This paper reports the features and regularities of the infrared spectra for two kinds of complexes containing R 2dtc ligand. The cubane like clusters containing R 2dtc ligand possess weak and wide peaks at 400—500 c...This paper reports the features and regularities of the infrared spectra for two kinds of complexes containing R 2dtc ligand. The cubane like clusters containing R 2dtc ligand possess weak and wide peaks at 400—500 cm -1 assigned to M μ 3S vibration,while the peaks at 330—380 cm -1 and 1 470—1 510 cm -1 can be assigned to M S dtc and C—N vibrations,respectively.The ν ( C—N ) and ν (C=S) vibrations for Me 2dtc cubane cluster exhibit blue shift and red shift,respectively,when compared with those of other R 2dtc ones.This would be attributed to the strong super conjugation of the methly group. The M μ 3S vibrations for both types of complexes [V 2Cu 2S 4(R 2dtc) 2(PhS) 2] 2- and [VCu 4S 4(R 2dtc) n(PhS) 4-n ] 3- ( n =0,1,2) occur at 480 and 465 cm -1 ,respectively.This small difference becomes a useful indication to distinguish the two types of clusters. Cluster complexes containing (R 2dtc) 2V 2O 2(μ S) 2 structural unit show the V=O vibration in the range of 844—970 cm -1 .It is noted that (Et 4N)[V 3S 2O 3(Et 2dtc) 3] contains two sets of the V=O bonds corresponding to two sets of V=O vibrations at 970 and 844 cm -1 .An additional coordination of the V=O bond to another metal atom obviously weakens the V=O bond to give rise to the red shift of the infrared frequency.Similar red shifts were also observed for other complexes and were discussed.展开更多
By use of a new ligand containing both salicylic acid moiety and salicylaldehyde Schiff base moiety, 5-（2-hydroxybenzylideneamino）-2-hydroxybenzoic acid （H3L）, a linear trinuclear Mn（II） complex was prepared. Th...By use of a new ligand containing both salicylic acid moiety and salicylaldehyde Schiff base moiety, 5-（2-hydroxybenzylideneamino）-2-hydroxybenzoic acid （H3L）, a linear trinuclear Mn（II） complex was prepared. This complex crystallizes in triclinic, space group P1 with a = 12.0196（7）, b = 13.7440（13）, c = 15.7554（14） , α = 111.529（3）, β = 96.691（2）, γ = 94.802（2）o, C96H100Mn3N6O32, Mr = 2014.64, V = 2382.0（3） 3, Z = 1, μ = 0.478, Dc = 1.404 g/cm3, F（000） = 1049, R = 0.0554 and wR = 0.1610 for 8973 observed reflections （I 〉 2σ（I））. The complex consists of a trinuclear cluster and two solvate ethanol molecules. Three linearly disposed Mn atoms, with an inversion center on the central one, are bridged by six carboxylate groups from six bulky mono-anionic ligands （H2L-）, and the octahedral coordination spheres for each of the metal centers are thus formed, with the aid of additional ligation of two small molecules （ethanol and water） to both ends. The magnetic properties of the title complex are also included in this paper.展开更多
A new mixed-ligand Mn（II）complex,namely [Mn（bipy）2（Huca）]·5H2O（1,bipy = 2,2＇-bipyridine,and H3uca = uracil-5-carboxylic acid）has been prepared and characterized by single-crystal X-ray diffraction,FT-IR ...A new mixed-ligand Mn（II）complex,namely [Mn（bipy）2（Huca）]·5H2O（1,bipy = 2,2＇-bipyridine,and H3uca = uracil-5-carboxylic acid）has been prepared and characterized by single-crystal X-ray diffraction,FT-IR spectroscopy and thermogravimetric analysis.It crystallizes in monoclinic,space group C2/c with a = 23.597（8）,b = 16.434（5）,c = 15.531（6）,β = 112.785（6）o,C25H28MnN6O9,Mr = 611.47,V = 5553（3）3,Z = 8,μ = 0.538,Dc = 1.463 g/cm3,F（000）= 2536,R = 0.0441 and wR = 0.1230 for all 5227 observed reflections（I 2σ（I））.The manganese（II）center is surrounded by three bidentate chelating ligands,and it displays a severely distorted octahedral geometry,with cis angles ranging from 72.14（6）to 109.78（6）o.Extensive intermolecular hydrogen bonds link the [Mn（bipy）2（Huca）] monomers and lattice water molecules to yield a three-dimensional supramolecular framework.TGA shows complete removal of all lattice water molecules above 270 ℃.展开更多
The crystal structure of the title compound [Mn(sapn)(H2O)2]Br (H2sapn = N,N?bis-(salicylidene)-1,3-diaminopropane) with formula C17H18N2O4MnBr and Mr = 449.18 has been determined by X-ray diffraction. The crystal is ...The crystal structure of the title compound [Mn(sapn)(H2O)2]Br (H2sapn = N,N?bis-(salicylidene)-1,3-diaminopropane) with formula C17H18N2O4MnBr and Mr = 449.18 has been determined by X-ray diffraction. The crystal is triclinic with space group P , a = 7.777(1), b = 10.459(2), c = 11.96(3), = 78.22(1), =75.16(8), = 86.80(5)? V = 919(3)3, Dc = 1.631g/cm3, F(000) = 456, = 2.917 cm-1 and Z = 2, with R = 0.0428 and wR = 0.1092 for 2427 reflections (I > 2s(I)). Two nitrogen and two oxygen atoms from the sapn group chelate to the MnⅢ ion, forming a distorted octahedral geometry together with two coordinated water molecules. A bromide anion exists outside as a counter ion.展开更多
A dinuclear manganese（Ⅱ） complex, [Mn2（μ-OAc）2（phen）4]（ClO4）2 1 （phen = phenanthroline）, has been prepared by the reaction of Mn（OAc）2-4H2O, phen, tartaric acid and NaClO4·H2O in MeOH/H2O solution. ...A dinuclear manganese（Ⅱ） complex, [Mn2（μ-OAc）2（phen）4]（ClO4）2 1 （phen = phenanthroline）, has been prepared by the reaction of Mn（OAc）2-4H2O, phen, tartaric acid and NaClO4·H2O in MeOH/H2O solution. The crystal structure has been determined by X-ray diffraction. The crystal is of monoclinic, space group P21/c with a = 9.6052（4）, b = 14.2353（7）, c = 18.8893（8） A, β= 96.584（1）° C52H38C12Mn2N8O12, Mr = 1147.68, V= 2565.8（2） A^3, Dc = 1.486 g/cm^3, F（000） = 1172,μ = 0.668 cm^-1 and Z = 2. The final refinement gave R = 0.0605 and wR = 0.1619 for 3203 reflections with I 〉 2σ（I）. The complex contains a dinuclear [Mn2（μ-OAc）2（phen）4]]^2＋ cation located at a centre of symmetry with two syn-anti acetate bridges between the Mn atoms. Each Mn atom is coordinated by four N atoms from two chelating phen ligands and two O atoms from a pair of bridging acetate groups to furnish a distorted octahedral geometry. Two ClO4 anions exist around the cation [Mn2（μ-OAc）2（phen）4]^2＋ as counter ions.展开更多
A new two-dimensional polymeric manganese compound [Mn（PhCOO）2（4,4＇-bipyridine）]n 1 has been prepared and structurally characterized by X-ray diffraction. The complex crystallizes in space group Pbcn with a = 18....A new two-dimensional polymeric manganese compound [Mn（PhCOO）2（4,4＇-bipyridine）]n 1 has been prepared and structurally characterized by X-ray diffraction. The complex crystallizes in space group Pbcn with a = 18.7158（2）, b = 11.6919（3）, c = 9.4799（2）A, V = 2074.42（7）A^3, Z = 4, Mr = 453.34, Dc = 1.452 g/cm^3, μ = 0.670 mm^-1 and F（000） = 932. The final refinement gave R = 0.0458 and wR = 0.1439 for 1358 observed reflections with Ⅰ〉 2σ（Ⅰ）. The complex consists of repeating units of Mn（PhCOO）2（4,4＇-bipyridine）. Each Mn center is sixcoordinated by four carboxylate O atoms of four benzoate anions and two pyridyl N atoms from bipy ligands to furnish a slightly distorted octahedral geometry. The two adjacent Mn atoms are connected by a pair of μ1,3-carboxylate groups to form infinite chains, which are further interlinked by bipy to complete a 2D grid network. The magnetic property of the polymeric complex has also been investigated.展开更多
The manganese benzoate complex Mn(phen)(PhCOO)2(H2O) (C26H20MnN2O5) has been synthesized, where phen = 1,10-phenanthroline. The molecular and crystal structures were determined by single-crystal X-ray diffraction. The...The manganese benzoate complex Mn(phen)(PhCOO)2(H2O) (C26H20MnN2O5) has been synthesized, where phen = 1,10-phenanthroline. The molecular and crystal structures were determined by single-crystal X-ray diffraction. The crystal is of monoclinic, space group P21/c with unit cell parameters: a = 10.7145(7), b = 21.218(1), c = 11.2743(7) ? ?= 117.7342(2), V = 2268.6(3) ?, Z = 4, Mr = 495.38, Dc = 1.450 g/cm3, ?= 0.623 mm-1, F(000) = 1020, T = 293(2) K, R = 0.0563 and wR = 0.1339 for 2468 observed reflections with I > 2s(I). In the crystal the manganese atom is five-coordinated by two chelated nitrogen atoms from phenanthroline, three oxygen atoms from two benzoates and one water molecule, completing a triangular bipyramid geometry. The complex exists in a dimer mode by intermolecular hydrogen-bonding interactions.展开更多
文摘This paper reports the features and regularities of the infrared spectra for two kinds of complexes containing R 2dtc ligand. The cubane like clusters containing R 2dtc ligand possess weak and wide peaks at 400—500 cm -1 assigned to M μ 3S vibration,while the peaks at 330—380 cm -1 and 1 470—1 510 cm -1 can be assigned to M S dtc and C—N vibrations,respectively.The ν ( C—N ) and ν (C=S) vibrations for Me 2dtc cubane cluster exhibit blue shift and red shift,respectively,when compared with those of other R 2dtc ones.This would be attributed to the strong super conjugation of the methly group. The M μ 3S vibrations for both types of complexes [V 2Cu 2S 4(R 2dtc) 2(PhS) 2] 2- and [VCu 4S 4(R 2dtc) n(PhS) 4-n ] 3- ( n =0,1,2) occur at 480 and 465 cm -1 ,respectively.This small difference becomes a useful indication to distinguish the two types of clusters. Cluster complexes containing (R 2dtc) 2V 2O 2(μ S) 2 structural unit show the V=O vibration in the range of 844—970 cm -1 .It is noted that (Et 4N)[V 3S 2O 3(Et 2dtc) 3] contains two sets of the V=O bonds corresponding to two sets of V=O vibrations at 970 and 844 cm -1 .An additional coordination of the V=O bond to another metal atom obviously weakens the V=O bond to give rise to the red shift of the infrared frequency.Similar red shifts were also observed for other complexes and were discussed.
基金supported by the NNSFC (Nos. 20633020 and 20973172)the 973 Program (No. 2009CB220009)the NSF of Fujian Province (Nos. 2008J0175 and 2007F3112)
文摘By use of a new ligand containing both salicylic acid moiety and salicylaldehyde Schiff base moiety, 5-（2-hydroxybenzylideneamino）-2-hydroxybenzoic acid （H3L）, a linear trinuclear Mn（II） complex was prepared. This complex crystallizes in triclinic, space group P1 with a = 12.0196（7）, b = 13.7440（13）, c = 15.7554（14） , α = 111.529（3）, β = 96.691（2）, γ = 94.802（2）o, C96H100Mn3N6O32, Mr = 2014.64, V = 2382.0（3） 3, Z = 1, μ = 0.478, Dc = 1.404 g/cm3, F（000） = 1049, R = 0.0554 and wR = 0.1610 for 8973 observed reflections （I 〉 2σ（I））. The complex consists of a trinuclear cluster and two solvate ethanol molecules. Three linearly disposed Mn atoms, with an inversion center on the central one, are bridged by six carboxylate groups from six bulky mono-anionic ligands （H2L-）, and the octahedral coordination spheres for each of the metal centers are thus formed, with the aid of additional ligation of two small molecules （ethanol and water） to both ends. The magnetic properties of the title complex are also included in this paper.
基金supported by the NNSFC (Nos.20973172 and 21071145)the 973 Program (No.2009CB220009)the NSF of Fujian Province (Nos.2008J0175 and 2007F3112)
文摘A new mixed-ligand Mn（II）complex,namely [Mn（bipy）2（Huca）]·5H2O（1,bipy = 2,2＇-bipyridine,and H3uca = uracil-5-carboxylic acid）has been prepared and characterized by single-crystal X-ray diffraction,FT-IR spectroscopy and thermogravimetric analysis.It crystallizes in monoclinic,space group C2/c with a = 23.597（8）,b = 16.434（5）,c = 15.531（6）,β = 112.785（6）o,C25H28MnN6O9,Mr = 611.47,V = 5553（3）3,Z = 8,μ = 0.538,Dc = 1.463 g/cm3,F（000）= 2536,R = 0.0441 and wR = 0.1230 for all 5227 observed reflections（I 2σ（I））.The manganese（II）center is surrounded by three bidentate chelating ligands,and it displays a severely distorted octahedral geometry,with cis angles ranging from 72.14（6）to 109.78（6）o.Extensive intermolecular hydrogen bonds link the [Mn（bipy）2（Huca）] monomers and lattice water molecules to yield a three-dimensional supramolecular framework.TGA shows complete removal of all lattice water molecules above 270 ℃.
基金This work was supported by The State Key Basic Research and Development Plan (G1998010100) NNSFC (No. 2973309029973047 and 39970177)
文摘The crystal structure of the title compound [Mn(sapn)(H2O)2]Br (H2sapn = N,N?bis-(salicylidene)-1,3-diaminopropane) with formula C17H18N2O4MnBr and Mr = 449.18 has been determined by X-ray diffraction. The crystal is triclinic with space group P , a = 7.777(1), b = 10.459(2), c = 11.96(3), = 78.22(1), =75.16(8), = 86.80(5)? V = 919(3)3, Dc = 1.631g/cm3, F(000) = 456, = 2.917 cm-1 and Z = 2, with R = 0.0428 and wR = 0.1092 for 2427 reflections (I > 2s(I)). Two nitrogen and two oxygen atoms from the sapn group chelate to the MnⅢ ion, forming a distorted octahedral geometry together with two coordinated water molecules. A bromide anion exists outside as a counter ion.
文摘A dinuclear manganese（Ⅱ） complex, [Mn2（μ-OAc）2（phen）4]（ClO4）2 1 （phen = phenanthroline）, has been prepared by the reaction of Mn（OAc）2-4H2O, phen, tartaric acid and NaClO4·H2O in MeOH/H2O solution. The crystal structure has been determined by X-ray diffraction. The crystal is of monoclinic, space group P21/c with a = 9.6052（4）, b = 14.2353（7）, c = 18.8893（8） A, β= 96.584（1）° C52H38C12Mn2N8O12, Mr = 1147.68, V= 2565.8（2） A^3, Dc = 1.486 g/cm^3, F（000） = 1172,μ = 0.668 cm^-1 and Z = 2. The final refinement gave R = 0.0605 and wR = 0.1619 for 3203 reflections with I 〉 2σ（I）. The complex contains a dinuclear [Mn2（μ-OAc）2（phen）4]]^2＋ cation located at a centre of symmetry with two syn-anti acetate bridges between the Mn atoms. Each Mn atom is coordinated by four N atoms from two chelating phen ligands and two O atoms from a pair of bridging acetate groups to furnish a distorted octahedral geometry. Two ClO4 anions exist around the cation [Mn2（μ-OAc）2（phen）4]^2＋ as counter ions.
基金This project was supported by the NNSFC (No. 20471061) the Science & Technology Innovation Foundation for the Young Scholars of Fujian Province (No. 2005J059)
文摘A new two-dimensional polymeric manganese compound [Mn（PhCOO）2（4,4＇-bipyridine）]n 1 has been prepared and structurally characterized by X-ray diffraction. The complex crystallizes in space group Pbcn with a = 18.7158（2）, b = 11.6919（3）, c = 9.4799（2）A, V = 2074.42（7）A^3, Z = 4, Mr = 453.34, Dc = 1.452 g/cm^3, μ = 0.670 mm^-1 and F（000） = 932. The final refinement gave R = 0.0458 and wR = 0.1439 for 1358 observed reflections with Ⅰ〉 2σ（Ⅰ）. The complex consists of repeating units of Mn（PhCOO）2（4,4＇-bipyridine）. Each Mn center is sixcoordinated by four carboxylate O atoms of four benzoate anions and two pyridyl N atoms from bipy ligands to furnish a slightly distorted octahedral geometry. The two adjacent Mn atoms are connected by a pair of μ1,3-carboxylate groups to form infinite chains, which are further interlinked by bipy to complete a 2D grid network. The magnetic property of the polymeric complex has also been investigated.
基金the State Key Basic Research and Development Plan (G1998010100)NNSFC (No. 30170229 and 29973047)
文摘The manganese benzoate complex Mn(phen)(PhCOO)2(H2O) (C26H20MnN2O5) has been synthesized, where phen = 1,10-phenanthroline. The molecular and crystal structures were determined by single-crystal X-ray diffraction. The crystal is of monoclinic, space group P21/c with unit cell parameters: a = 10.7145(7), b = 21.218(1), c = 11.2743(7) ? ?= 117.7342(2), V = 2268.6(3) ?, Z = 4, Mr = 495.38, Dc = 1.450 g/cm3, ?= 0.623 mm-1, F(000) = 1020, T = 293(2) K, R = 0.0563 and wR = 0.1339 for 2468 observed reflections with I > 2s(I). In the crystal the manganese atom is five-coordinated by two chelated nitrogen atoms from phenanthroline, three oxygen atoms from two benzoates and one water molecule, completing a triangular bipyramid geometry. The complex exists in a dimer mode by intermolecular hydrogen-bonding interactions.
