Inorganic Chemistry Communications (v.7, #10)

Contents list (iii-viii).

Crystal structure and energy transfer of trans-RSSR-[CrCl2(cyclam)]3[Cr(CN)6] · 14H2O by Marcos Flores-Alamo; Martha E. Sosa-Torres; Rubén A. Toscano; Enrique Camarillo; José M. Hernández; Héctor Murrieta (1087-1090).
Within the study of the counterion effect on the optical properties of the cation in trans-RSSR-[CrCl2(cyclam)]2ZnCl4, we synthesised and characterised by spectroscopic techniques and X-ray crystallography the trans-RSSR-[CrCl2(cyclam)]3[Cr(CN)6] · 14H2O (1) complex.Within the study of the counterion effect on the optical properties of the cation in trans-RSSR-[CrCl2(cyclam)]2ZnCl4, we synthesised and characterised by spectroscopic techniques and X-ray crystallography the trans-RSSR-[CrCl2(cyclam)]3[Cr(CN)6] · 14H2O (1) complex. The X-ray structural analysis of 1 shows that the crystal network involves hydrogen bonding distances of (N(1)H(1)⋯N(27)C(26) 2.29(7) and N(18)H(18)⋯N(27)C(26) 2.33(6) Å, and distances between cation and anion: Cr(1)⋯Cr(3) and Cr(2)⋯Cr(3) were found to be 6.999 and 6.924 Å. The lifetime emission for Cr(1)(2) was found to be 17 μs, while the lifetime for Cr(3) was found to be 100 μs. These values are a consequence of an energy transfer process. This energy transfer through the supramolecular interactions of the cation and anion via hydrogen bonding is probably responsible for the optical properties shown by 1 in the solid state.
Keywords: Macrocyclic chromium(III) complex; Hexacyanochromate; Supramolecular array; Hydrogen bonding; Luminescence; Energy transfer;

The crystal structure of the novel complex [HL]+[Zn(S2COEt)3] (L = 3,6-diaminoacridine) reveals that the three xantathe ligands show different coordination modes to the zinc, and cations and anions are arranged in a supramolecular array in which H-bonding interactions are present.A novel xanthate complex [HL]+[Zn(S2COEt)3] (L = 3,6-diaminoacridine) has been sythesized by reaction of [Zn(S2COEt)2] with 3,6-diaminoacridine hemisulfate. The structure of the compound reveals that the three xantathe ligands show different coordination modes to the zinc and cations and anions are arranged in a supramolecular array in which H-bonding interactions are present.
Keywords: Zinc(II) complexes; Xanthate; Diaminoacridine; Crystal structure; H-bonds;

A novel coordination polymer constructed from 1D neutral chains via inter-chain π–π stacking and hydrogen bonding.A novel 1D neutral coordination polymer, {[Cu(dtmp)(dmf)Cl2]dmf} n (1) (dtmp = 1,6-di(triazole-1-yl-methyl)-4-methylphenol, dmf = dimethyl formamide) was synthesized by reacting CuCl2  · 2H2O with the dtmp ligand. The crystal and molecular structure of the complex was determined by X-ray diffraction, in which the coordination geometry around the copper center is slightly distorted trigonal bypyramidal. One-dimensional chains have been formed through the metal and the ligand via coordination bonds, which are assembled further into a two-dimensional network by inter-chain synergic π–π stacking and hydrogen bonding.
Keywords: 1D coordination polymer; Crystal structure; π–π stacking; Hydrogen bonding;

The Keggin structure complex of carbenium ions: hydrothermal synthesis and characterization of [CH3CHCH3]3[PMo12O40] by Fang-fang Jian; Hai-Lian Xiao; Zhan-Ru Zhao; Ping-Ping Sun; Pu-Su Zhao (1100-1102).
A novel Keggin unit containing n-propylcarbocation complex, [CH3CHCH3]3[PMo12O40], was synthesized by a hydrothermal method in the presence of CuCl2. X-ray structure analysis has confirmed the presence of the [CH3CHCH3]+ cations in [CH3CHCH3]3[PMo12O40]. Its structure was also characterized by thermogravimetric analysis.A novel Keggin unit containing n-propylcarbocation complex, [CH3CHCH3]3[PMo12O40], was synthesized by a hydrothermal method in the presence of CuCl2. X-ray structure analysis has confirmed the presence of the [CH3CHCH3]+ cations in [CH3CHCH3]3[PMo12O40]. Its structure was also characterized by thermogravimetric analysis.
Keywords: Keggin structure; carbocation; hydrothermal reaction;

Indium compounds, [In{Se2P(OR)2}3](R = Et, i Pr), containing dialkyl diselenophosphato ligands were isolated and characterized. Indium atom is coordinated by three dsep ligands forming a distorted octahedral geometry. Weak intermolecular Se⋯Se interactions exist between adjacent molecules. VT 31P NMR studies suggest that In–Se bonds are labile in solution.Weak intermolecular Se⋯Se interactions exist between adjacent molecules of [In{Se2P(O i Pr)2}3] and form a loosely connected dimer. VT 31P NMR studies suggest that In–Se bonds are labile in solution.
Keywords: Diselenophosphates; Indium; Se⋯Se interactions; Supramolecular structure;

Synthesis and coordination of 7-diphenylphosphinoazaindole (dppai) by Heather L. Milton; Matthew V. Wheatley; Alexandra M.Z. Slawin; J. Derek Woollins (1106-1108).
Index entry: 7-diphenylphosphinoazaindole has been synthesised and coordinated as a P,N bidentate ligand.7-diphenylphosphinoazaindole has been synthesised and coordinated as a P,N bidentate ligand. Reaction of dppai with [PtCl2(cod)], [PtClMe(cod)] and [PtClPh(cod)] in dichloromethane gives [PtCl2(dppai-P,N)], [PtClMe(dppai-P,N)] and [PtClPh(dppai-P,N)] respectively.
Keywords: Ligands; Phosphines; Crystal structure;

N2,S-versus N3,S-coordination in thiosemicarbazonate complexes: only a steric influence? by José S. Casas; Eduardo E. Castellano; Javier Ellena; María S. García-Tasende; Agustín Sánchez; José Sordo; Ángeles Touceda-Varela (1109-1112).
A new diphenyllead(IV) thiosemicarbazonate complex in which one ligand is N2,S- and the other N3,S-coordinated throws light on factors influencing whether N2 or N3 is bound in N,S-coordinated thiosemicarbazone complexes.The factors that determine the formation of Nhydrazinic,S- or Niminic,S-coordinate thiosemicarbazonate complexes in the solid state are examined in the light of the X-ray structure of the complex [PbPh2(EtGTSC)2] · H2O (HEtGTSC = ethylglyoxylate thiosemicarbazone).
Keywords: Thiosemicarbazonate complexes; Diphenyllead(IV) complexes; Crystal structure;

The reaction of tris(dihydroxyphosphonomethyl)phosphinoxide, 2,2′-bipyridyne and copper(II) chloride gave rise to the complex [Cu(2,2′-bipy){OP(CH2PO3H2)(CH2PO3H)2}] n , where an intricate system of hydrogen bonding interactions creates a 2D layer network.The reaction of tris(dihydroxyphosphonomethyl)phosphinoxide, 2,2′-bipyridyne and copper(II) chloride gave rise to the complex [Cu(2,2′-bipy){OP(CH2PO3H2)(CH2PO3H)2}] n , where an intricate system of hydrogen bonding interactions creates a 2D layer network.
Keywords: Copper(II) complex; H-bonded network; Tripodal phosphonate; Crystal structure;

The first report of a cyano bridged one dimensional Sr(II)–Fe(II) nitrosyl complex [Sr(Phen)2(DMF)2][Fe(NO)(CN)5] having the structure A is reported. Its interesting spectroscopic properties are described.A new Cyano bridged Sr(II)–Fe(II) nitrosyl complex [Sr(Phen)2(DMF)2][Fe(NO)(CN)5] (Phen = 1,10 Phenanthroline and DMF = Dimethylformamide) has been synthesized and structurally characterized. The structure analysis revealed that the complex has a one-dimensional chain of [Sr(Phen)2(DMF)2][Fe(NO)(CN)5] unit, which is bridged by a cyano group. In other words [Sr(Phen)2(DMF)2]2+ units are bridged by [Fe(NO)(CN)5]2−.
Keywords: Heterobimetallic complex; Sr(II)–Fe(II); Cyanide-bridged complexes; Nitroprussides; Nitrosyl; Crystal structure;

A new mixed-valence copper(I,II) coordination polymer with 2-D interpenetrating framework based on paddle-wheel dicopper units by Yi-Hang Wen; Jian-Kai Cheng; Jian Zhang; Zhao-Ji Li; Yao Kang; Yuan-Gen Yao (1120-1123).
The hydrothermal reaction of isophthalatic acid, 4,4′-bipyridine and Cu(NO3)2  · 3H2O at 160 °C produces a new mixed-valence copper(I,II) coordination polymer with 2-D interpenetrating framework based on paddle-wheel dicopper units. It has been characterized by single-crystal X-ray diffraction, IR, XPS, EPR and TGA.A new mixed-valence copper(I,II) coordination complex with [Cu2O8] paddle-wheel dicopper units, [CuIICuI(ip)(ipH)(4,4′- bipy)3/2] n (ipH2  = isophthalatic acid; 4,4′-bipy = 4,4′-bipyridine) (1), has been hydrothermally synthesized and characterized by single-crystal X-ray diffraction, IR, XPS, EPR and TGA. It exhibits a 2-D interpenetrating grid framework, in which five-coordinated CuII and three-coordinated CuI environments are established.
Keywords: Hydrothermal synthesis; Mixed-valence; 2-D interpenetrating grid framework; Paddle-wheel dicopper units; Mixed-ligand; Copper complex;

Hybrid molecular systems were constructed based the hydrolysis and condensation process between ternary lanthanide complexes with 3-methacryloxypropyltrimethoxysilane and 1,10-phenanthroline and tetraethoxysilane, which exhibit strong green or red luminescence of Tb3+ and Eu3+ ions.Two ternary precursor lanthanides (abbreviated as Ln, terbium and europium) complexes with 3-methacryloxypropyltrimethoxysilane and 1,10-phenanthroline were successfully prepared. Then the resulting compounds and tetraethoxysilane further form luminescent hybrid systems with the hydrolysis and condensation of their alkoxy groups through an in situ sol–gel process. The intramolecular energy transfer process runs smoothly within these molecular-based hybrids in terms of sensitized functions of 1,10-phenanthroline and strong characteristic green or red emission of Tb3+ and Eu3+ has been achieved.
Keywords: Luminescence; 1,10-phenanthroline; Ternary molecular complex hybrids; TEOS; Europium; Terbium; 3-methacryloxypropyltrimethoxysilane;

Regioselective metal-directed self-assembly of a prototype double helical hairpin dinuclear complex by Edwin C. Constable; Inger Annette Hougen; Catherine E. Housecroft; Markus Neuburger; Silvia Schaffner; Louise A. Whall (1128-1131).
A new type of covalently linked bis(oligopyridine) ligand, L, has been prepared with a spacer group long enough to allow the formation of double helical M2L complexes; the solid-state structure of [Cu2L][PF6]3 shows regioselective formation of the “head-to-tail” hairpin complex.A new type of covalently linked bis(oligopyridine) ligand, 4, has been prepared with a spacer group long enough to allow the formation of double helical M2L complexes; the solid-state structure of [Cu2(4)][PF6]3 shows regioselective formation of the “head-to-tail” hairpin complex.
Keywords: Copper(I); Copper(II); Hairpin complex; Helicate; Oligopyridine ligand;

A novel cage cluster with nine-vertices 1 is obtained by the reaction of 2 with methylpropiolate. X-ray crystallography revealed that the open space of the incomplete cubane-type Mo3S4 core was covered by methyl-propiolate through three C–S bonds. 1H NMR spectroscopy showed an unusual low-magnetic-field resonance assignable to Hb of 1.A novel cage cluster with nine-vertices [Mo33-S)(μ3-SCH(CO2CH3)CHS2)(μ-OAc)2(dtp)3] (1) is obtained by the reaction of [Mo33-S)(μ-S)3(μ-OAc)(dtp)3(CH3CN)] (2) with methylpropiolate (MP) in acetonitrile containing acetic acid. X-ray crystallography revealed that the open space of the incomplete cubane-type Mo3S4 core was covered by a methyl-propiolate ligand through three C–S bonds. Cluster 1 has been characterized by 13C and 1H NMR and electronic spectroscopy.
Keywords: Cage cluster; Nine vertices; Molybdenum; Sulfur; Methylpropiolate; Adduct;

Synthesis and structure of bis{η5-1,2,3,4-tetramethyl-5-(dimethylsilylsulfido-κS)cyclopentadienyl}titanium(IV) by Jiřı́ Pinkas; Róbert Gyepes; Petr Štěpnička; Jiřı́ Kubišta; Michal Horáček; Karel Mach (1135-1138).
Sulfane cleaves both Si–N and Ti–Cl bonds in bis{η5-(N,N-dimethylaminodimethylsilyl)tetramethylcyclopentadienyl}dichlorotitanium(IV), [TiCl25-C5Me4(SiMe2NMe2)}2] (1) to give sulfido-tethered titanocene compound bis{η5-1,2,3,4-tetramethyl-5-(dimethylsilylsulfido-κS)cyclopentadienyl}titanium(IV) (4).Bis{η5-(N,N-dimethylaminodimethylsilyl)tetramethylcyclopentadienyl}dichlorotitanium(IV), [TiCl25-C5Me4(SiMe2NMe2)}2] (1), reacts with sulfane under cleavage of both Si–N and Ti–Cl bonds to give sulfido-tethered titanocene compound bis{η5-1,2,3,4-tetramethyl-5-(dimethylsilylsulfido-κS)cyclopentadienyl}titanium(IV), [Ti{η5-C5Me4(SiMe2S- κS)}2] (4), and dimethylamine hydrochloride as the byproduct. The crystal structure of compound 4 has been determined by single-crystal X-ray diffraction.
Keywords: Titanium; Titanocene; Pendant amine group; Sulfanolysis; Cyclopentadienylsulfide bridge; Crystal structure;

1D chain structure, NLO and luminescence properties of [ Zn 2 ( bpp ) ( pht ) 2 ] ∞ 1 by Yu-Biao Chen; Jian Zhang; Jian-Kai Cheng; Yao Kang; Zhao-Ji Li; Yuan-Gen Yao (1139-1141).
These infinite chain molecules stack in AA… and BB… patterns along b-axis and in an ABAB… pattern along a-axis. This kind of molecular packing makes 1 be arranged into a non-centrosymmetric space symmetry.The neutral one-dimensional coordination polymer [ Zn 2 ( bpp ) ( pht ) 2 ] ∞ 1 (bpp = 1,3-bis(4-pyridyl)propane, pht = 1,2-benzenedicarboxylate) (1) has been synthesized by the hydrothermal reaction of zinc sulfate with mixed ligands in mixed EtOH/H2O solution. The structure of complex 1 consists of an infinite neutral dinuclear zinc chain linked by pht and bpp ligands. The Kurtz powder technique shows that complex 1 has a powder SHG of about two times as large as that of potassium dihydrogen phosphate (KDP), which validates that complex 1 is a non-centrosymmetric crystal structure.
Keywords: Hydrothermal reaction; Coordination polymer; NLO; Luminescence; TGA;

Tetrahydrothiophene complexes of technetium(IV) by Adelheid Hagenbach; Ulrich Abram (1142-1144).
Neutral or anionic technetium(IV) complexes of the compositions [TcCl4(tht)2] or [TcBr5(tht)] are formed when hexachlorotechnetate(IV) or hexabromotechnetate(IV) react with tetrahydrothiophene (tht). The new compounds can be used as precursors for the synthesis of further technetium(IV) complexes.A technetium(IV) complex of the composition trans-[TcCl4(tht)2] (tht = tetrahydrothiophene) is formed during heating of K2TcCl6 in a mixture of tht and aqueous HCl. The thioether ligands are only weakly bonded and the red crystals slowly decompose under release of tht. The weak technetium–sulphur bonds are confirmed by Tc–S distances of 2.494(1) Å. The anionic thioether technetium(IV) complex [TcBr5(tht)] is formed by the reaction of (NBu4)2[TcBr6] with neat tht. The tetrabutylammonium salt of the complex is indefinitely stable in air.
Keywords: Technetium; Thioether; Tetrahydrothiophene; Synthesis; Crystal structure;

2-D open frameworks and blue fluorescence of two new zinc coordination polymers with mixed ligands by Ling Xu; Guo-Cong Guo; Bing Liu; Ming-Sheng Wang; Jin-Shun Huang (1145-1149).
Two new zinc compounds with bdc2− and 4,4′-bipy were obtained from diffusion method, in which the Zn atoms were bridged by the mixed ligands to form 2-D square net for 1 and 2-D interpenetrating herringbone-like structure for 2. Both compounds show strong blue fluorescence originated from the bdc2− ligand emission.Two new coordination polymers [Zn(bdc)(4,4′-bipy)(H2O)] · 1.5H2O (1) and [Zn2(bdc)2(4,4′-bipy)(EtOH)(H2O)2] · EtOH · 0.5H2O (2) (H2bdc: 1,3-benzenedicarboxylates, 4,4′-bipy: 4,4′-bipyridine) are obtained from the diffusion method. In 1, bdc2− ligand adopts μ211 coordination mode, while in 2, one of the two crystallographically independent bdc2− ligands is μ212 fashion, and the other one is similar to that in 1. The structure of 1 exhibits a 2-D square net and 2 features a 2-D interpenetrating herringbone-like structure. Both 1 and 2 show blue fluorescence owing to the photoluminescence from the bdc2− ligand emission.
Keywords: Zinc compounds; Diffusion; Crystal structure; Fluorescence;

A cyano-bridged Mn(III)–W(V) complex has been synthesized and characterized structurally and magnetically. The complex contains two-dimensional gridlike layers, which are connected by K+ ions giving rise to a 3D network. It exhibits 3D ferromagnetic ordering below 18.0 K and coercivity at 1.85 K.A hetero-bimetallic complex K[Mn(acacen)]2[W(CN)8] · 2H2O (acacen2−  = dianion of N,N′-ethylenebis(acetylacetonylideneaminato)) consists of two-dimensional gridlike {[Mn(acacen)]2[W(CN)8]} layers that are linked by K+ ions giving rise to a three-dimensional network. Ferromagnetic Mn(III)–W(V) coupling and magnetic ordering at 18.0 K (T c) have been observed in the complex.
Keywords: Crystal structure; Manganese complex; Tungsten complex; Schiff base; Cyanide bridging; Magnetic property;

Novel oxalate coordination mode and roles: synthesis, structure and fluorescence property of [Cd25-ox)(μ3-OH)2] with 3-D structure by Jing Lu; Yong Li; Kui Zhao; Ji-Qing Xu; Jie-Hui Yu; Guang-Hua Li; Xiao Zhang; Hai-Ying Bie; Tie-Gang Wang (1154-1156).
Coordination compound [Cd25-C2O4)(μ3-OH)2] displays a 3-D framework with two kinds of channels: 10-membered and helical 8-membered, in which the ox ligands adopt the μ5-bridging novel coordination mode and play a dual role simultaneously.A coordination compound [Cd25-C2O4)(μ3-OH)2] 1, which was synthesized from hydrothermal reactions, possesses some attractive structural features: (a) oxalate unit exhibits a five-bridging novel coordination mode and plays a dual role simultaneously; (b) [Cd(OH)] corrugated sheet and 3-D [Cd2(ox)] network are intercrossed with each other in the vertical direction. Compound 1 exhibits strong fluorescent emission.
Keywords: Hydrothermal synthesis; Coordination mode; Oxalate; Fluorescence;

Synthesis and characterization of highly conducting PyH[Pd(dmit)2]2 crystal by Qi Fang; Wen Xu; Hong Lei; Cui-Ying Xu; Bin Zhang; Dao-Ben Zhu (1157-1160).
A new molecular conductor PyH[Pd(dmit)2]2 (PyH = pyridinium) has been synthesized and its crystal structure been determined. The conductivity was measured to be as high as 2 × 102 Ω−1  cm−1 at room temperature. From 290 to 50 K, the crystal shows semi-conductivity and then turns to metallic conductivity.A new molecular conductor PyH[Pd(dmit)2]2 (PyH = pyridinium, dmit = 2-thioxo-1,3-dithiole-4,5-dithiolato) has been synthesized and structurally investigated. The room temperature conductivity at a certain direction on (0 0 1) plane was measured to be as high as a 2 × 102 Ω−1  cm−1. In the temperature range of 290–50 K, the crystal shows semi-conductivity with a small activation energy of 0.102 eV. In the range of 49–27 K, it exhibits metallic conducting behavior.
Keywords: Palladium complex; Synthesis; X-ray crystal structure; Conductivity;

The synthesis and characterization of a new Ph3Sn(IV) derivative of thymidine are reported.The synthesis and characterization of a new Ph3Sn(IV) derivative of thymidine are reported. The polyhedron around tin is trigonal bipyramidal in the solid-state with three phenyl groups in the equatorial positions, while the axial positions are occupied by 3′(O) and 2(O) of two thymidine. Ph3Sn(Thy) exhibited moderate anti-inflammatory and insignificant cardiovascular activity.
Keywords: Triorganotin(IV); Thymidine; Biological; Nucleoside;

A novel color change was observed on immobilization of a copper Schiff-base complex in Y-zeolitic matrix. Various physico-chemical studies have been undertaken to understand the mechanism of this chromotropism. A remarkable catalytic performance of the hybrid material was observed in the hydroxylation of phenol and 1-naphthol.The deep purple colored [Cu(3-EtO-salen)] [3-EtO-salenH2  =  N,N′-bis-(3-ethoxysalicylaldehyde)-ethylenediimine] turns yellow when encapsulated in NaY zeolite. The hybrid materials Cu(3-EtO-salen)–NaY as well as the pristine complex [Cu(3-EtO-salen)] have been characterized using several techniques like IR spectroscopy, electronic spectroscopy, X-ray powder diffraction, EPR spectroscopy to understand the mechanism of the color change. The hybrid material showed excellent catalytic activity in hydroxylation reactions towards phenol and 1-naphthol.
Keywords: Zeolite; Immobilization; Heterogeneous catalysis; Oxidation;

A binuclear tetrahedral zinc(II) complex of 2-(2-pyridyl)benzo[1,2-d;4,5-d′]diimidazole with strong blue fluorescence by Xiao-Ju Lin; Zhen Shen; Hai-Jun Xu; Yi-Zhi Li; Hong-Tao Zhang; Xiao-Zeng You (1167-1169).
The structure of a binuclear zinc(II) complex of pbdiim (pbdiim = 2-(2-pyridyl)benzo[1,2-d;4,5-d′]diimidazole) has been determined by X-ray crystallography analysis, it exhibits more planar structure and displays strong blue fluorescence at room temperature than the pbdiim molecule.A binuclear Zn(II) complex: Na[Zn2(pbdiim)Cl5] · 1.5H2O (pbdiim = 2-(2-pyridyl)benzo[1,2-d;4,5-d′]diimidazole) (1) has been prepared and the crystal structure determined by single-crystal X-ray diffraction. The pbdiim ligand coordinates to two zinc ions in which each zinc ion adopts a distorted tetrahedral geometry. Complex 1 has a more planar structure and displays strong blue fluorescence at room temperature than the pbdiim molecule.
Keywords: Zinc complex; Benzodiimidazole ligand; Crystal structure; Fluorescence;