Synthesis and structure of uranyl complexes with malonic acid dianions

The uranyl complexes with malonic acid dianions [UO₂(C₃H₂O₄)(CO(NH₂)₂)]·H₂O (1), [UO₂(C₃H₂O₄)(CONH₂NMe₂)]·H₂O (2), and [UO₂(C₃H₂O₄)(MeCONMe₂)] (3) were synthesized and characterized by X-ray crystallography. The structural units [UO₂(C₃H₂O₄)L] in the crystals of 1–3 refer to the AK²¹M¹ crystal chemical group (A = UO₂ ²⁺, K²¹ = C₃H₂O₄ ^2?, M¹ = L) of uranyl complexes; the crystals of 1 have a framework structure and 2 and 3 have a chain structure. Some structural features of the [UO₂(C₃H₂O₄)L] complex groups are discussed.     

Synthesis and properties of ZnII and CdII complexes with chiral N-derivatives of aminoacetic acid based on natural monoterpenes (+)-3-carene and (?)-��-pinene. Crystal structure of coordination polymer [Zn(HL)Cl��2H2O] n

Chiral sodium salts of N-derivatives of aminoacetic acid based on (+)-3-carene (HLNa) and (?)-??-pinene (HLNa) were synthesized. Complexes Zn(HL)Cl (1), Cd(HL)Cl·0.5H₂O (3), Zn(HL??)Cl·0.5H₂O (4), and Cd(HL??)Cl·0.5H₂O (5) were obtained. The single crystals of the coordination polymer [Zn(HL)Cl·2H₂O] _n (2) were grown. According to the X-ray diffraction analysis, the crystal structure of 2 consists of 1D chains built of Zn(HL)Cl and water molecules. The coordination polyhedron ClN₂O₂ is a distorted square pyramid. The HL^? ligand performs the chelating tetradentate-bridging function, and the COO^? group binds two adjacent Zn atoms. The IR spectroscopy data for compounds 1 and 3?C5 indicate the coordination of the COO^?, NOH, and NH functional groups. The excitation and photoluminescence (PLM) spectra of the solid samples of compounds HLNa, HL??Na, 1, and 3?C5 were recorded at room temperature. The compounds exhibit blue PLM. The intensity of PLM of the CdII complexes is higher than that of the ZnII complexes, which is a characteristic feature of PLM of the studied compounds.     

Scorpionate nickel complexes with dicarboxylic acid ligands: influence of different spanning dicarboxylato co-ligands on the structures

Three new scorpionate nickel complexes [Tp*Ni(Hglu)(H₂O)]·EtOH (1), Tp*Ni(Haze)(MeOH) (2), and Tp*Ni(HTA)(H₂O) (3) (Tp*?=?hydrotris(3,5-dimethylpyrazolyl)borate) with different spanning dicarboxylo co-ligands (H₂glu?=?glutaric acid, H₂aze?=?azelaic acid, H₂TA?=?tetradecane diacid) were synthesized by solution methods at room temperature. X-ray crystallographic analyses of complexes 1?C3 demonstrate that these three octahedral Ni scorpionate complexes each contain an anionic chelating dicarboxylic acid, O₂C(CH₂) _n COOH, n?=?3, 7, and 12, respectively. The sixth coordination site is occupied by an ethanol, methanol, or water that is hydrogen bonded to the terminal carboxylic acid end of the anionic dicarboxylic acid ligand from a different Tp*Ni complex in the crystal lattice. Through these abundant hydrogen bond interactions, complexes 1 and 2 form 2D hydrogen bonding network structures, respectively, while complex 3 has a 1D infinite double-chain structure. The results of quantum mechanical calculations and thermogravimetric analyses on these complexes are presented and discussed.     

Secondary interactions in the crystal structure of the iminate amine gold(III) complex [Au(C9H19N4)]I2

The acyclic iminate amine gold(III) complex iodide [Au(C₉H₁₉N₄)]I₂ (I) was obtained. The crystal structure of complex I is stabilized by weak secondary interactions N-H??I, C-H??Y (Y = I, Au, and ??), and Au??I forming an infinite 2D network. Double stacks of cations along the axis x are united through zigzag chains of H-bonds and of secondary contacts. Structure I contains 3?C14-membered cation-cation and cation-anion rings. The anions I(1)^? and I(2)^? act as bridges in structure I.     

3-(diallylamino)propanenitrile ((C3H5)2NC2H4CN, L) π-complexes with copper(I) ionic salts. Syntheses and crystal structures of compounds [Cu(H+L)ClO4]ClO4 · H2O, [Cu(H+L)BF4]BF4 · H2O, and [Cu(H+L)(H2O)]SiF6 · H2O

Qualitative single crystals of ??-complexes Cu(H⁺L)(ClO₄)]ClO₄ · H₂O (I), Cu(H⁺L)(BF₄)]BF₄ · H₂O (II), and [Cu(H⁺L)(H₂O)]SiF₆ · H₂O (III) are synthesized from solutions of 3-(diallylamino)propanenitrile (L) in propanol, ethanol, and methanol-water acidified with the corresponding acid to pH 3.5?C5 and from the copper(II) salts (Cu(ClO₄)₂ · 6H₂O, Cu(BF₄)₂ · 6H₂O, and CuSiF₆ · 4H₂O) using the alternating-current electrochemical method on copper wire electrodes. The crystal structures of the complexes are determined. All compounds crystallize in the monoclinic crystal system: complexes I and II are isostructural, space group P2₁/n, Z = 4. For compound III, space group P2₁/c, Z = 8. Unit cell parameters: for I a =7.8153(3), b = 16.7824(7), c = 12.4426(5) ?, ?? = 93.410(2)°, V = 1629.1(1) ?³; for II, a = 7.6755(4), b = 16.7119(7), c = 12.3784(6) ?, ?? = 94.354(2)°, V = 1583.2(1); and for III a = 9.826(2), b = 24.009(3), c = 12.061(2) ?, ?? = 91.820(6)°, V = 2843.9(7) ?³. The trigonal pyramidal coordination of the copper atom in complexes I-III is formed by two C=C bonds of the allyl groups of H⁺L, the nitrile N atom of the adjacent cation of the ligand, and the O or F atom of the ClO ₄ ^? or BF ₄ ^? anions. In structure III, the apical position of the pyramid is occupied by the O atom of the water molecule, since the SiF ₆ ^2? anion is considerably remote from the copper(I) atom. However, this anion is bound to the organic cation by hydrogen bonds F??H (2.05?C2.51 ?).     

Syntheses, characterization and ethylene polymerization of half-sandwich group IV metal complexes with tridentate [O,N,S] ligands

A series of half-sandwich group IV metal complexes with tridentate monoanionic phenoxy-imine arylsulfide [O NS] ligand [2-Bu t 4-Me-6-((2-(SC 6 H 5)C 6 H 4 N = CHC 6 H 2 O)](La) and dianionic phenoxy-amine arylsulfide [O N S] ligand [2-Bu t 4-Me-6-((2-(SC 6 H 5)C 6 H 4 N-CH 2 C 6 H 2 O)] 2(Lb) have been synthesized and characterized.Lb was obtained easily in high yield by reduction of ligand La with excess LiAlH 4 in cool diethyl ether.Half-sandwich Group IV metal complexes CpTi[O NS]Cl 2(1a),CpZr[O NS]Cl 2(1b),CpTi[O N S]Cl(2a),CpZr[O N S]Cl(2b) and Cp * Zr[O N S]Cl(2c) were synthesized by the reactions of La and Lb with CpTiCl 3,CpZrCl 3 and Cp * ZrCl 3,and characterized by IR,1 H-NMR,13 C-NMR and elemental analysis.In addition,an X-ray structure analysis was performed on ligand Lb.The title Group IV half-sandwich bearing tridentate [O,N,S] ligands show good catalytic activities for ethylene polymerization in the presence of methylaluminoxane(MAO) as co-catalyst up to 1.58 × 10 7 g-PE.mol-Zr 1.h 1.The good catalytic activities can be maintained even at high temperatures such as 100 ℃ exhibiting the excellent thermal stability for these half-sandwich metal pre-catalysts.     

Macrocyclic organotin(IV) carboxylates based on benzenedicarboxylic acid derivatives: Syntheses, crystal structures and antitumor activities

Six new organotin carboxylates based on 1,3-benzenedicarboxylic acid and 1,4-benzenedicarboxylic acid derivatives, namely (Ph₃Sn)₂(2,5-L¹)(C₂H₅OH)₂ (1) (2,5-H₂L¹ = 2,5-dibenzoylterephthalic acid), (Ph₃Sn)₂(2,5-L²)(C₂H₅OH)₂ (2) (2,5-H₂L² = 2,5-bis(4-methylbenzoyl)terephthalic acid), (Ph₃Sn)₂(2,5-L³)(C₂H₅OH)₂ (3) (2,5-H₂L³ = 2,5-bis(4-ethylbenzoyl)terephthalic acid), [(n-Bu₂Sn)₄(4,6-L¹)O₂(OH)(OC₂H₅)]₂·2(C₂H₅OH) (4) (4,6- H₂L¹ = 4,6-dibenzoylisophthalic acid), [(n-Bu₂Sn)₄(4,6-L¹)O₂(OH)(OC₄H₉)]₂·2(C₄H₉OH) (5) and [(n-Bu₂Sn)₄(4,6-L²)O₂(OH)(OC₂H₅)]₂·2(C₂H₅OH) (6) (4,6-H₂L² = 4,6-bis(4-methylbenzoyl)isophthalic acid), have been synthesized. All the organotin carboxylates have been characterized by elemental analysis, IR, ¹H and ¹³C NMR spectroscopy and X-ray crystallography diffraction analyses. The structural analysis reveals that complexes 1-3 show similar structures, containing binuclear triorganotin skeletons. The significant intermolecular O-H?O hydrogen bonds linked the complexes 1-3 to form a novel 2D network polymer with 38-member macrocycles. In complexes 4-6, two Sn₄O₄ ladders are connected by two 1,3-benzenedicarboxylic acid derivatives to yield ladder-like octanuclear architectures and form macrocycle with 24 atoms. In addition, the antitumor activities of complexes 1-6 have been studied.     

Synthesis and crystal structure of the salt of the protonated thiamine cation with the palladium(II) tetrachloride anion [HTA]2[PdCl4]Cl2 · 2H2O

The reaction of thiamine chloride hydrochloride with a solution of palladium chloride in hydrochloric acid gave a protonated thiamine salt [HTA]₂[PdCl₄]Cl₂ · 2H₂O (I) (TA is 4-methyl-3-[(2??-methyl-4??-amino-3??,4??-dihydropyrimidinyl-5??)methyl]-5-(2-hydroxyethyl)thiazolium cation, C₁₂H₁₆N₃O₂S). The crystal structure of I was determined by X-ray diffraction. The crystals are triclinic: a = 11.459(8) ?, b = 12.239(8) ?, c = 6.910(1) ?, ?? = 103.24(3)°, ?? = 76.95(3)°, ?? = 106.04(3)°, Z = 2, space group P $\bar 1$ . The structural units of I are doubly charged [HTA]²⁺ cations, [PdCl₄]^2? and Cl^? anions, and crystallization water molecules combined by hydrogen bonds and electrostatic interactions. The planar thiazolium and pyrimidine rings are in the F conformation, ??_t = 1.0°, ??_p = ?86.6°, and the dihedral angle between the planes is 85.5°. The torsion angles of the hydroxyethyl group are as follows: C(9)C(10)C(11)O(1), 175.6°; S(1)C(9)C(10)C(11), 33.2°; it is involved in the hydrogen bond with the free Cl^? anion. The sulfur atom forms a short (3.052 ?) intermolecular S-Cl contact with the chlorine atom of the [PdCl₄]^2? anion, which forms supramolecular chains.     

Ni(II) complexes with optically active bis(menthane), pinano-para-menthane ethylenediaminodioximes and pinano-para-menthane, bis(pinane) propylenediaminodioximes: Synthesis, structures, and properties

Reactions of Ni(NO₃)₂ · 6H₂O) in EtOH(iso-PrOH) with optically active bis(menthane) ethylene-diaminodioxime (H₂L¹), pinano-para-menthane ethylenediaminodioxime (H₂L²), pinano-para-menthane propylenediaminodioxime (H₂L³) and bis(pinane) propylenediaminodioxime (H₂L⁴) were used to synthesize [Ni(H₂L¹)NO₃[NO₃ · 2H₂O (I), [Ni(HL²)]NO₃ (II), [Ni(HL³)]NO₃ (III), and [Ni(HL⁴)]NO₃ (IV). X-ray diffraction study of paramagnetic complex I (μ_eff = 3.04 μB and diamagnetic complexes II and III revealed their ionic structures. A distorted octahedral polyhedron N₄O₂ in the cation of complex I is formed by the N atoms of tetradentate cycle-forming ligand, i.e., the H₂L¹ molecule, and the O atoms of the NO ₃ ^? anion acting as a bidentate cyclic ligand. In the cations of complexes II and III, containing a pinane fragment, the coordination core NiN₄ has the shape of a distorted square formed on coordination of tetradentate cycle-forming ligands, i.e., anions of the starting dioximes. The structure of diamagnetic complex IV is likely to be similar to the structures of complexes II and III.     

Synthesis and crystal structures of two new Zn(II) coordination polymers with 4,4′-dipyridyl disulfide and dicarboxylate acid

The title compounds, Zn(C₅H₆O₄)(Dpds) · 5H₂O (I) and Zn(C₆H₈O₄)(Dpds) (II) (C₅H₈O₄ = glutaric acid, Dpds = 4,4??-dipyridyl disulfide, and C₆H₁₀O₄ = adipic acid), are two-dimensional metal-organic coordination polymers. In I, the tetrahedra coordinated Zn atoms are bridged by glutarate anions and Dpds ligand to form a 2D layer parallel to (001) plane, which are connected by the 1D water tape notated as T4(2)₅(2) to build up 3D supramolecular architecture. In II, both Dpds ligands and adipate anions act as bidentate bridges, connecting the Zn(II) centers in a tetrahedral coordination geometry into a two-dimensional (4,4) layer. Each layer polycatenates adjacent layers, exhibiting the rare combination of 2D ?? 2D parallels interpenetration.     

X-ray diffraction investigation of siloxanes. I. Effects of organic substituents at the silicon atoms on the structure of acyclic trisiloxane-1,5-diols and on formation of different hydrogen bond systems

The molecular and crystal structure of four acyclic trisiloxane compounds, which differ in substituents at the silicon atoms (Ph-phenyl, mPh-methoxyphenyl, 2mPh-dimethoxyphenyl), was investigated by X-ray diffraction analysis. Due to intermolecular hydrogen bonding between the oxygen atoms of the diol fragments, the crystal structure of 1,1,5,5-tetramethyl-3,3-diphenyl-1,3,5-trisiloxane-1,5-diol (C₁₆H₂₄O₄Si₃) (I) is a double chain architecture with hydrogen-bonded dimeric motifs of C(8)R ₄ ⁴ (12) type in graph set representation. In 1,1,5,5-tetramethyl-3,3-(2-methoxybenzo)-1,3,5-trisiloxane-1,5-diol (C₁₈H₂₈O₆Si₃) (II) and 1,1,5,5-tetramethyl-3,3-(2,6-dimethoxybenzo)-1,3,5-trisiloxane-1,5-diol (C₂₀H₃₂O₈Si₃) (III), a double chain structure with a graph set R ₃ ³ (8)D ₃ ³ (10) is formed. In contrast to I–III, 1,1,3,3,5,5-hexaphenyl-1,3,5-trisiloxane-1,5-diol (C₃₆H₃₂O₄Si₃) (IV) has an intramolecular hydrogen bond S(8). The independent molecules are joined by O-H...O intermolecular hydrogen bonds into centrosymmetrical dimers; the system of hydrogen bonds in general may be described as S(8)R ₄ ⁴ (8).     

Synthesis and crystal structure of Cu(I) π-complexes with N-allyl-5-amino-1-phenyl-1H-1,2,3-triazole-4-carboxamide [Cu(C12H13N5O)(NO3)] · 0.5H2O and [Cu(C12H13N5O)(CF3COOH)]

Copper(I) ??-complexes of the compositions [Cu(C₁₂H₁₃N₅O)(NO₃)] · 0.5H₂O (1) and [Cu(C₁₂H₁₃N₅O)(CF₃COO)] (2) (C₁₂H₁₃N₅O is N-allyl-5-amino-1-phenyl-1H-1,2,3-triazole-4-carboxamide) were obtained by alternating-current electrochemical synthesis, and their crystal structures were studied by X-ray crystallography. Crystals of the compounds are monoclinic, space group C2/c with the unit cell parameters a = 21.3976(15) ?, b = 8.0335(4) ?, c = 18.6027(13) ?, ?? = 114.422(2)°, V = 2911.6(3) ?³, Z = 8 for 1; and a = 18.3578(18) ?, b = 9.8700(10) ?, c = 20.9094(18) ?, ?? = 106.883(3)°, V = 3625.3(6) ?³, Z = 8 for 2. In both structures, N-allyl-5-amino-1-phenyl-1H-1,2,3-triazole-4-carboxamide acts as a bridging tridentate chelating ligand and forms with copper(I) atoms infinite chains containing [CuC₄NO] seven-membered rings. The chains are linked to form a three-dimensional framework due to hydrogen bonds (N)H??O, which involve nitrogen atoms of amino and amide groups of the ligand. The coordination sphere of Cu(I) atoms consists of olefin bond of the allyl C=C group, O atom of the carbonyl group, N(3) atom of the triazole nucleus of the organic ligand, and an oxygen atom of nitrate (compound 1) or trifluoroacetate (compound 2) anion, respectively.     

Synthesis and some properties of anionic chloranilate complexes of iron(iii). Crystal and molecular structure of rubidium and cesium chloranilatoferrates

New anionic chloranilate complexes of iron(iii) Cs[Fe(C₆O₄Cl₂)₂(H₂O)₂]·4H₂O (1), Rb[Fe(C₆O₄Cl₂)₂(H₂O)₂]·4H₂O (2), Rb₂[Fe(C₆O₄Cl₂)₂(H₂O)₂]₂·5H₂O (3), Cs₃Fe(C₆O₄Cl₂)₃ (4), (Bu₄N)Fe(C₆O₄Cl₂)₂ (5), (Bu₄N)₄Fe₂(C₆O₄Cl₂)₅ (6), and (R₄N)₃Fe(C₆O₄Cl₂)₃ (R = Pr (7), Bu (8), C₅H₁₁ (9)) were synthesized in an aqueous medium. The Mössbauer spectra of the synthesized chloranilatoferrates are characteristic of the high-spin state of Fe^III in an octahedral oxygen coordination. The crystal and molecular structures of compounds 1–3 were determined by X-ray diffraction. The complex anions [Fe(C₆O₄Cl₂)₂(H₂O)₂]^2? involved in these compounds are composed of two chelate chloranilate ions and two water molecules trans-(1,2) or cis-coordinated (3) to the iron atom. Since tetraalkylammonium tris(chloranilato)ferrates 7–9 and binuclear complex 6 are soluble in many organic solvents, they are promising precursors for the synthesis of metal-organic coordination polymers. Tetrabutylammonium bis(chloranilato)ferrate (Bu₄N)Fe(C₆O₄Cl₂)₂ (5) is the first example of the preparation of an anionic chloranilate complex of iron(iii) with a plausible chain structure in an aqueous medium.     

Hydroxyl Ammonium and Diethyl Ammonium Glutaratouranylates: Synthesis and Structure

The structures of two new coordination polymers, namely, hydroxyl ammonium glutaratouranylate NH₃OH[UO₂(C₅H₆O₄)(C₅H₇O₄)] · H₂O (I) and diethyl ammonium glutaratouranylate NH₂(C₂H₅)₂[UO₂(C₅H₆O₄) (C₅H₇O₄)] · 2H₂O (II), have been characterized by single-crystal X-ray diffraction. It has been established that the structures of complexes I and II contain [UO₂(C₅H₆O₄)(C₅H₇O₄)]–infinite chains with the crystallochemical formula AQ⁰²B⁰¹ (\(\rm{A = UO_2^{2+}}, Q^{02} = C_5H_6O_4^{2-}, B^{01} = C_5H_7O_4^{-}\)). Despite the identical compositions, uranyl glutarate chains in the studied structures appreciably differ from each other by their geometry and linking. The specific features of nonbonded interactions in the structures of complexes I and II have been characterized by the Voronoi–Dirichlet method of molecular polyhedra.     

Synthesis and Crystal Structure of 4-Aminoquinolinium Dicitratoborate Monohydrate

4-Aminoquinolinium dicitratoborate monohydrate [(4-NH₂)C₉H₆NH][(C₆H₆O₇)₂B] · H₂O (I) has been synthesized for the first time. Single crystals have been studied by X-ray crystallography. The structural units of crystal I are large complex dicitratoborate anions with a spirane structure, 4-aminoquinolinium cations and crystal water molecules. The crystal packing of I is three-dimensional. Seventeen independent contacts O(N)-H?O and N-H?O,O’ form an intricate system of hydrogen bonds.     

Interfragment transmission of electronic effects of π-acceptor ligands in heterometallic triad complexes with trans-[Ru(Py)4(CN)2] as a central unit

The complex trans-[RuPy₄(CN)₂] cleaves chloride bridges in the binuclear rhodium(i) and palladium(ii) complexes [Rh(CO)₂Cl]₂, [Rh(η⁴-C₈H₁₂)Cl]₂, [(η⁴-C₈H₁₂)Rh(μ-Cl)₂Rh(CO)₂], [Pd(η³-C₃H₅)Cl]₂, and [(η₃-C₃H₅)Pd(μ-Cl)₂Rh(CO)₂] to form heterometallic triad complexes [(CO)₂ClRh(NC)RuPy₄(CN)RhCl(CO)₂] (1), [(η⁴-C₈H₁₂)ClRh(NC)RuPy₄(CN)RhCl-(η⁴-C₈H₁₂)] (2), [(CO)₂ClRh(NC)RuPy₄(CN)RhCl(η⁴-C₈H₁₂)] (3), [(η³-C₃H₅)ClPd(NC)-Ru(Py)₄(CN)PdCl(η³-C₃H₅)] (4), and [(CO)₂ClRh(NC)Ru(Py)₄(CN)PdCl(η₃-C₃H₅)] (5), respectively. In solutions, complex 3 coexists with equilibrium amounts of compounds 1 and 2; complex 5 is in the equilibrium with compounds 4 and 1. In both cases, the ratio of concentrations is close to binomial. Complexes 2 and 5 treated with [Rh(CO)₂Cl]₂ are converted into 1 with the simultaneous formation of [Rh(η⁴-C₈H₁₂)Cl]₂ and [Pd(η³-C₃H₅)Cl]₂, respectively. The δ_H and δ_C values for the ligands η⁴-C₈H₁₂, η³-C₃H₅, and CO are sensitive to the nature of the remote triad unit. The ligand effects are shown to be transmitted along the chain L′-M′-(NC)-Ru-(CN)-M″-L″.     

Synthesis and characterization of glycol-modified vanadium(V) oxoisopropoxide and their oximato derivatives: sol–gel transformations of [VO(OPr i )3], [VO{OCH2CH2OCH2CH2O}{OPr i }] and [VO{OCH2CH2OCH2CH2O}{ON=C(CH3)(C4H3S-2)}] to vanadia

Reaction of [VO(OPr ⁱ )₃] (1) with [O(CH₂CH₂OH)₂] in 1:1 molar ratio in anhydrous benzene yield glycol-modified precursor, [VO{OCH₂CH₂OCH₂CH₂O}{OPr ⁱ }] (2). Further reactions of (2) with internally functionalized oximes in anhydrous benzene yield heteroleptic complexes of the type [VO{OCH₂CH₂OCH₂CH₂O}{ON=C(R)(Ar)}] (3–8) {where R=CH₃, Ar=C₄H₃O-2 (3), C₄H₃S-2 (4), C₅H₄N-2 (5); and when R=H, Ar=C₄H₃O-2 (6), C₄H₃S-2 (7), C₅H₄N-2 (8)}. All these derivatives have been characterized by elemental analyses, molecular weight measurements and spectroscopic techniques. The crysoscopic molecular weight measurement as well as FAB mass study suggests dimeric nature of (2). However, FAB mass spectrum of (4), and the crysoscopic molecular weight measurements of (3), (4), (5) and (6) indicate the monomeric behavior of the oximato derivatives (3–8). Hexa-coordination around vanadium(V) has been proposed for both monomeric and dimeric derivatives. Sol–gel transformations of (1), (2) or (4) to vanadia [(a), (b) or (c), respectively] have been carried out at low sintering temperature (600 °C). The XRD patterns of (a), (b) or (c) indicate formation of a single orthorhombic phase in all the three cases. The SEM images suggest grain like [for (a) and (b)] and rod like [for (c)] morphology of the crystallites. IR, Raman spectra as well as EDX analyses indicate formation of pure vanadia. Absorption spectra of the vanadia (b) and (c) suggest energy band gaps of 2.53 and 2.65 eV, respectively.     

A new member of tetranuclear dinitrosyl iron complexes (DNICs) with 2-mercaptothiazoline ligand: synthesis,structure and properties

A new tetranuclear dinitrosyliron complex [(μ-SC₃H₄SN)Fe(NO)₂]₄ (2), each of a Fe center coordinated with two S or two N, was prepared by CO replacement from the reduced precursor (CO)₂Fe(NO)₂ with 1 equiv of HSC₃H₄SN (2-mercaptothiazoline) in the presence of O_2(g). The structure of 2 is similar to [(Imid-iPr)Fe(NO)₂]₄ (Imid-iPr = 2-isopropylimidazole) (Hess et al. J Am Chem Soc 133:20426–20434, 2011), and both complexes comprise a quadrilateral plane of irons with corresponding ligands, SC₃H₄SN^? or Imid-iPr^?, bridging the edges and two nitrosyl ligands capping the irons at the corners. An additional equiv of SC₃H₄SN^? was added to 2, which results in the mononuclear {Fe(NO)₂}⁹ (SC₃H₄SN)₂Fe(NO) ₂ ^? (3), in the manner of N bound-[SC₃H₄SN]. Reaction of (TMEDA)IFe(NO)₂ (TMEDA = tetramethylethylenediamine) and complex 3 leads to the formation of complex 2. Dinuclear complex [(μ-C₅H₇N₂)Fe(NO)₂]₂ (4) can be synthesized by the ligand displacement of SC₃H₄SN^? to C₅H₇N₂ ^? (3,5-dimethylpyrazolate) of 2 (Chong et al. Can J Chem 57:3119–3125, 1979). Complexes 2–4 were characterized by IR and UV–Vis. The molecular structures of 2 and 3 were determined by X-ray single crystal diffraction.     

Syntheses, crystal structures, thermal stabilities and luminescence of six M(II)-hydroxyphosphonoacetate materials

Hydrothermal reactions of Zn^II, Ba^II or Co^II ion with 2-hydroxyphosphonoacetic acid (H₃L) afforded six metal phosphonates, namely, [Zn₅(O₃PCH(OH)CO₂)₄(C₆H₉N₂)₂] (1), [(C₄H₁₂N₂)Zn₅(O₃PCH(OH)CO₂)₄(H₂O)₂] (2), [(C₃H₁₂N₂)_0.5Zn₅(HO₃PCH(OH)CO₂)(O₃PCH(OH)CO₂)₃(H₂O)₂]·0.75H₂O (3), [BaZn₂(O₃P CH(OH)CO₂)₂] (4), [Ba(HO₃PCH(OH)CO₂)] (5) and [(NH₄)₂Co₇(HO₃PCH(OH) CO₂)₆(HPO₄)₂(H₂O)₆]·4H₂O (6). In 1, zinc tetrahedra ([ZnO₄]) and octahedra ([ZnO₅N], [ZnO₆]) are bridged by 2-hydroxyphosphonoacetate with penta- and hexadendate modes into a hybrid layer, which is further pillared by the 3-picolylamines to form a 3D structure through Zn-N bonds and hydrogen bondings. Both 2 and 3 are 3D framework encapsulating piperazine and 1,2-propanediamine cations, respectively. In solids 4-6, the cross-linkages of [ZnO₄], [BaO₁₀] and [CoO₆] polyhedral with 2-hydroxyphosphonoacetate form 3D frameworks. Solids 3 and 4 behave thermally stable up to 250 and 300 °C under air atmosphere, respectively. It is interesting that the peak emission of solid 3 displays a 10 nm red-shift after simple heat-treatment.     

Synthesis and crystal structure of the complex N,N-dimethylanilinium dicitratoborate monohydrate

N,N-Dimethylanilinium dicitratoborate monohydrate [C₆H₅NH(CH₃)₂][(C₆H₆O₇)₂B]·H₂O (I) was synthesized for the first time. Single crystals were obtained in an aqueous solution; the crystal structure was studied by X-ray crystallography. Crystals of I are triclinic, space group $P\bar 1$ , a = 9.7017(2) ?, b = 11.0475(2) ?, c = 12.6282(2) ?, ?? = 106.595(2)°, ?? = 106.931(1)°, ?? = 103.568(1)°, V = 1163.97(4) ?³, Z = 2, ??_calc = 1.516 g/cm³. The structural units of compound 1 are large complex dicitratoborate anions with a spiran structure, N,N-dimethylanilinium cations, and crystal water molecules. The crystal packing is a three-dimensional framework. A hydrogen-bond system is formed by seven independent contacts O(N)-H??O.