Tricapped Trigonal Prismatic Environment Research Articles

Hydro-thermal synthesis and crystal structure of a new lanthanum(III) coordination polymer with fumaric acid.

The title compound, poly[di­aqua­tris­(μ4-but-2-enedioato)(μ2-but-2-enedioic acid)dilanthanum(III)], [La2(C4H2O4)3(C4H4O4)(H2O)2]n, was synthesized by the reaction of lanthanum chloride penta­hydrate with fumaric acid under hydro­thermal conditions. The asymmetric unit comprises an LaIII cation, one and a half fumarate dianions (L 2−), one a half-mol­ecule of fumaric acid (H2 L) and one coordinated water mol­ecule. Each LaIII cation has the same nine-coordinate environment and is surrounded by eight O atoms from seven distinct fumarate moieties, including one proton­ated fumarate unit and one water mol­ecule in a distorted tricapped trigonal–prismatic environment. The LaO8(H2O) polyhedra centres are edge-shared through three carboxyl­ate bridges of the fumarate ligand, forming chains in three dimensions to construct the MOF. The crystal structure is stabilized by O—H⋯O hydrogen-bond inter­actions between the coordin­ated water mol­ecule and the carboxyl­ate O atoms, and also between oxygen atoms of fumaric acid

A linear heterometallic bismuth-copper coordination polymer containing two types of organic ligands.

In the linear coordination polymer catena-poly[[[aqua(1,10-phenanthroline-κ(2)N,N')copper(II)]-μ-pyridine-2,6-dicarboxylato-κ(4)O(2):O(2'),N,O(6)-[(nitrato-κ(2)O,O')bismuth(III)]-μ-pyridine-2,6-dicarboxylato-κ(4)O(2),N,O(6):O(6')] dihydrate], {[Bi(III)Cu(II)(C7H3NO4)2(NO3)(C12H8N2)(H2O)]·2H2O}n, the Bi(III) cation is O,N,O'-chelated by the two pyridine-2,6-dicarboxylate ligands and O,O'-chelated by the nitrate anion, the nine coordinating atoms conferring a tricapped trigonal prismatic environment on the metal centre. Each pyridine-2,6-dicarboxylate ligand uses one of its carboxylate O atoms to bind to an aqua(1,10-phenanthroline)copper(II) unit, the Cu-O dative bonds giving rise to the formation of a ribbon motif. The Cu(II) cation exhibits a square-pyramidal geometry. The ribbon motif propagates along the shortest axis of the triclinic unit cell and the solvent water molecules are hydrogen bonded to the same ribbon.

Tridentate benzimidazole-pyridine-tetrazolates as sensitizers of europium luminescence.

We report on new anionic tridentate benzimidazole-pyridine-tetrazolate ligands that form neutral 3:1 complexes with trivalent lanthanides. The ligands are UV-absorbing chromophores that sensitize the red luminescence of europium with energy-transfer efficiency of 74-100%. The lifetime and quantum yield of the sensitized europium luminescence increase from 0.5 ms and 12-13% for the as-prepared solids to 2.8 ms and 41% for dichloromethane solution. From analysis of the data, the as-prepared solids can be described as aqua-complexes [Ln(κ(3)-ligand)2(κ(1)-ligand)(H2O)x] where the coordinated water molecules are responsible for the strong quenching of the europium luminescence. In solution, the coordinated water molecules are replaced by the nitrogen atoms of the κ(1)-ligand to give anhydrous complexes [Ln(κ(3)-ligand)3] that exhibit efficient europium luminescence. X-ray structures of the anhydrous complexes confirm that the lanthanide ion (La(III), Eu(III)) is nine-coordinate in a distorted tricapped trigonal prismatic environment and that coordination of the lanthanide ion by tetrazolate is weaker than by carboxylate.

Catena-Poly[[tris(acetonitrile-κN)praseodymium(III)]tris(μ-trifluoromethanesulfonato-κ2O:O′)

In the colourless title compound, [Pr(CF3O3S)3(CH3CN)3]n, the three trifluoro­methane­sulfonate anions form three bridges via O:O′-coordination between two PrIII atoms. The structure contains [Pr(NCMe)3-μ2(OTf)3—Pr(NCMe)3-μ2(OTf)3]n (NCMe is acetonitrile; OTf is trifluoromethanesulfonate) chains parallel to the a axis. The PrIII atom is nine-coordinate in a distorted tricapped trigonal-prismatic environment.

Poly[[tetraaqua-μ4-fumarato-di-μ3-fumarato-dineodymium(III)] trihydrate

The title coordination polymer, {[Nd2(C4H2O4)3(H2O)4]·3H2O}, was synthesized by the reaction of neodymium(III) nitrate hexa­hydrate with fumaric acid in a water–methanol (7:3) solution. The asymmetric unit comprises two Nd3+ cations, three fumarate dianions (L 2−), four aqua ligands and three uncoordinated water mol­ecules. The carboxyl­ate groups of the fumarate dianions exhibit different coordination modes. In one fumarate dianion, two carboxyl­ate groups chelate two Nd3+ cations, while one of the O atoms is coordinated to another Nd3+ cation. Another fumarate dianion bridges three Nd3+ cations: one of the carboxyl­ate groups chelates one Nd3+ cation, while the other carboxyl­ate group bridges two Nd3+ cations in a monodentate mode. The third fumarate dianion bridges four Nd3+ cations, where one of the carboxyl­ate groups chelates one Nd3+ cation and coordinates in a monodentate mode to a second Nd3+, while the second carboxyl­ate groups bridges two Nd3+ cations in a monodentate mode and one O atom is coordinated to one Nd3+ cation. The Nd3+ cations are in a distorted tricapped–trigonal prismatic environment and coordinated by seven O atoms from the fumarate ligands and two O atoms from water mol­ecules. The Nd3+ cations are linked by two carboxyl­ate O atoms and two carboxyl­ate groups, generating infinite Nd–O chains to form a three-dimensional framework. There are O—H⋯O and C—H⋯O hydrogen-bonding interactions between the coordin­ated and uncoordinated water mol­ecules and carboxyl­ate O atoms.

Poly[diaquabis(μ4-fumarato-κ4O1:O1′:O4:O4′)(μ4-fumarato-κ6O1:O1,O1′:O4:O4,O4′)(μ2-fumaric acid-κ2O1:O4)dipraseodymium(III)

The title complex, [Pr2(C4H2O4)3(C4H4O4)(H2O)2]n, was synthesized by reaction of praseodymium(III) nitrate hexa­hydrate with fumaric acid in a water–ethanol (4:1) solution. The asymmetric unit comprises a Pr3+ cation, one and a half fumarate dianions (L 2−), one half-mol­ecule of fumaric acid (H2L) and one coordinated water mol­ecule. The carboxyl­ate groups of the fumarate dianion and fumaric acid exhibit different coordination modes. In one fumarate dianion, two carboxyl­ate groups are chelating with two Pr3+ cations, and the other two O atoms each coordinate a Pr3+ cation. Each O atom of the second fumarate dianion binds to a different Pr3+ cation. The fumaric acid employs one O atom at each end to bridge two Pr3+ cations. The Pr3+ cation is coordinated in a distorted tricapped trigonal–prismatic environment by eight O atoms of fumarate dianion or fumaric acid ligands and one water O atom. The PrO9 coordination polyhedra are edge-shared through one carboxyl­ate O atom and two carboxyl­ate groups, generating infinite praseodymium–oxygen chains, which are further connected by the ligands into a three-dimensional framework. The crystal structure is stabilized by O—H⋯O hydrogen-bond inter­actions between the coordin­ated water mol­ecule and the carboxyl­ate O atoms.

Tetrakis(μ-4-tert-butylbenzoato)-κ3O:O,O′;κ3O,O′:O′;κ4O:O′-bis[aquabis(4-tert-butylbenzoato-κ2O,O′)(4-tert-butylbenzoic acid-κO)praseodymium(III)

The reaction of praseodymium nitrate and 4-tert-butyl­benzoic acid (tBBAH) in aqueous solution yielded the dinuclear title complex, [Pr2(C11H13O2)6(C11H14O2)2(H2O)2], which has non-crystallographic Ci symmetry. The two PrIII ions are linked by two bridging and two bridging–chelating tBBA ligands, with a Pr⋯Pr separation of 4.0817 (9) Å. Each PrIII ion is nine-coordinated by one chelating tBBA ion, one monodentate tBBAH ligand and one water mol­ecule in a distorted tricapped trigonal–prismatic environment. The complex mol­ecules are linked into infinite chains along the c axis by inter­molecular O—H⋯O hydrogen bonds.

Poly[[diaqua-μ6-succinato-di-μ5-succinato-didysprosium(III)] monohydrate

The title compound, {[Dy2(C4H4O4)3(H2O)2]·H2O}n, is isostructural with other lanthanide succinates of the same formula. The DyIII atom is nine-coordinated in a tricapped trigonal–prismatic environment by eight O atoms, derived from six carboxyl­ate groups and a water mol­ecule. One of the independent succinate anions is located about a crystallographic inversion center and the uncoordinated water mol­ecule lies on a twofold axis. The crystal structure comprises edge-shared DyO9 polyhedra linked by succinate bridges, forming a three-dimensional network architecture. Intra- and inter­molecular O—H⋯O hydrogen bonds are present in the crystal structure.

Tetrakis(μ-4-tert-butylbenzoato)-κ4O:O′;κ3O,O′:O′;κ3O:O,O′-bis[aqua(4-tert-butylbenzoato-κ2O,O′)(4-tert-butylbenzoic acid-κO)neodymium(III)

The reaction of neodymium nitrate and 4-tert-butyl­benzoic acid (tBBAH) in aqueous solution yielded the dinuclear title complex, [Nd2(C11H13O2)6(C11H14O2)2(H2O)2], which has non-crystallographic Ci symmetry. The two NdIII ions are linked by two bridging and two bridging–chelating tBBA ligands with an Nd⋯Nd separation of 4.0624 (5) Å. Moreover, each NdIII ion is coordinated by one chelating tBBA ion, one monodentate tBBAH ligand and one water mol­ecule. The nine-coordinated NdIII ion is in a distorted tricapped trigonal–prismatic environment. The mol­ecules are linked into infinite chains along the c axis by inter­molecular O—H⋯O hydrogen bonds. Three of the tert-butyl groups are disordered over two sets of sites with equal occupancies.

Propane-1,2-diaminium tris(pyridine-2,6-dicarboxylato-κ3O2,N,O6)zirconate(IV) trihydrate

In the title compound, (C3H12N2)[Zr(C7H3NO4)3]·3H2O, the ZrIV cation is chelated by three pyridine-2,6-dicarboxyl­ate anions in a distorted tricapped trigonal–prismatic environment. The crystal structure is stabilized by inter­molecular N—H⋯O and O—H⋯O hydrogen bonds.

Molecular models for WH6 under pressure

At atmospheric pressure, some tungsten hydrides exist as discrete molecular complexes in low temperature matrices, but are very reactive and cannot be isolated in bulk at room temperature. Under pressure, one observes WH in experiment at room temperature, and calculations indicate several other stoichiometries are stable, all extended and not molecular. This work aims at constructing a bridge between discrete molecules and the pressurized extended structures, with the emblematic example of WH6. The equilibrium structure, known as a distorted trigonal prismatic molecule, is likely to be a good acceptor. In numerical experiments, discrete WH6 molecular complexes are allowed to interact with each other in their ground states at T = 0 K and P = 1 atm. They spontaneously rearrange to form 1D-chains, with the W centers adopting a tricapped trigonal prismatic environment. The electronic structure of these chains is examined and related to that of the monomer and extended solids.

Tetra-kis[μ-2-(3,4-dimeth-oxy-phen-yl)acetato]-κO:O';κO,O':O;κO:O,O'-bis-{[2-(3,4-dimeth-oxy-phen-yl)acetato-κO,O'](1,10-phenanthroline-κN,N')samarium(III)}.

In the centrosymmetric dinuclear title complex, [Sm2(C10H11O4)6(C12H8N2)2], the SmIII ion is nine-coordinated by seven O atoms of five 2-(3,4-dimeth­oxy­phen­yl)acetate (DMPA) ligands and two N atoms of one bis-chelating 1,10-phenanthroline (phen) ligand, forming a distorted tricapped trigonal-prismatic environment. The DMPA ligands coordinate in bis-chelate, bridging and bridging tridentate modes. An intra­molecular C—H⋯O hydrogen bond occurs. Inter­molecular C—H⋯O inter­actions are also present in the crystal.

Triimidazolium tris(pyridine-2,6-dicarboxylato)dysprosate(III) trihydrate

The structure of the title compound, (C3N2H5)3[Dy(C7H3NO4)3]·3H2O, contains a mononuclear DyIII complex with the rare earth metal cation in a distorted tricapped trigonal–prismatic environment. The DyIII ion is in each case O,N,O′-chelated by three tridentate pyridine-2,6-dicarboxyl­ate anions. Three protonated imidazole mol­ecules act as counter-cations and three lattice water mol­ecules are also present. Numerous N—H⋯O and O—H⋯O hydrogen bonding inter­actions, some of which are bifurcated, help to stabilize the packing of the structure.

The new ternary phases of La3(Zn0.874Mg0.126)11and Ce3(Zn0.863Mg0.137)11

The new ternary intermetallic title compounds, namely trilanthanum undeca(zinc/magnesium), La(3)(Zn(0.874)Mg(0.126))(11), (I), and tricerium undeca(zinc/magnesium), Ce(3)(Zn(0.863)Mg(0.137))(11), (II), are isostructural and crystallize in the orthorhombic La(3)Al(11) structure type. These three phases belong to the same structural family, the representative members of which may be derived from the tetragonal BaAl(4) structure type by a combination of internal deformation and multiple substitution. Compared to the structure of La(3)Al(11), in (I), a significant decrease of 11.9% in the unit-cell b axis and an increase in the other two directions, of 3.6% along a and 5.2% along c, are observed. Such an atypical deformation is caused by the closer packing of atoms in the unit cell due to atom shifts that reflect strengthening of metallic-type bonding. This structural change is also manifested in a significant difference in the coordination around the smaller atoms at the 8l Wyckoff position (site symmetry m). The Al atom in La(3)Al(11) is in a tricapped trigonal prismatic environment (coordination number 9), while the Zn atoms in (I) and (II) are situated in a tetragonal antiprism with two added atoms (coordination number 10).

Tetrakis(μ2-3,4-dimethoxyphenylacetato)-κ3O,O′:O′;κ3O:O:O′;κ2O:O′;κ2O:O′-bis[(3,4-dimethoxyphenylacetato-κ2O,O′)(1,10-phenanthroline-κ2N,N)thulium(III)

In the title centrosymmetric dinuclear complex, [Tm2(C10H11O4)6(C12H8N2)2], the unique TmIII ion is coordin­ated by five 3,4-dimethoxy­phenyl­acetate (DMPA) ligands and and a bis-chelating 1,10-phenanthroline (phen) ligand via seven O atoms and two N atoms, forming a distorted tricapped trigonal-prismatic environment. The DMPA ligands coordin­ate in the bis-chelate, bridging and bridging tridentate modes.

Di-μ-methacrylato-bis[diaquabis(methacrylato)europium(III)] methacrylic acid disolvate

In the title centrosymmetric complex, [Eu2(C4H5O2)6(H2O)4]·2C4H6O2, the unique EuIII cation is coordinated by seven carb­oxylate O atoms from four methacrylate ligands and two water mol­ecules in a slightly disorted tricapped trigonal–prismatic environment. Two EuIII ions are bridged by carboxyl­ate groups, forming a dinuclear complex. The formula unit also contains two mol­ecules of methacrylic acid. In the crystal structure, mol­ecules are linked via inter­molecular O—H⋯O hydrogen bonds, forming one-dimensional chains propagating along the b-axis direction

A new chain-like polyoxometallate based on B-Anderson-type building blocks and rare earth metal ion linkers

In the title polymer chain, catena-poly[[[hexa-μ2-hydroxido-hexa-μ3-oxido-deca­oxido-chromium(III)hexa­molybdenum(IV)]-μ2-oxido-[hepta­aqua­neodymium(III)]- μ2-oxido] tetra­hydrate], [NdCrMo6O18(OH)6(H2O)7]·4H2O, the Nd atom has a tricapped trigonal-prismatic environment, being coordin­ated by two terminal O atoms from different [Cr(OH)6Mo6O18]3− units, and by seven water mol­ecules. In the crystal structure, hydrogen bonds result in the formation of a three-dimensional network and may be effective in the stabilization of the structure.

Structural Chemistry of Thorium Iodates

AbstractThe hydrothermal reaction of Th(NO3)4·xH2O with I2O5 in the presence of KCl results in the crystallization of α-Th(IO3)4(H2O) and β-Th(IO3)4(H2O). The structure of αTh(IO3)4(H2O) is three-dimensional and contains Th4+ cations bound by iodate anions and a coordinating water, creating a tricapped trigonal prismatic environment around the thorium centers. βTh(IO3)4(H2O) is layered, and contains ThO9 units that are best described as capped square antiprisms. Crystallographic data: (193 K, MoKα, λ = 0.71073 Å): α-Th(IO3)4(H2O), monoclinic, space group P21/c, a = 7.2335(3) Å, b = 24.6046(12) Å, c = 7.0150(3) Å, b = 112.1888(8)°, V = 1156.05(9), Z = 4, R(F) = 1.97%; βTh(IO3)4(H2O), monoclinic, space group C2/c, a = 33.928(1) Å, b = 5.7466(2) Å, c = 12.4509(5) Å, b = 107.9896(7)°, V = 2308.8(1), Z = 8, R(F) = 1.63%.

A novel 1D zigzag chain organic–inorganic polymer with Dawson-type polyoxometalates as building blocks: synthesis and crystal structure of H 1.5[Sm(H 2O) 8] 0.5[Sm(DMF) 6(H 2O)(α-P 2W 18O 62)]·DMF·3H 2O

A novel 1D chain organic–inorganic polymer H 1.5[Sm(H 2O) 8] 0.5[Sm(DMF) 6(H 2O)(α-P 2W 18O 62)]·DMF·3H 2O with Dawson-type polyoxometalates as building blocks has been synthesized by reaction of SmCl 3, DMF and α-H 6P 2W 18O 62· nH 2O in the mixed solution of acetonitrile and water in the bulk ratio of 1:1 and characterized by IR, UV spectra, TG-DTA technique, electrochemical behavior and X-ray single-crystal diffraction. X-ray single-crystal structural analysis displays that the title compound crystallizes in an orthorhombic lattice, P2 12 12 space group, with a=23.605(5), b=30.443(6), c=14.536(3) Å, α= β= γ=90°, V=10446(4) Å 3, Z=4, R 1=0.0493, wR 2=0.0783. [Sm(1)(DMF) 6(H 2O)] 3+ coordination cation is nine-coordinate with a distorted tricapped trigonal prismatic environment, which is bridged through W–O–Sm(1)–O–W linkages to build an unprecedented 1D zigzag linear chain structure by alternate polyoxometalate anions and metal coordination cations in the polymer, whereas [Sm(2)(H 2O) 8] 3+ coordination ion is a discrete unit incorporated into the gaps of the polyoxoanions with an eight-coordinate square antiprismatic geometry. Cyclic voltammetry reveals that the pH of the supporting electrolytic solution has a marked effect on the electrochemical behaviors.

Hydrothermal Syntheses, Crystal Structures, Magnetism and Fluorescence Quenching of Oxamidato‐Bridged Pentanuclear CuII4LnIII Complexes Containing Macrocyclic Ligands (Ln = Eu, Tb) and the Crystal Structure of a Hexanuclear NiII5SmIII Complex

AbstractThree novel oxamidato‐bridged complexes incorporating a macrocyclic oxamide of formula [(CuL)3{CuL(C2H5OH)}Eu(H2O)](ClO4)3·1.5H2O (1), [(CuL)3{CuL(C2H5OH)}Tb(H2O)](ClO4)3·2H2O (2) and [(NiL)5Sm](ClO4)3·2H2O (3) (CuL and NiL, H2L = 2,3‐dioxo‐5,6,14,15‐dibenzo‐1,4,8,12‐tetraazacyclopentadeca‐7,13‐dien), have been hydrothermally synthesized and structurally characterized. In these complexes, the central LnIII and external copper (or nickel) ions are bridged by macrocyclic oxamide groups. The EuIII (or TbIII) ion of 1 (or 2) resides in a distorted tricapped trigonal prismatic environment surrounded by eight oxygen atoms from four oxamide groups and one oxygen atom from a water molecule, whereas the SmIII ion of 3 resides in a distorted bicapped square antiprismatic environment surrounded by ten oxygen atoms from five oxamide groups. Furthermore, there are hydrogen bonding interactions in 1 and 2 between perchlorate, ethanol and water moieties. Especially for 1 and 2, O−H···O and weak coordination of ClO4− groups link the pentanuclear fragments and perchlorate ions to form a 1‐D supramolecular architecture. The fluorescence of EuIII and TbIII are almost completely quenched in 1 and 2. The magnetic properties of 1 and 2 have been characterized. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)