Solid state coordination chemistry of metal oxides: structural consequences of fluoride incorporation into the oxovanadium-copper-bisterpy-{O3P(CH2)nPO3}4- system, n= 1-5 (bisterpy = 2,2':4',4":2",2"'-quaterpyridyl-6', 6"-di-2-pyridine)

Hydrothermal reactions of a vanadate source, an appropriate Cu(II) source, bisterpy and an organodiphosphonate, H2O3P(CH2)nPO3H2(n= 1-5), in the presence of HF, yielded a family of materials of the type oxyfluorovanadium/copper-bisterpy/organodiphosphonate. Under similar reaction conditions, variations in diphosphonate tether length n provided the one-dimensional [{Cu2(bisterpy)}V2F2O2{HO3PCH2PO3}{O3PCH2PO3}](1) and [{Cu2(bisterpy)}V2F4O4{HO3P(CH2)2PO3H}](3), the two-dimensional [{Cu2(bisterpy)}V2F2O2(H2O)2{HO3P(CH2)2PO3}2] x 2H2O (2 x 2H2O), [{Cu2(bisterpy)(H2O2}V2F2O2{O3P(CH2)3PO3}{HO3P(CH2)3PO3H}(4) and [{Cu2(bisterpy)}V4F4O4(OH)(H2O){HO3P(CH2)5PO3}{O3P(CH2)5PO3}] x H2O (9 x H2O) and the three-dimensional [{Cu2(bisterpy)}3V8F6O17{HO3P(CH2)3PO3}4]0.8H2O (5 x 0.8H2O), [{Cu2(bisterpy)}V4F2O6{O3P(CH2)4PO3}2](8) and [{Cu2(bisterpy)(H2O)}2V8F4O8(OH)4{HO3P(CH2)5PO3H}2{O3P(CH2)5PO)}3] x 4.8H2O (10 x 4.8H2O). In addition, two members of the oxovanadium/Cu2(bisterpy)/organodiphosphonate family [{Cu2(bisterpy)}V2O4{HO3P(CH2)3PO3}2](6) and [{Cu2(bisterpy)}3V4O8(OH)2{O3P(CH2)3PO3}2{HO3P(CH2)3PO3}2] x 5H2O (7 x 5H2O) cocrystallized from the reaction mixture which provided 5. The overall architectures reveal embedded substructures based on V/P/O(F) clusters, chains, networks, and frameworks. In contrast to the oxovanadium/Cu2(bisterpy)/ organodiphosphonate family, several of the materials of this study also exhibit the direct condensation of vanadium polyhedra to produce binuclear and/or tetranuclear building units.     

Organic-inorganic hybrid materials: hydrothermal syntheses and structural characterization of bimetallic organophosphonate oxides of the type Mo/Cu/O/RPO(3)(2-)/organoimine

The hydrothermal reactions of a Cu(II) starting material, a molybdate source, 2,2'-bipyridine or terpyridine, and the appropriate alkyldiphosphonate ligand yield two series of bimetallic organophosphonate hybrid materials of the general types [Cu(n)(bpy)(m)Mo(x)O(y)(H(2)O)(p)[O(3)P(CH(2))(n)PO(3)](z)] and [Cu(n)(terpy)(m)Mo(x)O(y)(H(2)O)(p)[O(3)P(CH(2))(n)PO(3)](z)]. The bipyridyl series includes the one-dimensional materials [Cu(bpy)(MoO(2))(H(2)O)(O(3)PCH(2)PO(3))] (1) and [[Cu(bpy)(2)][Cu(bpy)(H(2)O)](Mo(5)O(15))(O(3)PCH(2)CH(2)CH(2)CH(2)PO(3))].H(2)O (5.H(2)O) and the two-dimensional hybrids [Cu(bpy)(Mo(2)O(5))(H(2)O)(O(3)PCH(2)PO(3))].H(2)O (2.H(2)O), [[Cu(bpy)](2)(Mo(4)O(12))(H(2)O)(2)(O(3)PCH(2)CH(2)PO(3))].2H(2)O (3.2H(2)O), and [Cu(bpy)(Mo(2)O(5))(O(3)PCH(2)CH(2)CH(2)PO(3))](4). The terpyridyl series is represented by the one-dimensional [[Cu(terpy)(H(2)O)](2)(Mo(5)O(15))(O(3)PCH(2)CH(2)PO(3))].3H(2)O (7.3H(2)O) and the two-dimensional composite materials [Cu(terpy)(Mo(2)O(5))(O(3)PCH(2)PO(3))] (6) and [[Cu(terpy)](2)(Mo(5)O(15))(O(3)PCH(2)CH(2)CH(2)PO(3))] (8). The structures exhibit a variety of molybdate building blocks including isolated [MoO(6)] octahedra in 1, binuclear subunits in 2, 4, and 6, tetranuclear embedded clusters in 3, and the prototypical [Mo(5)O(15)(O(3)PR)(2)](4-) cluster type in 5, 7, and 8. These latter materials exemplify the building block approach to the preparation of extended structures.     

Methanesulfonates of high-valent metals: syntheses and structural features of MoO2(CH3SO3)2, UO2(CH3SO3)2, ReO3(CH3SO3), VO(CH3SO3)2, and V2O3(CH3SO3)4 and their thermal decomposition under N2 and O2 atmosphere

Oxide methanesulfonates of Mo, U, Re, and V have been prepared by reaction of MoO(3), UO(2)(CH(3)COO)(2)·2H(2)O, Re(2)O(7)(H(2)O)(2), and V(2)O(5) with CH(3)SO(3)H or mixtures thereof with its anhydride. These compounds are the first examples of solvent-free oxide methanesulfonates of these elements. MoO(2)(CH(3)SO(3))(2) (Pbca, a=1487.05(4), b=752.55(2), c=1549.61(5) pm, V=1.73414(9) nm(3), Z=8) contains [MoO(2)] moieties connected by [CH(3)SO(3)] ions to form layers parallel to (100). UO(2)(CH(3)SO(3))(2) (P2(1)/c, a=1320.4(1), b=1014.41(6), c=1533.7(1) pm, β=112.80(1)°, V=1.8937(3) nm(3), Z=8) consists of linear UO(2)(2+) ions coordinated by five [CH(3)SO(3)] ions, forming a layer structure. VO(CH(3)SO(3))(2) (P2(1)/c, a=1136.5(1), b=869.87(7), c=915.5(1) pm, β=113.66(1)°, V=0.8290(2) nm(3), Z=4) contains [VO] units connected by methanesulfonate anions to form corrugated layers parallel to (100). In ReO(3)(CH(3)SO(3)) (P1, a=574.0(1), b=1279.6(3), c=1641.9(3) pm, α=102.08(2), β=96.11(2), γ=99.04(2)°, V=1.1523(4) nm(3), Z=8) a chain structure exhibiting infinite O-[ReO(2)]-O-[ReO(2)]-O chains is formed. Each [ReO(2)]-O-[ReO(2)] unit is coordinated by two bidentate [CH(3)SO(3)] ions. V(2)O(3)(CH(3)SO(3))(4) (I2/a, a=1645.2(3), b=583.1(1), c=1670.2(3) pm, β=102.58(3), V=1.5637(5) pm(3), Z=4) adopts a chain structure, too, but contains discrete [VO]-O-[VO] moieties, each coordinated by two bidentate [CH(3)SO(3)] ligands. Additional methanesulfonate ions connect the [V(2)O(3)] groups along [001]. Thermal decomposition of the compounds was monitored under N(2) and O(2) atmosphere by thermogravimetric/differential thermal analysis and XRD measurements. Under N(2) the decomposition proceeds with reduction of the metal leading to the oxides MoO(2), U(3)O(7), V(4)O(7), and VO(2); for MoO(2)(CH(3)SO(3))(2), a small amount of MoS(2) is formed. If the thermal decomposition is carried out in a atmosphere of O(2) the oxides MoO(3) and V(2)O(5) are formed.     

Solid state coordination chemistry of the copper(ii)-terpyridine/oxovanadium organophosphonate system: hydrothermal syntheses, structural characterization and magnetic properties

The hydrothermal reactions of CuSO4.5H2O, Na3VO4, 2,2':6':2'-terpyridine (terpy), and the appropriate organophosphonate ligand yield a series of materials of the Cu(ii)-terpy/oxovanadium organophosphonate family. The complexes exhibit distinct structures spanning one-, two- and three-dimensions and exhibiting diverse oxovanadium building blocks. Thus, [{Cu(terpy)}(V2O4)(O3PPh)(HO3PPh)2] (1) is one-dimensional and constructed from binuclear units of corner-sharing V(v) square pyramids. While [{Cu(terpy)}VO(O3PCH2PO3)] (2), [{Cu(terpy)}2(V4O10)(O3PCH2CH2PO3)] (3), and [{Cu(terpy)}(V2O4){O3P(CH2)3PO3}].2.5H(2)O (4.2.5H2O) are similarly one-dimensional, the V/O structural components consist of isolated V(iv) square pyramids, tetranuclear V(v) units of three tetrahedra and one square pyramid in a corner-sharing arrangement, and isolated V(v) tetrahedra and square pyramids, respectively. The second propylenediphosphonate derivative, [{Cu(terpy)}(V2O4){O3P(CH2)3PO3}] (5) is three-dimensional and exhibits isolated V(v) tetrahedra as the vanadate component. The two-dimensional structure of [{Cu(terpy)(H2O)}(V3O6){O3P(CH2)4PO3}] (6) is mixed valence with isolated V(iv) square pyramids and binuclear units of corner-sharing V(v) tetrahedra providing the V/O substructures.     

A building block approach to the synthesis of organic-inorganic oxide materials: the hydrothermal synthesis and network structure of [[Ni4(tpypyz)3][Mo5O15(O3PCH2CH2PO3)]2] x 23H2O (tpypyz = tetra-2-pyridylpyrazine)

The hydrothermal reaction of MoO3, [Ni(CH3CO2)2] x 4H2O, tpypyz, ethylenediphosphonic acid and water yields the 2D material [[Ni4(tpypyz)3][Mo5O15(O3PCH2CH2PO3)]2] x 23H2O (1 x 23H2O), constructed from [Mo5O15(O3PCH2CH2PO3)]4- clusters linked in one-dimension through the ethylene tethers of the diphosphonate component; these molybdodiphosphonate chains are in turn linked into a 2D network through the tetranuclear secondary metal-ligand subunit [Ni4(tpypyz)3]8+.     

Hydrothermal Synthesis and Crystal Structure of a New Phosphonate： {[Cu（1,10-phen）]2-（H2O3PCH2C6H4C6H4CH2PO3H）2-（HO3PCH2C6H4C6H4CH2PO3H） }n

1 INTRODUCTION Metal organophosphonates have attracted considerable attention for over three decades due to their potential or practical applications, include- ing ion exchanges[1, 2], molecular sensors[3] and optics[4, 5]. Recently, a number of porous m…     

A meso-helical coordination polymer from achiral dinuclear [Cu2(H3CCN)2(micro-pydz)3][PF6]2 and 1,3-bis(diphenylphosphanyl)propane-synthesis and crystal structure of 1 to infinity Cu(mu-pydz)2][PF6 (pydz=pyridazine)

Reaction of achiral [Cu2(H3CCN)2(mu-pydz)3][PF6]2 (1) (pydz = pyridazine) with bidendate 1,3-bis(diphenylphosphanyl)propane (2) in acetonitrile at room temperature in a 1:1 ratio yielded the mononuclear copper(I) complex [Cu[CH2(CH2PPh2)2]2][PF6] (3) together with new one-dimensional coordination polymer 1 to infinity[[Cu(mu-pydz)2][PF6]] (4). Air-sensitive single crystals of 4, suitable for X-ray structure determination, were grown from a mixture of dichloromethane/ hexane [crystal system: monoclinic; space group: C2/c: a = 21.910(3), b = 12.130(2), c = 25.704(3) A,beta = 110.08(10) degrees, V = 6416.65(16) A3]. The one-dimensional coordination polymer 1 to infinity[[Cu(mu-pydz)2][PF6]] (4) exhibits as outstanding feature the rare structure of a meso-helix.     

Intra and intermolecular magnetic interactions in a series of dinuclear Cu(II)/hxta complexes [H5hxta = N,N'-(2-hydroxy-1,3-xylylene)-bis-(N-carboxymethylglycine)]: correlation of magnetic properties with geometry

Nine dinuclear copper(II) complexes with hxta5- ligands [H5hxta = N,N'-(2-hydroxy-1,3-xylylene)-bis-(N-carboxymethylglycine)]: [Cu2(MeO-hxtaH)(H2O)2] x 4H2O (1), [Na(micro-H2O)2(H2O)6][Cu2(Cl-hxta)(H2O)3]2 x 6H2O (2), [Cu(H2O)6][Cu2(Me-hxta)(H2O)2](NO3) x 2H2O (3), [Cu2(R-hxtaH)(H2O)3] x 3H2O [R = Cl (4), CH3 (5), and MeO (6)], [Cu2(MeO-hxtaH2)(micro-X)(CH3OH)] x 3CH3OH [X = Cl (7), Br (8)] and K5Na(micro-H2O)10[Cu2(micro-CO3)(Me-hxta)]2 x 4H2O (9), have been synthesized and structurally characterized. In complexes 4-7, the dinuclear units are linked via novel pairwise supramolecular interactions involving the ligand carboxylate groups. The intra- and intermolecular magnetic interactions have been quantified, and the coupling constants have been related to the structural geometries.     

Synthesis of layered (2-D) V-based bimetallic oxalates from non-aqueous media that cannot be synthesized from aqueous media

The reaction of (NBu4)3[V(III)(ox)3] (1, ox = oxalate) and M(II) (M = Fe, Co, Ni, Cu) ions in MeCN, leads to the isolation of V-based coordination polymers of [N(n-Bu)4][Fe(II)V(II)I(ox)3].0.30[[N(n-Bu)4](BF4)] (2), [N(n-Bu)4][Co(II)V(III)(ox)3].0.75[[N(n-Bu)4](BF4)] (3), [N(n-Bu)4][Ni(II)V(III)(ox)3].0.20[[N(n-Bu)4](BF4)].0.20MeCN (4), and [N(n-Bu)4][Cu(II)V(III)(ox)2](BF4)2 (5) composition. Due to the lability of [V(III)(ox)3]3- to dissociate ox2-, these compounds cannot be prepared from aqueous media. 5 is best described as [N(n-Bu)4][V(III)Cu(II)(ox)2](BF4)2, and 2, 3, 4, and 5 are proposed to have a layered (2-D) motif for the MM(ox)x (x = 2, 3) extended framework. The [V(III)Cu(II)(ox)2] composition of 5 is reported for the first time for a bimetallic oxalate. 2 shows a weak antiferromagnetic interaction between Fe(II), S = 2 and V(III), S = 1 ions (theta = -9.4 K) within the 2-D layers. 3 and 5 do not magnetically order above 2 K. 4 magnetically order as ferromagnets below 2.55 K [taken as the onset of magnetization in chi'(T)], and has a glass transition temperature (chi'(max) at 1000 Hz) at 2.26 K.     

Heterometallic CeIII-FeIII-salicylate networks: models for corrosion mitigation of steel surfaces by the 'green' inhibitor,Ce(salicylate)3

The syntheses and structures of the novel Ce-Fe bimetallic complexes [[Fe(sal)2(bpy)]2Ce(NO3)(H2O)3].EtOH and [[Fe(sal)2(bpy)]4Ce2(H2O)11][salH]2.EtOH.3H2O (salH2 = salicylic acid) suggest Fe(3+)-sal2- units and Ce-OC(R)O-Fe bridging contribute to the formation of corrosion inhibitive layers on steel surfaces exposed to [Ce(salH)3(H2O)].     

Hydrothermal syntheses and structural characterizations of organic-inorganic hybrid materials of the M(II)-ligand/vanadium oxide system (M(II) = Cu(II) and Zn(II); ligand = 2,2'-bipyridine and 2,2':6',2"-terpyridine)

Investigation into the incorporation of complex transition metal-organic units into vanadium oxide structures has resulted in the preparation of several novel composite materials. Hydrothermal reactions of V(2)O(5), 2,2'-bipyridine, an appropriate Zn or Cu starting material, and H(2)O under a variety of conditions yielded the organic-inorganic hybrid materials [[Zn(2,2'-bpy)](2)V(4)O(12)] (1) and [Cu(2,2'-bpy)V(4)O(10.5)] (2). Blocking an additional coordination site on the secondary metal center by using a tridentate organonitrogen ligand, 2,2':6',2' '-terpyridine in place of 2,2'-bipyridine, allowed the isolation of [Cu(terpy)V(2)O(6)] (3) and [[Zn(terpy)](2)V(6)O(17)] (4). The structure of 1 is a two-dimensional zinc vanadate layer, composed of rings containing four corner-sharing [VO(4)] vanadium(V) tetrahedra linked through six zinc square pyramids, with the 2,2'-bipyridine groups attached to the zinc centers and directed above and below the plane of the layer. In contrast to 1, the layer of 2 is based on a two-dimensional vanadium oxide substructure composed of vanadium(IV) square pyramids and vanadium(V) tetrahedra with copper square pyramids attached through corner-sharing interactions with vanadium tetrahedra such that the bipyridine ligands attached to the copper sites form staggered stacks above and below the plane of the layer. Compound 3 consists of one-dimensional vanadium oxide chains of corner-sharing tetrahedra linked through copper-terpyridine units into a two-dimensional bimetallic oxide of composition [CuV(2)O(6)], while the layer structure of 4 contains more complex one-dimensional vanadium oxide chains composed of fused rings of six corner-sharing vanadium oxide tetrahedra which are linked into a layer through [Zn(terpy)](2+) units.     

Ligand influences on copper molybdate networks: the structures and magnetism of [Cu(3,4'-bpy)MoO(4)], [Cu(3,3'-bpy)(0.5)MoO(4)], and [Cu(4,4'-bpy)(0.5)MoO(4)].1.5H(2)O

The reactions of a Cu(II) salt, MoO(3), and the appropriate bipyridine ligand yield a series of bimetallic oxides, [Cu(3,4'-bpy)MoO(4)] (1), [Cu(3,3'-bpy)(0.5)MoO(4)] (2), and [Cu(4,4'-bpy)(0.5)MoO(4)].1.5H(2)O (3.1.5H(2)O). The structures of 1-3 exhibit three-dimensional covalent frameworks, constructed from bimetallic oxide layers tethered by the dipodal organoimine ligands. However, the [CuMoO(4)] networks are quite distinct. For structure 1, the layer consists of corner-sharing [MoO(4)] tetrehedra and [CuN(2)O(3)] square pyramids, while the layer of 2 is constructed from [MoO(4)] tetrehedra and binuclear [Cu(2)O(6)N(2)] units of edge-sharing copper square pyramids. The oxide substructure of 3 consists of [MoO(4)] tetrahedra corner-sharing with tetranuclear clusters of edge-sharing [CuO(5)N] octahedra. Crystal data: C(10)H(8)N(2)O(4)CuMo (1), orthorhombic Pbca, a = 12.4823(6) A, b = 9.1699(4) A, c = 19.5647(9) A, V = 2239.4(1) A(3), Z = 8; C(5)H(4)NO(4)CuMo (2), triclinic P, a = 5.439(1) A, b = 6.814(1) A, c = 10.727(2) A, alpha = 73.909(4)(o), beta = 78.839(4)(o); gamma = 70.389(4)(o); V = 357.6(1) A(3), Z = 2; C(10)H(8)N(2)O(8)Cu(2)Mo(2).3H(2)O 3.1.5H(2)O, triclinic P, a = 7.4273(7) A, b = 9.2314(8) A, c = 13.880(1) A, alpha = 71.411(2)(o), beta = 88.528(2)(o), gamma = 73.650(2)(o), V = 863.4(1) A(3), Z = 2. The magnetic properties of 1-3 arise solely from the presence of the Cu(II) sites, but reflect the structural differences within the bimetallic oxide layers. Compound 1 exhibits magnetic behavior consistent with ferromagnetic chains which couple antiferromagnetically at low temperature. Compound 2 exhibits strong antiferromagnetic dimeric interactions, with the magnetic susceptibility data consistent with the Bleaney-Bowers equation. Similarly, the magnetic susceptibility of 3 is dominated by antiferromagnetic interactions, which may be modeled as a linear S = 1/2 Heisenberg tetramer.     

Tri- and pentanuclear tungsten-(mu-S)-M clusters (M = W, Cu, Ag)

The thiotungstate [Et4N]2[OW(WS4)2], [Et4N]2.1, containing the linear [[S2W(VI)(mu-S)2]2W(IV)=O] core, was prepared from [Et4N]2[WS4] in the presence of the sulfide scavenger Cd2+. Addition of 1,2-bis(o-diphenylphosphinophenyl)ethane (diphosphine) and Cu+ or Ag+ to solutions of 1 in MeCN/DMF led to coordination of the (diphosphine)Cu/Ag fragments to the terminal sulfido ligands of 1, yielding novel linear pentanuclear, heterometallic clusters [mu-[OW(IV)(DMF)(W(VI)S4)2][M(diphosphine)]2], 2 (M = Cu) and 3 (M = Ag). Along with 2, the trinuclear cluster [[mu-(W(VI)S4)[Cu(diphosphine)(2)]], 4, was also obtained. The molecular and crystal structures of [Et4N]2.1, 2.MeCN, 3.MeCN, and 4.2MeCN.CH2Cl2 have been determined.     

Solid-state coordination chemistry of the oxomolybdate-organodiphosphonate/nickel-organoimine system: structural influences of the secondary metal coordination cation and diphosphonate tether lengths

The hydrothermal reactions of a molybdate source, a nickel(II) salt, tetra-2-pyridylpyrazine (tpyprz), and organodiphosphonic acids H(2)O(3)P(CH(2))(n)()PO(3)H(2) (n = 1-5) of varying tether lengths yielded a series of organic-inorganic hybrid materials of the nickel-molybdophosphonate family. A persistent characteristic of the structural chemistry is the presence of the [Mo(5)O(15)(O(3)PR)(2)](4)(-) cluster as a molecular building block, as noted for the one-dimensional materials [[Ni(2)(tpyprz)(2)]Mo(5)O(15)[O(3)P(CH(2))(4)PO(3)]]x6.65H(2)O (6x6.65H(2)O) and [[Ni(2)(tpyprz)(2)]Mo(5)O(15)[O(3)P(CH(2))(5)PO(3)]]x3.75H(2)O (8x3.75H(2)O), the two-dimensional phases [[Ni(4)(tpyprz)(3)][Mo(5)O(15)(O(3)PCH(2)CH(2)PO(3))](2)]x23H(2)O (3x23H(2)O) and [[Ni(3)(tpyprz)(2)(H(2)O)(2)](Mo(5)O(15))(Mo(2)O(4)F(2))[O(3)P(CH(2))(3)PO(3)](2)]x8H(2)O (5x8H(2)O), and the three-dimensional structures [[Ni(2)(tpyprz)(H(2)O)(3)]Mo(5)O(15)[O(3)P(CH(2))(3)PO(3))]]xH(2)O (4xH(2)O) and [[Ni(2)(tpyprz)(H(2)O)(2)]Mo(5)O(15) [O(3)P(CH(2))(4)PO(3)]]x2.25H(2)O (7x2.25H(2)O). In the case of methylenediphosphonic acid, the inability of this ligand to tether adjacent pentanuclear clusters precludes the formation of the common molybdophosphonate building block, manifesting in contrast a second structural motif, the trinuclear [(Mo(3)O(8))(x)(O(3)PCH(2)PO(3))(y)] subunit of [[Ni(tpyprz)(H(2)O)(2)](Mo(3)O(8))(2) (O(3)PCH(2)PO(3))(2)] (1) which had been previously observed in the corresponding methylenediphosphonate phases of the copper-molybdophosphonate family. Methylenediphosphonic acid also provides a second phase, [Ni(2)(tpyprz)(2)][Mo(7)O(21)(O(3)PCH(2)PO(3))]x3.5H(2)O (9x5H(2)O), which contains a new heptamolybdate cluster [Mo(7)O(21)(O(3)PCH(2)PO(3))](4)(-) and a cationic linear chain [Ni(tpyprz)](n)(4n+) substructure. The structural chemistry of the nickel-molybdophosphonate series contrasts with that of the corresponding copper-molybdophosphonate materials, reflecting in general the different coordination preferences of Ni(II) and Cu(II). Consequently, while the Cu(II)-organic complex building block of the copper family is invariably the binuclear [Cu(2)(tpyprz)](4+) subunit, the Ni(II) chemistry with tpyprz exhibits a distinct tendency toward catenation to provide [Ni(3)(tpyprz)(2)](6+), [Ni(4)(tpyprz)(3)](8+), and [Ni(tpyprz)](n)(4n+) building blocks as well as the common [Ni(2)(tpyprz)](4+) moiety. This results in a distinct structural chemistry for the nickel(II)-molybdophosphonate series with the exception of the methylenediphosphonate derivative 1 which is isostructural with the corresponding copper compound [[Cu(2)(tpyprz)(H(2)O)(2)](Mo(3)O(8))(2)(O(3)PCH(2)PO(3))] (2). The structural chemistry of the nickel(II) series also reflects variability in the number of attachment sites at the molybdophosphonate clusters, in the extent of aqua ligation to the Ni(II) tpyprz subunit, and in the participation of phosphate oxygen atoms as well as molybdate oxo groups in linking to the nickel sites.     

The hydrothermal syntheses and characterization of one- and two-dimensional structures constructed from metal-organic derivatives of polyoxometalates: [(Cu(bpy)2)(Cu(bpy)(H2O))(Mo5O15)(O3P(CH2)4PO3)].H2O and [(u2(tpypyz)(H2O)2)(Mo5O15)(O3PCH2CH2PO3)].5.5H2O [bpy = 2,2'-bipyridine,tpypyz = tetra(2-pyridyl)pyrazine

The hydrothermal reaction of CuSO(4).5H2O, Na2MoO(4).2H2O and 2,2'-bipyridine with the bridging diphosphonate ligand H2O3P(CH2)4PO3H2 yields the one-dimensional chain [(Cu(bpy)2)(Cu(bpy)(H2O)2)(Mo5O15)(O3P(CH2)4PO3)].H2O; the introduction of a second bridging component in the reaction of Cu(MeCO2)2.H2O, MoO3, H2O3PCH2CH2PO3H2 and tetra(2-pyridyl)pyrazine yields the network solid [(Cu2(tpypyz)(H2O)2)(Mo5O15)(O3PCH2CH2PO3)].5.5H2O.     

Structural diversity of the oxovanadium organodiphosphonate system: a platform for the design of void channels

The hydrothermal reactions of a vanadium source, an appropriate diphosphonate ligand, and water in the presence of HF provide a series of compounds with neutral V-P-O networks as the recurring structural motif. When the {O3P(CH2)(n)PO3}4- diphosphonate tether length n is 2-5, metal-oxide hybrids of type 1, [V2O2(H2O){O3P(CH2)(n)PO3}] x xH2O, are isolated. The type 1 oxides exhibit the prototypical three-dimensional (3-D) "pillared" layer architecture. When n is increased to 6-8, the two-dimensional (2-D) "pillared" slab structure of the type 2 oxides [V2O2(H2O)4{O3P(CH2)6PO3}] is encountered. Further lengthening of the spacer to n = 9 provides another 3-D structure, type 3, constructed from the condensation of pillared slabs to give V-P-O double layers as the network substructure. When organic cations are introduced to provide charge balance for anionic V-P-O networks, oxides of types 4-7 are observed. For spacer length n = 3, a range of organodiammonium cations are accommodated by the same 3-D "pillared" layer oxovanadium diphosphonate framework in the type 4 materials [H3N(CH2)(n)NH3][V4O4(OH)2 {O3P(CH)3PO3}2] x xH2O [n = 2, x = 6 (4a); n = 3, x = 3 (4b); n = 4, x = 2 (4c); n = 5, x = 1 (4d); n = 6, x = 0.5 (4e); n = 7, x = 0 (4f)] and [H3NR]y[V4O4(OH)2 {O3P(CH)3PO3}2] x xH2O [R = -CH2(NH3)CH2CH3, y = 1, x = 0 (4g); R = -CH3, n = 2, x = 3 (4h); R = -CH2CH3, y = 2, x = 1 (4i); R = -CH2CH2CH3, y = 2, x = 0 (4j); cation = [H2N(CH2CH3)2], y = 2, x = 0 (4k)]. These oxides exhibit two distinct interlamellar domains, one occupied by the cations and the second by water of crystallization. Furthermore, as the length of the cation increases, the organodiammonium component spills over into the hydrophilic domain to displace the water of crystallization. When the diphosphonate tether length is increased to n = 5, structure type 5, [H3N(CH2)2NH3][V4O4(OH)2(H2O){O3P(CH2)5PO3}2] x H2O, is obtained. This oxide possesses a 2-D "pillared" network or slab structure, similar in gross profile to that of type 2 oxides and with the cations occupying the interlamellar domain. In contrast, shortening the diphosphonate tether length to n = 2 results in the 3-D oxovanadium organophosphonate structure of the type 7 oxide [H3N(CH2)5NH3][V3O3{O3P(CH2)2PO3}2]. The ethylenediphosphonate ligand does not pillar V-P-O networks in this instance but rather chelates to a vanadium center in the construction of complex polyhedral connectivity of 7. Substitution of piperazinium cations for the simple alkyl chains of types 4, 5, and 7 provides the 2-D pillared layer structure of the type 6 oxides, [H2N(CH2CH2)NH2][V2O2{O3P(CH)(n)PO3H}2] [n = 2 (6a); n = 4 (6b); n = 6 (6c)]. The structural diversity of the system is reflected in the magnetic properties and thermal behavior of the oxides, which are also discussed.     

Synthesis, chemistry and structures of complexes of the dioxovanadium(V) halides VO2F and VO2Cl

[VO2F(L-L)] (L-L = 2,2'-bipyridyl, 1,10-phenanthroline, Me2N(CH2)2NMe2) and [VO2F(py)2] (py = pyridine) have been prepared from the corresponding [VOF3(L-L)] or [VOF3(py)2] and O(SiMe3)2 in MeCN solution. VO2F (itself made from VOF3 and O(SiMe3)2 in MeCN) forms [Me4N][VO2F2] with [Me4N]F, but does not react with neutral N- or O-donor ligands. VO2Cl, prepared from VOCl3 and ozone, reacts with 2,2'-bipyridyl or 1,10-phenanthroline to form [VO2Cl(L-L)], with pyridine or pyridine-N-oxide (L) to produce [VO2Cl(L)2], and with OPPh3 or OAsPh3 (L') gives [VO2Cl(L')]. A second product from the OPPh3 system is the ionic [VO2(OPPh3)3][VO2Cl2] containing a trigonal bipyramidal cation. Neither VO2F nor VO2Cl form isolable complexes with MeCN, thf or MeO(CH2)2OMe, and both are reduced by P-, As-, S- or Se-donor ligands. [Ph4As][VO2X2] (X = F or Cl) react with 2,2'-bipyridyl to form [VO2X(2,2'-bipyridyl)], but similar reactions with weaker O-donor ligands fail. The complexes have been characterised by IR, multinuclear NMR (1H, 19F, 51V or 31P) and UV-visible spectroscopy. X-ray crystal structures are reported for [VO2F(py)2], [VO2Cl(L)2] (L = py or pyNO) and [VO2(OPPh3)3][VO2Cl2].     

Syntheses and Properties of New Layered Alkali-Metal/Ammonium Vanadium(V) Methylphosphonates: M(VO(2))(3)(PO(3)CH(3))(2) (M = NH(4), K, Rb, Tl). Single-Crystal Structures of K(VO(2))(3)(PO(3)CH(3))(2) and NH(4)(VO(2))(3)(PO(3)CH(3))(2)

The hydrothermal syntheses of a family of new alkali-metal/ammonium vanadium(V) methylphosphonates, M(VO(2))(3)(PO(3)CH(3))(2) (M = K, NH(4), Rb, Tl), are described. The crystal structures of K(VO(2))(3)(PO(3)CH(3))(2) and NH(4)(VO(2))(3)(PO(3)CH(3))(2) have been determined from single-crystal X-ray data. Crystal data: K(VO(2))(3)(PO(3)CH(3))(2), M(r) = 475.93, trigonal, R32 (No. 155), a = 7.139(3) ?, c = 19.109(5) ?, Z = 3; NH(4)(VO(2))(3)(PO(3)CH(3))(2), M(r) = 454.87, trigonal, R32 (No. 155), a = 7.150(3) ?, c = 19.459(5) ?, Z = 3. These isostructural, noncentrosymmetric phases are built up from hexagonal tungsten oxide (HTO) like sheets of vertex-sharing VO(6) octahedra, capped on both sides of the V/O sheets by PCH(3) entities (as [PO(3)CH(3)](2-) methylphosphonate groups). In both phases, the vanadium octahedra display a distinctive two short + two intermediate + two long V-O bond distance distribution within the VO(6) unit. Interlayer potassium or ammonium cations provide charge balance for the anionic (VO(2))(3)(PO(3)CH(3))(2) sheets. Powder X-ray, TGA, IR, and Raman data for these phases are reported and discussed. The structures of K(VO(2))(3)(PO(3)CH(3))(2) and NH(4)(VO(2))(3)(PO(3)CH(3))(2) are compared and contrasted with related layered phases based on the HTO motif.     

First hexadecavanadate compound: hydrothermal synthesis and characterization of a three-dimensional framework [(Cu(1,2-pn)2)7(V16O38(H2O))2].4H2O

The hydrothermal reaction of V2O5, Cu(CH3COO)2.H2O, 1,2-diaminopropane and [N(CH3)4]OH yields the novel three-dimensional open-framework solid [(Cu(1,2-pn)2)7-(V16O38(H2O))2].4H2O constructed from the new mixed-valence [V16O38(H2O)]7- clusters interconnected through mu 2-[Cu(1,2-pn)2]2+ groups.     

Racemic monoperoxovanadium(V) complexes with achiral OO and ON donor set heteroligands: synthesis, crystal structure and stereochemistry of [NH3(CH2)2NH3][VO(O2)(ox)(pic)].2H2O and [NH3(CH2)2NH3][VO(O2)(ox)(pca)

Monoperoxovanadium(V) complexes, [NH3(CH2)2NH3][VO(O2)(ox)(pic)].2H2O (1) and [NH3(CH2)2NH3][VO(O2)(ox)(pca)] (2) [NH3(CH2)2NH3 = ethane-1,2-diammonium(2+), ox=oxalate(2-), pic=pyridine-2-carboxylate(1-), pca=pyrazine-2-carboxylate(1-)], were synthesized and characterized by X-ray analysis, IR and Raman spectroscopies. The five equatorial positions of the pentagonal bipyramid around the vanadium atoms are occupied by the eta2-peroxo ligand, two oxygen atoms of the ox, and the nitrogen atom of the pic or pca ligands, respectively. The oxo ligand and the oxygen atom of pic or pca are in the axial positions. Networks of X-HO (X=C, N or O) hydrogen bonds, and pi-pi interactions between aromatic rings in and anion-pi interactions in , determine the molecular packings and build up the supramolecular architecture. Three stereochemical rules for occupation of the donor sites in two-heteroligand [VO(O2)(L1)(L2)] complexes (L1, L2 are bidentate neutral or differently charged anionic heteroligands providing an OO, NN or ON donor set) are discussed. and crystallize as racemic compounds. The 51V NMR spectra proved that the parent complex anions of and partially decompose on dissolution in water to the monoperoxo-ox, -pic or -pca complexes.