Metallorganische 5d6‐Übergangsmetallkomplexe von zwei 1‐Methyl‐(2‐alkylthiomethyl)‐1H‐benzimidazol‐Liganden: Strukturen und elektrochemische Oxidation

Organometallic 5d⁶ Transition Metal Complexes of 1‐Methyl‐(2‐alkylthiomethyl)‐1H‐benzimidazole Ligands: Structures and Electrochemical Oxidation The complexes [(mmb)Re(CO)₃Cl], [(mtb)Re(CO)₃Cl], [(mmb)OsCl(Cym)](PF₆) and [(Cym)OsCl(mtb)](PF₆) where Cym = p‐cymene, mmb = 1‐methyl‐(2‐methylthiomethyl)‐1H‐benzimidazole and mtb = 1‐methyl‐(2‐tert‐butylthiomethyl)‐1H‐benzimidazole were synthesized and, except for the latter, structurally characterized. In comparison with other late transition metal compounds of these N‐S chelate ligands the rhenium(I) systems exhibit a balanced coordination to both N and S donor atoms. Anodic one‐electron oxidation produces EPR‐silent rhenium(II) states whereas the osmium(III) species [(mmb)OsCl(Cym)]²⁺ could be identified via EPR and UV/VIS spectroelectrochemistry.     

catena‐Poly­[[(di‐2‐pyridyl­amine)­silver(I)]‐μ‐nicotinato] and catena‐poly­[[(di‐2‐pyridyl­amine)silver(I)]‐μ‐2,6‐di­hydroxy­benzoato]

In catena‐poly­[[(di‐2‐pyridyl­amine‐κ²N,N′)silver(I)]‐μ‐nico­tinato‐κ²N:O], [Ag(C₆H₄NO₂)(C₁₀H₉N₃)]_n, the Ag^I atom is tetracoordinated by two N atoms from the di‐2‐pyridyl­amine (BPA) ligand [Ag—N = 2.3785 (18) and 2.3298 (18) Å] and by one N atom and one carboxyl­ate O atom from nicotinate ligands [Ag—N = 2.2827 (15) Å and Ag—O = 2.3636 (14) Å]. Bridging by nicotinate N and O atoms generates a polymeric chain structure, which extends along [100]. The carboxyl O atom not bonded to the Ag atom takes part in an intrachain C—H⋯O hydrogen bond, further stabilizing the chain. Pairs of chains are linked by N—H⋯O hydrogen bonds to generate ribbons. There are no π–π interactions in this complex. In catena‐poly­[[(di‐2‐pyridyl­amine‐κ²N,N′)silver(I)]‐μ‐2,6‐di­hydroxy­benzoato‐κ²O¹:O²], [Ag(C₇H₅O₄)(C₁₀H₉N₃)]_n, the Ag^I atom has a distorted tetrahedral coordination, with three strong bonds to two pyridine N atoms from the BPA ligand [Ag—N = 2.286 (5) and 2.320 (5) Å] and to one carboxyl­ate O atom from the 2,6‐di­hydroxy­benzoate ligand [Ag—O = 2.222 (4) Å]; the fourth, weaker, Ag‐atom coordination is to one of the phenol O atoms [Ag⋯O = 2.703 (4) Å] of an adjacent moiety, and this interaction generates a polymeric chain along [100]. Pairs of chains are linked about inversion centers by N—H⋯O hydrogen bonds to form ribbons, within which there are π–π interactions. The ribbons are linked about inversion centers by pairs of C—H⋯O hydrogen bonds and additional π–π interactions between inversion‐related pairs of 2,6‐di­hydroxy­benzoate ligands to generate a three‐dimensional network.     

γ‐Modification of poly[(N,N‐diethyl­dithio­carbamato)silver(I)]

In the title compound, catena‐poly[[tri­silver(I)‐tri‐μ₃‐N,N‐diethyl­dithio­carbamato‐3′κS:1κS′:2κS;1κS:2κS′:3κS;2κS:3κ²S,S′:1′κS′], [Ag₃(C₅H₁₀NS₂)₃]_n, the trigonally and tetra­hedrally coordinated Ag atoms are μ₃‐bridged by κ³‐ and κ⁴‐S₂CNEt₂ ligands to form a ribbon structure along the c axis. There is a twofold axis parallel to the b axis and passing through the tetra­hedrally coordinated Ag atom. The S₂CNEt₂ ligands coordinate the Ag atoms in η¹,η²‐ and η²,η²‐fashions, depending on the bridging S atoms. The distances between the trigonal Ag and S atoms are 2.4915 (11)–2.6205 (11) Å, while those between the tetra­hedral Ag and S atoms are 2.5457 (11) and 2.7145 (10) Å. The shortest Ag⋯Ag distance between trigonal Ag atoms is 2.8336 (7) Å, which indicates a weak Ag⋯Ag inter­action, whereas the shortest distance between trigonal and tetra­hedral Ag atoms is 3.463 (6) Å, which is considered as non‐bonding.     

Kristallstrukturen,spektroskopische Charakterisierung und Normalkoordinatenanalyse von (n‐Bu4N)2[M(ECN)4] (M = Pd,Pt; E = S,Se)

Crystal Structures, Spectroscopic Analysis, and Normal Coordinate Analysis of ( n ‐Bu₄N)₂[M(ECN)₄] (M = Pd, Pt; E = S, Se) The reaction of (NH₄)₂[PdCl₄] or K₂[PtCl₄] with KSCN or KSeCN in aqueous solutions yields the complex anions [Pd(SCN)₄]^2–, [Pt(SCN)₄]^2– and [Pt(SeCN)₄]^2–, which are converted into (n‐Bu₄N) salts with (n‐Bu₄N)HSO₄. (n‐Bu₄N)₂[Pd(SeCN)₄] is formed by treatment of (n‐Bu₄N)₂[PdCl₄] with (n‐Bu₄N)SeCN in acetone. X‐ray structure determinations on single crystals of (n‐Bu₄N)₂[Pd(SCN)₄] (monoclinic, space group P2₁/n, a = 13.088(3), b = 12.481(2), c = 13.574(3) Å, β = 91.494(15)°, Z = 2), (n‐Bu₄N)₂[Pd(SeCN)₄] (monoclinic, space group P2₁/n, a = 13.171(2), b = 12.644(2), c = 13.560(2) Å, β = 91.430(11)°, Z = 2) and (n‐Bu₄N)₂[Pt(SeCN)₄] (monoclinic, space group P2₁/n, a = 13.167(2), b = 12.641(1), c = 13.563(2) Å, β = 91.516(18)°, Z = 2) reveal, that the compounds crystallize isotypically and the complex anions are centrosymmetric and approximate planar. In the Raman spectra the metal ligand stretching modes of (n‐Bu₄N)₂[Pd(SCN)₄] ( 1 ) and (n‐Bu₄N)₂[Pt(SCN)₄] ( 3 ) are observed in the range of 260–303 cm^–1 and of (n‐Bu₄N)₂[Pd(SeCN)₄] ( 2 ) and (n‐Bu₄N)₂[Pt(SeCN)₄] ( 4 ) in the range of 171–195 cm^–1. The IR and Raman spectra are assigned by normal coordinate analysis using the molecular parameters of the X‐ray determination. The valence force constants are f_d(PdS) = 1.17, f_d(PdSe) = 1.17, f_d(PtS) = 1.44 and f_d(PtSe) = 1.42 mdyn/Å. The ⁷⁷Se NMR resonances are 23 for 2 , –3 for 4 and the ¹⁹⁵Pt NMR resonances 549 for 3 and 130 ppm for 4 .     

Tris[2‐(1,3‐thiazol‐2‐yl‐κN)‐1H‐benzimidazole‐κN3]zinc(II) dinitrate ethanol hemisolvate monohydrate at 100 K

The Zn^II center in the dicationic complex of the title compound, [Zn(C₁₀H₇N₃S)₃](NO₃)₂·0.5C₂H₅OH·H₂O, is in a distorted octahedral environment with imperfect noncrystallographic C₃ symmetry. Each 2‐(1,3‐thiazol‐2‐yl)‐1H‐benzimidazole ligand coordinates in a bidentate manner, with the Zn—N(imidazole) bond lengths approximately 0.14 Å shorter than the Zn—N(thiazole) bond lengths. Charge‐assisted hydrogen bonds connect cations, anions and water molecules. A lattice void is occupied by an ethanol solvent molecule disordered about a crystallographic inversion center and π‐stacking is observed between one type of symmetry‐related benzene rings.     

Polymeric (3‐amino‐2‐chloropyridine)nitratosilver(I)

In the title compound {alternative name: poly­[silver(I)‐μ‐(3‐­amino‐2‐chloro­pyridine)‐μ‐nitr­ato]}, [Ag(NO₃)(C₅H₅ClN₂)]_n the Ag^I atom is in an irregular AgN₂O₃ geometry, surrounded by one pyridyl N atom [Ag—N 2.283 (5) Å], one amine N atom [Ag—N 2.364 (6) Å] and three O atoms from different nitrate ions [Ag—O 2.510 (6)–2.707 (6) Å]. The Ag ions are bridged by the 3‐amino‐2‐chloro­pyridine ligands into helical chains. Adjacent uniform chiral chains are further interlinked through the NO₃ bridges into an interesting two‐dimensional coordination network in the solid.     

[η6‐1‐Chloro‐2‐(pyrrolidin‐1‐yl)benzene](η5‐cyclopentadienyl)iron(II) hexafluoridophosphate and (η5‐cyclopentadienyl){2‐[η6‐2‐(pyrrolidin‐1‐yl)phenyl]phenol}iron(II) hexafluoridophosphate

In the complex salt [η⁶‐1‐chloro‐2‐(pyrrolidin‐1‐yl)benzene](η⁵‐cyclopentadienyl)iron(II) hexafluoridophosphate, [Fe(C₅H₅)(C₁₀H₁₂ClN)]PF₆, (I), the complexed cyclopentadienyl and benzene rings are almost parallel, with a dihedral angle between their planes of 2.3 (3)°. In a related complex salt, (η⁵‐cyclopentadienyl){2‐[η⁶‐2‐(pyrrolidin‐1‐yl)phenyl]phenol}iron(II) hexafluoridophosphate, [Fe(C₅H₅)(C₁₆H₁₇NO)]PF₆, (II), the analogous angle is 5.4 (1)°. In both complexes, the aromatic C atom bound to the pyrrolidine N atom is located out of the plane defined by the remaining five ring C atoms. The dihedral angles between the plane of these five ring atoms and a plane defined by the N‐bound aromatic C atom and two neighboring C atoms are 9.7 (8) and 5.6 (2)° for (I) and (II), respectively.     

A one‐dimensional silver(I) coordination polymer based on the 2‐[2‐(pyridin‐4‐yl)‐1H‐benzimidazol‐1‐ylmethyl]phenol ligand exhibiting photoluminescence

A one‐dimensional Ag^I coordination complex, catena‐poly[[silver(I)‐μ‐{2‐[2‐(pyridin‐4‐yl)‐1H‐benzimidazol‐1‐ylmethyl]phenol‐κ²N²:N³}] perchlorate monohydrate], {[Ag(C₁₉H₁₅N₃O)]ClO₄·H₂O}_n, was synthesized by the reaction of 2‐[2‐(pyridin‐4‐yl)‐1H‐benzimidazol‐1‐ylmethyl]phenol (L) with silver perchlorate. In the complex, the L ligands are arranged alternately and link Ag^I cations through one benzimidazole N atom and the N atom of the pyridine ring, leading to an extended zigzag chain structure. In addition, the one‐dimensional chains are extended into a three‐dimensional supramolecular architecture via O—H...O hydrogen‐bond interactions and π–π stacking interactions. The complex exhibits photoluminescence in acetonitrile solution, with an emission maximum at 390 nm, and investigation of the thermal stability reveals that the network structure is stable up to 650 K.     

Metallation of Ligands with Biological Activity: Synthesis and X‐ray Characterization of the New Sulfathiazolato Complexes of Gold(I) and Silver(I): [(sulfathiazolato)AuPPh3] and [Ag(sulfathiazolato)]2 (sulfathiazole = N1‐2‐thiazolyl‐sulfanilamide)

Sulfathiazole reacts with [Ph₃PAu(CH₃COO)] in benzene and with Ag(CH₃COO) in methanol giving [(sulfathiazolato)AuPPh₃] ( 1 ) and {[Ag(sulfathiazolato)]₂}_n ( 2 ). While the lattice of 1 contains single molecules with linear N–Au–P bonds, compound 2 performs a polymeric, one‐dimensional assembling of [Ag(sulfathiazolato)]₂ dimers linked through intermolecular Ag···O=S=O interactions along the crystallographic axis b. The silver atoms achieve a tetrahedral configuration through Ag–Ag contacts which measure 2.8427(4) Å, considerably shorter than the normal bonding distance of metallic silver.     

A 1:2 complex of mercury(II) chloride with 1,3‐imidazole‐2‐thione

The Hg atom in the title monomeric complex, di­chloro­bis(3‐imidazolium‐2‐thiol­ato‐S)­mercury(II), [HgCl₂(C₃H₄N₂S)₂], is four‐coordinate having an irregular tetrahedral geometry composed of two Cl atoms [Hg—Cl 2.622 (2) and 2.663 (2) Å] and two thione S atoms [Hg—S 2.445 (2) and 2.462 (2) Å]. The monodentate thione ligand adopts a zwitterionic form and exists as the 3‐imidazolium‐2‐thiol­ate ion. The bond angle S1—Hg—S2 of 130.87 (8)° has the greatest deviation from ideal tetrahedral geometry. Intermolecular hydrogen bonds between two of the four N—H groups and one of the Cl atoms [3.232 (8) and 3.238 (7) Å] stabilize the crystal structure, while the other two N—H groups contribute through the formation of N—H?Cl intramolecular hydrogen bonds with the other Cl atom [3.121 (7) and 3.188 (7) Å].     

Darstellung,Kristallstrukturen, Schwingungsspektren und Normalkoordinatenanalyse von trans‐(n‐Bu4N)2[Pt(ECN)2(ox)2], E = S,Se

Synthesis, Crystal Structure, Vibrational Spectra, and Normal Coordinate Analysis of trans ‐( n ‐Bu₄N)₄[Pt(ECN)₂(ox)₂], E = S, Se By reaction of (n‐Bu₄N)₂[Pt(ox)₂] with (SCN)₂ and (SeCN)₂ in dichloromethane trans‐(n‐Bu₄N)₂[Pt(SCN)₂(ox)₂] ( 1 ) und trans‐(n‐Bu₄N)₂[Pt(SeCN)₂(ox)₂] ( 2 ) are formed. The crystal structures of 1 (triclinic, space group P1, a = 10.219(2), b = 11.329(2), c = 12.010(3) Å, α = 114.108(15), β = 104.797(20), γ = 102.232(20)°, Z = 1) and 2 (triclinic, space group P1, a = 10.288(1), b = 11.332(1), c = 12.048(1) Å, α = 114.391(9), β = 103.071(10), γ = 102.466(12)°, Z = 1) reveal, that the compounds crystallize isotypically with centrosymmetric complex anions. The bond lengths are Pt–S = 2.357, Pt–Se = 2.480 and Pt–O = 2.011 ( 1 ) und 2.006 Å ( 2 ). The oxalato ligands are nearly plane with O–C–C–O torsion angles of 1.7–3.6°. The via S or Se coordinated linear groups are inclined between both oxalato ligands with Pt–E–C angles of 100.4 (E = S) and 97.4° (Se). In the vibrational spectra the PtE stretching vibrations are observed at 299–314 ( 1 ) and 189–200 cm^–1 ( 2 ). The PtO stretching vibrations are coupled with internal vibrations of the oxalato ligands and appear in the range of 400–800 cm^–1. Based on the molecular parameters of the X‐ray determinations the IR and Raman spectra are assigned by normal coordinate analysis. The valence force constants are f_d(PtS) = 1.75, f_d(PtSe) = 1.35 and f_d(PtO) = 2.77 mdyn/Å. The NMR shifts are δ(¹⁹⁵Pt) = 5435.2 ( 1 ), 5373.7 ( 2 ) and δ(⁷⁷Se) = 353.2 ppm with the coupling constant ¹J(SePt) = 37.4 Hz.     

Sulfur‐assisted Chloride and Triphenylphosphine Dissociation of Palladium(II) Complex with Phenyloxythiocarbonyl,PhOC(S), Containing Ligand: X‐Ray Structure of [Pd(PPh3)2{η1‐C(S)OPh}(Cl)]

Treatment of Pd(PPh₃)₄ with phenylchlorothionoformate, PhOC(S)Cl, in dichloromethane at ?20 °C produces the phenyloxythiocarbonyl complex [Pd(PPh₃)₂{η¹‐C(S)OPh}(Cl)], 1 . The ³¹P{¹H} NMR spectrum of 1 shows the dissociation of either the chloride or the triphenylphosphine ligand to form complex [Pd(PPh₃)₂(η²‐SCOPh)][Cl], 2 or the dipalladium complex [Pd(PPh₃)Cl]₂(μ,η²‐SCOPh)₂, 3 . Continuous stirring of the dichloromethane solution of 1 at room temperature for 4 h forms the dipalladinum complex [Pd(PPh₃)Cl]₂(μ,η²‐SCOPh)₂, 3 as the final product. Respective reactions of 1 and Et₂NCS₂Na or dppa {bis(diphenylphosphino)amine} gives complex [Pd(PPh₃){η¹‐C(S)OPh}(η²‐S₂CNEt₂)], 4 or [Pd(PPh₃){η¹‐C(S)OPh}(η²‐dppa)][Cl], 5 . Complex 1 is determined by single‐crystal X‐ray diffraction and crystallized in the monoclinic space group P2₁ with Z = 4. The cell dimensions of 1 are as follows: a = 9.5613(1) Å, b = 33.6732(3) Å, c = 12.2979(1) Å.     

Synthesis and Crystal Structure of [La(phen)2(H2O)2(NO3)2]NO3 · 2(phen)(H2O) with phen = 1,10‐phenanthroline

The title compound [La(phen)₂(H₂O)₂(NO₃)₂](NO₃) · 2(phen)(H₂O) with phen = 1,10‐phenanthroline was prepared by the stoichiometric reaction of La(NO₃)₃ · 6 H₂O and 1,10‐phenanthroline monohydrate in a CH₃OH–H₂O solution. The crystal structure (triclinic, P 1 (no. 2), a = 11.052(2), b = 13.420(2), c = 16.300(2) Å, α = 78.12(1)°, β = 88.77(1)°, γ = 83.03(1)°, Z = 2, R = 0.0488, wR² = 0.1028) consists of [La(phen)₂(H₂O)₂(NO₃)₂]²⁺ complex cations, NO₃^– anions, phen and H₂O molecules. The La atom is 10‐fold coordinated by four N atoms of two bidentate chelating phen ligands and six O atoms of two H₂O molecules and two bidentate chelating NO₃^2– ligands with d(La–O) = 2.522–2.640 Å and d(La–N) = 2.689–2.738 Å. The intermolecular π‐π stacking interactions play an essential role in the formation of two different 2 D layers parallel to (001), which are formed by complex cations and uncoordinating phen molecules, respectively. The uncoordinated NO₃^– anions and H₂O molecules are sandwiched between the cationic and phen layers.     

Synthesis,Characterization, and Crystal Structure of [ReO(Me4tu)4](PF6)3 (tu = thiourea)

A new Re^V oxo complex with tetramethylthiourea, [ReO(Me₄tu)₄](PF₆)₃, has been synthesized by reduction of perrhenate with tin(II) chloride in strongly acidic solution in the presence of excess tetramethylthiourea. The complex has been characterized by elemental analysis and electronic and FTIR spectroscopy. The molecular structure of the compound was determined by X‐ray diffraction methods. The coordination polyhedron is a regular square pyramid with the substituted thiourea sulfur atoms in the equatorial positions [d(Re–S) = 2.339(3) Å] and the oxo ligand located in the summit [d(Re–O) = 1.63(2) Å]. Computational methods were employed to analyze the geometric and electronic structures of tetramethylthiourea and thiourea. Quantum mechanical studies suggest steric hindrance as the reason for the stabilization of the ReO³⁺ center instead of the Re^III one.     

Dinuclear Macrocyclic Quinoline Bridged Mercury and Silver Bis(N‐heterocyclic Carbene) Complexes: Synthesis,Structure, and Spectroscopic Studies

Quinoline bridged imidazolium precursors 5,8‐bis(N‐R‐imidazolylidenylmethylene)quinoline PF₆^– salts [H₂L](PF₆)₂ [R = Me ( 1a ), R = naphthylmethyl ( 1b )] were prepared by quaternization of N‐methylimidazole and N‐naphthylmethylimidazole with 5,8‐bis(bromomethyl)quinoline, respectively. Reaction of the imidazolium ligands 1a and 1b with Hg(OAc)₂ and Ag₂O in acetonitrile gave the macrocyclic transition metal carbene complexes [Hg₂L₂](PF₆)₄ ( 2a and 2b ) and [Ag₂L₂](PF₆)₂ ( 3a and 3b ), respectively. All the N‐heterocyclic carbene complexes were characterized in detail by NMR, ESI‐MS, and elemental analysis. Structures of complexes 2a and 3a were determined by X‐ray diffraction studies. Structural studies revealed that the coordination arrangement of the central mercury atom in complex 2a displays a tricoordinate mode and the molecular conformation results in a“closed” form with the bridging quinoline functionality in the macrocycle, whereas the silver complex 3a does not show an coordiantion between the bridging quinoline and the Ag^I ion, which results in an “open” conformation of the macrocycle. The Hg^II and Ag^I NHC complexes showed similar UV absorption and luminescence in acetonitrile solutions.     

Poly[μ2‐(N‐hydroxypyridine‐2‐carboxamidine)‐μ2‐nitrato‐silver(I)]

In the title complex, [Ag(NO₃)(C₆H₇N₃O)]_n or [Ag(NO₃)(pyaoxH₂)] (pyaoxH₂ is N‐hydroxypyridine‐2‐carboxamidine), the Ag⁺ ion is bridged by the pyaoxH₂ ligands and nitrate anions, giving rise to a two‐dimensional molecular structure. Each pyaoxH₂ ligand coordinates to two Ag⁺ ions using its pyridyl and carboxamidine N atoms, and the OH and the NH₂ groups are uncoordinated. Each nitrate anion uses two O atoms to coordinate to two Ag⁺ ions. The Ag...Ag separation via the pyaoxH₂ bridge is 2.869 (1) Å, markedly shorter than that of 6.452 (1) Åvia the nitrate bridge. The two‐dimensional structure is fishscale‐like, and can be described as pyaoxH₂‐bridged Ag₂ nodes that are further linked by nitrate anions. Hydrogen bonding between the amidine groups and the nitrate O atoms connects adjacent layers into a three‐dimensional network.     

Synthesis,Reactivity, and Crystal Structure of the η2‐Thiocarbamoyl Palladium Complex [Pd(PPh3)2(η2‐SCNMe2)][PF6]

The η¹‐thiocarbamoyl palladium complexes [Pd(PPh₃)(η¹‐SCNMe₂)(η²‐S₂R)] (R = P(OEt)₂, 2 ; CNEt₂, 3 ) and trans‐[Pd(PPh₃)₂(η¹‐SCNMe₂)(η¹‐Spy)], 4 , (pyS: pyridine‐2‐thionate) are prepared by reacting the η²‐thiocarbamoyl palladium complex [Pd(PPh₃)₂(η²‐SCNMe₂)][PF₆], 1 with (EtO)₂PS₂NH₄, Et₂NCS₂Na, and pySK in methanol at room temperature, respectively. Treatment of 1 with dppm (dppm: bis(diphenylphosphino)methane) in dichloromethane at room temperature gives complex [Pd(PPh₃)(η¹‐SCNMe₂)(η²‐dppm)] [PF₆], 5 . All of the complexes are identified by spectroscopic methods and complex 1 is determined by single‐crystal X‐ray diffraction.     

Syntheses and Crystal Structures of Ln(phen)2(NO3)3 with Ln = Pr,Nd, Sm,Eu, Dy,and phen = 1,10‐phenanthroline

Five new complex compounds of the formula Ln(phen)₂(NO₃)₃ were prepared. The X‐ray structural analyses indicate that they crystallize isostructurally in the monoclinic space group C2/c (no. 15) with cell dimensions for example for Pr(phen)₂(NO₃)₃: a = 11.194(1) Å, b = 18.095(2) Å, c = 13.101(2) Å, β = 100.52(1)°, V = 2609.1(6) ų, Z = 4. The crystal structures consist of [Ln(phen)₂(NO₃)₃] complex molecules. The rare earth atoms are coordinated by four N atoms of two phen ligands and six O atoms of three nitrato groups to complete a distorted bicapped dodecahedron. The [Ln(phen)₂(NO₃)₃] complex molecules are assembled via π‐π stacking interactions between the neighboring phen ligands to form 1D columnar chains, which are then arranged in the crystal structures according to pseudo 1D close‐packed patterns.     

Metallkomplexe mit N2O2S2‐Koordinationssphäre. Synthese und Charakterisierung der Cobalt(II)‐, Nickel(II)‐ und Kupfer(II)‐Komplexe eines 15‐ und eines 16‐gliedrigen N,N′‐bis(2‐hydroxyethyl)‐funktionalisierten makrocyclischen Liganden

Metal Complexes with N₂O₂S₂ Donor Set. Synthesis and Characterization of the Cobalt(II), Nickel(II), and Copper(II) Complexes of a 15‐ and a 16‐Membered Bis(2‐hydroxyethyl) Pendant Macrocyclic Ligand The macrocyclic ligands 6, 10‐bis(2‐hydroxyethyl)‐7, 8, 9, 11, 17, 18‐hexahydro‐dibenzo‐[e, n][1, 4, 8, 12]‐dithiadiaza‐cyclopentadecine ( 1 ) (L¹) and 5, 13‐bis(2‐hydroxyethyl)‐7, 8, 9, 10, 16, 17, 18, 19, 20‐nonahydro‐dibenzo‐[g, o][1, 9, 5, 13]‐dithiadiaza‐cyclohexadecine (L⁴) have been prepared. They form the stable complexes [CoL¹(‐H)CoL¹](ClO₄)₃ ( 2 ), [NiL¹](ClO₄)₂·MeOH ( 3 ), Λ‐[CuL¹](ClO₄)₂·MeOH ( 4a ) and rac‐[CuL¹](ClO₄)₂·MeOH ( 4b ), [NiL⁴](ClO₄)₂ ( 5 ), and [CuL⁴](ClO₄)₂ ( 6 ). The compounds 1 to 6 have been characterized by standard methods and single‐crystal X‐ray diffraction. In the complexes 2 to 6 the metal atoms are octahedrally coordinated by the N₂O₂S₂ donor set of the ligands. L¹ and L⁴ are folded herein along the N···M···S‐ and the N···M···N′‐axes, respectively. This results at the metal atom in a all‐cis‐configuration for the complexes of L¹ and a trans‐N₂‐cis‐O₂‐cis‐S₂‐configuration for the complexes of L⁴. The cobalt(II) complex 2 is a dimer, bridged by a rather short hydrogen bridge of 2.402(12)Å length. The copper(II) complexes of L¹ and L⁴ differ with respect to the Jahn‐Teller‐distortion.     

Anion‐directed Silver(I) Coordination Assemblies Based on 1‐(2‐Pyridyl)‐2‐(4‐pyridyl)‐1,2,4‐triazolewith Diverse Supramolecular Networks and Dichromate Removal Capabilities

A series of silver(I) supramolecular complexes, namely, {[Ag(L²⁴)](NO₃)}_n ( 1 ), [Ag₂(L²⁴)(NO₂)₂]_n ( 2 ), and {[Ag_1.25(L²⁴)(DMF)](PF₆)_1.25}_n ( 3 ) were prepared by the reactions of 1‐(2‐pyridyl)‐2‐(4‐pyridyl)‐1,2,4‐triazole (L²⁴) and silver(I) salts with different anions (AgNO₃, AgNO₂, AgPF₆). Single‐crystal X‐ray diffraction indicates that 1 – 3 display diverse supramolecular networks. The structure of dinuclear complex 1 is composed of a six‐membered Ag₂N₄ ring with the Ag ··· Ag distance of 4.4137(3) Å. In complex 2 , the adjacent Ag^I centers are interlinked by L²⁴ ligands into a 1D chain, the adjacent of which are further extended by the bridged nitrites to construct a 2D coordination architecture. Complex 3 shows a 3D (3,4)‐connected framework, which is generated by the linkage of L²⁴ ligands. All complexes were characterized by IR spectra, elemental analysis, and powder X‐ray diffraction. Notably, a structural comparison of the complexes demonstrates that their structures are predominated by the nature of anions. Additionally, 1 and 2 show efficient dichromate (Cr₂O₇^2–) capture in water system, which can be ascribed to the anion‐exchange.