Synthesis and X-Ray Crystal Structure of Two Novel Complexes: [M II(phen)3]2V4O12·phen·22H2O(M II=Co, Ni; phen=phenanthroline)

Summary. Two novel compounds, [Co(phen)₃]₂V₄O₁₂·phen·22H₂O (1) and [Ni(phen)₃]₂ V₄O₁₂·phen·22H₂O (2), were prepared from KVO₃–1,10-phenanthroline (phen)–Co(NO₃)₂, resp. NiCl₂–H₂O reaction systems. The compounds 1 and 2 are isomorphous and crystallize in triclinic system, space group P-1. Their crystal structures are formed by two types of layers parallel to 001: a cationic one consisting of [M^II(phen)₃]²⁺ ions and an anionic one containing the cyclic V₄O₁₂ ^4– anions. The solvate phenanthroline and crystal water molecules are located in the cationic and anionic layers, respectively. The IR spectra of 1 and 2 are consistent with the presence of the cyclic V₄O₁₂ ^4– anions in the complexes.Received November 13, 2002; accepted (revised) February 3, 2003 Published online June 2, 2003     

Two isotypic transition metal germanophosphates M(II)4(H2O)4[Ge(OH)2(HPO4)2(PO4)2] (M(II) = Fe, Co): synthesis, structure, Mössbauer spectroscopy, and magnetic properties

Synthetic, structural, thermogravimetric, M?ssbauer spectroscopic, and magnetic studies were performed on two new isotypic germanophosphates, M(II)(4)(H(2)O)(4)[Ge(OH)(2)(HPO(4))(2)(PO(4))(2)] (M(II) = Fe, Co), which have been prepared under hydro-/solvo-thermal conditions. Their crystal structures, determined from single crystal data, are built from zigzag chains of M(II)O(6)-octahedra sharing either trans or skew edges interconnected by [GeP(4)O(14)(OH)(4)](8-) germanophosphate pentamers to form three-dimensional neutral framework structure. The edge-sharing M(II)O(6)-octahedral chains lead to interesting magnetic properties. These two germanophosphates exhibit a paramagnetic to antiferromagnetic transition at low temperatures. Additionally, two antiferromagnetic ordering transitions at around 8 and 6 K were observed for cobalt compound while only one at 19 K for the iron compound. Low-dimensional magnetic correlations within the octahedral chains are also observed. The divalent state of Fe in the iron compound determined from the M?ssbauer study and the isothermal magnetization as well as thermal analyses are discussed.     

Hexaaquacobalt(II) and hexaaquacadmium(II) 4-nitro-2,3,5,6-tetraoxopyridinates [M(H2O)6](C5HN2O6)2 · 2H2O (M = Co and Cd): Synthesis, structures, and properties

The complexes [Cd(H₂O)₆](C₅HN₂O₆)₂ · 2H₂O (I) and [Co(H₂O)₆](C₅HN₂O₆)₂ · 2H₂O (II) were obtained in the crystalline state by reactions of cobalt chloride and cadmium chloride with ammonium 4-nitro-2,3,5,6-tetraoxopyridinate, (NH₄)₂ · (C₅HO₆N₂)₂. Their cocrystallization gave the heterometallic complex [Cd_0.32Co_0.68(H₂O)₆](C₅HN₂O₆)₂ · 2H₂O (III). The crystal and molecular structures of complexes I-III were determined by X-ray diffraction. It was demonstrated that the complexation reactions occur by replacement of two ammonium cations 4-nitro-2,3,5,6-tetraoxopyridinate by the complex cations [M(H₂O)₆]²⁺. The tetraoxopyridinate anions and the complex cations are hydrogen-bonded through the coordinated and crystallization water molecules as well as through the O atoms of the organic anion. The thermolysis of complexes I and II was examined by TGA.     

Crystal structure of [Co(NH3)5Cl]2(W10O32)·4H2O

By single crystal X-ray diffraction the crystal structure of the complex salt [Co(NH₃)₅Cl]₂(W₁₀O₃₂)·4H₂O is determined and the IR spectrum is interpreted. The crystal chemical analysis of the structure of complex cations and decatungstate anions and their packing in the structure is performed.     

Synthesis and characterization of one-dimensional coordination polymers, [M(sac)2(μ–pyz)(H2O)2] n [M=ZnII,CdII, pyz = pyrazine,and sac = saccharinate]

Two new coordination polymers, [M(sac)₂(μ–pyz)(H₂O)₂] _n [M=Zn^II(1), Cd^II(2), pyz =?pyrazine, and sac =?saccharinate], have been prepared and characterized by elemental analysis, FTIR spectroscopy, thermal analysis and single crystal X-ray diffraction. Both complexes are isomorphous and crystallize in the triclinic P 1 space group. The metal(II) ions are octahedrally coordinated by two sac, two aqua and two pyz ligands. The sac ligands are N-coordinated, while the pyz ligands are bridges between the metal centers, leading to one-dimensional linear chains. Intra-chain M–M separations in 1 and 2 are 7.218 and 7.498 Å, respectively. The individual chains are linked by strong OW–H ··· O(sac) hydrogen bonds into two–dimensional layers, which are further assembled into three–dimensional supramolecular networks by aromatic π(sac) ··· π(sac) stackings interactions.     

Infrared spectroscopic studies of some piperidine metal(II) clathrates: M(C5H11N)2Ni(CN)4·G (M = Co,Ni; G = m-xylene,p-xylene or o-xylene; M = Ni; G = dioxane)

IR spectra of M(C₅H₁₁N)₂Ni(CN)₄·G (M=Co, Ni; G=o-, m- or p-xylene; M=Ni; G=dioxane) are reported. These clathrates are analogues to the previously reported classical Hofmann-type clathrates.     

Crystal Structure of Calcium [Aqua(Nitrilotriacetatocobaltate(II)] Tetrahydrate,Ca[Co(Nta)(H2O)]2· 4H2O

Crystals of Ca[Co^II(Nta)]₂· 6H₂O (I), where Nta^3–is a nitrilotriacetate ion, were synthesized and studied using X-ray diffraction analysis. They were found to be monoclinic: a= 6.991(1), b= 10.031(1), c= 16.238(3) Å, = 98.50(1)°, V= 1126.2(3) ų, space group P2₁/n, Z= 2, R ₁= 0.0241, wR ₂= 0.0636, GOOF = 1.050 (for 3132 reflections with I> 2(I)). Structure Iis composed of {[Co(Nta)(H₂O)]^–}₁anion chains united by Ca²⁺cations into a three-dimensional framework. The coordination polyhedra of Co and Ca atoms are distorted octahedra. The Co(II) atom environment includes atoms N(1), O(1), O(3), and O(5) of one Nta^3–ligand, a carbonyl O(2)" atom of the neighboring anion fragment, and an O(w1) atom of the water molecule. The shortest bond is formed by the Co atom with the bridging O(2)" atom in trans-position relative to atom N(1). The Co–O(2)" distance (2.029 Å) is noticeably shorter than the other bond lengths, Co–O(Nta) (2.069–2.103 Å), Co–O(w1), and Co–N(1) (2.155 and 2.177 Å, respectively). Cations Ca²⁺are located in the inversion centers and involve in their coordination atoms O(4), O(6), O(w2), and the oxygen atoms symmetrically bond to them and arranged at 2.271(1), 2.420(1), and 2.351(2) Å, respectively. The structural formula of the title compound is {Ca(H₂O)₂[Co(Nta)(H₂O)]₂}₃· 2H₂O.     

Spectroscopic properties of [M(CN)5py]n− complexes [M  Fe(II), Co(III); py = pyridine]

The IR, electronic and NMR spectra of K₂[Co(CN)₅py]·H₂O and Na₃[fe(CN)₅py]·3H₂O, as well as the Mössbauer spectrum of the latter complex, are reported and discussed. In particular it is argued that the wavenumbers and intensities of the i.r.-active CN stretching vibrations and the NMR chemical shifts of the m- and p-but not o-protons suggest greater metal to ligand back π-bonding in the Fe(II) complex than in the Co(III) complex.     

Synthesis and Crystal Structure of [Ni(H2O)6][Ni(H2O)2(C4H2O4)]·4H2O

Reaction of a freshly prepared Ni(OH)_{2?2 x} (CO₃) _x ·yH₂O with maleic acid in H₂O at room temperature afforded [Ni(H₂O)₆][Ni(H₂O)₂(C₄H₂O₄)]·4H₂O, which consists of [Ni(H₂O)₆]²⁺ cations, [Ni(H₂O)₂(C₄H₂O₄)]^2? anions and lattice H₂O molecules. Ni atoms in cations are octahedrally coordinated and Ni atoms in anions are each octahedrally coordinated by bidentate chelating maleato ligands and two water molecules at trans positions. Cations and anions are interlinked by hydrogen bonds to form 1D chains, which are hexagonally arranged and connected by the lattice water molecules. When heated in a flowing argon stream, the compound decomposes, with complete dehydration being followed by dissociation of nickel maleate into NiO and maleic anhydride.     

Crystal structure of [Cu4(pytp)2(SO4)2(H2O)10](SO4)2 · 4H2O. A tetranuclear copper(II) complex with a new asymmetric ligand,pytp*, as a bridge

A new asymmetric bridge ligand, pytp, was prepared and characterized systematically by f.t.i.r., u.v.–vis., ¹H-n.m.r. and by FAB-MS spectroscopy. A tetranuclear Cu^II complex [Cu₄(pytp)₂(SO₄)₂(H₂O)₁₀](SO₄)₂·4H₂O (1) was prepared and characterized by elemental analysis and u.v.–vis. spectroscopy. A crystal structure analysis indicates that there are two different coordination spheres in (1) and that two of the copper centers are bridged by two ₂-SO₄ entities, creating a most unusual sulphate bridge.     

[Ru(NH3)6](MoO4)Cl·3H2O and [M(NH3)6](ReO4)3·2H2O (M = Ru, Ir). Synthesis and crystal structure

X-ray crystallographic analysis is used to determine the crystal structures of [Ru(NH₃)₆](MoO₄)Cl·3H₂O and [M(NH₃)₆](ReO₄)₃·2H₂O (M = Ru, Ir) complex salts. The features of the fragment packing are studied.     

超分子化合物[M(4,4''''-bipy)2(H2O)4]·(4,4''''-bipy)2·(3,5-diaba)2·8H2O](M=Co,Ni,Cd)的合成及晶体结构

合成了3个超分子化合物[M(4,4'-bipy)2(H2O)4]·(4,4'-bipy)2·(3,5-diaba)2·8H2O(M=Co(1),Ni(2),Cd(3);4,4'-bipy=4,4'-联吡啶;3,5-diaba=3,5-二氨基苯甲酸阴离子),用红外光谱、元素分析及X-射线单晶衍射进行了表征。3个化合物的晶体都属于单斜晶系,空间群为P2/c。晶体学参数:化合物1:a=0.9389(2)nm,b=0.7751(1)nm,c=3.9284(6)nm,β=90.14(2)°,V=2.85880(69)nm3,Z=4,Dc=1.397g·cm-3,F(000)=1266,μ=0.380mm-1,R1=0.0349,wR2=0.0829;化合物2:a=0.9383(2)nm,b=0.7753(1)nm,c=3.9218(6)nm,β=90.09(1)°,V=2.85280(68)nm3,Z=2,Dc=1.399g·cm-3,F(000)=1268,μ=0.420mm-1,R1=0.0366,wR2=0.0805;化合物3:a=0.94091(13)nm,b=0.77885(11)nm,c=3.9712(5)nm,β=90.10°,V=2.9102(7)nm3,Z=2,Dc=1.433g·cm-3,F(000)=1308,μ=0.454mm-1,R1=0.0468,wR2=0.0964。3,5-diaba未参与配位,在配位阳离子[M(4,4'-bipy)2(H2O)4]2 中,金属离子M髤与来自2个4,4'-bipy的2个氮原子和4个水分子的氧原子配位,呈八面体的几何构型。分子中还存在未配位的4,4'-bipy。通过配位阳离子、游离4,4'-bipy及未配位的3,5-diaba间的丰富氢键,构建成具有三维结构的超分子化合物。     

Syntheses and Crystal Structures of Four New Complexes [Mn(4,4′-bip)_2(OH_2)_4](DBA)·4H_2O and [M(OH_2)(HDPA)_2]·3H_2O (M = Mn,Co,Ni)

1 INTRODUCTION During the past years, dicarboxylic acids have been widely used as one polydentate ligand invo- lved in various metal chelation reactions to form transition or rare earth metal complexes with inter- esting properties in material science[1] and biological systems[2]. For example, Kim Y and his coworkers focused on the synthesis of copper(II) complexes containing malonate and pyrazine ligands to study their magnetic property and electronic conducti- vity[3]. The importance o…     

Crystal structures and vibrational spectra ofMSnF6·6H2O(M=Fe,Co, Ni)

Summary Single crystal X-ray structural data (atT=300 K) are reported for CoSnF₆·6H₂O (rhombohedral; R{ie61-1}-C _3i ² ;a=9.735(7) Å,c=10.095(7) Å, =120°;Z=3;R=0.047) and for NiSnF₆· 6H₂O (rhombohedral; R{ie61-2}-C _3i ² ;a=9.697(1)Å,c=10.021(1)Å, =120°;Z=3;R=0.038). The two compounds are isostructural to FeSnF₆·6H₂O. IR and Raman spectroscopic data (atT=300 and 75 K) are reported for hydrated and for partially deuterated samples ofMSnF₆·6H₂O (M=Fe, Co, Ni). Two rather similar (OD) stretching frequencies and one (HDO) bending frequency of isotopically dilute HDO molecules are observed for either of the three compounds, which is consistent with one crystallographically distinct water molecule forming two different, but rather similar O ... F hydrogen bonds.

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Kristallstrukturen und Schwingungsspektren vonMSnF₆·6H₂O (M=Fe, Co, Ni)

Zusammenfassung Die Kristallstrukturen von CoSnF₆·6H₂O (rhomboedrisch; R{ie61-3}-C _3i ² ;a=9.735(7) Å,c=10.095(7) Å, =120°;Z=3;R=0.047) und von NiSnF₆·6H₂O (rhomboedrisch; R{ie61-4}-C _3i ² ;a=9.697(1)Å,c=10.021(1)Å, =120°;Z=3;R=0.038) wurden mittels Röntgen-Einkristalldaten (beiT=300 K) bestimmt. Die beiden Verbindungen sind isostrukturell zu FeSnF₆·6H₂O. IR- und Raman-Spektren vonMSnF₆·6H₂O (M=Fe, Co, Ni) wurden von Proben mit unterschiedlichem Deuterierungsgrad gemessen (beiT=300 und 75 K). Bei allen drei Verbindungen findet man für isotopenverdünnte HDO Moleküle zwei nur geringfügig unterschiedliche (OD)-Valenzfrequenzen und eine (HDO)-Deformationsfrequenz, was mit der Existenz von nur einer Art von Wassermolekülen mit zwei verschiedenen, aber doch sehr ähnlichen O ... F Wasserstoffbrückenbindungen übereinstimmt.

     

Mono-Sulfonated Derivatives of Triphenylphosphine, [NH4]TPPMS and M(TPPMS)2 (TPPMS = P(Ph)2(m-C6H4SO− 3); M = Mn2+, Fe2+, Co2+ and Ni2+). Crystal Structure Determinations for [NH4][TPPMS]·½H2O, [Fe(H2O)5(TPPMS)]TPPMS, [Co(H2O)5TPPMS]TPPMS and [Ni(H2O)6](TPPMS)4·H2O

Preparation of the ammonium salt of TPPMS, [NH₄]TPPMS, TPPMS = PPh₂(m-C₆H₄SO^? ₃), greatly enhances water solubility and provides an efficient route to other metal complexes of TPPMS, M(TPPMS)₂ M = Mn²⁺, Co²⁺, Fe²⁺ and Ni²⁺. For Co²⁺ and Fe²⁺ the metal has an octahedral ligand environment with five water molecules and one TPPMS coordinated through the sulfonate oxygen; the second TPPMS is not coordinated. For Ni²⁺ the octahedral coordination sphere is composed of water molecules and the TPPMS ligands are not coordinated. Structures are fully reported for [NH₄]TPPMS·½H₂O and [Fe(H₂O)₅(TPPMS)]TPPMS and partially reported for [Co(H₂O)₅TPPMS]TPPMS and [Ni(H₂O)₆]TPPMS₂·H₂O. All of the structures show hydrophobic regions consisting of aromatic rings and hydrophilic regions with hydrogen-bonding interactions.     

金属串配合物[MM′M″(dpa)4(Cl)2](M=Co,Ni;M′,M″=Co,Rh)电子输运的理论研究

采用密度泛函理论DFT/BP86方法研究金属串配合物[MM'M″(dpa)₄(Cl)₂] [MM'M″=CoCoCo(1), CoCoRh(2), CoRhRh(3), NiCoRh(4)] 的结构和电子输运性质. 结果表明, 配合物1, 2和4的最稳定自旋态均存在1个(MM'M″)⁶⁺的离域$\sigma_{3}^{3}$键($\sigma^{2}\sigma_{nb}^{1}\sigma^{*0}$); 但配合物3具有1个(MM'M″)⁶⁺的离域$\sigma_{3}^{4}$键($\sigma^{2}\sigma_{nb}^{2}\sigma^{*0}$)和2个$\pi_{3}^{5}$键($\pi^{4}\pi_{nb}^{4}\pi^{*2}$), 故Rh—Rh键和Co—Rh键较强; Rh的引入使M—M键增强, Ni的引入则使M—M键减弱, 键强次序为Rh—Rh>Co—Rh>Co—Co>Ni—Co. 配合物14的传输通道均含有π和σ型轨道. 正偏压下, 配合物2和3的电流大于配合物1和4的. 负偏压下, 配合物4中出现负微分电阻效应. 配合物3中形成传输通道的σ_nbα/β和π^*α/β轨道能级分裂明显, (MM'M″)⁶⁺对β自旋的π^*轨道的贡献(88%)比α自旋(74%)的大, 使β自旋的电子更易传输, 具有较好的自旋过滤效应(70%80%).     

Synthesis and Crystal Structure of [Ni(II)(L)(py)_3]·(py)

1 INTRODUCTION Schiff bases and their metal complexes are useful reagents in organic synthesis[1], and they have exhi- bited some biological activities as anticancer and antitumor drugs[2]. The crystal structures and physi- cal and chemical properties of many Schiff bases and their transition metals complexes have been re- ported[3~5]. Further interest in the coordination che- mistry of nickel(II) arises from the role of these complexes in several catalytic reactions, such as electrocat…     

Crystal structure of the clathrate compound [dibromotetra(pyridine)copper(II)]·pyridine. Characterization by EXAFS of the pyridine desorption product

Powder samples of the new compound [Cu(C₅H₅N)₄·Br₂](C₅H₅N) and of its desorption product have been studied by EXAFS. The crystal structure of [Cu(C₅H₅N)₄Br₂]·(C₅H₅N) has been determined from three-dimensional X-ray diffraction data and refined to theR value 0.038 for 379 observed reflections. (orthorhombic,Ccca,a=12.033(8),b=14.764(3),c=16.768 Å,V=1897(3) ų,Z=4). The copper atom lies on a 222 symmetry site and is hexacoordinated with four nitrogen and two bromine atoms, forming an elongated octahedron with the bromine atoms in apical positions (Cu–Br distance: 3.201(2) , Cu–N1/N2 distances: 2.02(1)/2,07(1) ). The host molecules (Cu(C₅H₅N)₄Br₂) form layers parallel to the (001) plane. Cavities in the space between these layers, bound by pyridine ligands protruding into this space, are occupied by the guest molecules (C₅H₅N). The guest desorption at room temperature is accompanied by a chemical and structural destruction of the host, leading to the known compound Cu(C₅H₅N)₂Br₂.Supplementary Data relevant to this article (lists of observed and calculated structure factors, calculated positional parameters of H atoms, root-mean-square amplitudes of thermal vibration and anisotropic thermal parameters) have been deposited with the British Library as Supplementary Publication SUP 82163 (5 pages)