Crystal Structure and Characterization of a Large Polyoxotungstate (NH4)21{La(H2O)5[Ni(H2O)]2As4W40O140}·53H2O

The heteropolytungstate (NH4)₂₁{La(H₂O)₅[Ni(H₂O)]₂As₄W₄₀O₁₄₀}·53H₂O is obtained by the reaction of Na₂₇[NaAs₄W₄₀O₁₄₀]· 60H₂O with NiCl₂·6H₂O, La(NO₃)₃·6H₂O and NH₄Cl at pH‐4.5. The structure and chemical composition are determined by X‐ray diffraction analysis and elemental analysis. The crystal data and main structure refinement are a = 1.9551(3) nm, b = 2.4156(4) nm, c= 3.7068(6) nm, β = 91.505(3)°, V = 17.500 (5) nm³, monoclinic crystal system with space group P2₁/n, Z = 4, R₁ = 0.0573, wR₂ = 0.0717 [I >2<s?(I)], R₁, = 0.2463 and wR₂ = 0.1199 (all data). [La(H₂O)₅] {Ni(H₂O)}₂AS₄W₄₀O₁₄₀ has C₂, symmetry. IR spectra of the ligand [NaAs₄W₄₀O₁₄₀]^27‐ and its three complexes were discussed.     

Preparation,Structure and Properties of the One-Dimensional Polymeric Complex Na2[AlW3O4(O2CEt)8]2

Abstract

The heterometallic polymeric cluster Na₂[AlW₃O₄ (O₂CEt)₈]₂ (1) has been prepared by reaction of W(CO)₆ and NaWO₄·2H₂O with AlCl₃ at 120°C in propionic anhydride and characterized by X-ray crystallography, with the following crystal data: triclinic, space group P1, a = 12.205(5), b = 13.032(4), c = 13.925(3) Å, α = 90.21(3)°, β = 109.53(5)°, γ = 117.26(6)°, V = 1822.8(1)ų, Z = 1, R = 0.038 and R_w = 0.101. The structure consists of two triangular [W₃O₄(O₂CEt)₈]^4? cluster unit, which act as polydenate ligands to link Al³⁺ and Na⁺ ions forming a one–dimensional chain structure. IR spectra show characteristic [W₃O₄]⁴⁺ bands at 746–815 cm^?1. Thermal analysis reveals that the complex is air stable up to 250°C. Cluster 1 decomposes in hot aqueous 2 M HCl solution to produce discrete [W₃O₄]⁴⁺ units.     

The Mixed Valence Tungsten(IV,V) Compound Na[W2O2Br6]

The reaction of W₆Br₁₂, NaBr, and WO₂Br₂ in the presence of Br₂ in a sealed silica tube yields Na[W₂O₂Br₆] together with WOBr₄ and WO₂Br₂ in the low temperature zone (temperature gradient 1030/870 K). Na[W₂O₂Br₆] crystallizes orthorhombically in the space group Immm (no. 71) with a = 3.775 Å, b = 10.400 Å, c = 13.005 Å and Z = 2. Pairs of condensed trans-[WO₂Br₄] octahedra with a common Br₂ edge form along [100] double chains [W₂O_4/2Br₆]^1– via the oxygen atoms. The mixed valent tungsten atoms are bonded to W₂ pairs with a 2 c–3 e bond (d(W–W) = 2.946 Å, d(W–O) = 1.888 Å, d(W–Br^b) = 2.537 Å, d(W–Br^t) = 2.535 Å, ∢O–W–O = 177.4°, ∢Br^b–W–Br^b (endocyclic) = 109.0°). The Na⁺ cations connect the anionic double chains to form two-dimensional layers parallel (001), which interact by van der Waals forces. The cations are eightfold coordinated by a cube of the terminal Br^t ligands of the polymeric anions (d(Na–Br) = 3.138 Å). Na[W₂O₂Br₆] may be discussed as an intercalation compound of the oxide bromide WOBr₃.     

Syntheses of Monomeric,Dimeric, and Trimeric Complexes of Tungsten(VI), (V), (IV), and (III) with the 1,4,7-Triazacyclononane (L) Ligand. Crystal Structures of Dimeric [W2L2(μ2?OH)2Br2]Br2 · 2H2O and of Trimeric [W3L3(μ3?0)(μ2-0)3][ZnBr4]2

Reactions of WL(CO)₃ (L = 1, 4, 7-triazacyclononane; C₆H₁₅N₃) with bromine under different conditions afford the monomeric W^VI compound, WO₂LBr₂, or the monomeric W^V complex, WOLBr₃. The former dimerizes in aqueous solution, yielding the [W₂O₅L₂]²⁺ cation. Two diamagnetic isomers of the W^V -dimer, [W₂O₄L₂]²⁺, have been prepared : a yellow form with terminal oxo groups in cis-positions with respect to each other and a red species containing two terminal oxo-groups in trans-positions. The cationic W^IV -trinuclear cluster, [W₃O₄L₃]⁴⁺, has been isolated as the tetrabromozincate(2-) salt and its structure has been determined by single crystal X-ray diffraction. [W₃O₄L₃][ZnBr₄]₂ crystallizes in the monoclinic space group P2₁/c with a = 12.698(2) Å, b = 21.267(6) Å, c = 15.687(7) Å, β = 92.94(3)⁰, and V = 4222 ų, d_ealed. = 2.79 g cm^?3 for Z = 4, and mol wt 1773.2. The structure was solved by direct methods using 7399 unique reflections with I≥ 2.5 σ (I). Final residuals were R₁ = 0.089 and R₂ = 0.096. The structure consists of [W₃L₃O₄]⁴⁺ cations of the M₃X₁₃ cluster type and isolated ZnBr₄^2? anions. Three tungsten atoms occupy the corners of an equilateral triangle bridged by three μ₂-oxo- and one μ₃-oxo-ligands; each tungsten atom has a distorted octahedral environment of three oxygen and three nitrogen atoms. The short W - W distances of 2,52 Å and the diamagnetism indicate metal-metal bonding. The green, diamagnetic binuclear W_III complex, [W₂L₂(μ? OH)₂Br₂]Br₂ · 2 H₂O, has been prepared by reduction of monomeric WLOBr₃ in strongly acidic solution with zinc powder. The complex has been characterized by a single-crystal X-ray diffraction study; it crystallized in the orthorhombic space group Pnnm with a = 13.837(5) Å, b = 11.657(6) Å, c = 7.832 Å, and V = 1263 ų, d_calcd. = 2.67 g cm^?3 for Z = 2, and mol wt 1015.8. The structure was solved by direct methods using 783 unique reflections with I ? 2.5 σ(1). Final residuals were R₁ = 0.062 and R₂ = 0.084. The structure consists of dimeric cations [W₂L₂(μ? OH)₂Br₂]²⁺, bromide anions and molecules of water of crystallization. The tungsten centers are in a distorted octahedral environment of the tridentate N-donor igand, one coordinated bromide and two μ₂-hydroxo bridges (edge sharing), respectively. The bromide ligands are in trans-positions with respect to each other. The four-membered W₂(μ? OH)₂ ring is planar. The W? W distance of 2.477(3) Å together with its diamagnetism imply the presence of a strong metal-metal bond between the tungsten(II1) centers (σ²π²δ²).     

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.     

Two New Polyoxovanadate‐supported Transition Metal Complexes: [Zn(en)2][Zn(en)2(H2O)2][{Zn(en)(enMe)}As6V15O42(H2O)]·4H2O and [Zn2(enMe)2(en)3][{Zn(enMe)2}As6V15O42(H2O)]·4H2O

Two novel As‐V‐O cluster supported transition metal complexes, [Zn(en)₂][Zn(en)₂(H₂O)₂][{Zn(en)(enMe)}As₆V₁₅O₄₂(H₂O)]·4H₂O ( 1 ) and [Zn₂(enMe)₂(en)₃][{Zn(enMe)₂}As₆V₁₅O₄₂(H₂O)]·4H₂O ( 2 ), have been hydrothermally synthesized. The single X‐ray diffraction studies reveal that both compounds consist of discrete noncentral polyoxoanions [{Zn(en)(enMe)}As₆V₁₅O₄₂(H₂O)]^4? or [{Zn(enMe)₂}As₆V₁₅O₄₂(H₂O)]^4? cocrystallized with respective zinc coordination complexes. Interestingly, compounds 1 and 2 exhibit the first two polyoxovanadates containing As₈V₁₅O₄₂‐(H₂O)]^6? cluster decorated by only one transition metal complex. Crystal data: 1 , monoclinic, P2₁/n, a = 14.9037(4) Å, b = 18.1243(5) Å, c = 27.6103(7) Å, β = 105.376(6)°, Z = 4; 2 monoclinic, P2₁/n, a = 14.9786(7) Å, b = 33.0534(16) Å, c = 14.9811(5) Å, Z = 4.     

Synthesis,Crystal Structure,and Magnetic Properties of {[Cu(phen)]2(C4H2O4)2} · 4.5H2O with C4H4O4 = Maleic Acid

Reaction of CuCl₂ · 2H₂O, phenanthroline, maleic acid and NaOH in CH₃OH/H₂O (1:1 v/v) at pH = 7.0 yielded blue {[Cu(phen)]₂(C₄H₂O₄)₂} · 4.5H₂O, which crystallizes in the monoclinic space group C2/c (no. 15) with cell dimensions: a = 18.127(2)Å, b = 12.482(2)Å, c = 14.602(2)Å, β = 103.43(1)°, U = 3213.5(8)ų, Z = 4. The crystal structure consists of the centrosymmetric dinuclear {[Cu(phen)]₂(C₄H₂O₄)₂} complex molecules and hydrogen bonded H₂O molecules. The Cu atoms are each square‐pyramidally coordinated by two N atoms of one phen ligand and three carboxyl O atoms of two maleato ligands with one carboxyl O atom at the apical position (d(Cu‐N) = 2.008, 2.012Å, equatorial d(Cu‐O) = 1.933, 1.969Å, axial d(Cu‐O) = 2.306Å). Two square‐pyramids are condensed via two apical carboxyl O atoms with a relatively larger Cu···Cu separation of 3.346(1)Å. The dinuclear complex molecules are assembled via the intermolecular π—π stacking interactions into 1D ribbons. Crossover of the resulting ribbons via interribbon π—π stacking interactions forms a 3D network with the tunnels occupied by H₂O molecules. The title complex behaves paramagnetically between 5—300 K, following the Curie‐Weiss law _χm(T—θ) = 0.435 cm³ · mol^—1 · K with θ = 1.59 K.     

由氨基酸配位的铜修饰十二核钨单元构成的一维链状化合物(H3O)3{[Na3(H2O)13][(Cu(Gly)2)2(H2W12O42)]}·11H2O

The design and synthesis of organic-inorganichybrid compounds have aroused contemporary inter-est;not only owing to their diverse structures,but alsoto their potential applications in fields such as catal-ysis,medicine,analytical chemistry and photochem-i…     

Supramolecular Assemblies of Mononuclear and Polymeric Nickel(II) Glutarato Complexes via π‐π Stacking Interactions and Hydrogen Bonds: [Ni(H2O)3(phen)(C5H6O4)] · H2O and [Ni(H2O)2(phen)(C5H6O4)]

Syntheses of the sky blue complex compounds [Ni(H₂O)₃(phen)(C₅H₆O₄)] · H₂O ( 1 ) and [Ni(H₂O)₂(phen)(C₅H₆O₄)] ( 2 ) were carried out by the reactions of 1,10‐phenanthroline monohydrate, glutaric acid, NiSO₄ · 6 H₂O and Na₂CO₃ in CH₃OH/H₂O at pH = 6.9 and 7.5, respectively. The crystal structure of 1 (P 1 (no. 2), a = 14.289 Å, b = 15.182 Å, c = 15.913 Å, α = 67.108°, β = 87.27°, γ = 68.216°, V = 2934.2 ų, Z = 2) consists of hydrogen bonded [Ni(H₂O)₃‐ (phen)(C₅H₆O₄)]₂ dimers and H₂O molecules. The Ni atoms are octahedrally coordinated by two N atoms of one phen ligand, three water O atoms and one carboxyl O atom from one monodentate glutarato ligand (d(Ni–N) = 2.086, 2.090 Å; d(Ni–O) = 2.064–2.079 Å). Through the π‐π stacking interactions and intermolecular hydrogen bonds, the dimers are assembled to form 2 D layers parallel to (0 1 1). The crystal structure of 2 (P2₁/n (no. 14), a = 7.574 Å, b = 11.938 Å, c = 18.817 Å, β = 98.48°, V = 1682.8 ų, Z = 4) contains [Ni(H₂O)₂(phen)(C₅H₆O₄)_2/2] supramolecular chains extending along [010]. The Ni atoms are octahedrally coordinated by two N atoms of one phen ligand, two water O atoms and two carboxyl O atoms from different bis‐monodentate glutarato ligands with d(Ni–N) = 2.082, 2.105 Å and d(Ni–O) = 2.059–2.087 Å. The supramolecular chains are assembled into a 3 D network by π‐π stacking interactions and interchain hydrogen bonds. A TG/DTA of 2 shows two endothermic effects at 132 °C and 390 °C corresponding to the complete dehydration and the lost of phen.     

A Novel 3D Framework Coordination Polymer based on Succinato bridged Helical Chains Connected by 4, 4' ‐ Bipyridine: [Cu(bpy)(H2O)2(C4H4O4)]?2H2O

Blue needle—shaped crystals of [Cu(bpy)(H₂O)₂(C₄H₄O₄)]· 2H₂O were obtained by slow evaporation of a methanolic aqueous solution containing a fresh Cu(C₄H₄O₄)· 2H₂O precipitate, 4, 4′—bipyridine, and ammonia. Within the complex, the six—coordinated Cu atoms are linked by bis—monodentate gauche succinate anions into chains propagating helically around the [001] axis. The chains are interconnected by 4, 4′—bipyridine ligands into a 3D framework with the crystal H₂O molecules located in the channels along the [100], [010] and [110] directions. The Cu²⁺ ions are in distorted octahedral coordination of two nitrogen and four oxygen atoms (equatorial bonds: Cu—N 1.986(5), 2.015(5)Å; Cu—O 1.950(6), 1.954(6)Å; axial bonds Cu—O: 2.524(9), 2.539(8)Å). Furthermore, the thermal and magnetic behavior of the compound will be discussed. Crystal data: hexagonal, P6₁ (no. 169), a = 11.066(2)Å, c = 24.965(5)Å, V = 2647.5(8)ų, Z = 6, R = 0.0528 and wR₂ = 0.1103 for 1426 observed reflections (F_o² > 2σ(F_o²)) out of 2170 unique reflections.     

Neue Heteropolyanionen des M2X2W20‐Typs mit Antimon(III) als Heteroatom

New Heteropolyanions of the M₂X₂W₂₀ Structure Type with Antimony(III) as a Heteroatom The syntheses of two new heteropolyanions of the M₂X₂W₂₀ structure type are presented. They are characterized by X‐ray structure analysis and vibrational spectra. Na₆(NH₄)₄[Zn₂(H₂O)₆(WO₂)₂(SbW₉O₃₃)₂]·36H₂O (1) is monoclinic (P2₁/n) with a = 12.873(3)Å, b = 25.303(4)Å, c = 15.975(4)Å and β = 91.99(3)°. Na₁₀[Mn₂(H₂O)₆(WO₂)₂(SbW₉O₃₃)₂]·40H₂O (2) also crystallizes in the space group P2₁/n with a = 12.892(3)Å, b = 25.219(5)Å, c = 16.166(3)Å and β = 94.41(3)°. Both polyanions are isostructural to anions of this structure type containing other heteroatoms. They are built up by two β‐B‐SbW₉ fragments, which are derived from defect structures of the Keggin anion. These subÍunits are connected by two formal WO₂ groups with further stabilization by addition of two M(H₂O)₃ groups (M = Zn^II, Mn^II, Fe^III, Co^II) leading to the M₂X₂W₂₀‐type heteropolytungstates.     

Two scandium–biuret complexes: [Sc(C2H5N3O2)(H2O)5]Cl3·H2O and [Sc(C2H5N3O2)4](NO3)3

The scandium(III) cations in the structures of pentaaqua(biuret‐κ²O,O′)scandium(III) trichloride monohydrate, [Sc(C₂H₅N₃O₂)(H₂O)₅]Cl₃·H₂O, (I), and tetrakis(biuret‐κ²O,O′)scandium(III) trinitrate, [Sc(C₂H₅N₃O₂)₄](NO₃)₃, (II), are found to adopt very different coordinations with the same biuret ligand. The roles of hydrogen bonding and the counter‐ion in the establishment of the structures are described. In (I), the Sc³⁺ cation adopts a fairly regular pentagonal bipyramidal coordination geometry arising from one O,O′‐bidentate biuret molecule and five water molecules. A dense network of N—H...Cl, O—H...O and O—H...Cl hydrogen bonds help to establish the packing, resulting in dimeric associations of two cations and two water molecules. In (II), the Sc³⁺ cation (site symmetry 2) adopts a slightly squashed square‐antiprismatic geometry arising from four O,O′‐bidentate biuret molecules. A network of N—H...O hydrogen bonds help to establish the packing, which features [010] chains of cations. One of the nitrate ions is disordered about an inversion centre. Both structures form three‐dimensional hydrogen‐bond networks.     

Preparation and Crystal Structures of the Hydrous Mercury Tellurates,HgII(H4TeVIO6) and HgI2(H4TeVIO6)(H6TeVIO6)·2H2O

Single crystals of Hg^II(H₄Te^VIO₆) (colourless to light‐yellow, rectangular plates) and Hg^I₂(H₄Te^VIO₆)(H₆Te^VIO₆)·2H₂O (colourless, irregular) were grown from concentrated solutions of orthotelluric acid, H₆TeO₆, and respective solutions of Hg(NO₃)₂ and Hg₂(NO₃)₂. The crystal structures were solved and refined from single crystal diffractometer data sets (Hg^II(H₄Te^VIO₆): space group Pna2₁, Z = 4, a =10.5491(17), b = 6.0706(9), c = 8.0654(13)Å, 1430 structure factors, 87 parameters, R[F² > 2σ(F²)] = 0.0180; Hg^I₂(H₄Te^VIO₆)(H₆Te^VIO₆)·2H₂O: space group P1¯, Z = 1, a = 5.7522(6), b = 6.8941(10), c = 8.5785(10)Å, α = 90.394(8), β = 103.532(11), γ = 93.289(8)°, 2875 structure factors, 108 parameters, R[F² > 2σ(F²)] = 0.0184). The structure of Hg^II(H₄Te^VIO₆) is composed of ribbons parallel to the b axis which are built of [H₄TeO₆]^2— anions and Hg²⁺ cations held together by two short Hg—O bonds with a mean distance of 2.037Å. Interpolyhedral hydrogen bonding between neighbouring [H₄TeO₆]^2— groups, as well as longer Hg—O bonds between Hg atoms of one ribbon to O atoms of adjacent ribbons lead, to an additional stabilization of the framework structure. Hg^I₂(H₄Te^VIO₆)(H₆Te^VIO₆)·2H₂O is characterized by a distorted hexagonal array made up of [H₄TeO₆]^2— and [H₆TeO₆] octahedra which spread parallel to the bc plane. Interpolyhedral hydrogen bonding between both building units stabilizes this arrangement. Adjacent planes are stacked along the a axis and are connected by Hg₂²⁺ dumbbells (d(Hg—Hg) = 2.5043(4)Å) situated in‐between the planes. Additional stabilization of the three‐dimensional network is provided by extensive hydrogen bonding between interstitial water molecules and O and OH‐groups of the [H₄TeO₆]^2— and [H₆TeO₆] octahedra. Upon heating Hg^I₂(H₄Te^VIO₆)(H₆Te^VIO₆)·2H₂O decomposes into TeO₂ under formation of the intermediate phases Hg^II₃Te^VIO₆ and the mixed‐valent Hg^IITe^IV/VI₂O₆.     

Ion-selective properties of 1,8-bis [2-(dihydroxyphosphinyl)phenoxy]-3,6-dioxaoctane (H4L3), synthesis and vibrational spectra of copper and zinc complexes with H4L3, and crystal and molecular structure of [Cu(H4L3)(H2O)3][(H2L3)(H2O)]

The ion-selective properties of 1,8-bis[2-(dihydroxyphosphinyl)phenoxy]-3,6-dioxaoctane (H₄L³) have been studied and its potentiometric selectivity coefficients have been determined. New complexes [Cu(H₄L³)(H₂O)₃][(H₂L³)(H₂O)] (I) and Zn(H₄L³)(H₂L³) · 3H₂O, and Cu(H₂L³) · 2(H₂O) have been synthesized and characterized. The crystal and molecular structure of I has been determined by X-ray crystallography and vibrational spectroscopy. The crystals are monoclinic, a = 10.279(5) Å, b = 26.532(13) Å, c = 8.399(4) Å, β = 99.270(8)°, V = 2260.8(7) ų, Z = 2, space group Cm, R = 0.0347 for 4325 reflections with I > 2σ(I). Ionic compound I is composed of the [Cu(H₄L³)(H₂O)₃]²⁺ complex cations and [(H₂L³)(H₂O)]^2? anions. In the cation, the Cu²⁺ cation located in the m plane is bound to a tetragonal pyramidal (TP) array. The equatorial plane of the TP is formed by two phosphoryl oxygen atoms of the podand (Cu(1)-O, 1.921(2) Å) and two O atoms of two water molecules (av. Cu(1)-O, 1.981(3) Å). The third water molecule is at the axial vertex of the TP at a considerably larger distance (Cu(1)-O, 2.139(3) Å). The anion is of the host-guest type. The host is the deprotonated podand (H₂L³)^2?, and the guest is the water molecule. The latter is bound to the terminal hydroxyl groups of two phosphoryl groups of the podand by two acceptor hydrogen bonds and to two central ether oxygen atoms of the (H₂L³)^2? anion by one donor bifurcated hydrogen bond. The cations and anions in the structure are linked by hydrogen bonds to form chains parallel to the c axis.     

Crystal Structures of {[Cd(phen)](C6H8O4)3/3} and {[Cd(phen)](C7H10O4)3/3} · 2H2O with C6H10O4 = Adipic Acid and C7H12O4 = Pimelic Acid

Two coordination polymers {[Cd(phen)](C₆H₈O₄)_3/3} ( 1 ) and {[Cd(phen)](C₇H₁₀O₄)_3/3} · 2H₂O ( 2 ) were structurally characterized by single crystal X‐ray diffraction methods. In 1 (C2/c (no. 15), a = 16.169(2)Å, b = 15.485(2)Å, c = 14.044(2)Å, β = 112.701(8)°, U = 3243.9(7)ų, Z = 8), the Cd atoms are coordinated by two N atoms of one phen ligand and five O atoms of three adipato ligands to form mono‐capped trigonal prisms with d(Cd‐O) = 2.271‐2.583Å and d(Cd‐N) = 2.309, 2.390Å. The [Cd(phen)] moieties are bridged by adipato ligands to generate {[Cd(phen)](C₆H₈O₄)_3/3} chains, which, via interchain π—π stacking interactions, are assembled into layers. Complex 2 (P1¯(no. 2), a = 9.986(1)Å, b = 10.230(3)Å, c = 11.243(1)Å, α = 66.06(1)°, β = 87.20(1)°, γ = 66.71(1)°, U = 955.7(2)ų, Z = 2) consists of {[Cd(phen)](C₇H₁₀O₄)_3/3} chains and hydrogen bonded H₂O molecules. The Cd atoms are pentagonal bipyramidally coordinated by two N atoms of one phen ligand and five O atoms of three pimelato ligands with d(Cd‐O) = 2.213—2.721Å and d(Cd‐N) = 2.329, 2.372Å. Through interchain π—π stacking interactions, the {[Cd(phen)](C₇H₁₀O₄)_3/3} chains resulting from [Cd(phen)] moieties bridged by pimelato ligands are assembled in to layers, between which the hydrogen bonded H₂O molecules are sandwiched.     

One‐dimensional Cadmium(II) Coordination Polymers: Syntheses and Crystal Structures of [Cd(H2O)3(C5H6O4)]·2H2O,Cd(H2O)2(C6H8O4), and Cd(H2O)2(C8H12O4)

[Cd(H₂O)₃(C₅H₆O₄)]·2H₂O ( 1 ) and Cd(H₂O)₂(C₆H₈O₄) ( 2 ) were prepared from reactions of fresh CdCO₃ precipitate with aqueous solutions of glutaric acid and adipic acid, respectively, while Cd(H₂O)₂(C₈H₁₂O₄) ( 3 ) crystallized in a filtrate obtained from the hydrothermal reaction of CdCl₂·2.5H₂O, suberic acid and H₂O. Compound 1 consists of hydrogen bonded water molecules and linear {[Cd(H₂O)₃](C₅H₆O₄)_2/2} chains, which result from the pentagonal bipyramidally coordinated Cd atoms bridged by bis‐chelating glutarato ligands. In 2 and 3 , the six‐coordinate Cd atoms are bridged by bis‐chelating adipato and suberato ligands into zigzag chains according to {[Cd(H₂O)₃](C₅H₆O₄)_2/2} and {[Cd(H₂O)₂](C₈H₁₂O₄)_2/2}, respectively. The hydrogen bonds between water and the carboxylate oxygen atoms are responsible for the supramolecular assemblies of the zigzag chains into 3D networks. Crystallographic data: ( 1 ) P1¯ (no. 2), a = 8.012(1), b = 8.160(1), c = 8.939(1) Å, α = 82.29(1)°, β = 76.69(1)°, γ = 81.68(1)°, U = 559.6(1) ų, Z = 2; ( 2 ) C2/c (no. 15), a = 16.495(1), b = 5.578(1), c = 11.073(1) Å, β = 95.48(1)°, U = 1014.2(1) ų, Z = 4; ( 3 ) P2/c (no. 13), a = 9.407(2), b = 5.491(1), c = 11.317(2) Å, β = 95.93(3)°, U = 581.4(2) ų, Z = 2.     

Influence of the Organic Species and Oxoanion in the Synthesis of two Uranyl Sulfate Hydrates, (H3O)2[(UO2)2(SO4)3­(H2O)]·7H2O and (H3O)2[(UO2)2(SO4)3(H2O)]·4H2O,and a Uranyl Selenate‐Selenite [C5H6N][(UO2)(SeO4)(HSeO3)]

Two uranyl sulfate hydrates, (H₃O)₂[(UO₂)₂(SO₄)₃(H₂O)] · 7H₂O (NDUS) and (H₃O)₂[(UO₂)₂(SO₄)₃(H₂O)] · 4H₂O (NDUS1), and one uranyl selenate‐selenite [C₅H₆N][(UO₂)(SeO₄)(HSeO₃)] (NDUSe), were obtained and their crystal structures solved. NDUS and NDUSe result from reactions in highly acidic media in the presence of L ‐cystine at 373 K. NDUS crystallized in a closed vial at 278 K after 5 days and NDUSe in an open beaker at 278 K after 2 weeks. NDUS1 was synthesized from aqueous solution at room temperature over the course of a month. NDUS, NDUS1, and NDUSe crystallize in the monoclinic space group P2₁/n, a = 15.0249(4) Å,b = 9.9320(2) Å, c = 15.6518(4) Å, β = 112.778(1)°, V = 2153.52(9) ų,Z = 4, the tetragonal space group P4₃2₁2, a = 10.6111(2) Å,c = 31.644(1) Å, V = 3563.0(2) ų, Z = 8, and in the monoclinic space group P2₁/n, a = 8.993(3) Å, b = 13.399(5) Å, c = 10.640(4) Å,β = 108.230(4)°, V = 1217.7(8) ų, Z = 4, respectively.The structural units of NDUS and NDUS1 are two‐dimensional uranyl sulfate sheets with a U/S ratio of 2/3. The structural unit of NDUSe is a two‐dimensional uranyl selenate‐selenite sheets with a U/Se ratio of 1/2. In‐situ reaction of the L ‐cystine ligands gives two distinct products for the different acids used here. Where sulfuric acid is used, only H₃O⁺ cations are located in the interlayer space, where they balance the charge of the sheets, whereas where selenic acid is used, interlayer C₅H₆N⁺ cations result from the cyclization of the carboxyl groups of L ‐cystine, balancing the charge of the sheets.     

The Sodium (Iso)Cyanurates Nax[H3–xC3N3O3]·yH2O (x = 1–3, y = 0, 1): A Key‐Series for Understanding the Crystal Chemistry of Metal (Iso)Cyanurates

The (iso)cyanurates Na[H₂C₃N₃O₃] · H₂O, Na₂[HC₃N₃O₃] · H₂O, Na₂[HC₃N₃O₃], and Na₃[C₃N₃O₃] were synthesized phase pure from Na₂CO₃ · 10H₂O, NaOH, and cyanuric acid, respectively, in aqueous solution by carefully adjusting the crystallization conditions. The crystal structures of all compounds were determined by single‐crystal X‐ray diffraction {Na₂[HC₃N₃O₃] · H₂O: P1 , a = 3.51660(10) Å, b = 7.8300(3) Å, c = 11.3966(4) Å, α = 86.4400(10)°, β = 85.5350(10)°, γ = 85.0720(10)°, Z = 2, R₁ = 0.030, wR₂ = 0.078; Na₂[HC₃N₃O₃]: Pnma, a = 6.3409(6) Å, b = 12.2382(13) Å, c = 6.5919(7) Å, Z = 4, R₁ = 0.045, wR₂ = 0.079; Na₃[C₃N₃O₃]: R3 c, a = 11.7459(3) Å, c = 6.5286(3) Å, Z = 3, R₁ = 0.039, wR₂ = 0.066}. The structures show ribbons (Na[H₂C₃N₃O₃] · H₂O), dimers (Na₂[HC₃N₃O₃] · H₂O), chains (Na₂[HC₃N₃O₃]), or columns (Na₃[C₃N₃O₃]) of hydrogen‐bonded and parallel stacked (iso)cyanurate anions. These motifs are shown to be characteristic for certain degrees of protonation and hydration, and all (iso)cyanurate crystal structures found so far were classified accordingly. X‐ray powder patterns, thermogravimetry curves, IR and UV/Vis spectra were measured for all compounds.     

Molybdänhalogenidcluster mit sechs terminalen Alkoholatliganden: (C18H36N2O6Na)2[Mo6Cl8(OCH3)6] · 6CH3OH und (C18H36N2O6Na2)2[Mo6Cl8(OC6H5)6]

Molybdenum(II) Halide Clusters with six Alcoholate Ligands: (C₁₈H₃₆N₂O₆Na)₂[Mo₆Cl₈(OCH₃)₆] · 6CH₃OH and (C₁₈H₃₆N₂O₆Na)₂[Mo₆Cl₈(OC₆H₅)₆] . The reaction of Na₂[Mo₆Cl₈(OCH₃)₆] and 2,2,2-crypt yields (C₁₈H₃₆N₂O₆Na)₂[Mo₆Cl₈(OCH₃)₆] · 6 CH₃OH ( 1 ), which is converted to (C₁₈H₃₆N₂O₆Na)₂[Mo₆Cl₈(OC₆H₅)₆] ( 2 ) by metathesis with phenol. According to single crystal structure determinations ( 1 : P3 1c, a=14.613(3) Å, c=21.036(8) Å; 2 : P3 1c, a=15.624(1) Å, c=19.671(2) Å) the compounds contain anionic clusters [Mo₆Cl₈ⁱ(OR^a)₆]^2? ( 1 : d(Mo—Mo) 2.608(1) Å to 2.611(1) Å, d(Mo—Cl) 2.489(1) Å to 2.503(1) Å, d(Mo—O) 2.046(4) Å; 2 : d(Mo—Mo) 2.602(3) Å to 2.608(3) Å, d(Mo—Cl) 2.471(5) Å to 2.4992(5) Å, d(Mo—O) 2.091(14) Å). Electronic interactions of the halide cluster and the phenolate ligands in [Mo₆Cl₈(OC₆H₅)₆]^2? is investigated by means of UV/VIS spectroscopy and EHMO calculations.