trans‐Carbonylchloridobis(ferrocenyldiphenylphosphane‐κP)rhodium(I) dichloromethane monosolvate and trans‐carbonylchloridobis(ferrocenyldiphenylphosphane‐κP)iridium(I) dichloromethane monosolvate

The isomorphous crystal structures of the title compounds, [Fe₂M(C₅H₅)₂(C₁₇H₁₄P)Cl(CO)]·CH₂Cl₂ or trans‐[MCl(CO)(PPh₂Fc)₂]·CH₂Cl₂ (M = Rh or Ir, and Fc is ferrocenyl), are reported. The data collection for M = Rh was performed at 293 (2) K, while the M = Ir data were collected at 160 (2) K. The compounds crystallize with two independent half‐molecules in the asymmetric unit, both occupying inversion centres, and are accompanied by a single dichloromethane molecule on a general position. Due to the symmetry, there is 0.50/0.50 disorder present in the chloride and carbonyl positions. One molecule in each structure also has a second type of disorder in the chloride and carbonyl positions, which was refined over another two positions of equal distribution. The steric impact of the bulky PPh₂Fc ligands was evaluated using the Tolman cone‐angle model, resulting in an average value of 172° for the four molecules in both structures.     

trans‐Bis(thioacetato‐S)bis(triphenylphosphine‐P)nickel(II)

In the title compound, [Ni(C₂H₃OS)₂(C₁₈H₁₅P)₂], the Ni atom lies on an inversion centre and the tri­phenyl phosphine and thio­acetate ligands are bonded to the central Ni^II atom in a trans fashion, with Ni—S = 2.2020 (8) and Ni—P = 2.2528 (8) Å, and angle S—Ni—P = 92.47 (3)°.     

(5,10,15,20‐Tetraphenylporphyrinato‐κ4N)bis(l‐valine‐κN methyl ester)iron(III) trifluoromethylsulfonate dichloromethane solvate

The title compound, [Fe(C₄₄H₂₈N₄)(C₆H₁₃NO₂)₂](CF₃O₃S)·­CH₂Cl₂, is the first amino ester complex of iron porphyrins to be investigated using X‐ray diffraction and it can be considered as a model complex of cytochrome f. The Fe atom is six‐coordinate to four N atoms of the porphyrin ring and to two N atoms of the axial amino ester ligands.     

trans‐(4‐Amino‐2,2,6,6‐tetramethyl­piperidine‐N4)bis(pentane‐2,4‐dion­ato‐O,O′)(triphenylphosphine‐P)cobalt(III) hexafluorophosphate dichloromethane solvate

The complex cation in the title compound, [Co(C₅H₇O₂)₂(C₉H₂₀N₂)(C₁₈H₁₅P)]PF₆·CH₂Cl₂, is the first example of a Co^III complex in which a trans configuration for the coordinated monodentate phosphine and amine ligands has been confirmed by X‐ray analysis. Owing to the large steric bulkiness of the axial PPh₃ ligands influencing the interaction with the equatorial acetyl­acetonate ligands, the acetyl­acetonate planes bend away considerably from the PPh₃ ligands.     

cis‐[1,2‐Bis(diisopropylphosphino‐κP)‐1,2‐dicarba‐closo‐dodecaborane]dichloroplatinum(II) dichloromethane hemisolvate

The asymmetric unit of the title complex, [PtCl₂(C₁₄H₃₈B₁₀P₂)]·0.5CH₂Cl₂ or cis‐[PtCl₂{1,2‐(PⁱPr₂)₂‐1,2‐C₂B₁₀H₁₀}]·0.5CH₂Cl₂, contains one disordered solvent mol­ecule and two mol­ecules of the complex, in which each Pt^II atom displays slightly distorted square‐planar coordination geometry. The P atoms connected to the cage C atoms are coordinated to the Pt^II atom. The Pt—P distances vary slightly [2.215 (3) and 2.235 (4) Å] and the Pt—Cl distances are equal [2.348 (3) and 2.353 (5) Å].     

Bis(tetraphenylphosphonium) bis[cis‐1,2‐bis(methoxycarbonyl)ethylenedithiolato‐κ2S,S′]nickelate(II) and bis(tetraphenylphosphonium) bis[cis‐1,2‐bis(methoxycarbonyl)ethylenedithiolato‐κ2S,S′]nickelate(III) iodide

The crystal structures of the title compounds, (C₂₄H₂₀P)₂[Ni(C₆H₆O₄S₂)₂], (I), and (C₂₄H₂₀P)₂[Ni(C₆H₆O₄S₂)₂]I, (II), in the diamagnetic reduced (2–) and paramagnetic oxidized (1–) states, are reported at 200 and 293 K, respectively. In both compounds, the Ni atom lies on an inversion centre and the NiS₄ coordination is thus required to be exactly planar. In the diamagnetic complex, (I), the Ni—S distances are 2.1818 (7) and 2.1805 (6) Å, while they are 2.1481 (6) and 2.1392 (5) Å in the paramagnetic complex, (II). This results from both the different complex core oxidation states and the different conformations of the methoxycarbonyl groups.     

The three‐dimensional intermolecular network formed via water molecules in trans‐bis(nitrito‐κN)tetrakis(pyridine‐κN)ruthenium(II) dihydrate

The molecular geometry of the tetragonal crystal structure of the title compound, [Ru(NO₂)₂(C₅H₅N)₄]·2H₂O, differs from that previously determined by powder diffraction [Schaniel et al. (2010). Phys. Chem. Chem. Phys. 12 , 6171–6178]. In the [Ru(NO₂)(C₅H₅N)₄] molecule, the Ru atom lies at the intersection of three twofold axes (Wyckoff position 8b). It is coordinated by four N atoms of the pyridine rings, as well as by two N atoms of N‐nitrite groups. The last two N atoms are located on a twofold axis (Wyckoff position 16f). The O atoms of the water molecules are situated on a twofold axis (Wyckoff position 16e). Short intermolecular contacts are observed in the crystal structure, viz. N—O...OW and N—O...H—OW contacts between nitrite and water, and weak C—H...OW hydrogen bonds between pyridine and water. Thus, the intercalated water molecules act as bridges connecting the trans‐[Ru(NO₂)₂(py)₄] molecules into a three‐dimensional network.     

trans‐Diaquabis(nicotinamide‐κN)bis(salicylato‐κO)cobalt(II)

The title compound, [Co(C₇H₅O₃)₂(C₆H₆N₂O)₂(H₂O)₂], forms a three‐dimensional hydrogen‐bonded supramolecular structure. The Co^II ion is in an octahedral coordination environment comprising two pyridyl N atoms, two carboxylate O atoms and two O atoms from water molecules. Intermolecular N—H...O and O—H...O hydrogen bonds produce R₂²(8), R₂²(12) and R₂²(14) rings, which lead to two‐dimensional chains. An extensive three‐dimensional supramolecular network of C—H...O, N—H...O and O—H...O hydrogen bonds and C—H...π interactions is responsible for crystal structure stabilization. This study is an example of the construction of a supramolecular assembly based on hydrogen bonds in mixed‐ligand metal complexes.     

[Bis(2‐diphenylphosphinoethyl) sulfide‐κ3P,S,P′](triphenylphosphine‐κP)platinum(II) diperchlorate acetone solvate

In the title compound, [Pt(C₁₈H₁₅P)(C₂₈H₂₈P₂S)]­(ClO₄)₂·­C₃H₆O or [Pt(PPh₃)(PSP)](ClO₄)₂·CH₃COCH₃, where PSP is the potentially tridentate chelate ligand bis(2‐di­phenyl­phosphinoethyl) sulfide, all three donor groups of the PSP ligand are coordinated to the central Pt atom, with Pt—P = 2.310 (1) Å and Pt—S = 2.343 (1) Å. The fourth coordination site is occupied by the P donor of the tri­phenyl­phosphine ligand [Pt—P = 2.289 (1) Å]. The complex cation has exact mirror symmetry, with the S atom, the Pt atom and the P atom of the PPh₃ ligand in the mirror plane. The Pt atom has a distorted square‐planar coordination geometry. A π–π interaction is present between the phenyl rings of the PPh₃ ligand and the terminal –PPh₂ group of the PSP chelate.     

cis‐Bis(acetato‐κO)bis(dimethyl sulfide‐κS)platinum(II)

The title compound, cis‐[Pt(CH₃COO)₂(C₂H₆S)₂], crystallizes in the P2₁/c space group with a pseudo‐square‐planar coordination geometry. The complex forms centrosymmetric dimeric packing units, with C—H...O—Pt interactions and a short Pt...Pt distance [3.5868 (2) Å]. The coordination mode of the acetate ligands is monodentate and they are oriented almost perpendicular to the coordination plane. Cambridge Structural Database [Allen (2002). Acta Cryst. B 58 , 380–388] data show a preferred staggered conformation with respect to the coordination plane for Me₂S in complexes with Pt^II.     

trans‐Bis[3‐(2‐fluorophenyl)‐1‐(4‐nitrophenyl)triazenido‐κN3]bis(pyridine‐κN)palladium(II)

In the title complex, [Pd(C₁₂H₈FN₄O₂)₂(C₅H₅N)₂] or trans‐[Pd(FC₆H₄N=N—NC₆H₄NO₂)(C₅H₅N)₂], the Pd atom lies on a centre of inversion in space group P. The coordination geometry about the Pd²⁺ ion is square planar, with two deprotonated 3‐(2‐fluoro­phenyl)‐1‐(4‐nitro­phenyl)­triazenide ions, FC₆H₄N=N—NC₆H₄NO₂^?, acting as monodentate ligands (two‐electron donors), while two neutral pyridine mol­ecules complete the metal coordination sphere. The whole triazenide ligand is not planar, with the largest interplanar angle being 16.8 (5)° between the phenyl ring of the 2‐­fluorophenyl group and the plane defined by the N=N—N moiety. The Pd—N(triazenide) and Pd—N(pyridine) distances are 2.021 (3) and 2.039 (3) Å, respectively.     

The bis(acetonitrile‐κN)bis[N,N‐bis(diphenylphosphanyl)ethanamine‐κ2P,P′]iron(II) tetrabromidoferrate(II) and μ‐oxido‐bis[tribromidoferrate(III)] complex salts

Orange crystals of bis(acetonitrile‐κN)bis[N,N‐bis(diphenylphosphanyl)ethanamine‐κ²P,P′]iron(II) tetrabromidoferrate(II), [Fe(CH₃CN)₂(C₂₆H₂₅NP₂)₂][FeBr₄], (I), and red crystals of bis(acetonitrile‐κN)bis[N,N‐bis(diphenylphosphanyl)ethanamine‐κ²P,P′]iron(II) μ‐oxido‐bis[tribromidoferrate(III)], [Fe(CH₃CN)₂(C₂₆H₂₅NP₂)₂][Fe₂Br₆O], (II), were obtained from the same solution after prolonged exposure to atmospheric oxygen, resulting in partial oxidation of the [FeBr₄]²⁻ anion to the [Br₃FeOFeBr₃]²⁻ anion. The asymmetric unit of (I) consists of three independent cations, one on a general position and two on inversion centres, with two anions, required to balance the charge, located on general positions. The asymmetric unit of (II) consists of two independent cations and two anions, all on special positions. The geometric parameters within the coordination environments of the cations do not differ significantly, with the major differences being in the orientation of the phenyl rings on the bidentate phosphane ligand. The ethyl substituent in the cation of (II) and the Br atoms in the anions of (II) are disordered. The P—Fe—P bite angles represent the smallest angles reported to date for octahedral Fe^II complexes containing bidentate phosphine ligands with MeCN in the axial positions, ranging from 70.82 (3) to 70.98 (4)°. The average Fe—Br bond distances of 2.46 (2) and 2.36 (2) Å in the [FeBr₄]²⁻ and [Br₃FeOFeBr₃]²⁻ anions, respectively, illustrate the differences in the Fe oxidation states.     

trans‐Dichloro(dimethyl sulfide‐κS)(pyridine‐κN)platinum(II)

The structure of the title compound, [PtCl₂(C₅H₅N)(C₂H₆S)], consists of discrete mol­ecules in which the Pt‐atom coordination is slightly distorted square planar. The Cl atoms are trans to each other, with a Cl—Pt—Cl angle of 176.60 (7)°. The pyridine ligand is rotated 64.5 (2)° from the Pt square plane and one of the Pt—Cl bonds essentially bisects the C—S—C angle of the di­methyl sulfide ligand. In the crystal structure, there are extensive weak C—H⋯Cl interactions, the shortest of which connects mol­ecules into centrosymmetric dimers. A comparison of the structural trans influence on Pt—S and Pt—­N distances for PtS(CH₃)₂ and Pt(pyridine) fragments, respectively, in square‐planar Pt^II complexes is presented.     

trans‐Bis(cyano‐κC)(1,4,8,11‐tetraazacyclotetradecane‐κ4N)manganese(III) perchlorate,a low‐spin manganese(III) complex

The crystal structure of the low‐spin (S = 1) Mn^III complex [Mn(CN)₂(C₁₀H₂₄N₄)]ClO₄, or trans‐[Mn(CN)₂(cyclam)](ClO₄) (cyclam is the tetradentate amine ligand 1,4,8,11‐tetra­aza­cyclo­tetra­decane), is reported. The structural parameters in the Mn(cyclam) moiety are found to be insensitive to both the spin and the oxidation state of the Mn ion. The difference between high‐ and low‐spin Mn^III complexes is that a pronounced tetragonal elongation of the coordination octahedron occurs in high‐spin complexes and a slight tetragonal compression is seen in low‐spin complexes, as in the title complex.     

trans‐Carbonyliodotris(triphenylstibine‐κSb)rhodium(I)

The crystal structure of the title compound, [RhI(C₁₈H₁₅Sb)₃(CO)], represents a rare example of a crystallographically characterized five‐coordinate Rh^I–SbPh₃ complex. The compound crystallizes with the I—Rh—CO core on a threefold rotation axis, with three crystallographically equivalent tri­phenyl­stibine ligands. Selected geometric parameters are: Rh—I = 2.7159 (8), Rh—Sb = 2.5962 (4), Rh—C_CO = 1.825 (6) and C_CO—O 1.153 (6) Å, and Sb—Rh—I = 89.374 (10) and Sb—Rh—C_CO = 90.626 (10)°. The cone angle of the SbPh₃ ligand was determined as 137°, according to the Tolman model.     

trans‐Bis(dimethyl sulfoxide‐κO)bis(3‐oxo‐3,4‐dihydroquinoxaline‐2‐carboxylato‐κ2N1,O2)copper(II)

The title compound, [Cu(C₉H₅N₂O₃)₂(C₂H₆OS)₂], consists of octahedrally coordinated Cu^II ions, with the 3‐oxo‐3,4‐dihydroquinoxaline‐2‐carboxylate ligands acting in a bidentate manner [Cu—O = 1.9116 (14) Å and Cu—N = 2.1191 (16) Å] and a dimethyl sulfoxide (DMSO) molecule coordinated axially via the O atom [Cu—O = 2.336 (5) and 2.418 (7) Å for the major and minor disorder components, respectively]. The whole DMSO molecule exhibits positional disorder [0.62 (1):0.38 (1)]. The octahedron around the Cu^II atom, which lies on an inversion centre, is elongated in the axial direction, exhibiting a Jahn–Teller effect. The ligand exhibits tautomerization by H‐atom transfer from the hydroxyl group at position 3 to the N atom at position 4 of the quinoxaline ring of the ligand. The complex molecules are linked through an intermolecular N—H...O hydrogen bond [N...O = 2.838 (2) Å] formed between the quinoxaline NH group and a carboxylate O atom, and by a weak intermolecular C—H...O hydrogen bond [3.392 (11) Å] formed between a carboxylate O atom and a methyl C atom of the DMSO ligand. There is a weak intramolecular C—H...O hydrogen bond [3.065 (3) Å] formed between a benzene CH group and a carboxylate O atom.     

trans‐Diaquabis(3‐hydroxybenzoato‐κO1)bis(nicotinamide‐κN1)copper(II)

The title compound, [Cu(C₇H₅O₃)₂(C₆H₆N₂O)₂(H₂O)₂], is a two‐dimensional hydrogen‐bonded supramolecular complex. The Cu^II ion resides on a centre of symmetry and is in an octahedral coordination environment comprising two pyridine N atoms, two carboxylate O atoms and two O atoms from water molecules. Intermolecular N—H...O and O—H...O hydrogen bonds produce R₂²(4), R₂²(8) and R₂²(15) rings which lead to one‐dimensional polymeric chains. An extensive two‐dimensional network of N—H...O and O—H...O hydrogen bonds and C—H...π interactions are responsible for crystal stabilization.     

The exopolyhedral ligand orientation (ELO) in 3‐(nitrato‐κO)‐3,3‐bis(triphenylphosphane‐κP)‐3‐rhoda‐1,2‐dicarba‐closo‐dodecaborane(11) dichloromethane 2.2‐solvate

In the title compound, [Rh(C₂H₁₁B₉)(NO₃)(C₁₈H₁₅P)₂]·2.2CH₂Cl₂, studied as a 2.2‐solvate of what was assumed to be dichloromethane, the nitrate ligand lies cis with respect to both cage C atoms. Accordingly, the compound displays a pronounced preferred exopolyhedral ligand orientation (ELO) which is traced to both the greater trans influence of the cage B over the cage C atoms and the greater trans influence of the triphenylphosphane ligands over the nitrate ligand. The overall molecular architecture therefore agrees with that of a number of similar 3‐L‐3,3‐L′₂‐3,1,2‐closo‐MC₂B₉H₁₁ species in the literature.     

trans‐Chloridobis[(Z)‐1‐imino‐1‐methoxyethane‐κN](triphenylphosphane‐κP)platinum(II) chloride monohydrate

The title compound, [PtCl(C₃H₇NO)₂(C₁₈H₁₅P)]Cl·H₂O or trans‐[PtCl{Z‐HN=C(Me)OMe}₂(PPh₃)]Cl·H₂O, crystallizes from an acetone solution of isomeric trans‐[PtCl{E‐HN=C(Me)OMe}₂(PPh₃)]Cl. The two HN=C(Me)OMe ligands show typical π‐bond delocalization over the N—C—O group [Cini, Caputo, Intini & Natile (1995). Inorg. Chem. 34 , 1130–1137] and have the unprecedented Z–anti configuration. The relative orientation of the imino ether ligands is head‐to‐tail.     

trans‐[1,3‐Bis(2,4,6‐trimethylphenyl)imidazolidin‐2‐ylidene]dichlorido(triphenylphosphine‐κP)palladium(II)

The title complex, [PdCl₂(C₂₁H₂₆N₂)(C₁₈H₁₅P)], shows slightly distorted square‐planar coordination around the Pd^II metal centre. The Pd—C bond distance between the N‐heterocyclic ligand and the metal atom is 2.028 (5) Å. The dihedral angle between the two trimethylphenyl ring planes is 36.9 (2)°.