Crystal Structures of [Mn2(H2O)4(phen)2(C4H4O4)2] · 2 H2O and [Mn(phen)2(H2O)2][Mn(phen)2(C4H4O4)](C4H4O4) · 7 H2O

Reactions of 1,10‐phenanthroline monohydrate, Na₂C₄H₄O₄ · 6 H₂O and MnSO₄ · H₂O in CH₃OH/H₂O yielded a mixture of [Mn₂(H₂O)₄(phen)₂(C₄H₄O₄)₂] · 2 H₂O ( 1 ) and [Mn(phen)₂(H₂O)₂][Mn(phen)₂(C₄H₄O₄)](C₄H₄O₄) · 7 H₂O ( 2 ). The crystal structure of 1 (P1 (no. 2), a = 8.257(1) Å, b = 8.395(1) Å, c = 12.879(2) Å, α = 95.33(1)°, β = 104.56(1)°, γ = 106.76(1)°, V = 814.1(2) ų, Z = 1) consists of the dinuclear [Mn₂(H₂O)₄(phen)₂(C₄H₄O₄)₂] molecules and hydrogen bonded H₂O molecules. The centrosymmetric dinuclear molecules, in which the Mn atoms are octahedrally coordinated by two N atoms of one phen ligand and four O atoms from two H₂O molecules and two bis‐monodentate succinato ligands, are assembled via π‐π stacking interactions into 2 D supramolecular layers parallel to (101) (d(Mn–O) = 2.123–2.265 Å, d(Mn–N) = 2.307 Å). The crystal structure of 2 (P1 (no. 2), a = 14.289(2) Å, b = 15.182(2) Å, c = 15.913(2) Å, α = 67.108(7)°, β = 87.27(1)°, γ = 68.216(8)°, V = 2934.2(7) ų, Z = 2) is composed of the [Mn(phen)₂(H₂O)₂]²⁺ cations, [Mn(phen)₂(C₄H₄O₄)] complex molecules, (C₄H₄O₄)^2– anions, and H₂O molecules. The (C₄H₄O₄)^2– anions and H₂O molecules form 3 D hydrogen bonded network and the cations and complex molecules in the tunnels along [001] and [011], respectively, are assembled via the π‐π stacking interactions into 1 D supramolecular chains. The Mn atoms are octahedrally coordinated by four N atoms of two bidentate chelating phen ligands and two water O atoms or two carboxyl O atoms (d(Mn–O) = 2.088–2.129 Å, d(Mn–N) = 2.277–2.355 Å). Interestingly, the succinato ligands in the complex molecules assume gauche conformation bidentately to chelate the Mn atoms into seven‐membered rings.     

Koordinationspolymere 1, 2‐Dithiooxalato‐ und 1, 2‐Dithioquadratato‐Komplexe. Synthese und Strukturen von [BaCr2(bipy)2(1, 2‐dtox)4(H2O)2], [Ni(cyclam)(1, 2‐dtsq)]·2DMF, [Ni(cyclam)Mn(1, 2‐dtsq)2(H2O)2]·2H2O und [H3O][H5O2][Cu(cyclam)]3[Cu2(1, 2‐dtsq)3]2

Coordination Polymeric 1, 2‐Dithiooxalato and 1, 2‐Dithiosquarato Complexes. Syntheses and Structures of [BaCr₂(bipy)₂(1, 2‐dtox)₄(H₂O)₂], [Ni(cyclam)(1, 2‐dtsq)]·2DMF, [Ni(cyclam)Mn(1, 2‐dtsq)₂(H₂O)₂]·2H2₂, and [H₃O][H₅O₂][Cu(cyclam)]₃[Cu₂(1, 2‐dtsq)₃]₂ 1, 2‐Dithioxalate and 1, 2‐dithiosquarate ions have a pair of soft and hard donor centers and thus are suited for the formation of coordination polymeric complexes containing soft and hard metal ions. The structures of four compounds with building blocks containing these ligands are reported: In [BaCr₂(bipy)₂(1, 2‐dtox)₄(H₂O)₂] Barium ions and pairs of Cr(bipy)(1, 2‐dtox)₂ complexes form linear chains by the bisbidentate coordination of the dithiooxalate ligands towards Ba²⁺ and Cr³⁺. In [Ni(cyclam)(1, 2‐dtsq)]·2DMF short NÖH···O hydrogen bonds link the NiS₂N₄‐octahedra with C_2v‐symmetry to an infinite chain. In [Ni(cyclam)Mn(1, 2‐dtsq)₂(H₂O)₂]·2H₂O the 1, 2‐dithiosquarato ligand shows a rare example of S‐coordination towards manganese(II). The sulfur atoms of cis‐MnO₂S₄‐polyedra are weakly coordinated towards the axial sites of square‐planar NiN₄‐centers, thus forming a zig‐zag‐chain of Mn···Ni···Mn···Ni polyhedra. [H₃O][H₅O₂][Cu (cyclam)]₃[Cu₂(1, 2‐dtsq)₃]₂ contains square planar [Cu^II(cyclam)]²⁺ ions and dinuclear [Cu^I₂(1, 2‐dtsq)₃]^4— ions. Here each copper atom is trigonally planar coordinated by S‐donor atoms of the ligands. The Cu…Cu distance is 2.861(4)Å.     

Crystal Structures of [Mn2(H2O)4(bpy)2(C8H12O4)2] · 2 H2O and [Mn(H2O)2(bpy)(C8H12O4)2/2] · H2O with bpy = 2,2′‐bipyridine

Reaction of MnSO₄ · H₂O, 2,2′‐bipyridine (bpy), suberic acid and Na₂CO₃ in CH₃OH/H₂O yielded a mixture of [Mn₂(H₂O)₄(bpy)₂(C₈H₁₂O₄)₂] · 2 H₂O ( 1 ) and [Mn(H₂O)₂‐ (bpy)(C₈H₁₂O₄)_2/2] · H₂O ( 2 ). In both complexes, the Mn atoms are octahedrally coordinated by two N atoms of one bpy ligand and four O atoms of two trans positioned H₂O molecules and two suberato ligands (d(Mn–O) = 2.107–2.328 Å; d(Mn–N) = 2.250–2.330 Å). The bis‐monodentate suberato ligands bridge Mn atoms to form dinuclear [Mn₂(H₂O)₄(bpy)₂(C₈H₁₂O₄)₂] complex molecules in 1 and 1D [Mn(H₂O)₂(bpy)(C₈H₁₂O₄)_2/2] chains in 2 . Via the intermolecular hydrogen bondings and π‐π stacking interactions, the dinuclear molecules in 1 are assembled into 2D networks parallel to (100), between which the crystal H₂O molecules are sandwiched. The polymeric chains in 2 are linked together by interchain hydrogen bonding and π‐π stacking interactions into 3D networks with the crystal H₂O molecules located in tunnels along [010]. Crystal data for 1 : P2₁/c (no. 14), a = 10.092(1) Å, b = 11.916(2) Å, c = 17.296(2) Å, β = 93.41(1)° and Z = 2. Crystal data for 2 : P2₁/c (no. 14), a = 11.176(2) Å, b = 9.688(1) Å, c = 37.842(6) Å, β = 90.06(1)° and Z = 8.     

Two Novel CuII Phenanthroline Adipato Complexes with π‐π Stacking Interactions: [Cu(phen)2(C6H8O4)] · 4.5 H2O and [(Cu2(phen)2Cl2)(C6H8O4)] · 4 H2O

The blue copper complex compounds [Cu(phen)₂(C₆H₈O₄)] · 4.5 H₂O ( 1 ) and [(Cu₂(phen)₂Cl₂)(C₆H₈O₄)] · 4 H₂O ( 2 ) were synthesized from CuCl₂, 1,10‐phenanthroline (phen) and adipic acid in CH₃OH/H₂O solutions. [Cu(phen)₂‐ (C₆H₈O₄)] complexes and hydrogen bonded H₂O molecules form the crystal structure of ( 1 ) (P1 (no. 2), a = 10.086(2) Å, b = 11.470(2) Å, c = 16.523(3) Å, α = 99.80(1)°, β = 115.13(1)°, γ = 115.13(1)°, V = 1617.5(5) ų, Z = 2). The Cu atoms are square‐pyramidally coordinated by four N atoms of the phen ligands and one O atom of the adipate anion (d(Cu–O) = 1.989 Å, d(Cu–N) = 2.032–2.040 Å, axial d(Cu–N) = 2.235 Å). π‐π stacking interactions between phen ligands are responsible for the formation of supramolecular assemblies of [Cu(phen)₂(C₆H₈O₄)] complex molecules into 1 D chains along [111]. The crystal structure of ( 2 ) shows polymeric [(Cu₂(phen)₂Cl₂)(C₆H₈O₄)_2/2] chains (P1 (no. 2), a = 7.013(1) Å, b = 10.376(1) Å, c = 11.372(3) Å, α = 73.64(1)°, β = 78.15(2)°, γ = 81.44(1)°, V = 773.5(2) ų, Z = 1). The Cu atoms are fivefold coordinated by two Cl atoms, two N atoms of phen ligands and one O atom of the adipate anion, forming [CuCl₂N₂O] square pyramids with an axial Cl atom (d(Cu–O) = 1.958 Å, d(Cu–N) = 2.017–2.033 Å, d(Cu–Cl) = 2.281 Å; axial d(Cu–Cl) = 2.724 Å). Two square pyramids are condensed via the common Cl–Cl edge to centrosymmetric [Cu₂Cl₂N₄O₂] dimers, which are connected via the adipate anions to form the [(Cu₂(phen)₂Cl₂)(C₆H₈O₄)_2/2] chains. The supramolecular 3 D network results from π‐π stacking interactions between the chains. H₂O molecules are located in tunnels.     

Einfach und doppelt deprotonierte Maleinsäure in Praseodym‐hydrogenmaleat‐octahydrat,Pr(C4O4H3)3 · 8 H2O,und Praseodym‐maleatchlorid‐tetrahydrat,Pr(C4O4H2)Cl · 4 H2O

Single and Double Deprotonated Maleic Acid in Praseodymium Hydrogenmaleate Octahydrate, Pr(C₄O₄H₃)₃ · 8 H₂O, and Praseodymiummaleatechloride Tetrahydrate, Pr(C₄O₄H₂)Cl · 4 H₂O Single crystals of Pr(C₄O₄H₃)₃ · 8 H₂O grew by slow evaporation of a solution which had been obtained by dissolving Pr(OH)₃ in aqueous maleic acid. The triclinic compound (P1, Z = 2, a = 728.63(3), b = 1040.23(3), c = 1676.05(8) pm, α = 72.108(2)°, β = 87.774(2)°, γ = 70.851(2)°, R_all = 0.0261) contains Pr³⁺ ions in ninefold coordination of oxygen atoms which belong to two monodentate maleate ions and seven H₂O molecules. There is one further non‐coordinating maleate ion and one crystal water molecule in the unit cell. Thermal treatment of Pr(C₄O₄H₃)₃ · 8 H₂O leads first to the anhydrous compound which then decomposes to the respective oxide in two steps upon further heating. Evaporation of a solution of Pr(C₄O₄H₃)₃ · 8 H₂O which contained additional Cl^– ions yielded single crystals of Pr(C₄O₄H₂)Cl · 4 H₂O. In the crystal structure (monoclinic, P2₁/c, Z = 4, a = 866.0(1), b = 1344.3(1), c = 896.9(1) pm, β = 94.48(2)°, R_all = 0.0227), the Pr³⁺ ions are surrounded by nine oxygen atoms. The latter belong to four H₂O molecules and three maleate ions. Two of the latter act as bidentate ligands.     

Darstellung und Struktur der Komplexverbindungen trans‐[CoIII(py)4F2][H2F3] und [Pd(py)4]F2 · 1,5 HF · 2 H2O

Synthesis and Crystal Structures of the Complexes trans ‐[Co^III(py)₄F₂][H₂F₃] and [Pd(py)₄]F₂ · 1.5 HF · 2 H₂O The cobalt complex trans‐[Co(III)(py)₄F₂][H₂F₃] ( 1 ) has been prepared by electrochemical oxidation of CoF₂ in a pyridine/HF mixture and the palladium complex [Pd(py)₄]F₂ · 1.5 HF · 2 H₂O ( 2 ) has been obtained via halogen exchange between Pd(py)₂Cl₂ and AgF₂ in pyridine. 1 and 2 crystallize in the space group C2/c with a = 27.928(14), b = 9.019(3), c = 18.335(8) Å, β = 113.41(3)° for 1 and a = 28.183(9), b = 9.399(3), c = 17.397(6) Å, β = 104.66(3)° for 2 , respectively. Concerning the shape and location of the M(py)₄ fragments 1 and 2 are isostructural. The metal atoms occupy special positions in their unit cells with the result that four complex atoms have C₂ symmetry and four complex cations have C_i symmetry giving a total of Z = 8. In 1 two F^– ions complete an octahedral coordination around the Co atoms (Co–F 1.820(2) to 1.834(3) Å). In 2 the shortest Pd–F distance is 3.031(2) Å. This precludes the existence of Pd–F bonds. In 1 one can identify H₂F₃^– groups. In 2 there are larger aggregates, consisting of F^–, HF, and H₂O subunits, connected by H‐bridges. In spite of these differences, both complexes belong to the same type of structure, which may be of a common type M^x+(py)₄F_x · y HF · z H₂O.     

Hybrid Inorganic‐Organic Frameworks: Synthesis and Crystal Structures of RbFe(SO4)(C2O4)0.5·H2O and CsM(SO4)(C2O4)0.5·H2O (M = Mn,Fe)

Three new alkali metal transition metal sulfate‐oxalates, RbFe(SO₄)(C₂O₄)_0.5 · H₂O and CsM(SO₄)(C₂O₄)_0.5 · H₂O (M = Mn, Fe) were prepared through hydrothermal reactions and characterized by single‐crystal X‐ray diffraction, solid state UV/Vis/NIR diffuse reflectance spectroscopy, infrared spectra, thermogravimetric analysis, and powder X‐ray diffraction. The title compounds all crystallize in the monoclinic space group P2₁/c (no. 14) with lattice parameters: a = 7.9193(5), b = 9.4907(6), c = 8.8090(6) Å, β = 95.180(2)°, Z = 4 for RbFe(SO₄)(C₂O₄)_0.5 · H₂O; a = 8.0654(11), b = 9.6103(13), c = 9.2189(13) Å, β = 94.564(4)°, Z = 4 for CsMn(SO₄)(C₂O₄)_0.5 · H₂O; and a = 7.9377(3), b = 9.5757(4), c = 9.1474(4) Å, β = 96.1040(10)°, Z = 4 for CsFe(SO₄)(C₂O₄)_0.5 · H₂O. All compounds exhibit three‐dimensional frameworks composed of [MO₆] octahedra, [SO₄]^2– tetrahedra, and [C₂O₄]^2– anions. The alkali cations are located in one‐dimensional tunnels.     

An Azelaato‐bridged Dinuclear Copper(II) Complex, [Cu2(phen)2(C9H14O4)2] · 6 H2O (phen = 1,10‐phenanthroline)

The title compound [Cu₂(phen)₂(C₉H₁₄O₄)₂] · 6 H₂O was prepared by the reaction of CuCl₂ · 2 H₂O, 1,10‐phenanthroline (phen), azelaic acid and Na₂CO₃ in a CH₃OH/H₂O solution. The crystal structure (monoclinic, C2/c (no. 15), a = 22.346(3), b = 11.862(1), c = 17.989(3) Å, β = 91.71(1)°, Z = 4, R = 0.0473, wR² = 0.1344 for 4279 observed reflections) consists of centrosymmetric dinuclear [Cu₂(phen)₂(C₉H₁₄O₄)₂] complexes and hydrogen bonded H₂O molecules. The Cu atom is square‐planar coordinated by the two N atoms of the chelating phen ligand and two O atoms of different bidentate bridging azelaate groups with d(Cu–N) = 2.053, 2.122(2) Å and d(Cu–O) = 1.948(2), 2.031(2) Å. Two azelaate anions bridge two common Cu atoms via the terminal O atoms (d(C–O) = 1.29(2) Å; d(C–C) = 1.550(4)–1.583(4) Å). Phen ligands of adjacent complexes cover each other at distances of about 3.62 Å, indicating π‐π stacking interaction, by which the complexes are linked to 1 D bands.     

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.     

Two Heteroleptic Zinc(II) Complexes: [Zn(phen)(C9H15O6)2] and [Zn2(phen)2(H2O)2(C10H16O4)2] · 3H2O

Reactions of a freshly prepared Zn(OH)_2‐2x(CO₃)x · yH₂O precipitate, phenanthroline with azelaic and sebacic acid in CH₃OH/H₂O afforded [Zn(phen)(C₉H₁₅O₄)₂] ( 1 ) and [Zn₂(phen)₂(H₂O)₂(C₁₀H₁₆O₄)₂] · 3H₂O ( 2 ), respectively. They were structurally characterized by X‐ray diffraction methods. Compound 1 consists of complex molecules [Zn(phen)(C₉H₁₅O₄)₂] in which the Zn atoms are tetrahedrally coordinated by two N atoms of one phen ligand and two O atoms of different monodentate hydrogen azelaato groups. Intermolecular C(alkyl)‐H···π interactions and the intermolecular C(aryl)‐H···O and O‐H···O hydrogen bonds are responsible for the supramolecular assembly of the [Zn(phen)(C₉H₁₅O₄)₂] complexes. Compound 2 is built up from crystal H₂O molecules and the centrosymmetric binuclear [Zn₂(phen)₂(H₂O)₂(C₁₀H₁₆O₄)₂] complex, in which two [Zn(phen)(H₂O)]²⁺ moieties are bridged by two sebacato ligands. Through the intermolecular C(alkyl)‐H···O hydrogen bonds and π‐π stacking interactions, the binuclear complex molecules are assembled into layers, between which the lattice H₂O molecules are sandwiched. Crystal data: ( 1 ) C2/c (no. 15), a = 13.887(2), b = 9.790(2), c = 22.887(3)Å, β = 107.05(1)°, U = 2974.8(8)ų, Z = 4; ( 2 ) P1¯ (no. 2), a = 8.414(1), b = 10.679(1), c = 14.076(2)Å, α = 106.52(1)°, β = 91.56(1)°, γ = 99.09(1)°, U = 1193.9(2)ų, Z = 1.     

A Novel Adipate Bridged Supramolecular Layer: Crystal Structure of the Cobalt(II) Complex [(μ‐C6H8O4)4/2Co(μ‐H2O)2Co(H2O)4] · 4 H2O

The pale‐rose compound [(μ‐C₆H₈O₄)_4/2Co(μ‐H₂O)₂Co(H₂O)₄] · 4 H₂O was prepared from adipic acid and CoCO₃ in aqueous solution. The crystal structure (monoclinic, P2₁/n (no. 14), a = 8.061(1), b = 15.160(2), c = 9.708(2) Å, β = 90.939(7)°, Z = 2, R = 0.0405, wR² = 0.0971) consists of adipate bridged supramolecular [(μ‐C₆H₈O₄)_4/2Co(μ‐H₂O)₂Co(H₂O)₄] layers and hydrogen bonded H₂O molecules. The cobalt atoms Co1 and Co2 are distorted octahedrally coordinated by the O atoms of two bridging trans‐H₂O molecules and four bidentate adipate anions (Co1) and by the O atoms of two bridging trans‐H₂O molecules and four monodentate H₂O molecules (Co2), respectively. Equatorial bonds: d(Co1–O) = 2.048 Å (2 × ), 2.060 Å (2 × ); d(Co2–O) = 2.057 Å (2 × ), 2.072 Å (2 × ). Axial bonds: d(Co1–O) = 2.235 Å (2 × ); d(Co2–O) = 2.156 Å (2 × ).     

Synthese verbrückter binuklearer Titanocenverbindungen – Kristallstruktur von Cl2Ti[(C5H4)(C5H4)(Me)Si–Si(Me)(C5H4)(C5H4)]TiCl2 · PhMe

Synthesis of Bridged Binuclear Titanocene Compounds – Crystal Structure of Cl₂Ti[(C₅H₄)(C₅H₄)(Me)Si–Si(Me)(C₅H₄)(C₅H₄)]TiCl₂ · PhMe Starting from Cp₂(Me)Si–Si(Me)Cp₂ 1 the complexes X₂Ti[(C₅H₄)(C₅H₄)(Me)Si–Si(Me)(C₅H₄)(C₅H₄)]TiX₂ (X = Cl ( 2 a ); X = Me ( 3 )) were synthesized. The compounds were characterized by means of their ¹H‐ and ¹³C‐n.m.r. and MS‐spectra. The crystal structure of 2 a · PhMe was determined.     

Dicarboxylatgruppen als Liganden und Anionen in Aquamagnesiumkomplexen: Kristallstrukturen von [Mg (C4H2O4)(H2O)4] · H2O und [Mg(H2O)6](C4HO4)2 · 2H2O ((C4H2O4)2— = Fumarat; (C4HO4)— = Hydrogenacetylendicarboxylat)

Dicarboxylate Groups as Ligands and Anions in Aquamagnesium Complexes: Crystal Structures of [Mg (C₄H₂O₄)(H₂O)₄] · H₂O and [Mg(H₂O)₆](C₄HO₄)₂ · 2H₂O ((C₄H₂O₄)^2— = Fumarate; (C₄HO₄)^— = Hydrogenacetylenedicarboxylate) Crystals of tetraaqua(fumarato)magnesium‐hydrate ( 1 ) and hexaaquamagnesium‐bis(hydrogenacetylenedicarboxylate)‐dihydrate ( 2 ) were prepared by reacting MgCl₂ with sodium fumarate and acetylenedicarboxylic acid, respectively. In 1 cis‐Mg(H₂O)₄ units are bridged by α, Ö‐bonded fumarate groups. The resulting zig zag chains exhibit the maximum symmetry compatible with space group symmetry C2/c. 2 consists of layers of voluminous [Mg(H₂O)₆]²⁺ cations alternating with layers of C₄HO₄^— anions. The nearly planar anions are held together by parallel stacking and by short hydrogen bonds. Both structures contain efficient H bridging systems. 1 : Space group C2/c, Z = 4, lattice constants at 20 °C: a = 5.298(1), b = 13.178(2), c = 13.374(2)Å; ß = 94.79(2)°, R₁ = 0.024. 2 : Space group P1, Z = 1, lattice constants at 20 °C: a = 5.985(1), b = 6.515(1), c = 11.129(1)Å; α = 105.24(2), ß = 91.87(3), γ = 90.92(1)°, R₁ = 0.034.     

[(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.     

Co(C2(COO)2)(H2O)4 · 2 H2O und Co(C2(COO)2)(H2O)2: zwei Koordinationspolymere mit dem Acetylendicarboxylat‐Dianion

Co(C₂(COO)₂)(H₂O)₄ · 2 H₂O and Co(C₂(COO)₂)(H₂O)₂: Two Co‐ordination Polymers of the Acetylenedicarboxylate Dianion By reaction of CoCO₃ with an aqueous solution of acetylenedicarboxylic acid and subsequent crystallisation single‐crystals of Co(C₂(COO)₂)(H₂O)₄ · 2 H₂O were obtained (P2₁/a, Z = 2). In the solid state structure cobalt is octahedrally surrounded by four water molecules and two oxygen atoms of the carboxylate anions. These octahedra are connected to chains by the dicarboxylates. Already at ambient conditions Co(C₂(COO)₂)(H₂O)₄ · 2 H₂O looses four water molecules to give Co(C₂(COO)₂)(H₂O)₂ (isotypic to Mn[C₂(COO)₂] · 2 H₂O, C2/c, Z = 4). The cobalt cation is now octahedrally co‐ordinated by two water molecules and four oxygen atoms of the dicarboxylate ligands, which connect the Co octahedra to a three dimensional network. Thermoanalytical investigations show another mass loss at about 200 °C, which leads to non‐crystalline products. Measurements of the magnetic susceptibilities result in the expected behaviour for Co²⁺ in an octahedral co‐ordination (high spin, ⁴T₁ ground state). The effective magnetic moment at room temperature is n_eff = 5.51 μ_B.     

A New Succinato‐bridged Supramolecular Helix Chain: Crystal Structure of [Mn(H2O)2(bpy)(C4H4O4)] · H2O with bpy = 2,2′‐bipyridine

Yellow crystals of [Mn(H₂O)₂(bpy)(C₄H₄O₄)] · H₂O were obtained by the reaction of 2,2′‐bipyridine, succinic acid, MnSO₄ · H₂O and Na₂CO₃ in an aqueous methanol solution. The crystal structure (monoclinic, P2₁/c (no. 14), a = 8.294(1), b = 11.556(1), c = 17.064(1)Å, β = 95.181(6)°, Z = 4, R = 0.0349, wR² = 0.0887) consists of 1D supramolecular helix chains [Mn(H₂O)₂(bpy)(C₄H₄O₄)_2/2] and hydrogen bonded H₂O molecules. The Mn atoms are octahedrally coordinated by two N atoms of one bidentate chelating bpy ligand and four O atoms of two H₂O molecules and two bis‐monodentate bridging succinato ligands with d(Mn–O) = 2.139–2.237Å and d(Mn–N) = 2.268, 2.281 Å. The helix chains are held together by π‐π stacking interactions and hydrogen bonds.     

New Suberato‐bridged Supramolecular Layers: Crystal Structure of [Cu2(phen)2(C8H12O4)2] · 3 H2O with phen = 1,10‐phenanthroline

The reaction of CuCl₂ · 2 H₂O, 1,10‐phenanthroline (phen), suberic acid and Na₂CO₃ in a CH₃CN–H₂O solution yielded blue needle‐like crystals of [Cu₂(phen)₂(C₈H₁₂O₄)₂] · 3 H₂O. The crystal structure (monoclinic, P2₁/n, a = 10.756(2) Å, b = 9.790(2) Å, c = 18.593(4) Å, β = 91.15(3)°, Z = 2, R = 0.043, wR² = 0.1238) consists of suberato‐bridged [Cu₂(phen)₂(C₈H₁₂O₄)_4/2] layers and hydrogen bonded H₂O molecules. The Cu atoms are coordinated by two N atoms from one bidentate chelating phen ligand and three carboxyl O atoms from different suberato ligands to form distorted [CuN₂O₃] square‐pyramids with one carboxyl O atom at the apical position (d(Cu–N) = 2.017(2), 2.043(3) Å, basal d(Cu–O) = 1.936(2), 1.951(2) Å and axial d(Cu–O) = 2.389(2) Å). Two [CuN₂O₃] square‐pyramids are condensed via a common O–O edge to a centrosymmetric [Cu₂N₄O₄] dimer with the Cu…Cu distance of 3.406(1) Å indicating no interaction between Cu atoms. The resultant [Cu₂N₄O₄] dimers are interlinked by the tridentate suberato ligands to form [Cu₂(phen)₂(C₈H₁₂O₄)_4/2] layers parallel to (101). These are assembled via π‐π stacking interactions into 3D network with H₂O molecules in the tunnels extending in the [010] direction.     

Two new soluble iron–oxo complexes: [Fe2(μ‐O)(μ‐O2CCF3)2(O2CCF3)2(C10H8N2)2] and [Fe4(μ3‐O)2(μ‐O2CCF3)6(O2CCF3)2(C10H8N2)2]·CF3CO2H

Two new iron–oxo clusters, viz. di‐μ‐tri­fluoro­acetato‐μ‐oxo‐bis­[(2,2′‐bi­pyridine‐κ²N,N′)(tri­fluoro­acetato‐κO)­iron(III)], [Fe₂O(CF₃CO₂)₄(C₁₀H₈N₂)₂], and bis(2,2′‐bi­pyridine)­di‐μ₃‐oxo‐hexa‐μ‐tri­fluoro­acetato‐bis­(tri­fluoro­acetato)­tetrairon(III) tri­fluoro­acetic acid solvate, [Fe₄O₂(CF₃CO₂)₈(C₁₀H₈N₂)₂]·CF₃CO₂H, contain dinuclear and tetranuclear Fe^III cores, respectively. The Fe^III atoms are in distorted octahedral environments in both compounds and are linked by oxide and tri­fluoro­acetate ions. The tri­fluoro­acetate ions are either bridging (bidentate) or coordinated to the Fe^III atoms via one O atom only. The fluorinated peripheries enhance the solubility of these compounds. Formal charges for all the Fe centers were assigned by summing valences of the chemical bonds to the Fe^III atom.     

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.     

A three‐dimensional inorganic/organic hybrid material, [Ni2(4,4′‐bipy)3(H2O)2V4O12]·2.5H2O

The title compound, poly­[[[di­aqua(μ‐4,4′‐bipyridyl)­di­nickel(II)]‐bis(μ‐4,4′‐bipyridyl)‐di‐μ‐hexa­oxo­di­vana­date(2?)] 2.5‐hydrate], [Ni₂­(V₂O₆)₂­(C₁₀H₈N₂)₃­(H₂O)₂]·­2.5H₂O, has been prepared hydro­thermally and characterized by elemental analyses, IR spectroscopy and single‐crystal X‐ray diffraction. The structure consists of [V₂O₆], [Ni­(4,4′‐bipy)₄O₂] and [Ni­(H₂O)₂­(4,4′‐bipy)₂O₂] polyhedra, and water of crystallization. The Ni atoms and one bipyridyl group lie on centres of symmetry.