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1.
LiSr2[ReN4] and LiBa2[ReN4] – isotypic Nitridorhenates(VII) The quaternary nitridorhenates(VII) LiAE2[ReN4] (AE = Sr, Ba) were synthesized by reaction of the metals with molecular nitrogen at 850–900 °C. The plate‐like, nearly colourless crystals were investigated by X‐ray single crystal methods and were identified as isotypic phases: LiSr2[ReN4] (LiBa2[ReN4]); monoclinic, P21/m; a = 614.64(8) pm (651.04(12) pm), b = 585.97(6) pm (b = 598.86(9) pm), c = 689.70(17) pm (737.43(5) pm), β = 106.375(4)° (108.535(2)°); Z = 2. Crystals of the strontium compound were systematically twinned along [001]. In the crystal structures of the quaternary compounds the alkaline earth‐ and nitride‐ ions are arranged in the motif of the InNi2‐type structure. Strontium and barium are in a trigonal prismatic coordination by nitrogen (Sr–N: 261.0(7)–284.3(4) pm; Ba–N: 278.0(7)–303.0(6) pm). One half of the tetrahedral voids within the partial structure formed by stacking of trigonal prismatic rod layers is occupied by rhenium (formation of [ReVIIN4]5–‐tetrahedra; Re–N: 181.0(6)–184.5(8) pm), lithium takes the positions of the remaining tetrahedral sites (Li–N: 2 × 198(1) pm, 224(2) pm and 228(2) pm for the strontium phase). In the barium compound the lithium positions show a larger shift from the tetrahedral centres towards a tetrahedral plane (Li–N: 2 × 195(1) pm, 213(2) pm and 304(2) pm).  相似文献   

2.
The new carbodiimide compounds Li2RE2Sr(CN2)5 (RE = Sm, Gd, Eu, Tb) were prepared by a straight forward solid state metathesis reaction of REF3, SrF2, and Li2(CN2) at around 600 °C. The crystal structure of Li2Gd2Sr(CN2)5 was solved based on X‐ray single‐crystal diffraction data. Corresponding Li2RE2Sr(CN2)5 compounds were analyzed by isotypic indexing of their powder patterns. The crystal structure of Li2Gd2Sr(CN2)5 can be well related to that of Gd2(CN2)3, because both structures are based on layered structures composed of close packed layers of [N=C=N]2– sticks, alternating with layers of metal ions. The crystal structure of Li2Gd2Sr(CN2)5 can be considered to contain an ABC layer sequence of [N = C=N]2– layers with the interlayer voids being occupied by (three) distinct types of cations.  相似文献   

3.
Two new series of tetracyanamidogermanates were prepared by solid‐state reaction of appropriate amounts of REF3 (RE = rare earth), A2[GeF6] (A = alkaline), and Li2(CN2) in evacuated silica tubes. Powder X‐ray diffraction patterns of crystalline samples of KRE[Ge(CN2)4] and CsRE[Ge(CN2)4] were indexed isotypically to KRE[Si(CN2)4] and RbRE[Ge(CN2)4], respectively. Luminescence properties of Ce3+, Eu3+, and Tb3+ doped compounds and non‐linear optical properties (NLO) of KRE[Ge(CN2)4] are reported.  相似文献   

4.
5.
1‐Butyl‐3‐methylimidazolium tetrakis‐(bis(trifluoromethanesulfonyl)amide)yttrium(III), [bmim][Y(Tf2N)4], was obtained from the ionic liquid 1‐butyl‐3‐methylimidazoliumbis(trifluoromethanesulfonyl)amide, [bmim][Tf2N] and yttrium(III)bis(trifluoromethanesulfonyl)amide, Y(Tf2N)3. The crystal structure [monoclinic, C2/c (no. 15), a = 2096.(1), b = 1451.5(1), c = 1608.55(9) pm, β = 109.669(6)°, V = 4608.1(5)·106 pm3, Z = 4, R1 for 3874 symmetry independent reflections with I0>2σ(I0): 0.0438] contains YIII coordinated by four Tf2N‐ligands which all adopt a transoid‐conformation with respect to their –CF3 groups. The oxygen coordination polyhedron around YIII can be best described as a trigonal dodecahedron.One 1‐butyl‐3‐methylimidazolium cation compensates for the charge of the complex [Y(Tf2N)4]? anion.  相似文献   

6.
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   

7.
Synthesis and Crystal Structure of [N(Hex)4] [Cu2(CN)3] [N(Hex)4][Cu2(CN)3] has been prepared by solvothermal reaction of CuCN with Tetra‐n‐hexylammoniumiodide in acetone. The crystal structure is built up by condensed (CuCN)6 and (CuCN)7 rings, forming a zeolith type cyanocuprate(I) framework [Cu2(CN)3]. Space group R3; α = 44.482(6), c = 21.283(4) Å, V = 36471(9) Å3; Z = 9.  相似文献   

8.
Chloro- and Polyselenoselenates(II): Synthesis, Structure, and Properties of [Ph3(C2H4OH)P]2[SeCl4] · MeCN, [Ph4P]2[Se2Cl6], and [Ph4P]2[Se(Se5)2] By symproportionation of elemental selenium and SeCl4 in polar protic solvents the novel chloroselenates(+II), [SeCl4]2? and [Se2Cl6]2?, could be stabilized; they were crystallized with voluminous organic cations. They were characterized from complete X-ray structure analysis. Yellow-orange [Ph3(C2H4OH)P]2[SeCl4] · MeCN (space group P1 , a = 10.535(4), b = 12.204(5), c = 16.845(6) Å, α = 77.09(3)°, β = 76.40(3)°, γ = 82.75(3)° at 140 K) contains in its crystal structure monomeric [SeCl4]2? anions with square-planar coordination of Se(+II). The mean Se? Cl bond length is 2.441 Å. In yellow [Ph4P]2[Se2Cl6] (space group P1 , a = 10.269(3), b = 10.836(4), c = 10.872(3) Å, α = 80.26(3)°, β = 79.84(2)°, γ = 72.21(3)° at 140 K) a dinuclear centrosymmetric [Se2Cl6]2? anion, also with square-planar coordinated Se(+II), is observed. The average terminal and bridging Se? Cl bond distances are 2.273 and 2.680 Å, respectively. From redox reactions of elemental Se with boranate/thiolate in ethanol/DMF the bis(pentaselenido)selenate(+II) anion [Se(Se5)2]2? was prepared as a novel type of a mixed-valent chalcogenide. In dark-red-brown [Ph4P]2[Se(Se5)2] (space group P21/n, a = 12.748(4), b = 14.659(5), c = 14.036(5) Å, β = 108.53(3)° at 140 K) centrosymmetric molecular [Se(Se5)2]2? anions with square-planar coordination of the central Se(+II) by two bidentate pentaselenide ligands is observed (mean Se? Se bond lengths: 2.658 Å at Se(+II), 2.322 Å in [Se5]2?). The resulting six-membered chelate rings with chair conformation are spirocyclically linked through the central Se(+II). The vibrational spectra of the new anions are reported.  相似文献   

9.
Structure Relationships between Tetraselenium(2+) Hexachlorometalates: Synthesis and Crystal Structure of Se4[ReCl6] and the Solid State Phase Transition of Se4[MCl6](M = Zr, Hf). The reaction of Se, SeCl4, and ReCl4 in a closed, evacuated glass ampoule at 485 K yields dark‐red moisture sensitive crystals of Se4[ReCl6] (orthorhombic, Pccn, a = 1091.5(1), b = 1057.2(1), c = 1015.0(1) pm). The crystal structure consists of almost square‐planar Se42+ cations and slightly distorted octahedral [ReCl6]2— anions. Se4[ReCl6] is paramagnetic with a moment of 3.54 μB/Re according to a d3 configuration and Re(IV). The magnetic moment obeys the Curie‐Weiss law with a Weiss constant of —33 K. The already known compounds Se4[ZrCl6] and Se4[HfCl6] crystallize in a closely related structure with tetragonal symmetry (space group P42/ncm). Both undergo a phase transition in the solid state into an orthorhombic low temperature form, which is isotypic to Se4[ReCl6]. The phase transition was monitored by single crystal and powder diffraction, the transition temperature was determined to 193(1) K for Se4[ZrCl6]. The changes of the lattice constants with temperature imply a displacive transition of mainly second order which is allowed by the translationsgleiche supergroup‐subgroup relation of index 2 between the space groups. No phase transition into a tetragonal high‐temperature form could be observed for the orthorhombic Se4[ReCl6].  相似文献   

10.
The Crystal Structures of (NH4)2[ReCl6], [ReCl2(CH3CN)4]2[ReCl6] · 2CH3CN and [ReCl4(18)(Crown-6)] Brown single crystals of (NH4)2[ReCl6] are formed by the reaction of NH4Cl with ReCl5 in a suspension of diethylether. [ReCl2(CH3CN)4]2[ReCl6] · 2CH3CN crystallizes as brown crystal plates from a solution of ReCl5 in acetonitrile. Lustrous green single crystals of [ReCl4(18-crown-6)] are obtained by the reaction of 18-crown-6 with ReCl5 in a dichloromethane suspension. All rhenium compounds are characterized by IR spectroscopy and by crystal structure determinations. (NH4)2[ReCl6]: Space group Fm3 m, Z = 4, 75 observed unique reflections, R = 0.01. Lattice constant at ?70°C: a = 989.0(1) pm. The compound crystallizes in the (NH4)2[PtCl6] type, the Re? Cl distance is 235.5(1) pm. [ReCl2(CH3CN)4]2[ReCl6] · 2CH3CN: Space group P1, Z = 1, 2459 observed unique reflections, R = 0.12. Lattice dimensions at ?60°C: a = 859.0(1), b = 974.2(7), c = 1287.3(7) pm, α = 102.69(5)°, b? = 105.24(7)°, γ = 102.25(8)°. The structure consists of two symmetry-independent [ReCl2(CH3CN)4]+ ions with trans chlorine atoms, [ReCl6]2? ions, and included acetonitrile molecules. In the cations the Re? Cl bond lengths are 233 pm in average, in the anion they are 235 pm in average. [ReCl4(18-crown-6)]: Space group P21/n, Z = 4, 3 633 observed unique reflections, R = 0.06. Lattice dimensions at ?70°C: a = 1040.2(4), b = 1794.7(5), c = 1090.0(5) pm, b? = 108.91(4)°. The compound forms a molecular structure, in which the rhenium atom is octahedrally coordinated by the four chlorine atoms and by two oxygen atoms of the crown ether molecule.  相似文献   

11.
Metal Ampoules as Mini‐Autoclaves: Syntheses and Crystal Structures of [Al(NH3)4Cl2][Al(NH3)2Cl4] and (NH4)2[Al(NH3)4Cl2][Al(NH3)2Cl4]Cl2 The salts [Al(NH3)4Cl2]+[Al(NH3)2Cl4]≡AlCl3 · 3 NH3 ( 1 ) and (NH4+)2[Al(NH3)4Cl2]+[Al(NH3)2Cl4](Cl)2≡ AlCl3 · 3 NH3 · (NH4)Cl ( 2 ) have been obtained as single crystals during the reactions of aluminum and aluminum trichloride, respectively, with ammonium chloride in sealed Monel metal containers. The crystal structure of 1 was determined again [triclinic, P‐1; a = 574.16(10); b = 655.67(12); c = 954.80(16) pm; α = 86.41(2); β = 87.16(2); γ = 84.89(2)°], that of 2 for the first time [monoclinic, I2/m; a = 657.74(12); b = 1103.01(14); c = 1358.1(3) pm; β = 103.24(2)°].  相似文献   

12.
A three‐dimensional cyano‐bridged copper(II) complex, [Cu(dien)Ag(CN)2]2[Ag2(CN)3][Ag(CN)2] ( 1 ) (dien = diethylenetriamine), has been prepared and characterized by X‐ray crystallography. Complex 1 crystallized in the monoclinic space group P21/n with a = 6.988(2), b = 17.615(6), c = 12.564(4) Å, β = 90.790(5)°. The crystal consists of cis‐[Cu(dien)]2+ units bridged by [Ag(CN)2] to form a zig‐zag chain. The Ag atoms of the free and bridging [Ag(CN)2] link together to form additional infinite zig‐zag chains with short Ag···Ag distances. The presence of Ag···Ag interactions effectively increases the dimensionality from a 1‐D chain to a 3‐D coordination polymer.  相似文献   

13.
[WS4Cu2(Py)4]的合成及晶体结构   总被引:4,自引:0,他引:4  
(NH_4)_2WS_4、CuCl和(n-Bu)_4NBr在Ar气氛中,90℃下反应10 h,所得产物先后经CH_2Cl_2与CH_3OH处理,得一桔红色晶体。该晶体与吡啶反应,即得到桔红色针状晶体[WS_4Cu_2(Py)_4],属单斜晶系,空间群C2/c,晶胞参数:a=14.109(1),b=12.704(1),c=14.071(1);β=96.97(1)°;Z=4。结构用重原子法解出,经最小二乘法修正,偏离因子R=0.027。  相似文献   

14.
On the Crystal Structures of the Cyano Complexes [Co(NH3)6][Fe(CN)6], [Co(NH3)6]2[Ni(CN)4]3 · 2 H2O, and [Cu(en)2][Ni(CN)4] Of the three title compounds X‐ray structure determinations were performed with single crystals. [Co(NH3)6][Fe(CN)6] (a = 1098.6(6), c = 1084.6(6) pm, R3, Z = 3) crystallizes with the CsCl‐like [Co(NH3)6][Co(CN)6] type structure. [Co(NH3)6]2[Ni(CN)4]3 · 2 H2O (a = 805.7(5), b = 855.7(5), c = 1205.3(7) pm, α = 86.32(3), β = 100.13(3), γ = 90.54(3)°, P1, Z = 1) exhibits a related cation lattice, the one cavity of which is occupied by one anion and 2 H2O, whereas the other contains two anions parallel to each other with distance Ni…Ni: 423,3 pm. For [Cu(en)2][Ni(CN)4] (a = 650.5(3), b = 729.0(3), c = 796.5(4) pm, α = 106.67(2), β = 91.46(3), γ = 106.96(2)°, P1, Z = 1) the results of a structure determination published earlier have been confirmed. The compound is weakly paramagnetic and obeys the Curie‐Weiss law in the range T < 100 K. The distances within the complex ions of the compounds investigated (Co–N: 195.7 and 196.4 pm, Ni–C: 186.4 and 186.9 pm, resp.) and their hydrogen bridge relations are discussed.  相似文献   

15.
The Crystal Structures of {Li3(12-crown-4)2[HC(CN)2]3}, {Na(15-crown-5)[HC(CN)2]}, and {NaN(nBu)4[HC(CN)2]2 · THF} The preparation and the crystal structures of the title compounds 1 — 3 are described. 1 forms a polymeric chain structure, in which one of the lithium ions is linked by Li…NCC(H)CN… bridges. The remaining lithium ions form (12-crown-4)Li[NCC(H)CN] units, which are coordinated by one of the nitrogen atoms of the dicyanomethanide ions with the lithium ions of the chain. 2 forms an ion pair, in which the sodium ion is coordinated by the five oxygen atoms of the crown ether molecule and by one nitrogen atom of the dicyanomethanide ion. 3 has a threedimensional network, in which the sodium ions are coordinated in a distorted tetrahedral manner by the nitrogen atoms of the dicyanomethanide ions. In the cavities of the network the tetrabutylammonium ions and the THF molecules are found.  相似文献   

16.
[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   

17.
The alkalimetal phosphoraneiminates [KNPCy3]4, ( 1 ) [KNPCy3]4·2OPCy3 ( 2 ) and [CsNPCy3]4·4OPCy3 ( 3 ) (Cy = cyclohexyl) which are obtainable by the reaction of pottassium amide or cesium amide with Cy3PI2 or Cy3PBr2 in liquid ammonia, as well as the lithium derivative [Li4(NPPh3)(OSiMe2NPPh3)3(DME)] ( 4 ) have been characterized by crystal structure determinations. 4 has been formed by the insertion reaction of silicon greaze (‐OSiMe2)n into the LiN bonds of [LiNPPh3]6 in DME solution (DME = 1, 2‐dimethoxyethane). 1 : Space group P&1macr;, Z = 2, lattice dimensions at 193 K: a = 1389.8(1); b = 1408.1(1); c = 2205.2(2) pm; α = 78.952(10)?; β = 81.215(10)?; γ = 66.232(8)?; R1 = 0.0418. 2 : Space group Pbcn, Z = 4, lattice constants at 193 K: a = 2943.6(2); b = 2048.2(1); c = 1893.8(1) pm; R1 = 0.0428. 3 : Space group Cmc21, Z = 4, lattice dimensions at 193 K: a = 2881.6(2); b = 2990.2(2); c = 1883.7(2) pm; R1 = 0.0586. 4 ·1/2DME: Space group R&3macr;c, Z = 12, lattice dimensions at 193 K: a = b = 1583.5(1); c = 11755.3(5) pm; R1 = 0.0495. All complexes have heterocubane structures. In 1‐3 they are formed by four alkali metal atoms and by the nitrogen atoms of the (μ3‐NPCy3) groups, whereas 4 forms a "heteroleptic" Li4NO3 heterocubane.  相似文献   

18.
Synthesis and Crystal Structure of the Tetrameric Nitrido Complex [Cu(CH3CN)4]2[W4N4Cl14(CH3CN)2] . The title compound has been prepared by the reaction of CuCl with WNCl3 in acetonitrile solution, forming red, moisture sensitive crystals. They were characterized by IR spectroscopy and by an X-ray structure determination. Space group I2/a, Z = 4, 2 027 observed unique reflections, R = 0.049. Lattice dimensions at -80°C: a = 2 527.0, b = 971.9, c = 2 137.5 pm, β = 106.01°. The compound consists of [Cu(CH3CN)4]+ ions, which are arranged to form strands, and of anions [W4N4Cl14(CH3CN)2]2?, in which the tungsten atoms were located at the vertices of a square and are linked with one another via linear W?N? W bridges. Two of the four tungsten atoms have four chlorine atoms as terminal ligands, the other two tungsten atoms have three chlorine atoms and an acetonitrile molecule as terminal ligands.  相似文献   

19.
Synthesis, Crystal Structure, and Solid State Phase Transition of Te4[AsF6]2·SO2 The oxidation of tellurium with AsF5 in liquid SO2 yields Te42+[AsF6]2 which can be crystallized from the solution in form of dark red crystals as the SO2 solvate. The crystals are very sensitive against air and easily lose SO2, so handling under SO2 atmosphere or cooling is required. The crystal structure was determined at ambient temperature, at 153 K, and at 98 K. Above 127 K Te4[AsF6]2·SO2 crystallizes orthorhombic (Pnma, a = 899.2(1), b = 978.79(6), c = 1871.61(1) pm, V = 1647.13(2)·106pm3 at 297 K, Z = 4). The structure consists of square‐planar Te42+ ions (Te‐Te 266 pm), octahedral [AsF6] ions and of SO2 molecules which coordinate the Te4 rings with their O atoms in bridging positions over the edges of the square. At room temperature one of the two crystallographically independent [AsF6] ions shows rotational disorder which on cooling to 153 K is not completely resolved. At 127 K Te4[AsF6]2·SO2 undergoes a solid state phase transition into a monoclinic structure (P1121/a, a = 866.17(8), b = 983.93(5), c = 1869.10(6) pm, γ = 96.36(2)°, V = 1554, 2(2)·106 pm3 at 98 K, Z = 4). All [AsF6] ions are ordered in the low temperature form. Despite a direct supergroup‐subgroup relationship exists between the space groups, the phase transition is of first order with discontinuous changes in the lattice parameters. The phase transition is accompanied by crystal twinning. The main difference between the two structures lies in the different coordination of the Te42+ ion by O and F atoms of neighbored SO2 and [AsF6] molecules.  相似文献   

20.
金属磷酸盐材料在吸附、离子交换、离子传导和催化剂方面有潜在的应用前景[1~5]. 近年来, 通过水热反应合成了一些A-V-P-O化合物. 在这些化合物中, A一般为碱金属或有机阳离子, 如层状结构的[H2N(C4H8)2NH2][(VO)4(OH)4(PO4)2][6] 和[H2N(C2H4)3NH2][(VO)8(HPO4)3(PO4)4*(OH)2]*2H2O[6], 一维链状结构的 [H2NCH2CH2NH3(VO)(PO4)][7], 手性双螺旋结构的 [(CH3)2NH2]K4[(VO)10(H2O)2(OH)4(PO4)7]*H2O[8]以及具有三维骨架结构的化合物 [H3N(CH2)3NH3K(VO)3(PO4)3][9], [H3N(CH2)3NH3]2[V(H2O)2(VO)6(OH)2(HPO4)3(PO4)5]*3H2O[10]和[H3N(CH2)2NH3][(VO)3(H2O)2(PO4)2(HPO4)4][11].  相似文献   

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