共查询到20条相似文献,搜索用时 31 毫秒
1.
A. Leineweber H. Jacobs R. Eßmann P. Allenspach F. Fauth P. Fischer 《无机化学与普通化学杂志》2001,627(9):2063-2069
Diammine cobalt(II) chloride, Co(N(H, D)3)2Cl2 was prepared by decomposition of the corresponding hexaammines at 120 °C in dynamical vacuum. Crystal structures and magnetic properties of these materials were characterised by X‐ray and neutron powder diffraction, and heat capacity measurements. At ambient temperatures Co(N(H, D)3)2Cl2 crystallises in the Cd(NH3)2Cl2 type structure: space group Cmmm, Z = 2, a = 8.0512(2) Å, b = 8.0525(2) Å, c = 3.73318(9) Å (X‐ray data of the H compound). This structure consists of chains of edge‐sharing octahedra [CoCl4/2(NH3)2] running along the c‐axis. Neutron diffraction confirms that that the ND3 groups are rotationally disordered at ambient temperatures. At 1.5 K and 20 K neutron diffraction data reveal rotational ordering of the ND3 groups leading to doubling of the c‐axis and to Ibmm symmetry: a = 7.9999(6) Å, b = 7.9911(5) Å, c = 7.4033(3) Å (Z = 4, values for T = 1.5 K). Furthermore, antiferromagnetic ordering is present at these temperatures. It is caused by a ferromagnetic coupling of the magnetic moments at Co2+ (3.60(5) μB at 1.5 K, 3.22(5) μB at 20 K) along the octahedra chains [CoCl4/2(NH3)2] and antiferromagnetic coupling between neighbouring chains. According to heat capacity measurements the phase transition antiferromagnetic‐paramagnetic takes place at TN = 26 K. 相似文献
2.
Neutron Diffraction of the Low Temperature Modification of Rubidium Deutero Amide A polycrystalline sample of RbND2 was prepared by reaction of liquid ND3 and Rb (320 K, 4 d). Rietveld refinement of neutron powder diffraction data collected on the E2 (HMI-BENSC, Berlin) yielded the deuterium positions and allowed the temperature factors of all atoms to be refined anisotropically: space group P21/m, Z = 2, a = 4.846(1) Å, b = 4.136(1) Å, c = 6.396(2) Å, β = 98.051(7)°, N(I/σ(I) > 1) = 179, N(Var.) = 25, RP = 0.025, wRP = 0.032, RB(I/σ(I) > 1) = 0.095. In a monoclinic distorted rock salt structure the amide ions are oriented antiferroelectrically in almost planar zick-zack chains. 相似文献
3.
Neutron Powder Diffraction Measurements on [Zn(ND3)4]I2 at 1.5 K, 10 K, and 293 K: Hydrogen Bonds and Dynamic of ND3 Molecules Microcrystalline powder of [Zn(ND3)4]I2 can be prepared by the reaction of gaseous NH3 with dry ZnI2 at room temperature within 8 h. Neutron powder diffraction measurements at 1.5 K, 10 K and 293 K were used to localize all hydrogen atoms. Isolated [Zn(ND3)4]2+ tetrahedra are three dimensionally linked with 2- and 3-centre (bent and bifurcated) N? D …? I?-hydrogen bonds. Ammonia molecules are ordered at 1.5 K. Room temperature high thermal displacement parameters for D hint to the fact that NH3-dynamics take place. Lattice parameters 300 K [10 K; 1,5 K]: a = 10.3783(8) Å [10.3407(4) Å; 10.3381(5)], b = 7.5239(6) Å [7.3960(2) Å; 7.3935(4) Å], c = 13.088(1) Å [12.9731(4) Å; 12.9695(6) Å], space group: Pnma. 相似文献
4.
《Solid State Sciences》1999,1(4):233-243
Diamido-difluoro-tin Sn(ND2)2F2 can be produced by ammonolysis from (NH4)2SnF6 at 633 K. The compound is a product formed from Sn(ND3)2F4 during the ammonolysis reaction. Sn(ND2)2F2 isostructural with Sn(NH2)2F2 crystallizes in space group C2/m with lattice constants a = 1072.92(7), b = 325.97(1) pm, c = 505.79(4) pm and β = 105.713(6) ° (V = 170.28(1) ·106 pm3) containing two formula units per unit cell. Data refinement by the Rietveld method of neutron time-of-flight data collected at POLARIS yields a weighted profile R-value Rwp = 0.022. Tin is octahedrally coordinated by two fluorine atoms and four amido groups. The octahedra are connected to one-dimensional chains by edge sharing. The ND2 groups are in the bridging position whilst the fluorine atoms are terminal. Nearly linear (175.2(4) °) and angular (134.35(8) °) N-D···F hydrogen linkages connect the chains. 相似文献
5.
Positions of the Protons in Potassium Tetraamidozincate, K2Zn(NH2)4 X-ray single crystal data for K2Zn(NH2)4 allowed the determination of the so far unknown positions of the protons: P1 , Z = 2, a = 6.730(1) Å, b = 7.438(1) Å, c = 8.019(2) Å, α = 72.03(2)°, β = 84.45(2)°, γ = 63.82(1)°, Z(F0) with (F0)2 ≥ 3σ(F0)2 = 2166, Z(parameters) = 96, R/RW = 0.032/0.039. In the structure of K2Zn(NH2)2 the amide ions are nearly hexagonal close packed. One layer of octahedral holes parallel to (010) is fully occupied by potassium atoms and zinc is in an ordered way in a quarter of the tetrahedral holes of the next layer. The orientation of the protons of the amide ions is characteristic for this type of structure (filled up CdI2 type). 相似文献
6.
RbLi(NH2)2 and the fully deuterated compound are obtained in autoclaves by the reaction of RbNH2/RbND2 and Li metal in supercritical NH3/ND3 (470 K, 220 Mpa, 41 d). X‐ray single crystal and neutron powder diffraction led to a new type of crystal structure closely related to the ThCr2Si2type. It is an orthorhombic distorted variant with an ordered half occupation by lithium on tetrahedral sites of puckered 44 nets of amide ions to{[Li(NH2)1/1(NH2)3/3]} units and fully filled up sites of CN = 8 by Rb. The compound crystallizes in the space group Pnma with Z = 4 and a = 7.772 (2)Å, b = 3.843 (1)Å, c = 11.583 (2)Å. It contains an unexpected hydrogen bridge bonding system between crystallographic different amide ions. 相似文献
7.
The Crystal Structure of Barium Amide, Ba(NH2)2 Single crystals of barium amide can be obtained by the reaction of barium metal with ammonia during long times. At ? 70° C Ba reacts with the solvent very slowly. The resulting amide then is well crystallized. Crystals can also be grown at 125° C in a temperature grakient. In both cases 3 to 4 months are necessary to get crystals of about 0.1 mm in diameter. Barium amide is monoclinic a = 8.951 Å, b = 12.67 Å, c = 7.037 Å, und β = 123.5° with 8 formula units. The space group is Cc. All atoms occupy the general position. The structure of Ba(NH2)2 shows two different Ba atoms with respect to their surrounding. One of them is coordinated irregularly by 8 amide ions, the other by 7 amide ions. The nitrogen atoms have 11 neighbours to each other. This means, that they are relatively close packed. Barium amide has a coorkination type structure, whereas the low symmetry of the arrangement of the different ions may be explained by the dipole chracter of the anion, and by packing effects. 相似文献
8.
Na2Mn(NH2)4: A New Type of Layered Structure The structure of Na2Mn(NH2)4 was solved by X-ray single crystal data including H-positions: P21/c, Z = 4, a = 6.331(1) Å, b = 14.542(3) Å, c = 7.212(1) Å, β = 116.29(1)°, Z(F ≥ 3σ = (F)) = 1343, Z(parameters) = 96, R/RW = 0.023/0.029. The compound crystallizes in a new type of structure. Within layered blocks the amide ions are arranged with the motif of a hexagonal closest packing of spheres. Within these blocks alternating layers contain sodium in all octahedral sites and manganese in an ordered way in a quarter of tetrahedral sites. 相似文献
9.
Synthesis and Crystal Structure of K2(HSO4)(H2PO4), K4(HSO4)3(H2PO4), and Na(HSO4)(H3PO4) Mixed hydrogen sulfate phosphates K2(HSO4)(H2PO4), K4(HSO4)3(H2PO4) and Na(HSO4)(H3PO4) were synthesized and characterized by X‐ray single crystal analysis. In case of K2(HSO4)(H2PO4) neutron powder diffraction was used additionally. For this compound an unknown supercell was found. According to X‐ray crystal structure analysis, the compounds have the following crystal data: K2(HSO4)(H2PO4) (T = 298 K), monoclinic, space group P 21/c, a = 11.150(4) Å, b = 7.371(2) Å, c = 9.436(3) Å, β = 92.29(3)°, V = 774.9(4) Å3, Z = 4, R1 = 0.039; K4(HSO4)3(H2PO4) (T = 298 K), triclinic, space group P 1, a = 7.217(8) Å, b = 7.521(9) Å, c = 7.574(8) Å, α = 71.52(1)°, β = 88.28(1)°, γ = 86.20(1)°, V = 389.1(8)Å3, Z = 1, R1 = 0.031; Na(HSO4)(H3PO4) (T = 298 K), monoclinic, space group P 21, a = 5.449(1) Å, b = 6.832(1) Å, c = 8.718(2) Å, β = 95.88(3)°, V = 322.8(1) Å3, Z = 2, R1 = 0,032. The metal atoms are coordinated by 8 or 9 oxygen atoms. The structure of K2(HSO4)(H2PO4) is characterized by hydrogen bonded chains of mixed HnS/PO4– tetrahedra. In the structure of K4(HSO4)3(H2PO4), there are dimers of HnS/PO4– tetrahedra, which are further connected to chains. Additional HSO4– tetrahedra are linked to these chains. In the structure of Na(HSO4)(H3PO4) the HSO4– tetrahedra and H3PO4 molecules form layers by hydrogen bonds. 相似文献
10.
The possibility to synthesize and isolate different types of bismuth polyanions by dissolving various intermetallic precursors (binary samples from A‐Bi or ternary samples from A‐A'‐Bi systems, A and A' = K, Rb, Cs) in ethylenediamine or dimethylform amide in the presence of sequestering agents (2, 2, 2‐crypt or 18‐crown‐6) was investigated. The crystals of (2, 2, 2‐crypt‐K)2Bi4 ( 1 ) and (2, 2, 2‐crypt‐Rb)2Bi4 ( 2 ) compound were obtained from such solutions, the latter for the first time, and their structures were determined. The two compounds are isostructural (P1, Z=1, a = 11.052(2) Å, b = 11.370(2) Å, c = 11.698(2) Å, α = 61.85(3) °, β = 82.58(3) °, γ = 81.87(3) °, R1 = 0.058, wR2 = 0.149 for 1 and a = 11.181(2) Å, b = 11.603(2) Å, c = 11.740(2) Å, α = 61.96(3) °, β = 81.45(3) °, γ = 82.26(3) °, R1 = 0.041, wR2 = 0.109) and contain Bi42— square planar cluster anions and cryptated alkali metal cations. In the case of the presence of 18‐crown‐6 the Laves phases ABi2 (A = K, Rb, Cs) could be isolated from the solutions. A mechanism for the formation of ABi2 is proposed. 相似文献
11.
Scott Charles Janet A. Danis Sundeep P. Mattamana James C. Fettinger Bryan W. Eichhorn 《无机化学与普通化学杂志》1998,624(5):823-829
Ethylenediamine (en) solutions of [P7M(CO)3]3– (M = Cr, W) react with weak acids to give [HP7M(CO)3]2– ions where M = Cr ( 4 a ) and W ( 4 b ) in high yields. Competition studies with known acids revealed a pKa range for 4 b in DMSO of 17.9 to 22.6. The [P7M(CO)3]3– complexes also react with one-half equivalent of I2 to give 4 through an oxidation/hydrogen atom abstraction process. Labeling studies show that the abstracted hydrogen originates from the [K(2,2,2-crypt)]+ ions or from the solvent (DMSO-d6) in the absence of [K(2,2,2-crypt)]+ or other good hydrogen atom donors. In the solid state, the ions have no crystallographic symmetry but in solution they show virtual Cs symmetry (31P NMR spectroscopy) due to an intramolecular wagging process. Crystallographic data for [K(2,2,2-crypt)]2[HP7W(CO)3]: triclinic, P 1, a = 10.9709(8) Å, b = 13.9116(10) Å, c = 19.6400(14) Å, α = 92.435(6)°, β = 93.856(6)°, γ = 108.413(6)°, V = 2831.2(4) Å3, Z = 2, R(F) = 7.65%, R(wF2) = 14.17% for all 7400 reflections. For [K(2,2,2-crypt)]2[HP7Cr(CO)3]: triclinic, P 1, a = 12.000(3) Å, b = 14.795(3) Å, c = 17.421(4) Å, α = 93.01(2)°, β = 93.79(2)°, γ = 110.72(2)°, V = 2877(2) Å3, Z = 2. 相似文献
12.
Hydrogen Bonds in the Monoammoniates of Potassium and Cesium Amide X‐ray structure determination was carried out on the monoammoniates of potassium and cesium amide. Crystals of KNH2 · NH3 were grown from liquid NH3 at 50 °C > T > 20 °C. They crystallize in the cold part of a pressure resistant glass apparatus. Single crystals of CsNH2 · NH3 were obtained by zone‐melting at —30 °C in x‐ray capillaries. The following data characterize the crystal chemistry of the compounds: KNH2 · NH3 Cmc21, Z = 4 21 °C a = 3, 938(1) Å, b = 10, 983(3) Å, c = 5, 847(1) Å CsNH2 · NH3 Pnma, Z = 4 30 °C a = 7, 103(1) Å, b = 5, 390(1) Å, c = 10, 106(2) Å For CsNH2 · NH3 all hydrogen atom positions were successfully refined. The structure of both ammoniates may be described by a distorted hexagonal close packed arrangement of cations with the NH3 molecules in the octahedral and the NH2— anions in the trigonal bipyramidal interstices. The three H atoms of the NH3 molecules are involved in hydrogen bridge bonds to two amide ions with d(N(NH3)···N(NH2—)) = 2.60Å for the K and 3.19Å for the Cs compound and to a further NH3 molecule with d(N(NH3)···N(NH3)) = 2.98Å for the K and 3.56Å for the Cs compound. Structural relationship of the ammoniates to the monohydrates of KOH and RbOH is discussed. 相似文献
13.
Systematic studies on quaternary thio‐ and selenoborates containing heavier alkaline earth metal cations led to the two new isotypic crystalline phases Sr4.2Ba2.8(BS3)4S and Ba7(BSe3)4Se. Both compounds consist of trigonal‐planar BQ3 (Q = S, Se) units, isolated Q2– anions and the corresponding counter‐ions. The two new chalcogenoborates were prepared in solid state reactions from the metal sulfides (selenides), amorphous boron and sulfur (selenium). Evacuated carbon coated silica tubes were used as reaction vessels since temperatures up to 870 K were applied. Sr4.2Ba2.8(BS3)4S and Ba7(BSe3)4Se crystallize in the monoclinic space group C2/c (no. 15) with a = 9.902(3) Å, b = 23.504(9) Å, c = 9.884(3) Å, β = 90.01(3)° and Z = 4 in the case of the thioborate, while for the selenoborate the lattice parameters a = 10.513(2) Å, b = 25.021(5) Å, c = 10.513(2) Å, β = 90.10(3)° were determined. X‐ray powder patterns are compared to calculated diffraction data obtained from single crystal X‐ray structure determination. 相似文献
14.
Preparation and Crystal Structure of the Rubidium Calcium Amide, RbCa(NH2)3 In the system Rb/Ca/NH3 a ternary amide, RbCa(NH2)3, has been prepared by the reaction of the metals with supercritical NH3 at T = 573 K and P = 5 000 bar. The x-ray investigation of single crystals of the compound led to the structure: a = 7.080 ± 0.006 Å, b = 11.95 ± 0.01 Å, c = 6.540 ± 0.006 Å, and β = 108.5 ± 0.1°; space group: C2/c ? No. 15, Z = 4. The atomic arrangement shows onedimensional infinite face-sharing anion-octahedra, which are occupied by calcium. The rubidium connects the octahedra-chains. The orientation of the protons corresponds to the stronger electrostatic influence of the calcium – compared with that of the rubidium ions. 相似文献
15.
Gwo-Wei Tseng Maw-Cherng Suen Jhy-Der Chen Jiunn-Jer Hwang Yui Whei Chen-Yang Tai-Chiun Keng Ju-Chun Wang 《中国化学会会志》1999,46(4):545-550
The red complex trans-Mo2(O2CCH3)2(μ-dppa)2(BF4)2, 1 , was prepared by reaction of [Mo2(O2CCH3)2(CH3CN)6][BF4]2 with dppa (dppa = Ph2PN(H)PPh2) in THF. The reactions of Mo2(O2C(CH2)nCH3)4 with dppa and (CH3)3SiX (X = Cl or Br) afforded the complexes trans-Mo2X2(O2C(CH2)nCH3)2(μ-dppa)2 (X = Cl, n = 2, 2; X = Br, n = 2, 3; X = Cl, n = 10, 4 ; X = Cl, n = 12, 5 ). Their UV-vis, IR and 31P{1H}-NMR spectra have been recorded and the structures of 1, 2 and 3 have been determined. Crystal data for 1 : space group P21/n, a = 12.243(1) Å, b = 17.222(1) Å, c = 13.266(1) Å, β = 95.529(1)°, V = 2784.1(6) Å3, Z = 2, with final residuals R = 0.0509 and Rw = 0.0582. Crystal data for 24CH3Cl2: space group P21/n, a = 13.438(1) Å, b = 19.276(1) Å, c = 14.182(1) Å, β = 111.464(1)°, V = 3418.9(6) Å3, Z = 2, with final residuals R = 0.0492 and Rw = 0.0695. Crystal data for 3·4CH2Cl2: space group P21/n, a= 13.579(1) Å, b = 19.425(1) Å, c = 14.199(1) Å, β = 111.881(2)°, V = 3475.6(7) Å3, Z = 2, with final residuals R = 0.0703 and Rw = 0.0851. Comparison of the structural data shows that the effect of the axial ligand on weakening the Mo-Mo bond strength is X? > CH3CN > BF4?. The Tm values are 121.7 °C for 2 , 111.1 °C for 3 and 91.5 °C for 5 , respectively. 相似文献
16.
A. V. Ruseikina L. A. Solov’ev O. V. Andreev 《Russian Journal of Inorganic Chemistry》2014,59(3):196-201
The crystal structures of SrLnCuS3 (Ln = La, Pr) have been refined using X-ray powder diffraction data and the derivative difference minimization method in the anisotropic approximation for all atoms. The crystals are orthorhombic, space group Pnma, BaLaCuS3 structural type, unit cell parameters a = 11.2415(1) Å, b = 4.11053(6) Å, c = 11.5990(1) Å, V = 535.97(1) Å3 (SrLaCuS3) and a = 11.1171(1) Å, b = 4.09492(6) Å, c = 11.5069(2) Å, V = 523.84(1) Å3 (SrPrCuS3). The crystallographic positions of strontium and lanthanides are mixed by 21 and 11%, respectively. The SrLa-S and SrPr-S bond lengths range from 2.969(3) to 3.131(3) Å and from 2.924(2) to 3.056(2) Å, respectively. Distorted CuS4 tetrahedra form chains running along the b axis. One-capped Sr/LnS7 trigonal prisms form a three-dimensional structure with channels accommodating copper ions. The temperatures and enthalpies of incongruent melting are, respectively, 1513 K and 18 J/g (SrLaCuS3) and 1426 K and 34 J/g (SrPrCuS3). The compounds are IR transparent in the region of 3000–1800 cm?1. 相似文献
17.
《European Journal of Solid State and Inorganic Chemistry #》1998,35(2):117-132
New compounds, Sr2Ga(HPO4)(PO4)F2 and Sr2Fe2(HPO4)(PO4)2F2, have been prepared by hydrothermal synthesis (700°C, 180 MPa, 24 h) and characterized by single-crystal X-ray diffraction. Sr2Ga(HPO4)(PO4)F2 crystallizes in the monoclinic space group P21/n with a = 8.257(1) Å, b = 7.205(1) Å, c = 13.596(2) Å, β = 108.02(1)°, V = 769.2(2) Å3 and Z = 4 and Sr2Fe2(HPO4)(PO4)2F2 in the triclinic space group P21/n with a = 8.072(1) Å, b = 8.794(1) Å, c = 8.885(1) Å, α = 102.46(1)°, β = 115.95(1)°, γ = 89.95(1)°, V = 550.6(1) Å3 and Z = 2. Structures are both based on different sheets involving corner-linkage between octahedra and tetrahedra. The sheets are linked by Sr2+ cations. Structural relationships exist between the descloizite mineral and the title compounds. 相似文献
18.
Pale rose single crystals of SrMn2(PO4)2 were obtained from a mixture of SrCl2 · 6 H2O, Mn(CH3COO)2, and (NH4)2HPO4 after thermal decomposition and finally melting at 1100 °C. The new crystal structure of strontium manganese orthophosphate [P‐1, Z = 4, a = 8.860(6) Å, b = 9.054(6) Å, c = 10.260(7) Å, α = 124.27(5)°, β = 90.23(5)°, γ = 90.26(6)°, 4220 independent reflections, R1 = 0.034, wR2 = 0.046] might be described as hexagonal close‐packing of phosphate groups. The octahedral, tetrahedral and trigonal‐bipyramidal voids within this [PO4] packing provide different positions for 8‐ and 10‐fold [SrOx] and distorted octahedral [MnO6] coordination according to a formulation Mn Mn Mn Sr (PO4)4. Single crystals of β′‐Mn3(PO4)2 (pale rose) were grown by chemical vapour transport (850 °C → 800 °C, P/I mixtures as transport agent). The unit cell of β′‐Mn3(PO4)2 [P21/c, Z = 12, a = 8.948(2) Å, b = 10.050(2) Å, c = 24.084(2) Å, β = 120.50°, 2953 independent reflections, R1 = 0.0314, wR2 = 0.095] contains 9 independent Mn2+. The reinvestigation of the crystal structure led to distinctly better agreement factors and significantly reduced standard deviations for the interatomic distances. 相似文献
19.
Andrew L. Hector Stuart J. Henderson William Levason Michael Webster 《无机化学与普通化学杂志》2002,628(1):198-202
Hydrothermal syntheses of single crystals of rare earth iodates, by decomposition of the corresponding periodate, are presented. This appears to be a generic method for making rare earth iodate crystals in a short period of time. Single crystal X‐ray diffraction structures of the four title compounds are presented. Sc(IO3)3: Space group R3, Z = 6, lattice dimensions at 100 K; a = b = 9.738(1), c = 13.938(1) Å; R1 = 0.0383. Y(IO3)3 · 2 H2O: Space group P1, Z = 2, lattice dimensions at 100 K: a = 7.3529(2), b = 10.5112(4), c = 7.0282(2) Å, α = 105.177(1)°, β = 109.814(1)°, γ = 95.179(1)°; R1 = 0.0421. La(IO3)3 · ? H2O: Space group Pn, Z = 2, lattice dimensions at 100 K: a = 7.219(2), b = 11.139(4), c = 10.708(3) Å, β = 91.86(1)°; R1 = 0.0733. Lu(IO3)3 · 2 H2O: Space group P1, Z = 2, lattice dimensions at 120 K: a = 7.2652(9), b = 7.4458(2), c = 9.3030(3) Å, α = 79.504(1)°, β = 84.755(1)°, γ = 71.676(2)°; R1 = 0.0349. 相似文献
20.
E. Kandasamy 《Journal of Structural Chemistry》2013,54(1):177-181
The diacetato-bis(2-methyl-2-propylamine)zinc(II) compound crystallizes in the triclinic system, space group P-1 with unit cell parameters a = 10.0144(10)Å, b = 10.2687(10)Å, c = 10.5149(10)Å. α = 115.184(2)°, β = 97.489(2)°, γ = 114.066(2)°, ν = 830.85(14)Å3. The obtained solid state structure of (tBuNH2)2Zn(OOCCH3)2 shows both inter- and intramolecular NH—O hydrogen bond interactions which are analyzed. 相似文献