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1.
Two new iron–oxo clusters, viz. di‐μ‐tri­fluoro­acetato‐μ‐oxo‐bis­[(2,2′‐bi­pyridine‐κ2N,N′)(tri­fluoro­acetato‐κO)­iron(III)], [Fe2O(CF3CO2)4(C10H8N2)2], and bis(2,2′‐bi­pyridine)­di‐μ3‐oxo‐hexa‐μ‐tri­fluoro­acetato‐bis­(tri­fluoro­acetato)­tetrairon(III) tri­fluoro­acetic acid solvate, [Fe4O2(CF3CO2)8(C10H8N2)2]·CF3CO2H, contain dinuclear and tetranuclear FeIII cores, respectively. The FeIII atoms are in distorted octahedral environments in both compounds and are linked by oxide and tri­fluoro­acetate ions. The tri­fluoro­acetate ions are either bridging (bidentate) or coordinated to the FeIII atoms via one O atom only. The fluorinated peripheries enhance the solubility of these compounds. Formal charges for all the Fe centers were assigned by summing valences of the chemical bonds to the FeIII atom.  相似文献   

2.
Two new oxo complexes, namely hexa‐μ2‐acetato‐acetato­aquabis­(di‐3‐pyridylamine)di‐μ3‐oxo‐tetra­iron(III) chloride mono­hydrate ethanol 1.25‐solvate, [Fe4(C2H3O2)7O2(C10H9N3)2(H2O)]Cl·1.25C2H6O·H2O, (I), containing a tetra­nuclear [Fe43‐O)2]8+ unit, and 2‐methyl­imidazolium hexa‐μ2‐acetato‐acetatodiaqua‐μ3‐oxo‐triiron(III) chloride dihydrate, (C4H7N2)[Fe3(C2H3O2)7O(H2O)2]Cl·2H2O, (II), with a trinuclear [Fe33‐O)]7+ unit, are presented. Both structures are formed by two well differentiated entities, viz. a compact isolated cluster composed of FeIII ions coordinated to O2− and CH3CO2 anions, and an external group formed by a central Cl ion surrounded by different solvent groups to which the anion is bound through hydrogen bonding. In the case of (I), charge balance cannot be achieved within the groups, so the structure is macroscopically ionic; in the case of (II), in contrast, each group is locally neutral owing to the inter­nal compensation of charges. The trinuclear complex crystallizes with the metal cluster, chloride anion and 2‐methyl­imidazolium cation bisected by a crystallographic mirror plane.  相似文献   

3.
Two different zinc sulfite compounds have been prepared through the decomposition of pyrosulfite–­di­thionite ions in aqueous solution, viz. a dimeric complex, di‐μ‐sulfito‐κ3O,O′:O′′;κ3O:O′,O′′‐bis­[(4,4′‐di­methyl‐2,2′‐bi­pyridine‐κ2N,N′)­zinc(II)] dihydrate, [Zn2(SO3)2(C12H12N2)2]·2H2O, (I), which was solved and refined from a twinned sample, and an extended polymer, poly­[[aqua(1,10‐phenanthroline‐κ2N,N′)­zinc(II)]‐μ3‐sulfito‐κ2O:O′:O′′‐zinc(II)‐μ3‐sulfito‐κ3O:O:O′], [Zn2(SO3)2(C12H10N2)(H2O)]n, (II). In (I), the dinuclear ZnII complex has a center of symmetry. The cation is five‐coordinate in a square‐pyramidal arrangement, the anion fulfilling a bridging chelating role. Compound (II) comprises two different zinc units, one being five‐coordinate (square pyramidal) and the other four‐coordinate (trigonal pyramidal), and two independent sulfite groups with different binding modes to the cationic centers.  相似文献   

4.
A new ionic pentanuclear FeIII cluster, namely, triethylazanium tetrakis(μ2‐5‐amino‐1,2,3,4‐tetrazolido)tetrakis(μ3‐4‐chloro‐2‐{[(1H‐tetrazol‐1‐id‐5‐yl)imino]methyl}phenolato)di‐μ3‐oxido‐pentairon(III) acetonitrile monosolvate monohydrate, (C6H16N)[Fe5(C8H4ClN5O)4(CH2N5)4O2]·CH3CN·H2O, was synthesized using microvial synthesis methods and characterized by elemental analysis, FT–IR spectroscopy, single‐crystal X‐ray diffraction and thermogravimetric analysis. Magnetic studies reveal that the complex displays dominant antiferromagnetic intracluster interactions between the FeIII ions through the μ3‐oxide bridges.  相似文献   

5.
The title compound, [Dy2(C8H7O2)6(C12H8N2)2], forms binuclear complexes, viz. di‐μ‐4‐methyl­benzoato‐κ4O:O′‐bis[bis(4‐methyl­benzoato‐κ2O,O′)(1,10‐phenanthroline‐κ2N,N′)dyspros­ium(III)] tetra‐μ‐4‐methyl­benzoato‐κ8O:O′‐bis[(4‐methyl­benzoato‐κ2O,O′)(1,10‐phenanthroline‐κ2N,N′)dyspros­ium(III)]. There are two independent binuclear com­plexes in the asymmetric unit, both of which are centrosymmetric. In one, the DyIII ions are linked by two bridging 4‐­methyl­benzoate groups, while in the other, the DyIII ions are linked by four bridging 4‐methyl­benzoate groups. The remaining 4‐methyl­benzoate groups and 1,10‐phenanthroline units coordinate to just one metal ion in bidentate modes.  相似文献   

6.
The title compound, bis(2,2′‐methyl­imino­diethano­lato)‐1κ3O,N,O′;3κ3O,N,O′‐di‐μ3‐propane‐1,3‐diolato‐1:2:3κ8O:O,O′:O′‐μ‐propane‐1,3‐diolato‐1:3κ2O:O′‐propane‐1,3‐diolato‐2κ2O,O′‐trititanium(IV), [Ti3(C5H11NO2)2(C3H6O2)4], has four 1,3‐propane­diolate ligands binding in three different modes. Two ligands chelate adjacent Ti atoms with normal μ3‐O bridges, giving typical edge‐sharing of the Ti distorted octahedra, one chelating to the central Ti atom with no μ‐bridging, and the other spanning the cluster, binding only to the outermost Ti atoms. The two methyl­imino­diethano­late ligands each coordinate to the outer Ti atoms via their N and two O atoms. The Ti—O bond lengths range, in a self‐consistent fashion, from 1.816 (2) to 2.082 (2) Å, while the average Ti—N distance is 2.391 (3) Å.  相似文献   

7.
In catena‐poly[[aqua[1,3‐bis(pyridine‐3‐ylmethoxy)benzene‐κN]zinc(II)]‐μ2‐benzene‐1,4‐dicarboxylato‐κ2O1:O4], [Zn(C8H4O4)(C18H16N2O2)(H2O)]n, each ZnII centre is tetrahedrally coordinated by two O atoms of bridging carboxylate groups from two benzene‐1,4‐dicarboxylate anions (denoted L2−), one O atom from a water molecule and one N atom from a 1,3‐bis[(pyridin‐3‐yl)methoxy]benzene ligand (denoted bpmb). (Aqua)O—H...N hydrogen‐bonding interactions induce the formation of one‐dimensional helical [Zn(L)(bpmb)(H2O)]n chains which are interlinked through (aqua)O—H...O hydrogen‐bonding interactions, producing two‐dimensional corrugated sheets.  相似文献   

8.
Coordination polymers (CPs) have been widely studied because of their diverse and adjustable topologies and wide‐ranging applications in luminescence, chemical sensors, magnetism, photocatalysis, gas adsorption and separation. In the present work, two coordination polymers, namely poly[(μ5‐benzene‐1,3,5‐tricarboxylato‐κ6O1:O1′:O3:O3:O5,O5′){μ3‐1,3‐bis[(1,2,4‐triazol‐4‐yl)methyl]benzene‐κ3N:N′:N′′}di‐μ3‐hydroxido‐dicobalt(II)], [Co2(C9H3O6)(OH)(C12H12N6)]n or [Co2(btc)(OH)(mtrb)]n, (1), and poly[[diaquabis(μ3‐benzene‐1,3,5‐tricarboxylato‐κ3O1:O3:O5)bis{μ3‐1,3‐bis[(1,2,4‐triazol‐4‐yl)methyl]benzene‐κ3N:N′:N′′}tetra‐μ3‐hydroxido‐tetracopper(II)] monohydrate], {[Cu4(C9H3O6)2(OH)2(C12H12N6)2(H2O)2]·H2O}n or {[Cu4(btc)2(OH)2(mtrb)2(H2O)2]·H2O}n, (2), were synthesized by the hydrothermal method using 1,3‐bis[(1,2,4‐triazol‐4‐yl)methyl]benzene (mtrb) and benzene‐1,3,5‐tricarboxylate (btc3?). CP (1) exhibits a (3,8)‐coordinated three‐dimensional (3D) network of the 3,8T38 topological type, with a point symbol of {4,5,6}2{42·56·616·72·82}, based on the tetranuclear hydroxide cobalt(II) cluster [Co43‐OH)2]. CP (2) shows a (3,8)‐coordinated tfz‐d topology, with a point symbol of {43}2{46·618·84}, based on the tetranuclear hydroxide copper(II) cluster [Cu43‐OH)2]. The different (3,8)‐coordinated 3D networks based on tetranuclear hydroxide–metal clusters of (1) and (2) are controlled by the different central metal ions [CoII for (1) and CuII for (2)]. The thermal stabilities and solid‐state optical diffuse‐reflection spectra were measured. The energy band gaps (Eg) obtained for (1) and (2) were 2.72 and 2.29 eV, respectively. CPs (1) and (2) exhibit good photocatalytic degradation of the organic dyes methylene blue (MB) and rhodamine B (RhB) under visible‐light irradiation.  相似文献   

9.
The polymeric title compounds, namely catena‐poly[[[di‐μ‐but‐2‐enoato‐κ3O:O,O′;κ3O,O′:O′‐bis[diaquadibut‐2‐enoato‐κO2O,O′‐neodymium(III)]]‐μ‐4,4′‐bipyridyl N,N′‐dioxide‐κ2O:O′] 4,4′‐bipyridyl N,N′‐dioxide solvate] and the erbium(III) and yttrium(III) analogues, {[Ln2(C4H5O2)6(C10H8N2O2)(H2O)4]·C10H8N2O2}n (Ln = Nd, Er and Y), form from [Ln2(bt)6(H2O)4] dimers (bt is but‐2‐enoate) bridged by 4,4′‐bipyridyl dioxide (bno) spacers into sets of parallel chains; these linear arrays are interconnected by aqua‐mediated hydrogen bonds into broad two‐dimensional structures, which in turn interact with each other though the hydrogen‐bonded bridged bno solvent units. Both independent bno units in the structures are bisected by symmetry centres.  相似文献   

10.
The three title compounds, namely 4‐phenyl‐1H‐imidazolium hexa‐μ2‐chloro‐chloro‐μ4‐oxo‐tris­(4‐phenyl‐1H‐imidazole‐κN1)­tetra­copper(II) monohydrate, (C9H9N2)[Cu4Cl7O(C9H8N2)3]·H2O, hexa‐μ2‐chloro‐μ4‐oxo‐tetra­kis­(pyridine N‐oxide‐κO)tetra­copper(II), [Cu4Cl6O(C5H5NO)4], and hexa‐μ2‐chloro‐tetra­kis(2‐methyl‐1H‐imidazole‐κN1)‐μ4‐oxo‐tetra­copper(II) methanol trisolvate, [Cu4Cl6O(C4H6N2)4]·3CH4O, exhibit the same Cu4OCl6 framework, where the O atom at the centre of an almost regular tetra­hedron bridges four copper cations at the corners. This group is in turn surrounded by a Cl6 octa­hedron, leading to a rather globular species. This special arrangement of the CuII cations results in a diversity of magnetic behaviours.  相似文献   

11.
The title complex, catena‐poly[di‐μ3‐acetato‐κ6O:O:O′‐tetra‐μ2‐acetato‐κ4O:O4O:O′‐diaquabis(pyridine‐κN)trimanganese(II)], [Mn3(CH3COO)6(C6H5N)2(H2O)2]n, is a true one‐dimensional coordination polymer, in which the MnII centres form a zigzag chain along [010]. The asymmetric unit contains two metal centres, one of which (Mn1) lies on an inversion centre, while the other (Mn2) is placed close to an inversion centre on a general position. Since all the acetates behave as bridging ligands, although with different μ2‐ and μ3‐coordination modes, a one‐dimensional polymeric structure is formed, based on trinuclear repeat units (Mn1...Mn2...Mn2′), in which the Mn2 and Mn2′ sites are related by an inversion centre. Within this monomeric block, the metal–metal separations are Mn1...Mn2 = 3.36180 (18) Å and Mn2...Mn2′ = 4.4804 (3) Å. Cation Mn1, located on an inversion centre, displays an [MnO6] coordination sphere, while Mn2, on a general position, has a slightly stronger [MnO5N] ligand field, as the sixth coordination site is occupied by a pyridine molecule. Both centres approximate an octahedral ligand field. The chains are parallel in the crystal structure and interact via hydrogen bonds involving coordinated water molecules. However, the shortest metal–metal separation between two chains [5.3752 (3) Å] is large compared with the intrachain interactions. These structural features are compatible with a single‐chain magnet behaviour, as confirmed by preliminary magnetic studies.  相似文献   

12.
The title dodecanuclear Mn complex, namely dodeca‐μ2‐acetato‐κ24O:O′‐tetraaquatetra‐μ2‐nitrato‐κ8O:O′‐tetra‐μ4‐oxido‐octa‐μ3‐oxido‐tetramanganese(IV)octamanganese(III) nitromethane tetrasolvate, [Mn12(CH3COO)12(NO3)4O12(H2O)4]·4CH3NO2, was synthesized by the reaction of Mn2+ and Ce4+ sources in nitromethane with an excess of acetic acid. This compound is distinct from the previously known single‐molecule magnet [Mn12O12(O2CMe)16(H2O)4], synthesized by Lis [Acta Cryst. (1980), B 36 , 2042–2044]. It is the first Mn12‐type molecule containing nitrate ligands to be directly synthesized without the use of a preformed cluster. Additionally, this molecule is distinct from all other known Mn12 complexes due to intermolecular hydrogen bonds between the nitrate and water ligands, which give rise to a three‐dimensional network. The complex is compared to other known Mn12 molecules in terms of its structural parameters and symmetry.  相似文献   

13.
Reported here are the single‐crystal X‐ray structure analyses of bis‐μ‐methanol‐κ4O:O‐bis{[hydrotris(3‐phenyl‐2‐sulfanylidene‐2,3‐dihydro‐1H‐1,3‐imidazol‐1‐yl)borato‐κ3H,S,S′](methanol‐κO)sodium(I)}, [Na2(C27H22BN6S3)2(CH4O)4] (NaTmPh), bis‐μ‐methanol‐κ4O:O‐bis{[hydrotris(3‐isopropyl‐2‐sulfanylidene‐2,3‐dihydro‐1H‐1,3‐imidazol‐1‐yl)borato‐κ3H,S,S′](methanol‐κO)sodium(I)}–diethyl ether–methanol (1/0.3333/0.0833), [Na2(C18H28BN6S3)2(CH4O)4]·0.3333C4H10O·0.0833CH3OH (NaTmiPr), and a novel anhydrous form of sodium hydrotris(methylthioimidazolyl)borate, poly[[μ‐hydrotris(3‐methyl‐2‐sulfanylidene‐2,3‐dihydro‐1H‐1,3‐imidazol‐1‐yl)borato]sodium(I)], [Na(C12H16BN6S3)] ([NaTmMe]n). NaTmiPr and NaTmPh have similar dimeric molecular structures with κ3H,S,S′‐bonding, but they differ in that NaTmPh is crystallographically centrosymmetric (Z′ = 0.5) while NaTmiPr contains one crystallographically centrosymmetric dimer and one dimer positioned on a general position (Z′ = 1.5). [NaTmMe]n is a one‐dimensional coordination polymer that extends along the a direction and which contains a hitherto unseen side‐on η2‐C=S‐to‐Na bond type. An overview of the structural preferences of alkali metal soft scorpionate complexes is presented. This analysis suggests that these thione‐based ligands will continue to be a rich source of interesting alkali metal motifs worthy of isolation and characterization.  相似文献   

14.
Three alkaline earth metal salts of phenylacetic acid were examined and all were found to have similar structural types to analogous salts of benzoic and halobenzoic acids. Thus, a synchrotron study shows that the cations in catena‐poly[[[tetraaquamagnesium(II)]‐μ‐phenylacetato‐κ2O:O′] phenylacetate], {[Mg(C8H7O2)(H2O)4](C8H7O2)}n, form a one‐dimensional coordination polymer that propagates through Mg—O—C—O—Mg interactions involving both crystallographically independent Mg centres (Z′ = 2) and through translation along the a axis. The polymeric chains pack to give alternate inorganic layers and organic bilayers. The Ca and Sr species catena‐poly[[[diaqua(phenylacetato‐κ2O,O′)calcium(II)]‐μ3‐phenylacetato‐1′:1:1′′κ4O:O,O′:O′] monohydrate], {[Ca(C8H7O2)2(H2O)2]·H2O}n, and catena‐poly[[[diaqua(phenylacetato‐κ2O,O′)strontium(II)]‐μ3‐phenylacetato‐1′:1:1′′κ4O:O,O′:O′] monohydrate], {[Sr(C8H7O2)2(H2O)2]·H2O}n, are essentially isostructural. Both form one‐dimensional coordination polymers through a carboxylate group that forms four M—O bonds. The polymeric chains propagate via 21 screw axes parallel to the b axis and are further linked in the bc plane by hydrogen bonding involving the non‐metal‐bound water molecule. Similarly to the Mg salt, both have inorganic layers that alternate with organic bilayers.  相似文献   

15.
The new bifunctional ligand 4,4′‐(adamantane‐1,3‐diyl)bis(1,2,4‐triazole) (tr2ad) and benzene‐1,3,5‐tricarboxylate sustain complementary coordination bridging for the three‐dimensional framework of poly[[bis[μ3‐4,4′‐(adamantane‐1,3‐diyl)bis(1,2,4‐triazole)‐κ3N1:N2:N1′]bis(μ4‐benzene‐1,3,5‐tricarboxylato‐κ4O1:O1′:O3:O5)di‐μ3‐hydroxido‐κ6O:O:O‐tetracopper(II)] dihydrate], {[Cu4(C9H3O6)2(OH)2(C14H18N6)2]·2H2O}n. The net node is a centrosymmetric (μ3‐OH)2Cu4 cluster [Cu—O = 1.9525 (14)–2.0770 (15) Å and Cu...Cu = 3.0536 (5) Å] involving two independent copper ions in tetragonal pyramidal CuO4N and trigonal bipyramidal CuO3N2 environments. One carboxylate group of the anion is bridging and the other two are monodentate, leading to the connection of three hydroxide clusters and the generation of neutral coordination layers separated by 9.3583 (5) Å. The interlayer linkage is effected by μ3‐tr2ad ligands, with one triazole group N1:N2‐bridging and the second monodentate [Cu—N = 1.9893 (19), 2.010 (2) and 2.411 (2) Å]. In total, the hydroxide clusters are linked to six close neighbors within the carboxylate layer and to four neighbors via tr2ad bridges. Hydrogen bonding of solvent water molecules to noncoordinated triazole N atoms and carboxylate groups provides two additional links for the net, which adopts a 12‐connected topology corresponding to hexagonal closest packing. The study also introduces a new type of bis(triazole) ligand, which may find wider applications for supramolecular synthesis.  相似文献   

16.
In the linear coordination polymer catena‐poly[[[aqua(1,10‐phenanthroline‐κ2N,N′)copper(II)]‐μ‐pyridine‐2,6‐dicarboxylato‐κ4O2:O2′,N,O6‐[(nitrato‐κ2O,O′)bismuth(III)]‐μ‐pyridine‐2,6‐dicarboxylato‐κ4O2,N,O6:O6′] dihydrate], {[BiIIICuII(C7H3NO4)2(NO3)(C12H8N2)(H2O)]·2H2O}n, the BiIII cation is O,N,O′‐chelated by the two pyridine‐2,6‐dicarboxylate ligands and O,O′‐chelated by the nitrate anion, the nine coordinating atoms conferring a tricapped trigonal prismatic environment on the metal centre. Each pyridine‐2,6‐dicarboxylate ligand uses one of its carboxylate O atoms to bind to an aqua(1,10‐phenanthroline)copper(II) unit, the Cu—O dative bonds giving rise to the formation of a ribbon motif. The CuII cation exhibits a square‐pyramidal geometry. The ribbon motif propagates along the shortest axis of the triclinic unit cell and the solvent water molecules are hydrogen bonded to the same ribbon.  相似文献   

17.
In the title complex, catena‐poly[[[diaqua­calcium(I)]‐μ2‐aqua‐μ3‐benzoato‐κ4O:O,O′:O′] benzoate], {[Ca(C7H5O2)(H2O)3](C7H5O2)}n, obtained by the reaction of CaCl2 and potassium benzoate in water, the Ca atom is eight‐coordinated by four carboxyl­ate O atoms and four water mol­ecules. The structure consists of polymeric {[Ca(C6H5COO)(H2O)3]+} chains alternating with layers of uncoordinated C6H5COO anions. The nearly planar anions are linked to the chain by short hydrogen bonds to form a two‐dimensional network.  相似文献   

18.
Three isotypic rare earth complexes, catena‐poly[[aquabis(but‐2‐enoato‐κ2O,O′)yttrium(III)]‐bis(μ‐but‐2‐enoato)‐κ3O,O′:O3O:O,O′‐[aquabis(but‐2‐enoato‐κ2O,O′)yttrium(III)]‐μ‐4,4′‐(ethane‐1,2‐diyl)dipyridine‐κ2N:N′], [Y2(C4H5O2)6(C12H12N2)(H2O)2], the gadolinium(III) analogue, [Gd2(C4H5O2)6(C12H12N2)(H2O)2], and the gadolinium(III) analogue with a 4,4′‐(ethene‐1,2‐diyl)dipyridine bridging ligand, [Gd2(C4H5O2)6(C12H10N2)(H2O)2], are one‐dimensional coordination polymers made up of centrosymmetric dinuclear [M(but‐2‐enoato)3(H2O)]2 units (M = rare earth), further bridged by centrosymmetric 4,4′‐(ethane‐1,2‐diyl)dipyridine or 4,4′‐(ethene‐1,2‐diyl)dipyridine spacers into sets of chains parallel to the [20] direction. There are intra‐chain and inter‐chain hydrogen bonds in the structures, the former providing cohesion of the linear arrays and the latter promoting the formation of broad planes parallel to (010).  相似文献   

19.
The crystal structures of three unusual chromium organophosphate complexes have been determined, namely, bis(μ‐butyl 2,6‐di‐tert‐butyl‐4‐methylphenyl hydrogen phosphato‐κOO′)di‐μ‐hydroxido‐bis[(butyl 2,6‐di‐tert‐butyl‐4‐methylphenyl hydrogen phosphato‐κO)(butyl 2,6‐di‐tert‐butyl‐4‐methylphenyl phosphato‐κO)chromium](CrCr) heptane disolvate or {Cr22‐OH)22‐PO2(OBu)(O‐2,6‐tBu2‐4‐MeC6H2)‐κOO′]2[PO2(OBu)(O‐2,6‐tBu2‐4‐MeC6H2)‐κO]2[HOPO(OBu)(O‐2,6‐tBu2‐4‐MeC6H2)‐κO]2}·2C7H16, [Cr2(C19H32O4P)4(C19H33O4P)2(OH)2]·2C7H16, denoted ( 1 )·2(heptane), [μ‐bis(2,6‐diisopropylphenyl) phosphato‐1κO:2κO′]bis[bis(2,6‐diisopropylphenyl) phosphato]‐1κO,2κO‐chlorido‐2κCl‐triethanol‐1κ2O,2κO‐di‐μ‐ethanolato‐1κ2O:2κ2O‐dichromium(CrCr) ethanol monosolvate or {Cr22‐OEt)22‐PO2(O‐2,6‐iPr2‐C6H3)2‐κOO′][PO2(O‐2,6‐iPr2‐C6H3)2‐κO]2Cl(EtOH)3}·EtOH, [Cr2(C2H5O)2(C24H34O4P)3Cl(C2H6O)3]·C2H6O, denoted ( 2 )·EtOH, and di‐μ‐ethanolato‐1κ2O:2κ2O‐bis{[bis(2,6‐diisopropylphenyl) hydrogen phosphato‐κO][bis(2,6‐diisopropylphenyl) phosphato‐κO]chlorido(ethanol‐κO)chromium}(CrCr) benzene disolvate or {Cr22‐OEt)2[PO2(O‐2,6‐iPr2‐C6H3)2‐κO]2[HOPO(O‐2,6‐iPr2‐C6H3)2‐κO]2Cl2(EtOH)2}·2C6H6, [Cr2(C2H5O)2(C24H34O4P)2(C24H35O4P)2Cl2(C2H6O)2]·2C6H6, denoted ( 3 )·2C6H6. Complexes ( 1 )–( 3 ) have been synthesized by an exchange reaction between the in‐situ‐generated corresponding lithium or potassium disubstituted phosphates with CrCl3(H2O)6 in ethanol. The subsequent crystallization of ( 1 ) from heptane, ( 2 ) from ethanol and ( 3 ) from an ethanol/benzene mixture allowed us to obtain crystals of ( 1 )·2(heptane), ( 2 )·EtOH and ( 3 )·2C6H6, whose structures have the monoclinic P21, orthorhombic P212121 and triclinic P space groups, respectively. All three complexes have binuclear cores with a single Cr—Cr bond, i.e. Cr2O6P2 in ( 1 ), Cr2PO4 in ( 2 ) and Cr2O2 in ( 3 ), where the Cr atoms are in distorted octahedral environments, formally having 16 ē per Cr atom. The complexes have bridging ligands μ2‐OH in ( 1 ) or μ2‐OEt in ( 2 ) and ( 3 ). The organophosphate ligands demonstrate terminal κO coordination modes in ( 1 )–( 3 ) and bridging μ2‐κOO′ coordination modes in ( 1 ) and ( 2 ). All the complexes exhibit hydrogen bonding: two intramolecular Ophos…H—Ophos interactions in ( 1 ) and ( 3 ) form two {H[PO2(OR)2]2} associates; two intramolecular Cl…H—OEt hydrogen bonds additionally stabilize the Cr2O2 core in ( 3 ); two intramolecular Ophos…H—OEt interactions and two O…H—O intermolecular hydrogen bonds with a noncoordinating ethanol molecule are observed in ( 2 )·EtOH. The presence of both basic ligands (OH? or OEt?) and acidic [H(phosphate)2]? associates at the same metal centres in ( 1 ) and ( 3 ) is rather unusual. Complexes may serve as precatalysts for ethylene polymerization under mild conditions, providing polyethylene with a small amount of short‐chain branching. The formation of a small amount of α‐olefins has been detected in this reaction.  相似文献   

20.
Two new two‐dimensional coordination polymers, poly­[[[aqua(2,2′‐bi­pyridine‐κ2N,N′)manganese(II)]‐μ3p‐phenyl­enebis­(oxy­acet­ato)‐κ3O:O′:O′′] dihydrate], {[Mn(C10H8O6)(C10H8N2)(H2O)]·2H2O}n, (I), and poly­[[di‐μ‐aqua‐bis­[aqua­sodium(I)]]‐μ4p‐phenyl­enebis­(oxy­acetato)‐κO:O′,O′′:O′′′,O′′′′:O′′′′′], [Na2(C10H8O6)(H2O)4]n, (II), have been synthesized and characterized by X‐ray single‐crystal diffraction. In (I), there are two 1,4‐BDOA2− [p‐phenyl­enebis­(oxy­acetate) or, more commonly, benzene‐1,4‐dioxy­acetate] ligands, each lying about inversion centres, while in (II), there is one such ligand and it also has crystallographically imposed inversion symmetry. In (I), each MnII atom displays an octahedral MnN2O4 configuration, defined by three carboxyl O atoms of different 1,4‐BDOA2− groups, two N atoms of one 2,2′‐bi­pyridine ligand and one water mol­ecule. In (II), each NaI atom is octahedrally coordinated by one ether O atom, two carboxyl O atoms of different 1,4‐BDOA2− ligands and three water mol­ecules. The metal ions in complexes (I) and (II) are bridged by 1,4‐BDOA2− groups into two‐dimensional layer structures. Furthermore, three‐dimensional supramolecular networks are constructed via hydrogen bonds in (I) and (II), and by additional π–π stacking interactions in (I).  相似文献   

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