The structure of (1,2:5, 6η-cyclononatetraene) (η-cyclopentadienyl)cobalt,CoC14H15

The title compound crystallizes in the monoclinic space groupP2₁/a,a=11.50(2),b=7.724(1),c=12.599(3) Å,=102.22(5)°,Z=4. The structure was solved by direct methods and refined by full-matrix least squares toR=0.049 for 1032 observed reflections. The cobalt atom is -bonded to the cyclopentadienyl ring, with a mean Co-C distance of 2.07(1) Å, and also -bonded to the cyclonoatetraene ring at C(2)-C(3) and at C(6)-C(7), with a mean Co-C distance of 2.00(1) Å.     

Crystal structure of jinshajiangite from the Norra Kärr complex (Sweden)

The structure of the mineral jinshajiangite from the Norra Kärr alkaline complex (Sweden) was determined by single-crystal X-ray diffraction and refined to R = 6.7%. The monoclinic unit-cell parameters are a = 5.350(2) Å, b = 6.909(6) Å, c = 20.96(1) Å, β = 99.83(4)°, sp. gr. P2/m. This mineral is an Fe-rich analogue of surkhobite and perraultite, but it crystallizes in a different space group, and the unit-cell parameters a and b are two times smaller than those of these two minerals. The framework of jinshajiangite from Norra Kärr contains narrow and wide channels, which are occupied by Ca, Na, Ba, and K atoms in an ordered fashion.     

Synthesis and crystal structure of a dinuclear organometallic phosphonium ylid complex, [(η5-C5H5(CO)C2(ε-CO)(ε-CHP(C6H5)3)+][PF – 6 ]

The title compound crystallizes in the centrosymmetric monoclinic space group P2₁/n withZ=4. The cation consists of two (⁵-C⁵h⁵)Fe(CO) units which are linked via a metal-metal bond (Fe(1)–Fe(2)=2.530(1) Å), a bridging carbonyl ligand (Fe(1)–C(4)=1.912(8) Å. Fe(2)–C(4)=1.940(9) Å) and a bridging phosphonium ylid ligand (Fe(1)–C(1)=1.991(6) Å, Fe(2)–C(1)=1.985(6) Å and C(1)–P(1)=1.781(6) Å).     

A dinuclear cyanide-bridged complex, [(DMF)4(H2O)3LuCo(CN)6]·H2O

The crystal structure of the bimetallic cyanide bridged complex [(DMF)₄(H₂O)₃LuCo(CN)₆]·H₂O (1) was obtained by single-crystal X-ray diffraction. The central lutetium(III) ion is eight coordinate arranged in a square antiprism while the cobalt(III) ion is six coordinate, oriented octahedrally. Molecules in the crystal lattice are held together by a network of hydrogen bonding. Crystallization of 1 occurs in the centrosymmetric monoclinic space group P2₁/c (No. 14) with a = 13.875(2), b = 8.8352(9), c = 24.633(2) Å = 96.392(8)° and Z = 4.     

The crystal and molecular structure of trans-tetracarbonylbis(triphenyl-phosphine)chromium(0) in a new unit cell: Is the trans conformer more stable than the cis?

The crystal and molecular structure of trans-Cr(CO)₄(PPh₃)₂ has been determined by single crystal X-ray diffraction. The structure differs from one previously reported, packing in a different unit cell with no molecular center of symmetry. This asymmetry, coupled with the noncoplanarity of the four equatorial carbonyl ligands indicates that the structure is dominated by steric interactions. In spite of this, density functional calculations oncis-M(CO)₄(PPh₃)₂ vs. trans-M(CO)₄(PPh₃)₂, M = Cr, Mo, and W, predict that the gas phase cis conformer is more stable than the trans conformer for all three metals. The complex crystallizes in the triclinic space group with lattice parameters a = 10.139(5) Å, b = 10.583(5) Å, c =17.911(5) Å, = 75.860(5)°, = 77.410(5)°, = 65.930(5)°, V =1686.3(12) ų, Z =2.     

Interaction of cystamine with palladium(II) monoethanolaminate complex: Crystal structure of [Pd(NH2CH2CH2OH)4][Pd6(NH2CH2CH2S)8]Cl6 · 5H2O

The new compound [Pd(NH₂CH₂CH₂OH)₄][Pd₆(NH₂CH₂CH₂S)₈]Cl₆ · 5H₂O (I) is synthesized and its crystal structure is determined. The crystals are monoclinic, a = 25.625(6) Å, b = 9.633(5) Å, c = 24.847(7) Å, β = 91.47(2)°, Z = 4, and space group C2/c. The structural units of crystals I are the centrosymmetric hexanuclear [Pd₆(NH₂CH₂CH₂S)₈]⁴⁺ cations, the mononuclear [Pd(NH₂CH₂CH₂OH)4]²⁺ cations with C ₂ symmetry, the Cl^? anions, and crystallization water molecules. In the hexanuclear cation, the interaction between the Pd atoms occurs through the S atoms of the mercaptoethylaminate ligands. The Pd(2) and Pd(3) atoms and the ligands form two metallochelate fragments in which the N and S atoms are located in cis positions. The average lengths of the Pd-S and Pd-N bonds are equal to 2.274(1) and 2.074(6) Å, respectively. The metallochelate fragments are joined to each other and to their centrosymmetric analogues through the Pd(1) atom, which coordinates four S atoms [the average Pd-S_av bond length is 2.332(1) Å]. In the mononuclear cation, the Pd(4) atom coordinates four N atoms of the monoethylaminate ligands [the Pd-N bond lengths are 2.045(6) and 2.056(6) Å]. The shortest Pd?Pd distance is equal to 3.207(1) Å. The bonding in the structure is provided by numerous hydrogen bonds with the participation of all the H₂O molecules, NH₂ groups, and Cl^? anions.     

X-ray structure of [(μ-H)Os3(CO)10(μ-1,8-η2-C9H6N)]

Decacarbonyl--hydrido--1,8-²-quinoline-triosmium crystallizes in the triclinic space group P with a = 7.8551(6), b = 9.1283(8), c = 16.7915(8) Å, = 74.788(2), = 88.086(2), = 66.392(3)°, V = 1062.22(13)° ų, T = 150 K, and Z = 2. The molecule consists of an Os₃ triangle with the hydride and the heterocyclic ligand bridging the same Os—Os edge. The heterocyclic ligand is coordinated through the C(8) carbon and nitrogen atoms in a new -1,8-²-bonding mode. The Os—Os distances lie in the close range 2.8837(4)–2.9034(4) Å with an average value of 2.892(7) Å.     

Reactions of [Mn2(μ-pyS)2(CO)6] with bidentate phosphines: X-ray structure of [Mn(η2-pyS) (η2-dppp)(CO)2] [dppp = Ph2P(CH2)3PPh2, pySH = pyridine-2-thiol]

The dimeric complex [Mn₂(-pyS)₂(CO)₆] (1) reacted with 2 molar equivalents of Ph₂P(CH₂)₃PPh₂ (dppp) and Ph₂P(CH₂)₂PPh₂ (dppe) to give the respective monomeric chelate complexes [Mn(²-pyS)(²-dppp)(CO)₂] (2) and [Mn(²-pyS)(²-dppe)(CO)₂] (3). In contrast, with 2 molar equivalents of Ph₂P(CH₂)₅PPh₂ (dpppe), 1 gave the highly insoluble polymeric complex [Mn(²-pyS)(-dpppe)(CO)₂]n (4). An X-ray structure determination shows that 2 crystallizes in the monoclinic space group P2₁/n with a = 10.721(2) Å, b = 19.712(5) Å, c = 14.846(4) Å, = 109.06(2)°, V = 2965.5(14) ų, and Z = 4. The complex has a distorted octahedral geometry with the dppp ligand, one CO group and the N atom of the chelating pyS ligand occupying equatorial sites, and one CO group and the S atom of the pyS ligand lying in the axial positions.     

Synthesis and structure of a (4,4′-bipyridine) lanthanide(III) complex with tetraimine (2+2) macrocycle from 2,6-diformyl-4-chlorophenol and 1,3-diamino-2-hydroxypropane

A novel (2+2) macrocyclic Schiff base lanthanide(III) complex [La(H₄L)(NO₃)₃]·(4,4-bipy)·2H₂O has been synthesized by template condensation of 1,3-diamino-2-hydroxypropane and 2,6-diformyl-4-chlorophenol. The compound crystallizes in the orthorhombic space group Pnma with a = 16.400(3), b = 12.985(3), c = 19.118(4) Å, and Z = 4. In the macrocycle, La³⁺ was coordinated by two imino nitrogen atoms, two phenolic oxygen atoms, one pedant alcoholic oxygen atom, and six nitrate oxygen atoms. It is interesting that the neutral lanthanide macrocyle forms a saddlelike supramolecule with 4,4-bipyridine.     

Synthesis and X-ray crystal structure of an organometallic phosphonate [η6-1,2-C6H4(OCH3)(P(O)(OCH2CH3)2)]Cr(CO)3

The chiral, racemic, arene phosphonate complex, [t⁶-1,2-C₆H₄(OCH₃t)(P(O)(OCH²CH₃t)²)t] Cr(CO)₃ (1), was prepared via the reaction of 1,2-C₆H₄(OCH₃)(P(O)(OCH²CH₃)²) with Cr(CO)₆ in refluxing dioxane/THF. The title complex crystallized in P1 with the cell dimensions: a = 8.4893(4) Å, b = 11.0638(9) Å, c = 11.2135(8) Å, and = 62.151(8), = 105.154(5), = 112.426(6), giving a volume of 856.34(10) ų. The conformation of 1 is described as eclipsed (E) in which the methoxy substituent eclipses a carbonyl ligand of the tripod, and the phosphonate substituent is staggered.     

Ga_8(H_2O)_6(HPO_3)_(14)·(C_3N_2H_6)_3·H_3O:含有经典6* 1 SBU的新型三维开放骨架亚磷酸镓

为了丰富亚磷酸盐结构,为多孔材料的定向合成提供一定的实验数据,在溶剂热的条件下,以咪唑为结构导向剂合成了一个具有三维开放骨架结构的新型亚磷酸镓化合物Ga8(H2O)6(HPO3)14·(C3N2H6)3·H3O(化合物1),并通过粉末X-射线衍射、红外光谱、热重、ICP和CHN元素分析对化合物进行了表征。单晶X-射线衍射分析结果表明,化合物1属于三斜晶系,P-3c1空间群,晶胞参数为a=b=1.33388(8)nm,c=1.7886(2)nm,γ=120(4)°,Z=2。其结构是由Ga O6八面体和[HPO32-]假四面体单元相互连接构成。该结构沿着[100]和[010]方向具有12元环孔道。值得注意的是,在化合物1的结构中存在两种不同的次级结构单元(SBU):经典的6*1单元Ga3P4和齿轮状的Ga P6单元。     

Formation and mechanical behavior of (Fe0.5Ni0.5)80−xMoxB20 (x = 0–8) amorphous alloys

Glass forming ability, thermal stability and mechanical behavior of (Fe_0.5Ni_0.5)_80?xMo_xB₂₀ (x = 0, 2, 4, 6, 8) amorphous alloys were studied by XRD, TEM, SEM, DSC, tensile test, microhardness test and tearing test. The effects of Mo addition on glass formation, strength and ductility of (Fe_0.5Ni_0.5)_80?xMo_xB₂₀ amorphous alloys were discussed. The substitution of Mo for Fe and Ni simultaneously causes improvement in glass forming ability and thermal stability, and changes the crystallization process. The tensile fracture strength of amorphous alloy depends on both hardness and ductility; the alloy with high hardness and good ductility simultaneously also has a high tensile fracture strength. The (Fe_0.5Ni_0.5)₇₈Mo₂B₂₀ amorphous alloy exhibits good glass forming ability and the highest tensile fracture strength among (Fe_0.5Ni_0.5)_80?xMo_xB₂₀ alloys. Micro-plastic deformation occurred in ductile and brittle amorphous alloys that both show viscous flow characteristics. The mechanical behavior of (Fe_0.5Ni_0.5)_80?xMo_xB₂₀ amorphous alloys is related to the average outer shell electron concentration of metal atoms.     

Synthesis and crystal structure of (η5-C5H5)2Ti(NH(2,4-(C$${\equiv}$$CSiMe3)2C6H3))2

The crystal structure of the bis-amido complex of Ti(IV) (η⁵-C₅H₅)₂Ti(NH(2,4-(C CSiMe₃)₂C₆H₃))₂ is reported. This complex was prepared in 52% yield from the reaction of (η⁵-C₅H₅)₂TiCl₂ with two equivalents of LiNH(2,4-(C CSiMe₃)₂C₆H₃) (prepared in situ in THF at −78^∘C). The substituted aniline H₂N(2,4-(C CSiMe₃)₂C₆H₃) was prepared in 70% yield from the reaction of 2,4-dibromoaniline with Me₃SiC CH using conventional Pd/Cu coupling methodology. The molecular structure of (η⁵-C₅H₅)₂Ti(NH(2,4-(C CSiMe₃)₂C₆H₃))₂ (monoclinic, space group C2/c, Z = 4, a = 29.7523(5) Å, b = 9.5339(2) Å, c = 15.8864(3) Å, β = 93.022(1)^∘ features a titanium (IV) center with a distorted tetrahedral geometry which lies on a crystallographic twofold axis. The amido units are arranged so that steric interactions are minimized. The Ti– N distance is 2.016(2) Å.     

Reactions of [Mn2(μ-pyS)2(CO)6] (pySH=pyridine-2-thiol) with triphenylphosphine (PPh3), diphenylphosphine (PHPh2) and bis(diphenylphosphino)methane (dppm): X-ray crystal structure of [Mn(pyS)(η1-dppm)2(CO)2]

The dimeric complex [Mn₂(-pyS)₂(CO)₆] (1) reacted with 2 M equivalents of both PPh₃ and PHPh₂ to give the respective monomeric phosphine complexes [Mn(pyS)(L)(CO)₃][L = PPh₃ (2) and PHPh₂ (3)]; with 4 M equivalents of dppm, it yielded the complex [Mn(pyS)(¹-dppm)₂(CO)₂](4). An X-ray structure determination of 4 shows that it crystallizes in the monoclinic space group P2₁/n with a = 11.027(3), b = 24.984(7), c = 18.379(5) Å, = 99.870(8)°, V = 4988(2) ų, and Z = 4. The complex has an octahedral geometry with the chelating pyS ligand and two CO groups occupying the equatorial sites and the two monodentate dppm ligands lying in the trans positions.     

Synthesis and crystal structure of a coordinatively unsaturated organomercury iridium complex (PCP) Ir(HgPh) Cl (PCP = η3-2,6-( t Bu2PCH2)2C6H3)

The title compound (PCP) Ir(HgPh) Cl (1), (PCP = ³-2,6-( ^t Bu₂PCH₂)₂C₆H₃), is obtained by the reaction of (PCP) IrHCl and Ph₂Hg in toluene solution. Purple crystals of 1 were grown by slow evaporation of benzene solution of 1 and have been studied by X-ray crystallography. The space group is P2₁/n, a = 13.9384(8) Å, b = 15.1095(8) Å, c = 15.8148(9) Å, = 111.005(1)°, V = 3109.3(3) ų, Z = 4. The geometry at the iridium center is quasi-square pyramidal with Hg at the apical position; the Cl–Ir–C(PCP) angle is 175.87(8)°. The Ir–Hg–C(Ph) angle is 175.90(9)°. The Hg–Ir bond is unusually short: 2.5251(2) Å. This short distance is likely attributable to the absence of a ligand trans to the phenylmercury group. The resulting strong metal–mercury bond may explain the unusual stability of the complex and the failure to eliminate mercury as is commonly observed with organomercury–transition-metal complexes.     

X-ray structural and molecular mechanics investigation of cyclopentadienyl-carbonyl-triphenylophosphine-phenylacetyliron, (η5-C5H5)Fe(CO)(PPh3)(COCH2C6H5)

The crystal and molecular structure of cyclopentadienyl-carbonyl-triphenylphosphine-phenylacetyl-iron (1) has been determined on the basis of X-ray data. The crystals are triclinic, space groupP¯1 (Z=2) with cell dimensions:a=9.546(1),b=10.233(1),c=5.012(2) Å,=93.70(1),=101.12(1), =112.58(1)°. The structure was solved by direct methods and refined anisotropically by a full-matrix, least-squares procedure against 4964 independent reflections, givingR=0.0416. The MM calculations done for a model of1 reproduced satisfactorily the X-ray structure.On leave from the Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai, China.     

Synthesis of a chiral calixarene: 5,11,17,23-tetra (tert-butyl)-25,27-bis[((+)-camphor-10-sulfonyl)-oxy]-calix[4]arene-26,28-diol: crystal and molecular structure of its (1∶2) complex with toluene

The title compound was obtained by treatment ofp-tert-butylcalix[4]arene with (+) camphorsulfonyl chloride in triethylamine and toluene. A (12) complex with toluene has been found. Its structure has been determined by X-ray crystallography. Crystals are triclinic with space group P1,a=16.426(3),b=18.553(3),c=13.661(2) Å, =94.78(2), =110.76(2), =72.83(2)°,V=3720(2) ų,d _c =1.127 g/cm³ Z=2. Refinement based on 10495 observed reflections led to a finalR value of 0.100. The two independent molecules of calixarene in the asymmetric unit are in the cone conformation and the calixarene cavities are empty. The guest molecule occupies the interhost space. The norborane skelton of (+) camphorsulfonyl group is the same as ones found in literature. Only van der Waals interactions exist between the host and the guest molecules.