Crystal Structure Analysis of Tetras[L-tris(ethylenediamine) cobalt(Ⅲ)] tris[hexacyanoruthenate(Ⅱ)]

1 INTRODUCTION The tris(ethylenediamine) cobalt (Ⅲ) complex in which there are L and D configurations is one of the very interest cations due to the chirality among research complexes and the characterization of reaction on the ion-pair charge-transfer transitions. It has been mentioned in a lot of examples on the chirality and the structure, such as [L-Co(en)3]- [?Co(edta)]2Cl?0H2O[1], [(+)DCo(en)3]Cl3稨2O[2], [(+)-Co(en)3?-)-Cr(en)3]Cl?.1H2O[3], [()-Co(en)3] (SCN)3[4], [(+)D…     

Synthesis and characterisation of [tris(1,3-dithiole-2-thione-4,5-dithiolato)-stannate]2−, [Q]2[Sn(dmit)3], [tris(1,3-dithiole-2-one-4,5-dithiolato)stannate]2−, [Q]2[Sn(dmio)3] and [tris(1,3-dithiole-2-thione-4,5-selenolato)stannate]2−, [Q]2[Sn(dsit)3], complexes: Analysis of the structural variations of the [Sn(dmit)3]2− and [Sn(dmio)3]2− dianions

[Tris(1,3-dithiole-2-thione-4,5-dithiolato)stannate]²⁻, [Q]₂[Sn(C₃S₅)₃], [tris(1,3-dithiole-2-one-4,5-dithiolato)stannate]²⁻, [Q]₂[Sn(C₃S₄O)₃], and [tris(1,3-dithiole-2-thione-4,5-diselenolato)stannate]²⁻ [Q]₂[Sn(C₃S₃Se₂)₃], complexes, have been synthesised and characterised. Crystal structure determinations of [Q]₂[Sn(C₃S₅)₃] (Q=1,4-dimethylpyridinium, monoclinic and orthorhombic forms; NMe₄, NEt₄, and PPh₄) and [NEt₄]₂[Sn(C₃S₄O)₃] revealed variations in the overall dianion structures. The geometry about tin in each case is essentially octahedral with the chelate bite angles in the range 80.7(5)–87.45(4)°: the range of Sn–S distances is 2.5207(18)–2.571(17) Å. A statistical analysis, carried out on the crystal structure data for the six complexes, indicated that the most critical factors in controlling the overall shape of the dianion were the distances of the Sn atom from the dithiolate ligand planes [Sn–OOP]. Interanionic S⋯S interactions, within the sum of the van der Waals’ radii for two S atoms, are affected by the size of the cation, Q; the secondary connectivity is 3-dimensional for the smallest cations, Q=1,4-dimethylpyridinium and NMe₄, in chains for the somewhat larger cation, NEt₄ and is absent for the still larger, PPh₄ cation.     

[Phthalocyaninato(2–)]­antimony(III) chloride

The title antimony(III) complex, [Sb(C₃₂H₁₆N₈)]Cl or [SbPc]Cl (where Pc = C₃₂H₁₆N₈²⁻), has been obtained from the reaction of pure powdered antimony with 1,2-di­cyano­benzene under a stream of ICl vapour. The asymmetric unit of this complex consists of an [SbPc]⁺ cation and a Cl⁻ anion. The phthalocyaninate residue [SbPc]⁺ is not planar. The Sb atom lies 1.057 (3) Å from the plane defined by the four iso­indole N atoms. A combination of ionic and donor–acceptor interactions links the [SbPc]Cl mol­ecules to form centrosymmetric [(SbPc)Cl]₂ pseudo-dimers in the crystal. The Sb—Cl distances in the pseudo-dimer are not equivalent [3.043 (2) and 3.201 (2) Å]. The pseudo-dimers are weakly linked through Cl⃛H—C_benzo interactions to form a three-dimensional network. As a result of these interactions, the four Sn—N_isoindole bond lengths in the [SbPc]⁺ residue are not equivalent and the symmetry of the Sb—N core is only close to C_s.     

Synthesis and Crystal Structure of a Complex Bimetallic Salt [Ni(trans_[14]diene)] [Ni (mnt)_2]

1INTRoDUCTIONMacrocycliccoordinationcomPOundshavebeenwidelyinvestigatedinthepastdecadesbecauseoftheirrelationshiptocomplexesofbiologicalsignificancesuchasthePorphyrinsandcorrins(lJ.Structuresofmanymacrocycliccompoundshavebeenre-ported,especiallythecompoundscontainingN4macrocyclicligands"'.However,toourknowledge,onlyafewcrystalstructuresofcomplexbimetallicsaltscontainingmacrocyclicligandshavebeendeterminedbyX-raydiffractionmethod.Inthispa-per,werePortthesynthesisandstructureofthetit1ecom…     

Interpretation der Absorptionsspektren der Komplexionen [Mo(CN)8]4−, [Mo(CN)8]3−, [W(CN)8]4− und [W(CN)8]3−

Zusammenfassung Die Absorptions- und Reflexionsspektren der Oktocyanokomplexe desMo(IV) undW(IV) sowie die Absorptionsspektren der Oktocyanotomplexe desMo(V) undW(V) werden mitgeteilt. Die Spektren werden unter Zugrundelegung der durch Raman- und IR-spektroskopische Untersuchungen gefordertenD _4d-Symmetrie dieser Verbindungen interpretiert. Die beobachteten Banden niedriger Intensität (log<3) werden Übergängen in einem Termsystem zugeordnet, das für die Konfigurationend ² undd ₁ und die SymmetrieD _4d berechnet worden ist. Banden hoher Intensität (log>3) werden auf Übergänge in antibindende Zustände zurückgeführt, an denen höherep-Zustände des Zentralions sowie Ligandenzustände beteiligt sind. Die erhaltenen Werte des Feldparameters stimmen mit ligandenfeldtheoretischen Erwartungen überein.

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Absorption and reflection spectra of the octacyanides ofMo(IV) andW(IV) and the absorption spectra of the octacyanides ofMo(V) andW(V) are presented. The spectra are interpreted in terms of theD _4d symmetry of the compounds supported by investigations of Raman and infrared spectra. Bands of low intensity (log<3) correspond to transitions between levels obtained in the case of the configurationsd ² andd ¹ respectively, in a field ofD _4d symmetry. Bands of high intensity (log>3) are attributed to transitions into antibonding levels in which p-orbitals of the central ion and ligand orbitals participate. The values of the field parameter obtained are in accord with ligand field theory.

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Résumé Les spectres d'absorption et de réflexion des complexes octocyanurés duMo(IV) et duW(IV) ainsi que les spectres d'absorption des mêmes complexes deMo(V) et de W(V) sont présentés. Les spectres sont interprétés en supposant la symétrieD _4d des molécules indiquée par des analyses des spectres Raman et infrarouges. Les bandes de faible intensité (log<3) sont attribuées à des transitions dans un système de niveaux, calculé pour les configurationsd ² etd ¹, respectivement, en symétrieD _4d. Des bandes de forte intensité (log>3) sont attribuées à des transitions vers des niveaux antiliants auxquels participent des fonctions élevéesp de l'ion central et des fonctions des groupes liés. Les valeurs obtenues pour le paramètre de champ sont en accord avec les prévisions de la théorie.

     

Two-dimensional assembly of [Mn(III)₂Mn(II)₂] single-molecule magnets and [Cu(pic)₂] linking units (Hpic = picolinic acid)

In an attempt to develop novel coordination networks of SMMs, a Cu(II) picolinate complex has been used to coordinate S(T) = 9 tetranuclear Mn-based SMMs resulting in an intriguing 2D framework exhibiting a magnet-like behavior at low temperature.     

Ring and Cluster Structures of {Li[C(NtBu)2(HNtBu)]}2·(THF) and {Li2[C(NtBu)3]}2, Containing the Novel Anions [C(NtBu)2(HNtBu)]−- and [C(NtBu)3]2−

The reaction of tert.-butyl carbodiimide with one equivalent of LiNH^tBu in tetrahydrofuran at-78 °C produces {Li[C(N^tBu)₂(HN^tBu)]}₂-(THF) (1), which is an eight-membered Li₂C₂N₄ ring; the deprotonation of (1) with two equivalents of n-BuLi in tetrahydrofuran at -78 °C and recrystallisation of the product from n-pentane yielded the unsolvated dimer {Li₂[C(N^tBu)₃]}₂ (2), which adopts the structure of a distorted hexagonal prism.     

2-[Pyridin-2(4)-yl]-N-[ω-vinyloxyalkyl]ethanamines

Russian Journal of Organic Chemistry -     

Crystal Structures of Bis[aquachlorotriphenyltin(Ⅳ)] dihydrate·1,4,7,10,13,16-hexacyclooctadecane bis[aquachlorotriphenyltin(Ⅳ)]·1,4,7,10,13,16-hexacyclooct-adecane(3/1) and Bis[aquatrifluoroacetatotriphenyltin(Ⅳ)] dihydrate·1,4,7,10,13,16-hexa

1INTRODUCTIONSeveraldiorganotinchloridesformhydrateswhosecoordinatedwatermoleculesinteractviahydrogenbondswiththecrownethers.Thepolyether,18-crown-6,affordscomplexeshavingtheformulationof[RRSnCl2H2O]2C12H24O6(e.g.,R=R?=CH3[1];R=R?=C6H5[2];R=CH3,R?=C6H5[3]);atin-chlorinebridgeraisesthecoordinationnumberofthemetalatomstosix.Withtriphenyltinchlorideinplaceofthediorganotindichlorides,theouter-spherecoordinationcomplexexistsasanaquachlorotriphenyltinentitythatinteractswiththecrownethe…     

Crystal Structures of Bis[aquachlorotriphenyltin(Ⅳ)] dihydrate·1,4,7,10,13,16-hexacyclooctadecane bis[aquachlorotriphenyltin(Ⅳ)]·1,4,7,10,13,16-hexacyclooct-adecane (3/1) and Bis[aquatrifluoroacetatotriphenyltin(Ⅳ)] dihydrate·1,4,7,10,13,16-hexacyclooctad

In the crystal structures of the centrosymmetric isostructural co-crystals, bis[aqua- hlorotriphenyltin]dihydrate(1,4,7,10,13,16-hexacyclooctadecane-bis[aquachlorotriphenyltin(Ⅳ)]a 1,4,7,10,13,16-hexacyclooctadecane (3/1) 1 and bis[aquatrifluoroacetatotriphenyltin] dihydrateb 1,4,7,10,13,16-hexacyclooctadecane-bis[aquatrifluoroacetatotriphenyltin(IV)](1,4,7,10,13,16- hexacyclooctadecane(3/1) 2, the crown ether interacts with the triphenyltin unit through both the coordinated and lattice water molecules in one molecular entity, but only through the coordinated water molecule in the other. The tin atoms are five-coordinate in trans-trigonal bipyramidal environments. Compound 1 is refined on 204 variables and 4665 I > 3((I) reflections to R = 0.055, and compound 2 on 233 variables and 5721 I > 3((I) reflections to R = 0.052. For crystal 1: C192H244Cl8O38Sn8, fw = 4392.99, trigonal, R, a = 27.391(1), c = 23.007(1) A。, V = 14948(1) A。3, Z = 3, Dc = 1.464 g/cm3, F(000) = 6708 and μ = 1.162 mm－1; and for 2: C208H244F24O54Sn8, fw = 5013.55, trigonal, R, a = 28.775(1), c = 23.289(1) A。, V = 16699(1) A。3, Z = 3, Dc = 1.496 g/cm3, F(000) = 7620 and μ = 0.978 mm－1.     

Syntheses and Structures of μ-Oxo-Bis[dichloroiron(III)]-Bis-[2,6-Diacetylpyridinedioximate(-1)]Iron(II) and Related Compounds

The syntheses and structures of four new compounds are described. Two of these compounds are the anhydrous and dihydrate chloride salts of the diamagnetic bis(2,6-diacetylpyridinedioxime)iron(II) cation, [Fe(DAPDH₂)₂]²⁺. In this complex cation the DAPDH₂ ligand binds to the iron, as expected, through its three nitrogen atoms leaving the four oxime oxygen atoms protonated and uncoordinated. The third compound is (AsPh₄)₂[Fe₂OCl₆], a new salt of the well-known oxo-bridged diiron complex, [Fe₂OCl₆]^2?. The synthesis of (AsPh₄)₂[Fe₂OCl₆] is a high yield, straightforward, one-step preparation starting with AsPh₄Cl and ferrous chloride in methanol. In this synthesis Fe(II) is oxidized to Fe(III) by atmospheric O₂. The fourth new compound is the novel and unexpected triiron complex [Fe(DAPDH)₂Fe₂OCl₄]. This complex is derived from [Fe(DAPDH₂)₂)]²⁺ and [Fe₂OCl₆]^2? by removing the H⁺ from each of two adjacent oxime oxygen atoms of the former and one Cl^? from each of the Fe(III) ions of the latter. The resulting neutral fragments, Fe(DAPDH)₂ and Fe₂OCl₄, are joined via bonds linking the two oxime oxygen atoms to the two Fe(III) ions giving rise to an unusual eight membered chelate ring containing three iron ions, two nitrogen atoms and three oxygen atoms, one of which is the bridge between the two Fe(III) ions.     

金属有机自由基离子盐[Fe(CpMe)2][M(dmit)2]和[FeCp(Tol)]n[M(dmit)2]的合成和固体导电性质

报道了6个新的含均同或混合茂铁阳离子和[M(dmit)₂]阴离子的金属有机自由基离子盐类化合物[Fe(CpMe)₂]IM(dmit)₂]和[FeCp(Tol)],[M(dmit)₂]的合成和鉴定,测定了化合物的电导率,讨论了化合物的结构对电导率的影响,发现[Fe(CpMe)₂][M(dmit)₂]的室温电导率比相应的[M(mnt)₂]阴离子盐要高37个数量级.     

Synthesis and structures of two uranyl β-diketonate complexes [UO2(DBM)2(DEDPU)] and [UO2(PMBP)2(DEDPU)]

Two new uranyl β-diketonate complexes [UO₂(DBM)₂(DEDPU)] (1) and [UO₂(PMBP)₂(DEDPU)](CH₃C₆H₅)_0.5 (2), (HDBM?=?dibenzoylmethane, HPMBP?=?1-phenyl-3-methyl-4-benzoyl-5-pyrazolone, DEDPU?=?N,N′-diethyl-N,N′-diphenylurea) were synthesized and characterized. The coordination geometries of the uranyl atoms in 1 and 2 are distorted pentagonal bipyramidal, coordinated by one oxygen atom of DBDPU molecule and four oxygen atoms of two chelating DBM molecules in 1 and PMBP molecules in 2.     

测定游离离子浓度的分光光度法(样品离子增量法)的探讨——兼测[Ca~(2+)]、[Mg~(2+)]、[OH~-]离子浓度

从分子水平研究生命现象,为分析化学提供了许多新的课题,如从生物流体中测定游离离子浓度就是其中之一。游离离子浓度的生理重要性对于生物流体(血液、组织液)的研究具有特殊的意义,当它们的浓度是游离离子的水平时,其结果就更为明显。通常的分析方法是测定待侧元素的总量,这不是本课题所期待的目的,该特定问题的要求是: 1.要测定的是原有体系某元素的游离离子浓度:故若引入新的组份后破坏了原有体系的平衡,此时测定出某元素的游离离子浓度并非所求。后者仅代表新的化学平衡建立后的游离离子浓度。     

Phosphanstabilisierte organyltellurenylkationen, [RTe(PR′3)]+

Diorganyl ditellurides, RTeTeR (R = CH₃, p-FC₆H₄) are oxidized by nitrosyl salts, NO⁺X⁻ (X⁻ = BF₄⁻, ClO₄⁻) with formation of the respective organyl tellurenyl cations, RTe⁺ which can be stabilized with tri(n-butyl)phosphine as organyl tellurophosphonium cations, [RTe(P(n-C₄H₉)₃)]⁺.     

Electronic absorption and circular dichroism spectra of Δ-[Os(bipy)2(bipy−)]+, Δ-[Os(bipy)(bipy−)2]0 and Δ-[Os(bipy−)3]−

The electronic absorption and circular dichroism spectra of the complexes produced by the one-, two- and three-electron reduction of Δ-[Os(bipy)₃]²⁺ are reported for the first time. The spectra confirm that, as in the cases of the Fe^II and Ru^II analogues, the electrons are localised on the bipyridine ligand and the complexes are correctly formulated [Os(bipy)₂(bipy⁻)]⁺, [Os(bipy)(bipy⁻)₂]⁰ and [Os(bipy⁻)₃]⁻. The absorption spectra of the series of fully reduced complexes [M(bipy⁻)₃]⁻: M  Fe, Ru, Os are compared.     

[Ni(cien)2]2[Mn(NCS)6]·H2O的合成、晶体结构

硫氰酸根的结构为N三C-S-,其两端的N原子和S原子分别有一对和三对孤对电子,因此,硫氰酸根可采用多种不同的配位模式与金属离子发生配位.硫氰酸根可作为单齿配体与一个金属离子配位,形成M-SCN或M-NCS的单核配合物,也可以作为桥联配体同时与两个、三个甚至四个金属离子配位形成多核配合物[1-3];另一方面,硫氰酸根是一个具有一定共轭性的偶极子,可传递磁相作用.因此,选择硫氰酸根作为桥联配体,将多个顺磁金属离子桥联形成一维、二维或三维结构的多核金属配合物分子,并研究它们的磁性已成为分子磁学的一个研究领域[4-6].本文仅报道标题配合物的合成与晶体结构.     

Analysis of the metal–ligand bonds in [Mo(X)(NH2)3] (X = P, N, PO, and NO), [Mo(CO)5(NO)]+, and [Mo(CO)5(PO)]+

Quantum chemical calculations at the DFT level have been carried out for model complexes [Mo(P)(NH₂)₃] (1), [Mo(N)(NH₂)₃] (2), [Mo(PO)(NH₂)₃] (3), [Mo(NO)(NH₂)₃] (4), [Mo(CO)₅(PO)]⁺ (5), and [Mo(CO)₅(NO)]⁺ (6). The equilibrium geometries and the vibration frequencies are in good agreement with experimental and previous theoretical results. The nature of the Mo–PO, Mo–NO, Mo–PO⁺, Mo–NO⁺, Mo–P, and Mo–N bond has been investigated by means of the AIM, NBO and EDA methods. The NBO and EDA data complement each other in the interpretation of the interatomic interactions while the numerical AIM results must be interpreted with caution. The terminal Mo–P and Mo–N bonds in 1 and 2 are clearly electron-sharing triple bonds. The terminal Mo–PO and Mo–NO bonds in 3 and 4 have also three bonding contributions from a σ and a degenerate π orbital where the σ components are more polarized toward the ligand end and the π orbitals are more polarized toward the metal end than in 1 and 2. The EDA calculations show that the π bonding contributions to the Mo–PO and Mo–NO bonds in 3 and 4 are much more important than the σ contributions while σ and π bonding have nearly equal strength in the terminal Mo–P and Mo–N bonds in 1 and 2. The total (NH₂)₃Mo–PO binding interactions are stronger than for (NH₂)₃Mo–P which is in agreement with the shorter Mo–PO bond. The calculated bond orders suggest that there are only (NH₂)₃Mo–PO and (NH₂)₃Mo–NO double bonds which comes from the larger polarization of the σ and π contributions but a closer inspection of the bonding shows that these bonds should also be considered as electron-sharing triple bonds. The bonding situation in the positively charged complexes [(CO)₅Mo–(PO)]⁺ and [(CO)₅Mo–(NO)]⁺ is best described in terms of (CO)₅Mo → XO⁺ donation and (CO)₅Mo ← XO⁺ backdonation (X = P, N) using the Dewar–Chatt–Duncanson model. The latter bonds are stronger and have a larger π character than the Mo-CO bonds.