Di‐μ‐chloro‐bis­{bis­[2,5‐bis­(4‐methoxy­phenyl)‐1,3,4‐oxadiazole‐κ2C2′,N]iridium(III)] dichloro­methane disolvate

In the title compound, [Ir₂(C₁₆H₁₃N₂O₃)₄Cl₂]·2CH₂Cl₂, the two Ir atoms, 3.7075 (6) Å apart, are bridged by two Cl atoms which straddle a twofold axis of rotation through the two Ir atoms. Each Ir centre resides in a distorted octa­hedral environment completed by two chelating 2,5‐bis­(4‐methoxy­phenyl)‐1,3,4‐oxadiazole ligands, with trans‐N—N and cis‐C—C dispositions. In the stacking structure, there are two types of hydrogen bonds, involving the meth­oxy substitutent, an N atom of the oxadiazole ring and the dichloro­methane solvent mol­ecules.     

Dichloro­[(6R,7S,8S,14S)‐(–)‐sparteine‐κ2N,N′]mercury(II)

In the title compound, [HgCl₂(C₁₅H₂₆N₂)], the chiral alkaloid (6R,7S,8S,14S)‐(−)‐l ‐sparteine acts as a bident­ate ligand, with two Cl⁻ ligands occupying the remaining coordination sites, producing a distorted tetra­hedron. The N—Hg—N plane is twisted by 81.1 (2)° from the Cl—Hg—Cl plane. The mid‐point of the N⋯N line does not lie exactly on the Cl—Hg—Cl plane but is tilted towards one of the N atoms by 0.346 Å. Similarly, the mid‐point of the Cl⋯Cl line is tilted toward one of the Cl atoms by 0.163 Å. The packing structure shows that the complex is stabilized by two inter­atomic Cl⋯H contacts involving both Cl atoms and the methyl­ene or methine H atoms of the (−)‐sparteine ligand.     

Conformational change induced by hydration: trans‐dichloro­bis­[(1R,2R,3R,5S)‐(–)‐isopinocampheylamine]palladium(II) and trans‐dichloro­bis[(1S,2S,3S,5R)‐(+)‐isopinocampheylamine]palladium(II) hemihydrate

The title compounds, trans‐dichloro­bis[(1R,2R,3R,5S)‐(−)‐2,6,6‐trimethyl­bicyclo­[3.1.1]heptan‐3‐amine]palladium(II), [PdCl₂(C₁₀H₁₉N)₂], and trans‐dichloro­bis[(1S,2S,3S,5R)‐(+)‐2,6,6‐trimethyl­bicyclo­[3.1.1]heptan‐3‐amine]palladium(II) hemihydrate, [PdCl₂(C₁₀H₁₉N)₂]·0.5H₂O, present different arrangements of the amine ligands coordinated to Pd^II, viz. antiperiplanar in the former case and (−)anticlinal in the latter. The hemihydrate is an inclusion compound, with a Pd coordination complex and disordered water mol­ecules residing on crystallographic twofold axes. The crystal structure for the hemihydrate includes a short Pd⋯Pd separation of 3.4133 (13) Å.     

Di­chloro­[(6R,7S,8S,14S)‐(–)‐sparteine‐κ2N,N′]­nickel(II)

In the title compound, [NiCl₂(C₁₅H₂₆N₂)], the chiral alkaloid (6R,7S,8S,14S)‐(−)‐l ‐sparteine acts as a bidentate ligand, with two chloride ligands occupying the remaining coordination sites, producing a slightly distorted tetrahedron. The N—Ni—N plane in the title complex is twisted by 81.31 (11)° from the Cl—Ni—Cl plane. Other distortions of the tetrahedron are discussed.     

Bis(glycinato‐κ2N,O)dinitrosylmolybdenum(0) and bis(2‐aminoethanethiolato‐κ2N,S)dinitrosylmolybdenum(0) acetonitrile monosolvate

The title compounds, [Mo(C₂H₄NO₂)₂(NO)₂], (I), and [Mo(C₂H₆NS)₂(NO)₂]·CH₃CN, (II), contain distorted octahedral complexes in which the monoanionic N,S‐ and N,O‐bidentate ligands coordinate the molybdenum centres in different modes. The anionic O atoms of the glycinate ligands in (I) are coordinated trans to the nitrosyl ligands and the amine N atoms are located trans to each other, whereas in (II) the anionic S atoms are coordinated trans to each other and the amine N atoms are located trans to the nitrosyl ligands. Each compound has a single complete complex in the asymmetric unit on a general position. Six N—H...O contacts with N...O distances of less than 3.2 Å are observed in (I) between the amine groups and the nitrosyl and carboxylate O atoms. In the 1:1 solvate (II), the acetonitrile molecule forms short N—H...N contacts (N...N < 3.2 Å) between the solvent N atoms and one of the amine H atoms. In addition, three weak intermolecular N—H...S interactions (N...S > 3.3 Å) contribute to the stabilization of the structure of (II).     

Tetrakis(μ‐benzothiazole‐2‐thiolato)‐1:2κ4N:S2;1:2κ4S2:N‐dichloro‐1κCl,2κCl‐dirhenium(III)(Re—Re) dichloromethane solvate: a bridged complex with a long Re—Re quadruple bond

The title compound, [Re₂(C₇H₄NS₂)₄Cl₂]·CH₂Cl₂, consists of dirhenium mol­ecules with bridging N,S‐benzo­thia­zole‐2‐thiol­ate ligands, axial Cl^? ligands and intramolecular hydrogen bonding. These mol­ecules adopt somewhat staggered conformations, with a long Re—Re quadruple bond distance of 2.2716 (3) Å.     

[N,N′‐Bis(3‐aminopropyl)ethylenediamine‐κ4N,N′,N′′,N′′′](trithiocyanurato‐κ2N,S)zinc(II) ethanol solvate

In the crystal structure of the title compound, [N,N′‐bis(3‐­amino­propyl)­ethyl­enedi­amine‐κ⁴N,N′,N′′,N′′′][1,3,5‐triazine‐2,4,6(1H,3H,5H)‐tri­thionato(2−)‐κ²N,S]­zinc(II) ethanol sol­vate, [Zn(C₈H₂₂N₄)₂(C₃HN₃S₃)]·C₂H₆O, the Zn^II atom is octa­hedrally coordinated by four N atoms [Zn—N = 2.104 (2)–2.203 (2) Å] of a tetradentate N‐donor N,N′‐bis(3‐­amino­propyl)­ethyl­enedi­amine (bapen) ligand and by two S and N atoms [Zn—S = 2.5700 (7) Å and Zn—N = 2.313 (2) Å] of a tri­thio­cyanurate(2−) (ttcH²⁻) dianion bonded as a bidentate ligand in a cis configuration. The crystal structure of the compound is stabilized by a network of hydrogen bonds.     

6,6′‐Di­methoxy‐2,2′‐[(1R,2R)‐cyclo­hexane‐1,2‐diyl­bis­(nitrilo­methyl­idyne)]­diphenol: three C—H⃛O hydrogen bonds generate a three‐dimensional framework

Molecules of the title compound, alternatively called (R,R)‐N,N′‐bis(3‐methoxysalicylidene)‐trans‐cyclohexane‐1,2‐diamine, C₂₂H₂₆N₂O₄, contain two intramolecular O—H⃛N hydrogen bonds and adopt a conformation with approximate twofold rotational symmetry. The mol­ecules are linked by three C—H⃛O hydrogen bonds [H⃛O = 2.45–2.55 Å, C⃛O = 3.329 (2)–3.398 (2) Å and C—H⃛O = 142–172°] into a continuous framework.     

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)°.     

(1,3‐Dimethylimidazolidine‐2‐selone‐κSe)bis(1,10‐phenanthroline‐κ2N,N′)copper(II) bis(perchlorate) and bis(2,2′‐bipyridyl‐κ2N,N′)(imidazolidine‐2‐thione‐κS)copper(II) bis(perchlorate)

In the first title salt, [Cu(C₁₂H₈N₂)₂(C₅H₁₀N₂Se)](ClO₄)₂, the Cu^II centre occupies a distorted trigonal–bipyramidal environment defined by four N donors from two 1,10‐phenanthroline (phen) ligands and by the Se donor of a 1,3‐dimethylimidazolidine‐2‐selone ligand, with the equatorial plane defined by the Se and by two N donors from different phen ligands and the axial sites occupied by the two remaining N donors, one from each phen ligand. The Cu—N distances span the range 1.980 (10)–2.114 (11) Å and the Cu—Se distance is 2.491 (3) Å. Intermolecular π–π contacts between imidazolidine rings and the central rings of phen ligands generate chains of cations. In the second salt, [Cu(C₁₀H₈N₂)₂(C₃H₆N₂S)](ClO₄)₂, the Cu^II centre occupies a similar distorted trigonal–bipyramidal environment comprising four N donors from two 2,2′‐bipyridyl (bipy) ligands and an S donor from an imidazolidine‐2‐thione ligand. The equatorial plane is defined by the S donor and two N donors from different bipy ligands. The Cu—N distances span the range 1.984 (6)–2.069 (7) Å and the Cu—S distance is 2.366 (3) Å. Intermolecular π–π contacts between imidazolidine and pyridyl rings form chains of cations. A major difference between the two structures is due to the presence in the second complex of two N—H...O hydrogen bonds linking the imidazolidine N—H hydrogen‐bond donors to perchlorate O‐atom acceptors.     

trans‐Bis­[ethane‐1,2‐di­thiol­ato(2–)‐S,S′]­bis(2‐mer­cap­to­pyri­dine‐S)­tin(IV)

The title compound, [Sn(C₅H₅NS)₂(C₂H₄S₂)₂], was obtained from a 1:2 mixture of bis­(ethane‐1,2‐di­thiol­ato)­tin(IV) and 2‐mercapto­pyridine. The mol­ecules are discrete monomeric trans‐octahedral units, with the Sn^IV atom at the centre of symmetry, planar 2‐mercapto­pyridine zwitterions and SnS₂C₂ groups in twist–envelope conformations. The 2‐mercapto­pyridine ligands are monodentate and are bonded through the S atoms. The S—Sn distances between the S atom of edt (edt is ethane‐1,2‐di­thiol­ate) and the Sn atom are 2.473 (1) and 2.505 (1) Å, which are slightly longer than the S—Sn distance in Sn(edt)₂ of 2.390 (1) Å. The bond between the 2‐mercapto­pyridine S atom and the Sn atom are, remarkably, weaker than the S—Sn bond involving edt.     

Chlorotris(N,N′‐dicyclohexylthiourea‐S)tellurium(II) chloride,a tellurium complex with a TeClS3 coordination sphere

During the synthesis of a series of square‐planar [TeCl₂(stu)₂] complexes, where stu represents bulky di‐ or tetrasubstituted thio­ureas, the title compound, [TeCl{(C₆H₁₁NH)₂CS}₃]Cl or C₃₉H₇₂ClN₆S₃Te⁺·Cl^?, was the unexpected result when stu was N,N′‐di­cyclo­hexyl­thio­urea. The complex is square planar, with Te—S distances of 2.5803 (4), 2.6211 (4) and 2.8214 (4) Å, and a Te—Cl distance of 2.6485 (4) Å, indicating a small trans influence of the thio­urea ligand.     

2,2′‐Bipyridinium bis(perchlorate)

The title compound, [H₂bipy](ClO₄)₂ or C₁₀H₁₀N₂²⁺·2ClO₄^?, was obtained at the interface between an organic (2,2′‐bi­pyridine in methanol) and an aqueous phase (perchloric acid in water). The compound crystallizes in space group P and comprises discrete diprotonated trans‐bipyridinium cations, [H₂bipy]²⁺, and ClO₄^? anions. The cations and anions are connected through N—H?O and C—H?O hydrogen bonds [distances N?O 2.817 (4) and 2.852 (4) Å, and C?O 3.225 (6)–3.412 (5)Å]. The C—C bond distance between the two rings is 1.452 (5) Å. The bipyridinium cation has a trans conformation and the N—C—C—N torsion angle is 152.0 (3)°.     

Ein Beitrag zu Rhenium(II)‐, Osmium(II)‐ und Technetium(II)‐Thionitrosylkomplexen vom Typ [M(NS)Cl4py]—: Darstellung,Strukturen und EPR‐Spektren

A Contribution to Rhenium(II)‐, Osmium(II)‐, and Technetium(II)‐Thionitrosyl‐Complexes: Preparation, Structures, and EPR‐Spectra The reaction of [Re^VINCl₄]^— and [Os^VINCl₄]^— with S₂Cl₂ leads to the formation of the thionitrosyl complexes [M^II(NS)Cl₄]^— (M = Re, Os) which could not be isolated as pure compounds. Addition of pyridine to the reaction mixture results in the formation of the stable compounds trans‐(Ph₄P)[Os^II(NS)Cl₄py], trans‐(Hpy)[Os^II(NS)Cl₄py], trans‐(Ph₄P)[Re^II(NS)Cl₄py], and cis‐(Ph₄P)[Re^II(NS)Cl₄py]. The crystal structure analyses show for trans‐(Ph₄P)[Os^II(NS)Cl₄py] (monoclinic, P2₁/n, a = 12.430(3)Å, b = 18.320(4)Å, c = 15.000(3)Å, β = 114.20(3)°, Z = 4), trans‐(Hpy)[Os^II(NS)Cl₄py] (monoclinic, P2₁/n, a = 7.689(1)Å, b = 10.202(2)Å, c = 20.485(5)Å, β = 92.878(4)°, Z = 4), trans‐(Ph₄P)[Re^II(NS)Cl₄py] (triclinic, P1¯, a = 9.331(5)Å, b = 12.068(5)Å, c = 15.411(5)Å, α = 105.25(1)°, β = 90.23(1)°, γ = 91.62(1)°, Z = 2), and cis‐(Ph₄P)[Re^II(NS)Cl₄py] (monoclinic, P2₁/c, a = 10.361(1)Å, b = 16.091(2)Å, c = 17.835(2)Å, β = 90.524(2)°, Z = 4) M‐N‐S angles in the range 168‐175°. This indicates a nearly linear coordination of the NS ligand. The metal atom is octahedrally coordinated in all cases. The rhenium(II) thionitrosyl complexes (5d⁵ “low‐spin” configuration, S = 1/2) are studied by EPR in the temperature range 295 > T > 130 K. In addition to the detection of the complexes formed during the reaction of [Re^VINCl₄]^— with S₂Cl₂ EPR investigations on diamagnetically diluted powders and single crystals of the system (Ph₄P)[Re^II/Os^II(NS)Cl₄py] are reported. The ^{185, 187}Re hyperfine parameters are used to get information about the spin‐density distribution of the unpaired electron in the complexes under study. [Tc^VINCl₄]^— reacts with S₂Cl₂ under formation of [Tc^II(NS)Cl₄]^— which is not stable and decomposes under S₈ elimination and rebuilding of [Tc^VINCl₄]^— as found by EPR monitoring of the reaction.     

A cobalt(III) compound of a 13‐membered cyclic tetra­amine: trans‐(12,12‐dimethyl‐1,4,7,10‐tetra­aza­cyclo­tetra­decane)diisothio­cyanato­cobalt(III) tetra­isothio­cyanato­zinc(II) ethanol solvate

The title compound, [Co(NCS)₂(C₁₁H₂₆N₄)]₂[Zn(NCS)₄]·C₂H₅OH, has two similar cations with the Co^III atom coordinated in a planar fashion by the 13‐membered cyclic tetra­amine, in the 1R,4S,7R,10S configuration, and with trans isothio­cyanate ligands. The six‐membered chelate ring is in a chair conformation, with one axially and one equatorially oriented methyl substituent [mean Co—N = 1.948 (2) Å]. The `opposite' chelate ring (N<sup>4</sup> and N<sup>7</sup>) is in an eclipsed conformation [mean Co—N = 1.928 (2) Å], and the `side' chelate rings have gauche conformations. The mean Co—N_NCS distance is 1.928 (2) Å. Both cations have one Co—N—C group nearly linear and the other appreciably bent, with mean Co—N—C angles of 178.7 (1) and 160.4 (1)°, respectively. The [Zn(NCS)₄]²⁻ anion is approximately tetra­hedral, with Zn—N = 1.951 (1)–1.986 (1) Å, N—Zn—N = 104.5 (1)–111.9 (1)° and Zn—N—C = 152.5 (1)–179.4 (1)°. One NH group is hydrogen bonded to the ethanol O atom and the other NH groups are bonded to thio­cyanate S atoms, forming a network.     

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.     

The correct assignment of stereochemistry in di‐μ‐dichlorido‐bis{bis[2‐(5‐benzylsulfonyl)‐3‐fluoro‐2‐(pyridin‐2‐yl)phenyl‐κ2N,C1]iridium(III)} toluene monosolvate

The title complex, [Ir₂(C₁₈H₁₃FNO₂S)₄Cl₂]·C₇H₈, was crystallized from dichloromethane solution under a toluene atmosphere. It is a dimeric complex in which each of the two Ir^III centres is octahedrally coordinated by two bridging chloride ligands and by two chelating cyclometalated 2‐(4‐benzylsulfonyl‐2‐fluorophenyl)pyridine ligands. The crystal structure analysis unequivocally establishes the trans disposition of the two cyclometalated ligands bound to each Ir^III centre, contrary to our previous hypothesis of a cis disposition. The latter was based on the ¹H NMR spectra of a series of dimeric benzylsulfonyl‐functionalized dichloride‐bridged iridium complexes, including the compound described in the present work [Ragni et al. (2009). Chem. Eur. J. 15 , 136–148]. The toluene solvent molecules, embedded in cavities in the crystal structure, are highly disordered and could not be modelled successfully; their contribution was removed from the refinement using the SQUEEZE routine in the program PLATON [Spek (2009). Acta Cryst. D 65 , 148–155].     

The dinuclear copper(II) complexes di‐μ‐chlorido‐bis{[N,N′‐bis(4‐chlorobenzyl)propane‐1,2‐diamine]chloridocopper(II)} and di‐μ‐chlorido‐bis{[N,N′‐bis(3,4‐methylenedioxybenzyl)propane‐1,2‐diamine]chloridocopper(II)}

The two title dinuclear copper(II) complexes, [Cu₂Cl₄(C₁₇H₂₀Cl₂N₂)₂], (I), and [Cu₂Cl₄(C₁₉H₂₂N₂O₄)₂], (II), have similar coordination environments. In each complex, the asymmetric unit consists of one half‐molecule and the two copper centres are bridged by a pair of Cl atoms, resulting in complexes with centrosymmetric structures containing Cu(μ‐Cl)₂Cu parallelogram cores; the Cu...Cu separations and Cu—Cl—Cu angles are 3.4285 (8) Å and 83.36 (3)°, respectively, for (I), and 3.565 (2) Å and 84.39 (7)° for (II). Each Cu atom is five‐coordinated and the coordination geometry around the Cu atom is best described as a distorted square‐pyramid with a τ value of 0.155 (3) for (I) and 0.092 (7) for (II). The apical Cu—Cl bond length is 2.852 (1) Å for (I) and 2.971 (2) Å for (II). The basal Cu—Cl and Cu—N average bonds lengths are 2.2673 (9) and 2.030 (2) Å, respectively, for (I), and 2.280 (2) and 2.038 (6) Å for (II). The molecules of (I) are linked by one C—H...Cl hydrogen bond into a complex [10] sheet. The molecules of (II) are linked by one C—H...Cl and one N—H...O hydrogen bond into a complex [100] sheet.     

Di­bromo­[(–)‐sparteine‐κ2N,N′]­zinc(II)

In the title compound, di­bromo­[(6R,7S,8S,14S)‐1,3,4,7,7a,8,9,10,11,13,14,14a‐dodeca­hydro‐7,14‐methano‐2H,6H‐dipyrido­[1,2‐a:1′,2′‐e][1,5]­diazo­cine‐κ²N,N′]­zinc(II), [ZnBr₂(C₁₅H₂₆N₂)], the chiral nitro­gen‐chelating alkaloid (?)‐l ‐sparteine acts as a bidentate ligand, with two bromide ligands occupying the remaining coordination sites, producing a slightly distorted tetrahedral structure. The dihedral angle between the N—Zn—N and Br—Zn—Br planes is 82.4 (1)°. The distortion of the tetrahedral coordination is demonstrated by the fact that the midpoint of the N?N line does not lie in the Br—Zn—Br plane, but is tilted towards one of the N atoms by 0.164 Å. Similarly, the midpoint of the Br?Br line is tilted towards one of the Br atoms by 0.117 Å.     

[N,N′‐Bis(5‐bromo­salicyl­idene)‐1,3‐di­amino­propane]­nickel(II) and [N,N′‐­bis(5‐chloro­salicyl­idene)‐1,3‐­di­amino­propane]copper(II)

The title compounds, {4,4′‐di­bromo‐2,2′‐[1,3‐propane­diyl­bis(nitrilo­methyl­idyne‐N)]­diphenolato‐O,O′}nickel(II), [Ni(C₁₇­H₁₄­Br₂­N₂O₂)], and {4,4′‐di­chloro‐2,2′‐[1,3‐pro­pane­diyl­bis­(ni­trilo­methyl­idyne‐N)]­di­phen­ol­ato‐O,O′}­copper(II), [Cu­(C₁₇­H₁₄­Cl₂­N₂O₂)], lie on crystallographic twofold axes. In both structures, the metal coordination sphere is a tetrahedrally distorted square plane formed by the four‐coordinate N₂O₂ donor set of the Schiff base imine–phenol ligands. In the Ni compound, the Ni—O and Ni—N distances are 1.908 (3) and 1.959 (4) Å, respectively, while in the Cu compound, the Cu—O and Cu—N distances are 1.907 (2) and 1.960 (2) Å, respectively. The two Schiff base moieties, which themselves are nearly planar, are inclined at an angle of 29.26 (7)° for the Ni compound and 29.26 (5)° for the Cu compound.