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.     

The Structure of cis‐[Chloro(dimethylsulfoxide)bis(1, 10‐phenanthroline)ruthenium(II)]‐tetraphenylborate, [RuCl(DMSO)(1, 10‐phen)2][BPh4]

The complex cis‐[RuCl(DMSO)(phen)₂]BPh₄, where DMSO is dimethylsulfoxide and phen is 1, 10‐phenanthroline, crystallizes in the monoclinic space group P2₁/c with a = 19.505(4), b = 10.045(2), c = 21.199(4) Å, β = 90.137(4)°, V = 4153(2) ų, Z = 4, D_calc = 1.430 g cm^—3. The ruthenium coordination geometry is that of a slightly distorted octahedron with a cis‐RuN₄ClS arrangement of the ligand donor atoms. The Ru—Cl distance is 2.421(1) Å and the Ru—S distance 2.250(2) Å. The four Ru—N distances are 2.057(6), 2.066(4), 2.073(4), and 2.086(4) Å with the Ru—N bond trans to Cl the second shortest and the Ru—N bond trans to S the longest one.     

Diaquabis(2,5‐dihydroxybenzoato‐κO)bis(1,10‐phenanthroline‐κ2N,N′)strontium(II) bis(1,10‐phenanthroline) tetrahydrate

The title compound, [Sr(C₇H₅O₄)₂(C₁₂H₈N₂)₂(H₂O)₂]·2C₁₂H₈N₂·4H₂O, consists of an Sr^II complex, uncoordinated phenanthroline (phen) molecules and solvent water molecules. The Sr^II ion is located on a twofold axis and is coordinated by two phen ligands, two dihydroxybenzoate anions and two water molecules in a distorted tetragonal antiprismatic geometry. Partially overlapped arrangements exist between parallel coordinated and parallel uncoordinated phen rings; the face‐to‐face separations between the former (coordinated) and the latter (uncoordinated) rings are 3.436 (13) and 3.550 (14) Å, respectively. This difference suggests the effect of metal coordination on π–π stacking between phen rings.     

A trichloro‐bridged binuclear ruthenium complex with 1,1,1‐tris(diphenylphosphinomethyl)ethane

The tri­chloro‐bridged dinuclear Ru^II complex tri‐μ‐chloro‐bis{[1,1,1‐tris­(di­phenyl­phosphino­methyl)­ethane‐κ³P,P′,P′′]ruthenium(II)} hexa­fluoro­phosphate ethanol solvate, [Ru₂Cl₃(tripod)₂]PF₆·C₂H₆O, containing the tripod [1,1,1‐tris­(di­phenyl­phosphino­methyl)­ethane, C₄₁H₃₉P₃] ligand, was unexpectedly obtained from the reaction of [Ru^IIICl₃(tripod)] with 1,4‐bis­(di­phenyl­phosphino)­butane (dppb), followed by pre­cipitation with NH₄PF₆. The magnetic moment of the compound at room temperature indicates that the dinuclear [Ru₂(μ‐Cl)₃(tripod)₂]⁺ cation is diamagnetic. A single‐crystal X‐ray structure determination revealed that the two Ru atoms are bridged by the three Cl atoms. The coordination sphere of each Ru atom is completed by the three P atoms of a tripod ligand. The two P₃Ru units are exactly eclipsed, while the bridging Cl atoms are staggered with respect to the six P atoms. The Ru⋯Ru distance is 3.3997 (7) Å and the mean Cl—Ru—Cl bond angle is 77.7°.     

Bis(2,2′‐bi­pyridine‐κ2N,N′)(1,10‐phen­anthroline‐κ2N,N′)­ruthenium(II) tetra­cyano­platinate(II)

In the title compound, [Ru(C₁₀H₈N₂)₂(C₁₂H₈N₂)][Pt(CN)₄], cations and anions alternate along the a axis to afford a one‐dimensional network. The one‐dimensional character arises from the π–π stacking as well as from the electrostatic interactions formed between the phen (1,10‐phenanthroline) and [Pt(CN)₄]²⁻ units. Two adjacent one‐dimensional chains form further stacks based on the π–π stacking interactions between the phen moieties, where the interplanar spacing is 3.50 (1) Å.     

Di­aqua­bis(1,10‐phenanthroline‐κ2N,N′)­manganese(II) thiodiglycolate bis(1,10‐phenanthroline‐κ2N,N′)(thiodiglycolato‐κ2O,O′)­manganese(II) tridecahydrate

The title compound, [Mn(C₁₂H₈N₂)₂(H₂O)₂](C₄H₄O₄S)·[Mn(C₄H₄O₄S)(C₁₂H₈N₂)₂]·13H₂O, contains one dianion of thio­diglycolic acid (tdga²⁻) and two independent man­ganese(II) moieties, viz. [Mn(phen)₂(H₂O)₂]²⁺ and [Mn(tdga)(phen)₂], where phen is 1,10‐phenanthroline. The Mn^II atoms are octahedrally coordinated by four N atoms of two bidentate phen ligands [Mn—N = 2.240 (2)–2.3222 (19) Å] and either two water O atoms or two tdga carboxyl O atoms [Mn—O = 2.1214 (17)–2.1512 (17) Å]. The tdga ligand chelates as an O,O′‐bidentate ligand, forming an eight‐membered ring with one Mn atom. The free tdga²⁻ dianion is hydrogen bonded to an [Mn(phen)₂(H₂O)₂]²⁺ ion, with O⋯O distances of 2.606 (2) and 2.649 (2) Å. The crystal structure is further stabilized by an extensive network of hydrogen bonds involving 13 water mol­ecules.     

Synthesis,characterization and third-order nonlinear optical properties of ruthenium(II) complexes containing 2-(4-nitrophenyl)imidazo[4,5-f] [1,10]phenanthroline

Two novel Ru^II complexes [Ru(phen)₂(PNOPH)]²⁺ and [Ru(dmp)₂ (PNOPH)]²⁺ (phen = 1,10-phenanthroline, dmp = 2,9-dimethyl-1,10-phenanthroline, PNOPH = 2-(4-nitrophenyl)imidazo-[4,5-f][1,10]phenanthroline) and their deprotoned complexes were synthesized and characterized by ES–MS, ¹H - n.m.r, u.v.–vis. and electrochemistry. The crystal structure of the deprotonated complex [Ru(dmp)₂ (PNOP)][ClO₄] · CH₃CN was determined by means of X-ray single crystal diffraction. Nonlinear optical properties of the Ru^II complexes were investigated by Z-scan techniques in DMF solution, and all of them exhibited both NLO absorption and self-defocusing effect. The corresponding effective NLO susceptibilities |³ | of the complexes are 2.39 × 10^-12–5.80 × 10^-12 esu.     

Stereoselective association between optically active tris(1,10-phenanthroline)ruthenium(II) and tris(acetylacetonato)cobalt(III) in water

Stereoselective interactions between tris(acetylacetonato)cobalt(III) [Co(acac)₃] and optically active Λ-(+)₅₄₆-tris(1,10-phenanthroline)ruthenium(II) chloride [Λ-[Ru(phen)₃]Cl₂] were investigated by measuring the distribution coefficients of racemic Co(acac)₃ between carbon tetrachloride and water containing Λ-[Ru(phen)₃]²⁺ or pure water, and the optical rotations of the aqueous phase was measured over the temperature range 10–40° C. The Λ-isomer of Co(acac)₃ is “salted-in” more strongly by Λ-[Ru(phen)₃]²⁺ than the Δ-isomer. The association constants between Λ-[Ru(phen)]²⁺ and Λ- or Δ-Co(acac)₃ were calculated by using the optical rotation to give K(Λ-Λ) = 3.86 and K(Λ-Δ) = 3.80 at 25°C, respectively. The temperature dependence of the association constants showed that the enthalpy and entropy changes for the Λ-Λ association is slightly more positive than those for the Λ-Δ association. This was discussed from the viewpoint of hydrophobic interactions.     

Bis­[tris(2,2′‐bi­pyridine‐κ2N,N′)­ruthenium(II)] hexa­cyano­ferrate(III) chloride octahydrate

In the title compound, [Ru^II(C₁₀H₈N₂)₃]₂[Fe^III(CN)₆]Cl·8H₂O, the [Ru(bpy)₃]²⁺ (bpy is 2,2′‐bi­pyridine) cations and water mol­ecules afford intriguing microporous honeycomb layers, while the [Fe(CN)₆]³⁻ anions and the remainder of the water mol­ecules form anionic sheets based on extensive hydrogen‐bonding networks. The cationic and anionic layers alternate along the c axis. The Fe atom in [Fe(CN)₆]³⁻ lies on an inversion centre and the axial cyano ligands are hydrogen bonded to the water mol­ecules encapsulated within the micropores [N⋯O = 2.788 (5) Å], giving an unusual interpenetration between the cationic and anionic layers. On the other hand, the in‐plane cyano ligands are relatively weakly hydrogen bonded to the water mol­ecules [N⋯O = 2.855 (7) and 2.881 (8) Å] within the anionic sheets.     

A ruthenium complex with 1,5‐di­phenyl‐3‐thio­carbazone (dithizone) as monodentate ligands: bis(2,2′‐bipyridyl‐κ2N,N′)­bis­(dithizonato‐κS)ruthenium(II)

The title compound, [Ru(C₁₃H₁₁N₄S)₂(C₁₅H₈N₂)₂], has C₂ symmetry, with bidentate 2,2′‐bipyridyl ligands dictating a cis geometry around the Ru^II center. The monodentate S‐bonded dithizone ligands are almost planar, except for one of the phenyl rings, which is twisted by 34.2 (4)° from the N/N/C(S)/N/N plane. The Ru—S bond length is 2.4140 (13) Å, and the Ru—N bond lengths are 2.048 (4) and 2.074 (4) Å.     

Bis(μ‐2‐sulfonatobenzoato)bis[(1,10‐phenanthroline)­lead(II)] dihydrate

In the title centrosymmetric dimer, [Pb₂(sbc)₂(phen)₂]·2H₂O [sbc is the 2‐sulfonatobenzoate dianion (C₇H₄O₅S) and phen is 1,10‐phenanthroline (C₁₂H₈N₂)], each Pb^II ion is six‐coordinated by four O atoms, viz. carboxyl­ate and sulfonate O atoms from two sbc anions, and two N atoms from a 1,10‐phenanthroline ligand. One 1,10‐phenanthroline ligand and the carboxyl­ate group of one sbc ligand are chelated to each Pb^II cation, and the sulfonate group of the other sbc unit is monodentate. One O atom of the chelated carboxyl­ate group also bridges to the other Pb^II cation, so that each pair of Pb^II ions is bridged by two sbc anions and has the same coordination environment, forming a dinuclear ring. Each pair of Pb^II ions is thus connected by two different kinds of bridges, namely a carboxyl­ate short bridge and a carboxyl­ate–sulfonate long bridge. There is also a special position of site symmetry at the centre of the two Pb^II cations.     

New bipyridyl/phenanthroline ruthenium(II) and ruthenium(III) complexes possessing acetate appended thioether. Evidence for oxidative linkage isomerization

The acetate bearing dithioether, sodium di(2-carboxymethylsufanyl)maleonitrile, L¹ upon reaction with [Ru^II(bpy)₂Cl₂]·2H₂O, [Ru^II(phen)₂Cl₂]·2H₂O, [Ru^III(bpy)₂Cl₂]⁺ or [Ru^III(phen)₂Cl₂]⁺ in methanol formed complexes of the type [(bpy)₂Ru{S₂(CH₂COO)₂C₂(CN)₂}], (1), [(phen)₂Ru{S₂(CH₂COO)₂C₂(CN)₂}], (2), [(bpy)₂Ru{(OOCCH₂)₂S₂C₂(CN)₂}]⁺, (5) and [(phen)₂Ru{(OOCCH₂)₂S₂C₂(CN)₂}]⁺, (6) respectively. Four other Ru(III) complexes with di(benzylsulfanyl)maleonitrile, L², [(bpy)₂Ru{S₂(PhCH₂)C₂(CN)₂}]³⁺, (7) and [(phen)₂Ru{S₂(PhCH₂)₂C₂(CN)₂}]³⁺, (8), and with acetate, [(bpy)₂Ru(OOCCH₃)₂]⁺, (9) and [(phen)₂Ru(OOCCH₃)₂]⁺, (10) were also synthesized. In the cyclic voltammetry, complexes (1) and (2) exhibited quasireversible oxidation waves at 1.01 and 1.02 V vs. Ag/AgCl over GC electrode in DMF, while the corresponding Ru(III) L¹ complexes (5) and (6) exhibit reversible oxidation at E_1/2 0.59 and 0.58 V, respectively, under identical conditions. This is unlike the voltammetric behavior of the Ru(II) and Ru(III) L² complexes, wherein the complex pairs (3), (7) and (4), (8) exhibited identical voltammograms with single reversible one electron waves at E_1/2 0.98 and 0.92 V, respectively under identical conditions. The voltammograms of Ru(II)-L² complexes (3) and (4) also became irreversible in presence of nearly four molar equivalent of sodium acetate. Hence, the irreversible redox behavior of complexes (1) and (2) has been interpreted in terms of rapid linkage isomerization, i.e. shift in κ²-S,S′ to κ²-O,O′ coordination, following the Ru(II)/Ru(III) electrode process. The electronic spectra of Ru(III)-L¹ complexes (5) and (6) resemble closely with that of (9) and (10) instead of Ru(III)-L² complexes (7) and (8), further supports proposed linkage isomerization. The cationic complexes were obtained as [PF₆]⁻ salts and all compounds were characterized using analytical and spectral (IR, ¹H NMR, UV-vis and mass) data.     

Hydroxonium hydrate tris(2,4,6‐triamino‐1,3,5‐triazin‐1‐ium) bis[bis(pyridine‐2,6‐dicarboxylato)manganate(II/III)] hydroxide pyridine‐2,6‐dicarboxylic acid solvate pentahydrate

For charge balance in the title compound, (H₅O₂)(C₃H₇N₆)₃[Mn(C₇H₃NO₄)₂]₂(OH)·C₇H₅NO₄·5H₂O, it is assumed that the metal atom site is disordered Mn^II/Mn^III, probably due to partial air oxidation of the starting Mn^II species. The formula unit of the complex contains a hydroxonium hydrate cation, H₅O₂⁺, also known as the Zundel cation, with twofold symmetry. The O...O [2.445 (10) Å] and O...H distances [1.24 (2) Å] in the H₅O₂⁺ cation indicate a strong hydrogen bond. In addition, there is a hydroxide ion that is disordered with respect to a twofold rotation axis. One of the melaminium groups and the pyridine‐2,6‐dicarboxylate (pydc) ligand also reside on crystallographic twofold axes. The coordination environment of the Mn ion is distorted octahedral. Three intermolecular C=O...π interactions are observed, with distances of 3.536 (4), 3.262 (4) and 3.750 (4) Å between carboxylate C=O groups and the centroids of the aromatic rings of pydc and melaminium. There are numerous O—H...O, O—H...N, N—H...O, N—H...N and C—H...O hydrogen bonds. Most of the components of the structure are organized into one plane.     

Experimental and Theoretical Studies on DNA‐Binding and Spectral Properties of ‘Light Switch’ Complexes [Ru(L)2(ppn)]2+ (L=2,2′‐Bipyridine and 1,10‐Phenanthroline; ppn=Pteridino[6,7‐f] [1,10]phenanthroline‐11,13‐diamine)

The ligand pteridino[6,7‐f] [1,10]phenanthroline‐11,13‐diamine (ppn) and its Ru^II complexes [Ru(bpy)₂(ppn)]²⁺ ( 1 ; bpy=2,2′‐bipyridine) and [Ru(phen)₂(ppn)]²⁺ ( 2 ; phen=1,10‐phenanthroline) were synthesized and characterized by elemental analysis, electrospray MS, ¹H‐NMR, and cyclic voltammetry. The DNA‐binding behaviors of 1 and 2 were studied by spectroscopic and viscosity measurements. The results indicate that both complexes strongly bind to calf‐thymus DNA in an intercalative mode, with DNA‐binding constants K_b of (1.7±0.4)?10⁶ M ^?1 and (2.6±0.2)?10⁶ M ^?1, respectively. The complexes 1 and 2 exhibit excellent DNA‐‘light switch’ performances, i.e., they do not (or extremely weakly) show luminescence in aqueous solution at room temperature but are strongly luminescent in the presence of DNA. In particular, the experimental results suggest that the ancillary ligands bpy and phen not only have a significant effect on the DNA‐binding affinities of 1 and 2 but also have a certain effect on their spectral properties. [Ru(phen)₂(ppn)]²⁺( 2 ) might be developed into a very prospective DNA‐‘light switch’ complex. To explain the DNA‐binding and spectral properties of 1 and 2 , theoretical calculations were also carried out applying the DFT/TDDFT method.     

Comparative Study of Ruthenium(II) and Ruthenium(III) Complexes with the Ligand dmbpy (dmbpy = 4, 4′‐Dimethyl‐2, 2′‐bipyridine)

The complex cis‐[Ru^III(dmbpy)₂Cl₂](PF₆) ( 2 ) (dmbpy = 4, 4′‐dimethyl‐2, 2′‐bipyridine) was obtained from the reaction of cis‐[Ru^II(dmbpy)₂Cl₂] ( 1 ) with ammonium cerium(IV) nitrate followed by precipitation with saturated ammonium hexafluoridophosphate. The ¹H NMR spectrum of the Ru^III complex confirms the presence of paramagnetic metal atoms, whereas that of the Ru^II complex displays diamagnetism. The ³¹P NMR spectrum of the Ru^III complex shows one signal for the phosphorus atom of the PF₆^– ion. The perspective view of each [Ru^II/III(dmbpy)₂Cl₂]^0/+ unit manifests that the ruthenium atom is in hexacoordinate arrangement with two dmbpy ligands and two chlorido ligands in cis position. As the oxidation state of the central ruthenium metal atom becomes higher, the average Ru–Cl bond length decreases whereas the Ru–N (dmbpy) bond length increases. The cis‐positioned dichloro angle in Ru^III is 1.3° wider than that in the Ru^II. The dihedral angles between pair of planar six‐membered pyridyl ring in the dmbpy ligand for the Ru^II are 4.7(5)° and 5.7(4)°. The observed inter‐planar angle between two dmbpy ligands in the Ru^II is 89.08(15)°, whereas the value for the Ru^III is 85.46(20)°.     

Metal Derivatives of Heterocyclic‐2‐thiones: Crystal Structures of [Bis(diphenylphosphanyl)propane][bis(pyrimidine‐2‐thiolato)]ruthenium(II) and [Bis(diphenylphosphanyl)methane][bis(pyridine‐2‐thiolato)]ruthenium(II)

Ruthenium(II) Complexes containing pyrimidine‐2‐thiolate (pymS^–) and bis(diphenylphosphanyl)alkanes [Ph₂P–(CH₂)_m–PPh₂, m = 1, dppm; m = 2, dppe; m = 3, dppp; m = 4, dppb] are described. Reactions of [RuCl₂L₂] (L = dppm, dppp) and [Ru₂Cl₄L₃] (L = dppb) with pyrimidine‐2‐thione (pymSH) in 1:2 molar ratio in dry benzene in the presence of Et₃N base yielded the [Ru(pymS)₂L] complexes (pymS^– = pyrimidine‐2‐thiolate; L = dppm ( 1 ); dppp ( 3 ); dppb ( 4 )). The complex [Ru(pymS)₂(dppe)] ( 2 ) was indirectly prepared by the reaction of [Ru(pymS)₂(PPh₃)₂] with dppe. These complexes were characterized using analytical data, IR, ¹H, ¹³C, ³¹P NMR spectroscopy, and X‐ray crystallography (complex 3 ). The crystal structure of the analogous complex [Ru(pyS)₂(dppm)] ( 5 ) with the ligand pyridine‐2‐thiolate (pyS^–) was also described. X‐ray crystallographic investigation of complex 3 has shown two four‐membered chelate rings (N, S donors) and one six‐membered ring (P, P donors) around the metal atom. Compound 5 provides the first example in which Ru^II has three four‐membered chelate rings: two made up by N, S donor ligands and one made up by P, P donor ligand. The arrangement around the metal atoms in each complex is distorted octahedral with cis:cis:trans:P, P:N, N:S, S dispositions of the donor atoms. The ³¹P NMR spectroscopic data revealed that the complexes are static in solution, except 2 , which showed the presence of more than one species.     

Four supramolecular isomers of dichloridobis(1,10‐phenanthroline)cobalt(II): synthesis,structure characterization and isomerization

Crystal engineering can be described as the understanding of intermolecular interactions in the context of crystal packing and the utilization of such understanding to design new solids with desired physical and chemical properties. Free‐energy differences between supramolecular isomers are generally small and minor changes in the crystallization conditions may result in the occurrence of new isomers. The study of supramolecular isomerism will help us to understand the mechanism of crystallization, a very central concept of crystal engineering. Two supramolecular isomers of dichloridobis(1,10‐phenanthroline‐κ²N,N′)cobalt(II), [CoCl₂(C₁₂H₈N₂)₂], i.e. (IA) (orthorhombic) and (IB) (monoclinic), and two supramolecular isomers of dichloridobis(1,10‐phenanthroline‐κ²N,N′)cobalt(II) N,N‐dimethylformamide monosolvate, [CoCl₂(C₁₂H₈N₂)₂]·C₃H₇NO, i.e. (IIA) (orthorhombic) and (IIB) (monoclinic), were synthesized in dimethylformamide (DMF) and structurally characterized. Of these, (IA) and (IIA) have been prepared and structurally characterized previously [Li et al. (2007). Acta Cryst. E 63 , m1880–m1880; Cai et al. (2008). Acta Cryst. E 64 , m1328–m1329]. We found that the heating rate is a key factor for the crystallization of (IA) or (IB), while the temperature difference is responsible for the crystallization of (IIA) or (IIB). Based on the crystallization conditions, isomerization behaviour, the KPI (Kitajgorodskij packing index) values and the density data, (IB) and (IIA) are assigned as the thermodynamic and stable kinetic isomers, respectively, while (IA) and (IIB) are assigned as the metastable kinetic products. The 1,10‐phenanthroline (phen) ligands interact with each other through offset face‐to‐face (OFF) π–π stacking in (IB) and (IIB), but by edge‐to‐face (EF) C—H...π interactions in (IA) and (IIA). Meanwhile, the DMF molecules in (IIB) connect to neighbouring [CoCl₂(phen)₂] units through two C—H...Cl hydrogen bonds, whereas there are no obvious interactions between DMF molecules and [CoCl₂(phen)₂] units in (IIA). Since OFF π–π stacking is generally stronger than EF C—H...π interactions for transition‐metal complexes with nitrogen‐containing aromatic ligands, (IIA) is among the uncommon examples that are stable and densely packed but that do not following Etter's intermolecular interaction hierarchy.     

(Acetonitrile){2,6‐bis[1‐(2,4,6‐trimethylphenylimino)ethyl]pyridine}dichloridoruthenium(II) dichloromethane solvate

In the title compound, [RuCl₂(C₂H₃N)(C₂₇H₃₁N₃)]·CH₂Cl₂, the Ru^II ion is six‐coordinated in a distorted octahedral arrangement, with the two Cl atoms located in the apical positions, and the pyridine (py) N atom, the two imino N atoms and the acetonitrile N atom located in the basal plane. The two equatorial Ru—N_imino distances are almost equal (mean 2.087 Å) and are substantially longer than the equatorial Ru—N_py bond [1.921 (4) Å]. It is observed that the N_imino—M—N_py angle for the five‐membered chelate rings of pyridine‐2,6‐diimine complexes is inversely related to the magnitude of the M—N_py bond. The title structure is stabilized by intra‐ and intermolecular C—H...Cl hydrogen bonds, as well as by van der Waals interactions.     

(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.     

Hydrogen‐bonding and π–π stacking interactions in aquachloridobis(1,10‐phenanthroline)cobalt(II) chloride dichloridobis(1,10‐phenanthroline)cobalt(II) hexahydrate

The title compound, [CoCl(C₁₂H₈N₂)₂(H₂O)]Cl·[CoCl₂(C₁₂H₈N₂)₂]·6H₂O, is the first example of a new 1:1 cocrystal of the octahedral [CoCl₂(phen)₂] and [CoCl(phen)₂(H₂O)]⁺·Cl⁻ complexes (phen is 1,10‐phenanthroline). The latter form heterochiral dimers held by strong π–π stacking interactions via their phenathroline ligands, which confirms that π stacking is an important and reliable synthon in supramolecular design. In addition, the crystal structure is networked by H₂O...H₂O, H₂O...Cl⁻ and H₂O...Cl hydrogen bonds, which interconnect the different units of the cobalt complexes.