An iron(III) phosphonate cluster containing a nonanuclear ring.

This communication reports the first example of cyclic ferric clusters with an odd number of iron atoms capped by phosphonate ligands, namely, [Fe9(mu-OH)(7)(mu-O)2(O3PC6H9)8(py)12]. The magnetic studies support a S = 1/2 ground state with an exchange coupling constant of about J approximately equal to -30 K.

A two-step field-induced magnetic transition in a novel layered cobalt diphosphonate.

Compound Na6Co7(hedp)2(hedpH)4(H2O)4 x 8H2O (hedp = 1-hydroxyethylidenediphosphonate) with a novel layer structure is reported in this paper. The layer maybe viewed as made up from two types of chains each of composition Co3(hedp)2 and Co2(hedpH)2. Magnetic measurements at 1.8 K reveal a metamagnetic transition at ca. 6.5 kOe, followed by a second transition to a ferromagnetic state at ca. 30 kOe.

Template-Directed One- and Two-Dimensional Copper(II) Diphosphonates: Structures and Characterizations of (NH(4))(2)Cu(3)(hedp)(2)(H(2)O)(4), [NH(3)(CH(2))(4)NH(3)]Cu(3)(hedp)(2).2H(2)O, and [NH(2)(C(2)H(4))(2)NH(2)]Cu(3)(hedp)(2) (hedp = 1-Hydroxyethylidenediphosphonate).

Three new copper(II) diphosphonates, (NH(4))(2)Cu(3)(hedp)(2)(H(2)O)(4) (1), [NH(3)(CH(2))(4)NH(3)]Cu(3)(hedp)(2).2H(2)O (2), and [NH(2)(C(2)H(4))(2)NH(2)]Cu(3)(hedp)(2) (3), where hedp = 1-hydroxyethylidenediphosphonate, have been synthesized and characterized by single-crystal structural analysis. Crystal data: 1, monoclinic, P2(1)/n, a = 6.2137(13) Å, b = 14.747(2) Å, c = 11.1802(12) Å, beta = 105.83(2) degrees, Z = 2; 2, triclinic, P&onemacr;, a = 7.4840(12) Å, b = 8.032(3) Å, c = 10.007(2) Å, alpha = 111.68(2) degrees, beta = 96.188(14) degrees, gamma = 96.97(2) degrees, Z = 1; 3, triclinic, P&onemacr;, a = 7.0155(6) Å, b = 8.0904(9) Å, c = 9.2644(11) Å, alpha = 112.611(13) degrees, beta = 90.819(8) degrees, gamma = 92.824(7) degrees, Z = 1. The compound 1 is composed of infinite chains with a ladder-type motif. The compounds 2 and 3 adopt a two-dimensional layer structure which contains four- and eight-membered rings assembled from vertex-sharing {CuO(4)} units and {CPO(3)} tetrahedra. The magnetic properties of 3 have been investigated.

Dodecanuclear manganese(III) phosphonates with cage structures.

Treatments of Mn(O(2)CR)(2) (R = Me, Ph) with NBu(4)MnO(4) in CH(3)CN or CH(3)CN/CH(2)Cl(2) in the presence of acetic acid, delta(1)-cyclohexenephosphonic acid (C(6)H(9)PO(3)H(2)), and 2,2'-bipyridine or 1,10-phenanthroline result in three novel dodecamanganese(III) clusters [Mn(12)O(8)(O(2)CMe)(6)(O(3)PC(6)H(9))(7)(bipy)(3)] (1), [Mn(12)O(8)(O(2)CPh)(6)(O(3)PC(6)H(9))(7)(bipy)(3)] (2), and [Mn(12)O(8)(O(2)CPh)(6)(O(3)PC(6)H(9))(7)(phen)(3)] (3). They have a similar Mn(12) core of [Mn(III)(12)(mu(4)-O)(3)(mu(3)-O)(5)(mu-O(3)P)(3)] with a new type of topologic structure. Solid-state dc magnetic susceptibility measurements of complexes 1-3 reveal that dominant antiferromagnetic interactions are propagated between the magnetic centers. The ac magnetic measurements suggest an S = 2 ground state for compounds 1 and 3 and an S = 3 ground state for compound 2.

Field-induced magnetic transitions in metal phosphonates with ladderlike chain structures: (NH3C6H4NH3)M2(hedpH)2.H2O [M = Fe, Co, Mn, Zn; hedp = C(CH3)(OH)(PO3)2].

This paper reports the syntheses and characterization of four isomorphous compounds (NH(3)C(6)H(4)NH(3))M(2)(hedpH)(2).H(2)O [M = Fe (1), Co (2), Mn (3), Zn (4); hedp = C(CH(3))(OH)(PO(3))(2)]. Each contains two crystallographically different kinds of {M(2)(hedpH)(2)}(n) double chains, where the {M(2)(mu-O)(2)} dimer units are connected by O-P-O bridges. The double chains are connected through extensive hydrogen bonds, hence generating a three-dimensional supramolecular network. The temperature-dependent magnetic susceptibility measurements show dominant antiferromagnetic interactions in compounds 1-3, mediated through the mu-O and/or O-P-O bridges between the metal(II) centers. The magnetization measurements reveal that compounds 1-3 experience field-induced magnetic transitions at low temperatures.

Novel coordination polymer containing a mixed valence copper(I,II) phosphonate unit: Cu(I)(2)Cu(II)(hedpH(2))(2)(4,4'-bpy)(2).2H(2)O (hedp = 1-hydroxyethylidenediphosphonate).

This paper reports the synthesis and crystal structure of a novel mixed valence copper(I,II) compound, Cu(I)(2)Cu(II)(hedpH(2))(2)(4,4'-bpy)(2).2H(2)O (1), where hedp represents 1-hydroxyethylidenediphosphonate. The structure is composed of [Cu(I)(2)Cu(II)(hedpH(2))(2)] trimer units and 4,4'-bipyridine linkages, forming a two-dimensional brick-wall-like layer structure in the ab plane. The layers are stacked along the [001] direction with strong interlayer hydrogen bonds and pi-pi interactions, thus leading to the construction of a three-dimensional network.

One-dimensional cobalt diphosphonates exhibiting weak ferromagnetism and field-induced magnetic transitions.

This paper reports two new cobalt phosphonate compounds [NH3(CH2)nNH3]Co2(hedpH)2.2H2O [n = 4 (1), 5 (2)], where hedp is (1-hydroxyethylidene)diphosphonate [CH3C(OH)(PO3)2]. Both contain ladderlike chains with the same composition [Co2(hedpH)2](n)(2n-), where edge-shared [CoO6] octahedra are each bridged by O-P-O units. The chains are linked by very strong hydrogen bonds to form a three-dimensional open network with channels in which the diammonium counterions and lattice water reside. Magnetic studies reveal dominant antiferromagnetic interactions between the Co centers within the chain in both compounds. The field dependent magnetization confirms the occurrence of the field-induced magnetic transitions, with the critical fields ca. 25 kOe for 1 and 27.5 kOe for 2, respectively. In the case of compound 2, weak ferromagnetism is also observed at very low temperatures, possibly arising from spin canting of the antiferromagnetically coupled Co(II) ions in the chain. Crystal data: 1, monoclinic, P2(1)/c, a = 5.4868(8), b = 12.9116(18), and c = 15.251(2) A, beta = 98.843(2) degrees, V = 1067.6(3) A(3), Z = 2; 2, monoclinic, P2(1)/c, a = 5.4757(7), b = 12.7740(16), and c = 15.794(2) A, beta = 98.797(2) degrees, V = 1091.7(2) A(3), Z = 2.

cis-[1,4-Bis(diphenylphosphino)butane](mu-tetrathiotungstato)palladium(II) N,N'-dimethylformamide hemisolvate hemihydrate.

In the title compound, [1,4-bis(diphenylphosphino)butane-2kappa(2)P,P']di-mu-thio-1:2kappa(4)S-dithio-1kappa(2)S-palladium(II)tungsten(VI) N,N'-dimethylformamide hemisolvate hemihydrate, [PdWS(4)(C(28)H(28)P(2))].0.5C(3)H(7)NO.0.5H(2)O, the Pd atom is coordinated by two S atoms from the distorted-tetrahedral [WS(4)](2-) anion and two P atoms from the dppb molecule [dppb is 1,4-bis(diphenylphosphino)butane] in an approximately square-planar configuration. A puckered seven-membered ring is formed by the Pd atom and the dppb ligand.

Tris[diphenyl(2-pyridyl)phosphine]-micro(3)-iodo-tri-micro(3)-sulfido-sulfidotrisilvertungsten dichloromethane hemisolvate.

The title compound, [Ag(3)WIS(4)(C(17)H(14)NP)(3)].0.5CH(2)Cl(2), is a cubane-type heterometallic cluster containing diphenyl(2-pyridyl)phosphine (Ph(2)PPy). The pyridyl group of Ph(2)PPy remains uncoordinated, so the Ph(2)PPy ligand is monodentate and coordinates to one Ag atom. The W atom and three Ag atoms form a distorted tetrahedral geometry, capped by one I atom and three S atoms.