共查询到20条相似文献,搜索用时 46 毫秒
1.
Cs5[Na{W4N10}] was prepared from a mixture of NaNH2, CsNH2 and tungsten powder (molar ration 1 : 10 : 4) at 700°C in autoclaves. After the reaction is finished the nitride is embedded in an alkali metal matrix. Dark red crystals were isolated by washing out the alkali metal with liquid ammonia at room temperature. The structure of Cs5[Na{W4N10}] was solved by X-ray single crystal data: I41 (No. 80), Z = 4, a = 13.926(3) Å, c = 8.723(3) Å, Z(F) ≥ 3σ(F) = 1535, Z(Variables) = 63, R/Rw = 0.040/0.052. The compound is highly sensitive against moisture giving oxotungstates and ammonia. It contains a framework of tetrahedra [WNN3/21.5?]. Sodium shares four terminal nitrogen ligands. Including sodium a distorted, β-cristobalite type arrangement [Na{W4N10}5?] results. It contains caesium in all interstices formed by twelve nitrogen ligands in so-called Friauf polyhedra. 相似文献
2.
Tetraammine Lithium Cations Stabilizing Phenylsubstituted Zintl-Anions: The Compound [Li(NH3)4]2[Sn2Ph4] Ruby-red, brittle single crystals of [Li(NH3)4]2[Sn2Ph4] were synthesized by the reaction of diphenyltin dichloride and metallic lithium in liquid ammonia at ?35°C. The structure was determined from X-ray singlecrystal diffractometer data: Space group, P1 , Z = 1, a = 9.462(2) Å, b = 9.727(2) Å, c = 11.232(2) Å, α = 66.22(3)°, β = 85.78(3)°, γ = 61.83(3)°, R1 (F ? 4σF) = 5.13%, wR2 (F02 ? 4σF) = 10.5%, N(F ? 4σF) = 779, N(Var.) = 163. The compound contains to Sb2Ph4 isosteric centres [Sn2Ph4]2? as anions which are connected to rods by lithium cations in distorted tetrahedral coordination by ammonia. These rods are arranged parallel to one another in the b,c-plane, but stacked along [100]. 相似文献
3.
Cs4[Sc6C]Cl13 and Cs4[Pr6(C2)]I13 — Two Examples for the Missing Link in the Connectivity of [M6Z]X X Building Units Cs4[Sc6C]Cl13 (tetragonal, I41/amd, a = 1 540.5(4), c = 1 017.9(7) pm, c/a = 0.661, Z = 4, R = 0.038, Rw = 0.026) and Cs4[Pr6(C2)]I13 (a = 1 804.9(3), c = 1 259.5(3) pm, c/a = 0.698, R = 0.106, Rw = 0.068) are obtained as green-black and blue-black single crystals with brass-like metallic lustre through metallothermic reduction of ScCl3 and PrI3, respectively, with cesium in the presence of carbon in sealed tantalum containers. The, overall, isotypic compounds contain isolated [Sc6C] and [Pr6(C2)] clusters, respectively, that are surrounded by 18 halide (X) ligands (12 Xi and 6 Xa; X = Cl or I). The connection is carried out via the motif [M6Z]XXXX (M = Sc and Pr; Z = C and C2, respectively) and is thereby the missing link of the motifs of connection for the composition Ax[M6Z]X13. Analogous interconnection of [TiO6] octahedra is found in the anatase-type of structure of TiO2. 相似文献
4.
Synthesis and Crystal Structure of Na10[P4(NH)6N4](NH2)6(NH3)0.5 with an Adamantane-like Anion [P4(NH)6N4]4? Crystals of Na10[P4(NH)6N4](NH2)6(NH3)0.5 were obtained by the reaction of P3N5 with NaNH2 (molar ratio 1:20) within 5 d at 600°C in autoclaves. The following data characterize X-ray investigations: Fm3 m, Z = 8, a = 15.423(2) Å, Z(F) = 261 with F ≥ 3 σ(F) Z(Variables) = 27, R/Rw = 0.086/0.089 The compound contains the hitherto unknown anion [P4(NH)6N4]4?, which resembles adamantane. The total structure can be described as follows: The centers of gravity of units of [Na8(NH2)6(NH3)]2+ – 8Na+ on the corners of a cube, 6NH2? on the ones of an inscribed octahedron with NH3 in the center – follow the motif of a cubic-closest packed arrangement. Units of [Na12(NH2)6]6+ – 12Na+ on the corners of a cuboctahedron and 6NH2? on the ones of an inscribed octahedron – occupy all octahedral and those of [P4(NH)6N4]4? all tetrahedral sites. 相似文献
5.
The crystal structure of the title compound has been determined from three dimensional x-ray data obtained by the multiple film method. The space group is P2l/n and the cell dimensions are: a = 14.90, b = 16.84, c = 8.38 Å; β = 93.5° Z = 4. The structure is formed by discrete Co (en) and Fe(CN) ions, both of which have an octahedral configuration. The Fe(CN) ions are approximately octahedrally surrounded by the Co (en) ions while arrangement of Fe (CN) ions around the Co(en) ions completely differs from an octahedron. The mean Fe? C and Co? C dustances are 1.91 and 2.01 Å, respectively. The water molecules do not play an important role in the structure and all distances between oxygen and other atoms indicate the presence of very weak hydrogen bonds. The salts M (en)3 Q(CN)6 · H2O, where M = Co and Cr and Q = Cr, Mn, Fe and Co, are all isomorphous. 相似文献
6.
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
7.
The structure of (S4N3)2SbCI5 has been determined by X-ray methods using least-squares′ refinement. The compound crystallises monoclinic; C–P21/c, a = 9.24 Å, b = 17.77 Å, c = 11.29 Å, β = 110.06°, Z = 4. The antimony atom has a fivefold coordination the geometry being derived from a deformed octahedron, the S4N-rings retained their planar shape. 相似文献
8.
Synthesis, Crystal Structures, and Vibrational Spectra of [OsBr(acac)(PPh3)] and [OsBr(acac)(AsPh3)] By reaction of tetrabromoacetylacetonatoosmate(IV) with PPh3 or AsPh3 in ethanol the complexes [OsBr(acac)(PPh3)] ( 1 ) and [OsBr(acac)(AsPh3)] ( 2 ) are formed, which are purified by chromatography on silica gel. X-ray structure determinations of single crystals of ( 1 ) (monoclinic, space group P 21/n, a = 13.035(2), b = 18.2640(14), c = 16.636(3) Å, β = 112.776(14)°, Z = 4) and ( 2 ) (monoclinic, space group P 21/c, a = 13.23(5), b = 18.35(2), c = 16.65(2) Å, β = 112.9(5)°, Z = 4) result in mean bond distances Os–P = 2.413, Os–As = 2.483, Os–Br = 2.488 and Os–O = 2.037 Å. The vibrational spectra (10 K) exhibit the inner ligand vibrations of the acac, PPh3 and AsPh3 groups with nearly constant frequencies and the stretching vibrations of OsP at 499–522, of OsAs at 330–339, of OsBr at 213–214 and of OsO in the range 460–694 cm–1. 相似文献
9.
Synthesis and Structure Determination of Two Salts of the Trimetaphosphimic Acid, K3(PO2NH)3 and Rb3(PO2NH)3 The reaction between P3N5 and the corresponding alkalimetal hydroxide monohydrate under ammonothermal conditions (6 kbar, 450 °C after 10 d) in autoclaves leads to the salts of the trimetaphosphimic acid K3(PO2NH)3 resp. Rb3(PO2NH)3. The structure of K3(PO2NH)3 was solved by single crystals X-ray methods. The isotypic structure of Rb3(PO2NH)3 was solved by X-ray powder diffraction methods. K3(PO2NH)3: R3 (No. 148), a = 12.615(3) Å, c = 10.224(2) Å, Z = 6, R1/wR2 = 0.0276/0.0726, N(F > 2σ(F)) = 769, N(Var.) = 51.Rb3(PO2NH)3: R3 (No. 148), a = 12.9971(5) Å, c = 10.5485(5), Z = 6, RBragg(F) = 0.0626, 289 reflections. K3(PO2NH)3 and Rb3(PO2NH)3 contain six-membered rings P3N3 substituted by oxygen which are connected to double molecules by N–H … O bridge bonds. These twinmolecules are stacked in columns which form the motive of close packed rods. K+ resp. Rb+ are between these columns. They are coordinated by 6 O which belong to 5 different rings. 相似文献
10.
Synthesis and Structure of the First Ternary Lead(II) Copper(I) Oxide: PbCu2O2 PbCu2O2 can be prepared by solid state reaction or by precipitation from a basic aqueous solution. Single crystals of the new compound were prepared by recrystallisation from a molten mixture (PbO? Cu2O) and investigated by X-ray diffractometer technique. PbCu2O2 crystallizes isotypically with the homologue silver compound PbAg2O2 (monoclinic with a = 8.223 Å, b = 8.289 Å, c = 6.015 Å, β = 132.62°, Z = 4, space group C? C 1 2/c 1). The crystallographic data from the X-ray investigation are reported. The structure is built by endless [PbO4/4]- and [CuO2/4]-chains. Pb2+ has a one-sided asymmetric coordination with four next oxygen neighbours and Cu+ forms a stretched dumbbell with two oxygen atoms. 相似文献
11.
K3Au5Pb: Layers of [AuAu3/2] Gold Tetrahedra and [Pb2/2] Lead Chains Silver coloured, brittle single crystals of K3Au5Pb were synthesized by reaction of potassium azide with gold sponge and lead powder at T = 920 K. The structure of the compound (space group Imma, Z = 4, a = 5.646(1) Å, b = 19.500(4) Å, c = 8.412(1) Å) was determined from X-ray single-crystal diffractometry data. The gold lead partial structure consists of layers of [AuAu3/2] tetrahedra and [Pb2/2] zigzag chains with four-bonded lead atoms which are connected to a framework structure via Au–Pb contacts. The potassium atoms occupy channels within the gold lead partial structure. 相似文献
12.
Lithium Triamidostannate(II), Li[Sn(NH2)3] – Synthesis and Crystal Structure Rusty-red glistening, transparent crystals of Li[Sn(NH2)3] were obtained by reaction of metallic lithium with tetraphenyl tin in liquid ammonia at 110 °C. The structure was determined from X-ray single-crystal diffractometer data: Space group P 21/n, Z = 4, a = 8.0419(9) Å, b = 7.1718(8) Å, c = 8.5085(7) Å, β = 90.763(8)°, R1 (F o ≥ 4σ(F o)) = 2.8%, wR2 (F ≥ 2σ(F )) = 5.3%, N(F ≥ 2σ(F )) = 1932, N(Var.) = 65. The crystal structure contains trigonal pyramidal complex anions [Sn(NH2)3]– with tin at the apex, which are connected to layers of sequence A B A B … by lithium in tetrahedra-double units [Li(NH2)2/2(NH2)2]2. 相似文献
13.
On the Knowledge of Oxocobaltates(II). Na4[CoO3], the First Nesocobaltate(II) Newly prepared transparent, blood red single crystals of Na4[CoO3] (Na2O/?CoO’? Na:Co = 4.4:1, cobalt tube, 550°C, 20d, dry argon), crystallize triclinically, P1, a = 8.144, b = 6.220, c = 5.758 Å; α = 117.5, β = 89.9, γ = 111.2 (diffractometer data), Z = 2. There are carbonate-like, isolated [CoO3] groups, respectively parameters and distances see text. 2358 symmetry independent reflections (automatical four cycle diffractometer PW 1100, Mo–Kα, graphite monochromator, 4° ? Θ ? 36°), R = 0.0597. The Madelung Part of the Lattice Energy, MAPLE, Effective Coordination Numbers, ECoN and Mean Fictive Ionic Radii, MEFIR are calculated and discussed. 相似文献
14.
Gold-rich Aurides with Caesium: Cs1.34Rb0.66RbAu7 and Cs1.60Rb0.40RbAu7 Cs1,60Rb0,40RbAu7, Raumgruppe Cmmm, Z = 2, a = 5,677(1) Å, b = 13,273(3) Å, c = 7,288(1) Å, R1/wR2 = 0,0392/0,0892, Z(F) ≥ 2σ(F) = 700 and Z(Var.) = 23. Silver coloured, brittle single crystals of Cs1.34Rb0.66RbAu7 and Cs1.60Rb0.40RbAu7 were obtained by the reaction of CsN3, RbN3 and gold sponge at 903 K. The structures were determined from X-ray single-crystal diffractometry data: Cs1.34Rb0.66RbAu7, space group Cmmm, Z = 2, a = 5.657(1) Å, b = 13.265(4) Å, c = 7.281(2) Å, R1/wR2 = 0.0373/0,0628, N(F) ≥ 2σ(F) = 818 and N(var.) = 23. 相似文献
15.
Halogen Exchange at Re3-Clusters: A New Synthetic Route to Binary and Ternary Rhenium(III) Bromides. Crystal Structures of Cs2[Re3Br11] and Cs3[Re3Br3Cl9] The substitution of “inner” ligands in transition metal clusters in aqueous HX solutions is hitherto unknown. For the first time the substitution of bridging and terminal chloride for bromide ions was observed at rhenium clusters, [Re3(μ-Cli,b)3(Cl)(Cli,t)(3?x)(H2Oi,t)x](3?x)? (x = 0–3), via the reaction of “ReCl3 · 2 H2O” in hot hydrobromic acid solution under an inert gas atmosphere. This establishes a new synthetic route to ternary Re(III) bromides as well as to ReBr3. However, ternary Re(IV) bromides, A2ReBr6 (A = Rb, Cs), are dominating in the presence of oxygen, rhenium(III) bromides are only by-products. Dark brown rods of Cs2[Re3Br11] are obtained from argon saturated, hot hydrobromic acid solutions of “ReCl3 · 2 H2O” and CsBr. The crystal structure (orthorhombic, Pnma (Nr. 62); a = 955.51(5); b = 1 610.29(10); c = 1 372.70(9); Z = 4; Vm = 318.0(2) cm3mol?1; R = 0.084, Rw = 0.058) consists of defect clusters [Re3BrBrBr□i,t]2? in which one in plane, terminal position is not occupied. The substitution of “inner” ligands has been observed in the case of chloride for bromide only, the Bri,b and Ii,b ligands in ReBr3 and ReI3, respectively, are not substituted in hydrochloric acid even at temperatures as high as 100°C. Bordeaux red square pyramids of CsReBrCl3 = Cs3[Re3(μ-Bri,b)3ClCl] are obtained from hot hydrochloric acid solutions of ReBr3 · 2/3 H2O upon evaporation. CsReBrCl3 (orthorhombic, C2cm (Nr. 40); a = 1 419.0(1); b = 1 419.2(1); c = 1 080.30(8) pm; Z = 4; Vm = 327.6(3) cm3mol?1; R = 0.033, Rw = 0.028) is isostructural to the corresponding chloride CsReCl4. 相似文献
16.
Synthesis and Crystal Structure of Sodium Tetraoxo Nitrido Tungstate(VI), Na5WO4N Colourless crystals of Na5WO4N are obtained besides Na4WO2N2 [1] by the reaction of WO3 with NaNH2 (15:1) at 350°C ≥ T ≥ 750°C in autoclaves to prevent early decomposition of sodium amide. X-ray single crystal investigations are characterized by the following data:
- Na5WO4N: Cmc21 (No. 36), Z = 4
- a = 9.873(2) Å, b = 5.769(1) Å, c = 10.648(2) Å
- Z(F)≥ 3σ(F) = 2182, Z(Var.) = 55, R/Rw = 0.029/0.039
17.
The Crystal Chemistry of Copper Rare-Earth Oxotungstates: (I): triclinic-α-CuTbW2O8, (II): monoclinic-CuInW2O8 and (III): monoclinic-CuYW2O8 Single crystals of (I), (II) and (III) were prepared by recrystallisation in closed systems and examined by X-ray technique. (I): space group C? P1 , a = 7.3080, b = 7.8945, c = 7.1476 Å, α = 115.23, β = 116.21, γ = 56.98°, Z = 2; (II): space group C? C2/c, a = 9.6576, b = 11.6496, c = 4.9863 Å, β = 91.17°, Z = 4; (III): space group C? P2/n, a = 10.0504, b = 5.8214, c = 5.0224 Å, β = 94.23°, Z = 2. The crystal structures are discussed with respect to calculations of the coulombterms of lattice energy and possible valence states of Cu2+ and Mo5+. 相似文献
18.
Synthesis and Crystal Structure of Manganese(II) and Zinc Amides, Mn(NH2)2 and Zn(NH2)2 Metal powders of manganese resp. zinc react with supercritical ammonia in autoclaves in the presence of a mineralizer Na2Mn(NH2)4 resp. Na2Zn(NH2)4_.0.5NH3 to well crystallized ruby‐red Mn(NH2)2 (p(NH3) = 100 bar, T = 130°C, 10 d) resp. colourless Zn(NH2)2 (p(NH3) = 3.8 kbar, T = 250°C, 60 d). The structures including all H‐positions were solved by x‐ray single crystal data: Mn(NH2)2: I41/acd, Z = 32, a = 10.185(6) Å, c = 20.349(7) Å, N(Fo) with F > 3σ (F) = 313, N(parameter) = 45, R/Rw = 0.038/0.043. Zn(NH2)2: I41/acd, Z = 32, a = 9.973(3) Å, c = 19.644(5) Å, N(Fo) with F > 3σ (F) = 489, N(parameter) = 45, R/Rw = 0.038/0.043. Both compounds crystallize isotypic with Mg(NH2)2 [1] resp. Be(NH2)2 [2]. Nitrogen of the amide ions is distorted cubic close packed. One quarter of tetrahedral voids is occupied by Mn2+‐ resp. Zn2+‐ions in such an ordered way that units M4(NH2)6(NH2)4/2 occur. The H‐atoms of the anions have such an orientation that the distance to neighboured cations is optimum. 相似文献
19.
Synthesis and Structure of an Ammonium Diamidodioxophosphate(V), NH4PO2(NH2)2 The ammonolysis of P3N5 under ammonothermal conditions (T = 400°C, p(NH3) = 6 kbar, 14 d in autoclaves) in the presence of small definite amounts of water leads to the formation of NH4PO2(NH2)2. The structure was solved by single crystal X-ray methods. NH4PO2(NH2)2: P21/c (Nr. 14), a = 6.886(1) Å, b = 8.366(2) Å, c = 9.151(2) Å, β = 111.78(3)°, Z = 4, R1/wR2 = 0.026/0.072, Z(F > 2σ(F)) = 1183, N(variables) = 87. In NH4PO2(NH2)2 the anions [PO2(NH2)2]? are linked to chains by N? H …? N and N? H …? O bridge bonds. The ammonium ions are located between these chains and are donors for N? H …? O bridge bonds which connect the chains three-dimensionally. 相似文献
20.
K2NaGaP2, Cs2NaGaP2, K2NaGaAs2, K2NaInP2 and K2NaInAs2, Compounds with the Polyanions [MX4/2]3? (M?Ga, In; X?P, As) isosteric with SiS2 The title compounds are synthesized from stoichiometric mixtures of the elements or from Na, KP(KAs), Cs4P6 and MX (M?Ga, In; X?P, As) at 950K. They are isotypic and crystallize in the space group Ibam (No. 72) with Z=4. The anionic partial structure is characterized by infinite chains [MX4/2]3? which are isosteric to SiS2. Vibrational spectra are measured and interpreted based on the symmetry D4h-P(2/m 2/c)42/m of the isolated polymer chain [MX2]3?. A good agreement between observed and calculated frequencies is obtained by using a force field of the tetrameric fragment [M4X10]18? (three four-membered M2X2 rings). 相似文献