X-ray crystal structure of di-μ-carbonyldicarbonyl-bis(η5-pentamethylcyclopentadienyl)diruthenium

An X-ray diffraction study of [(⁵-C₅Me₅)Ru(CO)(-CO)]₂ was performed, revealing its dimeric structure and centrosymmetrictrans conformation. The Ru-Ru bond length (2.758(1) Å) and the separation between the Ru atom and the plane of the ⁵-C₅Me₅ ligand (1.923 Å) are greater than those in the Cp analog and in the isostructural Cp and C₅Me₅ complexes of iron; this effect is due to the s inductive effect of the Me groups.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 543–544, March, 1994.     

Synthesis and crystal structure of octaaqua(di-μ-bromo)dimanganese(II) dibromide 18-crown-6

A new crystalline complex octaaqua(di-μ-bromo)dimanganese(II) dibromide 18-crown-6, [Mn₂Br₂(H₂O)₈]Br₂ · 18C6, is synthesized and studied by X-ray diffraction analysis. The crystals of compound I are triclinic, space group $P\bar 1$ , a = 9.093 Å, b = 9.683, Å, c = 10.032 Å, α = 111.35°, β = 116.23°, γ = 92.64°, Z = 1. The structure is solved by a direct method and refined by the full-matrix least-squares method in the anisotropic approximation to R = 0.028 for 3276 independent reflections (CAD4 automated diffractometer, λMoK _α radiation). The [Mn₂Br₂(H₂O)₈]²⁺ complex cation lying at the inversion center is binuclear with two bridging Br atoms and eight water molecules. The coordination polyhedron of one Mn²⁺ cation is a distorted cis-octahedron with two Br atoms and four O atoms of the water molecules at its corners. The centrosymmetric 18C6 molecule has an usual conformation. A crystal of compound I contains a developed three-dimensional network of intermolecular (interionic) hydrogen bonds.     

Synthesis, reactivity and structural studies of (η-methylcyclopentadienyl)(η-tetraphenylcyclobutadiene)cobalt and its derivatives

(η⁵-methylcyclopentadienyl)(η⁴-tetraphenylcyclobutadiene)cobalt (1) and its derivatives, [(1-acetyl-2-methyl)η⁵-cyclopentadienyl](η⁴-tetraphenylcyclobutadiene)cobalt (2) [(1-acetyl-3-methyl)η⁵-cyclopentadienyl](η⁴-tetraphenylcyclobutadiene)cobalt (3) [(1-carbomethoxy-2-methyl)η⁵-cyclopentadienyl](η⁴-tetraphenylcyclobutadiene)cobalt (4) and [(1-carbomethoxy-3-methyl)η⁵-cyclopentadienyl](η⁴-tetraphenylcyclobutadiene) cobalt (5) have been prepared in yields varying from 11% to 28% by introducing the substituents on the cyclopentadienyl ring of methylcyclopentadienyl sodium and then reacting with diphenylacetylene and CoCl(PPh₃)₃. The carboxylic acids [(1-carboxy-2-methyl)η⁵-cyclopentadienyl](η⁴-tetraphenylcyclobutadiene)cobalt (6), [(1-carboxy-3-methyl)η⁵-cyclopentadienyl](η⁴-tetraphenylcyclobutadiene)cobalt (7) have been prepared after ester hydrolysis of compounds 4 and 5 using KOH/ethanol. [(1-dimethylaminomethyl-3-methyl)η⁵-cyclopentadienyl](η⁴-tetraphenylcyclobutadiene) cobalt (8), was prepared selectively by direct substitution on the cyclopentadienyl ring of (η⁵-methylcyclopentadienyl)(η⁴-tetraphenylcyclobutadiene)cobalt in 65% yield. The 1,2-isomer was formed only in traces in this reaction. Reactivity of (η⁵-methylcyclopentadienyl)(η⁴-tetraphenylcyclobutadiene)cobalt and its carbomethoxy derivative have been compared with (η⁵-cyclopentadienyl)(η⁴-tetraphenylcyclobutadiene)cobalt. All new compounds were characterized by ¹H and ¹³C NMR, FT-IR, mass spectra and CHN analysis. Compounds 2, 4, 6 and 8 have also been structurally characterized by single crystal X-ray structural analysis.     

The crystal and molecular structures of di-μ-hydroxy-bis(di-2-pyridylamine)dinitratodicopper(II) and aqua-μ-formato-triformato-bis(di-2-pyridylamine)dicopper(II) monohydrate

The preparation, magnetic and spectroscopic properties, crystal and molecular structures of binuclear complexes of formulae [Cu₂(dpyam)₂(OH)₂(ONO₂)₂] (I), [Cu₂(dpyam)₂(O₂CH)₄(OH₂)].H₂O (II) are described. (I) consists of pairs of copper atoms linked by two hydroxo bridges. The co-ordination geometry at each copper atom is distorted square-pyramidal, the basal plane consisting of two hydroxo oxygen atoms and two nitrogen atoms from a dpyam ligand, while the axial co-ordination sites are occupied by nitrate oxygen atoms. The copper(II) ions in (II) are also in a distorted square-pyramidal environment. They are bridged by a formate group in an anti–syn configuration from a basal position to an axial position, while another axial position is occupied by the water oxygen atom. From magnetic susceptibility measurements at room temperature, both complexes are found to exhibit antiferromagnetic interactions and some magneto-structural trends are discussed.     

Synthesis and molecular structure of (η-pentamethyl-cyclopentadienyl) (η-cyclopentadienyl) hexacarbonyl molybdenum tungsten

The metathesis reaction of Cp*(CO)₃MoBr and NaW(CO)₃Cp produced Cp*(CO)₃Mo-W(CO)₃Cp (1), featuring an unsupported Mo-W bond. Exposure of solutions of 1 to light leads to the quantitative formation of the corresponding homometallic dimers. In the solid state, the title complex exhibits an anti-arrangement of the η⁵-cyclopentadienyl and the η⁵-pentamethyl-cyclopentadienyl ligands and six terminal carbonyls. Comparison to corresponding complexes of molybdenum and tungsten reveals that the Mo-W distance is dictated by the presence of a Cp and a Cp* ligand. This is the first time that an unsupported Mo-W single bond distance is reported.     

Synthesis and crystal structure of dinuclear nickel (Ⅱ) complex

The crystal structure of Ni(Ⅱ) complex with 3-hydroxyl-1, 5-diazacycloheptane-N, N'-diacetate was determined by X-ray diffraction method. Crystal data for Ni2 (C9H14N2O5)2·2H2O: monoclinic, space group P21/n, a = 1.1717(5), b = 0.9794(3), c = 1.2971(2) nm, β= 96.62(3), V= 1.4786(7) nm3, Dc = 1.377 g/cm3, Z = 2,μ=13.321 cm-1 (Mo-Kα), F(000)=640. The final R and Rw are 0.075 and 0.089 respectively. The Ni(Ⅱ) ion forms 2:2 complex with ligand. Two ligands are bridged by two Ni(Ⅱ) atoms which are bridged by two O atoms. Every Ni(Ⅱ) is coordinated by two N atoms and four 0 atoms. The coordination polyhedron of the Ni(Ⅱ) ion is a distorted octahedron.     

Synthesis and crystal structure of β-hexanitrohexaazaisowurtzitane

A polycyclic caged compound with high strain—hexanitrohexaazaisowurtzitane (HNIW)—has been synthesized via a three-step reaction: condensation, hydrogenolysis debenzylation and nitrolysis, starting with benzylamine and glyoxal. HNIW is the most powerful high energy density compound (HEDC) ever tested. β-HNIW possesses a caged structure consisting of two five-membered rings and one six-membered ring with a nitro group attached to each of the six bridging nitrogens. The nitro group lies basically within a plane. The lengths of C—C bonds of β-HNIW range from 0. 156 nm to 0.159 nm, 0.002–0.005 nm longer than the sp³ C-C bond. The β-HNIW’s crystal belongs to orthorhombic system and space groupPca2₁ with parameters:a = 0.9670 (2),b = 1.1616 (2),c = 1.3032 (3) nm;V = 1.4638(5) nm³,Z = 4; D_c = 1.989 g/cm³ and D_m = 1.982 g/cm³. Project supported by the Advanced Research Funds (12060451867) from the Commission of Science and Technology for National Defence.     

Synthesis and crystal structure of β-hexanitrohexaazaisowurtzitane

A polycyclic caged compound with high strain——hexanitrohexaazaisowurtzitane (HNIW)——has been synthesized via a three-step reaction: condensation, hydrogenolysis debenzylation and nitrolysis, starting with benzylmine and glyoxal. HNIW is the most powerful high energy density compound (HEDC) ever tested. β-HNIW possesses a caged structure consisting of two five-membered rings and one six-membered ring with a nitro group attached to each of the six bridging nitrogens. The nitro group lies basically within a plane. The lengths of C--C bonds of β-HNIW range from 0.156 nm to 0.159 nm, 0.002--0.005 nm longer than the sp~3 C-C bond. The β-HNIW's crystal belongs to orthorhombic system and space group Pca2_1 with parameters: a=0.9670 (2), b=1.1616 (2), c=1.3032 (3) nm; V=1.4638(5) nm~3, Z=4; D_c=1.989 g/cm~3 and D_m=1.982 g/cm~3.     

Synthesis and crystal structure of pyridine and methanol coordinated a-octabutyloxyphthalocyaninatocobalt (II)

Phthalocyanines (Pcs) have been widely used as dyes and pigments, photoelectric materials and catalysts. They also bring general attention for potential applications, for example, in solar batteries and fuel cell, charge battery, electrochromic display devices, liquid crystal, sensors and molecular devices. The Pc抯 properties, such as spectroscopic, electronic, and magnetic properties, thermostabilities, and catalytic activities, may be adjusted by modifying the molecular structure. Therefor…     

Synthesis and crystal structure of cyclotris-(4,4′-thiodiphenylene ketone)

The side reaction of macrocyclization that occurs during the synthesis of poly-(1,4-phenylenesulfide ketone) by polycondensation of a 4,4-dihalobenzophenone with sodium sulfide was studied. It was found that the major product of this reaction is a cyclic trimer, cyclotris-(4,4"-thiodiphenylene ketone) (1). Despite the fact that ketone bridges are more rigid than sulfide bridges, the yield of the macrocycle is rather high, as it is in the synthesis of poly-(1,4-phenylenesulfide), and reaches 20% under high dilution conditions. The structure of 1 was investigated by X-ray diffraction analysis (R = 0.069 on 3138 reflections). Macrocycle 1 is strongly flattened in the crystal; the conformation observed is determined by the packing, since stereochemical analysis indicates high flexibility of the macrocycle. The solvate acetone molecules incorporated in the crystal are disordered, nevertheless, they are strongly fixed in the cavities and channels of the crystal structure.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1460–1466, August, 1994.     

Synthesis and crystal structure of pyridine and methanol coordinated α-octabutyloxyphthalocyaninatocobalt (II)

Crystal structure of pyridine and methanol axially coordinated 1,4,8,11,15,18,22,25-octabutyloxyphthalocyaninatocobalt(II)(viz. α-octabutyloxyphthalocyaninatocobalt) [(n-BuO)₈Pc]. Co(Py)(MeOH) (1) was determined by X-ray diffraction methods. Crystal data: monoclinic, space group P2₁/n, Z = 4, a = 1.06482(4), b = 3.5487(2), c = 1.79428(9) nm, β=103.246(2)°, V = 6.5792(5) nm³, μ = 0.325 mm^-1. The result shows that the ring skeleton of 1 maintains planar conformation, which is similar to that of unsubstituted phthalocyanine but is remarkably different from the saddle shape conformation of 1,4,8,11,15,18,22,25-octabutyloxyphthalocyaninatocopper (II) [(n-BuO)₈Pc]Cu(2), which has no axial coordination. In the structure of 1, the substituents butyloxy groups of 1 somewhat deviate from the ring plane, while pyridine and methanol are coordinated to the center atom Co from opposite sides of the ring plane. In addition, all molecules are stacked along axis a to form one-dimensional molecule chain, the neighboring molecules in the chain overlap to some extent with a benzene ring and a distance of 0.3565 nm.     

Synthesis of di-μ-oxo-tetra-(α-pentyloxy)tin(Ⅳ)phthalocynine

Axially substituted tin phthalocyanines, namely dichloride-tetra-(pentyloxy) tin (IV) phthalocyanine 3 and its dimmer di-cyanine 4 were synthesized. The catalytic effect of H2O-free CaCl2 in quinoline was used for condensation of dihydroxy tin phthalocyanine 3 to the cofacially array dimmer 4. Their structures were characterized by UV-vis, IR, elemental analysis, MS, as well as 1HNMR spectroscopy.     

Synthesis and crystal structure of cobalt(III) α-dioximates with pyrazine

A series of new coordination compounds of cobalt(III) trans-dioximates with pyrazine [CoCl(DH)₂Pz] · H₂O (I), [CoBr(DH)₂Pz] · H₂O (II), [Co(DH)₂Pz₂]NO₃ · H₂O (III), [Co(DH)₂Pz₂][BF₄] (IV), [Co(MgH)₂Pz₂][BF₄] (V), and [Co(NioxH)₂Pz₂][BF₄] (VI), where DH, MgH, and NioxH are dimethylglyoxime, methylglyoxime, and 1,2-cyclohexanedionedioxime monoanions, respectively, Pz is a pyrazine molecule were synthesized. The structures of compounds I, II, and VI were determined by X-ray diffraction. The Co(III) environment in these compounds is octahedral and the pseudomacrocyclic (DioxH⁻)₂ fragment occurs in the equatorial plane. This fragment is stabilized by O-H…O hydrogen bonds. The neutral Pz ligand is monodentate in all three compounds.     

Synthesis and X-ray crystal structure of a novel organometallic (μ3-oxido)(μ3-imido) trinuclear iridium complex

Reaction of the organometallic aqua ion [Cp*Ir(H(2)O)(3)](2+) with tert-butyl(trimethylsilyl)amine in acetone yielded a novel trinuclear (μ(3)-oxido)(μ(3)-imido)pentamethylcyclopentadienyliridium(III) complex, [(Cp*Ir)(3)(O)(N(t)Bu)](2+). Single crystal structure analyses show the complex can be isolated both in the double salt ((t)BuNH(3))[(Cp*Ir)(3)(O)(N(t)Bu)](CF(3)SO(3))(3) (1) and in the simple triflate [(Cp*Ir)(3)(O)(N(t)Bu)](CF(3)SO(3))(2) (2). The double salt is stabilized by hydrogen bonding between the tert-butylammonium ion and the three triflate anions. It is the first time that a trinuclear (μ(3)-oxido)(μ(3)-imido) transition metal complex has been structurally characterized.     

Synthesis,crystal structure and magnetic properties of triaquahexakis(μ2-betaine)(μ3-oxo)triiron(III) perchlorate heptahydrate

The synthesis and characterization of the oxo-centered carboxylato-bridged trinuclear iron(III) complex, triaquahexakis(₂-betaine)(₃-oxo)triiron(III) perchlorate heptahydrate are described. X-ray crystallography shows that the Fe^III atom in the complex has a slightly distorted octahedral geometry, coordinated by four oxygen atoms from different betaine ligands [Fe—;O = 2.009(3) 2.034(3) Å], one aqua ligand [Fe—O = 2.028(4) and 2.031(3) Å] and the central ₃-oxo atom [Fe—O = 1.917(2) and 1.917(3) Å]. The central oxygen is ideally coplanar with the plane of the three metal atoms. Magnetic susceptibility data (4–320 K) show the presence of an antiferromagnetic exchange interaction with a coupling constant of J = –20.2 cm^–1.     

Synthesis and crystal structure of polymeric aqua (2,2′-bipyridine)(μ-isonicotinato)copper(II) nitrate dihydrate

The title complex has been prepared and its crystal structure determined by X-ray diffraction methods. The complex crystallizes in the monoclinic space group P2₁/c. Cu(II) assumes a square pyramidal coordination geometry, formed by two isonicotinate anions, a bipyridine ligand and a coordinated water molecule. Each isonicotinate bridges two Cu atoms through pyridine-N and carboxyl-O atoms, respectively, to form zigzag polymeric chains. Between the polymeric chains, aromatic stacking and hydrogen bonding are observed.