐[SnCl₄(H₂O)₂]·2H₂O ( 1 ), [Sn₂Cl₆(OH)₂(H₂O)₂]·4H₂O ( 3 ), and [HL][SnCl₅(H₂O)]·2.5H₂O ( 4 ) were isolated from a CH₂Cl₂ solution of equimolar amounts of SnCl₄ and the ligand L (L=3‐acetyl‐5‐benzyl‐1‐phenyl‐4, 5‐dihydro‐1, 2, 4‐triazine‐6‐one oxime, C₁₈H₁₈N₄O₂) in the presence of moisture. 1 crystallizes in the monoclinic space group Cc with a = 2402.5(1) pm, b = 672.80(4) pm, c = 1162.93(6) pm, β = 93.787(6)° and Z = 8. 4 was found to crystallize monoclinic in the space group P2₁, with lattice parameters a = 967.38(5) pm, b = 1101.03(6) pm, c = 1258.11(6) pm, β = 98.826(6)° and Z = 2. The cell data for the reinvestigated structures are: [SnCl₄(H₂O)₂]·3H₂O ( 2 ): a = 1227.0(2) pm, b = 994.8(1) pm, c = 864.0(1) pm, β = 103.86(1)°, with space group C2/c and Z = 4; 3 : a = 961.54(16) pm, b = 646.29(7) pm, c = 1248.25(20) pm, β = 92.75(1)°, space group P2₁/c and Z = 4.     

Über die Schichtstruktur von Cu2(H2O)4[C4H4N2][C6H2(COO)4]·2H2O

The Layered Structure of Cu₂(H₂O)₄[C₄H₄N₂][C₆H₂(COO)₄]·2H₂O Triclinic single crystals of Cu₂(H₂O)₄[C₄H₄N₂][C₆H₂(COO)₄]·2H₂O have been grown in an aqueous silica gel. Space group (Nr. 2), a = 723.94(7) pm, b = 813.38(14) pm, c = 931.0(2) pm, α = 74.24(2)°, β = 79.24(2)°, γ = 65.451(10)°, V = 0.47819(14) nm³, Z = 1. Cu²⁺ is coordinated in a distorted, octahedral manner by two water molecules, three oxygen atoms of the pyromellitate anions and one nitrogen atom of pyrazine (Cu—O 194.1(2)–229.3(3) pm; Cu–N 202.0(2) pm). The connection of Cu²⁺ and [C₆H₂(COO)₄)]^4? yields infinite strands, which are linked by pyrazine molecules to form a two‐dimensional coordination polymer. Thermogravimetric analysis in air showed that the dehydrated compound was stable between 175 and 248 °C. Further heating yielded CuO.     

Die Kristallstruktur von MgHg(SCN)4 · 2 H2O

Crystal Structure of MgHg(SCN)₄ · 2 H₂O The crystal structure of the monoclinic MgHg(SCN)₄ · 2 H₂O (a ? 1 335.1(6) pm, b ? 531.6(5) pm, c ? 1 867.0(14) pm, β ? 92.3(1)°, Z ? 4, space group C2/c) contains nearly tetrahedral Hg(SCN)₄ and octahedral Mg(OH₂)₂(NCS)₄ groups. These groups are joined together with Hg? SCN? Mg bridges and are forming a network of layers.     

[Be3(μ3‐O)3(MeCN)6{Be(MeCN)3}3](I)6 – ein Berylliumkomplex mit Cyclo‐(Be3O3)‐Kern und sein Hydrolyseprodukt [Be(H2O)4](I)2·2MeCN

Single crystals of [Be₃(μ₃‐O)₃(MeCN)₆{Be(MeCN)₃}₃](I)₆·4CH₃CN ( 1 ·4CH₃CN) were obtained in low yield by the reaction of beryllium powder with iodine in acetonitrile suspension, which probably result from traces of beryllium oxide containing the applied beryllium metal. The compound 1 ·4CH₃CN forms moisture sensitive, colourless crystal needles, which were characterized by IR spectroscopy and X‐ray diffraction (Space group Pnma, Z = 4, lattice dimensions at 100(2) K: a = 2317.4(1), b = 2491.4(1), c = 1190.6(1) pm, R₁ = 0.0315). The hexaiodide complex cation 1 ⁶⁺consists of a cyclo‐Be₃O₃ core with slightly distorted chair conformation, stabilized by coordination of two acetonitrile ligands at each of the beryllium atoms and by a {Be(CH₃CN)₃}²⁺ cation at each of the oxygen atoms. This unique coordination behaviour results in coplanar OBe₃ units with short Be–O distances of 155.0 pm and 153.6 pm on average of bond lengths within the cyclo‐Be₃O₃ unit and of the peripheric BeO bonds, respectively. Exposure of compound 1 ·4CH₃CN to moist air leads to small orange crystal plates of [Be(H₂O)₄]I₂·2CH₃CN ( 3 ·2CH₃CN). According to the crystal structure determination (Space group C2/c, Z = 4, lattice dimensions at 100(2) K: a = 1220.7(1), b = 735.0(1), c = 1608.5(1) pm, β = 97.97(1)°, R₁ = 0.0394), all hydrogen atoms of the dication [Be(H₂O)₄]²⁺ are involved to form O–H ··· N and O–H ··· I hydrogen bonds with the acetonitrile molecules and the iodide ions, respectively. Quantum chemical calculations (B3LYP/6‐311+G**) at the model [Be₃(μ₃‐O)₃(HCN)₆{Be(HCN)₃}₃]⁶⁺ show that chair and boat conformation are stable and that the distorted chair conformation is stabilized by packing effects.     

Crystal Structure of Tetrakis (phenacetin) Dihydrogentetraiodide Dihydrate {[H5C2OC6H4N (H)C(CH3)O]4·H2I4·2H2O}

(Phenacetin)₄·₂I₄·2H₂O is triclinic, a = 13.641 (7), b = 12.807 (6), c = 7.201 (3) Å, α = 99.8 (4), b? = 86.5 (4), γ = 104.0 (5)°, P1 , Z = 1. The ordered crystal structure has been refined to R_F = 0.050, using 4173 independent reflections measured on a four-circle diffractometer with MoKa (graphite monochromator) radiation. The crystals are composed of alternating positively and negatively charged slices; each positive slice contains a double layer of stacks of hemi-protonated phenacetin molecules which are H-bonded through their carbonyl groups (d(O - - - O) = 2.432 (4) Å) while each negative slice contains a single layer of I^2?₄-ions linked in chains along [100] through H-bonds to pairs of water molecules. The axes of the phenacetin stacks are parallel to the planes of the (I^2?₄·2H₂O)-layers. The I^2?₄-ion is centro-symmetric and can be approximately represented as I^?- - - I–I- - - I^? (d(I^? - - - I) = 3.404 (1) Å; d(I–I) = 2.774 (1) Å). The compound is a pseudo-type A basic salt.     

M(H2O)2(4,4′‐bipy)[C6H4(COO)2]·2H2O (M = Mn2+, Co2+) – Zwei isotype Koordinationspolymere mit Schichtstruktur

M(H₂O)₂(4,4′‐bipy)[C₆H₄(COO)₂]·2H₂O (M = Mn²⁺, Co²⁺) – Two Isotypic Coordination Polymers with Layered Structure Monoclinic single crystals of Mn(H₂O)₂(4,4′‐bipy)[C₆H₄(COO)₂]·2H₂O ( 1 ) and Co(H₂O)₂(4,4′‐bipy)[C₆H₄(COO)₂]· 2H₂O ( 2 ) have been prepared in aqueous solution at 80 °C. Space group P2/n (no. 13), Z = 2; 1 : a = 769.20(10), b = 1158.80(10), c = 1075.00(10) pm, β = 92.67(2)°, V = 0.9572(2) nm³; 2 : a = 761.18(9), b = 1135.69(9), c = 1080.89(9) pm, β = 92.276(7)°, V = 0.9337(2) nm³. M²⁺ (M = Mn, Co), which is situated on a twofold crystallographic axis, is coordinated in a moderately distorted octahedral fashion by two water molecules, two oxygen atoms of the phthalate anions and two nitrogen atoms of 4,4′‐biypyridine ( 1 : M–O 219.5(2), 220.1(2) pm, M–N 225.3(2), 227.2(2) pm; 2 : Co–O 212.7(2), 213.7(2) pm, Co–N 213.5(3), 214.9(3) pm). M²⁺ and [C₆H₄(COO)₂)]^2? build up chains, which are linked by 4,4′‐biyridine molecules to yield a two‐dimensional coordination polymer with layers parallel to (001).Thermogravimetric analysis in air of 1 indicated a loss of water of crystallization between 154 and 212 °C and in 2 between 169 and 222 °C.     

Zur Reaktion von Makrozyklen mit Lanthanoiden. II. Die Strukturen von [K(thf)3]2[(C22H28N4)2Sm2] · 4THF und [(C22H22N4)Co] · DME

On the Reaction of Macrocycles with Lanthanoids. II. The Crystal Structures of [K(thf)₃]₂[(C₂₂H₂₈N₄)₂Sm₂] · 4 THF and [(C₂₂H₂₂N₄)Co] · DME In a complicated redox reaction [(TMTAA)K₂] and [SmI₂(thf)₂] form the polynuclear metal complex [K(thf)₃]₂[(TMTAT)₂Sm₂]. This complex crystallizes with four molecules THF per formula unit and its structure was determined by single crystal X-ray investigation (spacegroup P2₁/c (No. 14), z = 4, a = 998.0(2) pm, = b = 2618.3(6) pm, c = 1619.4(3) pm, β = 96.52(2)°). In the dimeric unit [(TMTAT)₂Sm₂]^2? the Sm³⁺ ions are bonded to the four N atoms of the macrocyclic ligand and one C₆H₄ ring of the second ligand is attached η⁶ like to one metal ion. Additionally two [K(thf)₃]⁺ fragments are bonded to this central unit, and therefor coordination number seven results for the K⁺ ion. [TMTAA]^2? is not reduced by [Cp₂Co] in a similar reaction. The monomeric paramagnetic complex [(TMTAA)Co] (μ_eff = 2,76 μ_B) is formed instead. The structure reveils a square planar coordination of the Co atom by the four N atoms of the TMTAA ligand (spacegroup C2/c (No. 15), z = 4, a = 1945.1(4) pm, b = 1165.6(2) pm, c = 1144.7(2) pm, β = 116.38(1)°).     

Die Kristallstruktur von BaHg(CN)4 · 4 Pyridin

Crystal Structure of BaHg(CN)₄ · 4 Pyridine The structure of the tetragonal BaHg(CN)₄ · 4 Pyridine (space group I4 , a = 1119.4(7), c = 1 057.9(7) pm, Z = 2, d_c = 1.87 g · cm^?3) contains tetrahedral Hg(CN)₄ and bisdisphenoide Ba(NC)₄(py)₄ groups, which are linked together by Hg? CN? Ba bridges. The BaHg(CN)₄ framework consists of a 3-dimensional network of all round edge-sharing tetrahedrons. The analogous strontium compound is isotype with a = 1 108.2(9) and c = 1 035.3(14) pm.     

Coordination Chemistry of [Nb2(S2)2]4+ Clusters: Preparation and Crystal Structures of K4[Nb2(S2)2(C2O4)4] · 6 H2O and (NH4)6[Nb2(S2)2(C2O4)4](C2O4)

Bis(disulfido)bridged Nb^IV cluster oxalate complexes [Nb₂(S₂)₂(C₂O₄)₄]^4– were prepared by ligand substitution reaction from the aqua ion [Nb₂(μ‐S₂)₂(H₂O)₈]⁴⁺ and isolated as K₄[Nb₂(S₂)₂(C₂O₄)₄] · 6 H₂O ( 1 ), (NH₄)₆[Nb₂(S₂)₂(C₂O₄)₄](C₂O₄) ( 2 ) and Cs₄[Nb₂(S₂)₂(C₂O₄)₄] · 4 H₂O ( 3 ). The crystal structures of 1 and 2 were determined. The crystals of 1 belong to the space group P1, a = 720.94(7) pm, b = 983.64(10) pm, c = 1071.45(10) pm, α = 109.812(1)°, β = 91.586(2)°, γ = 105.257(2)°. The crystals of 2 are monoclinic, space group C2/c, a = 1567.9(2) pm, b = 1906.6(3) pm, c = 3000.9(4) pm, β = 95.502(2)°. The packing in 2 shows alternating layers of cluster anions and of ammonium/uncoordinated oxalates perpendicular to the [1 0 1] direction. Vibration spectra, electrochemistry and thermogravimetric properties of the complexes are also discussed.     

1, 3, 4, 4'‐Tetra(triphenylphosphanimin)‐2‐iodo‐2‐butenal‐4‐carboniumiodid, [O=C(NPPh3)C(I)=C(NPPh3)‐C(NPPh3)2]+I‐

Pale yellow single crystals of [O=C(NPPh₃)C(I)=C(NPPh₃)‐C(NPPh₃)₂]⁺I^‐·1.5 thf ( 1 ·1.5 thf) have been obtained by the reaction of INPPh₃ with thallium in thf suspension. They are characterized by IR spectroscopy and by a crystal structure determination. 1 ·1.5 thf crystallizes in the monoclinic space group P2₁/n, Z = 4, lattice dimensions at ‐83?C: a = 1101.7(1), b = 3449.0(2), c = 2000.4(1) pm, β = 104.88(1)?, R₁ = 0.0382. 1 can be understood as a cationic variation of (Z)‐2‐butenale in which all H atoms are substituted by triphenylphosphoraneimine residues and by a iodine atom, respectively.     

Darstellung und Kristallstrukturen der ersten Alkalimetall‐hexacarbonatooxotetraberyllate: K6[Be4O(CO3)6] · 7 H2O und K6[Be4O(CO3)6]

Preparation and Crystal Structures of the first Alkalimetall‐hexacarbonato‐oxotetraberyllates: K₆[Be₄O(CO₃)₆] · 7 H₂O and K₆[Be₄O(CO₃)₆] K₆[Be₄O(CO₃)₆] · 7 H₂O has been prepared by dissolving freshly precipitated Be(OH)₂ in an aqueous KHCO₃ solution. After enriching the title compound by extraction with ethanol the heptahydrate crystallizes from the organic phase (triklin, P1¯ (No. 2) with a = 951, 01(11), b = 958, 45(12), c = 1601, 7(2) pm, α = 79, 253(13)°, β = 78, 943(12)°, γ = 65, 119(12)°, V_EZ = 1290, 6(3)·10⁶ pm³, Z = 2). Thermal decomposition forms rhombohedral crystals of the anhydrous compound (trigonal‐rhombohedric, R3¯ (No. 148) with a = 1416, 42(6), c = 1704, 5(1) pm, V_EZ = 2961, 4(3)·10⁶ pm³, Z = 6).     

Hydrate isomerism in [Cu(en)2(H2O)1.935]2[Fe(CN)6]·4H2O

The title compound, bis[di­aqua­bis­(ethyl­enedi­amine‐κ²N,N′)copper(II)­] hexa­cyano­iron(II) tetrahydrate, [Cu(C₂H₈N₂)₂(H₂O)_1.935]₂[Fe(CN)₆]·4H₂O, was crystallized from an aqueous reaction mixture initially containing CuSO₄, K₃[Fe(CN)₆] and ethyl­enedi­amine (en) in a 3:2:6 molar ratio. Its structure is ionic and is built up of two crystallographically different cations, viz. [Cu(en)₂(H₂O)₂]²⁺ and [Cu(en)₂(H₂O)_1.87]²⁺, there being a deficiency of aqua ligands in the latter, [Fe(CN)₆]⁴⁻ anions and disordered solvent water mol­ecules. All the metal atoms lie on centres of inversion. The Cu atom is octahedrally coordinated by two chelate‐bonded en mol­ecules [mean Cu—N = 2.016 (2) Å] in the equatorial plane, and by axial aqua ligands, showing very long distances due to the Jahn–Teller effect [mean Cu—O = 2.611 (2) Å]. In one of the cations, significant underoccupation of the O‐atom site is observed, correlated with the appearance of a non‐coordinated water mol­ecule. This is interpreted as the partial contribution of a hydrate isomer. The [Fe(CN)₆]⁴⁻ anions form quite regular octahedra, with a mean Fe—C distance of 1.913 (2) Å. The dominant intermolecular interactions are cation–anion O—H⋯N hydrogen bonds and these inter­actions form layers parallel to (001).     

Erdalkali-Fluoromanganate(III): BaMnF5 · H2O und SrMnF5 · H2O

Alkaline Earth Fluoromanganates(III): BaMnF₅ · H₂O and SrMnF₅ · H₂O Solid BaF₂ or SrF₂ forms with solutions of Mn³⁺ in aqueous hydrofluoric acid precipitates of hitherto unknown BaMnF₅ · H₂ and SrMnF₅ · H₂O respectively. X-ray structure determination on single crystals of both isotypic compounds (space group P2₁/m, Z = 2; BaMnF₅ · H₂O: a = 537.0(3), b = 817.2(2), c = 628.0(4) pm β = 111.17(5)°, R_w = 0.035 for 1403 reflections; SrMnF₅ · H₂O: a = 510.8(1), b = 792.0(2), c = 610.6(1) pm, β = 110.24(1)° R_w = 0.068 for 539 reflections) reveal pure [MnF₆]^3? octahedra connected with each other to infinite chains by sharing trans corners. The H₂O molecules are coordinated to the alkaline earth ions only and form weak O? H…F hydrogen bonds. The pronounced weakening of the Mn? F bonds within the chain direction (Mn? F 2X 212.7(1)/210.8(5) pm, 2X 183.8(3)/181.8(9) pm, 2X 186.9(2)/187.2(8) pm) may be due by halves to the Jahn-Teller-effect as can be deduced by bond valence calculations.     

Zur Reaktion von Makrozyklen mit Lanthanoiden. I. Die Struktur von [Li(thf)][(C22H22N4)2Ce] · THF

On the Reaction of Macrocycles with Lanthanoids. I. The Crystal Structure of [Li(thf)][(C₂₂H₂₂N₄)₂Ce] · THF In THF CeBr₃ forms with [(TMTAA)Li₂] the paramagnetic doubledecker complex [Li(thf)][(TMTAA)₂Ce]. The complex crystallizes with 1 Mol THF per formula unit. The structure was characterized by X-ray single crystal structure analysis (space group C2 (No. 5), z = 6, a = 1741.8(2) pm, b = 1622.1(2) pm, c = 2540.4(3) pm, β = 104.72(1)°). The sandwich-like arrangement of the heterocyclic ligands leads to a quadratic-prismatic coordination of the Ce³⁺ ion. One macrocyclic ligand is additionally coordinated by a [Li(thf)]⁺ fragment. The coordination of the Li ion is square pyramidal.     

New Fluoromanganate(III) Hydrates: Mn3F8 · 12H2O and AgMnF4 · 4H2O

Single crystals of fluoride hydrates Mn₃F₈ · 12 H₂O and AgMnF₄ · 4 H₂O have been prepared and characterized by X-ray methods. Mn₃F₈ · 12 H₂O crystallizes in the space group P1 (a = 623.0(3), b = 896.7(4), c = 931.8(4) pm, α = 110.07(2)°, β = 103.18(2)°, γ = 107.54(2)°, Z = 1); AgMnF₄ · 4 H₂O crystallizes in the space group P2₁/m (a = 700.9(2), b = 726.1(1), c = 749.4(3) pm, β = 107.17(3)°, Z = 2). Both structures contain Jahn-Teller-distorted [Mn(H₂O)₂F₄]^? anions as well as crystal water molecules and exhibit a complex hydrogen bond network between anions and cations, i. e. [Mn(H₂O)₆]²⁺ for the first and a polymeric [Ag(H₂O)₂]^? cation for the second compound.