Alkaline and alkaline earth metal complexes of dianhydride derivatives of clodronate and their hydrolysis products.

Alkaline and alkaline earth metal complexes of P,P'-diacetyl- (L1(2-)); new P,P'-dipropanoyl- (L2(2-)) and P,P'-dibenzoyl(dichloromethylene)bisphosphonates (L3(2-)) and their hydrolysis products were prepared and characterized using the single-crystal X-ray diffraction technique and spectroscopy, with the intention of studying the hydrolysis and coordinating properties of these potential prodrugs of clodronate. Na(2)L1 and Na(2)L2 formed the first crystalline hydrolysis product of these dianhydrides, 3D polymeric trisodium clodronate, [Na(3){Cl(2)C(PO(3))(2)}(H(2)O)(4)](n) (1). The other metal complexes prepared comprised the polymeric Ba(2+) complex of L1(2-) ligand [Ba{Cl(2)C(PO(2)O(C(O)Me))(2)}(H(2)O)(3)](n) (2); the new Sr(2+) complex of clodronic acid [{Sr(2)(Cl(2)C(PO(3))(2))(H(2)O)(4)}.H(2)O](n) (3), and the K(+) complex of the L3(2-) ligand [{K(2)Cl(2)C(PO(2)O(C(O)C(6)H(5)))(2)}O](n) (4). In addition, these L1(2-)-L3(2-) ligands have formed the same, previously published [NaMgCl(2)CP(2)O(6)H)(H(2)O)(5)](n) (5) and [{Ca(2)(Cl(2)C(PO(3))(2))(H(2)O)(6)}.4.5H(2)O](n) (6) by using the hydrolysis method in a systematic way. This study revealed that the Na(2)L1 and Na(2)L2 hydrolyze quite fast to structure 1 or form hydrolyzed metal complexes of clodronic acid, and hence the absorption in the body may not be increased by the use of Na(2)L1-Na(2)L2 as prodrugs. Na(2)L3, in turn, has a longer hydrolysis time and generally forms crystalline polymeric metal complexes without undergoing hydrolyzation. In addition, the masking of the two phosphonic acid groups by esterification to form clodronic dianhydrides does not prevent the formation of 2D polymeric metal complexes, which methylenebisphosphonates form as drugs on the hydroxyapatite surface of bone. Clodronate, however, is able to extend the dimensionality to 3D by coordination or hydrogen bonding.

Bis(µ(2)-phenyl-tellurolato)bis-(phenyl-tellurolato)tetra-µ(3)-tellurido-hexa-kis(triphenyl-phosphine)hexa-palladium(II) benzene nona-solvate.

The centrosymmetric title complex, [Pd(6)(C(6)H(5)Te)(4)Te(4)(C(18)H(15)P)(6)]·9C(6)H(6), contains two Pd(3)Te(2) cores that are joined into a cyclic hexa-nuclear complex by two bridging PhTe(-) groups. Each Pd(II) atom is coordinated by one triphenyl-phosphine ligand, one phenyl-tellurolate mol-ecule and two telluride ligands: two of the PhTe(-) ligands act as terminal ligands and two as bridging ligands. The three distinct Pd(II) atoms each show a slightly distorted PdPTe(3) square-planar coordination. The asymmetric unit also contains four and a half benzene solvent mol-ecules. Two of the benzene mol-ecules are disordered: one mol-ecule is distributed over two positions with site-occupancy factors of 0.529 (7) and 0.471 (7), while the other occupies two orientations about a centre of symmetry.

Poly[(acetone)tetraaqua[mu(6)-ethyl (dichloromethylene)diphosphonato][mu(5)-ethyl (dichloromethylene)diphosphonato]tribarium(II)].

The novel title compound, [Ba(3)(C(3)H(5)Cl(2)O(6)P(2))(2)(C(3)H(6)O)(H(2)O)(4)](n), has a polymeric two-dimensional network structure which lies parallel to the (10-1) plane. The asymmetric unit consists of three independent Ba(2+) ions, two of them eight-coordinated and the third nine-coordinated, and two independent ethyl (dichloromethylene)diphosphonate(3-) ligands, one acetone ligand and four aqua ligands. The coordination environments around the BaO(8) polyhedra are best described as bicapped trigonal prismatic, while the BaO(9) polyhedron is in a distorted tricapped trigonal prismatic geometry. The two diphosphonate ligands adopt different coordination modes. Both ligands chelate three metal cations, but one is coordinated to six metal cations in total and forms two six-membered and one four-membered chelate ring, while the other is coordinated to five metal cations in total and forms one six-membered and two four-membered chelate rings, the fifth unsubstituted O atom remaining uncoordinated.

Poly[[µ-aqua-aqua-[µ(4)-ethyl (dichloro-methyl-ene)diphospho-nato]sesqui-calcium(II)] acetone hemisolvate 4.5-hydrate].

The title compound, {[Ca(1.5)(C(3)H(5)Cl(2)O(6)P(2))(H(2)O)(2)]·0.5CH(3)COCH(3)·4.5H(2)O}(n), has a two-dimensional polymeric structure. The asymmetric unit contains two crystallographically independent Ca(2+) cations connected by a chelating and bridging ethyl (dichloro-methyl-ene)diphos-pho-n-ate(3(-)) ligand and an aqua ligand. One of the Ca atoms, lying on a centre of symmetry, has a slightly distorted octa-hedral geometry, while the other Ca atom is seven-coordinated in a distorted monocapped trigonal-prismatic geometry. The polymeric layers are further connected by extensive O-H⋯O hydrogen bonding into a three-dimensional supra-molecular network. The acetone solvent mol-ecule and one uncoordin-ated water mol-ecule are located on twofold rotation axes.

catena-Poly[[diaqua-cadmium(II)]-µ-(methyl morpholino dichloro-methylene-diphospho-nato)-κO,O':O''-[tetra-aqua-cadmium(II)]-µ-(methyl morpholino dichloro-methyl-enediphospho-nato)-κO:O',O''].

The asymmetric unit of the title compound, [Cd(C(6)H(11)Cl(2)NO(6)P(2))(H(2)O)(3)](n), contains two octahedrally coordinated Cd atoms located in special positions, one on a twofold rotation axis and the other on a centre of symmetry. The metal atoms are connected by methyl morpholino dichloro-methyl-enediphospho-nate ligands into chains in the c-axis direction. These chains are further connected by O-H⋯O hydrogen bonds into a layer-like construction along (100).

Synthetic applications of (Me3SiNSN)2E (E = S, Se) in chalcogen-nitrogen chemistry: formation and structural characterization of Cl2TeESN2 (E = S, Se) and [PPh4]2[Pd2(mu-Se2N2S)X4] (X = Cl, Br).

The reaction of (Me3SiNSN)2S with TeCl4 in CH2Cl2 affords Cl2TeS2N2 (1) and that of (Me3SiNSN)2Se with TeCl4 produces Cl2TeSeSN2 (2) in good yields. The products were characterized by X-ray crystallography, as well as by NMR and vibrational spectroscopy and EI mass spectrometry. The Raman spectra were assigned by utilizing DFT molecular orbital calculations. The pathway of the formation of five-membered Cl2TeESN2 rings by the reactions of (Me3SiNSN)2E with TeCl4 (E = S, Se) is discussed. The reaction of (Me3SiNSN)2Se with [PPh4]2[Pd2X6] yields [PPh4]2[Pd2(mu-Se2N2S)X4] (X = Cl, 4a; Br, 4b), the first examples of complexes of the (Se2N2S)2- ligand. In both cases, this ligand bridges the two palladium centers through the selenium atoms.

Structures of bisphosphonate metal complexes: zinc and cadmium complexes of clodronate and its partial ester derivatives.

Four new zinc and cadmium bisphosphonates [{NaZn(Cl2CP2O6H)(H2O)5}]n (1), [{Cd2(Cl2CP2O6)(H2O)4}.H2O]n (2), [{Zn(Cl2CP2O6Pri2)(H2O)3}.H2O]n (3), and [{Cd2(Cl2CP2O6Pri2)2(MeOH)2(H2O)2}.H2O]2 (4) have been prepared and their crystal structures determined by single-crystal X-ray diffractometry. Two bisphosphonate ligands were used: clodronate, (dichloromethylene)bis(phosphonate) and its symmetrical P,P'-diisopropyl ester derivative. The structure of the Zn complex 1 is three-dimensional, consisting of one-dimensional Zn-clodronate chains connected to the three-dimensional network by Na+ ions. The structure of Cd complex 2 consists of double layers, and a unique bond was found between the Cd2+ cation and a Cl atom of clodronate. Zn complex 3 consists of one-dimensional chains, but the binding of the bisphosphonate ligands is unique: in 3 the bisphosphonate ligand is only bidentate. Compound 4 is a tetramer, and hydrogen bonds hold the tetramers together, forming a layered structure.

Poly[[tetraaqua(mu7-hydrogen dichloromethylenebisphosphonato)(mu5-hydrogen dichloromethylenebisphosphonato)tribarium(II)] monohydrate].

The title compound, [[Ba(3)(CHCl(2)O(6)P(2))(2)(H(2)O)(4)].H(2)O](n) or [[Ba(3)(Cl(2)CP(2)O(6)H)(H(2)O)(4)].H(2)O](n), is two-dimensional. The asymmetric unit contains three independent Ba(2+) atoms, two chelating and bridging Cl(2)CP(2)O(6)H(3-) ligands and four aqua ligands, connected in layers parallel to the (100) plane. There are pores between the layers in the direction of the b axis filled with lattice water molecules.

The reactions of tellurium tetrahalides with triphenylphosphine under ambient conditions.

The reactions of tellurium tetrahalides and triphenylphosphine in tetrahydrofuran have been carried out under ambient conditions and afford [(Ph(3)PO)(2)H](2)[Te(2)X(10)] [X = Cl (1), Br (2)] and [(Ph(3)PO)(3)(OH(3)])(2)[TeI(6)] (4). The X-ray structures of 1 and 2 show that they are isostructural and contain discrete [Te(2)X(10)](2-) anions exhibiting octahedral coordination around both tellurium atoms with one shared edge and [Ph(3)POH...OPPh(3)](+) cations that show strong hydrogen bonds (the O...O distances are 2.399 and 2.404 A for 1 and 2, respectively). The compound 4 is built up with discrete octahedral hexaiodotellurate anions and [(Ph(3)PO)(3)(OH(3))](+) cations. The reaction of TeBr(4) and PPh(3) also results in the formation of formally zwitterionic Ph(3)PO(CH(2))(4)TeBr(4) (3). This reaction involves an unprecedented THF ring opening in which the oxygen atom becomes bonded to the phosphorus atom of triphenylphosphine and the carbon atom at the other end of the five-atomic chain becomes bonded to the tellurium atom of TeBr(4). The ring opening of the solvent THF is also taking place in the reaction involving tellurium tetraiodide, as indicated by the formation of C(4)H(8)TeI(2) (5). The reaction may initially lead to Ph(3)PI(2) that reacts with THF yielding Ph(3)PO and ICH(2)(CH(2))(2)CH(2)I. The latter species reacts with elemental tellurium producing 5. Depending on the conditions upon crystallization, two polymorphs of C(4)H(8)TeI(2) (5a and 5b) are observed. While the molecular structures of the two forms are virtually identical, their packing and intermolecular contacts are different. Two further minor products (6a and 6b) were isolated in the reaction of TeI(4) and PPh(3): Both are formally 1:1 adducts of 5 and TeI(4), but they differ considerably in their structures. 6a can be formulated as [C(4)H(8)TeI(+)](2)[Te(2)I(10)(2-)] and 6b as [C(4)H(8)TeI(+)](2)(TeI(3)(+))(2)(I(-))(4). The latter compound exhibits framework similar to that of the tetramers in gamma- and delta-TeI(4).

1,3,5,7-Tetraselena-2,4,6,8(2,5)-tetrathiophenaoctaphane.

The novel title tetraselenacalix[4]arene, C(16)H(8)S(4)Se(4) or [(C(4)H(2)S)Se](4), has a centrosymmetric cyclic molecular structure with approximate C(2h) molecular symmetry. The four thienyl rings are joined together by Se bridges and exhibit a syn-syn-anti-anti arrangement around the molecule. The lattice consists of skewed stacks of molecules, with chalcogen-chalcogen close contacts binding the stacks together, forming a two-dimensional network of molecules.

One-pot synthesis of 3,4-disubstituted 1H-pyrroles from 2-tropanones.

3,4-Disubstituted pyrroles (2, 3) were prepared from 6/7-carboxyethyl-3-phenyl-3-tropen-2-ones (1) regioselectively and with high yields by using tosylmethyl isocyanide (TosMIC). This procedure enables the synthesis of pyrroles substituted with two distinct groups: a phenyl group and a substituted pyrrolidine analogue. The crystal structure of product 2a was determined, and the analogous derivatives were identified by (1)H and (13)C NMR spectroscopy.

Magnetic Properties of a Series of Trinuclear Complexes (CuL)(2)Mn.xB (L Representing the Deprotonated Form of N-(4-Methyl-6-oxo-3-azahept-4-enyl)oxamic Acid and B Representing Respectively H(2)O (x = 5, 4.5, 3, 1), (CH(3))(2)SO (x = 2), and C(5)H(5)N (x = 4)). Crystal and Molecular Structure of (CuL)(2)Mn.2(CH(3))(2)SO.

A series of (Cu, Mn, Cu) complexes have been prepared and characterized. They may be described by the overall formula (CuL)(2)Mn.xB where L stands for the deprotonated form of N-(4-methyl-6-oxo-3-azahept-4-enyl)oxamic acid and B for respectively H(2)O (with x = 5, 4.5, 3, 1), (CH(3))(2)SO (with x = 2), and C(5)H(5)N (with x = 4). The crystal and molecular structures of (CuL)(2)Mn.2(CH(3))(2)SO have been solved. The crystals are monoclinic, space group P2(1)/n with cell constants a = 8.362(2) Å, b = 14.426(3) Å, c = 24.442(6) Å, and Z = 4. In each (Cu, Mn, Cu) molecular unit the central Mn(II) ion is bridged to two copper(II) ions through two oxamato groups. Short intermolecular Cu.Cu distances lead to the formation of a chain-like packing pattern running parallel to the c-axis. Magnetic susceptibility measurements have been performed for the six complexes. Five complexes display the same behavior which corresponds to the occurrence of antiferromagnetic Cu-Mn interactions within isolated trinuclear units. The J values are between -29.4(2) and -33.8(5) cm(-)(1). Surprisingly the field and temperature dependence of the magnetization for (CuL)(2)Mn.4.5H(2)O confirms that a magnetic phase transition occurs at low temperature and that, below T(c) = 37 K, the complex displays weak ferromagnetism.