μ‐Oxo‐bis{{2,2′‐[2,2‐di­methyl­propane‐1,3‐diyl­bis­(nitrilomethyl­idyne)]­diphenolato}­oxo­rhenium(V)}

The title compound, [Re₂O₃(C₁₉H₂₀N₂O₂)₂], is a hexacoordinate complex containing an [Re₂O₃]⁴⁺ core with a linear O=Re—O—Re=O bridge. The distorted octahedral coordination of the Re^V atom is achieved by an N₂O₂ donor set from the tetradentate imine–phenol ligand. The overall charge of the compound is neutral due to deprotonation of the phenol groups, and the terminating and bridging O atoms. The Re=O and Re—O bond distances of the [Re₂O₃]⁴⁺ core are 1.699 (4) and 1.911 (1) Å, respectively. The Re—O and Re—N bond distances of the equatorial plane are in the ranges 2.024 (4)–2.013 (4) and 2.128 (5)–2.120 (5) Å, respectively.     

Tetra­carbonyl­(di­phenyl­di­thio­phosphinato‐S,S′)­rhenium(I)

The title compound consists of [Re(C₁₂H₁₀PS₂)(CO)₄] mol­ecules in which the Re atom is octahedrally coordinated by four carbonyl groups and two di­thio­phosphinate S atoms. The main coordination distortion is imposed by the ligand bite angle of 78.29 (4)°. The bidentate coordination of the di­thio­phosphinate ligand involves almost equal Re—S [2.5366 (15) and 2.5535 (14) Å] and P—S distances [2.0100 (19) and 2.0212 (19) Å].     

cis‐Di­phenyl­bis(1,3,5‐tri­aza‐7‐phospha­adamantane‐κP)platinum(II)

The structure of the title compound, [Pt(C₆H₅)₂(C₆H₁₂N₃P)₂] or [Pt(Ph)₂(PTA)₂] (where Ph is phenyl and PTA is 1,3,5‐tri­aza‐7‐phosphaadamantane), is discussed. Selected geom­etric parameters are: Pt—P = 2.2888 (16) and 2.2944 (17) Å, Pt—C = 2.052 (5) and 2.064 (6) Å, C—Pt—C = 84.6 (2)° and P—Pt—P = 99.28 (6)°. The effective cone angle for the PTA ligands was calculated as 113°.     

Cis‐ and trans‐influences in [PtCl2(SPh2)2]

Both cis‐ and trans‐di­chloro­bis­(di­phenyl ­sulfide)­platinum(II), [PtCl₂(C₁₂H₁₀S)₂], crystallize as mononuclear pseudo‐square‐planar complexes. In the cis compound, the Pt—Cl distances are 2.295 (2) and 2.319 (2) Å, and the Pt—S distances are 2.280 (2) and 2.283 (2) Å. In the trans compound, Pt is located on a centre of inversion and the Pt—Cl and Pt—S distances are 2.2786 (15) and 2.3002 (12) Å, respectively.     

cis‐Bis­(dicyan­amido)bis(1,10‐phen­an­throline)­manganese(II) and cis‐bis(dicyan­amido)­bis(1,10‐phen­an­thro­line)­zinc(II)

The title compounds are isomorphous, comprised of neutral monomeric [M(phen)₂(dca)₂] [(I): M = Mn, (II): M = Zn; phen is 1,10‐phenanthroline, C₁₂H₈N₂; dca is dicyan­amide, C₂N₃] mol­ecules. In the mol­ecule, the divalent metal ion is in a distorted octahedral coordination environment formed by six N atoms from the phen and dca ligands. The Mn—N [2.144 (2)–2.319 (2) Å] and Zn—N [2.075 (2)–2.245 (2) Å] distances are in agreement with the difference in size of the two divalent ions.     

trans‐Di­iodo­bis(1,3,5‐tri­aza‐7‐phosphaadamantane)­platinum(II)

The crystal structure of the title compound, trans‐[PtI₂(C₆H₁₂N₃P)₂], describes one of the few platinum(II) complexes containing two of the water‐soluble 1,3,5‐tri­aza‐7‐phosphaadamantane ligands reported to date. The complex crystallizes on an inversion centre with the most important bond lengths and angles being Pt—P 2.3128 (12) Å, Pt—I 2.6022 (6) Å, P—Pt—I 90.94 (3)° and P′—Pt—I 89.06 (3)°.     

Chloro{2,2′‐[(1S,2S)‐1,2‐di­phenyl‐1,2‐ethanediyl­bis­(nitrilo­methyl­idyne)]­diphenolato‐κ4O,N,N′,O′}(ethanol‐κO)­manganese(III)

The crystal structure of the title compound, [MnCl(C₂₈H₂₂N₂O₂)(C₂H₆O)], has been determined at 173 (2) K in the non‐centrosymmetric space group P2₁2₁2₁. The asymmetric unit contains two molecular units. An intermolecular O—H⋯Cl hydrogen bond is formed between the OH group of an ethanol mol­ecule coordinated to the Mn atom and the coordinated Cl⁻ anion, and so polymeric chains of Mn‐containing fragments are formed [O—H⋯Cl = 3.1281 (16) and 3.1282 (15) Å]. The Mn atoms have a pseudo‐octahedral coordination sphere, with the four donor atoms of the Schiff base forming an equatorial plane [Mn—O distances are 1.8740 (13), 1.8717 (13), 1.8749 (13) and 1.8823 (13) Å, and Mn—N distances are 1.9868 (15), 1.9910 (14), 1.9828 (15) and 1.9979 (14) Å]. The axial positions are occupied by an ethanol mol­ecule [Mn—O distances of 2.3069 (15) and 2.3130 (15) Å] and a Cl⁻ ligand [Mn—Cl distances of 2.5732 (6) and 2.5509 (6) Å].     

Carbonyl(5‐nitrotropolonato‐κ2O1,O2)(tri­phenyl­phosphine‐κP)­rhodium(I)

The molecule of the title complex, [Rh(5‐NO₂trop)(C₁₈H₁₅P)(CO)] (5‐­NO₂trop is 2‐hydroxy‐5‐nitrocyclo­hepta‐2,4,6‐trienone, C₇H₄NO₄), has a distorted square‐planar geometry. Strong intramolecular and weak intermolecular hydrogen bonding is observed, with H⋯O distances of the order of 2.25 and 2.55 Å, respectively. The Rh—CO, Rh—O (trans to CO), Rh—O (trans to P) and Rh—P bond distances are 1.775 (7), 2.072 (4), 2.068 (4) and 2.2397 (17) Å, respectively, the O—Rh—O angle is 77.09 (16)° and the bidentate O—C—C—O torsion angle is 1.5 (7)°.     

A one‐dimensional iodine‐bridged PtII/PtIV mixed‐valence complex,catena‐poly[[[bis­(ethyl­ene­diamine)­platinum(II)]‐μ‐iodo‐[bis­(ethyl­ene­di­amine)platinum(IV)]‐μ‐iodo] hydrogenphosphate dihydrogenphosphate iodide trihydrate]

The title compound, {[Pt^IIPt^IVI₂(C₂H₈N₂)₄](HPO₄)(H₂PO₄)I·3H₂O}_n, has a chain structure composed of square‐planar [Pt(en)₂]²⁺ and elongated octa­hedral trans‐[PtI₂(en)₂]²⁺ cations (en is ethyl­ene­diamine) stacked alternately along the c axis and bridged by the I atoms; a three‐dimensionally valence‐ordered system exists with respect to the Pt sites. The title compound also has a unique cyclic tetra­mer structure composed of two hydrogenphosphate and two dihydrogenphosphate ions connected by strong hydrogen bonds [O⋯O = 2.522 (10), 2.567 (10) and 2.569 (11) Å]. The Pt and I atoms form a zigzag ⋯I—Pt^IV—I⋯Pt^II⋯ chain, with Pt^IV—I bond distances of 2.6997 (7) and 2.6921 (7) Å, inter­atomic Pt^II⋯I distances of 3.3239 (8) and 3.2902 (7) Å, and Pt^IV—I⋯Pt^II angles of 154.52 (3) and 163.64 (3)°. The structural parameters indicating the mixed‐valence state of platinum, expressed by δ = (Pt^IV—I)/(Pt^II—I), are 0.812 and 0.818 for the two independent I atoms.     

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.     

(2‐Methyl­quinolin‐8‐olato)­iron(III) and ‐copper(II) complexes

The crystal structures of tris(2‐methyl­quinolin‐8‐olato‐N,O)­iron(III), [Fe­(C₁₀­H₈­NO)₃], (I), and aqua­bis(2‐methyl­quinolin‐8‐olato‐N,O)­copper(II), [Cu­(C₁₀­H₈NO)₂­(H₂O)], (II), have been determined. Compound (I) has a distorted octahedral configuration, in which the central Fe atom is coordinated by three N atoms and three O atoms from three 2‐methylquinolin‐8‐olate ligands. The three Fe—O bond distances are in the range 1.934 (2)–1.947 (2) Å, while the three Fe—N bond distances range from 2.204 (2) to 2.405 (2) Å. In compound (II), the central Cu^II atom and H₂O group lie on the crystallographic twofold axis and the coordination geometry of the Cu^II atom is close to trigonal bipyramidal, with the three O atoms in the basal plane and the two N atoms in apical positions. The Cu—N bond length is 2.018 (5) Å. The Cu—O bond length in the basal positions is 1.991 (4) Å, while the Cu—O bond length in the apical position is 2.273 (6) Å. There is an intermolecular OW—H?O hydrogen bond which links the mol­ecules into a linear chain along the b axis.     

A head‐to‐head isomer of di‐μ‐pivalamidato‐κ4N,O‐bis­[(1,10‐phenanthroline‐κ2N,N′)­platinum(II)] dinitrate dihydrate

In the title compound, [Pt₂(C₅H₁₀NO)₂(C₁₂H₈N₂)₂](NO₃)₂·2H₂O, the intradimer Pt—Pt distance is relatively short [2.8489 (17) Å], which must be due to the strong intramolecular π–π‐stacking interactions between the phenanthroline moieties. The dimers stack along the c axis, forming one‐dimensional columns in which very intriguing d–d, π–π and d–π interactions exist. Although the dimer–dimer Pt...Pt distances are very long [4.340 (2) and 4.231 (2) Å], some short interdimer Pt...C contacts leading to strong interdimer associations are found [3.325 (19) and 3.402 (19) Å].     

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].     

Tris(8‐quinolinolato‐N,O)­cobalt(III) ethanol solvate

In the crystal of the title complex, [Co(C₉H₆NO)₃]·C₂H₅OH, the central Co atom has a distorted octahedral coordination comprised of three N atoms and three O atoms from the three 8‐quinolinolato ligands. The three Co—O bond distances are in the range 1.887 (2)–1.910 (2) Å, while the three Co—N bond distances range from 1.919 (2) to 1.934 (2) Å. The solvent ethanol mol­ecule forms an intermolecular O—H?O hydrogen bonding with a quinolinolato ligand.     

Di­carbonyl­(tropolonato)­rhodium(I), a redetermination

The mol­ecules of the title complex, [Rh(Trop)(CO)₂] (Trop is 2‐hydroxycyclo­hepta‐2,4,6‐trienonate, C₇H₅O₂), exhibit symmetrical but non‐crystallographic square‐planar molecular geometry, with Rh—C distances of 1.825 (10) and 1.826 (9) Å, Rh—O distances of 2.021 (5) and 2.032 (5) Å, and an O—Rh—O bite angle of 79.4 (2)°. Strong Rh⋯Rh and Rh⋯C intermolecular interactions of 3.683 (3) and 3.650 (5) Å, respectively, are also observed.     

(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.     

Three monoalkoxy‐substituted nido‐platinaboranes: [(PPh3)2PtB10H11‐8‐(OCH3)], [(PPh3)2PtB10H11‐8‐{OCH(CH3)2}] and [(PPh3)2PtB10H10‐9‐{OCH(CH3)2}]

Each of the title compounds, 8‐methoxy‐7,7‐bis­(tri­phenyl­phosphine‐P)‐8,9:10,11‐di‐μH‐7‐platina‐nido‐undecaborane di­chloro­methane hemisolvate, [Pt(CH₁₄B₁₀O)(C₁₈H₁₅P)₂]·0.5CH₂Cl₂, (I), 8‐isopropoxy‐7,7‐bis­(tri­phenyl­phosphine‐P)‐8,9:10,11‐di‐μH‐7‐platina‐nido‐undecaborane di­chloro­methane solvate, [Pt(C₃H₁₈B₁₀O)(C₁₈H₁₅P)₂]·CH₂Cl₂, (II), and 9‐isopropoxy‐7,7‐bis­(tri­phenyl­phosphine‐P)‐8,9:10,11‐di‐μH‐7‐platina‐nido‐undecaborane di­chloro­methane solvate, [Pt(C₃H₁₈B₁₀O)(C₁₈H₁₅P)₂]·CH₂Cl₂, (III), has an 11‐vertex nido polyhedral skeleton, with the 7‐platinum centre ligating to two exo‐polyhedral PPh₃ groups and an alkoxy‐substituted polyhedral borane ligand. Compounds (II) and (III) are isomers. The Pt—B distances are in the range 2.214 (7)–2.303 (7) Å for (I), 2.178 (16)–2.326 (16) Å for (II) and 2.205 (6)–2.327 (6) Å for (III).     

trans‐Di­chloro­tetrakis(4‐methylpyrimidine‐N1)­ruthenium(II)

The title compound, trans‐[Ru^IICl₂(N¹‐mepym)₄] (mepym is 4‐methylpyrimidine, C₅H₆N₂), obtained from the reaction of trans,cis,cis‐[Ru^IICl₂(N¹‐mepym)₂(SbPh₃)₂] (Ph is phenyl) with excess mepym in ethanol, has fourfold crystallographic symmetry and has the four pyrimidine bases coordinated through N¹ and arranged in a propeller‐like orientation. The Ru—N and Ru—Cl bond distances are 2.082 (2) and 2.400 (4) Å, respectively. The methyl group, and the N³ and Cl atoms are involved in intermolecular C—H?N and C—­H?Cl hydrogen‐bond interactions.     

Bis(2,2′‐bipyridine)(dicyanamido)­copper(II) tetrafluoroborate

In the title compound, [Cu(C₂N₃)(C₁₀H₈N₂)₂]BF₄, the Cu^II atom shows distorted trigonal‐bipyramidal geometry, with the dicyan­amido ligand in the equatorial plane. The two out‐of‐plane Cu—N bond lengths to bi­pyridine are 2.006 (3) and 1.998 (3) Å, whereas the in‐plane Cu—N distances are 2.142 (3) and 2.043 (3) Å to the bi­pyridine, and 2.015 (3) Å to the dicyan­amide.     

(4,6‐Dimercapto‐1,3,5‐triazine‐2‐thiol­ato‐S2)­tris­(tri­phenyl­phosphine‐P)gold(I) di­methyl­form­amide solvate

In the title compound, [Au(C₃H₂N₃S₃)(C₁₈H₁₅P)₃]·C₃H₇NO, the Au^I atom has a distorted tetrahedral geometry consisting of one uncoordinated di­methyl­form­amide mol­ecule, one tri­thio­cyanurate ligand and three PPh₃ ligands. The S—Au distance is 2.909 (2) Å, and the P—Au distances fall in the range 2.400 (14)–2.4074 (13) Å. The S—Au—P angles are 92.81 (6), 99.17 (6) and 104.21 (5)°, and the P—Au—P angles are 114.46 (5), 119.04 (5) and 119.66 (5)°.