The bis(η5‐cyclo­penta­dienyl)­methyl­zirconium(IV) methyl­tris­(penta­fluoro­phenyl)­borate ion pair

The title complex, [Zr(CH₃)(C₅H₅)₂][CH₃B(C₆F₅)₃], crystallizes as an ion pair linked through an unsymmetrical methyl bridge. The bridging Zr—Me distance [2.556 (2) Å] is significantly longer than the terminal Zr—Me distance [2.251 (3) Å], while the Zr—C—B angle approaches linearity [169.1 (2)°].     

Tri­benzyl(η5‐penta­methyl­cyclo­penta­dienyl)­hafnium(IV)

The title compound, [Hf(C₇H₇)₃(C₁₀H₁₅)], adopts a monomeric three‐legged piano‐stool structure. One benzyl ligand is disordered between two sites (44:56%) related by a ～30° rotation about an axis defined by the Hf atom and the ipso‐C atom of the benzyl ligand.     

Amido­bis­[η5‐1,3‐bis­(tri­methyl­silyl)­cyclo­penta­dienyl]­titanium(III)

The title compound, [Ti(C₁₁H₂₁Si₂)₂(NH₂)], crystallizes as a bent metallocene, with the NH₂ group oriented to maximize the π interaction between the N atom and the Ti^III center. The increased π bonding is reflected in a short Ti—N bond length of 1.933 (3) Å.     

Redetermination of hexa­carbonyl­(η5‐cyclo­penta­dienyl)­bis(μ3‐selenido)­diiron(II)­cobalt(II)

The structure of the title compound, hexa­carbonyl‐1κ³C,2κ³C‐[3(η⁵)‐cyclo­penta­dienyl]­bis(μ₃‐selenido)­diiron(II)­cobalt(II),[CoFe₂(μ₃‐Se)₂(C₅H₅)(CO)₆], was redetermined at room temperature and the correct C2/c space group was assumed instead of the previously reported P space group [Mathur et al. (1995). Organometallics, 14 , 2115–2118]. Analysis of the literature data showed that the previously reported triclinic parameters correspond to a primitive subcell of the actual monoclinic C‐centred cell with cell dimensions close to those found by us. The title compound appeared to be isostructural with the sulfur–selenium analogue.     

[η5,σ‐3,3‐Di­methyl‐1‐(2,3,4,5‐tetra­methyl­cyclo­penta­dienyl)­but‐1‐en‐2‐amino](η5‐penta­methyl­cyclo­penta­dienyl)titanium

The titanocene complex [Ti(C₁₀H₁₅)(C₁₅H₂₃N)] features a penta­methyl­cyclo­penta­dienyl ligand and a substituted cyclo­penta­dienyl ligand Me₄C₅R, where R is an amino functional group which is subsequently attached to the titanium metal centre. The structure has been determined to ascertain the conformational properties of the side chain with regard to extended conjugation between the π systems and the nature of the amino interaction with the metal centre.     

Di­methyl(2‐methyl­phenyl)­ammonium hydroxo­tris­(penta­fluoro­phenyl)­borate

In the title compound, [(CH₃)₂(C₇H₇)NH][(C₆F₅)₃B(OH)] or C₉H₁₄N⁺·C₁₈HBF₁₅O^?, the distorted tetrahedral borate anions are strongly hydrogen bonded to the substituted ammonium cations. The N?O separation in the N—H?O hydrogen bond is 2.728 (3) Å.     

Tri­benzyl{η5‐[2‐(p‐tolyl)­prop‐2‐yl]­cyclo­penta­dienyl}­zirconium

The title compound, [Zr(C₇H₇)₃(C₁₅H₁₇)], (I), crystallizes from light petroleum with two independent mol­ecules in the asymmetric unit. Whereas in the parent mol­ecule, Zr(η⁵‐C₅H₅)(CH₂Ph)₃, all three Zr—CH₂Ph angles are equal, in (I), they differ significantly. In spite of their different environments, both independent mol­ecules in (I) exhibit a small, an expected, and a large Zr—CH₂Ph angle. The angles are similar to those of the closely related tri­benzyl­[η⁵‐(benzyl­di­methyl­silyl)­cyclo­penta­dienyl]­zirconium complex. The smallest Zr—CH₂Ph angle and the consequently relatively short Zr?C_ipso distance are indicative of η²‐bonding of the benzyl group.     

Azido­[1,1′‐bis­(di­phenyl­phosphino)­ferrocene](penta­methyl­cyclo­penta­dienyl)­rhodium(III) hexa­fluoro­phosphate

In the title compound, azido‐2κN‐bis­[μ‐(1η⁵:2κP)‐di­phenyl­phosphino­cyclo­penta­dienyl][2(η⁵)‐penta­methyl­cyclo­penta­di­enyl]­iron(III)­rhodium(III) hexa­fluoro­phosphate, [{Rh(C₁₀H₁₅)(N₃)}{Fe(μ‐C₁₇H₁₄P)₂}]PF₆ or [FeRh(C₁₀H₁₅)(μ‐C₁₇H₁₄P)₂(N₃)]PF₆, the coordination sphere of Rh^III can be described as pseudo‐tetrahedral, composed of two P atoms from a 1,1′‐bis­(di­phenyl­phosphino)­ferrocene (dppf) ligand, an azido N atom and the centroid of the ring of a C₅Me₅ (Cp*) ligand. The two cyclo­penta­dienyl rings in the dppf moiety adopt an eclipsed conformation. The Rh⋯Fe distance is 4.340 (2) Å.     

(η6‐Hexamethylbenzene)(mesidine)­ditriflatoruthenium(II)

The crystal structure of the title complex, (η⁶‐hexamethylbenzene)bis(trifluoromethanesulfonato‐O)(2,4,6‐trimethylanil­ine‐N)ruthenium(II), [Ru(CF₃O₃S)₂(C₁₂H₁₈)(C₉H₁₃N)], is described. The complex has the classic three‐legged piano‐stool structure with a planar arene 1.667 Å from the metal, two monodentate O‐bound tri­fluoro­methane­sulfonate ligands [Ru—O 2.169 (2) and 2.174 (2) Å] and one N‐bound mesidine ligand [Ru—N 2.198 (2) Å]. The Ru—N distance is relatively long and the average Ru—O distance is relatively short when compared with previously characterized Ru^II complexes.     

[5,10,15,20‐Tetrakis­(penta­fluoro­phenyl)­porphyrinato]­iron(II) benzene disolvate

The title compound, [Fe(C₄₄H₈F₂₀N₄)]·2C₆H₆, contains a four‐coordinated Fe^II atom, which lies on a center of symmetry. The porphyrin macrocycle is planar, and the Fe—N bond distances are in the range 1.9891 (13)–1.9982 (13) Å. The spin state of the Fe^II atom is intermediate (S = 1), as confirmed by NMR spectroscopy. The asymmetric unit contains two half benzene mol­ecules, each lying about an independent inversion centre; one of the benzene rings is located just below (and by inversion symmetry, another is just above) the Fe atom, where it interacts weakly with the porphyrin ring.     

Tetrameric di­chloro­(tri­methyl­ammonio‐p‐toluene­sulfonamidate)­mercury(II)

In the title compound, hexa‐μ‐chloro‐di­chloro­tetrakis(N‐tri­methyl­ammonio‐p‐toluene­sulfonamidate‐κ²N,O)­tetramer­cury(II), [Hg{Me₃N(+)N(−)SO₂C₆H₄CH₃‐p}Cl₂]₄ or [Hg₄Cl₈(C₁₀H₁₆N₂O₂S)₄], four nearly linear and parallel Cl—Hg—Cl units associate through pairwise Hg⋯Cl interactions of 3.1–3.2 Å. Each Hg atom is also coordinated through N and O atoms to a yl­ide mol­ecule. The available structural data indicate that coordination of a sulfonyl‐stabilized nitro­gen yl­ide to a metal atom (Hg or Ag) has no detectable effect on its geometry.     

Di‐μ‐phenyl­thio‐bis­[bis(η5‐methyl­cyclo­penta­dienyl)(tetra­hydro­furan)lanthanum(III)] bis­(tetra­hydro­furan) solvate

The title complex, [La₂(C₆H₇)₄(C₆H₅S)₂(C₄H₈O)₂]·2C₄H₈O, is a centrosymmetric dimer bridged through the S atoms of the benzene­thiolate ligands. The bridging La₂S₂ unit is completely planar, while the geometry around the nine‐coordinate La atom is that of a distorted trigonal bipyramid. The La—S—La and S—La—S angles are 117.51 (4) and 62.5 (1)°, respectively, and the average La—S bond length is 2.9759 Å. The crystals contain two tetra­hydro­furan solvate mol­ecules for every complex mol­ecule.     

The effect of counter‐ions on the supra­molecular arrangement of (benzonitrile)[1,2‐bis(diphenylphosphino)ethane](η5‐cyclo­penta­dienyl)­iron(II) cations

The title compound, [1,2‐bis(diphenylphosphino)ethane](η⁵‐cyclo­penta­dienyl)(4‐nitro­benzonitrile)iron(II) iodide, [Fe(η⁵‐C₅H₅)(C₇H₄N₂O₂)(C₂₆H₄P₂)]I, crystallizes in the non‐centrosymmetric space group Cc, which is a promising result for obtaining quadratic non‐linear optical properties. However, the packing shows that the iodide counter‐ion promotes the cancellation of almost all the dipoles, resulting in a supra­molecular motif of cationic chains aligned in opposite directions making an angle of 35.2°. The use of PF₆⁻ as counter‐ion induces the crystallization of the complex in a centrosymmetric space group. These results show that the introduction of different counter‐ions, of different size and geometry, allows specific and directional inter­molecular inter­actions that can determine the formation of a particular type of crystal packing.     

Crystallographic report: Tricarbonyl(η5‐cyclopentadienyl)(dichloroindium) molybdenum

In the solid state, [{Cp(CO)₃Mo}InCl₂]∞ forms a one‐dimensional coordination polymer in which the indium atoms are coordinated by four chlorine atoms (In? Cl: 2.448(2)–3.004(2) Å) and a {Cp(CO)₃Mo} group (In? Mo: 2.750(1) Å) in a distorted trigonal bipyramidal environment. Copyright © 2004 John Wiley & Sons, Ltd.     

Di‐μ‐methoxy‐bis[(η5‐cyclopentadienyl)(nitrosyl‐κN)(trimethylsilylmethyl)molybdenum(II)]

The title complex, [Mo₂(C₅H₅)₂(CH₃O)₂(C₄H₁₁Si)₂(NO)₂], is formed in high yield by treating [CpMo(NO)(CH₂SiMe₃)₂] (Cp is cyclo­penta­dienyl) with methanol. The nitro­syl ligands are nearly linear [O—N—Mo 170.1 (4) and 170.1 (5)°], with short Mo—N bonds [1.769 (4) and 1.776 (4) Å] and long N—O bonds [1.216 (5) and 1.201 (4) Å]. The central four‐membered Mo₂O₂ ring exhibits an average Mo—O bond length of 2.15 Å.     

Chloro­bis­(di­methyl­amido)(η5‐2,5‐di­methyl­pyrrolyl)­titanium(IV), [Ti(NMe2)2(DMP)Cl]

The structure of the title compound, [Ti(C₂H₆N)₂(C₆H₈N)Cl], displays a η⁵‐coordination mode for the pyrrolyl ring, confirmed by the values of the slip parameter [0.073 (9) Å] and the fold angle [4.6 (6)°]. This coordination is confirmed by NMR data, which point to the involvement of the complex in a fluxional process in solution above 285 K, passing through an intermediate involving simultaneously a metal–aza­allyl and a metal–olefin bond.     

1‐(4‐Chloro­phenyl­sulfanyl)‐2‐nitro‐4‐(tri­fluoro­methyl)­benzene and 1‐(4‐chloro­phenyl­sulfanyl)‐4‐nitro‐2‐(tri­fluoro­methyl)­benzene

Two chemical isomers of 3‐nitro­benzotrifluoride, namely 1‐(4‐chloro­phenyl­sulfanyl)‐2‐nitro‐4‐(tri­fluoro­methyl)­benzene, C₁₃H₇ClF₃NO₂S, (I), and 1‐(4‐chloro­phenyl­sulfanyl)‐4‐nitro‐2‐(tri­fluoro­methyl)­benzene, C₁₃H₇ClF₃NO₂S, (II), have been prepared and their crystal structures determined with the specific purpose of forming a cocrystal of the two. The two compounds display a similar conformation, with dihedral angles between the benzene rings of 83.1 (1) and 76.2 (1)°, respectively, but (I) packs in P while (II) packs in P2₁/c, with C—H⋯O interactions. No cocrystal could be formed, and it is suggested that the C—H⋯O associations in (II) prevent intermolecular mixing and promote phase separation.     

Three ruthenocene derivatives: (η5‐4,7‐dimethylindenyl)(η5‐pentamethylcyclopentadienyl)ruthenium(II), [η5‐[2](4,7)indeno[2]paracyclophanyl](η5‐pentamethylcyclopentadienyl)ruthenium(II) and bis[η5‐[2](4,7)indeno[2]paracyclophanyl]­ruthenium(II)

In the title compounds, [Ru(C₁₀H₁₅)(C₁₁H₁₁)], (III), [Ru(C₁₀H₁₅)(C₁₉H₁₇)], (IV), and [Ru(C₁₉H₁₇)₂], (V), respectively, the coordinating ring systems are planar and parallel, with the Ru atoms lying at perpendicular distances of Ru–Cp* 1.790 (1) Å and Ru–indenyl 1.836 (1) Å in (III), Ru–Cp* 1.791 (1) Å and Ru–indenyl 1.837 (1) Å in (IV), and Ru–indenyl 1.812 (1) Å and 1.809 (1) Å in (V) (Cp* is penta­methyl­cyclo­penta­dienyl). The ring conformations are eclipsed for (III), staggered for (IV) and intermediate for (V). All three compounds show short intermolecular contacts from C—H groups to some ring centroids; these could be regarded as C—H?π hydrogen bonds. The mol­ecules of each compound are thus connected via the 2₁ screw axis to form layers parallel to the xy plane.