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1.
The title compound, aqua­chloro{2,2′‐[1,2‐ethanediyl­bis­(nitrilo­methyl­idyne)]­diphenolato‐κ4O,N,N′,O′}manganese(III),[MnCl(C16H14N2O2)(H2O)], is a neutral manganese(III) complex with a pseudo‐octahedral metal centre. The equatorial plane comprises the four donor atoms of the tetradentate Schiff base ligand [Mn—O 1.886 (4) and 1.893 (4) Å, and Mn—N 1.978 (5) and 1.982 (5) Å], with a water mol­ecule [Mn—O 2.383 (4) Å] and a Cl? ligand [Mn—Cl 2.4680 (16) Å] completing the coordination sphere. The distorted geometry is highlighted by the marked displacement of the MnIII ion out of the least‐squares plane of the four Schiff base donor atoms by 0.165 (2) Å. These monomeric MnIII centres are then linked into a polymeric array via hydrogen bonds between the coordinated water mol­ecule and the phenolic O‐atom donors of an adjacent MnIII centre [O—H?O 2.789 (5) and 2.881 (5) Å].  相似文献   

2.
A new dinuclear manganese complex, [Mn2L2(N3)2], was prepared by reaction of bis-Schiff base N,N'-bis(5-fluoro-2-hydroxybenzylidene)ethane-1,2-diamine (H2L) with manganese acetate and sodium azide in methanol. Both the Schiff base and the complex were characterized by physico-chemical methods and single crystal X-ray determination. The Schiff base crystallized in the orthorhombic space group Pbca with unit cell dimensions a?=?7.3191(7)?Å, b?=?6.0948(6)?Å, c?=?35.382(3)?Å, V?=?1578.3(3)?Å3, Z?=?4, R1?=?0.0481, wR2?=?0.1488. The manganese complex crystallized in the monoclinic space group P21/c with unit cell dimensions a?=?8.802(1)?Å, b?=?14.928(2)?Å, c?=?14.478(2)?Å, β?=?105.517(2)°, V?=?1833.0(4)?Å3, Z?=?2, R1?=?0.0768, wR2?=?0.1640. There are crystallographic inversion centers in both the ligand and the complex. The ligand coordinates to Mn through all the phenolate oxygens and imino nitrogens. The two Mn in the complex are bridged by two phenolate oxygens with separation of 3.549(1)?Å. Each Mn is octahedral with four donors of the Schiff base ligand defining the equatorial plane, and with one azido nitrogen and one phenolate oxygen of an adjacent Schiff base ligand occupying the axial positions. The Schiff base and the complex were tested in vitro for their antibacterial activities.  相似文献   

3.
Two manganese(II) bipyridine carboxylate complexes, [(bipy)2MnII(μ‐C2H5CO2)2MnII(bipy)2}2](ClO4)2 ( 1 ), and [MnII(ClCH2CO2)(H2O)(bipy)2]ClO4 · H2O ( 2 ) were prepared. 1 crystallizes in the triclinic space group P 1 with a = 8.604(3), b = 12.062(3), c = 13.471(3) Å, α = 112.47(2), β = 93.86(2), γ = 92.87(3)°, V = 1211.1(6) Å3 and Z = 1. In the dimeric, cationic complex with a crystallographic center of symmetry two 2,2′‐bipyridine molecules chelate each manganese atom. These two metal fragments are then bridged by two propionato groups in a syn‐anti conformation. The Mn…Mn distance is 4.653 Å. 2 crystallizes in the monoclinic space group P21/c with a = 9.042(1), b = 13.891(1), c = 21.022(3) Å, β = 102.00(1)°, V = 2569.3(5) Å3 and Z = 4. 2  is a monomeric cationic complex in which two bipyridine ligands chelate the manganese atom in a cis fashion. A chloroacetato and an aqua ligand complete the six‐coordination. Only in 2 is the intermolecular packing controlled by weak π‐stacking besides C–H…π contacts between the bipyridine ligands.  相似文献   

4.
Crystal and molecular structures of the planar neutral ligand, C26H16N8, and the four isomorphous five-coordinated metal complexes, [M(C26H16N8)(H2O)], M = Mn(II), Co(II), Cu(II), Zn(II), have been determined from three-dimensional X-ray diffraction data. The free ligand hpH2, C26H16N8, belongs to the P 21/c space group with Z=2, a=4.142(3), b=23.736(6), c=10.338(3) Ä, β=94.66(6)°. The metal complexes monohydrate Mhp-H2O all belong to the orthorhombic Pcab space group with Z=8. The dimensions are roughly 8.8×19.3×23.7 Å3. In each structure, the macrocyclic ligand has an almost planar conformation which differs from the saddle shaped ligand hydrate (hpH2·H2O) and the nickel complex [Nihp]5. The distances from the center of the macrocyclic ring to the nitrogen atom of the free ligand are 1.907(6) and 2.245(6)Å. The coordination geometry in these four complexes is square pyramidal with a water molecule as an axial ligand. The bond distances of M(II)-O(H2O), M(II)-N1 (imine), M(II)-N3 (pyridine) are: 2.19(1), 2.00(2), 2.27(2)Å respectively for the manganese complex; 2.08(1), 1.97(1), 2.23(1)Å for the cobalt complex; 2.33(1), 1.92(3), 2.18(1)Å for the copper complex; 2.110(5), 1.964(6), 2.252(6)Å for the zinc complex. The variation of metal-ligand distances can be correlated to the metal d orbital occupancy. A comparison with similar ligands will be presented.  相似文献   

5.
In the first title salt, [Cu(C12H8N2)2(C5H10N2Se)](ClO4)2, the CuII 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 CuII 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.  相似文献   

6.
A novel one-dimensional (1D) chain coordination polymer [Mn2(2,2′-dipha)2(phen)]n has been synthesized by hydrothermal reaction, and characterized by elemental analysis, IR spectroscopy, TGA, and X-ray diffraction. Orange crystals crystallized in the monoclinic system, space group C2/c with a = 19.393(7) Å, b = 19.183(7) Å, c = 19.729(7) Å, β = 90.826(6)°, V = 7338(5) Å3, Z = 8. In the crystal structure, one manganese atom is six-coordinated with four carboxylate oxygen atoms from one pentadentate 2,2′-dipha ligand and two tetradentate 2,2′-dipha ligands, and with two nitrogen atoms of one phen ligand, giving a slightly distorted octahedral geometry. The other manganese atom is five-coordinated with five oxygen atoms from two tetradentate 2,2′-dipha ligands and two pentadentate 2,2′-dipha ligands and has a trigonal bipyramidal environment. The TGA curve shows that the compound is stable below 310°.  相似文献   

7.
A Cu(II) complex of 2-benzylmercapto-5-methyl-1,3,4-thiadiazole was synthesized and characterized. The crystal structure of the copper complex and the free ligand were determined by single-crystal X-ray diffraction at room temperature: {[Cu(C10H10N2S2)2(Cl)2], P 1 triclinic, a = 8.1450(2) Å, b = 8.1690(2) Å, c = 10.8180(3) Å, α = 97.4040(12)°, β = 101.6270(11)°, γ = 116.1431(14)°; C10H10N2S2 ligand, Pbca orthorhombic, a = 8.7938(7) Å, b = 9.6491(7) Å, c = 25.3552(18) Å}. The metal complex framework consists of discrete units that provide crystalline stability through a network of van der Waals contacts. The Cu(II) is coordinated by two chloride ions and two 2-benzylmercapto-5-methyl-1,3,4-thiadiazole monodentate ligands showing a distorted square planar configuration. Both thiadiazole ligands coordinate through the N atom bonded to the benzylthio substituted C atom.

The FTIR spectroscopic data are consistent with this structural model. Analysis of the magnetic susceptibility from 5 K to room temperature indicates the presence of paramagnetic Cu(II), confirmed by the EPR spectrum.  相似文献   

8.
The synthesis and characterization of the first unique binuclear manganese(I) salicylate complex is described. The structure of the complex is unequivocally established with the help of an X-ray crystallographic study. The structure consists of two [MnO6] units, containing octahedral MnI ions, linked together by a bridging salicylato (Hsal) ligand and each MnI is chelated with a (H2sal) ligand. The complex possesses a metal oxidation state of +1 and is a rare example of a noncarbonyl or cyanide complex of a binuclear MnI species. The effective magnetic moment per binuclear molecule (μeff. at 27 °C is 8.07 μb, that also describes the manganese (+1) oxidation state.  相似文献   

9.
New azido-bridged [MnIII(salabza)(μ-1,3-N3)]n (1), and [CuII4(salabza)2(μ-1,1-N3)2(N3)2(HOCH3)2],(2) complexes with an unsymmetrical Schiff base ligand, {H2salabza = N,N’-bis(salicylidene)-2-aminobenzylamine}, have been synthesized, characterized by spectroscopic and electrochemical methods, and their crystal structures have been determined by X-ray diffraction. In complex 1, each manganese(III) atom is coordinated with N2O2 donor atoms from salabza and two adjacent Mn(III) centers are linked by an end-to-end (EE) azide bridge to form a helical polymeric chain with octahedral geometry around the Mn(III) centers. Complex 2 is a centrosymmetric tetranuclear compound containing two types of Cu(II) centers with square pyramidal geometry. Each terminal copper atom is surrounded by N2O2 atoms of a salabza ligand, and the oxygen atom of the methanol molecule. Each central copper(II) ion is coordinated with two phenoxo oxygen atoms from one salabza, one terminal azido, and two end-on (EO) bridging azido ligands. The central copper(II) ions are linked to each other by the two end-on (EO) azido groups.  相似文献   

10.
In the title one‐dimensional complex, {[MnIII(C9H10NO2)2]Cl}n, the Schiff base ligand 2‐[(2‐hydroxy­ethyl)­imino­methyl]­phenolate (Hsae) functions as both a bridging and a chelating ligand. The MnIII ion is six‐coordinated by two N and four O atoms from four different Hsae ligands, yielding a distorted MnO4N2 octahedral environment. Each [MnIII(Hsae)2]+ cationic unit has the Mn atom on an inversion centre and each [MnIII(Hsae)2]+ cation lies about another inversion centre. The chain‐like complex is further extended into a three‐dimensional network structure through Cl⋯H—O hydrogen bonds and C—H⋯π contacts involving the Hsae rings.  相似文献   

11.
Contributions on the Bonding Behaviour of Oxygen in Inorganic Solids. III [1] Mn2P2O7, Mn2P4O12 und Mn2Si(P2O7)2 — Crystal Growth, Structure Refinements and Electronic Spectra of Manganese(II) Phosphates By chemical vapour transport reactions in a temperature gradient single crystals of Mn2P2O7 (1050 → 950 °C) and Mn2P4O12 (850 → 750 °C) have been obtained using P/I mixtures as transport agent. Mn2Si(P2O7)2 was crystallized by isothermal heating (850 °C, 8d; NH4Cl as mineralizer) of Mn2P4O12 und SiO2. In Mn2Si(P2O7)2 [C 2/c, a = 17.072(1)Å, b = 5.0450(4)Å, c = 12.3880(9)Å, β = 103.55(9)°, 1052 independent reflections, 97 variables, R1 = 0.023, wR2 = 0.061] the Mn2+ ions show compressed octahedral coordination (d¯Mn—O = 2.19Å). The mean distance d¯Mn—O = 2.18Å was found for the radially distorted octahedra [MnO6] in Mn2P4O12 [C 2/c, Z = 4, a = 12.065(1)Å, b = 8.468(1)Å, c = 10.170(1)Å, β = 119.29(1)°, 2811 independent reflections, 85 variables, R1 = 0.025, wR2 = 0.072]. Powder reflectance spectra of the three pink coloured manganese(II) phosphates have been measured. The spectra show clearly the influence of the low‐symmetry ligand fields around Mn2+. Observed d—d electronic transition energies and the results of calculations within the framework of the angular overlap model (AOM) are in good agreement. Bonding parameters for the manganese‐oxygen interaction in [Mn2+O6] chromophors as obtained from the AOM treatment (B, C, Trees correction α, eσ, eπ) are discussed.  相似文献   

12.
The title complex salt, (C16H36N)[MnBr(C32H16N8)] or (TBA)[MnIIBr(Pc)] (TBA is tetrabutylammonium and Pc is phthalocyaninate), has been obtained as single crystals by the diffusion technique and its crystal structure was determined using X‐ray diffraction. The high‐spin (S = ) [MnIIBr(Pc)] macrocycle has a concave conformation, with an average equatorial Mn—N(Pc) bond length of 2.1187 (19) Å, an axial Mn—Br bond length of 2.5493 (7) Å and with the MnII cation displaced out of the 24‐atom Pc plane by 0.894 (2) Å. The geometry of the MnIIN4 fragment in [MnIIBr(Pc)] is similar to that of the high‐spin (S = ) manganese(II) tetraphenylporphyrin (TPP) in [MnII(1‐MeIm)(TPP)] (1‐MeIm is 1‐methylimidazole).  相似文献   

13.
A seven-coordinate manganese(II) complex with the tripod tetradentate ligand tris(N-methylbenzimidazol-2-ylmethyl)amine (Mentb), [Mn(Mentb)(salicylate)(DMF)](ClO4) ? (DMF), was synthesized and characterized by elemental, electrical conductivity, infrared, and UV-Vis spectral measurements. The crystal structure of the complex has been determined by single-crystal X-ray diffraction. MnII is bonded to a Mentb, a salicylate and dimethylformamide through four nitrogens and three oxygens, resulting in seven-coordination. Cyclic voltammograms of the complex indicate a quasi-reversible Mn3+/Mn2+ couple. The X-band electron paramagnetic resonance spectrum exhibits a six-line manganese hyperfine pattern with g = 2, A = 93, confirming that the material is high-spin Mn(II).  相似文献   

14.
The tetranuclear manganese(II) complex [Mn4(ppi)6](BPh4)2 ( 2 ) (Hppi = 2‐pyridylmethyl‐2‐hydroxy phenylimine) is prepared by using the precursor complex [Mn(ppi)2]·H2O ( 1 ). Based on UV/Vis‐ and IR‐spectroscopy data in combination with mass spectrometry it has been concluded that 1 is a mononuclear neutral MnII complex, in which two ppi ligands chelate the manganese atom. Compound 2 crystallizes in the triclinic space group P1¯ (no. 2), with a = 17.500(3), b = 17.955(4), c = 19.101(4) Å, α = 113.79(3)°, β = 111.33(3)°, γ = 93.91(3)°, V = 4950(2) Å3 and Z = 2. In the tetranuclear [Mn4(ppi)6]2+ complex cation Mn(1), Mn(2), and Mn(3) are equivalently coordinated by two deprotonated Hppi ligands leading to a N4O2 donor set. The environment of the central Mn(4) is formed by coordination of three [Mn(ppi)2] fragments resulting in a phenoxo bridged star‐shaped Mn4O6 core motif. The average distance of directly adjacent manganese ions is 3.310 Å, whereas the average distance of Mn(1), Mn(2), and Mn(3) among each other is 5.732 Å.  相似文献   

15.
A new two-dimensional polymeric copper(II) complex, [Cu2(heae)(N3)2] n , where heae stands for the dianion of N,N′-bis(N-hydroxyethylaminoethyl)oxamide, has been synthesized and characterized by elemental analysis, molar conductivity measurement, IR, electronic spectral studies and single-crystal X-ray diffraction. The compound crystallizes in the monoclinic system, P21/c space group with crystallographic data: a = 9.1588(18) Å, b = 6.6238(13) Å, c = 14.602(3) Å and Z = 2. The X-ray analysis reveals a two-dimensional copper(II) polymeric coordination network constructed by bis-tridentate chelated [Cu(trans-heae)Cu]2+ building blocks and end-on azido ligands. The environment around the copper(II) atom can be described as a square-based pyramid. The azido bridge is very asymmetric with one Cu–N bond distance short and the other long. The Cu ··· Cu separations through μ-trans-oxamidate and μ-azido bridges are 5.2996(13) Å and 4.2464(7) Å, respectively. The copper(II) complex is a polymer in the solid state, whereas in solution it exists as discrete neutral binuclear copper(II) species. Coordination mode of the azide in solution is proved by electronic spectra. The DNA-binding properties of the binuclear copper(II) species were investigated by emission spectral and electrochemical techniques, indicating the binuclear copper(II) complex binds to HS-DNA via a groove mode.  相似文献   

16.
Syntheses and Properties of cis -Diacidophthalocyaninato(2–)thallates(III); Crystal Structure of Tetra(n-butyl)ammonium cis -dinitrito(O,O ′)- and cis -dichlorophthalocyaninato(2–)thallate(III) Blue green cis-diacidophthalocyaninato(2–)thallate(III), cis[Tl(X)2pc2–] (X = Cl, ONO′, NCO) is prepared from iodophthalocyaninato(2–)thallium(III) and the corresponding tetra(n-butyl)ammonium salt, (nBu4N)X in dichloromethane, and isolated as (nBu4N)cis[Tl(X)2pc2–]. (nBu4N)cis[Tl(ONO′)2pc2–] ( 1 ) and (nBu4N)cis[Tl(X)2pc2–] · 0,5 (C2H5)2O ( 2 ) crystallize in the monoclinic space group P21/n with cell parameters for 1: a = 14.496(2) Å, b = 17.293(5) Å, c = 18.293(2) Å, β = 98.76(1)° resp. for 2 : a = 13.146(1) Å, b = 14.204(5) Å, c = 24.900(3) Å, β = 93.88(1)°; Z = 4. In 1 , the octa-coordinated Tl atom is surrounded by four isoindole-N atoms (Niso) and four O atoms of the bidental nitrito(O,O′) ligands in a distorted antiprism. The Tl–Niso distances vary between 2.257(3) and 2.312(3) Å, the Tl–O distances between 2.408(3) and 2.562(3) Å. In 2 , the hexa-coordinated Tl atom ligates four Niso atoms and two Cl atoms in a typical cis-arrangement. The average Tl–Niso distance is 2.276 Å, the average Tl–Cl distance is 2.550 Å. In 1 and 2 , the Tl atom is directed out of the centre of the (Niso)4 plane (CtN) towards the acido ligands (d(Tl–CtN) = 1.144(1) Å in 1 , 1.116(2) Å in 2 ), and the phthalocyaninato ligand is concavely distorted. The vertical displacements of the periphereal C atoms amounts up to 0.82 Å. The optical and vibrational spectra as well as the electrochemical properties are discussed.  相似文献   

17.
In the title neutral coordination polymer, [Cd(C6H3ClNO2)2(H2O)2]n, each CdII ion is coordinated by one N and four O atoms from three 2‐chloro­nicotinate ligands and by two aqua ligands, defining a distorted monocapped octahedral coordination geometry. Adjacent Cd atoms are linked by the pyridyl N atom and the bidentate carboxyl­ate functional group of a 2‐­chloro­nicotinate ligand, forming a one‐dimensional infinite chain along the b axis. The Cd⋯Cd distance is 8.112 (3) Å. These chains are linked by O—H⋯O and O—H⋯N hydrogen bonds into a three‐dimensional network structure.  相似文献   

18.
Bis(triphenylphosphine)iminium Bis(methoxo)phthalocyaninato(2–)ferrate(III) – Synthesis and Crystal Structure Chlorophthalocyaninato(2–)ferrate(III) reacts with bis(triphenylphosphine)iminium hydroxide in methanol/acetone solution to yield blue crystals of bis(triphenylphosphine)iminium bis(methoxo)phthalocyaninato(2–)ferrate(III). The complex salt crystallizes as an acetone/methanol solvate (bPNP)[Fe(OCH3)2pc2–] · (CH3)2CO · 1.5 CH3OH in the triclinic space group P 1 (no. 2) with the cell parameters a = 13.160(5) Å, b = 15.480(5) Å, c = 17.140(5) Å, α = 97.54(5)°, β = 91.79(5)°, γ = 95.44(5)°. The Fe atom is located in the centre of the pc2– ligand coordinating four isoindole N atoms (Niso) of the pc2– ligand and two O atoms of the methoxo ligands in a mutual trans arrangement. The average Fe–O and Fe–Niso distances are 1.887 and 1.943 Å, respectively. The cation adopts the bent conformation (< P–N–P = 140.4(2)°) with P–N distances of 1.579(3) and 1.575(3) Å.  相似文献   

19.
In the title compound [systematic name: aqua(1,10‐phenanthroline‐κ2N,N′)(pyridine‐2,6‐di­carboxyl­ato‐κ3O2,N,O6)manganese(II) monohydrate, [Mn(C7H3NO4)(C12H8N2)(H2O)]·H2O, the manganese(II) centre is surrounded by one bidentate phenanthroline ligand [Mn—N = 2.248 (3) and 2.278 (3) Å], one tridentate dipicolinate ligand [Mn—N = 2.179 (3) Å, and Mn—O = 2.237 (2) and 2.266 (2) Å] and one water mol­ecule [Mn—O = 2.117 (3) Å], and it exhibits a strongly distorted octahedral geometry, with trans angles ranging from 144.12 (9) to 158.88 (11)°. Extensive intermolecular hydrogen‐bonding interactions involving coordinated and uncoordinated water mol­ecules and the carboxyl O atoms of the dipicolinate ligand, as well as a stacking interaction involving the phenanthroline rings, are observed in the crystal structure.  相似文献   

20.
Two CoII complexes, Co(phen)(HL)2 ( 1 ) and [Co2(phen)2(H2O)4L2]·H2O ( 2 ) (H2L = HOOC‐(CH2)5‐COOH), were synthesized and structurally characterized on the basis of single crystal X‐ray diffraction data. In complex 1 the Co atoms are tetrahedrally coordinated by two N atoms of one phen ligand and two O atoms of different hydrogenpimelato ligands. Through π—π stacking interactions between carboxyl group and phen ligand, the complex molecules are assembled into 1D columnar chains, which are connected by intermolecular hydrogen bonds. Complex 2 consists of the centrosymmetric dinuclear [Co2(phen)2(H2O)4L2] molecules and hydrogen bonded H2O molecules. The Co atoms are each octahedrally surrounded by two N atoms of one phen ligand and four O atoms from two bis‐monodentate pimelato ligands and two H2O molecules at the trans positions. The results about thermal analyses, which were performed in flowing N2 atmosphere, on both complexes were discussed. Crystal data: ( 1 ) C2/c (no. 15), a = 13.491(1)Å, b = 9.828(1)Å, c = 19.392(2)Å, β = 100.648(1)°, U = 2526.9(4)Å3, Z = 4; ( 2 ) P1 (no. 2), a = 11.558(1)Å, b = 11.947(3)Å, c = 15.211(1)Å, α = 86.17(1)°, β = 75.55(1)°, γ = 69.95(1)°, U = 1910.3(3)Å3, Z = 2.  相似文献   

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