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.     

Synthesis, crystal structures, and properties of [Ca(H2O)2(Dmf@CB[6])(Bdc)] · DMF · 4H2O and [Ca(H2O)3(Dmf@CB[6])]Cl2 · 2H2O

Complexes [Ca(H₂O)₂(Dmf@CB[6])(Bdc)] · DMF · 4H₂O (I) and [Ca(H₂O)₃(Dmf@CB[6])]Cl₂ · 2H₂O (II) are synthesized by the heating (95°C) of a mixture of calcium chloride and cucurbit[6]uril (CB[6]) in a mixture of dimethylformamide (DMF) and water with the addition of terephthalic acid (H₂Bdc) in the case of complex I or triethylamine for complex II. The compounds are characterized by X-ray diffraction analysis, IR spectroscopy, and thermogravimetric and elemental analyses. The luminescence spectra are also recorded. According to the X-ray diffraction data, the calcium atom is coordinated by the oxygen atoms of the cucurbit[6]uril molecule, water molecules, and terephthalate anion (for I). The internal cavity of the cavitand is occupied by DMF.     

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.     

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

Russian Journal of Organic Chemistry -     

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.     

CRYSTAL STRUCTURE OF [Et_4N]_2[Mo_2O_2(μ-S)_2(S_2)_2]

<正> [(C2H5)4N]2[Mo2o2S2(S2)2], Mr = 676. 74, monoclinic, P21/c, a = 13.510(2), b = 14.373(2), c=14. 777(3)(?), β = 97.53(2)°, V = 2844.7(9) (?)3, Z = 4, Dc= 1. 58g/cm3, μ(MoKα) = 13.0cm-1, F(000) = 1384, R =0. 033 for 1803 observed reflections. The structure contains discrete [Mo2O2S2(S2)2]2- anions and Et4N+ cations. The two oxygen atoms bonded to the Mo atoms are in cis-form with respect to the Mo2S2 bridging unit, with an average Mo- O distance of 1. 678 (?), The Mo…Mo distance is 2. 832(1)(?).     

[Cp_2ErCl(THF)]_2的晶体结构

本文报导了(Cp_2ErCl(THF)]_2的晶体结构,晶体属单斜晶系,P2_1/c空间群。晶胞参数为a=8.141(2),b=21.218(6),c=8.597(2),β=107.77(2)°;V=1414.1(6) ~3;Z=2,D_c=1.90g/cm~3,F(000)=780,μ_c=66.3cm~(-1)(MoK_a)。最终的偏离因子R=0.047,R_(to)=0.048。结构分析表明,该配合物是以两个氯离子与金属离子桥联的二聚体形式存在。四氢呋喃中的氧原子同金属离子键合,Er—O键长为2.490(6),两个环戊二烯中的所有碳原子同金属离子间的平均键长为2.649,Er-Cl=2.666(3),Er—Cl-a=2.797(3),Er-Er_a=4.42,Cl-Er-Cl_a键角为72.2°。     

[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.     

Synthesis and X-ray diffraction study of cs3[UO2(CH3COO)3]2[UO2(CH3COO)(NCS)2(H2O)] and Cs5[UO2(CH3COO)3]3[UO2(NCS)4(H2O)] · 2H2O

Cs₃[UO₂(CH₃COO)₃]₂[UO₂(CH₃COO)(NCS)₂(H₂O)] (I) and Cs₅[UO₂(CH₃COO)₃]₃[UO₂ (NCS)₄(H₂O)] · 2H₂O (II) have been synthesized via the reaction between uranyl acetate and cesium thiocyanate in aqueous solution. According to single-crystal X-ray diffraction data, both compounds crystallize in monoclinic system with the unit cell parameters a = 18.7036(5) Å, b = 16.7787(3) Å, c = 12.9636(3) Å, β = 92.532(1)°, space group C2/c, Z = 4, R = 0.0434 (I); and a = 21.7843(3) Å, b = 24.6436(5) Å, c = 13.1942(2) Å, β = 126.482(1)°, space group Cc, Z = 4, R = 0.0273 (II). Uranium-containing structural units of compound (I) are mononuclear [UO₂(CH₃COO)₃]^? and [UO₂(CH₃COO)(NCS)₂(H₂O)]^? moieties, which correspond to the AB ₃ ⁰¹ and AB⁰¹M ₃ ¹ crystallochemical groups (A = UO ₂ ²⁺ , B⁰¹ = CH₃COO^?, M¹ = NCS^? and H₂O). The structure of compound II is built of [UO₂(CH₃COO)₃]^? and [UO₂(NCS)₄(H₂O)]^2? complexes, which belong to the AB ₃ ⁰¹ and AM ₅ ¹ crystallochemical groups, respectively. Uranium-containing complexes in both structures are linked into a framework by hydrogen bonds and electrostatic interactions with cesium cations. The IR spectra of compounds I and II agree well with X-ray diffraction data.     

配合物[2-NaPhthMePyNH_2]_2[Ni(mnt)_2]的合成及表征

合成了马来二氰基二硫烯镍(Ⅱ)配合物,[2-Na Phth Me Py NH2]2[Ni(mnt)2]([2-Na Phth Me Py NH2]+为1-(2'-萘苄基)-2-氨基吡啶鎓离子),并用元素分析,UV,IR,单晶X-射线衍射表征了其组成和结构。结果表明,配合物系单斜晶系,空间群P21/c,a=13.335(2),b=7.9458(12),c=17.480(3),α=90°,β=97.646(2)°,γ=90°,V=1835.7(5),Z=2。     

[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.     

Crossed beam reactions of methylidyne [CH(X2Π)] with D2-acetylene [C2D2(X1Σg(+))] and of D1-methylidyne [CD(X2Π)] with acetylene [C2H2(X1Σg(+))

The crossed molecular beam reactions of ground state methylidyne, CH(X(2)Π), with D2-acetylene, C(2)D(2)(X(1)Σ(g)(+)), and of D1-methylidyne, CD(X(2)Π), with acetylene, C(2)H(2)(X(1)Σ(g)(+)), were conducted under single collision conditions at a collision energy of 17 kJ mol(-1). Four competing reaction channels were identified in each system following atomic 'hydrogen' (H/D) and molecular 'hydrogen' (H(2)/D(2)/HD) losses. The reaction dynamics were found to be indirect via complex formation and were initiated by two barrierless-addition pathways of methylidyne/D1-methylidyne to one and to both carbon atoms of the D2-acetylene/acetylene reactant yielding HCCDCD/DCCHCH and c-C(3)D(2)H/c-C(3)H(2)D collision complexes, respectively. The latter decomposed via atomic hydrogen/deuterium ejection to form the thermodynamically most stable cyclopropenylidene species (c-C(3)H(2), c-C(3)D(2), c-C(3)DH). On the other hand, the HCCDCD/DCCHCH adducts underwent hydrogen/deuterium shifts to form the propargyl radicals (HDCCCD, D(2)CCCH; HDCCCH, H(2)CCCD) followed by molecular 'hydrogen' losses within the rotational plane of the decomposing complex yielding l-C(3)H/l-C(3)D. Quantitatively, our crossed beam studies suggest a dominating atomic compared to molecular 'hydrogen' loss with fractions of 81 ± 23% vs. 19 ± 10% for the CD/C(2)H(2) and 87 ± 30% vs. 13 ± 4% for the CH/C(2)D(2) systems. The role of these reactions in the formation of interstellar isomers of C(3)H(2) and C(3)H is also discussed.     

The unusual stability of [NpO2Cl4]2−: Synthesis and characterisation of [NpO2(DPPMO2)2Cl]2[NpO2Cl4] and [Ph3PNH2]2[NpO2Cl4]

The [NpO₂(DPPMO₂)₂Cl][NpO₂Cl₄] complex (where DPPMO₂ = bis(diphenylphosphino)methanedioxide) contains the linear neptunyl group, {NpO₂}²⁺, with two bidentate P=O donor ligands. Coordinating anion Cl^? fills the fifth equatorial coordination site yielding a complex of general formula [NpO₂(DPPMO₂)₂X]₂[Y] (1) (where X = Cl^? and Y = [NpO₂Cl₄]^2?. Reaction between our newly prepared neptunium starting material [NpO₂Cl₂(thf)]_n and phosphinimine ligand produced crystals of [Ph₃PNH₂]₂[NpO₂Cl₄] (2). Compounds 1 and 2 have been structurally characterised.     

Syntheses and characterization of three mercury(II) complexes, [Hg(phen)2(SCN)2], [Hg(2,2′-bipy)2(SCN)2] and [Hg(phen)2(NO3)2], thermal and fluorescence studies

Mercury(II) complexes of 1,10-phenanthroline (phen) and 2,2′-bipyridine (bipy), [Hg(phen)₂(SCN)₂] (1), [Hg(2,2′-bipy)₂(SCN)₂] (2) and [Hg(phen)₂(NO₃)₂] (3) have been synthesized and characterized by elemental analysis, IR, ¹H NMR and ¹³C NMR spectroscopy. The thermal stability of 1–3 were studied by thermal gravimetric (TG) and differential thermal analyses (DTA). The structure of 1 has been confirmed by X-ray crystallography. The complex is a monomer and the Hg atom has an unsymmetrical six-coordinate geometry, formed by four nitrogen atoms of the two phen ligands and two sulfur atoms of the two thiocyanate anions. Solid-state luminescent spectra of phen, 2,2′-bipy and 1–3 indicate emission with the maximum intensity at ca 467 nm upon excitation at 295 nm.     

微量热法研究 [Cu(phen)2]~(2 )、[Cu(bpy)_2]~(2 )与DNA的作用

用微量热法对菲咯啉合铜（ [Cu(phen)2]2＋）和联吡啶合铜（ [Cu(bpy)2]2＋）与小牛胸腺 DNA的相互作用进行了研究,依据 McGhee-Von Hippel邻近排斥方程确定了结合反应的平衡常数 K、结合位点距离 n及热力学参数Δ rHm、Δ rGm和Δ rSm。结果表明这两种铜的配合物与 DNA之间均可形成稳定的三元配合物,且反应为熵驱动过程, DNA与这些配合物的键合过程中同时存在插入和静电作用两种模式,插入作用的强弱与金属配合物中配体的平面性质有关。     

Disordered Crystal Structure of Bis[(2.2.2-Cryptand)Sodium] Bis[Aqua(Isothiocyanato)(μ-Isothiocyanato)Sodium] 2[Na(2.2.2-Crypt)]+ · [Na2(NCS)2(μ-NCS)2(H2O)2]2–

Crystals of bis[(2.2.2-cryptand)sodium] bis[aqua(isothiocyanato)(-isothiocyanato)sodium]: 2[Na(C₁₈H₃₆N₂O₆)]⁺ · [Na₂(NCS)₂(-NCS)₂(H₂O)₂]^2– (I) were synthesized and studied by X-ray diffraction analysis. The disordered structure of I (a = 12.715 Å, b = 10.458 Å, c = 21.767 Å, = 102.56°, space group P2₁/n) was solved by the direct method and refined by the full-matrix least-squares method in anisotropic approximation to R = 0.058 from 3896 independent reflections (CAD4 automated diffractometer, MoK ). The crystal consists of two complex ions [I¹]⁺ and [I²]^2– (molar ratio 2 : 1). The Na⁺ cation of the host–guest cation I¹ is coordinated by all eight heteroatoms (6O + 2N) of the cryptand ligand. The coordination polyhedron of this Na⁺ cation is a distorted cube. The atoms of two groups (CH₂–CH₂ and CH₂–O–CH₂–CH₂) in the cryptand ligand are disordered over two positions. The independent cation Na⁺ of the centrosymmetric binuclear complex anion I² is coordinated by one bifurcated O atom of the disordered water molecule and by three N atoms of the SCN^– ligands (including two bridging ligands). The coordination polyhedron of this Na⁺ caiotn is a distorted tetrahedron. The complex ions in the crystal structure of I are united by hydrogen bonds.     

Palladium(II) saccharinate complexes trans-[Pd(sac)2(LH)2] with amino- and acetylamino-pyridine co-ligands: molecular structures of trans-[PdCl2(2-ampyH)2].2dmf (2-ampyH = 2-amino-3-methylpyridine) and trans-[Pd(κ2-2-acmpy)2] (2-acmpyH = 2-acetylamino-3-methylpyridine)

Reaction of Na₂[PdCl₄] with two equivalents of amino- or acetylamino-pyridines (LH) affords trans-[PdCl₂-(LH)₂] {LH = 2-amino-3-methylpyridine (2-ampyH), 3-aminopyridine (3-apyH), 2-acetylamino-3-methylpyridine (2-acmpyH), 3-acetylamino-pyridine (3-acpyH)}. An X-ray crystal structure of trans-[PdCl₂(2-ampyH)₂] shows that the 2-ampy-H ligands are coordinated in a monodentate fashion via the nitrogen atoms of the pyridine rings. Treatment of trans-[PdCl₂(2-acmpyH)₂] with NEt₃ affords the cyclometalated complex, trans-[Pd(κ²-2-acmpy)₂], the X-ray structure of which shows that the 2-acmpy ligand is coordinated to palladium in a bidentate fashion via the nitrogen atom of the pyridine ring and oxygen. Reaction of trans-[PdCl₂(LH)₂] with two equivalents of sodium saccharinate affords the bis(saccharinate) complexes, trans-[Pd(sac)₂(LH)₂], in which the saccharinate anions are coordinated via the amide nitrogen atom.     

A kinetic study on the iron(III)-promoted aquation of [Cr(C2O4)2(picolinato)]2− and [Cr(C2O4)2(2-pyridineacetato)]2− complexes

Two [Cr(C₂O₄)₂(AB)]^2– type complexes, obtained from the reaction of cis-[Cr(C₂O₄)₂(H₂O)₂]^– with the AB ligand, [AB = picolinic (pyac) or 2-pyridine-ethanoic acid (pyeac) anions], were converted into [Cr(C₂O₄)(pyac)(H₂O)₂]⁰ and [Cr(C₂O₄)(pyeac)(H₂O)₂]⁰ compounds, respectively via Fe^III-induced substitution of the oxalato ligand. The aquation products were separated chromatographically and their spectral characteristics and acid dissociation constants determined. The kinetics of the oxalato ligand substitution were studied with a 10–40 fold excess of Fe^III over [Cr^III] at [H⁺] = 0.2 M and at constant ionic strength 1.0 M (Na⁺, H⁺, Fe³⁺, ClO^– ₄). The reaction rate law is of the form: r = k _obs[Cr^III], where k _obs = kQ[Fe^III]/(1 + Q[Fe^III]). The first-order rate constants (k), preequilibria quotients (Q) and activation parameters derived from the k values have been determined. The reaction mechanism is discussed in terms of a Lewis acid catalyzed (induced) ligand substitution.     

The coordination chemistry of mono and bis(di-2-pyridylamine)copper(II) complexes: preparation,characterization and crystal structures of [Cu(L)(NO2)2], [Cu(L)(H2O)2(SO4)], [Cu(L)2(NCS)](SCN)·0.5DMSO and [Cu(L)2(SCN)2]

The crystal structures of two mono(dpyam)copper(II) complexes, [Cu(dpyam)(NO₂)₂] (1) and [Cu(dpyam)(H₂O)₂(SO₄)] (2) and two dithiocyanate compounds containing bis(dpyam)copper(II) units, [Cu(dpyam)₂(NCS)](SCN)·0.5DMSO (3) and [Cu(dpyam)₂(SCN)₂] (4) have been determined by X-ray crystallography. The second orthorhombic form of the monomeric Cu(II) complex 1 was obtained by the reaction of di-2-pyridylamine (dpyam) with CuCl and NaNO₂ in water–methanol solution. Each copper(II) ion in 1 exhibits a tetrahedrally-distorted square base of the CuN₂O₂ chromophore, with off-the-z-axis coordinated nitrito groups weakly bound in approximately axial positions. Complex 2 is an example of a polymeric copper(II) derivative containing the bidentate bridging sulfate ligand in the long-bonded axial positions. Each copper(II) ion in 2 shows an elongated tetragonal octahedral stereochemistry. The CuN₄N′ chromophore of 3 involves a square-based pyramidal structure, slightly distorted towards a trigonal bipyramidal stereochemistry, τ=0.13. One of the SCN⁻ anions is bonded to the copper(II) ion via the N atom in the axial position of the square pyramid. Complex 4 is centrosymmetric and octahedrally elongated, with the SCN⁻ anions coordinating in axial positions via the S atom. The structures of complexes 1–4 and their ESR and electronic reflectance spectra are compared with those of related complexes.