(µ-Methylenediphosphonato-κ4 O,O':O'',O''')bis[(ethyl-ene-diamine-κ2 N,N')palladium(II)] tetra-hydrate.

The title compound, [Pd2(C2H8N2)2(CH2O6P2)]·4H2O, comprises of a binuclear mol-ecule (point group symmetry 2), with a twofold rotation axis running through the central C atom of the methyl-enedi-phospho-nate (MDP) anion. The PdII atom has a square-planar coordination environment defined by the N atoms of a bidentate ethyl-enedi-amine (en) ligand and two O atoms of the bridging MDP anion. In the crystal structure, metal complexes are arranged in layers parallel (001) and are sandwiched between layers containing disordered water mol-ecules of crystallization. Extensive intra-layer hydrogen bonds of the type N-H⋯O in the metal complex layer and O-H⋯O in the water layer, as well as O-H⋯O hydrogen bonds between the two types of layers, lead to the formation a three-dimensional network structure. The two lattice water mol-ecules are each equally disordered over two positions.

Crystal structure of di-chlorido-{4-[(E)-(meth-oxy-imino-κN)meth-yl]-1,3-thia-zol-2-amine-κN (3)}palladium(II).

In the title compound, [PdCl2(C5H7N3OS)], the Pd(II) atom adopts a distorted square-planar coordination sphere defined by two N atoms of the bidentate ligand and two Cl atoms. The mean deviation from the coordination plane is 0.029 Å. The methyl group is not coplanar with the plane of the metallacycle [torsion angle C-O-N-C = 20.2 (4)°]. Steric repulsion between the methyl group and atoms of the metallacycle is manifested by shortened intra-molecular H⋯C contacts of 2.27, 2.38 and 2.64 Å, as compared with the sum of the van der Waals radii of 2.87 Å. The amino group participates via one H atom in the formation of an intra-molecular N-H⋯Cl hydrogen bond. In the crystal, the other H atom of the amino group links mol-ecules via bifurcated N-H⋯(Cl,O) hydrogen bonds into chains parallel to [001].

Poly[[tri-µ-aqua-do-deca-aqua-tris-(µ3-1-hy-droxy-ethyl-idene-1,1-di-phospho-nato)tricalcium(II)tripalladium(II)] penta-hydrate].

The asymmetric unit of the title compound, {[CaPd{CH3OHC(PO3)2}(H2O)5]·5/3H2O} n , consists of one half of the complex [Pd{CH3OHC(PO3)2}](2-) anion (point group symmetry m..), one Ca(2+) cation [site symmetry (.2.)] that is surrounded by three water mol-ecules (one of which is on the same rotation axis) and by three disordered lattice water mol-ecules. The anions form a trinuclear metallocycle around a crystallographic threefold rotation axis. The cations are related by a twofold rotation axis to form a [Ca2(H2O)10](2+) dimer. The slightly distorted square-planar coordination environment of the Pd(II) atoms in the complex anions is formed by O atoms of the bidentate chelating phospho-nate groups of the 1-hy-droxy-ethyl-idene-1,1-di-phospho-nate ligands. In the crystal, cations are bound to anions through -Ca-O-P-O- bonds, as well as through O-H⋯O hydrogen bonds, resulting in a three-dimensional polymer. The structure is completed by five disordered solvent mol-ecules localized in cavities within the framework.

Binary salt of a palladium(II) complex with (phosphonomethyl)phosphonic (medronic) acid comprising 'handbell-like' [Pd{µ-CH2(PO3)2}]3 units.

The asymmetric unit of the title compound, dipotassium bis[hexaaquanickel(II)] tris(µ(2)-methylenediphosphonato)tripalladium(II) hexahydrate, K(2)[Ni(H(2)O)(6)](2)[Pd(3){CH(2)(PO(3))(2)}(3)]·6H(2)O, consists of half a {[Pd{CH(2)(PO(3))(2)}](3)}(6-) anion [one Pd atom (4e) and a methylene C atom (4e) occupy positions on a twofold axis] in a rare 'handbell-like' arrangement, with K(+) and [Ni(H(2)O)(6)](2+) cations to form the neutral complex, completed by three solvent water molecules. The {[Pd{CH(2)(PO(3))(2)}](3)}(6-) units exhibit close Pd···Pd separations of 3.0469 (4) Å and are packed via intermolecular C-H···Pd hydrogen bonds. The [KO(9)] and [NiO(6)] units are assembled into sheets coplanar with (011) and stacked along the [100] direction. Within these sheets there are [K(4)Ni(4)O(8)] and [K(2)Ni(2)O(4)] loops. Successive alternation of the sheets and [Pd{CH(2)(PO(3))(2)}](3) units parallel to [001] produces the three-dimensional packing, which is also supported by a dense network of hydrogen bonds involving the solvent water molecules.

Diaqua-bis-(dihydrogen 3-aza-niumyl-1-hy-droxy-propyl-idene-1,1-di-phos-phon-ato-κO,O')cobalt(II).

The asymmetric unit of title compound, [Co(C(3)H(10)NO(7)P(2))(2)(H(2)O)(2)], contains one half-mol-ecule of the complex. The Co(II) atom is located on an inversion centre and displays a distorted octa-hedral coordination geometry defined by four O atoms of two 3-aza-niumyl-1-hy-droxy-propyl-idene-1,1-bis-phospho-nato ligands in the equatorial plane and two water mol-ecules located in axial positions. The ligand mol-ecules, which exist in a zwitterionic state, form two six-membered chelate rings with chair conformations. In the crystal, mol-ecules are inter-linked by O-H⋯O and N-H⋯O hydrogen bonds, forming a three-dimensional supra-molecular structure.

A second triclinic polymorph of (1-ammonio-1-phosphono-eth-yl)phospho-nate.

The asymmetric unit of the second polymorph of the title compound, C(2)H(9)NO(6)P(2), contains one mol-ecule existing as a zwitterion. The N atom of the ammonio group is protonated and one of the phospho-nic acid groups is deprotonated. Bond lengths and angles are similar in both polymorphs. Besides the differences in cell parameters, the most significant structural difference between this structure and that of the first polymorph [Dudko, Bon, Kozachkova, Tsarik & Pekhno (2008 ▶), Ukr. Khim. Zh.74, 104-106] is the presence of strong symmetric hydrogen bonds between neighbouring phospho-nate groups. H atoms involved in these hydrogen bonds are located at inversion centres and O⋯O distances are observed in the range 2.458 (5)-2.523 (5) Å. These bonds and additional O-H⋯O and N-H⋯O hydrogen bonds inter-link the mol-ecules, giving a three-dimensional supromolecular network.

Poly[[diaqua[µ(5)-(R,S)-2-({2-[(1,2-di-carboxyl-atoeth-yl)amino]-eth-yl}amino)-butane-dioato]cobaltate(III)sodium] di-hydrate].

In the asymmetric unit of the title coordination polymer, {[CoNa(C(10)H(12)N(2)O(8))(H(2)O)(2)]·2H(2)O}(n), the Co(II) ion is coord-inated in a distorted octa-hedral environment, defined by two N atoms and four carboxyl-ate O atoms. Two Co(II) ions and two 2-({2-[(1,2-dicarboxyl-atoeth-yl)amino]-eth-yl}amino)-butane-dio-ate (EDDS) ligands form a dimeric complex dianion [Co(2)(EDDS)(2)]. These dimeric units are connected via Na(+) ions, forming a three-dimensional polymeric structure. In the crystal, the ligand N-H groups and the coordinated and solvent water mol-ecules are involved in inter-molecular N-H⋯O and O-H⋯O hydrogen bonding, reinforcing the three-dimensional polymeric structure.

Bis(1-ammonio-ethane-1,1-diyl-diphos-phonato-κO,O')diaqua-cobalt(II) nona-hydrate.

In the title compound, [Co(C(2)H(8)NO(6)P(2))(2)(H(2)O)(2)]·9H(2)O, the Co(II) atom has a slightly distorted octa-hedral coordination environment consisting of four deprotonated phospho-nate O atoms of two independent 1-amino-ethyl-idendiphospho-nate anions and complemented by the O atoms of two water mol-ecules in cis positions. The anions exists in the zwitterionic form (protonated amino group and two deprotonated phospho-nate O atoms) and constitute two six-membered chelate rings. The crystal structure also contains nine partly disordered uncoordinated water mol-ecules, which create an extensive three-dimensional network of strong O-H⋯O and N-H⋯O hydrogen bonds.

Bis[(1-ammonio-ethane-1,1-di-yl)diphospho-nato-κO,O']diaqua-nickel(II) nona-hydrate.

The title compound, [Ni(C(2)H(8)NO(6)P(2))(2)(H(2)O)(2)]·9H(2)O, exhibits a slightly distorted octa-hedral coordination environment around the Ni(II) atom. It contains two mol-ecules of 1-amino--ethyl-idenediphospho-nic acid in the zwitterionic form, coord-inated via O atoms from two phospho-nate groups and creating two six-membered chelate rings. Two water mol-ecules in cis positions complete the coordination environment of the Ni(II) atom. The title compound contains nine partly disordered solvent water mol-ecules, which create a three-dimensional network of strong O-H⋯O and N-H⋯O hydrogen bonds.

[1-(2-Oxidobenzyl-idene)-4-phenyl-thio-semicarbazidato-κO,N,S](pyridine-κN)copper(II).

In the structure of the title compound, [Cu(C(14)H(11)N(3)OS)(C(5)H(5)N)], the Cu(II) atom exhibits a slightly distorted square-planar CuN(2)OS coordination polyhedron consisting of a phenyl O, an azomethine N and a thio-amide S atom from the tridentate thio-semicarbazonate dianion, and the N atom of a pyridine mol-ecule. The thio-semicarbazonate ligand exists in the thiol tautomeric form as an E isomer. Rotational disorder of the pyridine and phenyl rings in a 1:1 ratio of the respective components is observed. An extensive network of weak N-H⋯S, C-H⋯O, C-H⋯N and C-H⋯S hydrogen-bonding inter-actions consolidates the structure.

Poly[[µ(2)-(1Z,N'E)-2-(1,3-benzothia-zol-2-ylsulfan-yl)-N'-(2-oxidobenzyl-idene-κO:O)acetohydrazidato-κO,N'](pyridine-κN)copper(II)].

In the title compound, [Cu(C(16)H(11)N(3)O(2)S(2))(C(5)H(5)N)](n), the Cu(II) atom displays a square-pyramidal CuN(2)O(3) coordination geometry with strong elongation in the vertex direction. The hydrazone mol-ecule is coordinated to the Cu(II) atom in a tridentate manner in the enolic form, creating five- and six-membered chelate metallarings. The pyridine mol-ecule completes the square-planar base of the copper coordination environment. The crystal structure displays zigzag polymeric Cu-O-Cu chains along [001]. Several weak π-π inter-actions between benzothia-zole rings were found in the same direction [centroid-centroid distances = 3.7484 (16), 3.7483 (16), 3.6731 (17) and 3.7649 (17) Å].

cis-(Pyridin-2-ylcarbonimidodithio-ato-κS,S')bis-(triphenyl-phosphane-κP)palladium(II).

The title compound, [Pd(C(6)H(4)N(2)S(2))(C(18)H(15)P)(2)], was obtained as a minor product from the reaction of trans-PdCl(2)(PPh(3))(2) with piperazine-1,4-dicarbothioic acid bis-(pyridin-2-yl)amide. The Pd(II) atom displays a slightly distorted square-planar PdP(2)S(2) geometry with a bidentately coordinated pyridin-2-ylcarbonimidodithio-ate ligand and two triphenyl-phosphine mol-ecules, coordinated in cis positions. The crystal structure features weak π-π [centroid-centroid distance =3.7327(15) Å] and C-H⋯π inter-actions and contains an almost spherically shaped void of 50.4 Å(3) per unit cell.

trans-Bis[(1-ammonio-pentane-1,1-di-yl)diphospho-nato-κO,O']diaqua-copper(II).

In the title compound, [Cu(C(5)H(14)NO(6)P(2))(2)(H(2)O)(2)], the Cu(II) atom occupies a special position on an inversion centre. It exhibits a distorted octa-hedral coordination environment consisting of two O,O'-bidentate (1-ammonio-pentane-1,1-di-yl)diphospho-nate anions in the equatorial plane and two trans water mol-ecules located in axial positions. The ligand mol-ecules are coordinated to the Cu(II) atom in their zwitterionic form via two O atoms from different phospho-nate groups, creating two six-membered chelate rings with a screw-boat conformation. The CuO(6) coordination polyhedron is strongly elongated in the axial direction with 0.6 Šlonger bonds than those in the equatorial plane. Intra-molecular N-H⋯O hydrogen bonding helps to stabilize the mol-ecular configuration. The presence of supra-molecular -PO(OH)⋯O(OH)P- units parallel to (100) and other O-H⋯O and N-H⋯O hydrogen bonds establish the three-dimensional set-up.