Hydro-ionothermal syntheses, crystal structures, and properties of five new divalent metal iminophosphonates

The use of a moderately hydrophobic ionic liquid, 1-butyl-2,3-dimethylimidazolium tetrafluoroborate ([BdMIM][BF(4)]), as a cosolvent with water, has been investigated in the synthesis of metal phosphonates. This hydro-ionothermal synthesis has been carried out through a systematic combinatorial investigation of several divalent metal chlorides and two related ligands, iminobis(methylphosphonic acid) and N-methyliminiobis(methylphosphonic acid). These reactions resulted in five new divalent metal phosphonates. We present here the synthetic techniques utilized as well as the X-ray structures and characteristic properties of each of these compounds. Co(HO(3)PCH(2)NH(2)CH(2)PO(3)H)(2), (1), consists of sheets that are hydrogen bonded together by pairs of P-O···H groups. Co(H(2)O)(2)(HO(3)PCH(2)NH(2)CH(2)PO(3)H)(2), (2), consists of chains that are connected through an extensive network of hydrogen bonds. Co(HO(3)PCH(2)NH(CH(3))CH(2)PO(3)H)(2), (3), is made up of sheets that are hydrogen bonded together by pairing P-O···H interactions. Zn(3)(O(3)PCH(2)NH(2)CH(2)PO(3))(2), (4), is isostructural to a previously reported cobalt compound which is a non-porous 3-dimensional network. CuClPO(3)CH(2)NH(2)CH(3), (5), formed as a result of an in situ N-C bond cleavage. Ladders built of Cu-O-P-O 8-membered rings are crosslinked by bridging chloride atoms to form sheets. 1, 3, 4 and 5 have been synthesized using the hydrophobic ionic liquid 1-butyl-2,3-dimethylimidazolium tetrafluoroborate ([BdMIM][BF(4)]) with water as a cosolvent, while 2 has been synthesized from identical conditions in the absence of the [BdMIM][BF(4)]. We also report the microwave assisted hydro-ionothermal synthesis of the known polymorph of 2, Co(H(2)O)(2)(HO(3)PCH(2)NH(2)CH(2)PO(3)H)(2), (6), synthesized in two hours providing high quality crystals in good yield. The compounds have been characterized by thermogravimetric analysis and IR spectroscopy, and their magnetic properties have been investigated.     

Synthesis, characterization, and crystal structures of two divalent metal diphosphonates with a layered and a 3D network structure

Reactions of N-methyliminobis(methylenephosphonic acid), CH(3)N(CH(2)PO(3)H(2))(2) (H(4)L), with divalent metal acetates under different conditions result in metal diphosphonates with different structures. Mn(H(3)L)(2).2H(2)O (complex 1) with a layer structure was prepared by a layering technique. It is triclinic, P1 macro with a = 9.224(3) A, b = 9.780(3) A, c = 10.554(3) A, alpha = 82.009(6) degrees, beta = 74.356(6) degrees, gamma = 89.853(6) degrees, Z = 2. The Mn(II) ion is octahedrally coordinated by six phosphonate oxygen atoms from four ligands, two of them in a bidentate and two in a unidentate fashion. Each MnO(6) octahedron is further linked to four neighboring MnO(6) octahedra through four bridging phosphonate groups, resulting in a two-dimensional metal phosphonate (002) layer. These layers are held together by strong hydrogen bonds between uncoordinated phosphonate oxygen atoms. The zinc complex Zn(3)(HL)(2) (complex 2) was synthesized by hydrothermal reactions (4 days, 438 K, autogenous pressure). It is monoclinic, P2(1)/n with a = 7.7788(9) A, b = 17.025(2) A, c = 13.041(2) A, beta = 94.597(2) degrees, Z = 4. The structure of complex 2 features a 3D network built from ZnO(4) tetrahedra linked together by bridging phosphonate groups. Each zinc cation is tetrahedrally coordinated by four phosphonate oxygen atoms from four ligands, each of which connects with six zinc atoms, resulting in voids of various sizes. Magnetic measurements for the manganese complex shows an antiferromagnetic interaction at low temperature. The effect of the extent of deprotonation of phosphonic acids on the type of complex formed is discussed.     

A novel organic-inorganic hybrid based on an 8-electron-reduced Keggin polymolybdate capped by tetrahedral, trigonal bipyramidal, and octahedral zinc: synthesis and crystal structure of (CH3NH3)(H2bipy)[Zn4(bipy)3(H2O)2MoV8MoVI4O36)(PO4)].4H2O

Hydrothermal reaction of H(3)PO(3), CH(3)NH(2), zinc(II) acetate, 4,4'-bipyridine (bipy), and (NH(4))(6)Mo(7)O(24).4H(2)O at 180 degrees C led to a novel organic-inorganic layered hybrid, [CH(3)NH(3)][H(2)bipy][Zn(4)(bipy)(3)(H(2)O)(2)Mo(V)(8)Mo(VI)O(36)(PO(4))].4H(2)O (1). Its structure was established by single-crystal X-ray diffraction. It crystallizes in the monoclinic space group P2(1)/c with cell parameters of a = 17.3032(2), b = 17.8113(3), and c = 23.4597 (4) A, beta = 106.410(1) degrees, V = 6935.6(2) A(3), and Z = 4. The structure of compound 1 features a novel 2D layer built from the 8e-reduced tetracapped Keggin [Zn(4)Mo(12)O(36)(PO(4))](3)(-) anions, which are further interconnected by bridging bipy ligands. The four zinc(II) ions are in tetrahedral, trigonal bipyramidal, and octahedral coordination geometries, respectively.     

Periodic trends in hexanuclear actinide clusters

Four new Th(IV), U(IV), and Np(IV) hexanuclear clusters with 1,2-phenylenediphosphonate as the bridging ligand have been prepared by self-assembly at room temperature. The structures of Th(6)Tl(3)[C(6)H(4)(PO(3))(PO(3)H)](6)(NO(3))(7)(H(2)O)(6)·(NO(3))(2)·4H(2)O (Th6-3), (NH(4))(8.11)Np(12)Rb(3.89)[C(6)H(4)(PO(3))(PO(3)H)](12)(NO(3))(24)·15H(2)O (Np6-1), (NH(4))(4)U(12)Cs(8)[C(6)H(4)(PO(3))(PO(3)H)](12)(NO(3))(24)·18H(2)O (U6-1), and (NH(4))(4)U(12)Cs(2)[C(6)H(4)(PO(3))(PO(3)H)](12)(NO(3))(18)·40H(2)O (U6-2) are described and compared with other clusters of containing An(IV) or Ce(IV). All of the clusters share the common formula M(6)(H(2)O)(m)[C(6)H(3)(PO(3))(PO(3)H)](6)(NO(3))(n)((6-n)) (M = Ce, Th, U, Np, Pu). The metal centers are normally nine-coordinate, with five oxygen atoms from the ligand and an additional four either occupied by NO(3)(-) or H(2)O. It was found that the Ce, U, and Pu clusters favor both C(3i) and C(i) point groups, while Th only yields in C(i), and Np only C(3i). In the C(3i) clusters, there are two NO(3)(-) anions bonded to the metal centers. In the C(i) clusters, the number of NO(3)(-) anions varies from 0 to 2. The change in the ionic radius of the actinide ions tunes the cavity size of the clusters. The thorium clusters were found to accept larger ions including Cs(+) and Tl(+), whereas with uranium and later elements, only NH(4)(+) and/or Rb(+) reside in the center of the clusters.     

A new organic-inorganic hybrid layered molybdenum(V) cobalt phosphate constructed from [H24(Mo16O32)Co16(PO4)24(OH)4(C5H4N)2(H2O)6](4-) wheels and 4,4'-bipyridine linkers

A new layered molybdenum cobalt phosphate, Na(2)[Co(H(2)O)(6)][(Mo(16)O(32))Co(16)(PO(4))(4) (HPO(4))(16)(H(2)PO(4))(4)(OH)(4)(C(10)H(8)N(2))(4)(C(5)H(4)N)(2)(H(2)O)(6)]·4H(2)O (1), has been hydrothermally synthesized and structurally characterized. 1 crystallizes in the monoclinic space group P2(1)/n with a = 15.6825(18) ?, b = 39.503(4) ?, c = 17.2763(17) ?, β = 93.791(2)°, V = 10679.4(18) ?(3), and Z = 2. A polyoxoanion of 1 exhibits an unusual organic-inorganic hybrid wheel-type cluster, in which two pyridine ligands link to the surface Co(II) atoms of a [H(24)(Mo(16)O(32))Co(16)(PO(4))(24)(OH)(4)(H(2)O)(6)] (namely, {Mo(16)Co(16)P(24)}) wheel via the Co-N bonds. Furthermore, each {Mo(16)Co(16)P(24)} wheel is connected to four adjacent wheels by four pairs of 4,4'-bipyridine linkers, forming a 2D layered network. The susceptibility measurement shows the existence of dominant antiferromagnetic interactions in 1.     

Uranyl heteropolyoxometalate: synthesis, structure, and spectroscopic properties

A novel uranium heteropolyoxometalate, [H(3)O](4)[Ni(H(2)O)(3)](4){Ni[(UO(2))(PO(3)C(6)H(4)CO(2))](3)(PO(4)H)}(4)·2.72H(2)O, has been prepared under mild hydrothermal conditions using the diethyl(2-ethoxycarbonylphenyl)phosphonate ligand and in situ ligand synthesis of the HPO(4)(2-) anion. The cluster is derived from a common UO(7), pentagonal bipyramid and is constructed by employing nickel(II) metal ions as linkers. The 3d-5f heteropolyoxometalate core incorporates 12 classical pentagonal uranyl groups and four Ni(2+) octahedral units.     

Template- and pH-directed assembly of diruthenium diphosphonates with different topologies and oxidation states

In the presence of organic templates, six diruthenium diphosphonates, namely, [H3N(CH2)3NH3]2[Ru2(hedp)2] (1), [H3N(CH2)4NH3]2[Ru2(hedp)2].4H2O (2), [H3N(CH2)5NH3]2[Ru2(hedp)2].4H2O (3), [H3N(CH2)3NH3][Ru2(hedp)(hedpH)].H2O (4), [H3N(CH2)4NH3][Ru2(hedpH(0.5))2].2H2O (5), and [H3N(CH2)5NH3]2[Ru2(hedp)2][Ru2(hedpH)2]] (6) [hedp = 1-hydroxyethylidenediphosphonate, CH3C(OH)(PO3)2] have been synthesized under hydrothermal conditions. Compounds 1-3 contain homovalent paddlewheel cores of Ru2(II,II)(hedp)2(4-) that are connected through edge-sharing of the [RuO5Ru] octahedra, resulting in infinite linear chains. Compounds 4-6 contain mixed-valent diruthenium(II,III) phosphonate paddlewheel cores of Ru2(II,III)(hedpH(n))2(3-2n)- that are connected by phosphonate oxygen atoms, forming distorted square-grid layers in 4 and 6 or a kagomé lattice in 5. Both the templates and the pH values are found to play important roles in directing the final products with particular topologies and oxidation states of the diruthenium unit. The magnetic studies show that weak antiferromagentic interactions are propagated between the homovalent diruthenium units in compounds 1-3. For compounds 4-6, weak ferromagnetic interactions are observed.     

Cobalt phosphonates: an unusual polymeric cobalt phosphonate containing a clathrated phosphonate anion and a layered bisphosphonate

Novel cobalt phosphonates [Co(H(2)O)(4)(H(4)L)][H(2)L].2H(2)O, 1, and Co(2)(H(2)O)(2)(L), 2, have been synthesized from 1,8-octylenediphosphonic acid (H(4)L). 1 has been fully characterized by X-ray single-crystal data, TGA, IR spectroscopy, and chemical analysis. The compound crystallizes in the triclinic space group P1 with a = 5.5415(8) A, b = 8.6382(8) A, c = 16.794 (2) A, alpha = 87.694(2) degrees, beta = 80.859(2) degrees, gamma = 76.005(2) degrees, V = 770.11(19) A(3), and Z = 1. A cobalt atom lies in the center of symmetry and is octahedrally coordinated by two oxygen atoms from two undissociated diphosphonic ligands H(4)L and four molecules of water. The cobalt atom and undissociated ligand H(4)L are combined to form polymeric chains along the c-axis, resulting in the formation of a one-dimensional framework. The positive charge on the cobalt atom remains upon coordination and is balanced by a negatively charged uncoordinated ligand (H(2)L) found as a clathrate in the lattice. Two lattice water molecules, hydrogen-bonded with the coordinated and uncoordinated ligands, complete the structure. The metal phosphonate chains are held together and bridge the uncoordinated anionic ligands by a number of strong hydrogen bonds, which make the structure possible. Cobalt phosphonate 2 has been characterized by TGA measurements, IR spectroscopy, and chemical analysis. The compound has a layered structure with an interlayer spacing of 14.26 A. Metal phosphonate layers are cross-linked by hydrocarbon chains. The water molecules are coordinated to the metal atom. According to IR data, compound 2 contains two equivalent PO bonds and one different PO bond, which may be a result of the different types of Co-O-P connectivity within one phosphonic group.     

N,N''''-(2-苯并咪唑基甲基)亚氨基甲基膦酸的双核镍化合物Ni2(bbimp)2(4,4''''-bipy)(H2O)2·2H2O和Ni2(bbimp)2(H2O)2][Ni(bbimp)(H2O)2]2·4H2O的晶体结构和磁学性质

该文报道了N,N′-(2-苯并咪唑基甲基)亚氨基甲基膦酸{bbimpH_2,[(C7H5N2)CH2]2NCH2PO3H2}的2个镍化合物Ni2(bbimp)2(4,4′-bipy)(H2O)2·2H2O(1)和[Ni2(bbimp)2(H2O)2][Ni(bbimp)(H2O)2]2·4H2O(2)。化合物1是4,4′-联吡啶作为桥连配体的中性双核结构。化合物2含有1个中性的[Ni2(bbimp)2(H2O)2]双核分子与2个中性的[Ni(bbimp)(H2O)2]单核分子。双核分子单元中的2个Ni!离子被2个膦酸氧桥连。在化合物2中,膦酸氧桥连的2个Ni!离子之间存在铁磁性相互作用。     

具有十二元环空旷骨架的Mn3Al6(PO4)12·4tren·11H2O的水热合成与表征

自从1982年美国联合碳化公司(U.C.C.)开发出系列磷酸铝分子筛(AlPO4-n,n代表不同的骨架类型)[1]以来,新型微孔结构磷酸铝的开发一直吸引着人们的广泛关注[2].与此同时,杂原子磷酸铝分子筛的研究受到了人们的高度重视,许多元素(Fe,Mn,Co,Zn等)可以作为杂原子进入磷酸铝的分子筛骨架[3～5].其中,含有特殊催化活性的过渡金属离子Mn的磷酸铝备受关注[6,7].1999年,徐耀华等[8]合成出具有新颖三维开放骨架的磷酸铝Al9(PO4)12(C24H91N16)·17H2O.最近,Beitone等[9,10]研究了Zn和Fe元素在此骨架中的取代情况.本文中,我们首次将Mn元素引入…     

Lanthanide diruthenium(II,III) compounds showing layered and PtS-type open framework structures

Two types of lanthanide diruthenium phosphonate compounds, based on the mixed-valent metal-metal bonded paddlewheel core of Ru(2)(hedp)(2)(3-) [hedp = 1-hydroxyethylidenediphosphonate, CH(3)C(OH)(PO(3))(2)], have been prepared with the formulas Ln(H(2)O)4[Ru(2)(hedp)(2)(H(2)O)2].5.5H(2)O (1.Ln, Ln = La, Ce) and Ln(H(2)O)4[Ru(2)(hedp)(2)(H(2)O)(2)].8H(2)O (2.Ln, Ln = La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er). In both types, each Ru(2)(hedp)2(H2O)23- unit is linked by four Ln(3+)ions through four phosphonate oxygen (OP) atoms and vice versa. The geometries of the {LnO(P4)} group, however, are different in the two cases. In 1.Ln, the geometry of {LnO(P4)} is closer to a distorted plane, and thus a square-grid layer structure is found. In 2.Ln, the geometry of {LnO(P4)} is better described as a distorted tetrahedron; hence, a unique PtS-type open-framework structure is observed. The channels generated in structures 2.Ln are filled with water aggregates with extensive hydrogen-bond interactions. The magnetic and electrochemical properties are also investigated.     

Anion-directed self-assembly of lanthanide-notp compounds and their fluorescence, magnetic, and catalytic properties

Reactions of 1,4,7-triazacyclononane-1,4,7-triyl-tris(methylenephosphonic acid) [notpH(6), C(9)H(18)N(3)(PO(3)H(2))3] with different lanthanide salts result in four types of Ln-notp compounds: [Ln{C(9)H(20)N(3)(PO(3)H)(2)(PO(3))}(NO(3))(H(2)O)].4H2O (1), [Ln = Eu (1 Eu), Gd (1 Gd), Tb (1 Tb)], [Ln{C(9)H(20)N(3)(PO(3)H)(2)(PO(3))}(H2O)]Cl.3H2O (2) [Ln = Eu (2 Eu), Gd (2 Gd), Tb (2 Tb)], [Ln{C(9)H(20)N(3)(PO(3)H)(2)(PO(3))}(H2O)]ClO4.8H2O, (3) [Ln = Eu (3 Eu), Gd (3 Gd)], and [Ln{C(9)H(20)N(3)(PO(3)H)(2)(PO(3))}(H2O)]ClO4.3H2O (4), [Ln = Gd (4 Gd), Tb (4 Tb)]. Compounds within each type are isostructural. In compounds 1, dimers of {Ln2(notpH4)2(NO3)2(H2O)2} are found, in which the two lanthanide atoms are connected by two pairs of O-P-O and one pair of mu-O bridges. The NO3- ion serves as a bidentate terminal ligand. Compounds 2 contain similar dimeric units of {Ln2(notpH4)2(H2O)2} that are further connected by a pair of O-P-O bridges into an alternating chain. The Cl- ions are involved in the interchain hydrogen-bonding networks. A similar chain structure is also found in compounds 3; in this case, however, the chains are linked by ClO4- counterions through hydrogen-bonding interactions, forming an undulating layer in the (011) plane. These layers are fused through hydrogen-bonding interactions, leading to a three-dimensional supramolecular network with large channels in the [100] direction. Compounds 4 show an interesting brick-wall-like layer structure in which the neighboring lanthanide atoms are connected by a pair of O-P-O bridges. The ClO4- counterions and the lattice water molecules are between the layers. In all compounds the triazamacrocyclic nitrogen atoms are not coordinated to the Ln(III) ions. The anions and the pH are believed to play key roles in directing the formation of a particular structure. The fluorescence spectroscopic properties of the Eu and Tb compounds, magnetic properties of the Gd compounds, and the catalytic properties of 4 Gd were also studied.     

Synthesis and characterization of a new bisphosphonic acid and several metal hybrids derivatives

Commercial bis-(4-bromophenyl)-ether, [BrC(6)H(4)](2)-O, has been used to prepare 4-[4'-(diethoxyphosphoryl)phenoxy]phenyl-phosphonic acid diethyl ester, [(CH(3)CH(2))(2)O(3)P-C(6)H(4)](2)-O, (I) following a slight modification of the Michaelis-Arbuzov reaction. The acid hydrolysis of I gave 4-(4'-phosphonophenoxy)phenyl phosphonic acid, [H(2)O(3)P-C(6)H(4)](2)-O (II), and both compounds have been characterized by (1)H NMR and (13)C NMR. The crystal structure of II has been determined by single-crystal X-ray diffraction. II crystallizes in an orthorhombic unit cell, space group Pbcn, with a = 7.822(3) A, b = 5.821(2) A, c = 28.982(9) A, and V = 1319.7(7) A(3). The final R factor was R1 = 0.0614. The structure is layered, being held together through a hydrogen bonding network. II has been used as precursor in the syntheses of new metal (Mn, Fe, Co, Ni, Cu, and Zn) bisphosphonates. The syntheses were carried out using a fixed metal/bisphosphonic acid molar ratio of 2.1:1 and the influence of the pH in the reactions has been studied. Nine new compounds have been isolated: Mn(2)(O(3)PC(6)H(4)OC(6)H(4)PO(3)).1.5H(2)O (III), Mn(5)(OH)(2)(O(3)PC(6)H(4)OC(6)H(4)PO(3))(2).2H(2)O (IV), Fe(HO(3)PC(6)H(4)OC(6)H(4)PO(3)).0.5H(2)O (V), Co(2)(O(3)PC(6)H(4)OC(6)H(4)PO(3)).2H(2)O (VI), Ni(2)(O(3)PC(6)H(4)OC(6)H(4)PO(3)).3H(2)O (VII), Ni(2)(O(3)PC(6)H(4)OC(6)H(4)PO(3)).2H(2)O (VIII), Cu(2)(O(3)PC(6)H(4)OC(6)H(4)PO(3)) (IX), Zn(2)(O(3)PC(6)H(4)OC(6)H(4)PO(3)) (X), and Zn(HO(3)PC(6)H(4)OC(6)H(4)PO(3)H) (XI). Compound IX crystallizes in an orthorhombic unit cell, space group Pbcn, and unit cell parameters a = 8.1012(5) A, b = 5.3109(3) A, c = 29.2595(5) A, and V = 1258.8(1) A(3). Its structure has been solved by ab initio powder diffraction and refined by the Rietveld method to R(F) = 0.042. IX has a pillared layer framework with highly distorted CuO(5) groups sharing edges to give isolated dimers. XI was indexed in a monoclinic unit cell, space group P112(1), with parameters a = 9.4991(9) A, b = 5.0445(5) A, c = 29.131(2) A, gamma = 91.945(7) degrees, and V = 1395.1(3) A(3). Its structure has been refined by the Rietveld method, R(F) = 0.054, since it is isostructural with the known compound, Zn[HO(3)P(C(6)H(4))(2)PO(3)H]. All solids were also characterized by thermal analysis and IR and UV-Vis spectroscopies.     

New types of metal squarato-phosphonates: condensation of aminodiphosphonate with squaric acid under hydrothermal conditions

The syntheses and crystal structures of the first copper(I) phosphonate, Cu2(H3L)(bipy)(2).2H2O 1 (H5L = C4HO3N(CH2PO3H2)2), which is also the first example of metal phosphonates formed by a type of organic reaction, and a novel luminescent Mn(II) squarate diphosphonate, {Mn[NH(CH2PO3H)2](H2O)2}2{Mn(C4O4)(H2O)4}.(C4H2O4) 2, have been reported. The structure of 1 features a layer architecture in which the Cu(I) centers are three coordinated, and the newly formed ligand acts as a bidentate metal linker. Compound 2 is composed of 1D chains of Mn[NH(CH2PO3H)2](H2O)2, 1D chains of {Mn(C4O4)(H2O)4}, as well as the neutral squaric acid molecules. These three types of building units are interconnected via hydrogen bonding.     

A novel cadmium aminophosphonate: X-ray powder diffraction structure, solid-state IR and NMR spectroscopic determination of the fine structure of the organic moieties

A new divalent cadmium phosphonate, Cd2Cl2(H2O)4(H2L), has been synthesized from the ethylenediamine-N,N'-bis(methylenephosphonic acid) (H4L). The obtained microcrystalline compound has been characterized by solid-state IR spectra and 13C, 31P, and 113Cd CP MAS NMR. The static 13P NMR spectra have been also recorded to give the delta11, delta22, and delta33 chemical shift parameters for both compounds. The spectral data, collected for Cd2Cl2(H2O)4(H2L), are in an agreement with its X-ray powder diffraction structure solved with the cell dimensions a = 16.6105(10), b = 7.1572(4), and c = 6.8171(4) A and beta = 98.327(4) degrees. The octahedral coordination sphere of the cadmium atoms consists of two phosphonate oxygen atoms, two water oxygen atoms, and the two chlorine atoms. Cadmium atoms are bridged by the chlorine atoms forming four-membered rings. The phosphorus atoms exhibit a tetrahedral coordination with two oxygen atoms bonded to the cadmium atoms with P-O distances of 1.503(10) and 1.504(10) A. The third oxygen atom, showing a longer P-O distance (1.546(9) A), is not bonded to the metal center, nor is it bonded to a proton. The combined IR and NMR proton-phosphorus cross-polarization kinetic data together with the X-ray data confirm that the cadmium phosphonate has the zwitterionic structure (NH2(+)CH2P(O2Cd2)O-) similar to the initial aminophosphonic acid H4L.     

Synthesis,characterization, and crystal structures of two new divalent metal complexes of N,N'-bis(phosphonomethyl)-1,10-diaza-18-crown-6: a hydrogen-bonded 1D array and a 3D network with a large channel

Reaction of N,N'-bis(phosphonomethyl)-1,10-diaza-18-crown-6 (H(4)L) with copper(II) acetate in 1:1 ethanol/water mixed solvents afforded a new crystal-engineered supramolecular metal phosphonate, Cu(H(2)L) (complex 1). By reaction of the same ligand with cadmium(II) nitrate in a 2:1 (M/L) ratio in methanol, a cadmium(II) complex with a 3D network structure was isolated, Cd(2.75)(L)(H(2)O)(7) x 1.5NO(3) x 7H(2)O x MeOH (complex 2). The copper(II) complex crystallized in the monoclinic space group P2(1)/c, with a =10.125(4), b = 14.103(6), and c = 14.537(6) A, beta = 91.049(8) degrees, V = 2075.4(16) A(3), and Z = 2. The Cu(II) ions in complex 1 are 6-coordinated by two phosphonate oxygen atoms, two nitrogen, and two oxygen atoms from the crown ether ring. Their coordination geometry can be described as Jahn-Teller-distorted octahedral, with elongated Cu-O(crown) distances (2.634(4) and 2.671(4) A for Cu(1) and Cu(2), respectively). The other two crown oxygen atoms remain uncoordinated. Neighboring two Cu(H(2)L) units are further interlinked via a pair of strong hydrogen bonds between uncoordinated phosphonate oxygen atoms, resulting in a one-dimensional supramolecular array along the a axis. The cadmium(II) complex is tetragonal, P4(2)/n (No. 86) with a = 20.8150(9) and c = 18.5846(12) A, V = 8052.0(7) A(3), and Z = 8. Among four cadmium(II) atoms in an asymmetric unit, one is 8-coordinated by four chelating phosphonate groups, the second one is 8-coordinated by 6 coordination atoms from a crown ring and two oxygen atoms from two phosphonate groups, the third Cd(II) atom is octahedrally coordinated by three aqua ligands and three phosphonate oxygen atoms from three phosphonate groups, and the fourth one is 6-coordinated by four aqua ligands and two oxygen atoms from two phosphonate groups in a distorted octahedral geometry. These cadmium atoms are interconnected by bridging phosphonate tetrahedra in such a way as to form large channels along the c direction, in which the lattice water molecules, methanol solvent, and nitrate anions reside. The effect of extent of deprotonation of phosphonic acids on the type of complex formed is also discussed.     

Structure,magnetism, and electrochemistry of the multinickel polyoxoanions [Ni6As3W24O94(H2O)2]17-, [Ni3Na(H2O)2(AsW9O34)2]11-, and [Ni4Mn2P3W24O94(H2O)2]17-

The three novel, multi-nickel-substituted heteropolytungstates [Ni(6)As(3)W(24)O(94)(H(2)O)(2)](17)(-) (1), [Ni(3)Na(H(2)O)(2)(AsW(9)O(34))(2)](11)(-) (2), and [Ni(4)Mn(2)P(3)W(24)O(94)(H(2)O)(2)](17)(-) (3) have been synthesized and characterized by IR, elemental analysis, electrochemistry, and magnetic studies. Single-crystal X-ray analysis was carried out on Na(16.5)Ni(0.25)[Ni(6)As(3)W(24)O(94)(H(2)O)(2)].54H(2)O, which crystallizes in the triclinic system, space group P1, with a = 17.450(4) A, b = 17.476(4) A, c = 22.232(4) A, alpha = 85.73(3) degrees, beta = 89.74(3) degrees, gamma = 84.33(3) degrees, and Z = 2, Na(11)[Ni(3)Na(H(2)O)(2)(AsW(9)O(34))(2)].30.5H(2)O, which crystallizes in the triclinic system, space group P1, with a = 12.228(2) A, b = 16.743(3) A, c = 23.342(5) A, alpha = 78.50(3) degrees, beta = 80.69(3) degrees, gamma = 78.66(3) degrees, and Z = 2, and Na(17)[Ni(4)Mn(2)P(3)W(24)O(94)(H(2)O)(2)].50.5H(2)O, which crystallizes in the monoclinic system, space group P2(1)/c, with a = 17.540(4) A, b = 22.303(5) A, c = 35.067(7) A, beta = 95.87(3) A, and Z = 4. Polyanion 1 consists of two B-alpha-(Ni(3)AsW(9)O(40)) Keggin moieties linked via a unique AsW(6)O(16) fragment, leading to a banana-shaped structure with C(2)(v)() symmetry. The mixed-metal tungstophosphate 3 is isostructural with 1. Polyanion 2 consists of two lacunary B-alpha-[AsW(9)O(34)](9)(-) Keggin moieties linked via three nickel(II) centers and a sodium ion. Electrochemical studies show that 1-3 exhibit a unique and reproducible voltammetric pattern and that all three compounds are stable in a large pH range. An investigation of the magnetic properties of 1-3 indicates that the exchange interactions within the trimetal clusters are ferromagnetic. However, for 1 and 3 intra- and intermolecular interactions between different trinuclear clusters are also present.     

Self-assembled dinuclear,trinuclear, tetranuclear,pentanuclear, and octanuclear Ni(II) complexes of a series of polytopic diazine based ligands: structural and magnetic properties

The nickel coordination chemistry of a series of polytopic diazine (N-N) based ligands has been examined. Self-assembly reactions lead to examples of dinuclear, trinuclear, tetranuclear, pentanuclear, and octanuclear complexes, all of which exhibit magnetic exchange coupling, with antiferromagnetic and ferromagnetic examples. Structural details are presented for [(L1)(2)Ni(2)(H(2)O)(2)](NO(3))(4).3H(2)O (1), [(L2)(2)Ni(3)(H(2)O)(2)](NO(3))(6).8H(2)O (2), [(L3)(4)Ni(4)(H(2)O)(8)] (NO(3))(4).8H(2)O (3), [(L4)(2)Ni(5)(H(2)O)(10)(NO(3))](NO(3))(7).8H(2)O (4), and [(L5)(4)Ni(8)(H(2)O)(8)](BF(4))(8).16H(2)O (5). Compound 1 crystallizes in the monoclinic system, space group P2(1)/c, with a = 14.937(1) A, b = 18.612(2) A, c = 20.583(2) A, beta = 108.862(2) degrees, Z = 4. Compound 2 crystallizes in the orthorhombic system, space group P2(1)2(1)2, with a = 21.771(4) A, b = 13.700(2) A, c = 20.017(3) A, Z = 4. Compound 3 crystallizes in the tetragonal system, space group P4(3), with a = 12.9483(7) A, c = 33.416(3) A, Z = 4. Compound 4 crystallizes in the triclinic system, space group P(-)1, with a = 12.6677(8) A, b = 18.110(1) A, c = 19.998(1) A, alpha = 100.395(1) degrees, beta = 109.514(1) degrees, gamma = 109.686(1) degrees, Z = 2. Compound 5 crystallizes in the monoclinic system, space group P2(1)/n, with a = 21.153(5) A, b = 35.778(9) A, c = 21.823(5) A, beta = 97.757(6) degrees, Z = 4. The linear trinuclear Ni(II) complex (2) has a cis-N-N single bond bridge, and a water bridge linking the central Ni(II) to each external Ni(II) center in each of two similar trinuclear subunits, and exhibits intramolecular ferromagnetic exchange (J = 5.0 cm(-1)). A novel octanuclear metallacyclic ring structure exists in 5, with trans-N-N single bond bridges linking adjacent Ni(II) centers, leading to quite strong intramolecular antiferromagnetic exchange (J = -30.4 cm(-1)).     

Synthesis, Crystal Structure and Water-induced Reversible Crystal-to-amorphous Transformation Property of [{Ni(IBG)(4,4'-bipy)(a2O)2}·3a2O]n

A novel NiⅡ complex[{Ni(IBG)(4,4'-bipy)(H2O)2}·3H2O]n1(H2IBG=isophthaloylbisglycine and 4,4'-bipy=4,4'-bipyridine)has been synthesized and characterized by singlecrystal X-ray diffraction,elemental analysis,IR spectra and thermogravimetric analysis.It crystallizes in monoclinic,space group P2/c with a=15.5420(7),b=22.4344(1),c=8.3455(5)(A),β=101.538(3)°,V=2670.1(7)(A)3,Z=4,C22H32N4NiO13,Mr=619.23,Dc=1.443 g/cm3,F(000)=1296.0,μ(MoKa)=0.750 mm-1,the final R=0.0570 and wR=0.1445 for 2296 observed reflections with I>2σ(I).In the structure,the NiⅡ metal center is coordinated in an octahedral environment arranged by two water molecules,two carboxylate oxygen atoms and two nitrogen atoms from two4,4'-bipy ligands.Thermal decomposition and powder X-ray diffraction results indicate that the transformation from the crystal form,[{Ni(IBG)(4,4'-bipy)(H2O)2}·3H2O]n,to the amorphous powder,Ni(IBG)(4,4'-bipy)(H2O)2,is reversible,so the latter form may be utilized as an absorbing agent for water and water vapor.     

Amine-templated linear vanadium sulfates with different chain structures

Amine-templated vanadium sulfates of the formula [HN(CH(2))(6)NH][(V(IV)O)(2)(OH)(2)(SO(4))(2)].H(2)O, I, [H(3)N(CH(2))(2)NH(3)][V(III)(OH)(SO(4))(2)].H(2)O, II, and [H(2)N(CH(2))(4)NH(2)][(V(IV)O)(H(2)O)(SO(4))(2)], III, have been prepared under hydrothermal conditions. These vanadium sulfates add to the new emerging family of organically templated metal sulfates. Compound I has a linear chain structure consisting of V(2)O(8) square-pyramid dimers connected by corner-sharing SO(4) tetrahedra, creating four-membered rings along the chain. Both II and III possess simple linear chain topologies formed by VO(6) octahedra and SO(4) tetrahedra, with II having the tancoite chain structure. Compound I crystallizes in the triclinic space group P1 (No. 2) with a = 7.4852(4) A, b = 9.5373(5) A, c = 11.9177(6) A, alpha = 77.22 degrees, beta = 76.47(2) degrees, gamma = 80.86 degrees, Z = 2. Compound II: monoclinic, space group P2(1)/c (No. 14), a = 6.942(2) A, b = 10.317(3) A, c = 15.102(6) A, beta = 90.64(4) degrees, Z = 4. Compound III: triclinic, space group P1 (No. 2) with a = 6.2558(10) A, b = 7.0663(14) A, c = 15.592(4) A, alpha = 90.46(2) degrees, beta = 90.47(2) degrees, gamma = 115.68(2) degrees, Z = 2. Magnetic susceptibility measurements reveal weak antiferromagnetic interactions in I and III and ferromagnetic interactions in II.