Mononukleare Kupfer(II)‐Komplexe von dioxaalkylenund alkylenverbrückten Bis‐isoharnstoffen

Mononuclear Copper(II) Complexes of Dioxaalkylene and Alkylene Bridged Bis‐isoureas By reaction of N‐benzoylthiocarbamic‐O,S‐diethylester with primary diamines (oxa)alkylene bridged isoureas 1 have been prepared. They yield with Cu^II neutral chelates 2 with tetradentate ligand coordination. The structures of the ligand 1 a and of the related Cu^II complex 2 a have been determined by X‐ray crystal structure analysis. They show an enamine tautomer in the ligand and a slightly tetrahedrally distorted coordination with an (oxa)alkylene bridge between the trans arranged N ligator atoms in the complex.     

3‐(Arylhydrazono)pentane‐2, 4‐diones and their Complexes with Copper(II) and Nickel(II) — Synthesis and Crystal Structures

A series of new 3‐(arylhydrazono)pentane‐2, 4‐diones ( 1 ‐ 6 ) synthesized from pentane‐2, 4‐dione and diazonium salts of respective anilines using the procedure of Japp‐Klingemann are described. Complexes with Cu^II and Ni^II salts are prepared ( 7 ‐ 10 , respectively). Spectroscopic properties of these compounds have been studied and X‐ray crystal structures of selected hydrazones ( 3 , 4 , 6 ) and of the hydrazone complexes ( 7 ‐ 10 ) are reported. The structures of the uncomplexed hydrazones feature an intramolecular N‐H···O interaction to yield a six‐membered H‐bond ring reflecting preference of the hydrazone tautomeric structure. All the complexes are mononuclear 2:1 (L:M) structures of six‐membered chelate type involving N₂O₂ binding sites that are quadratic arranged but differ in the entire coordination environment dependent on the metal and the ligand substitution including distorted octahedral and quadratic pyramidal coordination geometries in the Cu^II complexes 7 and 8 or nearly regular square planar coordination geometry in the Ni^II complexes 9 and 10 , respectively. In the crystal packings, strong and weak H‐bond interactions cause supramolecular network structures.     

1-Ethoxycarbonyl-3-ferrocenyl-propan-1,3-dion und Ferrocen-1,1'bis(2,4-dioxobutansäureethylester) als Liganden für Übergangsmetallionen. Kristallstruktur von Bis(1-ethoxycarbonyl-3-ferrocenyl-propan-1,3dionato)kupfer(II)

1-Ethoxycarbonyl-3-ferrocenyl-propane-1,3-dion and Ferrocene-1,1′bis(2,4-dioxobutanoic acid ethylester) as Ligands for Transition Metal Ions. Crystal Structure of Bis(1-ethoxycarbonyl-3-ferrocenyl-propane-1,3dionato)copper(II) The ligands 1-ethoxycarbonyl-3-ferrocenyl-propane-1,3-dion and ferrocene-1,1′-bis(2,4-dioxo-butanoic acid ethylester) have been prepared by reaction of acetylferrocene or 1,1′-diacetylferrocene and diethyl oxalate. They yield neutral chelates with Cu^II, Ni^II, Zn^II, Co^II, and Mn^II. The acid dissociation constants of the ligands and the stability constants of their metal complexes including Fe^II complexes are reported. The structure of bis(1-ethoxycarbonyl-3-ferrocenyl-propane-1,3-dionato)copper(II) was determined by X-ray structure analysis. A cis arrangement with a nearly square planar coordination sphere at the Cu atom is found.     

[N,N′‐Bis­(salicyl­idene)‐2,2‐di­methyl‐1,3‐propane­diaminato]­nickel(II) and [N,N′‐bis­(salicyl­idene)‐2,2‐di­methyl‐1,3‐propane­diaminato]copper(II)

In the title compounds, {2,2′‐[2,2‐di­methyl‐1,3‐propane­diyl­bis­(nitrilo­methyl­idyne)]­diphenolato‐κ⁴N,N′,O,O′}nickel(II), [Ni(C₁₉H₂₀N₂O₂)], and {2,2′‐[2,2‐di­methyl‐1,3‐propane­diyl­bis­(nitrilo­methyl­idyne)]­diphenolato‐κ⁴N,N′,O,O′}copper(II), [Cu(C₁₉H₂₀N₂O₂)], the Ni^II and Cu^II atoms are coordinated by two iminic N and two phenolic O atoms of the N,N′‐bis­(salicyl­idene)‐2,2‐di­methyl‐1,3‐propane­diaminate (SALPD^2?, C₁₇H₁₆N₂O₂^2?) ligand. The geometry of the coordination sphere is planar in the case of the Ni^II complex and distorted towards tetrahedral for the Cu^II complex. Both complexes have a cis configuration imposed by the chelate ligand. The dihedral angles between the N/Ni/O and N/Cu/O coordination planes are 17.20 (6) and 35.13 (7)°, respectively.     

Bis{1‐n‐hex­yl‐3‐meth­yl‐4‐[1‐(phenyl­imino)prop­yl]‐1H‐pyrazol‐5‐olato}­copper(II): a new copper(II) complex with a chelating alkyl­pyrazolone‐based enamine

The title compound, [Cu(C₁₉H₂₆N₃O)₂], is the first reported complex of the alkyl­pyrazolone‐derived ligand 1‐n‐hexyl‐3‐methyl‐4‐[1‐(phenylimino)propyl]‐1H‐pyrazol‐5(4H)‐one. The most notable feature is the imine–enol character presented by the ligand due to coordination, in spite of its enamine–ketone structure in the free state. The ligand chelates through N and O atoms, resulting in a square‐planar coordination around the Cu^II atom, which lies on an inversion centre.     

Synthese,Struktur und EPR‐Untersuchungen von binuklearen Bis(N,N,N‴,N‴‐tetraisobutyl‐N′,N″‐isophthaloylbis(thioureato))‐Komplexen des CuII,NiII, ZnII,CdII und PdII

Synthesis, Structure and EPR Investigations of binuclear Bis(N,N,N?,N?‐tetraisobutyl‐N′,N″‐isophthaloylbis(thioureato)) Complexes of Cu^II, Ni^II, Zn^II, Cd^II and Pd^II The synthesis of binuclear Cu^II‐, Ni^II‐, Zn^II‐, Cd^II‐ and Pd^II‐complexes of the quadridentate ligand N,N,N?,N?‐tetraisobutyl‐N′,N″‐isophthaloylbis(thiourea) and the crystal structures of the Cu^II‐ and Ni^II‐complexes are reported. The Cu^II‐complex crystallizes in two polymorphic modifications: triclinic, (Z = 1) and monoclinic, P2₁/c (Z = 2). The Ni^II‐complex was found to be isostructural with the triclinic modification of the copper complex. The also prepared Pd^II‐, Zn^II‐ and Cd^II‐complexes could not be characterized by X‐ray analysis. However, EPR studies of diamagnetically diluted Cu^II/Pd^II‐ and Cu^II/Zn^II‐powders show axially‐symmetric g and A ^Cu tensors suggesting a nearly planar co‐ordination within the binuclear host complexes. Diamagnetically diluted Cu^II/Cd^II powder samples could not be prepared. In the EPR spectra of the pure binuclear Cu^II‐complex exchange‐coupled Cu^II‐Cu^II pairs were observed. According to the large Cu^II‐Cu^II distance of about 7,50Å a small fine structure parameter D = 26·10^?4 cm^?1 is observed; T‐dependent EPR measurements down to 5 K reveal small antiferromagnetic interactions for the Cu^II‐Cu^II dimer. Besides of the dimer in the EPR spectra the signals of a mononuclear Cu^II species are observed whose concentration is T‐dependent. This observation can be explained assuming an equilibrium between the binuclear Cu^II‐complex (Cu^II‐Cu^II pairs) and oligomeric complexes with “isolated” Cu^II ions.     

Chelatbildung mit 1,3-Diamino-2-methylenpropanen

Chelate Formation with 1,3-Diamino-2-methylene Propane1 1,3-Diamino-2-methylene propane and its N, N′ alkylated derivatives form crystalline chelates with Co^II (1:3), Ni^II (1:1, 1:2 and 1:3), Pd^II (1:1, 1:2), Rh^III (1:1) and Cu^II (1:2). Experiments for preparation of olefin complexes were unsuccessful. By potentiometric measurements the base strengths of the ligands as well as the stability constants of the Co^II, Ni^II, Pd^II, Cu^II, Zn^II, Cd^II chelates were evaluated and the kinetics of the formation of the 1:1 Pd^II complex is investigated. The magnetic behaviour of the Co^II?, Pd^II? and Cu^II? chelates is normal, whereas[Ni(dia)₂(H₂O)₂] (ClO₄)₂ shows anormal behaviour due to configurational isomerism between square planar and octahedral ligand geometry in solid state in type of a LIFSCHITZ -isomerism. The ESR-spectra of the Cu^II?compounds are discussed and the bonding parameters of the Cu? N?bonds were calculated.     

Designing a heterotrinuclear CuII—NiII—CuII complex from a mononuclear CuII Schiff base precursor with dicyanamide as a coligand: synthesis,crystal structure,thermal and photoluminescence properties

Schiff bases are considered `versatile ligands' in coordination chemistry. The design of polynuclear complexes has become of interest due to their facile preparations and varied synthetic, structural and magnetic properties. The reaction of the `ligand complex' [CuL] {H₂L is 2,2′‐[propane‐1,3‐diylbis(nitrilomethanylylidene)]diphenol} with Ni(OAc)₂·4H₂O (OAc is acetate) in the presence of dicyanamide (dca) leads to the formation of bis(dicyanamido‐1κN¹)bis(dimethyl sulfoxide)‐2κO,3κO‐bis{μ‐2,2′‐[propane‐1,3‐diylbis(nitrilomethanylylidene)]diphenolato}‐1:2κ⁶O,O′:O,N,N′,O′;1:3κ⁶O,O′:O,N,N′,O′‐dicopper(II)nickel(II), [Cu₂Ni(C₁₇H₁₆N₂O₂)₂(C₂N₃)₂(C₂H₆OS)₂]. The complex shows strong absorption bands in the frequency region 2155–2269 cm⁻¹, which clearly proves the presence of terminal bonding dca groups. A single‐crystal X‐ray study revealed that two [CuL] units coordinate to an Ni^II atom through the phenolate O atoms, with double phenolate bridges between Cu^II and Ni^II atoms. Two terminal dca groups complete the distorted octahedral geometry around the central Ni^II atom. According to differential thermal analysis–thermogravimetric analysis (DTA–TGA), the title complex is stable up to 423 K and thermal decomposition starts with the release of two coordinated dimethyl sulfoxide molecules. Free H₂L exhibits photoluminescence properties originating from intraligand (π–π*) transitions and fluorescence quenching is observed on complexation of H₂L with Cu^II.     

A mixed bridged trinuclear copper(II)–1,10‐phenanthroline complex with a linear structure

The title compound, diaqua‐1κO,3κO‐di‐μ‐hydroxido‐1:2κ²O:O,2:3κ²O:O‐di‐μ‐methacrylato‐1:2κ²O:O′,2:3κ²O:O′‐bis(1,10‐phenanthroline)‐1κ²N,N′;3κ²N,N′‐tricopper(II) dinitrate dihydrate, [Cu₃(C₄H₅O₂)₂(OH)₂(C₁₂H₈N₂)₂(H₂O)₂](NO₃)₂·2H₂O, has the central Cu atom on an inversion centre. The three Cu^II atoms are in a linear arrangement linked by methacrylate and hydroxide groups. The coordination environments of the Cu^II ions are five‐coordinated distorted square‐pyramidal for the outer Cu atoms and four‐coordinated square‐planar for the central Cu atom. All nitrate ions, hydroxide groups and water molecules are linked by hydrogen bonds, forming a linear structure. The complex exhibits ferromagnetic exchange coupling, which is helpful in elucidating magnetic interactions between copper ions and other metallic ions in heteronuclear complexes.     

A novel two‐dimensional nickel(II) coordination polymer with 1,4‐bis(1,2,4‐triazol‐1‐ylmethyl)benzene and azide ligands

The coordination geometry of the Ni^II atom in the title complex, poly[diazidobis[μ‐1,4‐bis(1,2,4‐triazol‐1‐ylmethyl)benzene‐κ²N⁴:N^4′]nickel(II)], [Ni(N₃)₂(C₁₂H₁₂N₆)₂]_n, is a distorted octahedron, in which the Ni^II atom lies on an inversion centre and is coordinated by four N atoms from the triazole rings of two symmetry‐related pairs of 1,4‐bis(1,2,4‐triazol‐1‐ylmethyl)benzene (bbtz) ligands and two N atoms from two symmetry‐related monodentate azide ligands. The Ni^II atoms are bridged by four bbtz ligands to form a two‐dimensional (4,4)‐network.     

Synthese,Strukturen und X‐/Q‐Band‐EPR‐Untersuchungen von N,N‐Diethyl‐N′‐3,5‐di(trifluormethyl)benzoylthioureato‐Komplexen des CuII,NiII und PdII sowie EPR‐spektroskopische Charakterisierung eines CuII‐CuII‐Dimers

The synthesis and the structures of (i) the ligand N,N‐Diethyl‐N′‐3,5‐di(trifluoromethyl)benzoylthiourea HEt₂dtfmbtu and (ii) the Ni^II and Pd^II complexes of HEt₂dtfmbtu are reported. The ligand coordinates bidendate forming bis chelates. The Ni^II and the Pd^II complexes are isostructural. The also prepared Cu^II complex could not be characterized by X‐ray analysis. However, the preparation of diamagnetically diluted powders Cu/Ni(Et₂dtfmbtu)₂ and Cu/Pd(Et₂dtfmbtu)₂ suitable for EPR studies was successful. The EPR spectra of the Cu/Ni and Cu/Pd systems show noticeable differences for the symmetry of the CuS₂O₂ unit in both complexes: the Cu/Pd system is characterized by axially‐symmetric g< and A ^cu tensors; for the Cu/Ni system g and A ^Cu have rhombic symmetry. EPR studies on frozen solutions of the Cu^II complex show the presence of a Cu^II‐Cu^II dimer which is the first observed for Cu^II acylthioureato complexes up to now. The parameters of the fine structure tensor were used for the estimation of the Cu^II‐Cu^II distance.     

Structure,Characterization, and Metal‐Complexation Properties of a New Tetraazamacrocycle Containing Two Phenolic Pendant Arms

The new tetraazamacrocycle 2 (=2,2′‐[[7‐Methyl‐3,7,11,17‐tetraazabicyclo[11.3.1]heptadeca‐1(17),13,15‐triene‐3,11‐diyl]bis(methylene)]bis(4‐bromophenol)) was synthesized and used as a ligand for different metal‐ion complexes. The X‐ray crystal structures of the complexes of the general formula [M(H‐ 2 )]⁺NO ?MeOH (M=Ni²⁺, Zn²⁺), in which only one of the two pendant phenolic OH groups of 2 is deprotonated, were determined. In both complexes, the coordination environment is of the [5+1] type, the four N‐atoms of the macrocyclic framework defining a square‐planar arrangement around the metal center, with similar Ni? N and Zn? N distances of 1.961(9) to 2.157(9) Å and 2.021(9) to 2.284(8) Å, respectively. In contrast, the M? O distances are markedly different, 2.060(6) and 2.449(8) Å in the Ni^II complex, and 2.027(7) and 2.941(9) Å in the Zn^II complex. The UV/VIS spectra of the Ni^II and Cu^II complexes with ligand 2 , and the EPR spectra of the Cu^II system, suggest the same type of structure for the complexes in solution as in the solid state. Theoretical studies by means of density functional theory (DFT) confirmed the experimental structures of the Ni^II and Zn^II complexes, and led to a proposal of a similar structure for the corresponding Cu^II complex. The calculated EPR parameters for the latter and comparison with related data support this interpretation. The singly occupied molecular orbital (SOMO) in these systems is mainly made of a d orbital of Cu, with a strong antibonding (σ*) contribution of the axially bound phenolate residue.     

Zur Komplexbildung von N-(Thiocarbamoyl)benzamidinen

Complex Formation of N-(Thiocarbamoyl) benzamidines N-(Thiocarbamoyl)benzamidines 1 and N-(Thiocarbamoyl)-N′-phenyl-benzamidines 2 form in alcoholic solutions with Ni²⁺, Cu²⁺, Pd²⁺, Co³⁺, and Ag⁺ ions well crystallized chelates 1a ? h and 2a? h , respectively, with N/S coordination. The X-ray photoelectron spectra evidence the NH group as ligator in the case of chelates of 1 and the increased donor capacity compared with the isosteric oxygen ligator atom bound to nickel. This is confirmed by d-¹H-n.m.r. spectroscopy analyzing the value of ΔG_c^≠ for the rotational barrier for the Et₂N group of 1a     

Transition metal complexes with ­thiosemicarbazide‐based ligands. XLIII.

In the title compound, [ZnCl(C₂H₇N₃S)₂]Cl, the Zn^II ion is five‐coordinated in a distorted trigonal–bipyramidal arrangement, with the hydrazine N atoms located in the apical positions. The structure is stabilized by N—H?Cl hydrogen bonds, which involve both the Cl atoms and all the hydrogen donors, except for one of the two thio­amide N atoms. A comparison of the geometry of thio­semicarbazide and S‐­methyl­iso­thio­semicarbazide complexes with Zn^II, Cu^II and Ni^II shows the pronounced influence of the hydrogen‐bond network on the coordination geometry of Zn^II compounds.     

EPR Spectroscopy of 4, 4′‐Bis(tert‐butyl)‐2, 2′‐bipyridine‐1, 2‐dithiolatocuprates(II) in Host Lattices with Different Coordination Geometries

A series of new heteroleptic MN₂S₂ transition metal complexes with M = Cu²⁺ for EPR measurements and as diamagnetic hosts Ni²⁺, Zn²⁺, and Pd²⁺ were synthesized and characterized. The ligands are N₂ = 4, 4′‐bis(tert‐butyl)‐2, 2′‐bipyridine (tBu₂bpy) and S₂ =1, 2‐dithiooxalate, (dto), 1, 2‐dithiosquarate, (dtsq), maleonitrile‐1, 2‐dithiolate, or 1, 2‐dicyanoethene‐1, 2‐dithiolate, (mnt). The Cu^II complexes were studied by EPR in solution and as powders, diamagnetically diluted in the isostructural planar [Ni^II(tBu₂bpy)(S₂)] or[Pd^II(tBu₂bpy)(S₂)] as well as in tetrahedrally coordinated[Zn^II(tBu₂bpy)(S₂)] host structures to put steric stress on the coordination geometry of the central CuN₂S₂ unit. The spin density contributions for different geometries calculated from experimental parameters are compared with the electronic situation in the frontier orbital, namely in the semi‐occupied molecular orbital (SOMO) of the copper complex, derived from quantum chemical calculations on different levels (EHT and DFT). One of the hosts, [Ni^II(tBu₂bpy)(mnt)], is characterized by X‐ray structure analysis to prove the coordination geometry. The complex crystallizes in a square‐planar coordination mode in the monoclinic space group P2₁/a with Z = 4 and the unit cell parameters a = 10.4508(10) Å, b = 18.266(2) Å, c = 12.6566(12) Å, β = 112.095(7)°. Oxidation and reductions potentials of one of the host complexes, [Ni(tBu₂bpy)(mnt)], were obtained by cyclovoltammetric measurements.     

Preparation and characterization of metal complexes containing a NS donor ligand derived from S-benzyldithiocarbazate and p-nitrobenzaldehyde. X-ray crystal structure of the nickel(II) chelate

Summary A series of metal (Cu, Ni, Zn, Cd and Pd) complexes of a Schiff base ligand derived from S-benzyldithiocarbazate and p-nitrobenzaldehyde were prepared and characterized. The Schiff base acts as a single negatively-charged bidentate ligand forming stable neutral metal complexes. Magnetic and spectroscopic data suggest a square planar structure for the Cu^II, Ni^II and Pd^II chelates. Single X-ray diffraction analysis of the Ni^II chelate established that the Schiff base loses a proton from its tautomeric thiol form and coordinates to the metal via the thiolato sulfur and -nitrogen. The geometry around Ni^II is square planar with two equivalent Ni-N and Ni-S bonds; the two nitrobenzyl rings and the coordination plane are almost isoplanar, giving a delocalized electronic system.     

Synthese,Strukturen, NMR‐ und EPR‐spektroskopische Untersuchungen an Übergangsmetallkomplexen monofluorsubstituierter Acylselenoharnstoffliganden

Synthesis, Structures, NMR and EPR Investigations on Transition Metal Complexes of monofluorosubstituted Acylselenourea Ligands The syntheses and the structures of the ligand N, N‐diethyl‐N′‐(2‐fluoro)benzoylselenourea HEt₂mfbsu and the complexes [Ni(Et₂mfbsu)₂] and [Zn(Et₂mfbsu)₂] as well as of the ligand N, N‐diisobutyl‐N′‐(2‐fluoro)benzoylselenourea HBuⁱ₂mfbsu and the complexes [Ni^II(Buⁱ₂mfbsu)₂] and [Pd^II(Buⁱ₂mfbsu)₂] are reported. The ligands coordinate bidendately forming bischelates. The Pd^II and Ni^II complexes are cis coordinated; in [Zn^II(Et₂mfbsu)₂] the ligands are tetrahedrally arranged. The structure of the also obtained bis[diisobutylamino‐(2‐fluorobenzoylimino)methyl]diselenide is reported. The Cu^II complexes of both selenourea ligands could not be isolated. They were obtained as oils. Their EPR spectra, however, confirm the presence of Cu^II bischelates unambiguously. Detailed NMR investigations ‐ ¹H‐, ¹³C‐ and ¹⁹F‐COSY, HMBC and HMQC ‐ on [M^II(Et₂mfbsu)₂] (M = Ni^II, Zn^II) allow an exact assignment of all signals to the magnetically active nuclei of the complexes.     

Synthese,Strukturen, EPR‐ und ENDOR‐spektroskopische Untersuchungen an Übergangsmetallkomplexen von N,N‐Diisobutyl‐N′‐(2, 6‐difluor)benzoylselenoharnstoff

Synthesis, Structures, EPR and ENDOR Investigations on Transition Metal Complexes of N, N‐diisobutyl‐N′‐(2, 6‐difluoro)benzoyl selenourea The synthesis and the structures of the Ni^II and Pd^II complexes of the ligand N, N‐diisobutyl‐N′‐(2, 6‐difluoro)benzoylselenourea HBuⁱ₂dfbsu are reported. The ligands coordinate bidentately forming bis‐chelates. The structure of the ligand could not be obtained, however, the structure of its O‐ethyl ester will be reported. Attempts to prepare the Cu^II complex result only in the formation of oily products. However, the Cu^II complex could be incorporated into the corresponding Ni^II and Pd^II compounds. From this diamagnetically diluted powder and single‐crystal samples were obtained being suitable for EPR‐ENDOR measurements. We report X‐ and Q‐band EPR investigations on the systems [Cu/Ni(Buⁱ₂dfbsu)₂] and [Cu/Pd(Buⁱ₂dfbsu)₂] as well as a single‐crystal X‐band EPR study for [Cu/Ni(Buⁱ₂dfbsu)₂]. The obtained ^{63, 65}Cu and ⁷⁷Se hyperfine structure tensors allow a determination of the spin‐density distribution within the first coordination sphere. In addition, orientation selective ¹⁹F Q‐band pulse ENDOR investigations on powder‐samples of [Cu/Ni(Buⁱ₂dfbsu)₂] have been performed. The hyperfine structure tensors of two intramolecular ¹⁹F atoms could be determined. According to the small ¹⁹F couplings only a vanishingly small spin‐density of < 1 % was obtained for these ¹⁹F atoms.     

A trinuclear palladium(II) complex containing N,S‐coordinating 2‐(benzylsulfanyl)anilinide and 1,3‐benzothiazole‐2‐thiolate ligands with a central square‐planar PdN4 motif

The reaction of dichlorido(cod)palladium(II) (cod = 1,5‐cyclooctadiene) with 2‐(benzylsulfanyl)aniline followed by heating in N,N‐dimethylformamide (DMF) produces the linear trinuclear Pd₃ complex bis(μ₂‐1,3‐benzothiazole‐2‐thiolato)bis[μ₂‐2‐(benzylsulfanyl)anilinido]dichloridotripalladium(II) N,N‐dimethylformamide disolvate, [Pd₃(C₇H₄NS₂)₂(C₁₃H₁₂NS)₂Cl₂]·2C₃H₇NO. The molecule has symmetry and a Pd...Pd separation of 3.2012 (4) Å. The outer Pd^II atoms have a square‐planar geometry formed by an N,S‐chelating 2‐(benzylsulfanyl)anilinide ligand, a chloride ligand and the thiolate S atom of a bridging 1,3‐benzothiazole‐2‐thiolate ligand, while the central Pd^II core shows an all N‐coordinated square‐planar geometry. The geometry is perfectly planar within the PdN₄ core and the N—Pd—N bond angles differ significantly [84.72 (15)° for the N atoms of ligands coordinated to the same outer Pd atom and 95.28 (15)° for the N atoms of ligands coordinated to different outer Pd atoms]. This trinuclear Pd₃ complex is the first example of one in which 1,3‐benzothiazole‐2‐thiolate ligands are only N‐coordinated to one Pd centre. The 1,3‐benzothiazole‐2‐thiolate ligands were formed in situ from 2‐(benzylsulfanyl)aniline.     

First‐row transition metal–pyridine (py)–sulfate [(py)xM](SO4) complexes (M = Ni,Cu and Zn): crystal field theory in action

The crystal structures of three first‐row transition metal–pyridine–sulfate complexes, namely catena‐poly[[tetrakis(pyridine‐κN)nickel(II)]‐μ‐sulfato‐κ²O:O′], [Ni(SO₄)(C₅H₅N)₄]_n, (1), di‐μ‐sulfato‐κ⁴O:O‐bis[tris(pyridine‐κN)copper(II)], [Cu₂(SO₄)₂(C₅H₅N)₆], (2), and catena‐poly[[tetrakis(pyridine‐κN)zinc(II)]‐μ‐sulfato‐κ²O:O′‐[bis(pyridine‐κN)zinc(II)]‐μ‐sulfato‐κ²O:O′], [Zn₂(SO₄)₂(C₅H₅N)₆]_n, (3), are reported. Ni compound (1) displays a polymeric crystal structure, with infinite chains of Ni^II atoms adopting an octahedral N₄O₂ coordination environment that involves four pyridine ligands and two bridging sulfate ligands. Cu compound (2) features a dimeric molecular structure, with the Cu^II atoms possessing square‐pyramidal N₃O₂ coordination environments that contain three pyridine ligands and two bridging sulfate ligands. Zn compound (3) exhibits a polymeric crystal structure of infinite chains, with two alternating zinc coordination environments, i.e. octahedral N₄O₂ coordination involving four pyridine ligands and two bridging sulfate ligands, and tetrahedral N₂O₂ coordination containing two pyridine ligands and two bridging sulfate ligands. The observed coordination environments are consistent with those predicted by crystal field theory.