Two- and three-dimensional coordination polymers of lanthanide tartrate: synthesis,crystal structures and luminescence

Several new coordination polymers of lanthanide tartrate with three types of topological structures, namely [Ln₂(DL-tart)₃(H₂O)₃] · 1.5H₂O [Ln = La (1), Nd (2), and Sm (3)], [Ln₂(D-tart)₃(H₂O)₂] · 3H₂O [Ln = Eu (4), Tb (5), and Dy (6)], and [Lu(C₄H₄O₆)(C₄H₅O₆)] · 2.5H₂O (7), have been synthesized by hydrothermal synthesis. X-ray crystallographic analysis reveals that 1 is a unique 3-D network, whereas 5 with a 3-D network and 7 with a 2-D network are isomorphous with their analogs. All lanthanide ions are nine-coordinate through oxygen donors. Four different coordination modes of tartrate occur in these complexes. Luminescence spectra reveal that 4, 5, and 6 emit characteristic luminescence of corresponding lanthanide ions.     

Assembly of four copper(II)–2,2′-biimidazole complex-supported Strandberg-type phosphomolybdates

Four Strandberg-type phosphomolybdate-based Cu(II) complexes of 2,2′-biimidazole (C₆H₆N₄, H₂biim) and H₂O molecules, namely [Cu(H₂biim)₂(H₂O)][Cu(H₂biim)₂(HPO₄)₂(Mo₅O₁₅)]·2H₂O (1), [{Cu(H₂biim)(H₂O)}₂{μ-Cu(H₂biim)(H₂O)}(P₂Mo₅O₂₃)]₂·20H₂O (2), [Cu(H₂biim)₂][{Cu(H₂biim)(H₂O)₂}{Cu(H₂biim)₂}(HPO₄)(PO₄)(Mo₅ O₁₅)]₂·20H₂O (3), and [Cu(H₂biim)₂(H₂O)][Cu(H₂biim)₂(HPO₄)₂(Mo₅O₁₅)]·6H₂O (4) have been synthesized and characterized by physico-chemical and spectroscopic methods. Single-crystal X-ray diffraction analysis reveals that compound 1 consists of a mono-supporting heteropolyoxoanion [Cu(H₂biim)₂(H₂P₂Mo₅O₂₃)]²⁻and an isolated [Cu(H₂biim)₂(H₂O)]²⁺ cation. Compound 2 is composed of two tetra-supporting heteropolyoxoanions linked via two Cu(II) complex fragments. In compound 3, there exist two symmetrical bi-supported polyoxoanion clusters and an isolated [Cu(H₂biim)₂]²⁺ fragment lying in the center of the clusters. Compound 4 is also constructed from a [Cu(H₂biim)₂(H₂P₂Mo₅O₂₃)]²⁻ polyoxoanion and a [Cu(H₂biim)₂(H₂O)]²⁺ cation, but it has a different space group and packing interactions compared with compound 1.     

Synthesis,Crystal Structure and Magnetic Properties of Diaqua(1,10-Phenanthroline-N,N')-Hydrogenmaleatocopper(Ii) Hydrogenmaleate Monohydrate

Reaction of freshly-prepared CuCO₃, phenanthroline monohydrate and maleic acid in CH₃OH/H₂O(1 : 1 v/v) at pH=2.13 yielded diaqua(1,10-phenanthroline-N,N')hydrogenmaleatocopper(II) hydrogenmaleate monohydrate, [Cu(phen)(H₂O)₂(C₄H₃O₄)](C₄H₃O₄)(H₂O), which consists of [Cu(phen)(H₂O)₂(C₄H₃O₄)]⁺ complex cations, hydrogenmaleate anions and lattice H₂O molecules. Within the complex cations, the Cu atoms are each square-pyramidally coordinated by two N atoms of one chelating phen ligand and three O atoms of two H₂O molecules and one hydrogenmaleato ligand with one H₂O molecule at the apical position (d(Cu-N) = 2.001, 2.009 Å, equatorial d(Cu-O) = 1.966 Å and axial d(Cu-O) = 2.235 Å). Through hydrogen bonding, the complex cations, hydrogenmaleate anions and lattice H₂O molecules are assembled into 1D chains, which are held together by weak Cu···O interactions (3.139 Å) to form corrugated 2D layers. Significant π-π stacking interactions between neighboring phen ligands leads to supramolecular assembly of the 2D layers. Over the temperature range 5-300 K, the complex obeys the Currie-Weiss law with an effective magnetic moment of 1.78 BM at room temperature.     

Four inorganic–organic hybrid complexes built from tetravanadate and macrocyclic oxamide

Four inorganic–organic hybrid compounds, [M₂(CuL)₄(V₄O₁₂)]·2H₂O (M?=?Co (1), Mn (2)), [Mn₂(NiL)₄(V₄O₁₂)]·2H₂O (3), and [Zn₂(CuL)₄(V₄O₁₂)]·2CH₃OH·2H₂O (4) (M′L, H₂L?=?2,3-dioxo-5,6,14,15-dibenzo-1,4,8,12-tetraazacyclo-pentadeca-7,13-dien), have been synthesized and characterized by elemental analysis, IR, UV, fluorescence spectra, and X-ray diffraction analysis. Single-crystal X-ray analysis reveal that both [V₄O₁₂]^4? and M₂V₄ adapt a chair-like configuration in four structures. The cyclovanadate group [V₄O₁₂]^4? is a tetradentate bridging ligand linking two [M(M′L)₂]²⁺ fragments, producing centroantisymmetric heterometallic hexanuclear [M₂M′₄] complexes. The variable-temperature magnetic susceptibility measurements (2–300?K) of 1 and 2 show weak antiferromagnetic interactions.     

Synthesis,structures, luminescent and dielectric properties of lanthanide coordination polymers

Under hydrothermal conditions, four lanthanide coordination polymers were synthesized based on 4-(4,5-dicarboxy-1H-imidazol-2-yl)pyridine 1-oxide (H₃DCImPyO), with the molecular forumulas [Eu(HDCImPyO)·(H₂O)₂·(CHO₂)]_n (1), [Sm(HDCImPyO)·(H₂O)₂·(HCO₂)]_n (2), {[La(HDCImPyO)·(H₂O)·(HCO₂)]·O₂}_n (3) and {[Y(HDCImPyO)·(C₂O₄)·(H₂O)₂]·H₂O}_n (4). With diverse coordination modes, they were further characterized by elemental analysis, infrared spectroscopy, dielectric measurement, and single-crystal X-ray structural analysis. Complexes 1 and 2 were isostructural and had similar structures with {4⁴, 6²} topology. Complex 1 exhibited strong fluorescent emission in the solid state at room temperature. In 3, HDCImPyO^2? adopted μ₄-kO, O′: kO′, O′′: O′′′: O′′′′ coordination to bridge four La(III) ions to form a 3-D framework with {4. 5²}₂{4². 5¹⁰. 6¹². 7. 8³} topology. In 4, both HDCImPyO^2? ligands and Y³⁺ cations were simplified as linkers to form an interpenetrating 3-D framework with {4¹³. 6²}₂{4²². 6⁶} topology.     

Three 1-D molybdenum(V) phosphates with copper/nickel coordination cations

Three 1-D reduced molybdenum(V) phosphates, [Ni(OH)₂][Na₂(H₂O)₃]₂{Ni[(MoO₂)₆(OH)₃(HPO₄)₃(PO₄)]₂}?·?2C₆H₁₄N₂?·?2H₃O?·?5H₂O (1), [Ni(H₂O)₂][K(H₂O)₅]₂{Ni[(MoO₂)₆(OH)₃(HPO₄)₃(PO₄)]₂}?·?2C₆H₁₄N₂?·?2H₃O?·?4H₂O (2), and [Cu(H₂O)₂][Na(H₂O)₅]₂{Cu[(MoO₂)₆(OH)₃(HPO₄)₃(PO₄)]₂}?·?2C₆H₁₄N₂?·?2H₃O?·?4H₂O (3), have been hydrothermally synthesized and structurally characterized by single-crystal X-ray diffraction. The crystallographic analysis reveals that 1 is based on {Ni[Mo₆O₁₂(OH)₃(HPO₄)₃(PO₄)]₂} clusters connected through {[Ni(OH)₂][Na₂(H₂O)₃]₂} pentanuclear mixed-metal cluster units to yield unusual 1-D chains along the c-axis, which further form 3-D supramolecular networks via hydrogen-bonding. Compounds 2 and 3 are heterogeneous isostructural compounds. Both are built from M[Mo₆P₄]₂ (M?=?Ni or Cu) blocks as the structural motif combined with [MO₄(H₂O)₂] (M?=?Ni or Cu) octahedra to form 1-D chains, where M[Mo₆P₄]₂ (M?=?Ni or Cu) is bonded by [M′(H₂O)₅] (M′?=?K or Na). Furthermore, bulk carbon paste electrode modified with 1 (1-CPE) displays good electrocatalytic activity toward reduction of nitrite or bromate.     

Synthesis and Crystal Structure of a Fumaratocopper(II) Complex with Bipyridine

The title complex [Cu₂(C₄H₂O₄)₂(bipy)₂(H₂O)₃] · 3H₂O (bipy = 2,2'-bipyridine) was prepared and its crystal structure determined by X-ray diffraction methods. Both Cu(II) atoms of the binuclear complex assume square pyramidal coordination. The fumarate groups display different coordination modes. One fumarate group bridges two Cu(II) ions to form a binuclear complex while another fumarate group terminally coordinates to a Cu(II) atom with one carboxyl group free from coordination. The terminally coordinated fumarate showed unusual disorder, which may be due to an intermolecular H-bonding interaction. Close stacking of bipy rings is observed as verified by the distance of 3.46 Å between parallel ring planes. IR spectra were assigned based on the molecular structure.     

Solvothermal synthesis and characterization of coordination polymers of cobalt(II) and zinc(II) with succinic acid

The complexes [Co(C₄H₄O₄)]_n (1) and [Zn(im)₂(C₄H₄O₄)]_n (2) (C₄H₄O₄ = succinate dianion, suc; im = imidazole) have been synthesized solvothermally and characterized by elemental analysis, IR, TG–DTA, and single-crystal X-ray diffraction techniques. Complex 1 is the first anhydrous member of the cobalt succinate family and has high thermal stability under a static air atmosphere, up to 425 °C, and complex 2 is a 1D coordination polymer. In addition, a new synthesis method and some properties of the known [Co(HCOO)₂·2H₂O]_n (3) complex are reported. After in situ synthesis of 3 via decomposition of DMF at 140 °C, it was found that complex 3 can adsorb some solvents repeatedly and is selective for H₂O.     

Ten complexes constructed by two reduced Schiff base tetraazamacrocycle ligands: syntheses,structures, magnetic and luminescent properties

Ten new complexes, [Cu₂(L¹)(NO₃)₂]·2H₂O (1), [Cu₄(L¹)₂]·4ClO₄·H₂O (2), [Cu₂(L¹)(H₂O)₂]·(adipate) (3), [Cu₆(L¹)₂(m-bdc)₄]·2DMF·5H₂O (4), [Cu₂(L¹)(Hbtc)]·5H₂O (5), [Cu₂(L¹)(H₂O)₂]·(ntc)·3H₂O (6), [Co₂(L²)]·[Co(MeOH)₄(H₂O)₂] (7), [Co₃(L²)(EtOH)(H₂O)] (8), [Ni₆(L²)₂(H₂O)₄]·H₂O (9) and [Zn₄(L²)(OAc)₂]·0.5H₂O (10), have been synthesized. 1 displays a [Cu₂(L¹)(NO₃)₂] monomolecular structure. 2 shows a supramolecular chain including [Cu₂L¹]²⁺. In 3, two Cu(II) ions are connected by L¹ to form a [Cu₂(L¹)(H₂O)₂]²⁺ cation. In 4, the m-bdc anions bridge Cu(II) ions and L¹ anions to form a layer. Both 5 and 6 display 3-D supramolecular structures. 7 consists of both [Co₂L²]^2? and [Co(MeOH)₄(H₂O)₂]²⁺ units. 8 and 9 show infinite chain structures. In 10, Zn(II) dimers are linked by L² to generate a 3-D framework. The magnetic properties for 4 and 8 and the luminescent property for 10 have been studied.     

Functionalized Sandwich-Type Polyoxometalates Based on the Polynuclear Manganese Cluster and Imidazole Ligands

Two polynuclear manganese(II) sandwiched heteropolytungstates, Na₁₀(HC₃H₄N₂){[Na(H₂O)][Mn(C₃H₄N₂)]₃[SbW₉O₃₃]₂}·20H₂O (1) and (C₄H₇N₂)₁₀[Mn₄(H₂O)₂(PW₉O₃₄)₂] (2), have been obtained by conventional aqueous synthesis method and characterized by IR spectra, TG, elemental analyses and single crystal X-ray diffraction. In compound 1, the three-nuclear manganese cluster is sandwiched by two [B-α-SbW₉O₃₃]⁹⁻ units, and each manganese (II) is coordinated by one imidazole (im) molecule. Differently, compound 2 has a four-nuclear manganese (II) cluster with two coordination water molecules. The 2-methylimidazole (mim) molecules float around the polyanions and connect them into a 3D supramolecular framework by hydrogen bondings. The magnetic investigation for compound 1 indicates the existence of weak antiferromagnetic interaction in the sandwiched three-nuclear [Mn(C₃H₄N₂)]₃ cluster.     

Supramolecular interactions in high molecular weight bisdithiocarbamate adducts of divalent Zn(II), Cd(II), and Hg(II): spectral,VBS, and single crystal X-ray structural studies on MS4N2 chromophores

This article describes supramolecular interactions induced in a high molecular weight dithiocarbamate, padtc, by its design. Synthesis, spectral studies involving zinc, cadmium and mercury, padtc, and adducts with tmed, such as [Zn(padtc)₂] (1), [Zn(padtc)₂(tmed)]?·?C₆H₅CH_3?·?0.5(H₂O) (2), [Cd(padtc)₂] (3), [Cd(padtc)₂(tmed)]?·?C₆H₅CH₃?·?0.36(H₂O) (4), [Hg(padtc)₂]?·?H₂O (5), [Hg(padtc)₂(2,2′-bipy)]?·?H₂O (6), [Hg(padtc)₂(1,10-phen)]?·?H₂O (7), and [Hg(padtc)₂(oxine)]?·?H₂O (8) (where padtc^??=?N,N′-(iminodiethylene)bisphthalimidedithiocarbamate, 1,10-phen?=?1,10-phenanthroline, tmed?=?tetramethylethylenediamine, 2,2′-bipy?=?2,2′-bipyridine, oxine?=?8-hydroxyquinoline) along with the single crystal X-ray structural analysis of [Zn(padtc)₂(tmed)]?·?C₆H₅CH₃?·?0.5(H₂O) (2) and [Cd(padtc)₂(tmed)]?·?C₆H₅CH₃?·?0.36(H₂O) (4) are reported. All the complexes were characterized by IR, NMR (¹H and ¹³C), and thermogravimetric study. The IR spectra of the complexes show the contribution of the thioureide form to the structures. In ¹³C NMR spectra, the most important thioureide (N¹³CS₂) carbon signals are observed at 210–212?ppm. Single crystal X-ray structural analyses of 2 and 4 show the presence of extensive supramolecular interactions stabilizing the solid-state structure. Both zinc and cadmium are in a distorted octahedral environment with MS₄N₂ chromophores. VBS of Zn and Cd are 1.76 and 1.98, respectively, supporting the correctness of the determined structure and the valence of the central metal ions.     

Studies on two cadmium(II) and two zinc(II) complexes of 4′-chloro-2,2′ : 6′,2″-terpyridine with 1 : 1 or 1 : 2 ratio of metal and ligand

The reaction between 4′-chloro-2,2′ : 6′,2″-terpyridine (tpyCl) with d¹⁰ transition-metal ions produced two cadmium(II) and two zinc(II) metal complexes, formulated as [Cd(tpyCl-κ ³ N,N′,N″)(NO₃-κ ² O,O′)(NO₃-κO)(H₂O-κO)] (1), [Cd(tpyCl-κ ³ N,N′,N″)₂](ClO₄)₂ (2), [Zn(tpyCl-κ ³ N,N′,N″)₂](ClO₄)₂ (3), and [Zn(tpyCl-κ ³ N,N′,N″)₂](BF₄)₂ (4). Supramolecular interactions include coordinative bonding, O–H ··· O, O–H ··· Cl, C–H ··· F, and C–H ··· Cl hydrogen bonding and π–π stacking, all of which play essential roles in forming different frameworks of 1–4.     

Structural diversity controlled by alkali/alkaline earth metals for heterometallic AeI/AeII-ZnII coordination polymers based on 4-nitrobenzene-1,2-dicarboxylate

Six heterometallic Zn(II) coordination polymers, Zn(H₂O)₃(FNA) (1), [NH₄]₂[Zn(H₂O)₂(FNA)₂] (2), [ZnNa₂(FNA)₂]·3H₂O (3), [ZnK₂(FNA)₂]·H₂O (4), [ZnRb₂(FNA)₂]·2H₂O (5) and [ZnMg(FNA)₂]·4H₂O (6) (H₂FNA = 4-nitrobenzene-1,2-dicarboxylic acid), were synthesised by introducing different alkali/alkaline earth (Ae^I/Ae^II) metals. These complexes exhibit diverse structures with the different Ae^I/Ae^II metals used and distinct ligand coordination modes the ions provide. For 1 and 2, the Zn(II) centres with distorted octahedra are connected by FNA to form 1-D chain structures. The Zn(II) centres in 3–6 with distorted tetrahedra are linked by FNA to form 2-D anionic grid layers. For 3–5, these 2-D anionic grid layers are connected by alkali metal (Na, K and Rb) with the O–Ae^I–O connectivity to exhibit 3-D framework structures, while 6 features a 2-D Zn–Mg network. Luminescence properties of 1–6 have been investigated.     

Copper(II) and zinc(II) complexes of pyridine‐2,6‐di­carboxyl­ic acid

The title compounds, bis­(pyridine‐2,6‐di­carboxyl­ato‐N,O,O′)copper(II) monohydrate, [Cu(C₇H₄NO₄)₂]·H₂O, andbis(pyridine‐2,6‐dicarboxylato‐N,O,O′)zinc(II) trihydrate, [Zn(C₇H₄NO₄)₂]·3H₂O, have distorted octahedral geometries about the metal centres. Both metal ions are bonded to four O atoms and two pyridyl‐N atoms from the two terdentate ligand mol­ecules, which are nearly perpendicular to each other. The copper(II) complex has twofold crystallographic symmetry and contains two different ligand mol­ecules, one of which is neutral and another doubly ionized. In contrast, the zinc(II) complex contains two identical singly ionized ligand mol­ecules. Both crystal structures are stabilized by O—H?O intermolecular hydrogen bonds between the complex and the water mol­ecules.     

Disulfonated azo dyes: metal coordination and ion‐pair separation in twelve MII compounds of Ponceau Xylidine and Crystal Scarlet

The structures of seven divalent metal cation compounds of Ponceau Xylidine {PX; systematic name of dication: 4‐[2‐(3,4‐dimethylphenyl)hydrazin‐1‐ylidene]‐3‐oxo‐3,4‐dihydronaphthalene‐2,7‐disulfonate}, also known as Acid Red 26, CI 16150, and of five divalent metal cation compounds of Crystal Scarlet {CS; systematic name of dication: 8‐[2‐(naphthalen‐1‐yl)hydrazin‐1‐ylidene]‐7‐oxo‐7,8‐dihydronaphthalene‐1,3‐disulfonate}, also known as Acid Red 44, CI 16250, are presented. These are hexaaquamagnesium(II) PX dimethylformamide (DMF) monosolvate, [Mg(H₂O)₆](C₁₈H₁₄N₂O₇S₂)·C₃H₇NO, (I); heptaaquacalcium(II) PX 2.5‐hydrate, [Ca(H₂O)₇](C₁₈H₁₄N₂O₇S₂)·2.5H₂O, (II); catena‐poly[aqua(μ‐DMF)tris(DMF)bis(μ₃‐PX)distrontium(II)], [Sr(C₁₈H₁₄N₂O₇S₂)(C₃H₇NO)₂(H₂O)_0.5]_n, (III); the transition‐metal series hexaaquametal(II) PX DMF monosolvate, [M(H₂O)₆](C₁₈H₁₄N₂O₇S₂)·C₃H₇NO, where M (metal) = Co, (IV), Ni, (V), Cu, (VI), and Zn, (VII); heptaaquacalcium(II) CS monohydrate, [Ca(H₂O)₇](C₂₀H₁₃N₂O₇S₂)·H₂O, (VIII); octaaquastrontium(II) CS monohydrate, [Sr(H₂O)₈](C₂₀H₁₃N₂O₇S₂)·H₂O, (IX); catena‐poly[[triaqua(DMF)barium(II)]‐μ‐CS], [Ba(C₂₀H₁₃N₂O₇S₂)(C₃H₇NO)(H₂O)₃]_n, (X); tetrakis(DMF)(CS)copper(II) monohydrate, [Cu(C₂₀H₁₃N₂O₇S₂)(C₃H₇NO)₄]·H₂O, (XI); and catena‐poly[[[aquatris(DMF)zinc(III)]‐μ‐CS] diethyl ether hemisolvate], {[Zn(C₂₀H₁₃N₂O₇S₂)(C₃H₇NO)₃(H₂O)]·0.5C₄H₁₀O}_n, (XII). In all cases, the structures obtained were solvates with dimethylformamide (DMF) and/or water present. The disulfonated naphthalene‐based azo anions adopt hydrazone tautomeric forms. The structures of the Mg salt and of four transition‐metal forms (M = Co, Ni, Cu and Zn) of PX are found to form an isostructural series. All have solvent‐separated ion‐pair (SSIP) type structures and the formula [M(H₂O)₆][PX]·DMF. The Ca salt of PX also has an SSIP structure, but has a higher hydration state, [Ca(H₂O)₇][PX]·2.5H₂O. In contrast, the Sr salt of PX, [Sr(PX)(DMF)₂(H₂O)_0.5]_n forms a one‐dimensional coordination polymer. Both the Ca and the Sr salt of CS have an SSIP structure, namely [Ca(H₂O)₇][CS]·H₂O and [Sr(H₂O)₈][CS]·H₂O, whilst the heavier Ba analogue, [Ba(CS)(DMF)(H₂O)₃]_n, forms a one‐dimensional coordination polymer. Unlike PX, two CS structures containing transition metals are found to be coordination complexes, [Cu(CS)(DMF)₄]·H₂O and {[Zn(CS)(DMF)₃(H₂O)]·0.5Et₂O}_n. This suggests that CS is a better ligand than PX for transition metals. The Cu complex forms discrete molecules with Cu in a square‐pyramidal environment, whilst the Zn species is a one‐dimensional coordination polymer based on octahedral Zn centres.     

Iron,nickel and zinc malates coordination compounds cynthesis,characterization and thermal behaviour

The coordinations compounds (NH₄)[Fe(C₄H₄O₅)(OH)₂]·0.5H₂O, [Ni(C₄H₄O₅)]·3H₂O and [Zn(C₄H₄O₅)]·5H₂O were synthesized by a precipitation method and characterized by chemical analysis, spectral (IR, UV-VIS) and magnetical investigations. In the range 50-600°C stepped thermal decompositions occur with formation of anhydrous malates, malonates, oxoacetates (iron and nickel compounds) and hydroxocarbonate (Zn compound) as intermediates observed by FT-IR spectroscopy. α-Fe₂O₃, NiO and ZnO constitute the final decomposition products. This revised version was published online in July 2006 with corrections to the Cover Date.     

A series of lanthanide-organic frameworks constructed by 2-methyl imidazole dicarboxylate and oxalate: synthesis,structures, and properties

Five lanthanide(III) coordination polymers with 2-methyl-1H-imidazole-4,5-dicarboxylic acid (H₃MIDC) and ammonium oxalate, {[(Ln1)₂(HMIDC)₂(C₂O₄)(H₂O)₃]?·?3H₂O} _n (Ln1?=?Nd (1), Sm (2)), {[Eu₂(HMIDC)₂(C₂O₄)(H₂O)₃]?·?0.5EtOH?·?3H₂O} _n (3), {[Ce₂(HMIDC)₂(C₂O₄)(H₂O)₃]?·?EtOH?·?3H₂O} _n (4), and {[Gd₂(HMIDC)₂(C₂O₄)(H₂O)₃]?·?MeOH?·?3H₂O} _n (5), have been prepared and structurally characterized. Single-crystal X-ray diffraction analyses reveal that 1 and 2 are isostructural, as are 3, 4, and 5. Each exhibits a 3-D open framework, which is built by a regular 2-D grid connected by HMIDC^2? and Ln(III). The luminescence and thermal properties of these complexes have been investigated as well.     

Supramolecular Systems Based on Ca2+, [Mo3O2S2Cl6(H2O)3]2s-, [Mo3S4Cl6.75Br0.25(H2O)2]3s- and Cucurbit[6]uril

Adducts of cucurbit[6]uril with Ca²⁺ and trinuclear cluster chloroaquacomplexes (H₉O₄)₂(H₇O₃)₂[(Ca(H₂O)₅)2(C₃₆H₃₆N₂₄O₁₂)]Cl₈·0.67H₂O (1) and [(Ca(H₂O)₅)₂(C₃₆H₃₆N₂₄O₁₂)]× [Mo₃O₂S₂Cl₆(H₂O)₃]₂·13H₂O (2) are obtained and structurally characterized. The structures of both compounds contain polymeric [Ca(H₂O) _n ]₂² CB[6]∞ cations that form infinite columns; the space between them is filled with Cl^s- (1) and [Mo₃O₂S₂Cl₆(H₂O)₃]^2s- (2). A new (H₇O₃)₂(H₅O₂)× [Mo₃S₄Cl_6.25Br_0.25(H₂O)₂](C₃₆H₃₆N₂₄O₁₂)·CH₂Cl₂·6H₂O complex (3) is also obtained and structurally characterized.     

Synthesis and structure of uranyl complexes with malonic acid dianions

The uranyl complexes with malonic acid dianions [UO₂(C₃H₂O₄)(CO(NH₂)₂)]·H₂O (1), [UO₂(C₃H₂O₄)(CONH₂NMe₂)]·H₂O (2), and [UO₂(C₃H₂O₄)(MeCONMe₂)] (3) were synthesized and characterized by X-ray crystallography. The structural units [UO₂(C₃H₂O₄)L] in the crystals of 1–3 refer to the AK²¹M¹ crystal chemical group (A = UO₂ ²⁺, K²¹ = C₃H₂O₄ ^2?, M¹ = L) of uranyl complexes; the crystals of 1 have a framework structure and 2 and 3 have a chain structure. Some structural features of the [UO₂(C₃H₂O₄)L] complex groups are discussed.