Structural study of complex [Rh(NH3)5(NO2)](NO3)2·H2O, [Rh(NH3)5(NO2)][Pd(NO2)4], and K2[Rh(NH3)(NO2)5]·H2O salts

Compounds [Rh(NH₃)₅(NO₂)](NO₃)₂·H₂O (I) with a = 7.6230(3) Å, b = 7.6230(3) Å, c = 10.3584(4) Å, space group I-42m, Z = 2, d _calc = 2.026 g/cm³, V = 601.93(4) ų, Rh-NH_{3 eq} = 2.074 Å, Rh-NH_{3 ax} (NO₂) = 2.048 Å; [Rh(NH₃)₅(NO₂)][Pd(NO₂)₄] (II) with a = 8.095(3) Å, b = 22.422(8) Å, c = 7.887(3) Å, β = 98.559(17)°, space group Cc, Z = 4, d _calc = 2.461 g/cm³, V = 1415.6(9) ų, Rh-NH_{3 eq} = 2.069 Å, Rh-NH_{3 ax} = 2.090 Å, Rh-NO₂ = 2.002 Å; K₂[Rh(NH₃)(NO₂)₅]·H₂O (III) with a = 7.5177(5) Å, b = 20.9856(15) Å, c = 7.7017(5) Å, space group Cmc2₁, Z = 4, d _calc = 2.439 g/cm³, V = 1215.05(14) ų, Rh-NH_{3 ax} (NO₂) = 2.094 Å, Rh-NO_{2 eq} = 2.030 Å are synthesized and studied using single crystal X-ray diffraction.     

COMPLEX SALTS [Pd(NH3)4][Pd(NH3)3NO2] [CrOx3]·H2O AND [Pd(NH3)4][Pd(NH3)3NO2] [CoOx3]·H2O AND SOLID SOLUTIONS [Pd(NH3)4] [Pd(NH3)3NO2][CoOx3]x[RhOx3]1–x·H2O : PROMISING PRECURSORS FOR POROUS NANOALLOYS

Journal of Structural Chemistry - New complex salts [Pd(NH3)4][Pd(NH3)3NO2][CrOx3]·H2O I, [Pd(NH3)4][Pd(NH3)3NO2][CoOx3]·H2O II, and a series of solid solutions...     

Comparative study of crystal structures of [M(NH3)5NO2]XY and [M(NH3)5ONO]XY. Crystal structure of [Co(NH3)5NO2](NO3)2·0.25H2O

The crystal structure of [Co(NH₃)₅NO₂](NO₃)₂·0.25H₂O has been determined. Co₁N₈O_8.25H_15.5, a=7.582(3), c=10.331(3) Å, V=593.9(5) ų, d_calc=1.782 g/cm³ for Z=2, space group I 4mm (C _4v ⁹ , No. 107). The structure is of the island type. Complex (distorted octahedral) cations are bonded to the NO ₃ ^? anions by electrostatic forces. Crystallization water is located in the vicinity of the labile NO₂ group.     

为什么[Co(NH3)5Cl]2+与[Co(NH3)6]3+的颜色不同?

结合对［Ｃｏ（ＮＨ３）５Ｃｌ］＾２）与［Ｃｏ（ＮＨ３）６］＾３＋的颜色的比较，阐述配体场理论中有关电子组态、能级、轨道、配体场谱项及谱项间跃迁等基本概念及难点。即使不做严格的量子化学计算，从直观的物理模型、简单的分子轨道理论、群论方法及有关谱图中也能获得有用信息。     

Binary Complexes [M(NH3)5Cl][PdCl4] · H2O (M = Rh, Co): Crystal Structure of [Rh(NH3)5Cl][PdCl4] · H2O

Monohydrates of chloropentammine rhodium(III) and chloropentammine cobalt(III) tetracloropalladates(II) were synthesized. Single crystals of [Rh(NH₃)₅Cl][PdCl₄] · H₂O were obtained and studied by Xray diffraction. The crystallographic data are as follows: a = 7.8730(16) Å, b = 10.905(2) Å, c = 16.038(3) Å, = 102.70(3)°, V = 1343.3(5) ų, space group P2₁/c, Z = 4, d_calc = 2.422 g/cm³. The structure consists of alternating layers of [Rh(NH₃)₅Cl]²⁺ complex cations and [PdCl₄]^2- complex anions. Each anion layer contains two crystallographically independent Pd atoms, and the square coordination environment of one of these atoms is converted to a bipyramide. The structure of the compound [Co(NH₃)₅Cl][PdCl₄] · H₂O is determined and its unitcell parameters are refined: a = 7.813(3) , b = 10.896(4) , c = 15.966(5) , = 102.85(4)°, V = 1325.2(8) ³, and d_calc = 2.148 g/cm³. The synthesis temperature is shown to have an effect on the content of hydrated and anhydrous complexes in the mixture formed during precipitation of these binary salts from aqueous solutions.     

Crystal structure of Lebedinskii’s trisulfitotriammine Na3[Rh(SO3)3(NH3)3]·6H2O

A single crystal X-ray diffraction study of Na₃[Rh(SO₃)₃(NH₃)₃]·6H₂O was carried out (X8 APEX BRUKER automated diffractometer, MoK _α radiation, graphite monochromator); crystal data are a = 10.1844(1) Å, c = 64.0815(13) Å, V = 5756.17(14) ų, space group R $\bar 3$ c, Z = 12. The general motif of the structure was analyzed in terms of the mutual spatial arrangement of the [(NH₃)₃Rh(SO₃)₃-Na-(SO₃)₃Rh(NH₃)₃]^5? fragments, where the Na⁺ cation is surrounded by six oxygen atoms belonging to six SO₃ groups. This cation resides on the inversion center, all Na-O distances are identical, 2.347 Å. The selected fragments follow the nodes of a rhombohedral sublattice (a _c = 12.19 Å, α_c = 49.38°) formed by the intersection of three symmetry-related families of planes (1 0 2).     

关于[Co(NH3)5NO2]Cl2键合异构体相互转化的研究

[Co(NH_3)_5NO_2]Cl_2是最早发现和首先分离得到的第一个键合异构体。长期被认为只有氧配位的[Co(NH_3)_5ONO]Cl_2异构体会向氮配位的[Co(NH_3)_5NO_2]Cl_2异构体转化。本文认为氮配位的异构体也会向氧配位的异构体转化,并测定和报导了这种转化的速率常数。     

Trimercurated acetaldehyde. The crystal structures of 2[OHg3CCHO]NO3 · HNO3 and [HOHg2(NO3Hg)CCHO]NO3

Three new compounds 2[OHg₃CCHO]NO₃ · HNO₃ (A), [HOHg₂(NO₃Hg)CCHO]NO₃ (B) and (NO₃Hg)₃CCHO (C), have been successively obtained by mercuration of acetaldehyde with mercuric nitrate containing increasing concentrations of nitric acid. All of them contain trimercurated acetaldehyde. The orthorhombic crystals of A built up of parallel infinite networks of the polymeric trimercurated oxonium [OHg₃CCHO]_nⁿ⁺ cation, while the monoclinic crystals of B contain polymeric dimercurated oxonium [HoHg₂(NO₃Hg)CCHO]_nⁿ⁺¹ cation in the form of an infinite helical chain. The structures were determined by X-ray diffraction and refined by full-matrix least-squares to the R value of 0.050 for A and 0.063 for B. The Hg-C and Hg-O distances are in the ranges 2.04 to 2.11 Å and 2.11 to 2.18 Å, respectively. The crystals of C were not suitable for X-ray structure analysis.     

Structure of [NH3(CH2)4NH3]2P4O12·2H2O

After a short survey of what is the present state of the cyclophosphates associated with the organic molecule NH₂(CH₂)₄NH₂, we report chemical preparation and crystal structure for a new example of such compounds. [NH₃(CH₂)₄NH₃]₂P₄O₁₂.2H₂O is monoclinic (S.G. : P2₁/n), with Z = 2 and the following unit-cell parameters : a = 7.6728(8) Å, b = 18.962(3) Å, c = 7.9789(9) Å β = 111.751(9)°. Bidimensional layer arrangement of P₄O₁₂ rings connected to the water molecules thanks to weak H-bonds run parallel to the ab plane. The organic groupements located between these inorganic planes perform the three-dimensional cohesion by NH····O hydrogen bonds.     

顺-[Pt(NH3)2Cl2]与核苷的作用

用分光光度法研究了37℃、pH=5.5、0.1M NaClO₄介质中cis[Pt(NH₃)₂Cl₂]和DNA组成物--鸟嘌呤核苷、腺嘌呤核苷、胞嘧啶核苷及胸腺嘧啶核苷的作用。发现顺-[Pt^Ⅱ(NH₃)₂]与前三种核苷能生成组成为1:1、1:2二种络合物,与胸腺嘧啶核苷不作用。所测得一级和二级表观生成常数,以及作用初速分别有如下大小次序:Guo>Ado>Cyt》Thy;Guo>Ado>Cyt》Thy.在所得结果基础上讨论了顺-[Pt(NH₃)₂Cl₂]和癌细胞中DNA作用的可能方式。     

[NH4][(CH3)2NH2]2[Ta(C2O4)4]·2H2O: the first (oxalato)tantalate(V) complex structurally characterized

Abstract  The compound [NH₄][(CH₃)₂NH₂]₂[Ta(C₂O₄)₄]·2H₂O has been synthesized and characterized by elemental and TG/DTA analyses, IR spectroscopy and by the single-crystal X-ray diffraction study. The structure comprises the [Ta(C₂O₄)₄]³⁻ anion, NH₄ ⁺ and [(CH₃)₂NH₂]⁺ cations and crystallization water molecules. The Ta atom is octacoordinated by oxygen atoms from four bidentate oxalate groups forming a coordination polyhedron close to the triangular dodecahedron. The charge-assisted hydrogen bonds from both cations connect the [Ta(C₂O₄)₄]³⁻ anions into a three-dimensional framework. Graphical Abstract  The synthesis and properties of [NH₄][(CH₃)₂NH₂]₂[Ta(C₂O₄)₄]·2H₂O, the first structurally characterized compound with the tetra(oxalato)tantalate(V) anion, is reported.      

Synthesis and Structure of [Pd(NH3)4][cis-Pd(NH3)2(SO3)2][Pd(NH3)3(SO3)] · H2O

A new palladium compound [Pd(NH₃)₄][cis-Pd(NH₃)₂(SO₃)₂][Pd(NH₃)₃(SO₃)] · H₂O (I) was synthesized and its structure was studied by X-ray powder diffraction method. In the course of the synthesis, the initial trans-diamminesulfite anionic complex is transformed into the cis-configuration. Further heating in aqueous solution results in isomerization of a substance into a neutral complex [Pd(NH₃)₃(SO₃)]. Crystals I are triclinic: a = 10.3297(2) Å, b = 14.1062(3) Å, c = 6.8531(1) Å, = 101.36(0)°, = 92.74(0)°, = 92.71(0)°, space group P1¯. Structure I consists of the columns with alternating cis-[Pd(NH₃)₂(SO₃)₂]^2– and [Pd(NH₃)₃(SO₃)] complexes and [Pd(NH₃)₄]²⁺ ions between the columns.     

Lanthanide nitrate complexes of diphenylmethylphosphine oxide: synthesis and spectroscopic studies. Crystal structures of [La(Ph2MePO)3(NO3)3], [La(Ph2MePO)4(NO3)3]·xMe2CO and [Yb(Ph2MePO)4(NO3)2]PF6

The reaction of Ln(NO₃)₃·6H₂O (Ln=lanthanide except Pm) with Ph₂MePO in a 1:3 or 1:4 ratio in acetone or ethanol produces [Ln(Ph₂MePO)₃(NO₃)₃] which have been characterised by analysis, IR, ¹H and ³¹P{¹H} NMR spectroscopy and conductance measurements. The [Ln′(Ph₂MePO)₃(NO₃)₃] (Ln′=Pr–Tb) exist only as tris complexes in solution and are unaffected by the presence of excess Ph₂MePO. In contrast the [Ln″(Ph₂MePO)₃(NO₃)₃] (Ln″=Ho–Lu) partially decompose in CH₂Cl₂ solution into [Ln″(Ph₂MePO)₄(NO₃)₂]⁺, and [Ln″(Ph₂MePO)₄(NO₃)₂]PF₆ are readily isolated from Ln″(NO₃)₃, Ph₂MePO and NH₄PF₆ in acetone. For lanthanum only, a neutral 1:4 complex [La(Ph₂MePO)₄(NO₃)₃] was isolated. X-ray crystal structures show that [La(Ph₂MePO)₃(NO₃)₃] contains nine-coordinate La, whilst [La(Ph₂MePO)₄(NO₃)₃]·xMe₂CO contains a ten-coordinate metal centre. The structure of [Yb(Ph₂MePO)₄(NO₃)₂]PF₆ reveals an eight-coordinate cation and all complexes contain bidentate nitrato-groups.     

Influence of the outer-sphere cation nature on the crystal structures of salts with a cis-[Rh(NH3)2(NO2)4]− anion

Complex rhodium(III) salts of the composition cis-M[Rh(NH₃)₂(NO₂)₄]·nH₂O, where M = K⁺, Cs⁺, Ag⁺, (CH₃)₄N⁺, are synthesized and described. Their molecular and crystal structures are determined by single crystal X-ray diffraction.     

银氨溶液中的溶质是[Ag(NH3)2]OH吗

先从理论上证明了教材中所给的配制方法配制出来的银氨溶液中的溶质不是[Ag(NH3)2]OH而是[Ag(NH3)2]NO3,然后又利用对照实验对这一结论进行了实验验证。     

Synthesis and characterisation of [tris(1,3-dithiole-2-thione-4,5-dithiolato)-stannate]2−, [Q]2[Sn(dmit)3], [tris(1,3-dithiole-2-one-4,5-dithiolato)stannate]2−, [Q]2[Sn(dmio)3] and [tris(1,3-dithiole-2-thione-4,5-selenolato)stannate]2−, [Q]2[Sn(dsit)3], complexes: Analysis of the structural variations of the [Sn(dmit)3]2− and [Sn(dmio)3]2− dianions

[Tris(1,3-dithiole-2-thione-4,5-dithiolato)stannate]²⁻, [Q]₂[Sn(C₃S₅)₃], [tris(1,3-dithiole-2-one-4,5-dithiolato)stannate]²⁻, [Q]₂[Sn(C₃S₄O)₃], and [tris(1,3-dithiole-2-thione-4,5-diselenolato)stannate]²⁻ [Q]₂[Sn(C₃S₃Se₂)₃], complexes, have been synthesised and characterised. Crystal structure determinations of [Q]₂[Sn(C₃S₅)₃] (Q=1,4-dimethylpyridinium, monoclinic and orthorhombic forms; NMe₄, NEt₄, and PPh₄) and [NEt₄]₂[Sn(C₃S₄O)₃] revealed variations in the overall dianion structures. The geometry about tin in each case is essentially octahedral with the chelate bite angles in the range 80.7(5)–87.45(4)°: the range of Sn–S distances is 2.5207(18)–2.571(17) Å. A statistical analysis, carried out on the crystal structure data for the six complexes, indicated that the most critical factors in controlling the overall shape of the dianion were the distances of the Sn atom from the dithiolate ligand planes [Sn–OOP]. Interanionic S⋯S interactions, within the sum of the van der Waals’ radii for two S atoms, are affected by the size of the cation, Q; the secondary connectivity is 3-dimensional for the smallest cations, Q=1,4-dimethylpyridinium and NMe₄, in chains for the somewhat larger cation, NEt₄ and is absent for the still larger, PPh₄ cation.     

Organically templated zinc selenites: MIL-86 or [H2N(CH2)2NH2]2·Zn4(SeO3)4 and MIL-87 or [H3N(CH2)3NH3]4·Zn4(SeO3)8

Two new organically templated zinc selenites MIL-86 or [H₂N(CH₂)₂NH₂]₂·Zn₄(SeO₃)₄ and MIL-87 or [H₃N(CH₂)₃NH₃]₄·Zn₄(SeO₃)₈ have been prepared by the reaction of ZnO with SeO₂ under hydrothermal conditions in the presence of organic amines. Crystal data: MIL-86, monoclinic, space group P2₁/n, a=6.7712(4) Å, b=9.4520(5) Å, c=8.0295(4) Å, β=113.601(1)°, V=470.91(4) ų; MIL-87, orthorhombic, space group Pbcm, a=8.8311(3) Å, b=7.8391(2) Å, c=16.2992(4) Å, V=1128.36(6) ų. MIL-86 combines the structural features of templated networks and coordination polymers. Its structure is built up from ZnO₃N tetrahedra and SeO₃ pseudo-pyramids as the polyhedral building units. The ZnN bond corresponds to a direct link between zinc and the ethylenediamine template. In the other hand, MIL-87 is built up from chains of vertex-linked ZnO₄ and SeO₃ building units crosslinked by 1,3-diammonium propane cations. These structures are understood by comparison with the already known organically templated zinc phosphites.     

Synthesis and Characterization of [NH3（CH2）2NH2（CH2）2NH3]BiCl6

1 INTRODUCTION During the past decade, a series of organic-inor- ganic hybrid compounds based on metal halide units have been prepared and studied[1]. The combination of organic and inorganic components at the mole- cular level affords us the opportunity to design new hybrid materials and modulate the properties of components[2]. As a result, some interesting proper- ties, such as non-linear optical[3], interesting magne- tic[4], efficient luminescence[2], ideal thermal and mechanical sta…     

Octahedral cluster Mo complexes (Bz3NH)3[Mo6OCl13] and (Bz3NH)2[Mo6Cl14] · 2CH3CN: Synthesis, crystal structure and properties

The salts (Bz₃NH)₃[Mo₆OCl₁₃] (I) and (Bz₃NH)₂[Mo₆Cl1₄] · 2CH3CN (II) were obtained by reacting melted tribenzylamine with cluster Mo compounds. Compound II contains a known cluster anionic complex [Mo₆Cl₁₄]^2?. Compound I includes novel cluster anionic complex [Mo₆OCl₁₃]^3?, where one internal Cl atom is replaced by the O atom. Complex II exhibits phosphorescence in a long-wavelength region of visible spectrum.