Fmoc-D-Bip(4-Cl)-OH

The common feature of the four iridium(III) salt complexes, (bis-{[(di-phenyl-phosphan-yl)meth-yl]di-phenyl-phosphanyl-idene}(eth-oxy-oxoethanyl-idene)methane-κ4 P,C,C',P')chlorido-hydridoiridium(III) chloride methyl-ene chloride 2.75-solvate (4), (bis-{[(di-phenyl-phosphan-yl)meth-yl]di-phenyl-phosphanyl-idene}(eth-oxy-oxoethanyl-idene)methane-κ4 P,C,C',P')chlorido-(eth-oxy-oxoethanido)iridium(III) chloride-methanol-water (1/1/0.5) (5), (bis-{[(di-phenyl-phosphan-yl)meth-yl]di-phenyl-phosphanyl-idene}(eth-oxy-oxoethanyl-idene)methane-κ4 P,C,C',P')di-chlorido-iridium(III) chloride-methanol-water (1/1/2) (6) and (bis-{[(di-phenyl-phosphan-yl)meth-yl]di-phenyl-phosphanyl-idene}(eth-oxy-oxoethanyl-idene)methane-κ4 P,C,C',P')carbon-yl(eth-oxy-oxoethanide)iridium(III) dichloride-meth-yl-ene chloride-water (1/2/1.5) (7) or in terms of their formulae [Ir(C55H50O2P4)ClH]Cl·2.75CH2Cl2 (4), [Ir(C4H7O2)(C55H50O2P4)Cl]Cl·CH3OH·0.5H2O (5), [Ir(C55H50O2P4)Cl2]Cl·CH3OH·2H2O (6) and [Ir(C4H7O2)(C55H50O2P4)(CO)]Cl2·2CH2Cl2·1.5H2O (7) is a central IrIII atom coordin-ated in a distorted octa-hedral fashion by a PCCP ligand system and two additional residues, such as chlorides, a hydride, a carbonyl or an alkyl unit. Thereby, the PCP pincer ligand system and the residue trans to the carbodi-phospho-rane (CDP) C atom surround the iridium(III) transition metal in the equatorial plane under the formation of two five-membered dissimilar chelate rings [C-CCDP-P (4, 5, 6 and 7) for the first ring: 120.2 (3), 121.9 (5), 111.2 (3) and 121.7 (2) °; for the second ring: 112.1 (3), 113.5 (5), 120.5 (3) and 108.3 (2)°]. A cyclo-propane-like heterocycle is positioned approximately orthogonal (84.21-88.85°) to the equatorial plane, including an alkyl-idene bridge connecting the IrIII atom and the coordinating CDP atom of the PCP subunit. In general, the neutral PCCP ligand system coordinates the metal in a tetra-dentate way via three Lewis acid/base bonds and by an alkyl-idene unit presenting strengthened inter-actions. In all the crystal structures, (disordered) solvent mol-ecules are present in the voids of the packed mol-ecules that inter-act with the positively charged complex and its chloride counter-ion(s) through weak hydrogen bonding.

A novel sodium bismuth oxo-cuprate phosphate chloride, Na6Cu7BiO4(PO4)4[Cl2.23(OH)0.77], containing square-kagomé layers of Cu2+ has been synthesized by hydrothermal techniques. The compound crystallizes in the tetragonal space group P4/nmm, a = 10.0176(4), c = 10.8545(6), Z = 2, V = 1089.3(1) Å3, R1 = 0.021, wR = 0.053, S = 1.32. Its composite crystal structure includes [O4Cu6Bi]7+ layers, which are formed by the clusters of oxygen-centered tetrahedra [OCu3Bi]. These positively charged two periodic fragments are intercalated in a negatively charged [CuNa6Cl3(PO4)4]7- matrix built by Na-centered polyhedra, PO4 tetrahedra, and CuO4Cl pyramids. The composite character of the crystal structure of Na6Cu7BiO4(PO4)4[Cl2.23(OH)0.77], as well as the way of its self-assembly, are discussed in close connection with the sulfohalite Na6ClF(SO4)2 salt. It is shown that the "host-guest" model of the formation of the tetragonal Na6Cu7BiO4(PO4)4[Cl2.23(OH)0.77] phase is due to the group-subgroup symmetry relation with the cubic crystal structure of mineral sulfohalite and is also supported by the crystallization condition in excess sodium chloride. The magnetic subsystem of Na6Cu7BiO4(PO4)4[Cl2.23(OH)0.77] is represented by a dense square-kagomé network of 2Cu1 and 4Cu2 ions, decorated with weakly bonded Cu3 ions. Measurements of magnetization and heat capacity indicate the absence of long-range order up to 2 K, which makes this compound a candidate for a highly demanded spin liquid.

In the title hetero-dinuclear complex, [CuSm(C(22)H(24)N(2)O(4))Cl(3)(CH(3)OH)(2)], the Cu(II) cation is N,N',O,O'-chelated by a 6,6'-dimeth-oxy-2,2'-[cyclo-hexane-1,2-diylbis(nitrilo-methanylyl-idene)]diphenolate ligand, and one Cl(-) anion further coordinates to the Cu(II) cation to complete the distorted square-pyramidal coordination geometry, while the Sm(III) cation is chelated by four O atoms from the same ligand, and is further coordinated by two methanol mol-ecules and two Cl(-) anions in an bicapped trigonal-prismatic geometry. Intra- and inter-molecular O-H⋯Cl hydrogen bonds are present in the structure.