THE CRYSTAL STRUCTURE OF [Co(TPPO)_4][Co (NCS)_3TPPO]_2

The title complex [Co(TPPO)_4] [Co(NCS)_2TPPO]_2 (TPPO=triphenylphosphine oside) was prepared by solvent evaporation method. Its crystal structure was determined by x-ray diffraction method. The crystal is rhombohedral with space group R3. The unit cell parameters are presented and the structure has been refined to a final R of 0.064.     

Synthesis, properties, and thermal decomposition of compounds [Co(En)3][Fe(CN)6] · 2H2O and [Co(En)3]4[Fe(CN)6]3 · 15H2O

Binary complex salts, [Co(En)₃][Fe(CN)6] · 2H₂O and [Co(En)₃]₄[Fe(CN)₆]₃ · 15H₂O, are synthesized. The properties of the salts and their thermolysis in air, dihydrogen, and argon are studied. Oxides of the central ions of the binary complex salts are found to be the thermolysis products in an oxidative atmosphere. Solid solutions (intermetallic compounds) CoFe are the thermolysis products in the reductive atmosphere, whereas intermetallides containing considerable amounts of C and N and an impurity of Co and Fe oxides are the thermolysis products in an inert atmosphere. Gaseous thermolysis products in dihydrogen and argon are NH₃, hydrocarbons, and ethylenediamine.     

Spectroelectrochemical studies of [Mo(dtc)_4][Eu(dtc)_4] and [Mo(dtc)_4][Er(dtc)_4]

Redox and spectroscopic properties of the eight-coordination complexes of molybdenum and the rare-earth elements Eu or Er with N,N-diethyldithiocarbamate (dtc) were characterised by cyclic voltamrnetry and UV-visible absorption spectra.The complex cation [Mo(dtc)4]+ is more stable than the complex anions [Eu(dtc)4]-and [Er(dtc)4]-in redox processes,and possesses good redox reversibility.The electron transfer number,formal standard electrode potential in the redox process for the complex cation and its diffusion coefficients were obtained by in aitu spectroelectro-chemistry.     

Synthesis and Characterization of Tetrametal Cluster [Co2(CO)6][μ-HC2CH2OCH2C2H-μ][Co2(CO)6]

The treatment of dipropargyl ether HC2CH2OCH2C2H with Co2(CO)8 resulted in the formation of a novel cluster [Co2(CO)6][μ-HC2CH2OCH2C2H-μ][Co2(CO)6]. The cluster was characterized by C/H analyses, IR and 1H NMR spectroscopy and X-ray crystal structure determination. It belongs to monoclinic system, space group P21/c with the following crystallographic parameters: a=18.149(2), b=7.0111(7), c=20.897(2)(A), β=115.318(7)°, V=2403.7(5)(A)3, Z=4, Mr=665.97, Dc=1.840 g·cm-3, F(000)=1304.00, μ(Mo-Kα)=27.76 cm-1 and R=0.030 for 2372 observed reflections.     

Synthesis, crystal structure and properties of a new organic-inorganic hybrid Dawson-like polyoxotungstate [Co(2,2''''-bpy)3]2[Co(2,2''''-bpy)2Cl][Co(2,2''''-bpy)2]H2-[SbW18O60]·4H2O

A new organic-inorganic hybrid polyoxometalate based on Dawson-like polyoxotungstate anion [SbW18O60]9-, formulated [Co(2,2'-bpy)3]2[Co(2,2'-bpy)2Cl][Co(2,2'-bpy)2]H2[SbW18O60]·4H2O (2,2'-bpy= 2,2(-bipyridine) has been synthesized from Sb2O3, Na2WO4, CoCl2, and 2,2'-bipyridine materials by hydrothermal method, and which was characterized by elemental analyses, IR, XPS, EPR, TG, and X-ray single crystal diffraction. Structure analysis shows that the polyoxoanion self-assembled under hydrothermal conditions consists of a Dawson-like polyoxotungstate cluster anion [SbW18O60]9- encapsulating a pyramidal {SbO3} group within the {W18} cluster cage. EPR spectra show that the high-spin octahedral CoⅡ and low-spin CoⅡ ions coexist in the title compound. Magnetic properties indicate that the compound is antiferromagnetic.     

Structure of thiocarbamide-containing cobalt(III) dioximates with [BeF4]2− and [BF4]− anions

The crystal structure of the complexes [Co(DH)₂(Tu)₂]₂[BeF₄]·C₂H₅OH (I) and [Co(DfH)₂(Tu)₂][BF₄] 0.5H₂ (II) (where DH^? is the dimethylglyoxime monoanion, DfH^? is the α-benzyldioxime monoanion, and Tu is thiourea) has been determined by X-ray diffraction analysis. The coordination polyhedron of the Co³⁺ atom is an N₄S₂ octahedron formed by four nitrogen atoms of the dioxime molecule and two sulfur atoms of the fragments of thiourea (Tu); the latter have parallel and perpendicular orientations relative to the dioxime residue. The deviation of the cobalt atom from the four-angle plane (formed by the nitrogen atoms of the dimethylglyoxime residues) does not exceed 0.019 Å. The Co-N and Co-S distances vary from 1.877(3) Å to 1.901(3) Å and from 2.280(1) Å to 2.307(1) Å, respectively. The statistically disordered cations [BeF₄]^2? and [BF₄]^? play an important role in crystal formation — they form a complex system of hydrogen bonds.     

[Li(THF)_4][GdCl_4(THF)_2]的晶体结构

氯化钆与对-甲基苯基锂在四氢呋喃中反应得到产物之一为[Li(THF)_4][GdCl_4-(THF)_2],(M_r=738.2),在-70℃下进行X-射线衍射研究。其晶体属单斜晶系,P2/n空间群。晶体学参数为a=13.263(2),b=8.474(1),c=14.961(0);β=99.72(1)°,V=1657.23(?)~3,Z=2,D_c=1.48g/cm~3,F(000)=750,μ_c=24.2cm~(-1),最终偏离子为R=0.0614。研究结果表明,本题晶体是离子型晶体,围绕Gd~(3+)的四个Cl~-离子和两个THF分子的氧原子构成畸变的八面体。Li~+周围的四个THF分子的氧原子构成一个近似的四面体。     

[Co(NioxH)2(PPh3)2]SiF5and [Co(NioxH)2(Thio)2]2SiF6· 3H2O Complexes: Synthesis and Structure

Compounds that form in the CoSiF₆· 6H₂O–NioxH₂–A–water–alcohol system, where A is thiourea (Thio) or triphenylphosphine (PPh₃) and NioxH₂is 1,2-cyclohexanedione dioxime, were synthesized and characterized by X-ray diffraction analysis. Crystal structures of the [Co(NioxH)₂(PPh₃)₂]SiF₅and [Co(NioxH)₂(Thio)₂]₂SiF₆· 3H₂O complexes were established. In octahedral Co(III) complexes, two radicals of 1,2-cyclohexanedione dioxime are bound by a hydrogen bond and are located in the equatorial plane. The intramolecular (– and H bonds) and intermolecular (C–H···F and H bonds) interactions in the crystal are discussed.     

Magneto-structural studies of two new cobalt(II)-N,N-diisobutylisonicotinamide compounds: [CoLCl2]n and [Co(L)2(H2O)4][CoLBr3]2·2H2O

Two similar synthetic pathways using the ligand N,N-diisobutylisonicotinamide (L) with anhydrous CoX(2) salts (being X = Cl(-), Br(-)) led to different species: a one-dimensional system, [CoLCl(2)](n), 1, and an ionic product [Co(L)(2)(H(2)O)(4)][CoLBr(3)](2)·2H(2)O, 2, respectively. Compound 1 is a polymer in which ligand L coordinates to tetrahedral Co(II) ions in a bidentate bridging fashion using the pyridine nitrogen and carbonyl oxygen atoms. Compound 2 consists of one octahedral cationic [Co(L)(2)(H(2)O)(4)](2+) entity and two tetrahedral anionic [CoLBr(3)](-) units. In this system, the ligand molecules coordinate only through the pyridine nitrogen atoms. The magnetic properties of 1 and 2 were investigated in the temperature range of 2.0 to 300.0 K and correlations between both (due to the existence of similar features) examined. The study of the magnetic properties of 1 was carried out by considering each Co(II) ion as a perfectly isolated system, hence, J = 0, but taking into account a significant zero-field splitting contribution due to distortions on the tetrahedral environment of the cobalt atoms. The fit of the magnetic susceptibility data together with reduced magnetization vs H/T measurements provided similar parameters (|D| = 10.8 cm(-1), g(⊥) = 1.92, g(‖) = 2.92 for the former and |D| = 11.04 cm(-1)and g = 2.05 for the latter, respectively). On the other hand, the magnetic response of compound 2 has been analyzed using a model which considers the presence of two tetrahedral and one octahedral Co(ii) ions (Co(Td) and Co(Oh)). The study was carried out in two separated blocks, above and below 80 K, where only the most significant effects at each interval of temperature were considered. As a result, the analysis of the magnetic data shows weak antiferromagnetic interactions between the Co(Oh)and the two Co(Td) ions (J = -0.41 cm(-1)) in 2. The best fit parameters were g(Co(Td)) = 2.89, g(Co(Oh)) = 3.50, |D(Co(Td))| = 10.62 cm(-1), |E(Co(Td))| = 2.95 cm(-1), Δ = 240.9 cm(-1) and J(L-S) = -107.1 cm(-1), from where λ was calculated with a final value of -144.8 cm(-1) (J(L-S) = Aκλ). The approximations performed to obtain these values provide reasonable results in agreement with compound 1 and also to other systems in the literature.     

Crystal Structure of [Et_4N][Sm(S_2CNEt_2)_4]

The crystal structure of .[Et4N][Sm(S2CNEt2)4] was determined by X-ray diffraction technique. The crystal crystallizes in monoclinic system, space group P21/n with a= 1. 1695(3), b=2.0821(6), c=1.7420(7) nm, β=99. 79(3)°? Z=4, Dc= 1. 39 g/ cm3, μ(Mo/KTσ) = 18. 4 cm-1, F(000) = 1812. The structure was solved by Patterson and Fourier techniques and refined by least-squares method to a final conventional R of 0. 053 for 3116 (Ⅰ> 3σ- (Ⅰ)) reflections. Each asymmetric unit contains two ions [Sm (S2CNEt2)4]-1 and [Et4N] +1, having distance between central atoms N5 and Sm3+ to be 0. 6522 nm. The atom Sm is coordinated by eight sulphur atoms. The Sm-S distance lies in the range of 0. 285-0. 290 nm with an average of 0. 288 nm.     

[Co(3,3-tri)(men)Cl][ZnCl_4]和[Co(3,3-tri)(cmen)Cl][ZnCl_4]两体系配合物的合成及两经式异构体的晶体结构

分别合成了 [Co(3, 3-tri)(men)Cl][ZnCl4]、[Co(3, 3-tri)(cmen)Cl][ZnCl4] (3, 3-tri = N-(3-胺基丙基)-1, 3-丙二胺,men = N-甲基乙二胺,cmen = 1, 2-二胺基-丙烷) 2体系的部分配合物异构体,用单晶 X-射线衍射分析方法解析了2异构体的晶体结构。其中 [Co(3, 3-tri)(men)Cl][ZnCl4] 体系的一异构体Ⅰ的化学简式为 CoCl(C9H27N5)ZnCl4,晶体属正交晶系,空间群 Pca21,a = 16.788(2),b = 7.964(1),c = 14.416(2) 牛琕 =1927.3(4) ?,Dc = 1.747 g/cm3,Z = 4,F(000) = 1032,Mr = 506.91,R = 0.0352,wR =0.0935;[Co(3, 3-tri)(cmen)Cl]2+ 体系的一异构体Ⅱ的化学简式为 CoCl(C9H27N5)ZnCl4稨2O, 晶体属三斜晶系,空间群 P ,a = 9.511(3), b = 9.972(3),c = 11.694(3) 牛琣 = 68.367(5),b = 85.196(6),?= 86.580(5),V = 1026.9(5)?3,Dc = 1.698 g/cm3,Z = 2,F(000) = 536,Mr = 524.92,R = 0.0494,wR = 0.1180。两异构体中 Co3+ 为六配位,晶胞中对映体比例均为1:1。在配合物异构体Ⅰ和Ⅱ中,三元胺以经式排布,三元胺配体(3, 3-tri)仲胺上的氢相对于Cl分别处于顺位(syn-)和反位(anti-);二元胺配体氮(或邻位碳)取代的胺基氮原子(N*)与三元胺配体中的仲氮原子分别处于对位(trans(N*))和邻位(cis(N*))。     

[Co(2,3-tri)(cmen)Cl][ZnCl4]体系两异构体的晶体结构

用单晶 X-射线衍射分析方法解析了[Co（2,3-tri）（cmen）Cl][ZnCl4]（2,3-tri=N-（2-胺基乙基）-1,3-丙二胺,cmen=1,2-二胺基-丙烷,化学简式:CoCl（C9H25N5）ZnCl4,Mr=492.88）体系中的 2个异构体的晶体结构。其中异构体m2[ZnCl4]晶体属单斜晶系,空间群P21/c,a=10.7741（2）,b=15.3411（7）,c=11.7710（3）A,β=100.928（3）°,V=1909.8（4）A3,Dc=1.714g/cm3,Z=4,F（000）=1000,R=0.0488,wR=0.1301,晶胞中含4个配合物阳离子,4个[ZnCl4]2-阴离子;异构体m4＇[ZnCl4]晶体属三斜晶系,空间群P1,a=8.8472（5）,b=10.0484（7）,c=11.9139（9）A,α=90.456（3）,β=99.972（3）°,γ=112.836（3）°,V=957.8（3）A3,Dc=1.709g/cm3,Z=2,F（000）=520,R=0.0493,wR=0.1174,晶胞中含有2个配合物阳离子,2个[ZnCl4]2-阴离子。两异构体中Co3+为六配位。在结构单元中对映体的比例均为1:1。     

COMPLEX SALTS [Pd(NH3)4][Pd(NH3)3NO2] [CrOx3]·H2O AND [Pd(NH3)4][Pd(NH3)3NO2] [CoOx3]·H2O AND SOLID SOLUTIONS [Pd(NH3)4] [Pd(NH3)3NO2][CoOx3]x[RhOx3]1–x·H2O : PROMISING PRECURSORS FOR POROUS NANOALLOYS

Journal of Structural Chemistry - New complex salts [Pd(NH3)4][Pd(NH3)3NO2][CrOx3]·H2O I, [Pd(NH3)4][Pd(NH3)3NO2][CoOx3]·H2O II, and a series of solid solutions...     

Identification of the cobalt(II) chloride ‘mixed’ solvate Co4Cl8(H2O)4(MeCN)6: the ionic structure trans-[Co(H2O)2(MeCN)4] trans-[Co(H2O)2(MeCN)2(CoCl4)2]

The structure of the title compound features mononuclear octahedral Co^II cations, trans-[Co(H₂O)₂(MeCN)₄]²⁺, and trinuclear anions, trans-[Co(H₂O)₂(MeCN)₂(CoCl₄)₂]^2–; the latter centrosymmetric units contain a central octahedral Co(H₂O)₂(MeCN)₂ moiety with two tetrahedral [CoCl₄]^2– ligands. These two large ions are held in a network of intra- and inter-molecular hydrogen bonding.     

Ionic liquid [bmim][BF4] acts as solvent and promoter for synthesis of halo-containing N-arylphthalimides

A new synthetic process of N-arylphthalimide and halo-containing N-arylphthalimides through the reaction between phthalic anhydride and aromatic amines bearing halo groups in[bmim][BF_4]was described,ionic liquid[bmim][BF_4]acted as the dual role of solvent and promoter.     

A cyanide-containing cobalt(III) complex [Co(phen)2(CN)2][Co(phen)(CN)4]·4.5H2O: hydrothermal synthesis,crystal structure and spectroscopic properties

A cyanide-containing cobalt(III) complex, [Co(phen)₂(CN)₂][Co(phen)(CN)₄]?·?4.5H₂O (1: phen?=?1,10-phenanthroline) has been synthesized by hydrothermal techniques and characterized by elemental analyses, IR spectroscopy, UV–vis spectroscopy and single-crystal X-ray diffraction methods. The complex is triclinic, space group P 1 , with a?=?11.0047(16), b?=?12.9587(19), c?=?15.076(2)?Å, α?=?100.060(2), β?=?102.061(2), γ?=?91.803(2)°, V?=?2065.0(5)?ų, Z?=?2, and R ₁ [I?>?2σ(I)]?=?0.0481. The molecular unit of 1 consists of a cation/anion pair with interstitial water molecules in the crystal lattice. The combination of coordinative, hydrogen bonding and π–π stacking interactions results in the stabilization of a supramolecular solid-state architecture.     

Novel polyselenidoarsenate and selenidoarsenate: solvothermal synthesis and characterization of [Co(phen)3][As2Se2(μ-Se3)(μ-Se5)] and [Co(phen)3]2[As8Se14

Novel cobalt polyselenidoarsenate [Co(phen)(3)][As(2)Se(2)(μ-Se(3))(μ-Se(5))] (1; phen = 1,10-phenanthroline) was methanolothermally synthesized by the reaction of CoCl(2), As(2)O(3), and Se templated by phen in a CH(3)OH solvent at 130 °C. The same reaction in a H(2)O solvent yielded cobalt selenidoarsenate [Co(phen)(3)](2)[As(8)Se(14)] (2). In 1, the AsSe(+) units are alternately joined by the μ-Se(3)(2-) and μ-Se(5)(2-) bridging ligands to form a novel helical polyselenidoarsenate chain [As(2)Se(2)(μ-Se(3))(μ-Se(5))(2-)](∞). In 2, eight pyramidal AsSe(3) units are connected via corner sharing into the new member of the selenidoarsenate aggregate [As(8)Se(14)](4-) with a condensation grade of 0.571, which represents the first discrete selenidoarsenate(III) with a condensation grade of above 0.50. The octahedral complex [Co(phen)(3)](2+) is formed in situ to act as a countercation in compounds 1 and 2. 1 and 2 exhibit steep absorption band gaps at 2.09 and 2.16 eV, respectively.     

Synthesis, crystal structure and properties of a new organic-inorganic hybrid Dawson-like polyoxotungstate [Co(2,2′-bpy)_3]_2[Co(2,2′-bpy)_2Cl][Co(2,2′-bpy)_2]H_2- [SbW_(18)O_(60)]·4H_2O

A new organic-inorganic hybrid polyoxometalate based on Dawson-like polyoxotungstate anion [SbW18O60]9, formulated [Co(2,2′-bpy)3]2[Co(2,2′-bpy)2Cl][Co(2,2′-bpy)2]H2[SbW18O60]·4H2O (2,2′-bpy= 2,2′-bipyridine) has been synthesized from Sb2O3, Na2WO4, CoCl2, and 2,2′-bipyridine materials by hydrothermal method, and which was characterized by elemental analyses, IR, XPS, EPR, TG, and X-ray single crystal diffraction. Structure analysis shows that the polyoxoanion self-assembled under hydrothermal conditions consists of a Dawson-like polyoxotungstate cluster anion [SbW18O60]9 en- capsulating a pyramidal {SbO3} group within the {W18} cluster cage. EPR spectra show that the high-spin octahedral CoII and low-spin CoII ions coexist in the title compound. Magnetic properties in- dicate that the compound is antiferromagnetic.     

Binary Complexes [M(NH3)5Cl][PdCl4] · H2O (M = Rh, Co): Crystal Structure of [Rh(NH3)5Cl][PdCl4] · H2O

Monohydrates of chloropentammine rhodium(III) and chloropentammine cobalt(III) tetracloropalladates(II) were synthesized. Single crystals of [Rh(NH₃)₅Cl][PdCl₄] · H₂O were obtained and studied by Xray diffraction. The crystallographic data are as follows: a = 7.8730(16) Å, b = 10.905(2) Å, c = 16.038(3) Å, = 102.70(3)°, V = 1343.3(5) ų, space group P2₁/c, Z = 4, d_calc = 2.422 g/cm³. The structure consists of alternating layers of [Rh(NH₃)₅Cl]²⁺ complex cations and [PdCl₄]^2- complex anions. Each anion layer contains two crystallographically independent Pd atoms, and the square coordination environment of one of these atoms is converted to a bipyramide. The structure of the compound [Co(NH₃)₅Cl][PdCl₄] · H₂O is determined and its unitcell parameters are refined: a = 7.813(3) , b = 10.896(4) , c = 15.966(5) , = 102.85(4)°, V = 1325.2(8) ³, and d_calc = 2.148 g/cm³. The synthesis temperature is shown to have an effect on the content of hydrated and anhydrous complexes in the mixture formed during precipitation of these binary salts from aqueous solutions.