0000000000002551
AUTHOR
Jorunn Sletten
Synthesis crystal structure and magnetic properties of [Fe2(bpym)(C5O5)2(H2O)4]·2H2O and two polymorphs of [Fe2(bpym)(C4O4)2(H2O)6]·2H2O (bpym = 2,2′-bipyrimidine)
Abstract Two dinuclear iron(II) complexes of formulae [Fe2(bpym)(C5O5)2(H2O)4]·2H2O (1) and [Fe2(bpym)(C4O4)2(H2O)6]·2H2O (2) (bpym = 2,2-bipyrimidine, C5O52 = dianion of croconic acid (4,5-dihydroxycylopent-4-ene-1,2,3-trione) and C4O42 = dianion of squaric acid (3,4-dihydroxycyclobut-3-ene-1,2-dione)) were prepared and their crystal structures (at 103 K) determined by X-ray diffraction methods. The structure of 1 consists of neutral centrosymmetric [Fe2(bpym)(C5O5)2(H2O)4] units and water molecules of crystallization which are linked by an extensive network of hydrogen bonds. The coordination geometry around each iron atom is that of a compressed octahedron with bpym nitrogen atoms and cr…
Preparation and structural studies on dibutyltin(IV) complexes with pyridine mono- and dicarboxylic acids
Abstract A number of organotin(IV) complexes with pyridine mono- and dicarboxylic acids (containing ligating –COOH group(s) and aromatic {N} atoms) were prepared in the solid state. The bonding sites of the ligands were determined by means of FT-IR spectroscopic measurements. It was found that in most cases the –COO− groups form bridges between two central {Sn} atoms, thereby leading to polymeric (oligomeric) complexes. On this basis, the experimental 119Sn Mossbauer spectroscopic data were treated with partial quadrupole splitting approximations. The calculations predicted the existence of complexes with octahedral (oh) and trigonal-bipyramidal (tbp) structures, but the formation of comple…
Dithiosquarate (dtsq) complexes of nickel(II). Syntheses and crystal structures of [Ni(phen)2(1,2-dtsq)]·3.5H2O, [Ni(phen)2(1,3-dtsq)] and [Ni(tren)(1,2-dtsq)] [phen=1,10-phenanthroline; tren=tris(2-aminoethyl)amine]
Abstract The new nickel(II) complexes [Ni(phen)2(1,2-dtsq)]·3.5H2O (1), [Ni(phen)2(1,3-dtsq)] (2) and [Ni(tren)(1,2-dtsq)] (3) [1,2-dtsq=dianion of 3,4-dimercapto-3-cyclobutene-1,2-dione, 1,3-dtsq=dianion of 3-hydroxy-4-mercapto-2-thioxo-3-cyclobuten-1-one, phen=1,10-phenanthroline and tren=tris(2-aminoethyl)amine] have been synthesized and characterized by single-crystal X-ray diffraction. Their structures are made up of neutral [Ni(phen)2(1,n-dtsq)] [1 (n=2) and 2 n=3)] and [Ni(tren)(1,2-dtsq)] (3) mononuclear units. The nickel atom is six-coordinated in all three cases: four nitrogen atoms from two bidentate phen (1 and 2) or a tetradentate tren (3) groups and either two sulfur (1 and 3)…
Mono-, di- and trinuclear 2,3,5,6-tetrakis(2-pyridyl)pyrazine (tppz)-containing copper(II) complexes: syntheses, crystal structures and magnetic properties.
Three new copper(ii) complexes of formula [Cu(tppz)(NCO)(2)].0.4H(2)O (1), [Cu(2)(tppz)Br(4)](2) and [Cu(3)(tppz)(C(5)O(5))(3)(H(2)O)(3)].7H(2)O (3)[tppz = 2,3,5,6-tetrakis(2-pyridyl)pyrazine; C(5)O(5)(2-) = croconate, dianion of 4,5-dihydroxycyclopent-4-ene-1,2,3-trione] have been synthesised and structurally characterized by X-ray diffraction methods. The structure of complex is made up of neutral [Cu(tppz)(NCO)(2)] mononuclear units and uncoordinated water molecules. The mononuclear units are grouped by pairs to give a rather short copper-copper distance of 3.9244(4) angstroms. The structure of complex 1 consists of neutral tppz-bridged [Cu(2)(tppz)Br(4)] dinuclear units, the copper-copp…
Iron(III), chromium(III) and cobalt(II) complexes with squarate: Synthesis, crystal structure and magnetic properties
The preparation and variable temperature-magnetic investigation of three squarate-containing complexes of formula [Fe 2 (OH) 2 (C 4 O 4 ) 2 (H 2 O) 4 ]·2H 2 O ( 1 ) [Cr 2 (OH) 2 (C 4 O 4 ) 2 (H 2 O) 4 ]·2H 2 O ( 2 ) and [Co(C 4 O 4 )(H 2 O) 4 ] n ( 3 ) [H 2 C 4 O 4 = 3.4-dihydroxycyclobutene-1,2-dione (squaric acid)] together with the crystal structures of 1 and 3 are reported. Complex 1 contains discrete centrosymmetric [Fe 2 (OH) 2 (C 4 O 4 ) 2 (H 2 O) 4 ] diiron(II) units where the iron pairs are joined by a di-μ-hydroxo bridge and two squarate ligands acting as bridging groups through adjacent oxygen atoms. Two coordinated water molecules in cis position complete the octahedral environ…
Squarate and croconate in designing one- and two-dimensional oxamidato-bridged copper(II) complexes: synthesis, crystal structures and magnetic properties of 〚Cu 2 (apox)(C 4 O 4 )(H 2 O) 2 〛 n · n H 2 O and 〚Cu 4 (apox) 2 (C 5 O 5 ) 2 〛·6 H 2 O
Abstract The reaction of squarate (C4O42–, dianion of 3,4-dihydroxycyclobut-3-ene-1,2-dione) and croconate (C5O52–, dianion of 4,5-dihydroxycyclopent-4-ene-1,2,3-trione) with the dinuclear 〚Cu2(apox)〛2+ copper(II) complex 〚H2apox = N,N’-bis(3-aminopropyl)oxamide〛 in aqueous solution affords the compounds of formula 〚Cu2(apox)(C4O4)(H2O)2〛n·n H2O (1) and 〚Cu4(apox)2(C5O5)2〛·6 H2O (2). Crystals of 1 are monoclinic, space group C2/c, with a = 12.5527(9), b = 7.4161(6), c = 18.5198(12) A, β = 100.578(6)° and Z = 4. Crystals of 2 are triclinic, space group P 1 with a = 9.732(5), b = 9.795(2), c = 10.285(3) A, α = 84.95(2), β = 77.30(3), γ = 85.61(3)° and Z = 1. The structure of complex 1 consist…
Synthesis, X‐ray Crystal Structure and Magnetic Properties of Oxalato‐Bridged Copper( II ) Complexes with 2,3‐Bis(2‐pyridyl)pyrazine, 2,3‐Bis(2‐pyridyl)quinoxaline and 2,2′‐Bipyrazine as Peripheral Ligands
Five oxalate-containing copper(II) complexes of formula [Cu(dpq)(H2O)(ox)]·5H2O (1), [Cu(dpp)(H2O)(ox)]·H2O (2), [Cu(bpz)(ox)]n (3), [Cu2(dpp)2(H2O)2(NO3)2(ox)]·4H2O (4) and [Cu2Cl2(bpz)2(H2O)2(ox)][Cu(bpz)(H2O)2(ox)]·2H2O (5) [dpq = 2,3-bis(2-pyridyl)quinoxaline; dpp = 2,3-bis(2-pyridyl)pyrazine; bpz = 2,2′-bipyrazine; ox = oxalate] were prepared and their structures were determined by X-ray diffraction on single crystals. Complexes 1 and 2 are discrete mononuclear complexes with oxalate and dpq (1)/dpp (2) acting as bidentate ligands. Complex 3 is a neutral oxalato-bridged (2,2′-bipyrazine)copper(II) chain where the oxalate adopts a bidentate/monodentate coordination mode, whereas 4 is an…
Syntheses, crystal structures and magnetic properties of copper(II) polynuclear and dinuclear compounds with 2,3-bis(2-pyridyl)pyrazine (dpp) and pseudohalide as ligands
Abstract The preparation, crystal structures and magnetic properties of four heteroleptic copper(II) complexes with 2,3-bis(2-pyridyl)pyrazine (dpp) and azide, cyanate or thiocyanate as ligands are reported, [Cu(dpp)(N3)2]n (1), [Cu(dpp)(NCO)2]n (2), [Cu(dpp)(NCS)2]2 (3) and [Cu(H2O)(dpp)(NCS)2]2·2H2O (4). Compounds 1 and 2 are isomorphous, triclinic, space group P1, and consist of mononuclear building blocks featuring copper atoms with close to square planar coordination geometries. The mononuclear units are, however, associated into chains through weak axial Cu–N bonds formed by end-on asymmetrically bridging azido/cyanato groups and by pyridyl nitrogen atoms. Taking these contacts into a…
Trans-dicyanobis(acetylacetonato)ruthenate(III) as a precursor to build novel cyanide-bridged RuIII–MII bimetallic compounds [M=Co and Ni]
Abstract The use of the mononuclear complex trans-[Ru(acac)2(CN)2]− as a ligand towards the preformed species [Ni2L(H2O)2Cl2], [Co(dmphen)](NO3)2, [Ni(dmphen)](NO3)2 and [Co(H2O)6](NO3)2 afforded the novel cyanide-bridged bimetallic compounds of formula [{Ru(acac)2(CN)2}{Ni2(L)(H2O)2}]{Ru(acac)2(CN)2}·2H2O (1), [{Ru(acac)2(CN)2}{Co(dmphen)(NO3)}]·H2O (2) and [{Ru(acac)2(CN)2}{Ni(dmphen)(NO3)}]·H2O (3) and [{Ru(acac)2(CN)2}2Co] (4) [Hacac = acetylacetone, dmphen = 2,9-dimethylphenanthroline and H2L = 11,23-dimethyl-3,7,15,19-tetrazatricyclo[19.3.1.19,13]hexacosa-2,7,9,11,13(26),14,19,21(25),22,24-decaene-25,26-diol]. Their syntheses, X-ray crystal structures and magnetic properties are repor…
Synthesis, crystal structure and magnetic properties of the first structurally characterized 1,2-dithiocroconato-containing Cu(II) complex, [Cu(bpca)(H2O)]2[Cu(1,2-dtcr)2]·2H2O
Abstract The first crystal and molecular structure of a transition metal complex containing 1,2-dithiocroconate (1,2-dtcr, dianion of 1,2-dimercaptocylopent-1-ene-3,4,5-trione), [Cu(bpca)(H2O)]2[Cu(1,2-dtcr)2]·2H2O (where bpca is the bis(2-pyrdidylcarbonyl)amide anion), has been determined by single crystal X-ray diffraction methods. The compound crystallizesin the monoclinic syste, space group P21/c, with a = 11.661(3), b = 20.255(6), c = 8.265(3) A , s = 107.26(2)° and Z = 2. The structure is formally built of [Cu(1,2-dtcr)2]2− and [Cu(bpca)(H2O)]+ ions and water of hydration. The copper atom of the anion is situated at a crystallographic inversion centre, bonded to four sulfur atoms in a…
2,3,5,6-Tetrakis(2-pyridyl)pyrazine (tppz)-containing iron(II) complexes: Syntheses and crystal structures
Abstract The preparation and crystal structure of two iron(II) complexes of formula PPh4-mer-[Fe(tppz)(CN)3] · 7H2O (1) and [Fe(tppz)2][Fe(NCS)4] (2) [tppz = 2,3,5,6-tetrakis(2-pyridyl)pyrazine; PPh 4 + = tetraphenylphosphonium cation ] are reported here. The structure of 1 consists of mononuclear mer-tricyano[2,3,5,6-tetrakis(2-pyridyl)pyrazine]ferrate(II) anions, tetraphenylphosphonium cations and crystallization water molecules. Three carbon atoms from three cyanide groups in a mer arrangement and three nitrogen atoms from a tridentate tppz ligand build a somewhat distorted octahedral surrounding around the iron atom in 1. The values of the Fe–C [1.925(6)–1.947(5) A] and Fe–N [1.870(4)–1…
Syntheses, crystal structures and magnetic properties of one- and two-dimensional pap-containing copper(II) complexes (pap = pyrazino[2,3- f ][4,7]phenanthroline)
Three polynuclear complexes containing copper(II) and pyrazino[2,3-f][4,7]phenanthroline (pap) as the basic building blocks have been prepared [Cu2(pap)(H2O)2(NO3)3]n[NO3]n1, [Cu4(pap)4Cl7]nCln·15nH2O 2, and [Cu4(pap)4(H2O)4(C4O4)2]n[C4O4]n[NO3]2n·12nH2O 3, and their crystal structures and variable-temperature magnetic susceptibilities determined. Compound 1 is a single stranded zigzag chain where pap and nitrate alternate as bridges between the copper atoms. The copper coordination geometry is to a first approximation distorted square pyramidal, but with an additional semi-coordinated oxygen from non-bridging nitrate groups. The bridging nitrate coordinates in the apical position to both c…
Syntheses, crystal structures and magnetic properties of polynuclear 1,4,5,8,9,12-hexaazatriphenylene (hat)-bridged copper(II) complexes
Three polynuclear compounds containing copper(II) and 1,4,5,8,9,12-hexaazatriphenylene (hat) as the basic building blocks have been prepared, [Cu4(hat)2Cl8]n·6nH2O 1, [Cu(hat)(H2O)2]n[NO3]2n2, and [Cu2(hat)(H2O)6]n[SO4]2n·2nH2O 3, their crystal structures determined and variable-temperature magnetic susceptibility data measured. The basic building block in 1 is the dinuclear [Cu2(hat)Cl4] entity, two such units being connected to tetranuclear units through relatively strong axial Cu–Cl bonds (out-of-plane di-μ-chloro bridges). Weaker axial Cu⋯Cl interactions link the units into a sheet structure. In 2 and 3 hat-bridged copper(II) chains extending along glide planes are present. hat serves a…
Crystal structures and magnetic properties of the squarate-O1,On-bridged dinuclear copper(II) complexes [Cu2(phen)4(C4O4)](CF3SO3)2 · 3H2O (n=2) and [Cu2(bipy)4(C4O4)](CF3SO3)2 · 6H2O (n=3)
Abstract Two dinuclear copper(II) complexes of the formula [Cu2(phen)4(C4O4)](CF3SO3)2 · 3H2O (1) and [Cu2(bipy)4(C4O4)](CF3SO3)2 · 6H2O (2) [phen=1,10-phenanthroline, bipy=2,2′-bipyridine and C4O4 2−=dianion of 3,4-dihydroxy-3-cyclobuten-1,2-dione (squaric acid)] have been synthesized and characterized by single-crystal X-ray diffraction. Their structures consist of [Cu2(phen)4(C4O4)]2+ (1) and [Cu2(bipy)4(C4O4)]2+ (2) dinuclear copper(II) cations, uncoordinated CF3SO3 − anions and crystallization water molecules. The copper is in a distorted square pyramidal environment: one squarate-oxygen atom and three phen- (1) or bipy- (2) nitrogen atoms of two phen (1) or bipy (2) terminal ligands f…
Solid state polymerization causing transition to a ferromagnetic state. Crystal structures and magnetic properties of [Cu2(dpp)(H2O)(dmso)Cl4]·dmso and [Cu2(dpp)Cl4]n (dpp = 2,3-bis(2-pyridyl)pyrazine)
The preparation, crystal structures and variable-temperature magnetic susceptibility data for [Cu2(dpp)(H2O)(dmso)Cl4]·dmso (1a) and [Cu2(dpp)Cl4]n (2) (dpp = 2,3-bis(2-pyridyl)pyrazine, dmso = dimethyl sulfoxide) are reported. 1a consists of dinuclear dpp-bridged molecules with chlorine, water and dmso serving as terminal ligands. The two copper atoms are crystallographically independent, with distorted square pyramidal and trigonal bipyramidal coordination geometries, respectively. In a first approximation 2 may be described as a chain compound with out-of-plane mono-μ-chloro bridges (Cu–Cl–Cu–Cl). Only one of the crystallographically independent copper atoms participates in this chain fo…
Preparation, crystal structure and magnetic properties of di-2-pyridylamine (dpa) copper(II) complexes [Cu(dpa)(N3)2]n and [Cu2(dpa)2(NCO)4]
Abstract The preparation, crystal structures and magnetic properties of two copper(II) complexes with di-2-pyridylamine (dpa) as end-cap ligand and azide (1) and cyanate (2) as bridging groups, [Cu(dpa)(N3)2]n (1) and [Cu2(dpa)2(NCO)4] (2), are reported. Compound 1 consists of uniform chains of copper(II) ions bridged by single μ-1,1-azido groups whereas that of compound 2 is made up of centrosymmetric dicopper(II) units with double μ-1,1-N-cyanate bridges, the other two cyanate groups acting as terminal ligands. The copper atoms in 1 and 2 are five-coordinated with two nitrogen atoms of a bidentate dpa ligand (1 and 2), one nitrogen atom from a terminally bound azide (1)/cyanate (2) and tw…
Copper(II) complexes of 1,4,5,8,9,12-hexaazatriphenylene with oxalate, squarate, perchlorate as auxiliary ligands or counter ion
Abstract The crystal structures of [Cu(hat)(H2O)(ox)]·H2O (I), [Cu(hat)(H2O)3(sq)]·3H2O (II) and [Cu(hat)(H2O)2](ClO4)2·4H2O (III) have been determined from X-ray single crystal diffraction data (hat=1,4,5,8,9,12-hexaazatriphenylene, ox=oxalate, sq=squarate=dianion of 3,4-dihydroxy-cyclobut-3-ene-1,2-dione). Compound I crystallises in the triclinic system, space group P 1 with a=6.6626(10), b=9.2001(14), c=12.9954(19) A , α=103.301(15), β=91.414(21), γ=105.523(13)°, Z=2; compound II in the orthorhombic system, space group P212121 with a=6.9274(2), b=8.4327(3), c=34.0577(14) A , Z=4; and compound III in the monoclinic system, space group C2/c with a=22.6652(10), b=9.2220(10), c=16.1400(10) A…
Cu(II) and Cu(I) complexes with 1,2-dithiosquarate as a ligand; from molecular compounds to supramolecular network structures
Abstract Four new complexes of copper(II) and/or copper(I) with 1,2-dtsq as a ligand have been synthesized and characterized by single crystal X-ray diffraction methods, [CuII(terpy)(1,2-dtsq)] (1), [CuII(dmen)(1,2-dtsq)]n (2), {[CuII(dmen)2][CuI(1,2-dtsq)]2}n·2nH2O(3) and {[CuII(men)2][CuI (1,2-dtsq)]2}n·nH2O (4) (1,2-dtsq = 1,2-dithiosquarate, dianion of 3,4-dimercapto-1-cyclobutene-1,2-dione; dmen = N,N-dimethylethylenediamine; men = N-methylethylenediamine, terpy = 2,2′:6,2″-terpyridine). Compound 1 consists of neutral [CuII(terpy)(1,2-dtsq)] mononuclear units which are held together by O⋯H–C and van der Waals interactions. Compound 2 is built of neutral [CuII(dmen)(1,2-dtsq)] entities …
Manganese(II) complexes with croconate and 2-(2-pyridyl)imidazole ligands: Syntheses, X-ray structures and magnetic properties
Abstract The mixed-ligand complexes of manganese(II) of formula [Mn(pyim)2(C5O5)] (1) and [Mn(pyim)(H2O)(C5O5)]n · 2.5nH2O (2) [pyim = 2-(2-pyridyl)imidazole and C 5 O 5 2 - = croconate (dianion of 4,5-dihydroxy-4-cyclopentene-1,2,3-trione)] have been prepared and their structures determined by X-ray crystallographic methods. Compound 1 is a tris-chelated mononuclear complex where the manganese atom is six-coordinate: four nitrogen atoms from two pyim molecules and two oxygen atoms from a croconate group build a somewhat distorted octahedral surrounding around the metal atom. The resulting neutral mononuclear units are linked to each other through double bridges which are constituted by th…
Three one-dimensional systems with end-to-end dicyanamide bridges between copper(ii) centres: structural and magnetic properties
The preparation, crystal structures and magnetic properties of three different copper(II) chains of formula [Cu(pyim)(H2O)(dca)]n(NO3)n (1), [Cu(dpa)(dca)2]n (2) and [Cu(bpa)(dca)2]n (3) [pyim = 2-(2-pyridyl)imidazole, dca = dicyanamide anion, dpa = 2,2′-dipyridylamine and bpa = 1,2-bis(4-pyridyl)ethane] are reported. A chain structure with single, symmetrical, end-to-end dca bridges is found in compound 1. This bridging mode, with two short, equatorially coordinated Cu–N bonds has not been previously observed in the [Cu(dca)Xn] (X = coligand) family of compounds. The copper atom in 1 has a distorted square pyramidal geometry with a bidentate pyim ligand and two nitrile nitrogen atoms from …
Hydrogen-bonded 2-(2-pyridyl)imidazole (pyim) manganese(II) complexes as building blocks for molecular assembling: Syntheses and structural characterization of cis-[Mn(pyim)2X2] compounds (X=, NCO− and NCS−)
Abstract The preparation and crystal structures of three new manganese(II) complexes with 2-(2-pyridyl)imidazole (pyim) and pseudohalides as ligands, cis-[Mn(pyim)2(N3)2] (1), cis-[Mn(pyim)2(NCO)2] (2) and cis-[Mn(pyim)2(NCS)2] (3), are reported. The structural building block in each structure is a mononuclear, neutral complex unit. The metal ion in each case adopts a distorted octahedral coordination geometry with the two pseudohalide ligands in cis positions. The main differences between the molecular structures of the three compounds are associated with the orientation of the anionic ligands. Hydrogen bonds between imidazole N–H and the metal-coordinated nitrogen atom of the pseudohalide…
Synthesis, spectroscopic and structural characterization of [Cu(phen)(C5O5)(H2O)]·H2O, [Ni(terpy)(C5O5)(H2O)]·H2O and [Ni(terpy)2](NO3)2·0.5H2O
Abstract The new mononuclear complexes [Cu(phen)(C5O5)(H2O)]·H2O (1), [Ni(terpy)(C5O5)(H2O)]·H2O (2) and [Ni(terpy)2](NO3)2·0.5H2O (3) [phen=1,10-phenanthroline, C 5 O 5 2 − =dianion of the 4,5-dihydroxycyclopent-4-ene-1,2,3-trione and terpy=2,2′:6′,2″-terpyridine] have been synthesized and characterized by single-crystal X-ray diffraction. The copper atom of 1 has a distorted square pyramidal environment with two phen-nitrogen and two croconate-oxygen atoms building the equatorial plane and a water molecule in the apical position. The nickel atom of 2 exhibits a distorted NiN3O3 octahedral coordination, which may be described either as tetragonally compressed or as skewed trapezoidal bipyr…
Syntheses, crystal structures and magnetic properties of dinuclear copper(II) complexes with pyrazino[2,3-f ][4,7]phenanthroline (pap) as bridging ligand
Three dinuclear copper(II) complexes with pyrazino[2,3-f][4,7]phenanthroline (pap) as bridging ligand have been prepared; [Cu2(pap)(C2O4)2]·5H2O 1, [Cu2(pap)(H2O)7(SO4)]SO4·3H2O 2 and [Cu2(pap)(H2O)3(NO3)3]NO33. These are the first metal complexes of pap which have been characterized by X-ray crystallography and magnetic susceptibility measurements. In 1 the dinuclear complex is intercepted by a mirror plane; the bridging pap and the terminal oxalate ligands are bidentate in the equatorial plane of copper. In addition copper has weak axial interactions to oxygen atoms of oxalate in two neighbouring molecules. In 2 the two crystallograpically independent copper atoms are both six-co-ordinate…
Chains and channels in polynuclear copper(II) complexes with 2,3-bis(2-pyridyl)pyrazine (dpp) as bridging ligand; syntheses, crystal structures and magnetic properties
Abstract The preparation and crystal structures for three Cu(II) polynuclear, chain complexes with 2,3-bis(2-pyridyl)pyrazine (dpp) as bridging ligand are reported, [Cu(dpp)(H2O)2]n(NO3)2n·2n/3H2O (1), [Cu(dpp)(H2O)2]n(CF3SO3)2n (2), and [Cu(dpp)(H2O)2]n(BF4)2n·2nH2O (3). For the latter compound the crystal structure at four different temperatures have been studied. Variable-temperature magnetic susceptibility data and ESR measurements of 1–3 and of the related copper(II) chain [Cu(dpp)(H2O)2]n(ClO4)2n·2nH2O (4) (whose structure was previously reported) have been performed. Compounds 1 and 2 crystallize in the same trigonal space group, R 3 c; 3 is orthorhombic, space group Pbca. Complexes …
Preparation, crystal structures and magnetic properties of three thiocyanato-bridged copper(II) complexes with 2,2′-biimidazole or 2-(2′-pyridyl)imidazole as terminal ligands
The synthesis, crystal structures and variable temperature magnetic investigation of three new thiocyanato-bridged copper(II) complexes with 2,2′-biimidazole (H2bim) or 2-(2′-pyridyl)imidazole) (pyim) as coligands, {[Cu(H2bim)2][Cu(H2bim)(NCS)2(SCN)0.6667(NO3)0.3333]2} · 2H2O (1), [Cu(H2bim)(NCS)2]n (2) and [Cu(pyim)(NCS)2]n (3) are reported. Complex 1 contains centrosymmetric trinuclear species where central [Cu(2)(H2biim)2]2+ cations and peripheral [Cu(1)(H2biim)(NCS)2(SCN)]− anions are linked through single end-to-end thiocyanato bridges. Complexes 2 and 3 are made up of neutral zigzag chains of copper(II) ions linked by single (2) and double (3) end-to-end thiocyanato bridges. A bidenta…
Structural analysis and magnetic properties of the copper(II) dicyanamide complexes [Cu2(dmphen)2(dca)4], [Cu(dmphen)(dca)(NO3)] and [Cu(4,4′-dmbpy)(H2O)(dca)2] (dca=dicyanamide; dmphen=2,9-dimethyl-1,10-phenanthroline; 4,4′-dmbpy=4,4′-dimethyl-2,2′-bipyridine)
Abstract The preparation, crystal structures and magnetic properties of three copper(II) compounds of formulae [Cu2(dmphen)2(dca)4] (1), [Cu(dmphen)(dca)(NO3)]n (2) and [Cu(4,4′-dmbpy)(H2O)(dca)2] (3) (dmphen=2,9-dimethyl-1,10-phenanthroline, dca=dicyanamide and 4,4′-dmbpy=4,4′-dimethyl-2,2′-bipyridine) are reported. The structure of 1 consists of discrete copper(II) dinuclear units with double end-to-end dca bridges whereas that of 2 is made up of neutral uniform copper(II) chains with a single symmetrical end-to-end dca bridge. Each copper atom in 1 and 2 is in a distorted square pyramidal environment: two (1) or one (2) nitrile-nitrogen atoms from bridging dca groups, one of the nitrogen…
Syntheses, crystal structures and magnetic properties of di- and trinuclear croconato-bridged copper(ii) complexes
The new croconato-bridged copper(II) compounds [Cu2(terpy)2(H2O)2(C5O5)](NO3)2·H2O (1) and [Cu3(phen)5(C5O5)2](CF3SO3)2 (2) (C5O52− = croconate, dianion of 4,5-dihydroxycyclopent-4-ene-1,2,3-trione; terpy = 2,2′:6′,2″-terpyridine; phen = 1,10-phenanthroline) have been prepared, and their crystal structures and variable temperature magnetic susceptibilities determined. The structure of complex 1 consists of croconato-bridged dinuclear [Cu2(terpy)2(H2O)2(C5O5)]2+ complex ions, nitrate counter ions and water of hydration. The croconato ligand exhibits an asymmetrical bis-bidentate coordination mode through four of its five oxygen atoms. The two crystallographically independent copper atoms hav…
Syntheses, crystal structures and magnetic properties of new oxalato-, croconato- and squarato-containing copper(ii) complexesElectronic supplementary information (ESI) available: Stereoview of the structure of compound 2 (Fig. S1) and X-ray data as described in the text. See http://www.rsc.org/suppdata/nj/b3/b301212n/
The preparation and magnetic investigation of five mononuclear copper(II) complexes of formula [Cu(pyim)(C2O4)(H2O)]·2H2O (1), [Cu(pyim)(C4O4)(H2O)2]·2H2O (2), Cu(pyim)(C5O5)·2.5H2O (3), [Cu(H2bim)(C2O4)(H2O)]·H2O (4) and [Cu(bpz)(C5O5)(H2O)] (5) [pyim=2-(2-pyridyl)imidazole, H2bim=2,2′-biimidazole, bpz=2,2′-bipyrazine, C2O42−=dianion of oxalic acid, C4O42−=dianion of squaric acid and C5O52−=dianion of croconic acid] are reported. The crystal structures of 1, 2, 4 and 5 have been determined. The copper atom has a distorted square pyramidal geometry in this family of complexes: two nitrogen atoms from the bidentate nitrogen donor [pyim (1 and 2), H2bim (4) and bpz (5)] and two oxygen atoms e…
Syntheses, crystal structures and magnetic properties of copper(ii) dicyanamide complexes; dinuclear, chain and ladder compounds
The preparation, crystal structures and magnetic properties of three heteroleptic copper(II) complexes with dicyanamide (dca) bridges, [Cu(bpca)(H2O)(dca)]2 (1) (bpca = bis(2-pyridylcarbonyl)amidate), [Cu(bpy)(dca)2]n (2) (bpy = 2,2′-bipyridine), [Cu2(bpm)(dca)4]n (3) (bpm = 2,2′-bipyrimidine) are reported. In addition, magnetic susceptibility measurements of the sheetlike polymer [Cu(phen)(dca)2] (4) (phen = 1,10-phenanthroline), structurally characterized previously, have been performed. In complex 1 pairs of mononuclear structural building blocks, [Cu(bpca)(dca)(H2O)], are loosely connected through a 1,3-dca bridge in which nitrile is equatorially bound and the amide is semi-coordinated …
Syntheses, crystal structures and magnetic properties of chromato-, sulfato-, and oxalato-bridged dinuclear copper(II) complexes
Abstract Four dinuclear copper(II) complexes of formula [Cu2(bpca)2(H2O)3(CrO4)]·H2O (1), [Cu2(bpca)2(H2O)3(SO4)]·H2O (2), [Cu2(bpca)2(H2O)2(C2O4)]·2H2O (3), and [Cu2(bpca)2(C2O4)] (4) [bpca=bis(2-pyridylcarbonyl)amide anion] have been synthesized and their magnetic behavior has been investigated as a function of temperature. The structures of 1–3 have been determined by single-crystal X-ray diffraction, whereas the structure of 4 was already known. The structures of this family of complexes are made up of neutral chromateO1,O1′ (1), sulfateO1,O1′ (2) and oxalateO1,O2:O1′,O2′-bridged (3 and 4) dinuclear copper(II) units. The two copper atoms within the dinuclear unit of the isomorphous c…