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1.
The one‐dimensional chain catena‐poly­[[aqua(2,2′:6′,2′′‐terpyridyl‐κ3N)­nickel(II)]‐μ‐cyano‐κ2N:C‐[bis­(cyano‐κC)nickelate(II)]‐μ‐cyano‐κ2C:N], [Ni(terpy)(H2O)]‐trans‐[Ni‐μ‐(CN)2‐(CN)2]n or [Ni2­(CN)4­(C15H11N3)(H2O)], consists of infinite linear chains along the crystallographic [10] direction. The chains are composed of two distinct types of nickel ions, paramagnetic octahedral [Ni(terpy)(H2O)]2+ cations (with twofold crystallographic symmetry) and diamagnetic planar [Ni(CN)4]2? anions (with the Ni atom on an inversion center). The [Ni(CN)4]2? units act as bidentate ligands bridging through two trans cyano groups thus giving rise to a new example of a transtrans chain among planar tetra­cyano­nickelate complexes. The coordination geometry of the planar nickel unit is typical of slightly distorted octahedral nickel(II) complexes, but for the [Ni(CN)4]2? units, the geometry deviates from a planar configuration due to steric interactions with the ter­pyridine ligands.  相似文献   

2.
The title compound, catena‐poly­[[μ‐cyano‐1:2κ2C:N‐dicyano‐1κ2C‐bis(N,N‐di­methyl­ethyl­enedi­amine‐2κ2N,N′)­pallad­ium(II)­copper(II)]‐μ‐cyano‐1:2′κ2C:N], [CuPd(CN)4(C4H12N2)2]n, consists of infinite quasi‐linear chains with all metal positions on centers of symmetry. The paramagnetic [Cu(dmen)2]2+ cations are linked by diamagnetic [Pd(CN)4]2− anions via bridging cyano groups, which occupy trans positions in both cation and anion, giving rise to 2,2‐TT‐type chains. The coordination polyhedron of the paramagnetic Cu atom is an octahedron exhibiting typical elongation due to the Jahn–Teller effect, with two longer Cu—N([triple‐bond]C) bonds in the axial positions [2.5528 (13) Å] and four shorter Cu—Ndmen bonds (dmen is N,N‐dimethylethylenediamine) in the equatorial plane [1.9926 (11) and 2.1149 (12) Å]. The Cu—N[triple‐bond]C angle is 138.03 (12)°. Neighboring chains form weak N—H⋯NC hydrogen bonds.  相似文献   

3.
Three complex compounds with the compositions Cu(NH3)3Ni(CN)4 (CuA), Zn(NH3)3Ni(CN)4 (ZnA), and Cd(NH3)3Ni(CN)4 (CdA) were prepared and identified. Their structures were examined by the methods of infrared spectroscopy and X-ray powder diffraction and compared with one another. The thermal stabilities and stoichiometries of thermal decomposition were investigated with a derivatograph. It follows from the results that the thermal stability increases in the sequence CuA < ZnA < CdA.
Zusammenfassung Drei Komplexverbindungen der Zusammensetzung Cu(NH3)3Ni(CN)4 (CuA), Zn(NH3)3Ni(CN)4 (ZnA) und Cd(NH3)3Ni(CN)4 (CdA) wurden dargestellt und identifiziert. Die Strukturen der Verbindungen wurde infrarotspektroskopisch und röntgendiffraktometrisch untersucht und miteinander verglichen. Die thermische Stabilität und die Stöchiometrie der thermischen Zersetzung wurden mittels eines Derivatographen untersucht. Die thermische Stabilität nimmt in der Reihenfolge CuA < ZnA < CdA zu.

Cu(NH3)3Ni(CN)4 (CuA), Zn(NH3)3Ni(CN)4 (ZnA) Cd(NH3)3Ni(CN)4 (CdA). , . . , CuA  相似文献   

4.
The title compound, catena‐poly[[bis[(triazacyclononane‐κ3N,N′,N′′)copper(II)]‐di‐μ‐cyanido‐κ4N:C‐palladate(II)‐di‐μ‐cyanido‐κ4C:N] dibromide bis[[(triazacyclononane‐κ3N,N′,N′′)copper(II)]‐μ‐cyanido‐κ2N:C‐[dicyanidopalladate(II)]‐μ‐cyanido‐κ2C:N] monohydrate], {[Cu2Pd(CN)4(C6H15N3)2]Br2·[Cu2Pd2(CN)8(C6H15N3)2]·H2O}n, (I), was isolated from an aqueous solution containing tacn·3HBr (tacn is 1,4,7‐triazacyclononane), Cu2+ and tetracyanidopalladate(2−) anions. The crystal structure of (I) is essentially ionic and built up of 2,2‐electroneutral chains, viz. [Cu(tacn)(NC)–Pd(CN)2–(CN)–], positively charged 2,4‐ribbons exhibiting the composition {[Cu(tacn)(NC)2–Pd(CN)2–Cu(tacn)]2n+}n, bromide anions and one disordered water molecule of crystallization. The O atom of the water molecule occupies two unique crystallographic positions, one on a centre of symmetry, which is half occupied, and the other in a general position with one‐quarter occupancy. One of the tacn ligands also exhibits disorder. The formation of two different types of one‐dimensional structural motif within the same structure is a unique feature of this compound.  相似文献   

5.
[Tetrakis(acetonitrile)‐dibromo‐nickel(II)]‐di‐acetonitrile was obtained from a solution of nickel(II) dibromide in acetonitrile at 258 K. The crystal structure [monoclinic, P21/n (no.14), a = 1005.5(5), b = 831.3(5) , c = 1131.7(5) pm, β = 106.263(5)°, V = 908.1(8)·106 pm3, Z = 2, R1 for 1580 reflections with I0>2σ(I0): 0.0505] contains sixfold coordinated NiII atoms. Two trans coordinating bromide anions and four equatorial acetonitrile molecules form an elongated octahedron around the central NiII atom. [Ni(CH3CN)4Br2] octahedra are connected via hydrogen bonds to neighboring octahedra as well as to solvate acetonitrile molecules.  相似文献   

6.
The title compound, poly­[[[di­aqua(μ‐4,4′‐bipyridyl)­di­nickel(II)]‐bis(μ‐4,4′‐bipyridyl)‐di‐μ‐hexa­oxo­di­vana­date(2?)] 2.5‐hydrate], [Ni2­(V2O6)2­(C10H8N2)3­(H2O)2]·­2.5H2O, has been prepared hydro­thermally and characterized by elemental analyses, IR spectroscopy and single‐crystal X‐ray diffraction. The structure consists of [V2O6], [Ni­(4,4′‐bipy)4O2] and [Ni­(H2O)2­(4,4′‐bipy)2O2] polyhedra, and water of crystallization. The Ni atoms and one bipyridyl group lie on centres of symmetry.  相似文献   

7.
The new cyano complexes of formulas PPh(4)[Fe(III)(bipy)(CN)(4)] x H(2)O (1), [[Fe(III)(bipy)(CN)(4)](2)M(II)(H(2)O)(4)] x 4H(2)O with M = Mn (2) and Zn (3), and [[Fe(III)(bipy)(CN)(4)](2)Zn(II)] x 2H(2)O (4) [bipy = 2,2'-bipyridine and PPh(4) = tetraphenylphosphonium cation] have been synthesized and structurally characterized. The structure of complex 1 is made up of mononuclear [Fe(bipy)(CN)(4)](-) anions, tetraphenyphosphonium cations, and water molecules of crystallization. The iron(III) is hexacoordinated with two nitrogen atoms of a chelating bipy and four carbon atoms of four terminal cyanide groups, building a distorted octahedron around the metal atom. The structure of complexes 2 and 3 consists of neutral centrosymmetric [[Fe(III)(bipy)(CN)(4)](2)M(II)(H(2)O)(4)] heterotrinuclear units and crystallization water molecules. The [Fe(bipy)(CN)(4)](-) entity of 1 is present in 2 and 3 acting as a monodentate ligand toward M(H(2)O)(4) units [M = Mn(II) (2) and Zn(II) (3)] through one cyanide group, the other three cyanides remaining terminal. Four water molecules and two cyanide nitrogen atoms from two [Fe(bipy)(CN)(4)](-) units in trans positions build a distorted octahedron surrounding Mn(II) (2) and Zn(II) (3). The structure of the [Fe(phen)(CN)(4)](-) complex ligand in 2 and 3 is close to that of the one in 1. The intramolecular Fe-M distances are 5.126(1) and 5.018(1) A in 2 and 3, respectively. 4 exhibits a neutral one-dimensional polymeric structure containing two types of [Fe(bipy)(CN)(4)](-) units acting as bismonodentate (Fe(1)) and trismonodentate (Fe(2)) ligands versus the divalent zinc cations through two cis-cyanide (Fe(1)) and three fac-cyanide (Fe(2)) groups. The environment of the iron atoms in 4 is distorted octahedral as in 1-3, whereas the zinc atom is pentacoordinated with five cyanide nitrogen atoms, describing a very distorted square pyramid. The iron-zinc separations across the single bridging cyanides are 5.013(1) and 5.142(1) A at Fe(1) and 5.028(1), 5.076(1), and 5.176(1) A at Fe(2). The magnetic properties of 1-3 have been investigated in the temperature range 2.0-300 K. 1 is a low-spin iron(III) complex with an important orbital contribution. The magnetic properties of 3 correspond to the sum of two magnetically isolated spin triplets, the antiferromagnetic coupling between the low-spin iron(III) centers through the -CN-Zn-NC- bridging skeleton (iron-iron separation larger than 10 A) being very weak. More interestingly, 2 exhibits a significant intramolecular antiferromagnetic interaction between the central spin sextet and peripheral spin doublets, leading to a low-lying spin quartet.  相似文献   

8.
以[Fe(CN)4(bipy)]2-为建筑块和[Ni(pn)2]2+在水溶液中反应,合成了{[Ni(pn)2][Fe(CN)4(bipy)]}2·3H2O(pn=1,3-丙二胺)。通过X-射线单晶衍射确定了其晶体结构。该配合物属单斜晶系,P21/n空间群,晶胞参数为:a  相似文献   

9.
From the 1:1 system of [Cu(dien)2](NO3)2 and K[Ag(CN)2] in water (dien is diethyl­enetri­amine, C4H13N3), the novel compound catena‐poly­[bis­[[μ‐cyano‐1:2κ2C:N‐diethyl­enetri­amine‐2κ3N‐copper(II)silver(I)]‐μ‐cyano‐1:2′κ2C:N] di­cyano­silver(I) tri­cyanodisilver(I)], [CuAg(CN)2(dien)]2[Ag(CN)2][Ag2(CN)3], has been isolated. The structure is formed from positively charged [–Cu(dien)–NC–Ag–CN–]nn+ chains and two isolated centrosymmetric [Ag(CN)2]? and [Ag2(CN)3]? anions. In the cationic chains, the Cu atoms are linked by bridging di­cyano­argentate groups, and the deformed square‐pyramidal coordination polyhedron of the CuII cation is formed from a tridentate chelate‐like bonded dien ligand and two N‐bonded bridging cyano groups. One of the bridging cyano groups occupies the apical (ap) position [mean Cu—­Neq = 2.02 (2) Å, and Cu—Nap = 2.170 (3) Å; eq is equatorial]. Short argentophilic interactions in the range 3.16–­3.30 Å are present in the crystal structure.  相似文献   

10.
The crystal structures of two square tetracyanocomplexes were determined. [Ni(dien)2][Ni(CN)4]·2H2O (NDNCH) and [Ni‐(dien)2][Pd(CN)4] (NDPC) (dien = diethylene triamine) exhibit ionic structures consisting of mer‐[Ni(dien)2]2+ cations and [Ni(CN)4]2‐ or [Pd(CN)4]2‐ anions, respectively. Moreover, the structure of NDNCH is completed by two water molecules of crystallisation. In both compounds hydrogen bonds contribute to the stabilisation of the structure. NDNCH dehydrates on air quickly yielding anhydrous [Ni(dien)2][Ni(CN)4] (NDNC). Its thermal decomposition proceeds in a complicated process followed by aerial oxidation of metallic nickel to NiO.  相似文献   

11.
The title complex, poly[bis(μ6‐pyridine‐2,6‐dicarboxylato N‐oxide)nickel(II)disilver(I)], [Ag2Ni(C7H3NO5)2]n or [Ag2Ni(pydco)2]n (H2pydco = pyridine‐2,6‐dicarboxylic acid N‐oxide), has a two‐dimensional sheet structure. The two carboxylate groups adopt two coordination modes. The NiII ion displays a distorted octahedral geometry, bonded to two carboxylate O atoms of two different pydco ligands and four O donors from another two ligands, i.e. two carboxylate O atoms and two N‐oxide O atoms. The AgI ion adopts a tetrahedral coordination, linked by three O atoms of three different carboxylate groups and an N‐oxide O atom.  相似文献   

12.
The one‐dimensional coordination polymer catena‐poly[[[di‐μ2‐acetato‐tetrakis[μ3‐(pyridin‐2‐yl)methanolato]tetracopper(II)]‐di‐μ2‐diacetamidato] acetonitrile monosolvate], {[Cu4(C6H6NO)4(CH3COO)2(C2N3)2]·CH3CN}n, has been prepared from the direct reaction of 2‐(hydroxymethyl)pyridine with Cu(OAc)2·H2O (OAc is acetate) in a methanol–acetonitrile mixture. The four Cu centres are bridged by four O atoms from discrete (pyridin‐2‐yl)methanolate ligands and two acetate groups, forming a capped [Cu4O4] cubane core. Each core is doubly bridged to each of two adjacent cores by [N(CN)2] anions, resulting in one‐dimensional chains. The magnetic properties of the complex were also studied.  相似文献   

13.
The title compound, hexa­ammonium tetra‐μ3‐selenido‐tetra­kis­(tri­cyano­molybdenum) hexahydrate, is isostructural with the Mo/S, W/S and W/Se analogues. The structure contains disordered cyclic hydrogen‐bonded [{(NH4)(H2O)}3]3+ cations and [Mo4Se4(CN)12]6? cluster anions with 3m symmetry. The cation assembly consists of alternating ammonium and water mol­ecules linked by N—H?O hydrogen bonds. The anion has a typical cubane cluster structure. The cations and anions are linked together by hydrogen bonds involving the terminal N atoms of the CN groups.  相似文献   

14.
Bis(tetra­hydro­borato)­[1,1,2,2‐tetra­methyl‐1,2‐ethyl­enebis­(η5‐cyclo­penta­dienyl)]­zirconium, (I), was synthesized by the reaction of the zirconocene dichloride with lithium tetra­hydro­borate. Crystals suitable for X‐ray structure analysis were obtained by recrystallization from toluene. The mol­ecule adopts an appproximate C2v symmetry. Both tetra­hydro­borate ligands are η2‐coordinated and tilted by 18–19° out of the equatorial plane; the angle B1—Zr1—B2 is 104.7°. The cyclo­penta­dienyl rings show a normal η5‐coordinaton, with a centroid–Zr–centroid angle of 124.3°.  相似文献   

15.
In the tetra­methyl­arsonium salt of 2,5‐di­chloro‐7,7,8,8‐tetra­cyano­quinodimethanide [systematic name: tetra­methyl­arson­ium 2,2′‐(2,5‐dichlorocyclohexa‐2,5‐diene‐1,4‐diylidene)bis(propanedinitrile)], C4H12As+·C12H2Cl2N4? or [As(CH3)4](C12H2Cl2N4), the cation lies disordered about a twofold axis and the radical ion lies about an inversion center forming a uniform [interplanar distance 3.35 (2) Å] and one‐dimensional stacking without any slip. The electrical conductivity of the single crystal at room temperature was less than 10?9 S cm?1, and the temperature dependence of para­magnetic susceptibility obeyed a one‐dimensional antiferromagnetic Heisenberg model with a spin‐exchange integral of 83 K in the temperature range 1.8–320.0 K.  相似文献   

16.
catena‐Poly[[[dichloridoiron(II)]‐μ‐N,N′‐bis(2‐pyridylmethylene)benzene‐1,4‐diamine] methanol disolvate], [FeCl2(C18H14N4)]·2CH3OH, forms a one‐dimensional coordination polymer. The polymeric chains run parallel to the c axis. O—H...Cl—Fe and C—H...O hydrogen‐bonding interactions with methanol solvent molecules stabilize the open supramolecular framework. Each FeII atom adopts an octahedral geometry coordinated by four N atoms from two N,N′‐bis(2‐pyridylmethylene)benzene‐1,4‐diamine ligands and completed by two cis Cl atoms. The compound has C2 (and Ci) molecular symmetry, which is coincident with the crystallographic twofold symmetry at (0, y, ). The one‐dimensional structure is propagated via the crystallographic inversion center located at the benzene ring centroid (0, , 0).  相似文献   

17.
Vanadium tellurites display a rich structural chemistry with interesting physical properties, such as second harmonic generation (SHG). Tellurites, i.e. Te4+Ox, are often observed in unusual structures and form various structural motifs, including isolated clusters, chains, layers, and three‐dimensional networks. Similarly, vanadates, i.e. V5+Ox, show rich structural features, such as VO4 tetrahedra, VO5 square pyramids or trigonal bipyramids, and VO6 octahedra. Strontium vanadium tellurite, Sr7V4Te12O41, was obtained from the melt of the solid‐state reaction of SrTeO4 and VO2 in a sealed quartz tube as it cooled from 973 K. The crystal structure exhibits a one‐dimensional latticework along the a axis comprised of paired Sr3Te3Ox units, namely Sr6Te6O2x+1, with corner‐shared TeO4 polyhedra – and specifically the Te lone‐pair electrons – facing outward in the bc plane. The Sr6Te6O2x+1 latticework is helical and is layered in the b‐axis direction against sheets of corner‐shared VO4 tetrahedra, and is linked in the c‐axis direction via individual corner‐shared SrO8 square prisms.  相似文献   

18.
The title compound, catena‐poly[[[bis(ethylenediamine‐κ2N,N′)platinum(II)]‐ μ‐chlorido‐[bis(ethylenediamine)platinum(IV)]‐μ‐chlorido] tetrakis{4‐[(4‐hydroxyphenyl)diazenyl]benzenesulfonate} dihydrate], {[PtIIPtIVCl2(C2H8N2)4](HOC6H4N=NC6H4SO3)4·2H2O}n, has a linear chain structure composed of square‐planar [Pt(en)2]2+ (en is ethylenediamine) and elongated octahedral trans‐[PtCl2(en)2]2+ cations stacked alternately, bridged by Cl atoms, along the b axis. The Pt atoms are located on an inversion centre, while the Cl atoms are disordered over two sites and form a zigzag ...Cl—PtIV—Cl...PtII... chain, with a PtIV—Cl bond length of 2.3140 (14) Å, an interatomic PtII...Cl distance of 3.5969 (15) Å and a PtIV—Cl...PtII angle of 170.66 (6)°. The structural parameter indicating the mixed‐valence state of the Pt atom, expressed by δ = (PtIV—Cl)/(PtII...Cl), is 0.643.  相似文献   

19.
A new 1,3,4‐oxadiazole bridging bent organic ligand, 2,5‐bis{5‐methyl‐2‐[(4‐pyridyl)methoxy]phenyl}‐1,3,4‐oxadiazole, C28H24N4O3, L, has been used to create three novel one‐dimensional isomorphic coordination polymers, viz. catena‐poly[[[dichloridomercury(II)]‐μ‐2,5‐bis{5‐methyl‐2‐[(4‐pyridyl)methoxy]phenyl}‐1,3,4‐oxadiazole] methanol monosolvate], {[HgCl2(C28H24N4O3)]·CH3OH}n, catena‐poly[[[dibromidomercury(II)]‐μ‐2,5‐bis{5‐methyl‐2‐[(4‐pyridyl)methoxy]phenyl}‐1,3,4‐oxadiazole] methanol monosolvate], {[HgBr2(C28H24N4O3)]·CH3OH}n, and catena‐poly[[[diiodidomercury(II)]‐μ‐2,5‐bis{5‐methyl‐2‐[(4‐pyridyl)methoxy]phenyl}‐1,3,4‐oxadiazole] methanol monosolvate], {[HgI2(C28H24N4O3)]·CH3OH}n. The free L ligand itself adopts a cis conformation, with the two terminal pyridine rings and the central oxadiazole ring almost coplanar [dihedral angles = 5.994 (7) and 9.560 (6)°]. In the HgII complexes, however, one of the flexible pyridylmethyl arms of ligand L is markedly bent and helical chains are obtained. The HgII atom lies in a distorted tetrahedral geometry defined by two pyridine N‐atom donors from two L ligands and two halide ligands. The helical chains stack together via interchain π–π interactions that expand the dimensionality of the structure from one to two. The methanol solvent molecules link to the complex polymers through O—H...N and O—H...O hydrogen bonds.  相似文献   

20.
The title compound, catena‐poly[[chloridotetrakis(ethylenediamine‐κ2N,N′)samarium(III)] [indium(III)‐di‐μ‐tellurido‐indium(III)‐di‐μ‐tellurido]], {[SmCl(C2H8N2)4][In2Te4]}n, consists of a one‐dimensional sinusoidal {[InTe2]}n anionic chain and [SmCl(en)4]2+ cations (en is ethylenediamine). The only other previously reported lanthanide analogue, viz. [LaCl(en)4][In2Te4], contains more usual linear one‐dimensional {[InTe2]}n anion chains [Chen, Li, Chen & Proserpio (1998). Inorg. Chim. Acta, 273 , 255–258]. The one‐dimensional polymeric {[InTe2]}n chain is built of InTe4 tetrahedra sharing opposite edges. The SmIII ion in the [SmCl(en)4]2+ cation is nine‐coordinated by eight N atoms from four bidentate en molecules and by one chloride ion to form a monocapped square‐antiprismatic geometry. The presence or absence of N—H...Cl hydrogen bonding is shown to affect the conformation of the anion.  相似文献   

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