The μ3-cyclopentadienylidene ligand: X-ray structure of [Ru4(CO)5 {P(OMe)3}(μ3-C5H4)2(η-C5H5)2]

UV irradiation of [Ru₂(CO)₄(η-C₅H₅)₂] yields the tri- and tetra-ruthenium complexes [Ru₂(CO)₄(η-C₅H₅){η-C₅H₄Ru(CO)₂(η-C₅H₅)}] and [Ru₄(CO)₆(μ₃-C₅H₄)₂(η-C₅H₅)₂]. The μ₃-C₅H₄ ligand in the latter has been characterised through an X-ray diffraction study on [Ru₄(CO)₅{P(OMe)₃}(μ₃-C₅H₄)₂(η-C₅H₅)₂].     

An Organically Templated Copper Pentaborate with Infinite Metallo-chains:[Cu(C3N2H4)4][Cu(CH3COO)2(C3N2H4)2(H2O)2][B5O6(OH)4]2

A novel organically templated copper pentaborate, [Cu(C₃N₂H₄)₄][Cu(CH₃COO)₂(C₃N₂H₄)₂(H₂O)₂]‐ [B₅O₆(OH)₄]₂, was synthesized by hydrothermal reaction and characterized by elemental analysis, single‐crystal X‐ray diffraction, FT‐IR spectroscopy, Raman spectroscopy and TGA. The crystal structure of this compound consists of two copper‐centered polyhedra and two discrete [B₅O₆(OH)₄]^? pentaborate anions, which are linked together through intensive hydrogen bonding interactions, forming a 3D framework with large channels along c axis. The discrete pentaborate anions form infinite layers by hydrogen bonds. Moreover, the two crystallographically different octahedral coppers are connected by common oxygen atom to form an infinite chain.     

N(nPr)4[B5O6(OH)4][B(OH)3]2 and N(nBu)4[B5O6(OH)4][B(OH)3]2: Clathrates with a diamondoid arrangement of hydrogen-bonded pentaborate anions

Single-crystal X-ray structure analyses of N(nPr)₄[B₅O₆(OH)₄][B(OH)₃]₂,1, and N(nBu)₄ [B₅O₆(OH)₄][B(OH)₃]₂,2, reveal that these materials are novel clathrates, the isotypic host structures of which are three-dimensional assemblies of hydrogen-bonded [B₅O₆(OH)₄]^– ionsand B(OH)₃ molecules. The assembly of only the pentaborate anions is a distorted (i.e., along [102] elongated) fourconnected diamond-related network. The N(nPr) ₄ ⁺ and N(nBu) ₄ ⁺ ions are trapped within the complex three-dimensional channel systems of the host frameworks. Both1 and2 crystallize monoclinically with space groupP2₁/c andZ=4. The cell constants are:1:a=13.592(5),b=12.082(2),c=17.355(6) Å, =106.60(2)° (298K);2:a=13.874(3),b=12.585(1),c=17.588(4) Å, =107.04(1)° (238 K). The results obtained by both¹¹B and¹³C MAS NMR spectroscopy are discussed. Thermogravimetric studies under a flowing inert-gas atmosphere suggest that water, stemming from polycondensation of the hydrous borate species, is released from the clathrates at ca. 443 K (1) and 398 K (2) before the decomposition of the organic cations starts at ca. 603 K (1) and 603 K (2).Author for correspondence. Supplementary Data relating to this article are deposited with the British Library as supplementary publication No. SUP 82172 (82 pages).     

Influence of hydrogen bonding on the assembly of six-membered vanadium borophosphate cluster anions: synthesis and structures of (NH4)2(C2H10N2)6[Sr(H2O)5]2[V2P2BO12](6)10H2O, (NH4)2(C3H12N2)6[Sr(H2O)4]2[V2P2BO12](6)17H2O, and (NH4)3(C4H14N2)4 5[Sr(H2O)5]2[Sr(H2O)4][V2P2BO12]6 10H2O

Three new strontium vanadium borophosphate compounds, (NH4)2(C2H10N2)6[Sr(H2O)5]2[V2P2BO12]6 10H2O (Sr-VBPO1) (1), (NH4)2(C3H12N2)6[Sr(H2O)4]2[V2P2BO12]6 17H2O (Sr-VBPO2) (2), and (NH4)3(C4H14N2)4.5[Sr(H2O)5]2[Sr(H2O)4][V2P2BO12]6 10H2O (Sr-VBPO3) (3) have been synthesized by interdiffusion methods in the presence of diprotonated ethylenediamine, 1,3-diaminopropane, and 1,4-diaminobutane. Compound 1 has a chain structure, whereas 2 and 3 have layered structures with different arrangements of [(NH4) [symbol: see text] [V2P2BO12]6] cluster anions within the layers. Crystal data: (NH4)2(C2H10N2)6[Sr(H2O)5]2[V2P2BO12]6 10H2O, monoclinic, space group C2/c (no. 15), a = 21.552(1) A, b = 27.694(2) A, c = 20.552(1) A, beta = 113.650(1) degrees, Z = 4; (NH4)2(C3H12N2)6[Sr(H2O)4]2[V2P2BO12]6 17H2O, monoclinic, space group I2/m (no. 12), a = 15.7618(9) A, b = 16.4821(9) A, c = 21.112(1) A, beta = 107.473(1) degrees, Z = 2; (NH4)3(C4H14N2)4.5[Sr(H2O)5]2[Sr(H2O)4] [V2P2BO12]6 10H2O, monoclinic, space group C2/c (no. 15), a = 39.364(2) A, b = 14.0924(7) A, c = 25.342(1) A, beta = 121.259(1) degrees, Z = 4. The differences in the three structures arise from the different steric requirements of the amines that lead to different amine-cluster hydrogen bonds.     

Group 2 metal salts of pyromellitic acid: [Mg(H2O)6](C10H4O8) and [Ba(C10H4O8)(H2O)5]

Structural determinations of the magnesium(II) and barium(II) salts of pyromellitic acid (benzene‐1,2,4,5‐tetra­carboxyl­ic acid) are presented. Hexa­aqua­magnesium(II) benzene‐1,2,4,5‐tetra­carboxyl­ate(2−), [Mg(H₂O)₆](C₁₀H₄O₈), (I), and penta­aqua­[benzene‐1,2,4,5‐tetra­carboxyl­ato(2−)]­barium(II), [Ba(C₁₀H₄O₈)(H₂O)₅], (II), are both centrosymmetric and both possess a 1:1 metal–ligand ratio, but the two structures are found to differ in that the magnesium salt contains a hexaaqua cation and possesses only hydrogen‐bonding interactions between cations and anions, while the barium salt exhibits coordination of the carboxyl­ate ligand to the nine‐coordinate metal centre. In (I), both ions sit on a 2/m site symmetry, and in (II), the cation and anion are located on m and i site symmetries, respectively.     

Synthesis and reaction of the novel complex [AsPh4][OsCl5(H2O). X-ray structure analysis of [AsPh4][OsCl5(H2O)].2EtOH and [AsPh4][OsCl5(EtOH)].EtOH

The synthesis and characterization of the anionic mononuclear and homobinuclear osmium complexes [AsPh4][OsCl5L].xEtOH [L = H2O, x = 2 (9); L = EtOH, x = 1 (10a); L = py, x = 0 (10b)] and [AsPh4]2[Cl5Os(pyz)OsCl5] (12) (pyz = pyrazine) are described. Upon reduction in a chloride-containing medium, OsO4 (1) affords the osmium(IV) species [OsCl5(H2O)]- (2), which could be isolated by extraction with n-tributyl phosphate (TBP). Complex 9 is the first fully characterized chloroaquo complex of Os(IV). This complex is an effective starting material for the preparation of novel species, such as 10a, 10b, and 12. The X-ray structures of 9 and 10a were determined. Both compounds crystallize in the monoclinic space group P2(1)/n. 9: C28H34AsCl5O3Os, a = 10.910(4) A, b = 17.127(5) A, c = 17.555(7) A, beta = 103.77(2) degrees, V = 3186(2) A3, and Z = 4. 10a: C28H32AsCl5O2Os, a = 10.7762(2) A, b = 17.3939(1) A, c = 17.1477(3) A, beta = 103.645(1) degrees, V = 3123.45(8) A, and Z = 4. Complexes 9 and 10a crystallize with two and one molecule of EtOH and are bonded via hydrogen bridges to the H2O and EtOH ligand in 9 and 10a, respectively.     

Umsetzung von C(NMe2)4 mit Ni(CO)4 – Synthesen und Strukturen von [C(NMe2)3][(CO)3NiC(O)NMe2], [C(NMe2)3]2[Ni5(CO)12] und [C(NMe2)3]3[Ni6(CO)12][O2CNMe2]

Reaction of C(NMe₂)₄ with Ni(CO)₄ – Syntheses and Structures of [C(NMe₂)₃][(CO)₃NiC(O)NMe₂], [C(NMe₂)₃]₂[Ni₅(CO)₁₂], and [C(NMe₂)₃]₃[Ni₆(CO)₁₂][O₂CNMe₂] The reaction of C(NMe₂)₄ with Ni(CO)₄ in THF produces the carbamoyl complex [C(NMe₂)₃][(CO)₃NiC(O)NMe₂] ( 1 ); side products are the purple cluster compound [C(NMe₂)₃]₂[Ni₅(CO)₁₂] · THF ( 2 · THF) and the red cocristallization product [C(NMe₂)₃]₃[Ni₆(CO)₁₂][O₂CNMe₂] ( 3 ). All compounds were studied by X‐ray diffraction analyses. The cations of 3 are all disordered but not those of 1 and 2 . The unit cell of 1 contains two crystallographically independent anions (I and II) which differ in the dihedral angle between the plane of the carbamoyl ligand and the plane defined by the atoms C_Carbamoyl–Ni–CO amounting 0° in the anion I and 18° in the anion II.     

[HN(C2H5)3][B5O6(OH)4]的合成、结构和热稳定性

利用水热法合成了五硼酸三乙胺[HN(C2H5)3][B5O6(OH)4], 并利用单晶X射线衍射技术解析了其结构, 同时利用傅立叶红外分析、元素分析及热分析技术加以佐证. 该化合物属于单斜晶系, 其空间群为P21/c, 相应的晶胞参数为a=1.0036(2) nm, b=1.1353(2) nm, c=1.4843(3) nm和β=106.54(3)°. 它由孤立的五硼酸阴离子[B5O6(OH)4]-和三乙胺阳离子[HN(C2H5)3]+构成. 五硼酸阴离子[B5O6(OH)4]-通过氢键构成三维网状结构, [HN(C2H5)3]+位于其中的孔道中.     

X-ray Diffraction Studies of Molecular Ferrimagnet [P(C6H5)4][MnFe(C2O4)3] on Heating

A structure of the [P(C₆H₅)₄][MnFe(C₂O₄)₃] single crystal is studied by X-ray diffraction within the 100–370 K temperature interval. The phase transition observed in the 150–170 K region is probably due to the cooperative ordering of the axial phenyl rings of the organic cations in the special positions.     

Theoretical study of isoelectronic molecules: B6H10, 2-CB5H9, 2,3-C2B4H8, 2,3,4-C3B3H7, and 2,3,4,5-C4B2H6

Isoelectronic molecules regarding B6H10, 2-CB5H9, 2,3-C2B4H8, 2,3,4-C3B3H7, and 2,3,4,5-C4B2H6 are studied by the density functional B3LYP/6-311G(d,p) method and the electron propagator theory in the partial third-order quasiparticale approximation, as well as the extrapolated calculation with the coupled-cluster CCSD(T) theory. The calculated ionization potentials are in good agreement with the experimental data from photoelectron spectroscopy. Valence structures are characterized with natural orbital bond (NBO) theory, exhibiting the multiple three-center two-electron bonds B-H-B, B-B-B, C-B-B, B-C-B, and C-B-C, and chemical bond rearrangements in the cations.     

Lyotropic liquid-crystalline mesophases of [Zn(H2O)6](NO3)2-C12EO10-CTAB-H2O and [Zn(H2O)6](NO3)2-C12EO10-SDS-H2O systems

The mixture of two surfactants (C12EO10-CTAB and C12EO10-SDS) forms lyotropic liquid-crystalline (LLC) mesophases with [Zn(H2O)6](NO3)2 in the presence of a minimum concentration of 1.75 H2O per C12EO10. The metal ion/C12EO10 mole ratio can be increased up to 8.0, which is a record high metal ion density in an LLC mesophase. The metal ion concentration can be increased in the medium by increasing the CTAB/C12EO10 or SDS/C12EO10 mole ratio at the expense of the stability of the LLC mesophase. The structure and some thermal properties of the new mesophase have been investigated using XRD, POM, FTIR, and Raman techniques.     

Co(en)3[B4O5(OH)4]Cl·3H2O和[Ni(en)3][B5O6(OH)4]2·2H2O的合成、结构以及热力学性质

利用水热法合成了两种过渡金属配合物为模板剂的含水硼酸盐晶体Co(en)3[B4O5(OH)4]Cl·3H2O(1) 和 [Ni(en)3][B5O6(OH)4]2·2H2O (2),并通过元素分析、X射线单晶衍射、红外光谱及热重分析对其进行了表征。化合物1晶体结构的主要特点是在所有组成Co(en)33+, [B4O5(OH)4]2–, Cl– 和 H2O之间通过O–H…O、O–H…Cl、N–H…Cl和N–H…O四种氢键连接形成网状超分子结构。化合物2晶体结构的特点是[B5O6(OH)4]–阴离子通过O–H…O氢键连接形成沿a方向有较大通道的三维超分子骨架,模板剂[Ni(en)3]2+阳离子和结晶水分子填充在通道中。