The effects of substitution on tetrakis­(substituted imidazole)­copper(II) tri­fluoro­methane­sulfonates

The organic ligands 4‐methyl‐1H‐imidazole and 2‐ethyl‐4‐methyl‐1H‐imidazole react with Cu(CF₃SO₃)₂·6H₂O to give tetrakis(5‐methyl‐1H‐imidazole‐κN³)­cop­per(II) bis­(tri­fluoro­methane­sulfonate), [Cu(C₄H₆N₂)₄](CF₃SO₃)₂, and aqua­tetrakis(2‐ethyl‐5‐methyl‐1H‐imidazole‐κN³)copper(II) bis(tri­ fluoro­methane­sulfonate), [Cu(C₆H₁₀N₂)₄(H₂O)](CF₃SO₃)₂. In the former, the Cu atom has an elongated octahedral coordination environment, with four imidazole rings in equatorial positions and two tri­fluoro­methane­sulfonate ions in axial positions. This conformation is similar to those in the analogous complexes tetrakis­(imidazole)­cop­per(II) tri­fluoro­methane­sulfonate and tetrakis(2‐methyl‐1H‐imidazole)­cop­per(II) tri­fluoro­methane­sulfonate. In the second of the title compounds, the ethyl groups block the central Cu atom, and a square‐pyramidal coordination environment is formed around the Cu atom, with the substituted imidazole rings in the basal positions and a water mol­ecule in the axial position.     

Bis{bis­[5‐tert‐butyl‐2‐oxido‐3‐(1‐pyridinio­methyl)­phenyl]­methane}­dioxouranium bis­(tri­fluoro­methane­sulfonate) pyridine disolvate: a uranyl bis­(diphenoxide) complex resulting from homooxacalixarene cleavage

The title compound, [UO₂(C₃₃H₃₈N₂O₂)₂](CF₃SO₃)₂·2C₅H₅N, has been obtained by reaction of U^IV tri­fluoro­methane­sulfonate with p‐tert‐butyl­tetrahomodioxacalix­[4]­arene in pyridine. The uranyl ion lies on an inversion centre and is bound to two O atoms from each diphenoxide ligand, which gives the usual square‐planar equatorial environment. The zwitterionic diphenoxide species results from nucleophilic attack by pyridine on the benzylic ether C atoms of the homooxacalixarene, assisted by initial U coordination to the ether groups, with subsequent metal oxidation giving the uranyl moiety.     

Chloro­bis­(tri­phenyl­phosphine)­nickel(I)

Crystals of the title compound, [NiCl(C₁₈H₁₅P)₂], contain one mol­ecule per asymmetric unit with no short intermolecular interactions. This is noteworthy since previous studies have reported that the formally 15‐electron species oligomerizes in the solid state. The nickel(I) centre has a distorted trigonal–planar coordination geometry, the origin of which is suggested to be electronic in nature.     

Aqua­bis­(crotonato)­bis­(pyridine)­copper(II)

The title compound, [Cu(O₂CCH=CHCH₃)₂(C₅H₅N)₂(H₂O)], crystallizes as a monomer, with the copper ion in a pentacoordinated square‐pyramidal environment, bisected by a twofold axis passing through the metal atom and the apex. The mol­ecules organise in chains connected by hydrogen bonds running along the unique b axis.     

trans‐Chloro­(methyl)­bis­(tri­cyclo­hexyl­phosphine)­platinum(II)

The crystal structure of the title compound, [PtCl(CH₃)(C₁₈H₃₃P)₂], is isostructural with various platinum(II) and palladium(II) complexes containing two bulky tri­cyclo­hexyl­phosphine ligands in a trans orientation. The Pt atom resides on an inversion centre, resulting in a 50% statistical disorder in the chloro and methyl positions. The most significant geometrical parameters are Pt—P 2.3431 (8), Pt—­Cl 2.440 (4) and Pt—C1 2.179 (13) Å, and P—Pt—P 180, P—Pt—Cl 89.15 (12) and 90.85 (12), and C—Pt—Cl 172.7 (5)°. The effective and Tolman cone angles for the tricyclohexylphosphine ligands were calculated as 160 and 162°, respectively.     

Di­methyl­phenyl­sulfonium tri­fluoro­methane­sulfonate and methyl­di­phenyl­sulfonium tri­fluoro­methane­sulfonate

The bonding geometry of sulfur in the cations of the title compounds, C₈H₁₁S⁺·CF₃SO₃^? and C₁₃H₁₃S⁺·CF₃SO₃^?, respectively, is similar and is independent of the ratio of the Me/Ph substituents. As expected, in both cations, the S—Ph bonds are somewhat shorter than the S—Me bonds. In both crystal structures, the interaction between cations and anions is similar.     

Aqua­bis­(benzo­nitrile)(o‐benzo­quin­one di­imine)(tri­phenyl­phosphine)­ruthenium(II) bis­(tetra­fluoro­borate) hydrate

The Ru atom in the title compound, [Ru(C₆H₅CN)₂{P(C₆H₅)₃}{C₆H₄(NH)₂}(H₂O)](BF₄)₂·H₂O, has six‐coordinate octahedral geometry, with a trans arrangement of the tri­phenyl­phosphine ligand and the water mol­ecule. The asymmetric unit contains one complex cation, two tetra­fluoro­borate anions and one solvent water mol­ecule, which is disordered over two sites (ratio of occupancies 0.70:0.30).     

[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.     

High‐temperature phase of trans‐tetra­aqua­bis­(tri­fluoro­acetato‐O)­manganese(II)

The title compound, [Mn(CF₃COO)₂(H₂O)₄], crystallizes in the monoclinic space group C2/c. At about 215 K, it undergoes a reversible phase transition, which leads to crystal twinning. The crystal structure of the high‐temperature phase was determined at 220 K. The Mn²⁺ ion lies on a twofold axis and is octahedrally coordinated by two monodentate tri­fluoro­acetate ligands in apical positions and by four equatorial aqua ligands, two of which lie on the twofold axis. Hydro­gen‐bonding interactions connect the complex mol­ecules, generating a three–dimensional network.     

Bis[bis­(2‐pyridylcarbon­yl)­aminato]­iron(III) perchlorate acetonitrile disolvate

The title compound, [Fe(C₁₂H₈N₃O₂)₂]ClO₄·2C₂H₃N, contains Fe^III in a distorted octa­hedral coordination environment, with the Fe—N(pyridine) bonds significantly longer than the Fe—N(amine) bonds. The crystal packing involves a bifurcated C—H⋯(O,O) contact that is also found in all other [M(C₁₂H₈N₃O₂)₂] complexes reported previously.     

Bis­(ethyl­enedi­amine‐N,N′)(pyrimidine‐2‐carboxyl­ato‐N1,O)­cobalt(III) bis­(tri­fluoro­methane­sulfonate) dihydrate

In the title compound, the coordination geometry of the Co^III atom is only slightly distorted from regular octahedral, and the racemic nature of the material was confirmed by X‐ray structure analysis.     

Bis[bis­(3‐phenyl­pyrazol‐1‐yl)­(pyrazol‐1‐yl)­methane]­copper(II) bis­(per­chlor­ate) acetonitrile disolvate

The title copper(II) complex, [Cu(C₂₂H₁₈N₆)₂](ClO₄)₂·2C₂H₃N, comprises two neutral substituted tris­(pyrazol‐1‐yl)­methane ligands bonded to a central Cu^II ion, which is positioned on a crystallographic inversion center. Six Cu—N bonds are arranged in a distorted octa­hedral fashion. The unsubstituted pyrazole rings on each ligand are oriented trans with respect to each other, inter­digitated with the two 3‐phenyl­pyrazole rings of the other ligand.     

Polymeric bis­(glycolato)­cobalt(II)

In the title compound, poly­[cobalt(II)‐bis(μ‐hydroxy­acetato‐O¹,O²:O^1′)], [Co(C₂H₃O₃)₂]_n, units of [Co(C₂H₃O₃)₂] constitute a bidimensional sheet coordination polymer in which each Co^II atom lies on an inversion centre and is octahedrally coordinated to glycolate ligands in a trans configuration. Carbonyl O atoms from adjacent units complete the octahedral environment.     

trans‐Di­chloro­bis­(tri­phenyl­phosphine‐P)­platinum(II)

Two different crystals (A and B) were used to structurally characterize trans‐[PtCl₂(PPh₃)₂] and to study random and systematic errors in derived parameters. The compound is isomorphous with trans‐[PdCl₂(PPh₃)₂] and with one of the polymorphs of trans‐[PtMeCl(PPh₃)₂] reported previously. Half‐normal probability plot analyses based on A and B show realistic s.u.'s and negligible systematic errors. R.m.s. calculations give very good agreement between A and B, 0.0088 Å. Important geometrical parameters are Pt—P = 2.3163 (11) Å, Pt—Cl = 2.2997 (11) Å, P—Pt—Cl = 87.88 (4) and 92.12 (4)°. Half‐normal probability plots and r.m.s. calculations were also used to compare the title compound with the palladium analogue, showing small systematic differences between the compounds. The torsion angles around the Pt—P bond were found to be very similar to those reported for isomorphous complexes, as well as to the torsion angles around the Pt—As bond in trans‐[PtCl₂(AsPh₃)₂]. The NMR coupling constants for the title compound are similar to Pt—P coupling constants reported for analogous trans complexes.     

Bis­[bis­(di­phenyl­phosphino­methyl)­phenyl­phosphine]­di­chloro­tetra­gold(I) bis­[chloro­tris­(penta­fluoro­phenyl)­aurate(III)]

The cation of the title compound, [Au₄(PPh₂CH₂PPhCH₂PPh₂)₂Cl₂][Au(C₆F₅)₃Cl]₂ or [Au₄Cl₂(C₃₂H₂₉P₃)₂][AuCl(C₆F₅)₃]₂, displays a rhomboidal geometry for the Au atoms, with short Au?Au distances of 3.104 (2) and 3.185 (1) Å; the linear coordination at the Au^I atoms is distorted: P—Au—P 164.7 (2)° and P—Au—Cl 170.67 (11)°. The anion shows the expected square‐planar geometry at Au^III, with the Au atom 0.022 (5) Å out of the plane of the four donor atoms.     

Chloro­bis­(tri­phenyl­phosphine)­nickel(I) tetra­hydro­furan solvate and an unsolvated trigonal phase of chloro­tris­(tri­phenyl­phosphine)­nickel(I)

In [NiCl(C₁₈H₁₅P)₂]·C₄H₈O, the Ni atom is coordinated by three ligands in a distorted trigonal–planar configuration, with a P—Ni—P angle of 111.52 (2)°. In [NiCl(C₁₈H₁₅P)₃], there are three independent mol­ecules in the asymmetric unit, with each Ni—Cl bond on a crystallographic threefold rotation axis. Each Ni centre is tetrahedrally bound. The Ni atoms in both compounds have a d⁹ configuration and a formal oxidation state of Ni^I. A comparison is made between the form of [NiCl(PPh₃)₃] presented here and that of a known toluene solvate.     

Di­chloro­bis­(di­benzyl­amino)­bis­(tetra­hydro­furan)­zirconium(IV) toluene hemisolvate

The title complex, [ZrCl₂(C₄H₈O)₂(C₁₄H₁₄N)₂]·0.5C₇H₈, was prepared in an unusual manner by utilizing [Mg{N(CH₂Ph)₂}₂] as a ligand transfer reagent. The Zr atom lies in a distorted octahedral environment where steric repulsion from the large di­benzyl­amino ligands leads to a widening of the N—Zr—N angle [99.95 (9)°] and corresponding compression of other angles [Cl—Zr—Cl 160.95 (3)° and O—Zr—O 78.22 (7)°]. This distortion is compared with those found in the previously determined structures of the di­methyl­amino and diethyl­amino analogues.     

Bis­(iso­propyl­amino)­methyl­carbenium tetrakis­(penta­fluoro­phenyl)­gallate

The title compound, [MeC(NHⁱPr)₂][Ga(C₆F₅)₄] crystallizes as discrete ions forming interionic hydrogen bonds of the type N—H?F.     

trans‐(Methanol)(methyl­di­phenyl­phosphine)­bis­(pentane‐2,4‐dionato)­cobalt(III) hexa­fluoro­phosphate hydrate

The title compound [Co(C₅H₇O₂)₂(C₁₃H₁₃P)(CH₄O)]PF₆·H₂O, (I), which was converted from trans‐[Co(acac)₂(PMePh₂)(H₂O)]PF₆ (acac is pentane‐2,4‐dionato) by recrystallization from aqueous methanol, has been confirmed as have a coordinated methanol ligand. The molecular structure of the complex cation, trans‐[Co(acac)₂(PMePh₂)(MeOH)]⁺, is similar to that of the above aqua complex found in the ClO₄ salt [Kashiwabara et al. (1995). Bull. Chem. Soc. Jpn, 68 , 883–888]. The Co—O bond length for the coordinated methanol is 2.059 (3) Å. There is an intermolecular hydrogen bond between the OH group of the coordinated methanol and one of the O atoms of the acac ligands in an adjacent complex cation [O5?O3′ = 2.914 (4) Å], giving a centrosymmetric dimeric dicationic complex.     

Bis(μ‐di‐2‐pyridyl­aminato 1‐oxide)­bis­[(tri­fluoro­acetato)copper(II)] aceto­nitrile disolvate

The crystal structure of the title compound, [Cu₂(C₂F₃O₂)₂(C₁₀H₈N₃O)₂]·2CH₃CN, contains discrete [Cu₂(CF₃COO)₂(O‐dpa)₂] mol­ecules (O‐dpaH is di‐2‐pyridyl­amine 1‐oxide) which have imposed crystallographic twofold symmetry and an aceto­nitrile mol­ecule of solvation. The O‐dpa⁻ ligand is both bidentate and bridging, linking two Cu atoms with a separation of 3.4270 (11) Å. Each Cu atom is surrounded by four coordinated atoms that are almost coplanar, with dimensions Cu—N = 1.940 (2) and 1.984 (3) Å, and Cu—O = 1.912 (2) and 1.945 (2) Å.