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1.
Ying‐Hong Lu Hoong‐Kun Fun Suchada Chantrapromma Ibrahim Abdul Razak Zhen Shen Jing‐Lin Zuo Xiao‐Zeng You 《Acta Crystallographica. Section C, Structural Chemistry》2001,57(8):911-913
The title dinuclear di‐μ‐oxo‐bis[(1,4,8,11‐tetraazacyclotetradecane‐κ4N)manganese(III,IV)] diperchlorate nitrate complex, [Mn2O2(C10H24N4)2](ClO4)2(NO3) or [(cyclam)MnO]2(ClO4)2(NO3), was self‐assembled by the reaction of Mn2+ with 1,4,8,11‐tetraazacyclotetradecane in aqueous media. The structure of this compound consists of a centrosymmetric binuclear [(cyclam)MnO]3+ unit, two perchlorate anions and one nitrate anion. While the low‐temperature electron paramagnetic resonance spectra show a typical 16‐line signal for a di‐μ‐oxo MnIII/MnIV dimer, the magnetic susceptibility studies also confirm a characteristic antiferromagnetic coupling between the electronic spins of the MnIV and MnIII ions. 相似文献
2.
Li‐Fang Zhang Zhong‐Hai Ni Zhi‐Min Zong Xian‐Yong Wei Chun‐Hua Ge Hui‐Zhong Kou 《Acta Crystallographica. Section C, Structural Chemistry》2005,61(12):m542-m544
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
3.
Jianli Lin Deping Cheng Yueqing Zheng Duanjun Xu Yuanzhi Xu 《Acta Crystallographica. Section C, Structural Chemistry》2000,56(5):523-524
In the title MnII complex, [Mn2(C10H2O8)(H2O)10]·H2O, two independent binuclear molecules bridged by the 1,2,4,5‐benzenetetracarboxyl anion exist in a unit cell, with each anion lying about an inversion centre. One of the Mn—Owater distances [2.2922 (13) Å] is significantly longer than the MnII—Owater distances reported so far for MnII complexes and very close to the Mn—Owater distances found in the axial direction of MnIII complexes. 相似文献
4.
Kinetic studies on the oxidation of 2‐mercaptosuccinic acid by dinuclear [Mn2III/IV(μ‐O)2(cyclam)2](ClO4)3] ( 1 ) (abbreviated as MnIII–MnIV) (cyclam = 1,4,8,11‐tetraaza‐cyclotetradecane) have been carried out in aqueous medium in the pH range of 4.0–6.0, in the presence of acetate buffer at 30°C by UV–vis spectrophotometry. In the pH region, two species of complex 1 (MnIII–MnIV and MnIII–MnIVH, the later being μ‐O protonated form) were found to be kinetically significant. The first‐order dependence of the rate of the reactions on [Thiol] both in presence and absence of externally added copper(II) ions, first‐order dependence on [Cu2+] and a decrease of rate of the reactions with increase in pH have been rationalized by suitable sequence of reactions. Protonation of μ‐O bridge of 1 is evidenced by the perchloric acid catalyzed decomposition of 1 to mononuclear Mn(III) and Mn(IV) complex observed by UV–vis and EPR spectroscopy. The kinetic features have been rationalized considering Cu(RSH) as the reactive intermediate. EPR spectroscopy lends support for this. The formation of a hydrogen bonded outer‐sphere adduct between the reductant and the complex in the lower pH range prior to electron transfer reactions is most likely to occur. © 2004 Wiley Periodicals, Inc. Int J Chem Kinet 36: 170–177 2004 相似文献
5.
David Martínez Majid Motevalli Michael Watkinson 《Acta Crystallographica. Section C, Structural Chemistry》2002,58(4):m258-m260
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
6.
Paul V. Bernhardt Nathan L. Kilah 《Acta Crystallographica. Section C, Structural Chemistry》2005,61(5):m245-m249
The pendent‐arm macrocyclic hexaamine trans‐6,13‐dimethyl‐1,4,8,11‐tetraazacyclotetradecane‐6,13‐diamine (L) may coordinate in tetra‐, penta‐ or hexadentate modes, depending on the metal ion and the synthetic procedure. We report here the crystal structures of two pseudo‐octahedral cobalt(III) complexes of L, namely sodium trans‐cyano(trans‐6,13‐dimethyl‐1,4,8,11‐tetraazacyclotetradecane‐6,13‐diamine)cobalt(III) triperchlorate, Na[Co(CN)(C13H30N6)](ClO4)3 or Na{trans‐[CoL(CN)]}(ClO4)3, (I), where L is coordinated as a pentadentate ligand, and trans‐dicyano(trans‐6,13‐dimethyl‐1,4,8,11‐tetraazacyclotetradecane‐6,13‐diamine)cobalt(III) trans‐dicyano(trans‐6,13‐dimethyl‐1,4,8,11‐tetraazacyclotetradecane‐6,13‐diaminium)cobalt(III) tetraperchlorate tetrahydrate, [Co(CN)2(C14H32N6)][Co(CN)2(C14H30N6)](ClO4)4·4H2O or trans‐[CoL(CN)2]trans‐[Co(H2L)(CN)2](ClO4)4·4H2O, (II), where the ligand binds in a tetradentate mode, with the remaining coordination sites being filled by C‐bound cyano ligands. In (I), the secondary amine Co—N bond lengths lie within the range 1.944 (3)–1.969 (3) Å, while the trans influence of the cyano ligand lengthens the Co—N bond length of the coordinated primary amine [Co—N = 1.986 (3) Å]. The Co—CN bond length is 1.899 (3) Å. The complex cations in (II) are each located on centres of symmetry. The Co—N bond lengths in both cations are somewhat longer than in (I) and span a narrow range [1.972 (3)–1.982 (3) Å]. The two independent Co—CN bond lengths are similar [1.918 (4) and 1.926 (4) Å] but significantly longer than in the structure of (I), again a consequence of the trans influence of each cyano ligand. 相似文献
7.
John A. Schlueter Urs Geiser 《Acta Crystallographica. Section C, Structural Chemistry》2003,59(4):m146-m148
The crystal structure of the title compound, [Mn(C9H5N4O)2(H2O)2], conventionally denoted Mn(EtO‐TCA)2(H2O)2, where EtO‐TCA is 2‐ethoxy‐1,1,3,3‐tetracyanopropenide, is described. The EtO‐TCA anions bridge MnII centers through one of the nitrile N atoms of each of their two dicyanomethanide groups, thus forming dibridged chains along ab. These chains are linked into two‐dimensional sheets through hydrogen bonding. The seven‐atom bridge, which results in a long Mn⃛Mn intrachain interaction [9.0044 (4) Å], as well as the large interchain separations [8.3288 (4) and 8.5220 (4) Å] prohibit long‐range magnetic ordering down to temperatures as low as 1.55 K. 相似文献
8.
Arindam Mukherjee Robert W. Gable Colette Boskovic 《Acta Crystallographica. Section C, Structural Chemistry》2007,63(2):m71-m73
The molecule of the title compound, tetra‐μ2‐acetato‐diaquadi‐μ2‐chloro‐tetrachlorotetrakis[μ4‐3‐hydroxy‐2,2‐bis(oxidomethyl)propanolato]tetramethanoldi‐μ3‐methanolato‐di‐μ5‐oxo‐octamanganese(II)tetramanganese(III), [Mn4IIIMn8II(CH3O)2(C2H3O2)4(C5H9O4)4Cl6O2(CH4O)4(H2O)2], displays a centre of symmetry. The structure of the {Mn4IIIMn8IIO18Cl2}10− core is composed of three layers and features two oxo ligands binding in a rare μ5‐mode. 相似文献
9.
In‐Gyung Oh Jong‐Ha Choi Woo‐Taik Lim Ki‐Min Park 《Acta Crystallographica. Section C, Structural Chemistry》2004,60(6):m238-m240
In the title compound, [Cr(ONO)2(cyclam)]NO2 (cyclam is 1,4,8,11‐tetraazacyclotetradecane, C10H24N2), the complex cation is located on a twofold symmetry axis. The central Cr atom has a distorted octahedral coordination, involving two Cr—O bonds, with the monodentate nitrite O atoms adopting a cis configuration, and four Cr—N bonds. The mean Cr—N and Cr—O distances are 2.0895 (14) and 1.9698 (14) Å. 相似文献
10.
Xin‐Qiang Wang Wen‐Tao Yu Dong Xu Guang‐Hui Zhang Yan‐Ling Geng 《Acta Crystallographica. Section C, Structural Chemistry》2005,61(6):m278-m280
The title complex, [MnHg(NCS)4(C2H5NO)2]n, consists of slightly distorted MnN4O2 octahedra and HgS4 tetrahedra. Each MnII cation is bound to four N atoms of the NCS groups and two O atoms of the N‐methylformamide (NMF) ligands in a cis configuration. Each HgII cation is coordinated to four S atoms of NCS groups. Each pair of MnII and HgII cations is connected by an –NCS– bridge, forming an infinite three‐dimensional –Mn—NCS—Hg– network. 相似文献
11.
Xu‐Xiu Yan Li‐Ping Lu Miao‐Li Zhu 《Acta Crystallographica. Section C, Structural Chemistry》2004,60(5):m221-m223
The crystal structure of the title compound, tetrachloro[μ‐1,1,4,7,7‐pentakis(1H‐benzimidazol‐2‐ylmethyl)‐1,4,7‐triazaheptane]dimanganese(II) methanol pentasolvate tetrahydrate, [Mn2Cl4(C44H43N13)]·5CH4O·4H2O, contains an asymmetric dinuclear MnII–DTPB [DTPB is 1,1,4,7,7‐pentakis(1H‐benzimidazol‐2‐ylmethyl)‐1,4,7‐triazaheptane] complex with an intra‐ligand bridging group (–NCH2CH2N–), as well as several solvate molecules (methanol and water). Both MnII cations have similar distorted octahedral coordination geometries. One MnII cation is coordinated by a Cl− anion and five N atoms from the ligand, and the other is coordinated by three Cl− anions and three N atoms of the same ligand. The Mn⋯Mn distance is 7.94 Å. A Cl⋯H—O⋯H—O⋯H—N hydrogen‐bond chain is also observed, connecting the two parts of the complex. 相似文献
12.
Li‐Qin Xiong Chuan‐Min Qi Hui Yu Sheng‐Wen Liang 《Acta Crystallographica. Section C, Structural Chemistry》2007,63(3):m117-m119
In the title complex, [Mn(C8H4NO6)2(H2O)4]·2H2O, cyclic water tetramers forming one‐dimensional metal–water chains have been observed. The water clusters are trapped by the co‐operative association of coordination interactions and hydrogen bonds. The MnII ion resides on a center of symmetry and is in an octahedral coordination environment comprising two O atoms from two 5‐carboxy‐2‐nitrobenzoate ligands and four O atoms from water molecules. 相似文献
13.
Yu Liu Duan‐Jun Xu Chen‐Hsiung Hung 《Acta Crystallographica. Section C, Structural Chemistry》2005,61(4):m155-m157
In the title polymeric complex, [Mn(C6H8O4)(C7H6N2)2(H2O)]n, the MnII atom is surrounded by two adipate dianions, two benzimidazole molecules and one coordinated water molecule. The Mn atoms and coordinated water molecule are located on a twofold axis, and the bridging adipate ligand is located on an inversion center. The adipate dianions bridge neighboring MnII atoms to form polymeric chains. Each MnII atom is seven‐coordinate, the longest Mn—O bond length being 2.5356 (16) Å. 相似文献
14.
Tao Liu Bing‐Wu Wang Yi‐Hong Chen Zhe‐Ming Wang Prof. Song Gao Prof. 《无机化学与普通化学杂志》2008,634(4):778-783
Two mixed‐valent disc‐like hepta‐nuclear compounds of [FeIIFeIII6(tea)6](ClO4)2 ( 1Fe , tea = N(CH2CH2O)33?) and [MnII3MnIII4(nmdea)6(N3)6]·CH3OH ( 2Mn , nmdea = CH3N(CH2CH2O)22?) have been synthesized by the reaction of Fe(ClO4)2·6H2O with triethanolamine (H3tea) for the former and reaction of Mn(ClO4)2·6H2O with diethanolamine (H2nmdea) and NaN3 for the later, respectively. 1Fe has the cationic cluster with a planar [FeIIFeIII6] core consisting of one central FeII and six rim FeIII atoms in hexagonal arrangement. The Fe ions are linked by the oxo‐bridges from the alcohol arms in the manner of edge‐sharing of their coordination octahedra. 2Mn is a neutral cluster with a [MnII3MnIII4] core possessing one central MnII atom surrounded by six rim Mn ions, two MnII and four MnIII. The structure is similar to 1Fe but involves six terminal azido ligands, each coordinate one rim Mn ion. 1Fe showed dominant antiferromagnetic interaction within the cluster and long‐range ordering at 2.7 K. The cluster probably has a ground state of low spin of S = 5/2 or 4/2. The long‐range ordering is weak ferromagnetic, showing small hysteresis with a remnant magnetization of 0.3 Nβ and a coercive field of 40 Oe. Moreover, the isofield of lines 1Fe are far from superposition, indicating the presence of significant zero–field splitting. Ferromagnetic interactions are dominant in 2Mn . An intermediate spin ground state 25/2 is observed at low field. In high field of 50 kOe, the energetically lowest state is given by the ms = 31/2 component of the S = 31/2 multiplet due to the Zeeman effect. Despite of the large ground state, no single‐molecule magnet behavior was found above 2 K. 相似文献
15.
Alejandro Pascual‐Álvarez Julia Vallejo Dr. Emilio Pardo Prof. Dr. Miguel Julve Prof. Dr. Francesc Lloret Dr. J. Krzystek Dr. Donatella Armentano Prof. Dr. Wolfgang Wernsdorfer Dr. Joan Cano 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(48):17299-17307
We report on a novel manganese(III)–porphyrin complex with the formula [MnIII(TPP)(3,5‐Me2pyNO)2]ClO4?CH3CN ( 2 ; 3,5‐Me2pyNO=3,5‐dimethylpyridine N‐oxide, H2TPP=5,10,15,20‐tetraphenylporphyrin), in which the MnIII ion is six‐coordinate with two monodentate 3,5‐Me2pyNO molecules and a tetradentate TPP ligand to build a tetragonally elongated octahedral geometry. The environment in 2 is responsible for the large and negative axial zero‐field splitting (D=?3.8 cm?1), low rhombicity (E/|D|=0.04) of the high‐spin MnIII ion, and, ultimately, for the observation of slow magnetic‐relaxation effects (Ea=15.5 cm?1 at H=1000 G) in this rare example of a manganese‐based single‐ion magnet (SIM). Structural, magnetic, and electronic characterizations were carried out by means of single‐crystal diffraction studies, variable‐temperature direct‐ and alternating‐current measurements and high‐frequency and ‐field EPR spectroscopic analysis followed by quantum‐chemical calculations. Slow magnetic‐relaxation effects were also observed in the already known analogous compound [MnIII(TPP)Cl] ( 1 ; Ea=10.5 cm?1 at H=1000 G). The results obtained for 1 and 2 are compared and discussed herein. 相似文献
16.
Sujin Han Jinkwon Kim 《Acta Crystallographica. Section C, Structural Chemistry》2002,58(10):m521-m522
The title compound, [Mn(NCS)2(C18H12N6)2(CH4O)2], contains a centrosymmetric octahedral MnII centre and three pairs of trans‐coordinating ligands. It is the first example of a mononuclear metal complex with the 2,4,6‐tri(4‐pyridyl)‐1,3,5‐triazine (tpt) ligand. Intermolecular π–π stacking of the planar tpt ligands, as well as hydrogen bonds between pyridyl N and methanol H atoms, results in the formation of a three‐dimensional network. 相似文献
17.
Jun‐Fang Guo Dr. Xiu‐Teng Wang Dr. Bing‐Wu Wang Dr. Guan‐Cheng Xu Dr. Song Gao Prof. Lap Szeto Wing‐Tak Wong Prof. Wai‐Yeung Wong Prof. Tai‐Chu Lau Prof. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2010,16(11):3524-3535
Four cyano‐bridged 1D bimetallic polymers have been prepared by using the paramagnetic building block trans‐[Ru(acac)2(CN)2]? (Hacac=acetylacetone): {[{Ni(tren)}{Ru(acac)2(CN)2}][ClO4]?CH3OH}n ( 1 ) (tren=tris(2‐aminoethyl)amine), {[{Ni(cyclen)}{Ru(acac)2(CN)2}][ClO4]? CH3OH}n ( 2 ) (cyclen=1,4,7,10‐tetraazacyclododecane), {[{Fe(salen)}{Ru(acac)2(CN)2}]}n ( 3 ) (salen2?=N,N′‐bis(salicylidene)‐o‐ethyldiamine dianion) and [{Mn(5,5′‐Me2salen)}2{Ru(acac)2(CN)2}][Ru(acac)2(CN)2]? 2 CH3OH ( 4 ) (5,5′‐Me2salen=N,N′‐bis(5,5′‐dimethylsalicylidene)‐o‐ethylenediimine). Compounds 1 and 2 are 1D, zigzagged NiRu chains that exhibit ferromagnetic coupling between NiII and RuIII ions through cyano bridges with J=+1.92 cm?1, z J′=?1.37 cm?1, g=2.20 for 1 and J=+0.85 cm?1, z J′=?0.16 cm?1, g=2.24 for 2 . Compound 3 has a 1D linear chain structure that exhibits intrachain ferromagnetic coupling (J=+0.62 cm?1, z J′=?0.09 cm?1, g=2.08), but antiferromagnetic coupling occurs between FeRu chains, leading to metamagnetic behavior with TN=2.6 K. In compound 4 , two MnIII ions are coordinated to trans‐[Ru(acac)2(CN)2]? to form trinuclear Mn2Ru units, which are linked together by π–π stacking and weak Mn???O* interactions to form a 1D chain. Compound 4 shows slow magnetic relaxation below 3.0 K with ?=0.25, characteristic of superparamagnetic behavior. The MnIII???RuIII coupling constant (through cyano bridges) and the MnIII???MnIII coupling constant (between the trimers) are +0.87 and +0.24 cm?1, respectively. Compound 4 is a novel single‐chain magnet built from Mn2Ru trimers through noncovalent interactions. Density functional theory (DFT) combined with the broken symmetry state method was used to calculate the molecular magnetic orbitals and the magnetic exchange interactions between RuIII and M (M=NiII, FeIII, and MnIII) ions. To explain the somewhat unexpected ferromagnetic coupling between low‐spin RuIII and high‐spin FeIII and MnIII ions in compounds 3 and 4 , respectively, it is proposed that apart from the relative symmetries, the relative energies of the magnetic orbitals may also be important in determining the overall magnetic coupling in these bimetallic assemblies. 相似文献
18.
Yu Zhang Hanbing Tao Chunying Duan Yizhi Li Longgen Zhu 《Acta Crystallographica. Section C, Structural Chemistry》2002,58(3):m188-m189
In the centrosymmetric title complex, [Mn(C7H8N2O2)4(H2O)2](ClO4)2, the MnII ion is in an octahedral environment, with the equatorial plane being defined by the O atoms of four monodentate carboxylate groups, and the octahedron being completed by two trans‐coordinated water molecules. There are intramolecular hydrogen bonds between the coordinated water molecules and the non‐coordinated O atoms of the carboxylate groups. Hydrogen bonds between the amino groups and the carboxylate groups of neighbouring molecules generate a layered hydrogen‐bonded network. 相似文献
19.
Jun Luo Xin‐Rong Zhang Li‐Li Cui Wei‐Quan Dai Bao‐Shu Liu 《Acta Crystallographica. Section C, Structural Chemistry》2006,62(12):m614-m616
The two new title complexes, [Mn(C5H3N6)2(H2O)2] and [Zn(C5H3N6)2(H2O)2], are isomorphous. In both compounds, the metal atom is located on an inversion center and is coordinated by four N atoms from two 5‐(pyrazin‐2‐yl)‐1H‐tetrazolate anions in the basal plane and by two O atoms of water ligands in the apical positions to form a distorted octahedral geometry. Intermolecular hydrogen‐bond interactions between the uncoordinated N atoms of the tetrazolate anions and the H atoms of the water molecules lead to the formation of a three‐dimensional network. 相似文献
20.
Jaromír Marek Zdenk Trvní
ek Pavel Kopel 《Acta Crystallographica. Section C, Structural Chemistry》2003,59(11):m429-m431
The title compound, [Mn(C12H8N2)2(H2O)2](C4H4O4S)·[Mn(C4H4O4S)(C12H8N2)2]·13H2O, contains one dianion of thiodiglycolic acid (tdga2−) and two independent manganese(II) moieties, viz. [Mn(phen)2(H2O)2]2+ and [Mn(tdga)(phen)2], where phen is 1,10‐phenanthroline. The MnII atoms are octahedrally coordinated by four N atoms of two bidentate phen ligands [Mn—N = 2.240 (2)–2.3222 (19) Å] and either two water O atoms or two tdga carboxyl O atoms [Mn—O = 2.1214 (17)–2.1512 (17) Å]. The tdga ligand chelates as an O,O′‐bidentate ligand, forming an eight‐membered ring with one Mn atom. The free tdga2− dianion is hydrogen bonded to an [Mn(phen)2(H2O)2]2+ ion, with O⋯O distances of 2.606 (2) and 2.649 (2) Å. The crystal structure is further stabilized by an extensive network of hydrogen bonds involving 13 water molecules. 相似文献