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.     

Synthese und Kristallstruktur von Blei(II)‐oxidhalogenid‐Alkoholaten mit unterschiedlichen Verknüpfungsvarianten von Pb4O4‐Heterokubaneinheiten

Synthesis and Crystal Structure Determination of Lead(II) Oxide Halide Alcoholates with Different Connectivity of Pb₄O₄ Heterocubane‐like Subunits The reaction of red lead(II) oxide (Litharge) and lead(II) halide (Cl^? and Br^?) with diethylene glycole at a temperature of 180 °C leads to the isotypic compounds [Pb₆(C₄H₈O₃)O₂Cl₆] (1) and [Pb₆(C₄H₈O₃)O₂Br₆] (2) . In a similar synthesis with PbI₂ as educt at temperature of 160 °C the two modifications β‐[Pb₆(C₄H₈O₃)O₂I₆] (3) and α‐[Pb₆(C₄H₈O₃)O₂I₆] (4) were found, whereas at a reaction temperature of 180 °C [Pb₉(C₂H₄O₂)(C₄H₈O₃)O₃I₈] (5) was surprisingly obtained as product. The X‐ray diffraction data show that at a temperature of 180 °C a splitting of the ether took place. The cited compounds show cubane like subunits built by lead and oxygen atoms. These fragments are connected by alkoholate molecules. In 5 additionally an I₆ octahedra centered by lead is observed.     

Polyol-Metall-Komplexe. XIII [1]. Na2[Be(C4H6O3)2] · 5H2O und Na2[Pb(C4H6O3)2] · 3H2O – zwei homoleptische Bis-polyolato-metallate mit Beryllium und mit Blei

Polyol Metal Complexes. XIII. Na₂[Be(C₄H₆O₃)₂] · 5H₂O and Na₂[Pb(C₄H₆O₃)₂] · 3H₂O – Two Homoleptic Bis Polyolato Metallates with Beryllium and with Lead Na₂[Be(C₄H₆O₃)₂] · 5H₂O ( 1 ) and Na₂[Pb(C₄H₆O₃)₂] · 3H₂O ( 2 ) crystallize from concentrated, alkaline aqueous solutions. The polyol anhydroerythritol is deprotonated twice in the mononuclear, homoleptic complex anions. The preference of beryllium for the binding of cis-furanoid diols is shown. In 2 , a stereochemically active lone pair at the central atom is the reason for the construction of low dimensional aggregates from three plumbate and three sodium ions.     

Bariumstannat‐Pulver durch hydrothermale Synthese und durch Thermolyse von Bariumzinn(IV)‐glykolaten. Synthese und Struktur von [Ba(C2H6O2)4][Sn(C2H4O2)3] und [Ba(C2H6O2)2][Sn(C2H4O2)3]·CH3OH

Barium Stannate Powders from Hydrothermal Synthesis and by Thermolysis of Barium‐Tin(IV)‐Glycolates. Synthesis and Structure of [Ba(C₂H₆O₂)₄][Sn(C₂H₄O₂)₃] and [Ba(C₂H₆O₂)₂][Sn(C₂H₄O₂)₃]·CH₃OH The hydrothermal reaction as well as the microwave assisted hydrothermal reaction of SnO₂·aq with barium hydroxide gives Ba[Sn(OH)₆] ( 1 ) as powder with bar like particles. Compound 1 of the same morphology can also be isolated from a hydrothermal reaction of [Ba(C₂H₆O₂)₄][Sn(C₂H₄O₂)₃] ( 3 ). The reaction of SnO₂·aq with Ba(OH)₂·8H₂O in ethylene glycol yields the glycolate [Ba(C₂H₆O₂)₄][Sn(C₂H₄O₂)₃] ( 3 ), which forms in methanol the solvate [Ba(C₂H₆O₂)₂][Sn(C₂H₄O₂)₃]·CH₃OH ( 4 ). Compounds 1 , 3 and 4 react at different temperatures to BaSnO₃ ( 2 ) consisting of powders with different morphologies; because of the grain size of the resulting powders compounds 3 and 4 are suitable as precursor for the fabrication of corresponding ceramics.     

Synthese und Kristallstruktur von [C(NMe2)3]2[(CO)4Fe(μ‐InCl2)2Fe(CO)4]

Synthesis and Crystal Structure of [C(NMe₂)₃]₂[(CO)₄Fe(μ‐InCl₂)₂Fe(CO)₄] Treatment of [C(NMe₂)₃]₂[(CO)₄FeInCl₃] ( 1 ) with hot water produces the dinuclear complex [C(NMe₂)₃]₂[(CO)₄Fe(μ‐InCl₂)₂Fe(CO)₄] ( 2 ) which could be crystallized from dichloromethane/pentane. 2 crystallizes in the monoclinic space group P2₁/n with a = 835.7(1), b = 1187.8(1), c = 1902.7(1) pm, β = 91.877(5)° and Z = 2. The anion contains a four‐membered Fe—In—Fe—In ring with octahedral environment at the iron atom and tetrahedral coordination at the In atom.     

Synthese,Kristallstruktur und thermischer Abbau von Mg(H2O)6[B12H12] · 6 H2O

Synthesis, Crystal Structure, and Thermal Decomposition of Mg(H₂O)₆[B₁₂H₁₂] · 6 H₂O By reaction of an aqueous solution of the free acid (H₃O)₂[B₁₂H₁₂] with MgCO₃ and subsequent isothermic evaporation of the resulting solution to dryness, colourless, bead‐shaped single crystals of the dodecahydrate of magnesium dodecahydro closo‐dodecaborate Mg(H₂O)₆[B₁₂H₁₂] · 6 H₂O (cubic, F4₁32; a = 1643.21(9) pm, Z = 8) emerge. The crystal structure is best described as a NaTl‐type arrangement in which the centers of gravity of the quasi‐icosahedral [B₁₂H₁₂]^2— anions (d(B—B) = 178—180 pm, d(B—H) = 109 pm) occupy the positions of Tl^— while the Mg²⁺ cations occupy the Na⁺ positions. A direct coordinative influence of the [B₁₂H₁₂]^2— units at the Mg²⁺ cations is however not noticeable. The latter are octahedrally coordinated by six water molecules forming isolated hexaaqua complex cations [Mg(H₂O)₆]²⁺ (d(Mg—O) = 206 pm, 6×). In addition, six “zeolitic” water molecules are located in the crystal structure for the formation of a strong O—H^δ+···^δ—O‐hydrogen bridge‐bonding system. The evidence of weak B—H^δ—···^δ+H—O‐hydrogen bonds between water molecules and anionic [B₁₂H₁₂]^2— clusters is also considered. Investigations on the dodecahydrate Mg[B₁₂H₁₂] · 12 H₂O (≡ Mg(H₂O)₆[B₁₂H₁₂] · 6 H₂O) by DTA/TG measurements showed that its dehydration takes place in two steps within a temperature range of 71 and 76 °C as well as at 202 °C, respectively. Thermal treatment eventually leads to the anhydrous magnesium dodecahydro closo‐dodecaborate Mg[B₁₂H₁₂].     

Kristallstruktur von Natrium‐Dihydrogencyamelurat‐Tetrahydrat Na[H2(C6N7)O3] · 4 H2O

Crystal Structure of Sodium Dihydrogencyamelurate Tetrahydrate Na[H₂(C₆N₇)O₃] · 4 H₂O Sodium dihydrogencyamelurate‐tetrahydrate Na[H₂(C₆N₇)O₃]·4 H₂O was obtained by neutralisation of an aqueous solution, previously prepared by hydrolysis of the polymer melon with sodium hydroxide. The crystal structure was solved by single‐crystal X‐ray diffraction ( a = 6.6345(13), b = 8.7107(17), c = 11.632(2) Å, α = 68.96(3), β = 87.57(3), γ = 68.24(3)°, V = 579.5(2) ų, Z = 2, R1 = 0.0535, 2095 observed reflections, 230 parameters). Both hydrogen atoms of the dihydrogencyamelurate anion are directly bound to nitrogen atoms of the cyameluric nucleus, thus proving the preference of the keto‐tautomere in salts of cyameluric acid in the solid‐state. The compound forms a layer‐like structure with an extensive hydrogen bonding network.     

Zwei Dodekahydro‐closo‐Dodekaborate mit Lone‐Pair‐Kationen der 6. Periode im Vergleich: Tl2[B12H12] und Pb(H2O)3[B12H12]·3H2O

During the reaction of an aqueous solution of (H₃O)₂[B₁₂H₁₂] with Tl₂CO₃ anhydrous thallium(I) dodecahydro‐closo‐dodecaborate Tl₂[B₁₂H₁₂] is obtained as colorless, spherical single crystals. It crystallizes in the cubic system with the centrosymmetric space group Fm$\bar{3}$ (a = 1074.23(8) pm, Z = 4) in an anti‐CaF₂ type structure. Four quasi‐icosahedral [B₁₂H₁₂]^2– anions (d(B–B) = 180–181 pm, d(B–H) = 111 pm) exhibit coordinative influence on each Tl⁺ cation and provide a twelvefold coordination in the shape of a cuboctahedron (d(Tl–H) = 296 pm). There is no observable stereochemical activity of the non‐bonding electron pairs (6s² lone pairs) at the Tl⁺ cations. By neutralization of an aqueous solution of the acid (H₃O)₂[B₁₂H₁₂] with PbCO₃ and after isothermic evaporation colorless, plate‐like single crystals of lead(II) dodecahydro‐closo‐dodecaborate hexahydrate Pb(H₂O)₃[B₁₂H₁₂] · 3H₂O can be isolated. This compound crystallizes orthorhombically with the non‐centrosymmetric space group Pna2₁ (a = 1839.08(9), b = 1166.52(6), c = 717.27(4) pm, Z = 4). The crystal structure of Pb(H₂O)₃[B₁₂H₁₂] · 3H₂O is characterized as a layer‐like arrangement. The Pb²⁺ cations are coordinated in first sphere by only three oxygen atoms from water molecules (d(Pb–O) = 247–248 pm). But a coordinative influence of the [B₁₂H₁₂]^2– anions (d(B–B) = 173–181 pm, d(B–H) = 93–122 pm) on lead has to be stated, too, as three hydrogen atoms from three different hydroborate anions are attached to the Pb²⁺ cations (d(Pb–H) = 258–270 pm) completing their first‐sphere coordination number to six. These three oxygen and three hydrogen ligands are arranged as quite irregular polyhedron leaving enough space for a stereochemical lone‐pair activity (6sp) at each Pb²⁺ cation. Since additional intercalating water of hydration is present as well, both classical H–O^δ– ··· ^+δH–O‐ and unconventional B–H^δ– ··· ^+δH–O hydrogen bonds play a significant role in the stabilization of the entire crystal structure.     

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.     

(Ph4P)2[Be3(μ‐OH)3(H2O)6]Cl5: Kristallstruktur und DFT‐Rechnungen

Bis(tetraphenylphosphonium)‐tris(μ‐hydroxo)hexaaquatriberylliumpentachloride, (Ph₄P)₂[Be₃(μ‐OH)₃(H₂O)₆]Cl₅ ( 1 ), was surprisingly obtained by reaction of (Ph₄P)N₃ · n H₂O with BeCl₂ in dichloromethane suspension and subsequent crystallization from acetonitrile to give single crystals of composition 1· 5.25CH₃CN. According to the crystal structure determination space group P , Z = 2, lattice dimensions at 100 K: a = 1354.8(2), b = 1708.7(2), c = 1753.2(2) pm, α = 114.28(1)°, β = 94.80(1)°, γ = 104.51(1)°, R₁ = 0.0586] the [Be₃(μ‐OH)₃(H₂O)₆]³⁺ cations form six‐mem‐bered Be₃O₃ rings with boat conformation and distorted tetrahedrally coordinated beryllium atoms with the terminally coordinated H₂O molecules. The structure ist characterized by a complicated three dimensional hydrogen‐bridging network including O–H ··· O, O–H ··· Cl, and O–H ··· NCCH₃ contacts. DFT calculations result in nearly planar [Be₃(OH)₃] six‐membered ring conformations.     

Synthese und Kristallstruktur von Cadmium‐Dodekahydro‐closo‐Dodekaborat‐Hexahydrat,Cd(H2O)6[B12H12]

Synthesis and Crystal Structure of Cadmium Dodecahydro closo‐Dodecaborate Hexahydrate, Cd(H₂O)₆[B₁₂H₁₂] Through neutralization of the aqueous free acid (H₃O)₂[B₁₂H₁₂] with cadmium carbonate (CdCO₃) and after isothermic evaporation of the resulting solution, colourless lath‐shaped single crystals of Cd(H₂O)₆[B₁₂H₁₂] are obtained. Cadmium dodecahydro closo‐dodecaborate hexahydrate crystallizes at room temperature in the monoclinic system (space group: C2/m) with the lattice constants a = 1413.42(9), b = 1439.57(9), c = 749.21(5) pm and β = 97.232(4)° (Z = 4). The crystal structure of Cd(H₂O)₆[B₁₂H₁₂] can be regarded as a monoclinic distortion variant of the CsCl‐type structure. Two crystallographically different [Cd(H₂O)₆]²⁺ octahedra (d(Cd–O) = 227–230 pm) are present which only differ in their relative orientation. The intramolecular bond lengths for the quasi‐icosahedral [B₁₂H₁₂]^2? cluster anions range in the intervals usually found for dodecahydro closo‐dodecaborates (d(B–B) = 177–179 pm, d(B–H) = 103–116 pm). The hydrogen atoms of the [B₁₂H₁₂]^2? clusters have no direct coordinative influence on the Cd²⁺ cations. Due to the fact that no “zeolitic” crystal water molecules are present, a stabilization of the lattice takes place mainly via the B–H^δ?···^+δH–O hydrogen bonds.     

Hydrothermal Synthesis,Structures and Thermal Stability of Two Novel Lanthanide Complexes: [Er4(tp)6(H2O)6], [Lu(tp)1.5(H2O)3]

Two novel lanthanide complexes with the formula [Er₄(tp)₆(H₂O)₆] ( 1 ) and [Lu(tp)_1.5(H₂O)₃] ( 2 ) (tp = terephthalate) were synthesized by treating Er(NO₃)₃, Lu(NO₃)₃ with terephthalic acid under hydrothermal conditions, respectively. The structures were determined by X‐ray crystallography. The crystal 1 is of orthorhombic, space group Pbca(61) with a = 9.6656(2) Å, b = 26.2338(5) Å, c = 37.9022(7) Å, C₄₈H₃₆Er₄O₃₀, M = 1761.81, Z = 8, V = 9610.69(32) ų, F(000) = 6688, R₁ = 0.0326 and ωR = 0.0650. The crystal of 2 is of triclinic, space group with a = 7.8204(1) Å, b = 9.5355(1) Å, c = 10.6348(1) Å, α = 68.869(1)°, β = 71.081(1)°, γ = 75.151(1)°, C₂₄H₂₄Lu₂O₁₈, M = 475.19, Z = 2, V = 690.98(1) ų, F(000) = 454, R₁ = 0.0215 and ωR = 0.0474. Both of the two coordination polymers exhibit sandwich‐like packing structures.     

[(C6H10)(NH3)2][Ni(H2O)4C6H2(COO)4]·4H2O – A Coordination Polymer with the Chain‐like Polyanion {Ni(H2O)4[C6H2(COO)4]2−}n

Triclinic single crystals of [(C₆H₁₀)(NH₃)₂][Ni(H₂O)₄C₆H₂(COO)₄]·4H₂O have been prepared in aqueous solution at 55 °C. Space group (Nr. 2), a = 691.23(6), b = 924.84(5), c = 1082.43(7) pm, α = 74.208(6)°, β = 75.558(7)°, γ = 68.251(6)°, V = 0.60985(7) nm³, Z = 1. The Nickel(II) species, located on a crystallographic inversion centre, is coordinated in a trans‐octahedral fashion by two oxygen atoms stemming from the centrosymmetric pyromellitate anions and four from water molecules (Ni–O 205.82(12) – 208.11(13) pm). The connection between Ni²⁺ and [C₆H₂(COO)₄)]^4? leads to infinite chain‐like polyanions extending parallel to with {Ni(H₂O)₄[C₆H₂(COO)₄]^2?}_n composition. [(C₆H₁₀)(NH₃)₂]²⁺‐cations are accomodated between the chains, compensating for the negative charge of the polyanions. Thermogravimetric analysis in air showed that the loss of water of crystallisation occurs in two steps between 102 and 206 °C, corresponding to the loss of 6 and 2 water molecules per formula unit, respectively. The dehydrated sample was stable between 206 and 353 °C. Further decomposition yielded nickel(II) oxide (NiO).     

Direct Synthesis of PbO Nanoparticles From a Lead(II) Nano Coordination Polymer Precursor: Synthesis,Crystal Structure,and DFT Calculations of [Pb2(dmp)2(μ‐N3)2(μ‐ClO4)2]n with the First Pb2‐(μ‐ClO4)2 Unit

Nanostructures of a new coordination polymer of divalent lead with the ligand 2, 9‐dimethyl‐1, 10‐phenanthroline (dmp) containing the first Pb₂‐(μ‐ClO₄)₂ motif, [Pb₂(dmp)₂(μ‐N₃)₂(μ‐ClO₄)₂]_n ( 1 ), was synthesized by a sonochemical method that produces the coordination polymers at nano size. The new nanostructure was characterized by scanning electron microscopy, X‐ray powder diffraction, IR, ¹H NMR and ¹³C NMR spectroscopy, and elemental analysis. Compound 1 was structurally characterized by single‐crystal X‐ray diffraction and the single‐crystal X‐ray data shows that the coordination number of Pb^II ions is six, (PbN₄O₂), with two N‐donor atoms from aza‐aromatic base ligands and four O‐donors from two perchlorate anions and two N‐donors from two azide anions. It has a “stereo‐chemically active” electron lone pair, and the coordination sphere is hemidirected. The supramolecular features in these complexes are guided and controlled by weak directional intermolecular interactions. The chains interact with each other through π–π stacking interactions creating a 3D framework. The structure of the title complex was optimized by density functional theory calculations. Calculated structural parameters and IR spectra for the title complex are in agreement with the crystal structure. The PbO nanoparticles were obtained by thermolysis of 1 at 180 °C with oleic acid as a surfactant. The average diameter of the nanoparticles was estimated by the Scherrer equation to be 23 nm. The morphology and size of the prepared PbO samples were further observed using SEM.     

Oxalato‐ und Quadratato‐Komplexe hochkoordinierter Metallionen: Die Raumnetzstrukturen von La2(C2O4)(C4O4)2(H2O)8 · 2,5 H2O und K[Bi(C2O4)2] · 5 H2O

Oxalato‐ and Squarato‐Bridged Threedimensional Networks: The Crystal Structures of La₂(C₂O₄)(C₄O₄)₂(H₂O)₈ · 2.5 H₂O and K[Bi(C₂O₄)₂] · 5 H₂O The title compounds have been formed by hydrolysis of amino‐ and thioderivatives of squaric acid in the presence of La^III and Bi^III ions. Both compounds are threedimensional coordination polymers in the solid state, as shown by single crystal X‐ray crystallography. In La₂(C₂O₄)(C₄O₄)₂(H₂O)₈ · 2.5 H₂O oxalato‐bridged pairs of LaO₉ polyhedra are connected with identical neighbouring polyhedra by squarate ions. In K[Bi(C₂O₄)₂] · 5 H₂O each Bi atom is fourfold linked to other Bi atoms by the oxalate ions. The resulting 3D network shows a diamond‐like topology with square‐shaped channels. In both structures the channels are partially filled by water molecules.     

Benzodithiazolium‐Chlorooxomolybdate(V): Darstellung und Kristallstruktur von (C6H4NS2)[MoOCl4] und (C6H4NS2)[MoOCl4·H2O]

Benzodithiazolium Chlorooxomolybdate(V): Preparation and Crystal Structure of (C₆H₄NS₂)[MoOCl₄] and (C₆H₄NS₂)[MoOCl₄·H₂O] Red benzo‐1,3,2‐dithiazolium‐chlorooxomolybdate(V) (C₆H₄NS₂)[MoOCl₄] ( 1 ) was obtained by the reaction of benzo‐1,3,2‐dithiazoliumchloride and molybdenum(V)chloride oxide in dichlormethane under solvothermal conditions at 70 °C. In the presence of small amounts of concentrated hydrochloric acid the yellow compound (C₆H₄NS₂)[MoOCl₄·H₂O] ( 2 ) is formed under analogue conditions. Both crystal structures ( 1 : monoclinic, C2/c, a = 799.2(1), b = 2091.5(2), c = 791.5(1) pm, β = 102.2(1)°, Z = 4; 2 : monoclinic, Cc, a = 953.7(1), b = 2468.9(3), c = 608.1(1) pm, β = 112.5(1)°, Z = 4) contain the planar benzo‐1,3,2‐dithiazolium ion. Within the structure of 1 the molybdenum atoms in the [MoOCl₄]^? ions are coordinated in a square pyramidal fashion with an oxygen atom in apical position and the basal plane formed by chlorine atoms. The nitrogen atom of the cation, which bears a partial negativ charge, expands the coordination to a distorted octahedron. The structure therefore is made up of ionic pairs {(C₆H₄NS₂)⁺ [MoOCl₄]^?} with a Mo–N distance of 266 pm. 1 is paramagnetic with a magnetic moment of 1.7 B.M. corresponding to one unpaired electron per formula unit. In the structure of 2 the coordination of the [MoOCl₄]^? ion is expanded by the oxygen atom of a coordinating water molecule. The structure is dominated by hydrogen bonds between the oxygen atoms of the [MoOCl₄·H₂O]^? ions which cause the concatenation of the anions to infinite chains.     

Das erste Vanadium(III)‐Borophosphat: Darstellung und Kristallstruktur von CsV3(H2O)2[B2P4O16(OH)4]

The First Vanadium(III) Borophosphate: Synthesis and Crystal Structure of CsV₃(H₂O)₂[B₂P₄O₁₆(OH)₄] CsV₃(H₂O)₂[B₂P₄O₁₆(OH)₄] was prepared under mild hydrothermal conditions (T = 165 °C) from mixtures of CsOH_(aq), VCl₃, H₃BO₃, and H₃PO₄ (molar ratio 1 : 1 : 1 : 2). The crystal structure was determined by X‐ray single crystal methods (monoclinic; space group C2/m, No. 12): a = 958.82(15) pm, b = 1840.8(4) pm, c = 503.49(3) pm; β = 110.675(4)°; Z = 2. The anionic partial structure contains oligomeric units [BP₂O₈(OH)₂]^5–, which are built up by a central BO₂(OH)₂ tetrahedron and two PO₄ tetrahedra sharing common corners. V^III is octahedrally coordinated by oxygen of adjacent phosphate tetrahedra and OH groups of borate tetrahedra as well as oxygen of phosphate tetrahedra and H₂O molecules, respectively (coordination octahedra VO₄(OH)₂ and VO₄(H₂O)₂). The oxidation state +3 for vanadium was confirmed by measurements of the magnetic susceptibility. The trimeric borophosphate groups are connected via vanadium centres to form layers with octahedra‐tetrahedra ring systems, which are likewise linked via V^III‐coordination octahedra. Overall, a three‐dimensional framework constructed from VO₄(OH)₂ and VO₄(H₂O)₂ octahedra as well as BO₂(OH)₂ and PO₄ tetrahedra results. The structure contains channels running along [001], which are occupied by Cs⁺ in a distorted octahedral coordination (CsO₄(H₂O)₂).     

Lamellare Schichten auf der Grundlage von Wasserstoffbrücken und π‐Stapelung: Kristallstrukturen der Metall(II)‐Komplexe [Cd{C6H4(SO2)2N}2(H2O)4] und [Cu{C6H4(SO2)2N}2(H2O)4]·2 H2O

The title complexes, obtained by treating hot aqueous solutions of ortho‐benzenedisulfonimide with solid CdCO₃ or CuO, have been characterized by low‐temperature X‐ray diffraction (both triclinic, space group P&1macr;, Z = 1, metal ions on inversion centres). The cations have trans‐octahedral coordinations provided by two Cd‐N bonded or two Cu‐O bonded anions and four water molecules [Cd‐N 234.7(2) pm; Cu‐O(anion) 240.4(1) pm, elongated by Jahn‐Teller distortion]; the copper complex contains two further, non‐coordinating, water molecules per formula unit. In both structures, the uncharged zero‐dimensional building blocks are associated via strong hydrogen bonds O(W)‐H···A and one short C‐H···O bond to form two‐dimensional assemblies comprising an internal polar lamella of metal cations, (SO₂)₂N groups and water molecules, and hydrophobic peripheral regions consisting of vertically protruding benzo rings. Carbocycles drawn alternatingly from adjacent layers form π‐stacking arrays, in which the parallel aromatic rings display intercentroid distances in the range 365‐385 pm and vertical ring spacings in the range 345‐385 pm.