X-ray structure of [Os3(CO)10(μ-Ph2PCH2PPh2)]

Decacarbonyl--bis(diphenylphosphino)methane triosmium crystallizes in the monoclinic space group P2₁/c with a = 24.422(5), b = 12.381(2), c = 24.788(5) Å, = 103.69(3)°, V = 7282 (2) ų, and Z = 8. The molecule consists of a triangular arrangement of osmium atoms with the organic ligand bridging two adjacent osmium atoms at equatorial sites. The Os—Os distances lie in the close range 2.8563(9)–2.8895(11) Å with an average value of 2.87(1) Å.     

Molecular structure of [(tBu)2Al(μ-Cl)]2

The crystal and molecular structure of [(^tBu)₂Al(μ-Cl)]₂ has been determined. The bond lengths and geometry about aluminum are similar to that in [Me₂Al(μ-Cl)]₂ and [(Mes)₂Al(μ-Cl)]₂ suggesting that the geometry about the aluminum is defined by the steric repulsion between the alkyl groups on adjacent aluminum centers and not steric congestion between ligands on individual aluminum centers. Crystal data: Triclinic, $P\bar 1$ ,a=6.514(1),b=8.628(2),c-11.236(2)c=11.236(2) Å, α=102.05(3), β=105.32(3), γ=103.47(3)°,V=567.2(3) ų,Z=1,R=0.063,R _w =0.067.     

Molecular structure of [(tBu)2Al(μ-NHtBu)]2

The crystal and molecular structure of [(^tBu)₂Al(-NH^tBu)]₂ has been determined. The unit cell contains two independent molecules with only slight variation in the orientation of thetert-butyl ligands. Crystal data: Triclinic, ,a=9.0138(6),b=10.2944(8),c=15.791(1) , =91.262(6), =89.822(6), =106.141(6)°,V=1407.2(2) ų,Z=2,R=0.039,R _w=0.041.     

Molecular structure of [(tBu)2Al(μ-OPh)]2

The molecular structure of [(^tBu)₂Al(-OPh)]₂ has been determined. The intramolecular steric interaction between the phenyl groups and thetert-butyl ligands results in the geometry about aluminum being significantly distorted from tetrahedral, with the AlC₂ planes are pitched 62° with respect to the Al₂O₂ plane. The greater distortion from tetrahedral about aluminum, and the orientation of the phenoxide ring more nearly perpendicular to the M₂O₂ core as compared to that in [(^tBu)₂Ga(-OPh)]₂ are all consistent with increased^tBu...Ph steric interaction as a consequence of the smaller M₂O₂ core for [(^tBu)₂Al(-OPh)]₂. Crystal data: tetragonal, I4₁/acd,a=16.44(1),c=21.41(1) Å,V=5788(7) ų,Z=8,R=0.047,R _w=0.045.     

Synthesis and crystal and molecular structure of the [MoO2(L)(H2O)] · H2O complex (L 2− is the anion of 2-[N-(hydroxynaphtylidene)amino]propan-1,2,3-triol)

A new compound of dioxomolybdenum(VI)—[MoO₂(L)(H₂O)] · H₂O, where L ^2? = 2-[N-(hydroxynaphtylidene)amino]propan-1,2,3-triol)—is synthesized. Its structure is determined by X-ray diffraction. The Mo atom has an octahedral coordination formed by two oxo ligands located cis with respect to one another, two O atoms and the N atom of the tridentate bis(chelate) L ^2? ligand, and the O atom of a water molecule. The crystallization water molecule is connected with two complex molecules by O-H…O hydrogen bonds.     

Crystal and molecular structure of dipotassium-aquapentachlororhodate (III): (K2)++ [RhCl5(H2O)]2−

The structure of K₂[RhCl₅(H₂O)] has been established by X-ray crystallography. It crystallizes in the orthorhombic space groupPcmn, with cell dimensionsa=7.065(1),b=9.453(1),c=13.567(1) Å,V=906.1(3) ų,Z=4,M _r =376.4,D _x =2.76 g cm^–3,F(000)=712,T=293 K. The final wasR=0.046. The rhodium atom has a distorted octahedral coordination involving five chlorine atoms and an oxygen of the water molecule with Rh, O, and three chlorine atoms on the mirror plane. Rh-Cl distances range from 2.284(7) Å to 2.345(7) Å. The Cl(4)O intermolecular distance, 3.140(12) Å indicates strong hydrogen bonding between oxygen and chlorine atoms of the neighboring octahedra.N. C. L. Communication No. 5353.     

Decarbonylation Reaction of [Os3(CO)10(μ-H)(μ-SN2C4H5)]: X-ray Structures of the Two Isomers of [Os3(CO)9(μ-H)(μ 3-η 2-SN2C4H5)]

Abstract  The thermal reaction of [Os₃(CO)₁₀(μ-H)(μ-SN₂C₄H₅)] (1) at 110 °C afforded the new compound [Os₃(CO)₉(μ-H)(μ ₃-η ²-SN₂C₄H₅)] (2) in 84% yield. Compound 2 exists as two isomers, which differ in the disposition of the bridging hydride ligand. Both of the isomers of 2 have been characterized by a combination of elemental analysis, infrared and ¹H NMR spectroscopic data together with single crystal X-ray crystallography. The isomers crystallize together in the triclinic space group P-1 with a = 10.4775(2), b = 13.3056(3), c = 15.0325(3) ?, α = 110.8890(10), β = 99.3880(10), γ = 96.1620(10)°, Z = 2 and V = 1900.31(7) ?³. Index Abstract  The synthesis and the molecular structures of the two isomers of [Os₃(CO)₉(μ-H)(μ ₃-η ²-SN₂C₄H₅)] are described. The isomers differ in the disposition of the hydride ligand.      

Crystal and molecular structure of octacarbonyl[bis(bispentafluorophenylarsenido)] dimolybdenum,Mo2(CO)8[μ-As(C6F5)2]2

The X-ray crystallographic structure determination of Mo₂(CO)₈[-As(C₆F₅)₂]₂ reveals that the compound crystallizes in the tetragonal space groupP42₁ c witha=14.915(3),c=16.732(3) Å,V=3722(1) ų, andZ=4. Least-squares refinement based on 1474 independent observed data [(F _obs)3(F _obs)] resulted in a finalR value of 0.038. The Mo-Mo distance of 3.132(1) Å is longer than found in analogous phosphido-bridged molybdenum systems. The central Mo₂As₂ rhombus is nearly flat and the coordination geometry of the Mo atoms is essentially octahedral. An unusual staggering of the Mo(CO)₄ groups by 15.8° and short intramolecular C₆F₅CO contacts support the presence of a strong steric interaction between the Mo(CO)₄ and As(C₆F₅)₂ groups.     

Crystal and molecular structure of di-μ-chlorobis [N-(2-hydroxyethyl)salicylideneiminato-N,0,0′ copper(II)] hemihydrate

The structure of the title compound. [Cu₂Cl₂(C₉H₁₀NO₂)₂]·1/2H₂O. has been determined from single crystal X-ray diffraction data. The structure was solved by direct methods. Full-matrix leastsquares refinement of structural parameters led to a conventionalR factor of 0.056 for 3689 intensities above 3σ(l). There are two independent molecules [A andB] of the title compound in the asymmetric unit. These molecules are linked to one water molecule by a system of four hydrogen bonds. The comlexes contain pairs of deformed square-pyramidal copper(II) centers. A tridetate ligand L forms two condensed chelate rings with mean Cu?O_(C?O)+1.900(6), mean Cu?O_(C?OH)+2.004(6) and mean Cu?N-1.930(6)Å. A chloride ions complete the tetrahedral distorted basal plane of each Cu(II) ion forming a square pyramid with the longer fifth apical Cu?Cl bridging bond. The Cu...Cu nonbonding distances in the complexes are 3.445(1)Å for moleculeA and 3.494(1)Å for moleculeB.     

Crystal structure of [{MoBr2(O){OPH(OPr i )2}2}2(μ-O)]

[{MoBr₂(O){OPH(OPr ⁱ )₂}₂}₂(μ-O)] (1) crystallizes in the monoclinic space group P2₁/n, with a = 13.063(17) Å, b = 11.818(14) Å, c = 15.889(17) Å, β = 90.30(1)°, Z = 2. The dimeric structure contains a bridging oxygen atom at a crystallographic center of symmetry. Each octahedral molybdenum center has trans-bromide ligands, and two cis-OPH(OPr ⁱ )₂ units, with a terminal oxygen atom trans to one of the OPH(OPr ⁱ )₂ units.     

Synthesis and characterization of the dodecanuclear heterobimetallic Mo—Cu—S cage cluster: (Ph4P)2[{Mo2Cu2O2S2(S2)2}3(μ6-S)]

The complex (Ph₄P)₂[Mo₂S₂O₂(S₂)(S₄)] reacts with CuBr to give the dodecanuclear heterobimetallic Mo—Cu—S cage cluster: (Ph₄P)₂[{Mo₂Cu₂O₂S₂(S₂)₂}₃(₆-S)] (1), which crystallizes in the triclinic space group P1¯, a = 14.445(5), b = 15.396(5), c = 18.858(5) Å, = 103.12(3), = 101.93(2), = 113.92(3)°, and V = 3517(2) ų for Z = 2. The anion 1 can be described as a cage with S^2– at the center binding to six Cu atoms; the cage has two big windows each composed of a puckered Cu₃S₆ 9-membered ring.     

Crystal structure and vibrational spectra of hydrazinium (2+) tri-μ-fluoro bis[pentafluorozirconate (IV)] fluoride and vibrational spectra of its hafnium analogue

Monoclinic (N₂H₆)₃Zr₂F₁₃·F crystallizes in space group P2₁-C ₂ ² (No. 4) with unit cell dimensionsa=5.670(1),b=10.984(2),c=10.601(2) Å,=93.88(1)°,V=658.7(4) ų andZ=2. Two different types of N₂H₆ ²⁺ ions are present. One is involved in strong H-bonds to F^– ions in infinite chains running along the a axis (the shortest N-F distance is 2.437(5) Å), and the other links the structure through weaker bi- and trifurcated H-bonds to fluorine ligands of the Zr₂F₁₃ ^5– ions. The N-N bond lengths range from 1.430(5) to 1.446(5) Å with apparently no meaningful correlation to the type of N₂H₂ ²⁺ ions. The Zr₂F₁₃ ^5– ions have very nearly C₂ point symmetry and are formed by joining two distorted bicapped trigonal prisms of ZrF₈-units through a common face. Distances of Zr-F terminal bonds range from 2.015(2) to 2.112(2) Å and of bridging bonds from 2.133(2) to 2.212(2) Å. (N₂H₆)₃Hf₂F₁₃·F is isomorphous. The vibrational spectra of the two compounds are nearly identical, with the exception of a strong infrared band, which is assigned to a stretching mode with the moving central atom within the anion. The anion part of the spectrum is simple, showing broad unresolved bands. The cation part shows two types of N₂H₆ ^– ions. H-Bonding is strongly present in the spectra, but no simple correlations with the H-bond strength is evident.     

The structure of solvate [Cu2(DfH)4(4,4′-Bipy)] · 2DMF

The crystal structure of [Cu₂(DfH)₄(4,4′-Bipy)] · 2DMF prepared by the reaction of copper(II) acetate with diphenylglyoxime (DfH₂) and 4,4′-bipyridine (4,4′-Bipy) was established by X-ray diffraction. The crystals are monoclinic; a = 15.5192(9) Å, b = 16.2427(11) Å, c = 14.0753(7) Å, β = 101.36(3)°, V = 3478.5(5) ų, Z = 2, and sp. gr. P2₁/c. The crystal structure is composed of discrete dinuclear molecules [Cu₂(DfH)₄(4,4′-Bipy)] and dimethylformamide (DMF) molecules. The coordination polyhedron of the Cu atom (the coordination number is 5) is a tetragonal bipyramid formed by the nitrogen atoms of two monodeprotonated bidentate oxime groups and the bidentate bridging 4,4′-Bipy ligand. The DMF molecules occupy the cavities formed by the dinuclear molecules [Cu₂(DfH)₄(4,4′-Bipy)]. The compound was characterized by IR and NMR spectroscopy.     

Synthesis and X-ray structure of [(μ-H)Ru3(CO)8(μ-Cl)(μ-dppm)] [dppm = bis(diphenylphosphino)methane]

The reaction of [Ru₃(CO)₁₀(-dppm)] 1 with PPhCl₂ in refluxing CHCl₃ results in the isolation of [(-H)Ru₃(CO)₈(-Cl)(-dppm)] 3 in 10% yield. Compound 3, which has been structurally characterized by crystallographic methods, is also formed from the reaction of 1 with H₂ in refluxing CCl₄. The compound crystallizes in the monoclinic space group P2₁/c with a = 16.814(2), b = 18.7590(12), c = 11.486(2) Å, = 97.745(11)°, V = 3589.8(8) ų, and Z = 4. The hydride and chloride ligands bridge the same edge of the triruthenium cluster as the dppm ligand.     

Synthesis and X-ray structure of tetrakis[μ-(3,4-dimethoxy-α-β-dihydrocinnamato)] dimethanoldicopper(II)

The synthesis, magnetic, and structural properties of the title compound are reported. The crystals are triclinic, space groupP¯1, witha=15.084(2),b=11.820(1),c=7.5253(7) Å, =71.50(1),=77.61(1), =68.68(1)° andZ=1; the structure was solved by Patterson and Fourier methods and refined toR 0.0351 for 4147 observed reflections. The content of the unit cell consists of a centrosymmetrical copper acetate-like molecule in which each copper can be described as square-pyramidally surrounded by four carboxylic oxygens in the basal plane [1.955(2)–1.970(2) Å], one methanolic oxygen in the apical site [2.206(2) Å] and a CuCu interaction of 2.612(5) Å at a sixth position of a distorted octahedron. The dimers are packed by means of hydrogen bonds formed between the methanolic OH group and the carboxylic O(2) atom of one adjacent complex and by normal Van der Waals contacts. The subnormal magnetic moment, characteristic of exchange interactions between the two copper(II) ions, and the energy of the d-d band observed are consistent with the reported dinuclear copper(II) acetate-like structure.     

Crystal structure of catena-poly[diaqua(μ-iminodiacetato-N,O,O′: O″)cobalt(II)]

The crystal structure of the [Co(C₄H₅NO₄)(H₂O)₂] complex has been determined by X-ray diffraction analysis (λMo, R = 0.0237 for 768 reflections). The crystals are orthorhombic, a = 14.345(1) Å, b = 5.234(1) Å, c = 9.780(1) Å, Z = 4, d _calcd = 2.045 g cm^?3, and space group Pca2₁. The donor atoms (one N and two O atoms) of the iminodiacetate ion (Ida) are located on the same octahedron face around the Co atom [Co-N, 2.120(3) Å; Co-O, 2.063(3) and 2.151(3) Å]. The O atoms of two water molecules are in the trans positions relative to the O atoms of the carboxylate groups [Co-O, 2.126(3) and 2.157(3) Å]. The sixth coordination site is occupied by the O atom of the adjacent Ida ion [Co-O, 2.054(3) Å], which results in the formation of infinite chains in the structure.     

Synthesis and crystal structure of a palladium dimer containing ferrocenyldiphenylphosphine, trans-[Pd(μ-Cl)(CH3)(PPh2Fc)]2

The chloro-bridged dimeric complex, trans-[Pd(-Cl)(CH₃)(PPh₂Fc)]₂, was prepared by reaction of [Pd(Cl)(CH₃)(COD)] (COD = cis,cis-1,5-cyclooctadiene) with 1 equivalent of PPh₂Fc (PPh₂Fc = ferrocenyldiphenylphosphine) in acetone medium. The complex was characterized by ¹H and ³¹P NMR spectroscopy and a single crystal X-ray diffraction study revealed a trans geometry. The compound crystallizes in the triclinic space group P1, a = 11.476(2) Å, b = 14.059(3) Å, c = 14.658(3) Å and = 82.34(3)°, = 75.09(3)°, and = 68.48(3)° with Z = 2. Most important geometrical parameters include bond lengths Pd(1)–P(1) 2.2165(10), Pd(2)–P(2) 2.2290(10), Pd(1)–C(1) 2.157(3), Pd(2)–C(2) 2.079(4), Pd(1)–Cl(1) 2.4329(13), Pd(1)–Cl(2) 2.4106(11), Pd(2)–Cl(1) 2.4169(10), and Pd(2)–Cl(2) 2.4414(13) Å and bond angles P(1)–Pd(1)–C(1) 87.47(8), P(1)–Pd(1)–Cl(2) 176.88(4), C(1)–Pd(1)–Cl(1) 173.93(7), P(2)–Pd(2)–C(2) 89.03(11), P(2)–Pd(2)–Cl(1) 174.18(4), and C(2)–Pd(2)–Cl(2) 173.50(11)°. The effective and Tolman cone angles for P(1) were calculated as 170 and 167° and that for P(2) as 179 and 177°, respectively.     

Reaction of ethyl diazoacetate with Co3(CO)9(μ3-CCl): Isolation and X-ray structures of Co3(CO)9(μ3-CCO2Et), Co3(CO)9(μ3-CCH2CO2Et), and [Co3(CO)9(μ3-CCHCO2Et)]2

The reaction between the tricobalt cluster Co₃(CO)₉(₃-CCl) (1) and AlCl₃, followed by treatment with ethyl diazoacetate, N₂CHCO₂Et, affords a complex mixture of products in low yields. Column chromatography has allowed the isolation of the four cluster compounds Co₃(CO)₉(₃-CH) (2), Co₃(CO)₉(₃-CCO₂Et) (3), Co₃(CO)₉(₃-CCH₂CO₂Et) (4), and [Co₃(CO)₉(₃-CCHCO₂Et)]₂ (5). Clusters 4 and 5 are new and have been fully characterized in solution by IR and ¹H NMR spectroscopy. The molecular structures of clusters 3–5 have also been determined by single-crystal X-ray diffraction analysis. Co₃(CO)₉(₃-CCO₂Et) crystallizes in the triclinic space group P , a = 8.8393(5), b = 14.727(1), c = 15.272(1) Å, = 93.361(6), = 105.509(5)°, = 100.336(6)°, V = 1872.6(2) ų, Z = 4, and d _calc = 1.823 g/cm³. Co₃(CO)₉(₃-CCH₂CO₂Et) crystallizes in the monoclinic space group P2₁/n, a = 9.3806(7), b = 9.2617(8), c = 22.455(2) Å, = 94.483(7)°, V = 1944.9(3) ų, Z = 4, and d _calc = 1.803 g/cm³. [Co₃(CO)₉(₃-CCHCO₂Et)]₂ crystallizes in the monoclinic space group C2/c, a = 21.585(2), b = 8.7977(7), c = 20.784(1) Å, = 104.807(6)°, V = 3815.8(5) ų, Z = 4, and d _calc = 1.835 g/cm³. Plausible pathways leading to the formation of clusters 2, 4, and 5 are discussed.     

Formation of a samarium alkoxide–aryloxide complex containing a novel butterfly framework: X-ray crystal structures of Sm4(μ3-O-i-Pr)3(μ2-O-i-Pr)4(O-i-Pr)2(O-2,6-i-Pr2C6H3)3(THF) and [Ti(O-i-Pr)2(O-2,6-i-Pr2C6H3) (μ-O-i-Pr)]2

Reaction of a 1:1 mixture of Sm[N(SiMe₃)₂]₃ and Ti(O-i-Pr)₄ with three equivalents of 2,6-di-iso-propylphenol, followed by crystallization from hexane/THF, leads to isolation of the tetranuclear samarium alkoxide Sm₄(₃-O-i-Pr)₃(₂-O-i-Pr)₄(O-i-Pr)₂(O-2,6-i-Pr₂C₆H₃)₃(THF) (1), in addition to the dimeric titanium alkoxide [Ti(O-i-Pr)₂(O-2,6-i-Pr₂C₆H₃)(-O-i-Pr)]₂ (2). 1 crystallizes in the space group while 2 crystallizes in space group P2₁/c. Cell parameters for 1: a = 15.928(6), b = 17.677(7), c = 18.99(1) Å, = 113.24(3), = 94.99(4), = 109.59(2)°, V = 4477(4) ų, D _calc = 1.350 Mg/m³, and Z = 2. Cell parameters for 2: a = 25.336(2), b = 12.082(1), c = 15.570(2) Å, = 96.510(8)°, V = 4735.4(8) ų, D _calc = 1.129 mg/m³, and Z = 4.