Inorganic Chemistry Communications (v.5, #12)

Contents List (iii-iv).

[Zn(BDC)(H2O)2] n : a novel blue luminescent coordination polymer constructed from BDC-bridged 1-D chains via interchain hydrogen bonds (BDC = 1,4-benzenedicarboxylate) by Li-Na Zhu; Lei Z. Zhang; Wen-Zhen Wang; Dai-Zheng Liao; Peng Cheng; Zong-Hui Jiang; Shi-Ping Yan (1017-1021).
A novel coordination polymer [Zn(BDC)(H2O)2] n 1 (where BDC = 1,4-benzenedicarboxylate), has been synthesized and characterized by X-ray diffraction. 1 crystallizes in the monoclinic space group C2/c, a=15.09(2) Å, b=5.058(7) Å, c=12.196(16) Å, β=103.62(2)°, V=904(2)  A ̊ 3 , Z=4. The most striking feature of 1 is that it consists of a high-dimensional network structure constructed from BDC-bridged 1-D chains via interchain hydrogen bonds. The coordination sphere of the zinc(II) ion is a distorted tetrahedron completed by four oxygen atoms from two water molecules and two BDC ligands. BDC adopts the bis-monodentated (synanti) coordination mode linking two adjacent zinc(II) ions. 1 shows strong blue photoluminescence as the result of the fluorescence from the intraligand emission excited state.
Keywords: Zinc; Coordination polymer; Crystal structure; Luminescence;

The hydrothermal reaction of ciprofloxacin (1) with Cu(BF4)2·6H2O yields a copper complex having a molecular formula, [Cu(cf)2(BF4)2]·6H2O (cf = ciprofloxacin), which is characterized by spectroscopic and electrochemical measurements as well as single crystal X-ray studies [a=9.1079(13), b=9.6112(16), c=11.4542(18) Å, α=90.518 (19)°, β=99.160 (18)°, γ=93.315 (19)°, P1bar, Z=1]. The F2O4 donor atom set forms a (4+2) distorted octahedral geometry around the central copper atom; which has a highly facile copper redox couple (+0.23 V). The copper conjugate exhibits a significant enhancement in the antitubercular activity probably arising out of its rapid intracellular reduction leading to oxygen activation, which is detrimental to the mycobacteria.
Keywords: X-ray crystal structure; Ciprofloxacin; Hydrothermal reaction; Antimycobacterial activity;

The reaction of three-dimensional (3D) CuO (tenorite) with 1,4-naphthalenedicarboxylic acid and 2,2-dipyridylamine under hydrothermal conditions produced the first 1,4-naphthalenedicarboxylate bridged coordination dimmer linked via hydrogen-bonding water molecule into a two-dimensional (2D) network structure. Instead of using simple inorganic salts, the 3D solid-state CuO was used as the copper-ion source for the reaction. The hydrogen-bonding water molecules in the network structure were completely lost below 250 °C and the dimmer was decomposed from 250 to 310 °C.
Keywords: Coordination polymer; Two-dimensional structure; Hydrothermal reaction; Copper oxide; Hydrogen bonds; Naphthalenedicarboxylate;

Preparation and properties of octa-substituted phthalocyanines peripherally substituted with phenyl derivatives by Tamotsu Sugimori; Masaharu Torikata; Jun Nojima; Shinobu Tominaka; Kaori Tobikawa; Makoto Handa; Kuninobu Kasuga (1031-1033).
2,3,9,10,16,17,23,24-Octa-substituted phthalocyanines modified with phenyl, tolyl, tert-butylphenyl, and trifluoromethylphenyl groups and their nickel(II) complexes were prepared and characterized. The phthalonitriles with the phenyl derivatives, which are precursors of the phthalocyanines, were synthesized from 4,5-dichlorophthalonitrile and phenyl boronic acids by use of Suzuki-coupling reaction.
Keywords: Octa-substituted phthalocyanines; Suzuki-coupling; Solubility; Spectroscopy;

A series of N-para-(ferrocenyl)benzoyl amino-acid esters, para-Fc(C6H4)CONHCH(R)CO2CH3 {Fc = (η5-C5H5)Fe(η5-C5H4); R = H, CH3, CH2CH(CH3)2, CH2C6H5}, 36 have been prepared by coupling para-(ferrocenyl)benzoic acid to the amino-acid esters (gly, l-Ala, l-Leu, l-Phe) using the standard 1,3-dicyclohexylcarbodiimide (DCC), 1-hydroxybenzotriazole (HOBt) protocol. The compounds were fully characterized by a range of spectroscopic techniques including FAB-MS. The X-ray crystal structures of the parent para-(ferrocenyl)benzoyl methyl ester, Fc-C6H4CO2Me, 1 and a chiral derivative N-{para-(ferrocenyl)benzoyl}-l-alanine methyl ester, Fc-C6H4CONHCH(CH3)CO2Me, 4 have been determined.
Keywords: Ferrocene; Biomaterials; Bioorganometallic chemistry; FAB-MS; X-ray crystal structures; Amino-acid esters;

Isostructural organic–inorganic hybrids of P,P -diphenyl-methylenediphosphinate (CH2(P(Ph)O2)2)2− with divalent transition metals by Elisabetta Berti; Franco Cecconi; Carlo A. Ghilardi; Stefano Midollini; Annabella Orlandini; Emanuela Pitzalis (1041-1043).
New organic–inorganic hybrid materials have been synthesized by reaction in water solution of manganese, cobalt or nickel acetates with P,P -diphenylmethylenediphosphinic acid and all the two-dimensional structure coordination polymers obtained have been found to be isomorphous.
Keywords: Organic–inorganic hybrids; Crystal structures; Polymeric complexes; Manganese complexes; Cobalt complexes; Nickel complexes;

Cobalt(II) and manganese(II) complexes of unsymmetric compartmental ligands bearing adjacent {N2O} and {N,S,O} donor sets by Harry Adams; Scott Clunas; David E. Fenton; Gillian Handley; Paul E. McHugh (1044-1047).
The crystal structures of the dinuclear cobalt(II) complex, [ Co 2( L 5)(OAc)(NCS)2(CH 3 OH)], and the trinuclear manganese(II) complex, [ Mn 3( L 7)2(OAc)2(NCS)2 ], are reported.
Keywords: Dinuclear complexes; Cobalt(II); Manganese(II); Crystal structures;

Ruthenium-acetylide barbituric derivatives: evidence for H-bonding donor effects by Jean-Luc Fillaut; Julien Andriès; Johann Perruchon (1048-1051).
Ruthenium-σ-acetylide derivatives connected to barbituric acceptors through a π-conjugated bridge are subject to drastic color changes depending on the nature of the solvent, especially when the barbituric head bears NH groups. A comparative study of the solvatochromism of two homomorphic compounds is described, which underlines the H-bond donor character of such systems.
Keywords: σ-Acetylide complexes; Ruthenium; Solvatochromism; Hydrogen-bonding; Charge transfer;

The novel complex Ind(CO)3Mo–Ru(CO)2Cp (1) (Ind=η5-indenyl,Cp=η5-cyclopentadienyl), as well as other hetero and homo metallic complexes of molybdenum and ruthenium are catalyst precursors in the aerobic oxidation of THF under ambient conditions. Selectivities towards γ-butyrolactone of up to 70% are obtained. For the first time in this transformation, propylformate is isolated besides the lactone.
Keywords: Hetero bimetallic; Molybdenum; Ruthenium complex; Catalytic aerobic oxidation; Cyclic ether;

Comparison of 1-hydroxymethyl-3,5-dimethylpyrazole and 1-benzyl-2-hydroxymethylimidazole coordination properties towards copper(II) by Barbara Barszcz; Tadeusz Głowiak; Julia Jezierska; Krystyna Kurdziel (1056-1058).
Using 1-hydroxymethyl-3,5-dimethylpyrazole as the starting ligand and 2-propanol as the solvent and a molar ratio Cu:L, 1:4, a dinuclear Cu(II) complex has been obtained. The microanalytical data and the crystal structure reveal that the dicopper complex with two bridging methoxide groups contains the 3,5DMePz, 1-CH2O-3,5DMePz and BF4 ligands which are received during the coordination process. The compound shows an antiferromagnetic intramolecular interaction between the Cu(II) ions.
Keywords: Crystal structures; Dicopper(II) complex; Pyrazole complex; Alkoxo bridged compounds;

Novel luminescent samarium(III) chelates by Harri Hakala; Päivi Liitti; Katri Puukka; Jari Peuralahti; Kristiina Loman; Jarkko Karvinen; Pia Ollikka; Alice Ylikoski; Veli-Matti Mukkala; Jari Hovinen (1059-1062).
A series of new stable, luminescent samarium(III) chelates were synthesized and their photophysical properties were measured. The iodoacetamido activated chelate coupled to a peptide was used in a caspase-3 assay.
Keywords: Samarium chelates; Luminescence;

A dinickel(II) complex of a [5,6]-unsymmetrical Schiff base compartmental ligand by Harry Adams; Scott Clunas; David E. Fenton (1063-1065).
In contrast to the reactions of [5,5]-unsymmetrical Schiff base compartmental ligands with Ni(ClO4)2 or Ni(BF4)2, which lead to cleavage of the iminic pendant arm of the ligand, the reaction of Ni(BF4)2 with the [5,5]-unsymmetrical Schiff base compartmental ligand 2-{[(2-dimethylaminoethyl)ethylamino]-methyl}-4-methyl-6-[(2-pyridin-2-yl-ethylimino)methyl] phenol, HL 7 , gave a dinuclear nickel(II) complex in which the integrity of the ligand was retained.
Keywords: Crystal structure; Dinuclear nickel(II) complex;

Preparation of an externally uncomplexed carbamoylborane dimer by Robert F Cunico; Chong Zheng (1066-1068).
B,B-Bismesityl-N-methyl-N-(methoxymethyl)carbamoylborane has been isolated as the dimer from the reaction of dimesitylboron fluoride with N-methyl-N-(methoxymethyl)carbamoyl(trimethyl)silane.
Keywords: Carbamoylsilane; Carbamoylborane; Dimesitylboron;

Epoxidation of olefins catalyzed by molybdenum–siloxane compounds by Marta Abrantes; Anabela A Valente; Martyn Pillinger; Isabel S Gonçalves; João Rocha; Carlos C Romão (1069-1072).
The triphenylsiloxy complex MoO2(OSiPh3)2 and a related polyhedral metallasiloxane formulated as [MoO2(O2SiPh2)] n have been tested as catalysts for the liquid phase epoxidation of cyclic olefins by tert-butylhydroperoxide at 55 °C. The initial activities increased in the order 1-octene <  trans-2-octene < cyclododecene < cyclooctene and the corresponding epoxides were the only observed products. The best results were obtained without the addition of any co-solvents (other than decane), forming solid–liquid systems. Cyclooctene oxide was obtained in quantitative yield within 7.5 h of reaction, and the solid catalysts could be recycled without measurable loss of activity.
Keywords: Metallasiloxanes; Molybdenum; Oxomolybdenum complexes; Epoxidations; tert-Butylhydroperoxide;

The first examples of triply bonded dirhenium(II) complexes that contain β-diketonate ligands by Mani Ganesan; Pramesh N. Kapoor; Phillip E. Fanwick; Richard A. Walton (1073-1077).
The reaction of Re 2 Cl 4(μ-dppm)2  (dppm=Ph 2 PCH 2 PPh 2) with Tl(acac) affords the bis-acetylacetonate complex Re2Cl2(acac)2(μ-dppm)2 (1) via the intermediacy of Re2Cl3(acac)(μ-dppm)2 (2). These are the first examples of β-diketonate complexes of the electron-rich triple bond. Solutions of 1 in non-aqueous solvents slowly convert to 2, which in the presence of an oxygen source decomposes to Re2(μ-O)(O)2Cl4(μ-dppm)2 and Re2(μ-O)2(O)2Cl4(μ-dppm)2 (3). The single crystal X-ray structures of 13 have been determined; the Re–Re distances (in Å) are 2.2968(3), 2.2542(5) and 3.1415(7), respectively.
Keywords: Dirhenium(II) complexes; Multiple metal–metal bonds; Acetylacetonate; β-Diketone ligands;

DNA binding of mixed-metal supramolecular Ru, Pt complexes by Zhenglai Fang; Shawn Swavey; Alvin Holder; Brenda Winkel; Karen J Brewer (1078-1081).
The mixed-metal supramolecular complexes [(tpy)Ru(PEt2Ph)(dpp)PtCl2](PF6)2 and [(tpy)Ru(PEt2Ph)(bpm)PtCl2](PF6)2 are of interest in that they couple light absorbing ruthenium centers to a reactive metal site through a communicative bridge (tpy=2,2:6,2′′-terpyridine, bpm=2,2-bipyrimidine and dpp=2,3-bis(2-pyridyl)pyrazine). These systems have been studied and shown to avidly bind to DNA, greatly reducing its mobility through an agarose gel.
Keywords: Supramolecular; Ruthenium; Platinum; DNA binding; Mixed-metal;

Crystallisation of the sodium perchlorate adduct of N,N -dipyridyl-bis-aza-18-crown-6 from acidic aqueous conditions yielded [(H3O)(N,N -dipyridyl-bis-aza-18-crown-6)][ClO4] and [Na·N,N -dipyridyl-bis-aza-18-crown-6]2 [(H+)2 N,N -dipyridyl-bis-aza-18-crown-6][ClO4]4·2H2O. The conformations of crown ethers were significantly influenced by incorporation of an H3O+ or sodium ion, or protonation of the amino nitrogen atoms resulting in three different structures for the macrocycle.The conformations of the N,N -dipyridyl-bis-aza-18-crown-6 host molecule are significantly influenced by incorporation of an H3O+ or sodium ion guest, or protonation of the amino nitrogen atoms; resulting in three different structures for the macrocycle.
Keywords: Macrocyclic compounds; Crown ethers; X-ray crystallography; Oxonium ions;

Crystal structure of a new oximato-bridged one-dimension(1D) chain-like copper complex polymer {[Cu4(dmg)2(Hdmg)2(H2dmg)2(H2O)2](ClO4)2} by Xuan-Wen Liu; Sheng Chu; Xiao-Qing Wang; Yang Zhang; Ruji Wang; Guang-Qiu Shen; De-Zhong Shen (1086-1089).
A novel copper complex polymer {[Cu4(dmg)2(Hdmg)2(H2dmg)2(H2O)2](ClO4)2} (H2dmg=dimethylglyoxime) has been synthesized and its structure was determined by X-ray single crystal diffraction methods. The complex polymer is like a 1D infinite chain with topological type as a sequence of fused rings connected by out-planar CuO bonds, in which oximato groups (NO) act as two-dentate bridges to link center Cu2+ cations. This structure shows that oximes have great perspective in coordination chemistry and supramolecular polymer chemistry. Molecular structure and spectroscopic properties of the polymer complex were discussed in the article.
Keywords: Crystal structure; Copper complex; H2dmg; 1D-chain; Oximato-bridged;

The reaction of the elongated Schiff base 1,4-bis(4-pyridyl)-2,3-diaza-1,3-butadiene and PbI2 in DMF gave rise to two- and one-dimensional organic–inorganic hybrid compounds [PbI2(C12H10N4)]2n ·0.5n(C12H10N4) (1) and [PbI2(C12H10N4)] n (2), respectively, at different M/L ratios 2:1 and 1:1,and their structures were determined by single-crystal X-ray crystallography. Compound 1 exhibits 2D-layered structure formed from PbI2 chains bridged by the Schiff base with the free ligand regularly lying between two layers, while compound 2 possesses a 1D-zig-zag chain where lead atom is in the rarely observed four-coordinate holodirected configuration. 2 is the first example of PbI2-based polymer with terminal coordinated iodine atoms.
Keywords: Lead; Schiff-base; Coordination polymer; Crystal structure;

The macrocyclic tetranuclear copper(II) complex [L2Cu4(μ-CO3)2](ClO4)4·4H2O is synthesized by [2 + 2] condensation of the organic ligand L and a rational [2 + 2] assembly of the polynuclear complex; the structure, stability and catalase-like activity are investigated.
Keywords: Macrocycle; Tetranuclear copper(II) complex; Catalase-like activity;