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1.
The title compound, [Cd2(SO3)2(C18H12N6)2]·8H2O, is a dimer built up around a symmetry center, where the sulfite anion displays a so far unreported coordination mode in metal‐organic complexes; the anion binds as a μ2‐sulfite‐κ4O,O′:O′,O′′ ligand to two symmetry‐related seven‐coordinate CdII cations, binding through its three O atoms by way of two chelate bites with an O atom in common, which acts as a bridge. The cation coordination is completed by a 2,4,6‐tri‐2‐pyridyl‐1,3,5‐triazine ligand acting in its usual tridentate mode.  相似文献   

2.
Employing in situ N‐alkylation of the conjugated compound 9,10‐bis(4‐pyridyl)anthracene (bpanth) as structure‐directing agent, a 3D inorganic‐organic hybrid iodoplumbate, [Me2(bpanth)][Pb4I10] ( 1 ), was solvothermally prepared. The in situ N‐alkylation of bpanth with alcohols was investigated. 1 features a novel 3D open framework based on an interesting Pb6I24 cluster. UV/Vis spectroscopy analyses indicate that 1 is a potential semiconductor material with a narrow energy gap of 2.06 eV. It exhibits good catalytic activity in the visible‐light‐drived degradation of an organic dye. This work further illustrates that introducing conjugated organic molecules as templates is conducive to achieving semiconducting hybrid halometallates with narrow band gaps.  相似文献   

3.
catena‐Poly­[[[bis­[di­aqua(4,4′‐bi­pyridine)­cadmium(II)]‐bis­[μ‐(N′′‐carboxy­methyl­diethyl­enetri­amine‐N,N,N′,N′′‐tetra­ace­ta­to)­cadmium(II)]]‐μ‐4,4′‐bi­pyridine] tetradecahydrate], [Cd4­(C14H19N3O10)2(C10H8N2)3(H2O)4]·14H2O or [Cd4(HD­TPA)2(BPY)3(H2O)4]·14H2O, where BPY is 4,4′‐bi­pyridine and HDTPA4? is N′′‐carboxy­methyl­diethyl­enetri­amine‐N,N,N′,N′′‐tetra­acetate, consists of a one‐dimensional coordination polymer formed from a secondary building unit which comprises four Cd centres. The chain structure of the title compound was obtained by the use of a multidentate organic ligand, N,N,N′,N′′,N′′‐diethyl­enetri­amine­penta­acetic acid (H5DTPA), which forms multiple chelate rings with the Cd metal centres. An extended network is formed via hydrogen bonds.  相似文献   

4.
The structures of two new sulfate complexes are reported, namely di‐μ‐sulfato‐κ3O,O′:O′′‐bis{aqua­[2,4,6‐tris(2‐pyridyl)‐1,3,5‐triazine‐κ3N1,N2,N6]­cadmium(II)} tetra­hydrate, [Cd2(SO4)2(C16H12N6)2(H2O)2]·4H2O, and di‐μ‐sulfato‐κ2O:O′‐bis­[(2,2′:6′,2′′‐ter­pyridine‐κ3N1,N1′,N1′′)­zinc(II)] dihydrate, [Cd2(SO4)2(C15H11N3)2]·2H2O, the former being the first report of a Cd(tpt) complex [tpt is 2,4,6‐tris(2‐pyridyl)‐1,3,5‐triazine]. Both compounds crystallize in the space group P and form centrosymmetric dimeric structures. In the cadmium complex, the metal center is heptacoordinated in the form of a pentagonal bipyramid, while in the zinc complex, the metal ion is in a fivefold environment, the coordination geometry being intermediate between square pyramidal and trigonal bipyramidal. Packing of the dimers leads to the formation of planar structures strongly linked by hydrogen bonding.  相似文献   

5.
The title complex, bis[μ3cisN‐(2‐aminopropyl)‐N′‐(2‐carboxylatophenyl)oxamidato(3−)]‐1:2:4κ7N,N′,N′′,O:O′,O′′:O′′′;2:3:4κ7O′′′:N,N′,N′′,O:O′,O′′‐bis(2,2′‐bipyridine)‐2κ2N,N′;4κ2N,N′‐dichlorido‐1κCl,3κCl‐tetracopper(II) dihydrate, [Cu4(C12H12N3O4)2Cl2(C10H8N2)2]·2H2O, consists of a neutral cyclic tetracopper(II) system having an embedded centre of inversion and two solvent water molecules. The coordination of each CuII atom is square‐pyramidal. The separations of CuII atoms bridged by cisN‐(2‐aminopropyl)‐N′‐(2‐carboxylatophenyl)oxamidate(3−) and carboxyl groups are 5.2096 (4) and 5.1961 (5) Å, respectively. A three‐dimensional supramolecular structure involving hydrogen bonding and aromatic stacking is observed.  相似文献   

6.
The structures of five compounds consisting of (prop‐2‐en‐1‐yl)bis[(pyridin‐2‐yl)methylidene]amine complexed with copper in both the CuI and CuII oxidation states are presented, namely chlorido{(prop‐2‐en‐1‐yl)bis[(pyridin‐2‐yl)methylidene]amine‐κ3N,N′,N′′}copper(I) 0.18‐hydrate, [CuCl(C15H17N3)]·0.18H2O, (1), catena‐poly[[copper(I)‐μ2‐(prop‐2‐en‐1‐yl)bis[(pyridin‐2‐yl)methylidene]amine‐κ5N,N′,N′′:C2,C3] perchlorate acetonitrile monosolvate], {[Cu(C15H17N3)]ClO4·CH3CN}n, (2), dichlorido{(prop‐2‐en‐1‐yl)bis[(pyridin‐2‐yl)methylidene]amine‐κ3N,N′,N′′}copper(II) dichloromethane monosolvate, [CuCl2(C15H17N3)]·CH2Cl2, (3), chlorido{(prop‐2‐en‐1‐yl)bis[(pyridin‐2‐yl)methylidene]amine‐κ3N,N′,N′′}copper(II) perchlorate, [CuCl(C15H17N3)]ClO4, (4), and di‐μ‐chlorido‐bis({(prop‐2‐en‐1‐yl)bis[(pyridin‐2‐yl)methylidene]amine‐κ3N,N′,N′′}copper(II)) bis(tetraphenylborate), [Cu2Cl2(C15H17N3)2][(C6H5)4B]2, (5). Systematic variation of the anion from a coordinating chloride to a noncoordinating perchlorate for two CuI complexes results in either a discrete molecular species, as in (1), or a one‐dimensional chain structure, as in (2). In complex (1), there are two crystallographically independent molecules in the asymmetric unit. Complex (2) consists of the CuI atom coordinated by the amine and pyridyl N atoms of one ligand and by the vinyl moiety of another unit related by the crystallographic screw axis, yielding a one‐dimensional chain parallel to the crystallographic b axis. Three complexes with CuII show that varying the anion composition from two chlorides, to a chloride and a perchlorate to a chloride and a tetraphenylborate results in discrete molecular species, as in (3) and (4), or a bridged bis‐μ‐chlorido complex, as in (5). Complex (3) shows two strongly bound Cl atoms, while complex (4) has one strongly bound Cl atom and a weaker coordination by one perchlorate O atom. The large noncoordinating tetraphenylborate anion in complex (5) results in the core‐bridged Cu2Cl2 moiety.  相似文献   

7.
In the new tin(IV) and copper(II) complexes, cis‐dichlorido‐trans‐dimethyl‐cis‐bis(N,N′,N′′‐tricyclohexylphosphoric triamide‐κO)tin(IV), [Sn(CH3)2Cl2(C18H36N3OP)2], (I), and trans‐diaquabis(N,N′,N′′‐tricyclohexylphosphoric triamide‐κO)copper(II) dinitrate–N,N′,N′′‐tricyclohexylphosphoric triamide (1/2), [Cu(C18H36N3OP)2(H2O)2](NO3)2·2C18H36N3OP, (II), the N,N′,N′′‐tricyclohexylphosphoric triamide (PTA) ligands exist as hydrogen‐bonded dimers via P=O...H—N interactions around the metal center. The asymmetric unit in (I) consists of one complete complex molecule located on a general position. The SnIV coordination geometry is octahedral with two cis hydrogen‐bonded PTA ligands, two cis chloride ligands and two trans methyl groups. The asymmetric unit in (II) contains one half of a [Cu(PTA)2(H2O)2]2+ dication on a special position (site symmetry for the Cu atom), one nitrate anion and one free PTA molecule, both on general positions. The complex adopts a square‐planar trans‐[CuO2O2] coordination geometry, with the CuII ion coordinated by two PTA ligands and two water molecules. Each of the noncoordinated PTA molecules is hydrogen bonded to a neighboring coordinated PTA molecule and an adjacent water molecule; the phosphoryl O atom acts as a double‐H‐atom acceptor. The P atoms in the PTA ligands of both complexes and in the noncoordinated hydrogen‐bonded molecules in (II) adopt a slightly distorted tetrahedral environment.  相似文献   

8.
Phosphoric triamides have extensive applications in biochemistry and are also used as O‐donor ligands. Four new mixed‐amide phosphoric triamide structures, namely racNtert‐butyl‐N′,N′′‐dicyclohexyl‐N′′‐methylphosphoric triamide, C17H36N3OP, (I), racN,N′‐dicyclohexyl‐N′‐methyl‐N′′‐(p‐tolyl)phosphoric triamide, C20H34N3OP, (II), N,N′,N′′‐tricyclohexyl‐N′′‐methylphosphoric triamide, C19H38N3OP, (III), and 2‐[cyclohexyl(methyl)amino]‐5,5‐dimethyl‐1,3,2λ5‐diazaphosphinan‐2‐one, C12H26N3OP, (IV), have been synthesized and studied by X‐ray diffraction and spectroscopic methods. Structures (I) and (II) are the first diffraction studies of acyclic racemic mixed‐amide phosphoric triamides. The P—N bonds resulting from the different substituent –N(CH3)(C6H11), (C6H11)NH–, 4‐CH3‐C6H4NH–, (tert‐C4H9)NH– and –NHCH2C(CH3)2CH2NH– groups are compared, along with the different molecular volumes and electron‐donor strengths. In all four structures, the molecules form extended chains through N—H…O hydrogen bonds.  相似文献   

9.
A simple and green method that uses [Ru(Me3tacn)Cl3] ( 1 ; Me3tacn=N,N′,N′′‐trimethyl‐1,4,7‐triazacyclononane) as catalyst, aqueous H2O2 as the terminal oxidant, and Al2O3 and NaCl as additives is effective in the cis‐dihydroxylation of alkenes in aqueous tert‐butanol. Unfunctionalized alkenes, including cycloalkenes, aliphatic alkenes, and styrenes (14 examples) were selectively oxidized to their corresponding cis‐diols in good to excellent yield (70–96 %) based on substrate conversions of up to 100 %. The preparation of cis‐1,2‐cycloheptanediol (119 g, 91 % yield) and cis‐1,2‐cyclooctanediol (128 g, 92 % yield) from cycloheptene and cyclooctene, respectively, on the 1‐mol scale can be achieved by scaling up the reaction without modification. Results from Hammett correlation studies on the competitive oxidation of para‐substituted styrenes (ρ=?0.97, R=0.988) and the detection of the cycloadduct [(Me3tacn)ClRuHO2(C8H14)]+ by ESI‐MS for the 1 ‐catalyzed oxidation of cyclooctene to cis‐1,2‐cyclooctanediol are similar to those of the stoichiometric oxidation of alkenes by cis‐[(Me3tacn)(CF3CO2)RuVIO2]+ through [3+2] cycloaddition (W.‐P. Yip, W.‐Y. Yu, N. Zhu, C.‐M. Che, J. Am. Chem. Soc. 2005 , 127, 14239).  相似文献   

10.
In the crystal structure of the title compound, [N,N′‐bis(3‐­amino­propyl)­ethyl­enedi­amine‐κ4N,N′,N′′,N′′′][1,3,5‐triazine‐2,4,6(1H,3H,5H)‐tri­thionato(2−)‐κ2N,S]­zinc(II) ethanol sol­vate, [Zn(C8H22N4)2(C3HN3S3)]·C2H6O, the ZnII atom is octa­hedrally coordinated by four N atoms [Zn—N = 2.104 (2)–2.203 (2) Å] of a tetradentate N‐donor N,N′‐bis(3‐­amino­propyl)­ethyl­enedi­amine (bapen) ligand and by two S and N atoms [Zn—S = 2.5700 (7) Å and Zn—N = 2.313 (2) Å] of a tri­thio­cyanurate(2−) (ttcH2−) dianion bonded as a bidentate ligand in a cis configuration. The crystal structure of the compound is stabilized by a network of hydrogen bonds.  相似文献   

11.
The reaction of the imide–nitride complex [{Ti(η5‐C5Me5)(μ‐NH)}33‐N)] with potassium iodide in pyridine at room temperature affords the adduct di‐μ‐iodido‐1:1′κ4I‐bis{tri‐μ3‐imido‐1:2:3κ3N;1:2:4κ3N;1:3:4κ3N‐μ3‐nitrido‐2:3:4κ3N‐tris[2,3,4(η5)‐pentamethylcyclopentadienyl](pyridine‐1κN)‐tetrahedro‐potassiumtrititanium(IV)}, [K2Ti6(C10H15)6I2N2(NH)6(C5H5N)2] or [(C5H5N)(μ‐I)K{(μ3‐NH)3Ti35‐C5Me5)33‐N)}]2. The crystal structure contains two [KTi3N4] cube‐type units held together by two bridging I atoms. There is a centre of inversion located in the middle of this unprecedented discrete K2I2 unit. The geometry around K is best described as distorted trigonal prismatic, with three imide groups, two bridging I atoms and one pyridine ligand.  相似文献   

12.
Bis­[μ‐1‐(3‐pyridyl)­ethanone oxime‐κ2N:N′]­bis­[nitrato­sil­ver(I)], [Ag2(NO3)2(C7H8N2O)2], crystallizes as a centrosymmetric binuclear macrocylic complex containing silver(I) ions bridged by the organic 1‐(3‐pyridyl)­ethanone oxime ligand. The ligand coordinates via the pyridine and the oxime N atoms. A similar metal–ligand arrangement was found in the copper(I) complex catena‐poly­[[bis­[μ‐1‐(3‐pyridyl)­ethano­ne oxime‐κ2N:N′]­dicopper(I)]‐di‐μ‐iodo], [Cu2I2(C7H8N2O)2]n, but here the centrosymmetric macrocycles are connected by double anion bridges, resulting in the formation of a one‐dimensional coordination polymer.  相似文献   

13.
In the title three‐dimensional tetrazolate‐based coordination polymer, poly[bis(μ3‐cyanido‐κ3N:C:C)[μ5‐5‐(pyridin‐4‐yl)tetrazolato‐κ5N:N′:N′′:N′′′:N′′′′]tricopper(I)], [Cu3(C6H4N5)(CN)2]n, there are two types of coordinated CuI atoms. One type exhibits a tetrahedral environment and the other, residing on a twofold axis, adopts a trigonal coordination environment. The closest Cu...Cu distance is only 2.531 (2) Å, involving a bridging cyanide C atom. All four tetrazolate and the pyridine N atom of the 4‐(pyridin‐4‐yl)‐1H‐tetrazolate anion are coordinated to these CuI atoms and exhibit a μ5‐bridging mode. The three‐dimensional coordination network can be topologically simplified as a rarely observed (3,3,4,5)‐connected network with the Schläfli symbol (4.6.84)2.(42.6.87).(6.82)3.  相似文献   

14.
The reactions of the new nitrilotriacetic acid N′,N′,N′‐tri(salicyloyl)trihydrazide (Ntash) with the corresponding metal salts gave four new complexes [Pb4(bshz)2] · 2DMF ( 1 ), [Co2(bshz)(C5H5N)6] · 2ClO4 · (C5H5N) · 2H2O ( 2 ), [Cu3(fshz)2(C5H5N)2] ( 3 ), and [Zn3(fshz)2(C5H5N)3]n · 2DMF ( 4 ), in which two multidentate ligands, namely N,N′‐disalicyloylhydrazine (H4bshz) and N‐formylsalicylhydrazide (H3fshz) were generated in situ from Ntash. The structures of these complexes were determined by single‐crystal X‐ray diffraction analysis. Complex 1 presents a novel tetranuclear lead(II) cluster structure with the four lead(II) cations in “hemidirected” coordination spheres. The neighboring tetranuclear clusters of 1 are connected by DMF molecules through weak Pb–O bonds, forming one‐dimensional ribbons. Complexes 2 and 3 show dinuclear and linear trinuclear structures with the corresponding CoIII and CuII ions in distorted octahedral and square‐planar coordination environments, respectively. Complex 4 exhibits a one‐dimensional zigzag chain structure. The magnetic properties of 3 and the photoluminescent properties of 4 were also investigated.  相似文献   

15.
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   

16.
In N,N,N′,N′‐tetraethyl‐N′′‐(4‐fluorobenzoyl)phosphoric triamide, C15H25FN3O2P, (I), and N‐(2,6‐difluorobenzoyl)‐N′,N′′‐bis(4‐methylpiperidin‐1‐yl)phosphoric triamide, C19H28F2N3O2P, (II), the C—N—C angle at each tertiary N atom is significantly smaller than the two P—N—C angles. For the other new structure, N,N′‐dicyclohexyl‐N′′‐(2‐fluorobenzoyl)‐N,N′‐dimethylphosphoric triamide, C21H33FN3O2P, (III), one C—N—C angle [117.08 (12)°] has a greater value than the related P—N—C angle [115.59 (9)°] at the same N atom. Furthermore, for most of the analogous structures with a [C(=O)NH]P(=O)[N(C)(C)]2 skeleton deposited in the Cambridge Structural Database [CSD; Allen (2002). Acta Cryst. B 58 , 380–388], the C—N—C angle is significantly smaller than the two P—N—C angles; exceptions were found for four structures with the N‐methylcyclohexylamide substituent, similar to (III), one structure with the seven‐membered cyclic amide azepan‐1‐yl substituent and one structure with an N‐methylbenzylamide substituent. The asymmetric units of (I), (II) and (III) contain one molecule, and in the crystal structures, adjacent molecules are linked via pairs of N—H...O=P hydrogen bonds to form dimers.  相似文献   

17.
The reaction of [(η5‐L3)Ru(PPh3)2Cl], where; L3 = C9H7 ( 1 ), C5Me5 (Cp*) ( 2 ) with acetonitrile in the presence of [NH4][PF6] yielded cationic complexes [(η5‐L3)Ru(PPh3)2(CH3CN)][PF6]; L3= C9H7 ([3]PF6) and L3 = C5Me5 ([4]PF6), respectively. Complexes [3]PF6 and [4]PF6 reacts with some polypyridyl ligands viz, 2,3‐bis (α‐pyridyl) pyrazine (bpp), 2,3‐bis (α‐pyridyl) quinoxaline (bpq) yielding the complexes of the formulation [(η5‐L3)Ru(PPh3)(L2)]PF6 where; L3 = C9H7, L2 = bpp, ([5]PF6), L3 = C9H7, L2 = bpq, ([6]PF6); L3 = C5Me5, L2 = bpp, ([7]PF6) and bpq, ([8]PF6), respectively. However reaction of [(η5‐C9H7)Ru(PPh3)2(CH3CN)][PF6] ([3]PF6) with the sterically demanding polypyridyl ligands, viz. 2,4,6‐tris(2‐pyridyl)‐1,3,5‐triazine (tptz) or tetra‐2‐pyridyl‐1,4‐pyrazine (tppz) leads to the formation of unexpected complexes [Ru(PPh3)2(L2)(CH3CN)][PF6]2; L2 = tppz ([9](PF6)2), tptz ([11](PF6)2) and [Ru(PPh3)2(L2)Cl][PF6]; L2 = tppz ([10]PF6), tptz ([12]PF6). The complexes were isolated as their hexafluorophosphate salts. They have been characterized on the basis of micro analytical and spectroscopic data. The crystal structures of the representative complexes were established by X‐ray crystallography.  相似文献   

18.
The title compound, [Ag(C3H6N6)2]NO3, has an alternating two‐dimensional bilayer structure supported by extensive hydrogen bonds. The [Ag(melamine)2]+ cationic monomers (melamine is 1,3,5‐triazine‐2,4,6‐triamine) are connected via N—H...N hydrogen bonds to form two‐dimensional sheets. Nitrate groups are sandwiched between two sheets through N—H...O hydrogen bonds. An almost perfectly linear coordination geometry is found for the AgI ions. The triazine ligands are slightly distorted due to π–π interactions.  相似文献   

19.
In the tetranuclear copper complex tetrakis[μ‐3,5‐bis(2‐pyridyl)‐1,2,4‐triazolido]bis[3,5‐bis(2‐pyridyl)‐1,2,4‐triazolido]dicopper(I)dicopper(II) dihydrate, [CuI2CuII2(C12H8N5)6]·2H2O, the asymmetric unit is composed of one CuI center, one CuII center, three anionic 3,5‐bis(2‐pyridyl)‐1,2,4‐triazole (2‐BPT) ligands and one solvent water molecule. The CuI and CuII centers exhibit [CuIN4] tetrahedral and [CuIIN6] octahedral coordination environments, respectively. The three independent 2‐BPT ligands adopt different chelating modes, which link the copper centers to generate a chair‐like tetranuclear metallomacrocycle with metal–metal distances of about 4.4 × 6.2 Å disposed about a crystallographic inversion center. Furthermore, strong π–π stacking interactions and O—H...N hydrogen‐bonding systems link the tetracopper clusters into a two‐dimensional supramolecular network.  相似文献   

20.
Solvothermal reactions of Cu2(OH)2CO3 with 1,3‐bis(pyridin‐4‐yl)propane (bpp) in the presence of aqueous ammonia in 4‐iodotoluene/CH3CN or 1,4‐diiodobenzene/CH3CN afforded two [Cu2I2]‐based coordination polymers, namely catena‐poly[[[di‐μ‐iodido‐dicopper(I)]‐bis[μ‐1,3‐bis(pyridin‐4‐yl)propane‐κ2N:N′]] p‐toluidine tetrasolvate], {[Cu2I2(C13H14N2)2]·4C7H9N}n, (I), and the analogous 1,4‐diiodobenzene monosolvate, {[Cu2I2(C13H14N2)2]·C6H4I2}n, (II). The [Cu2I2] unit of (I) lies on a centre of symmetry at the mid‐point of the two I atoms, while that of (II) has a twofold axis running through the I...I line. In (I) and (II), each Cu centre is tetrahedrally coordinated by two μ‐I and two N atoms from two different bpp ligands. Each rhomboid [Cu2I2] unit can be considered as a four‐connecting node linked to the symmetry‐related [Cu2I2] units via two pairs of bpp ligands to form a one‐dimensional double chain along the c axis. The dimensions of the [Cu2I2(bpp)2]2 rings in (I) and (II) are different, which may be due to the presence of different guest solvent molecules in the structures. In (I), one p‐toluidine molecule, derived from an Ullmann coupling reaction of 4‐iodotoluene with ammonia, interacts with the [Cu2I2] cluster fragment through N—H...I hydrogen bonds, while the two p‐toluidine molecules interact via N—H...N hydrogen bonds. In (II), two I atoms of each 1,4‐diiodobenzene molecule are linked to the I atoms of the [Cu2I2] fragments from a neighbouring chain via I...I secondary interactions.  相似文献   

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