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1.
Of 27 typical structures of niobates and tantalates, five structures are assigned to the F-type of cation sublattice (ABC-packing of trigonal 36 planes), eight structures are referred to the I-type (body-centered cation sublattice), and eight structures are considered to be the β-K2UF6 type with a hollow hexagonal framework centered by a scanty-type cation. In two cases (Mg3Nb6O11 and Cu5Ta11O30), the cation framework consists of two types of different-scale nets that are commensurate in a plane. In some structures (K2Ta4F4O9, ThTa2O7, and β-K2UF6 type), the “splittng” plane effect is noted for the first time: the neighboring nonequivalent planes of the same family (dhkl≈1.9 Å) are filled by cations according to the complement principle, when the vacant sites of one plane lie over the occupied sites of another and vice versa. These structures are treated as modified hexagonal one-layered (AA) type. In the structure of La2TaO4Cl3, the Cl? anion enters the cation matrix, i.e., occupies the vacant sites of its nets.  相似文献   

2.
Crystal structures of Cs4[Re6Te8(CN)6]·2H2O (1) and Ba2[Re6Te8(CN)6]· 12H2O (2) are determined. Crystals 1 are orthorhombic, a = 14,282(1), b = 12.910(1), c = 18.040(1) Å, Vcell = 3326.3(8) Å3, space group Pbcn, Z = 4, dcalc = 5.715 g/cm3, R(F) = 0.0482 for 3193 Fhkl > 4σ(F). Crystals 2 are triclinic, a = 9.671(3), b = 9.697(4), c = 11.039(4) Å, α = 89.86(3), β = 72.34(3), γ = 82.46(3)°, Vcell = 977.2(6) Å3, space group P1, Z = 1, dcalc = 4.733 g/cm3, R(F) = 0.0490 for 3226 Fhkl > 4σ(F). In both structures, the [Re6Te8(CN)6]4? anions form a distorted primitive cubic packing with distances between the centers 9.02-9.63 Å in 1 and 9.70-11.04 Å in 2. The Cs+ cations in 1 lie near the face centers of the cubes formed by the onions. In 2, cation pairs (Ba2+)2 bonded to two solvate water molecules are formed; the pairs lie at the centers of the anion cubes. In structures 1 and 2, there are shortened contacts between the tellurium atoms belonging to the neighboring anions (3.75-4.09 and 3.95-4.22 Å, respectively).  相似文献   

3.
In the title compound, [CuCl(C6H6N4)(H2O)][Cu(C4H5NO4)Cl]·H2O, the CuII atom in the cation is coordinated by one Cl ion, two N atoms of the 2,2′‐biimidazole ligand and one aqua ligand. Within the anion, the CuII atom is bonded to one Cl ion, and one N and two O atoms of the imino­diacetate ligand. Neighbouring cations and anions are connected to each other by Cu·Cl semi‐coordination bonds of 2.830 (12) and 3.071 (12) Å, forming a Cu2Cl2 rectangular unit. The dinuclear units further link into a polymeric chain along the a axis through Cu·Oaqua interactions of 2.725 (3) Å. Including the long coordination bonds, the geometries around the Cu atoms in the cation and anion are square‐pyramidal and distorted octahedral, respectively.  相似文献   

4.
Methyliminodiacetic acid (H2Mida) and imidazole react with copper(II) to form crystals of the square pyramidal complex [Cu(Mida)Im]. One N and two O atoms of the Mida ligand (Cu-N 2.010(1) Å, Cu-O 1.955(1) Å, and 1.978(1) Å) and the imidazole N atom (1.950(1) Å) lie at the base of the pyramid. The carboxyl O atom of the neighboring complex lies at the apical position (2.411(1) Å); in this way the individual complexes are linked into infinite zigzag chains. Substitution of imidazole by 1,10-phenanthroline gave [Cu2(Mida)2(Phen)H2O]·2H2O crystals with two nonequivalent centrosymmetric octahedral anions [Cu(Mida)2]2? of face type (Cu-N 2.023 Å and 2.028(2) Å, Cu-Oax 2.579 Å and 2.530(2) Å, Cu-Obas 1.952 Å and 1.936(2) Å). The anions serve as bridges in chains between the [Cu(Phen)H2O]2+ cation fragments to which they are bonded by their axial carboxyl groups. The Cu atom of the cation has a [4+1] environment (with the H2O molecule lying on the axis of the pyramid, and with two N atoms of the ligand and two O atoms of the anions lying at the base).  相似文献   

5.
The complexes [Co(DH)2(Sam)2]2[ZrF6]·5H2O (I) and [Co(DH)2(Sam)2][BF4]·H2O (II), where DH? is the dimethylglyoxime monoanion, and Sam is para-aminobenzenesulfamide (sulfanilamide, white streptocid), were synthesized, and their crystal structures were determined by X-ray diffraction analysis. The coordination polyhedron of the Co3+ atom is an N6 octahedron formed by four nitrogen atoms of the two dimethylglyoxime residues and two nitrogen atoms of the Sam fragments. The latter are realized in virtually parallel orientation relative to the polyhedron of the metal atom and its equatorial plane; the average value of the dihedral angles is 26.8(1)°, and there is π-π interaction between the benzene rings of the Sam fragments and the π delocalized equatorial metallocycle. The deviation of the cobalt atom from the four-angle plane is up to 0.009(1) Å. The (Co-N)DH? and (Co-N)Sam distances in the [Co(DH)2(Sam)2]+ complex cations vary from 1.892(2) Å to 1.907(3) Å and from 2.000(2) Å to 2.012(2) Å, respectively. The [ZrF6]2? and [BF4]? complex anions play the major role in crystal formation; they produce a substantial effect on the formation of a complex system of hydrogen bonds.  相似文献   

6.
A combination of high resolution thermogravimetric analysis coupled to a gas evolution mass spectrometer has been used to study the thermal decomposition of synthetic hydrotalcites reevesite (Ni6Fe2(CO3)(OH)16·4H2O) and pyroaurite (Mg6Fe2(SO4,CO3)(OH)16·4H2O) and the cationic mixtures of the two minerals. XRD patterns show the hydrotalcites are layered structures with interspacing distances of around 8.0. Å. A linear relationship is observed for the d(001) spacing as Ni is replaced by Mg in the progression from reevesite to pyroaurite. The significance of this result means the interlayer spacing in these hydrotalcites is cation dependent. High resolution thermal analysis shows the decomposition takes place in 3 steps. A mechanism for the thermal decomposition is proposed based upon the loss of water, hydroxyl units, oxygen and carbon dioxide.  相似文献   

7.
The title compound, [Cu(C24H46N6O2)]Cl2·8H2O, contains a centrosymmetric cation, with the anions and water mol­ecules on general sites. The coordination geometry around the CuII ion is an axially elongated octahedron, with Cu—N distances of 2.0448 (17) and 2.0847 (17) Å, and a Cu—O1 distance of 2.3138 (16) Å.  相似文献   

8.
A new dumbbell‐type 4,4′‐bipy‐bridged dinuclear copper(II) complex, [Cu2(4,4′‐bipy)L2(H2O)2](ClO4)4 · 8CH3OH · 10H2O, where L = 1‐[bis(3‐aminopropyl)amino]‐2‐ propanol and bipy = bipyridine, has been synthesized and characterized, X‐ray crystallographic analysis shows that the [Cu2(4,4′‐bipy)L2(H2O)2]4+ cations and water molecules generate layer structures extending parallel to bc planes through hydrogen bonding interactions of O–H ··· O and C–H ··· O. The layers are also connected by hydrogen bonding interactions involving methanol, water, and perchlorate anions. These interactions lead to the formation of rectangular channels of 12.3 Å × 6.0 Å along the crystallographic c axis. Perchlorate anions fill in each channel in a sandwich‐like packing mode, they are joined with the adjacent layers by water heptamers. Magnetic susceptibility measurements show that the magnetic exchange interaction is weak although it has a regular π‐type electron transfer pathway. Furthermore, the electrochemical and thermogravimetric properties of the complex were also investigated.  相似文献   

9.
Cubic [Ta6Br12(H2O)6][CuBr2X2]·10H2O and triclinic [Ta6Br12(H2O)6]X2·trans‐[Ta6Br12(OH)4(H2O)2]·18H2O (X = Cl, Br, NO3) cocrystallize in aqueous solutions of [Ta6Br12]2+ in the presence of Cu2+ ions. The crystal structures of [Ta6Br12(H2O)6]Cl2·trans‐[Ta6Br12(OH)4(H2O)2]·18H2O ( 1 ) and [Ta6Br12(H2O)6]Br2·trans‐[Ta6Br12(OH)4(H2O)2]·18H2O ( 3 )have been solved in the triclinic space group P&1macr; (No. 2). Crystal data: 1 , a = 9.3264(2) Å, b = 9.8272(2) Å, c = 19.0158(4) Å, α = 80.931(1)?, β = 81.772(2)?, γ = 80.691(1)?; 3 , a = 9.3399(2) Å, b = 9.8796(2) Å, c = 19.0494(4) Å; α = 81.037(1)?, β = 81.808(1)?, γ = 80.736(1)?. 1 and 3 consist of two octahedral differently charged cluster entities, [Ta6Br12]2+ in the [Ta6Br12(H2O)6]2+ cation and [Ta6Br12]4+ in trans‐[Ta6Br12(OH)4(H2O)2]. Average bond distances in the [Ta6Br12(H2O)6]2+ cations: 1 , Ta‐Ta, 2.9243 Å; Ta‐Bri , 2.607 Å; Ta‐O, 2.23 Å; 3 , Ta‐Ta, 2.9162 Å; Ta‐Bri , 2.603 Å; Ta‐O, 2.24 Å. Average bond distances in trans‐[Ta6‐Br12(OH)4(H2O)2]: 1 , Ta‐Ta, 3.0133 Å; Ta‐Bri, 2.586 Å; Ta‐O(OH), 2.14 Å; Ta‐O(H2O), 2.258(9) Å; 3 , Ta‐Ta, 3.0113 Å; Ta‐Bri, 2.580 Å; Ta‐O(OH), 2.11 Å; Ta‐O(H2O), 2.23(1) Å. The crystal packing results in short O···O contacts along the c axes. Under the same experimental conditions, [Ta6Cl12]2+ oxidized to [Ta6Cl12]4+ , whereas [Nb6X12]2+ clusters were not affected by the Cu2+ ion.  相似文献   

10.
Complexes of 2, 6‐bis(hydroxymethyl)pyridine (dhmp) with different CuII salts [CuCl2·6H2O, Cu(ClO4)2·6H2O, Cu(NO3)2·3H2O, Cu(CH3COO)2·H2O] are prepared ( 1 — 5 , respectively), studied by IR, and their crystal structures reported. Dependent on the anion kind, influences on the distortion of the co‐ordination polyhedron, the distribution of donor sites, the formation of a mono‐ or binuclear complex, and the resultant packing structure of the complex are observed, although in no case the counterions of the used CuII salts or water of hydration were found in the co‐ordination sphere. Crystal structures of 1 — 5 indicate hexaco‐ordination of the CuII ions with N2O4‐environment and show that 1 — 4 are mononuclear 2:1 (L:M) complexes, but 5 is a binuclear 4:2 complex. Crystallization of Cu(ClO4)2·6H2O with dhmp yielded two different complexes ( 2 / 3 ). In 3 , one of the dhmp components is mono‐deprotonated and acts as an anionic ligand. The same behavior is found in 5 . Whereas in the neutral ligand complexes 1 , 2 and 4 the basal planes are occupied by O donors, and N atoms are in the axial positions of the octahedrons, in 3 and 5 the bases are formed by two O and two N donor atoms, and O atoms are in the axes. Moreover, complex 3 shows the N atoms in trans position, but 5 in cis position. The packing of the cationic complex units is typical of strong and weak H bond interactions involving the counterions and hydroxylic or aromatic hydrogen atoms to yield complex network structures.  相似文献   

11.
The monoclinic modification of ZrF4·3H2O, isostructural to HfF4·3H2O, is synthesized and structurally studied for the first time. Unlike the triclinic modification of ZrF4·3H2O with a dimeric structure, the synthesized compound has a polymer structure formed from infinite chains composed of ZrF6(H2O)2 groups sharing F…F edges. The crystal structure of HfF4·3H2O, previously determined by the photo method, is refined. The refined data on the geometric characteristics of the coordination polyhedron of the Hf atom and the system of hydrogen bonds in the structure are obtained.  相似文献   

12.
Two complexes, [Cu2(TFSA)(2,2′-bpy)4]?·?TFSA?·?8H2O (1) and {[Cu(4,4′-bpy)(H2O)2]?·?TFSA?·?6H2O} n (2) (H2TFSA?=?tetrafluorosuccinic acid, 2,2′-bpy?=?2,2′-bipyridine, and 4,4′-bpy?=?4,4′-bipyridine), have been synthesized and structurally characterized by X-ray structural analyses. Complex 1 is a binuclear molecule bridged by TFSA ligands; 2 is a 1-D chain bridged by 4,4′-bpy ligands. The asymmetric units of the two complexes are composed of cationic complexes [Cu2(TFSA)(2,2′-bpy)4]2+ (1) and [Cu(4,4′-bpy)(H2O)2]2+ (2), free TFSA anion, and independent crystallization water molecules. A unique 2-D hybrid water–TFSA anionic layer by linkage of {[(H2O)8(TFSA)]2?} n fragments consisting of 1-D T6(0)A2 water tape and TFSA anionic units by hydrogen bonds in 1 was observed. Unique 2-D hybrid water–TFSA anionic layer generated by the linkage of {[(H2O)6(TFSA)]2?} n fragments consisting of cyclic water tetramers with appended water molecules and TFSA anionic units, and 1-D metal–water tape [Cu–H2O?···?(H2O)6?···?H2O?] n in 2 were found. 3-D supramolecular networks of the two complexes consist of cationic complexes and water–TFSA anionic assemblies connected by hydrogen bonds.  相似文献   

13.
For the first time, new hybrid organic-inorganic layered zirconium pentafluorides of methylammonium, glycinium, and β-alanine with the composition (CH3NH3)ZrF5·0.5H2O, (H3NCH2COOH)ZrF5·2H2O, and (H3N(CH2)2COOH)ZrF5 are synthesized and their structures are analyzed. In the studied compounds, CN of the Zr atom is 8, and its coordination polyhedron represents a dodecahedron sharing its 6 vertex with three neighboring Zr polyhedra. The Zr dodecahedra are joined with each other in planar netlike anion layers of the composition 2[ZrF5]. The anion layers are hydrogen bonded into a three-dimensional structure by H2O cations and molecules.  相似文献   

14.
The title compund, [Cu2(OH)2(C22H25N3)2](ClO4)2, is a copper(II) dimer, with two [CuL]2+ units [L is bis(6‐methyl‐2‐pyridylmethyl)(2‐phenylethyl)amine] bridged by hydroxide groups to define the {[CuL](μ‐OH)2[CuL]}2+ cation. Charge balance is provided by perchlorate counter‐anions. The cation has a crystallographic inversion centre halfway between the CuII ions, which are separated by 3.0161 (8) Å. The central core of the cation is an almost regular Cu2O2 parallelogram of sides 1.931 (2) and 1.935 (2) Å, with a Cu—O—Cu angle of 102.55 (11)°. The coordination geometry around each CuII centre can be best described as a square‐based pyramid, with three N atoms from L ligands and two hydroxide O atoms completing the coordination environment. Each cationic unit is hydrogen bonded to two perchlorate anions by means of hydroxide–perchlorate O—H...O interactions.  相似文献   

15.
The thermolysis of fluorozirconates (M2ZrF6, M5Zr4F21 · 3H2O, MZrF5 · H2O, Rb2Zr3OF12, and Cs2Zr3F14 · 1.5H2O) and fluorosulfatozirconates (M2ZrF4SO4, Rb3Zr2F9SO4 · 2H2O, and Cs8Zr4F2(SO4)11 · 16H2O) with M = K, Rb, or Cs in undried air was studied by thermal analysis in tandem with X-ray powder diffraction. The X-ray luminescence (XRL) intensity was determined for these compounds and their thermolysis products. A mixture of Rb2Zr3OF12 and Rb2ZrF6 luminescent phases was detected in the thermolysis products of Rb5Zr4F21 · 3H2O and RbZrF5 · H2O for the first time. After heat treatment, a considerable quantum yield was observed for ZnZrF6 · 5H2O, ZnZrF6 · 6H2O, and ZnZr2F10 · 7H2O. The XRL luminescence was affected by the composition of the phase and the density of excited states (F* and O*).  相似文献   

16.
Blue needle—shaped crystals of [Cu(bpy)(H2O)2(C4H4O4)]· 2H2O were obtained by slow evaporation of a methanolic aqueous solution containing a fresh Cu(C4H4O4)· 2H2O precipitate, 4, 4′—bipyridine, and ammonia. Within the complex, the six—coordinated Cu atoms are linked by bis—monodentate gauche succinate anions into chains propagating helically around the [001] axis. The chains are interconnected by 4, 4′—bipyridine ligands into a 3D framework with the crystal H2O molecules located in the channels along the [100], [010] and [110] directions. The Cu2+ ions are in distorted octahedral coordination of two nitrogen and four oxygen atoms (equatorial bonds: Cu—N 1.986(5), 2.015(5)Å; Cu—O 1.950(6), 1.954(6)Å; axial bonds Cu—O: 2.524(9), 2.539(8)Å). Furthermore, the thermal and magnetic behavior of the compound will be discussed. Crystal data: hexagonal, P61 (no. 169), a = 11.066(2)Å, c = 24.965(5)Å, V = 2647.5(8)Å3, Z = 6, R = 0.0528 and wR2 = 0.1103 for 1426 observed reflections (Fo2 > 2σ(Fo2)) out of 2170 unique reflections.  相似文献   

17.
Two crystal modifications of a novel complex bis(μ2-chloro)tetrachlorodicuprate(II) bis[(18-crown-6)potassium, [K{(18-crown-6)}2Cu2Cl6] were synthesized and studied by X-ray diffraction. The structures of two monoclinic modifications—Iα (space group P21/n, a = 9.053, b = 33.815, c = 13.469 Å, β = 101.29°, Z = 4) and Iβ (space group P21/c, a = 10.991, b = 8.187, c = 22.542 Å, β = 98.15°, Z = 2) were solved by the direct method and refined by the full-matrix least-squares method in anisotropic approximation to R = 0.073 (Iα) and 0.068 (Iβ) for 4883 (Iα) and 3525 (Iβ) independent reflections (CAD-4 automated diffractometer, λMoK α). The molecules of Iα and Iβ consist of the central binuclear complex anion [Cu2Cl6]2? and two peripheral host-guest cationic fragments [K(18-crown-6)]+, each linked with the [Cu2Cl6]2? anions through the K-Cl bonds. The molecule of Iα and centrosymmetric Iβ molecule have different structures, since they have different orientation of the [K(18-crown-6)]+ fragments relative to the central [Cu2Cl6]2? anion. The coordination polyhedron of the Cu2+ cation in the latter anion in Iα and Iβ is intermediate between flattened tetrahedron and square. In the [K(18-crown-6)]+ ions of Iα and Iβ, the K+ cation has the distorted hexagonal pyramidal coordination polyhedron with six O atoms of the 18-crown-6 ligand in a base and bifurcate vertex at two Cl atoms of the [Cu2Cl6]2? anion. The 18-crown-6 ligands of Iα and Iβ have standard crown conformation.  相似文献   

18.
Lithium pertechnetate trihydrate was obtained and its crystal structure was examined; LiTcO4 · 3H2O crystallizes in hexagonal crystal system as colorless elongated prismatic crystals (space group P63/mc, Z = 2; at 100 K: a = 7.8604(1) Å, c = 5.4164(1) Å). This compound is isostructural with LiClO4 · 3H2O, LiBrO4 · 3H2O, and LiMnO4 · 3H2O.  相似文献   

19.
The absolute configuration was determined for the title compound, C38H70NO13+·Cl?·3.5H2O. The cation contains a 14‐membered macrocyclic lactone and two sugars, namely cladinose and desos­amine. The six‐membered rings of the sugars adopt chair conformations. The structure is stabilized by strong hydrogen bonds, with O?O distances in the range 2.486 (9)–2.830 (5) Å; other distances are N?O = 2.860 (5), N?Cl = 3.134 (4) and O?Cl = 3.303 (4) Å.  相似文献   

20.
The crystal structures of sodium 4‐({4‐[N,N‐bis(2‐hydroxy­ethyl)­amino]­phenyl}diazenyl)­benzoate 3.5‐hydrate, Na+·C17H18N3O4?·3.5H2O, (I), and potassium 4‐({4‐[N,N‐bis(2‐hydroxy­ethyl)­amino]­phenyl}diazenyl)­benzoate dihydrate, K+·C17H18N3O4?·2H2O, (II), are described. The results indicate an octahedral coordination around sodium in (I) and a trigonal prismatic coordination around potassium in (II). In both cases, coordination around the metal cation is achieved through O atoms of the water mol­ecules and hydroxy groups of the chromophore. The organic conjugated part of the chromophore is approximately planar in (I), while a dihedral angle of 30.7 (2)° between the planes of the phenyl rings is observed in (II).  相似文献   

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