共查询到20条相似文献,搜索用时 15 毫秒
1.
Torsten Küppers Eduard Bernhardt Christian W. Lehmann Dr. Helge Willner Prof. Dr. 《无机化学与普通化学杂志》2007,633(10):1666-1672
The Tetracyanoboronic Acids H[B(CN)4]·n H2O, n = 0, 1, 2 Treatment of an aqueous solution of Na[B(CN)4] with an acidic cation exchange resin leads to a solution of the strong tetracyanoboronic acid. Evaporation of the solution at room temperature yields colourless single crystals of [H5O2][B(CN)4] ( , a = 9.5830(2) Å, c = 14.25440(3) Å, Z = 1). Further drying of [H5O2][B(CN)4] (mp. 115 °C) in vacuum at 50 °C gives polycrystalline [H3O][B(CN)4] (P63mc, a = 8.704(1) Å, c = 6.152(1) Å, Z = 2), which is thermally stable up to 145 °C. The anhydrous polycrystalline acid H[B(CN)4] is formed quantitatively by reacting Me3SiNCB(CN)3 with gaseous HCl. This acid starts to decompose at 190 °C with loss of HCN. All three acids were further characterized by vibrational spectroscopy, and elemental analysis. 相似文献
2.
Torsten Küppers Martin Köckerling Prof. Dr. Helge Willner Prof. Dr. 《无机化学与普通化学杂志》2007,633(2):280-284
The new tetracyanoborate K[B(CN)4]·CH3CN was synthesized by dissolution of the solvent‐free K[B(CN)4] in acetonitrile and subsequent careful crystallization. The crystal structure has been determined by single‐crystal X‐ray diffraction. It crystallizes in the orthorhombic space group P212121 with Z = 4. Some comparisons with related structures are made, and the vibrational spectrum is discussed. 相似文献
3.
Preparation, Crystal Structure, Thermal Decomposition, and Vibrational Spectra of [Co(NH3)6]2[Be4O(CO3)6] · 10 H2O [Co(NH3)6]2[Be4O(CO3)6] · 10 H2O is a suitable compound for the quantitative determination of beryllium. It can be obtained by reaction of aqueous solutions of carbonatoberyllate with [Co(NH3)6]Cl3. The crystal structure (trigonal‐rhombohedral, R3c (Nr. 161), a = 1071,6(1) pm, c = 5549,4(9) pm, VEZ = 5519(1) · 106 pm3, Z = 6, R1(I ≥ 2σ(I)) = 0,037, wR2(I ≥ 2σ(I)) = 0,094) contains [Co(NH3)6]3+‐ and [Be4O(CO3)6]6–‐ions, which are directly hydrogen bonded as well as with water molecules. The complex cations and anions occupy the positions of a distorted anti‐CaF2‐type. The thermal decomposition, IR and Raman spectra are presented and discussed. 相似文献
4.
Preparation and Crystal Structures of the first Alkalimetall‐hexacarbonato‐oxotetraberyllates: K6[Be4O(CO3)6] · 7 H2O and K6[Be4O(CO3)6] K6[Be4O(CO3)6] · 7 H2O has been prepared by dissolving freshly precipitated Be(OH)2 in an aqueous KHCO3 solution. After enriching the title compound by extraction with ethanol the heptahydrate crystallizes from the organic phase (triklin, P1¯ (No. 2) with a = 951, 01(11), b = 958, 45(12), c = 1601, 7(2) pm, α = 79, 253(13)°, β = 78, 943(12)°, γ = 65, 119(12)°, VEZ = 1290, 6(3)·106 pm3, Z = 2). Thermal decomposition forms rhombohedral crystals of the anhydrous compound (trigonal‐rhombohedric, R3¯ (No. 148) with a = 1416, 42(6), c = 1704, 5(1) pm, VEZ = 2961, 4(3)·106 pm3, Z = 6). 相似文献
5.
Dr. Jianguo Zhang Lei Wei Yan Cui Tonglai Zhang Zunning Zhou Li Yang 《无机化学与普通化学杂志》2011,637(11):1527-1532
A new coordination complex, [Co(DAT)2(H2O)4](HTNR)2 · 2H2O [DAT = 1,5‐diaminotetrazole, HTNR = 2,4,6‐trinitroresorcinol (styphnic acid)], was obtained in high yield and characterized by elemental analysis and Fourier‐transform infrared (FT‐IR) spectroscopy. The molecular structure of [Co(DAT)2(H2O)4](HTNR)2 · 2H2O in the crystalline state is determined by X‐ray crystallography is as follows: monoclinic, C2/c, a = 19.216(3) Å, b = 5.4992(8) Å, c = 30.418(5) Å, β = 104.500(5), V = 3112.0(8) Å3, Z = 4, ρcalc. = 1.851 g · cm–3, R1 = 0.0271 and wR2 = (all data) 0.0674. The central cobalt(II) cation is coordinated by two nitrogen atoms of two DAT and four oxygen atoms of four H2O ligand molecules to form a six‐coordinate and slightly distorted octahedral structure. Extensive intermolecular hydrogen bonds link molecular units of [Co(DAT)2(H2O)4(HTNR)2 · 2H2O together to form a 3D net structure with pore canals. The thermal decomposition mechanism for the title compound was predicted based on DSC, TG‐DTG, and FT‐IR analyses and non‐kinetic parameters of the first exothermic process were estimated by applying the Kissinger, Starink, and Ozawa–Doyle methods. 相似文献
6.
The title complex {[Co(dimb)2(H2O)2]·(NO3)2·(H2O)2}n ( 1 ) (dimb = 1,3‐di(imidazol‐1‐ylmethyl)‐5‐methylbenzene) has been hydrothermally synthesized by the reaction of dimb with Co(NO3)2·6H2O in aqueous solution. The cobalt(II) atoms are linked by bridging dimb ligands to form 2D corrugated and wavy networks containing Co4(dimb)4 macrocyclic motifs. Two neighboring independent layers interlinked each other in a parallel fashion to construct three‐dimensional structure by O–H···O, N–H···O and C–H···O hydrogen bonds. Magnetic measurement shows the weak antiferromagnetic interaction with a one‐dimensional chain model in the range of 5–300 K, with J of –0.68 cm−1. 相似文献
7.
The new hexathiodiphosphate(IV) hydrates K4[P2S6] · 4 H2O ( 1 ), Rb4[P2S6] · 6 H2O ( 2 ), and Cs4[P2S6] · 6 H2O ( 3 ) were synthesized by soft chemistry reactions from aqueous solutions of Na4[P2S6] · 6 H2O and the corresponding heavy alkali‐metal hydroxides. Their crystal structures were determined by single crystal X‐ray diffraction. K4[P2S6] · 4 H2O ( 1 ) crystallizes in the monoclinic space group P 21/n with a = 803.7(1), b = 1129.2(1), c = 896.6(1) pm, β = 94.09(1)°, Z = 2. Rb4[P2S6] · 6 H2O ( 2 ) crystallizes in the monoclinic space group P 21/c with a = 909.4(2), b = 1276.6(2), c = 914.9(2) pm, β = 114.34(2)°, Z = 2. Cs4[P2S6] · 6 H2O ( 3 ) crystallizes in the triclinic space group with a = 742.9(2), b = 929.8(2), c = 936.8(2) pm, α = 95.65(2), β = 112.87(2), γ = 112.77(2)°, Z = 1. The structures are built up by discrete [P2S6]4? anions in staggered conformation, the corresponding alkali‐metal cations and water molecules. O ··· S and O ··· O hydrogen bonds between the [P2S6]4? anions and the water molecules consolidate the structures into a three‐dimensional network. The different water‐content compositions result by the corresponding alkali‐metal coordination polyhedra and by the prefered number of water molecules in their coordination sphere, respectively. The FT‐Raman and FT‐IR/FIR spectra of the title compounds have been recorded and interpreted, especially with respect to the [P2S6]4? group. The thermogravimetric analysis showed that K4[P2S6] · 4 H2O converted to K4[P2S6] as it was heated at 100 °C. 相似文献
8.
Thermal expansion of materials is a comparatively easy‐understood physical property. Prussian blue analogues are of particular interest in engineering as new zero thermal expansion materials. We investigated the thermal expansion in K0.46Co1.27[Fe(CN)6] · 5.5H2O by x‐ray powder diffraction. This compound is a good example of a zero thermal expansion material. The origin of zero thermal expansion is considered to be the low frequency transverse vibrational motion of the cyano bridges. 相似文献
9.
The two novel thioantimonate(V) compounds [Mn(C6H18N4)(C6H19N4)]SbS4 ( I ) and [Mn(C6H14N2)3][Mn(C6H14N2)2(SbS4)2]·6H2O ( II ) were synthesized under solvothermal conditions by reacting elemental Mn, Sb and S in the stoichiometric ratio in 5 ml tris(2‐aminoethyl)amine (tren) at 140 °C or chxn (trans‐1, 2‐diaminocyclohexane, aqueous solution 50 %) at 130 °C. Compound I crystallises in the triclinic space group P1¯, a = 9.578(2), b = 11.541(2), c = 12.297(2)Å, α = 62.55(1), β = 85.75(1), γ = 89.44(1)°, V = 1202.6(4)Å3, Z = 2, and II in the monoclinic space group C2/c, a = 32.611(2), b = 13.680(1), c = 19.997(1)Å, β = 117.237(5)°, V = 7931.7(8)Å3, Z = 4. In I the Mn2+ cation is surrounded by one tetradentate tren molecule, one protonated tren acting as a monodentate ligand and a monodentate [SbS4]3— anion yielding a distorted octahedral environment. In II one unique Mn2+ ion is in an octahedral environment of three bidentate chxn molecules and the second independent Mn2+ ion is coordinated by two chxn ligands and two monodentate [SbS4]3— units leading to a distorted octahedral surrounding. The compounds were investigated and characterized with thermal and spectroscopic methods. 相似文献
10.
Michael Neukirch Sonja Tragl H.‐Jürgen Meyer Torsten Küppers Helge Willner 《无机化学与普通化学杂志》2006,632(6):939-944
M[B(CN)4]2: Two new Tetracyanoborate Compounds with divalent Cations (M = Zn, Cu) The reaction of ZnO or CuO with [H3O][B(CN)4] in aqueous solution yielded single crystals of Zn[B(CN)4]2 and Cu[B(CN)4]2, respectively. The compounds were characterized by single‐crystal X‐ray diffraction. Zn[B(CN)4]2 ( (no. 164), a = b = 7.5092(9) Å, c = 6.0159(6) Å, Z = 1) crystallizes isotypic with Hg[B(CN)4]2. The structure of Cu[B(CN)4]2 (C2/m (no. 12), a = 13.185(3) Å, b = 7.2919(9) Å, c = 6.029(1) Å, β = 93.02(2)°, Z = 2) can be considered as a super‐structure, resulting from Jahn‐Teller distortion of the Cu2+ ions. Magnetic measurements were performed for the copper compound. Vibrational spectra and thermal stabilities were compared with the known mercury(II) tetracyanoborate. 相似文献
11.
Single crystals of Sr[B(C6H5O7)2](H2O)4 · 3H2O, a new borate‐citrate material, were grown with sizes up to 8 × 6 × 2 mm by slow evaporation of water at room temperature. The structure of Sr[B(C6H5O7)2](H2O)4 · 3H2O was determined by single‐crystal X‐ray diffraction. It crystallizes in the monoclinic space group P21/c, with a = 11.363(3) Å, b = 18.829(4) Å, c = 11.976(3) Å, β = 110.736(3)°, and Z = 4. The SrO8 dodecahedra, BO4 tetrahedra and citrate groups are linked together to form chains. The compound was characterized by IR and UV/Vis/NIR transmittance spectroscopy as well as thermal analysis. 相似文献
12.
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
13.
A New Energetic Complex [Co(2,4,3‐tpt)2(H2O)2]·2NO3: Synthesis,Structure, and Catalytic Thermal Decomposition for Ammonium Perchlorate
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The energetic complex, [Co(2,4,3‐tpt)2(H2O)2] · 2NO3 ( 1 ) [2,4,3‐tpt = 3‐(2‐pyridyl)‐ 4‐(4'‐pyridyl)‐5‐(3′‐pyridyl)‐1H‐1,2,4‐triazole], was synthesized and characterized by single‐crystal X‐ray diffraction, thermogravimetric analyses, elemental analysis, X‐ray powder diffraction, and IR spectroscopy. The title complex is a 0D motif with a unit of [Co(2,4,3‐tpt)2(H2O)2]2+, whereas NO3– ions not only act as counter anions to balance the charge of the CoII cations, but also provide hydrogen bond interactions, which make the 0D motif into a 1D chain. Furthermore, the thermal decomposition of ammonium perchlorate (AP) with complex 1 was explored by differential scanning calorimetry (DSC) over the temperature range from 50–500 °C. AP is completely decomposed in a shorter time in the presence of complex 1 , and the decomposition heat of the mixture is 2.143 kJ g–1, significantly higher than pure AP. By Kissinger's method, the ratio of Ea/ln(A) is 11.87 for the mixture, which indicates that complex 1 shows good catalytic activity toward AP decomposition. 相似文献
14.
Michael Berkei Eduard Bernhardt Markus Schürmann Michael Mehring Helge Willner 《无机化学与普通化学杂志》2002,628(8):1734-1740
Preparation, Spectroscopic Characterization and Crystal Structures of Mercury(II)‐bis(tetracyanoborate) Hg[B(CN)4]2 and Dimercury(I)‐bis(tetracyanoborate) Hg2[B(CN)4]2 Hg[B(CN)4]2 ( 1 ) is synthesised by the reaction between Hg(NO3)2 and K[B(CN)4]2. In a comproportionation reaction of 1 with elemental mercury the corresponding mercury(I) salt Hg2[B(CN)4]2 ( 2 ) is obtained. The compounds were characterised by vibrational‐ and NMR‐spectroscopy, and their crystal structures were determined. Hg[B(CN)4]2 crystallizes in the trigonal system in the space group P3¯m1 with a = 781.75(3) pm, c = 601.68(2) pm, V = 318.44(2)Å3, and one formula unit per unit cell. For Hg2[B(CN)4]2 an orthorhombic unit cell with a = 568.9(1) pm, b = 3280.9(7) pm, c = 601.68(2) pm, V = 1389.6(5)Å, and Z = 4 is observed. 相似文献
15.
Dr. Marek Daszkiewicz Mariusz K. Marchewka Iryna Typilo Lubomir D. Gulay Dariya Semenyshyn 《无机化学与普通化学杂志》2011,637(10):1409-1413
The crystal structure of distrontium octacyanotungstate decahydrate, Sr2[W(CN)8] · 10H2O, was solved using X‐ray single crystal diffraction. The tungsten atom lies on a two fold axis. Eight cyanide anions create tetragonal antiprismatic coordination sphere of tungsten atom. The two edge‐sharing tetragonal antiprisms of [Sr(NC)3(OH2)5], create a dimer, [Sr2(CN)6(H2O)6(μ‐H2O)2], which lies on the inversion center. One symmetry independent water molecule is located in a void of 40 Å3. Vibrational (FT‐IR and FT‐Raman spectroscopic) behavior of main structural units is discussed. It was spectroscopically confirmed that the geometry of [W(CN)8]4– anion is slightly distorted from that corresponding to “free” anion. The number of observed bands is significantly lower than that expected for C2 point group. 相似文献
16.
The crystal structure of [Lu(HOCH2COO)2(H2O)4][Lu(HOCH2COO)4] ( 1 ) and Dy2(OCH2COO)2(HOCH2COO)2 · 4H2O ( 2) were determined by X‐ray crystallography. The space group of 1 and 2 are P2/c and P21/c, respectively. In 1 , discrete anions and cations held together by hydrogen bonds form the lattice, while the structure of 2 is a 3‐D network of cross‐linked metal‐ligand chains. The lanthanides are eight‐coordinated by chelating glycolate ligands and water molecules with distorted dodecahedral coordination. The core of 2 is a centrosymmetric dimer complex formed by two dysprosium atoms bridged by two oxygen atoms from deprotonated hydroxyl groups of glycolate ligands. The vibration spectra of the crystals were also measured and compared to each other. 相似文献
17.
利用水热法合成了两种过渡金属配合物为模板剂的含水硼酸盐晶体Co(en)3[B4O5(OH)4]Cl·3H2O(1) 和 [Ni(en)3][B5O6(OH)4]2·2H2O (2),并通过元素分析、X射线单晶衍射、红外光谱及热重分析对其进行了表征。化合物1晶体结构的主要特点是在所有组成Co(en)33+, [B4O5(OH)4]2–, Cl– 和 H2O之间通过O–H…O、O–H…Cl、N–H…Cl和N–H…O四种氢键连接形成网状超分子结构。化合物2晶体结构的特点是[B5O6(OH)4]–阴离子通过O–H…O氢键连接形成沿a方向有较大通道的三维超分子骨架,模板剂[Ni(en)3]2+阳离子和结晶水分子填充在通道中。 相似文献
18.
Several rare‐earth cyclotriphosphate hydrates were obtained from mixtures of sodium cyclotriphosphates and the respective rare‐earth chlorides. Nd(P3O9) · 3H2O [P$\bar{6}$ , Z = 3, a = 677.90(9), c = 608.67(9) pm, R1 = 0.016, wR2 = 0.038, 312 data, 36 parameters] was obtained by a solid state reaction and is isotypic with respective rare‐earth phosphate hydrates, while all the others adopt new structure types. Nd(P3O9) · 4.5H2O [C2/c, Z = 8, a = 1644.6(3), b = 756.11(15), c = 1856.1(4) pm, β = 97.25(3)°, R1 = 0.032, wR2 = 0.081, 1763 data, 194 parameters], Nd(P3O9) · 5H2O [P21/c, Z = 4, a = 773.75(15), b = 1149.1(2), c = 1394.9(3) pm, β = 106.07(3)°, R1 = 0.042, wR2 = 0.082, 1338 data, 194 parameters], Pr(P3O9) · 5H2O [P$\bar{1}$ , Z = 2, a = 745.64(15), b = 889.07(18), c = 934.55(19) pm, α = 79.00(3), β = 80.25(3), γ = 66.48(3), R1 = 0.059, wR2 = 0.089, 1468 data, 193 parameters], Na3Nd(P3O9)2 · 6H2O [P21/n, Z = 4, a = 1059.78(18), b = 1207.25(15), c = 1645.7(4) pm, β = 99.742(17), R1 = 0.047, wR2 = 0.119, 1109 data, 351 parameters] and Na3Pr(P3O9)2 · 6H2O [P21/n, Z = 4, a = 1061.42(16), b = 1209.0(2), c = 1635.5(3) pm, β = 99.841(13), R1 = 0.035, wR2 = 0.062, 1323 data, 350 parameters] were obtained by careful crystallization at room temperature. A thorough structure discussion is given. The infrared spectrum of Nd(P3O9) · 4.5H2O is also reported. 相似文献
19.
Yang Yang Jian Wu Yu Wang Jiang Zhu Ruibin Liu Prof. Dr. Changgong Meng 《无机化学与普通化学杂志》2011,637(1):137-141
A new protonated borophosphate (H3O)Mg(H2O)2[BP2O8]·H2O ( 1 ) was synthesized under mild hydrothermal conditions and characterized by single‐crystal X‐ray diffraction, FTIR spectroscopy and TG‐DTA. The compound crystallizes in the hexagonal system, space group P6(1)22 (No 178), a = 9.4462(7) Å, c = 15.759(2) Å, V = 1217.8(2) Å3, and Z = 6. There exist infinite helical $^1_\infty$ {[BP2O8]3–} ribbons built up from corner‐sharing PO4 and BO4 tetrahedra, which are connected by MgO4(H2O)2 leading to an infinite three‐dimensional open‐framework. The H3O+ ions are located at the free thread of the helical ribbons, whereas crystallized water occupy the channels of the helical ribbons. The dehydration of the compound occurs at a higher temperature which is presumably due to the anisotropic hydrogen bonds in the crystal structure. The luminescent properties of the compound were studied. 相似文献
20.
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