Crystal structure of [Co(NH3)5Cl]2(W10O32)·4H2O

By single crystal X-ray diffraction the crystal structure of the complex salt [Co(NH₃)₅Cl]₂(W₁₀O₃₂)·4H₂O is determined and the IR spectrum is interpreted. The crystal chemical analysis of the structure of complex cations and decatungstate anions and their packing in the structure is performed.     

Crystal structures of [Pd(NH3)3(NO2)][Rh(NH3)2(NO2)4] and [PdEn2][Rh(NH3)(NO2)5]·0.75H2O

The structure of double complex salts [Pd(NH₃)₃(NO₂)][Rh(NH₃)₂(NO₂)₄] and [PdEn₂][Rh(NH₃)(NO₂)₅]·0.75H₂O is determined by single crystal X-ray diffraction. In the structures, the main structural moieties are identified.     

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.     

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.     

[Ru(NH3)6](MoO4)Cl·3H2O and [M(NH3)6](ReO4)3·2H2O (M = Ru, Ir). Synthesis and crystal structure

X-ray crystallographic analysis is used to determine the crystal structures of [Ru(NH₃)₆](MoO₄)Cl·3H₂O and [M(NH₃)₆](ReO₄)₃·2H₂O (M = Ru, Ir) complex salts. The features of the fragment packing are studied.     

Synthesis and crystal structure of [UO2CrO4(C5NH5COO)] · 0.25H2O

[UO₂CrO₄(C₅NH₅COO)] · 0.25H₂O crystals have been synthesized and studied by X-ray diffraction and IR spectroscopy. The compound crystallizes in monoclinic system with the unit cell parameters a = 7.2362(3) ?, b = 13.8847(6) ?, c = 10.7204(5) ?, ?? = 90.037(2)°, space group P2₁/n, Z = 4, R = 0.0236. The structure consists of [UO₂CrO₄(C₅NH₅COO)] chains, which run in the direction [100] and correspond to the AT³B⁰¹ crystallochemical formula, where A = UO ₂ ²⁺ , T³ = CrO ₄ ^2? , and B⁰¹ is nicotinic acid molecules in the form of zwitter ions. The results of analyzing nonbonded interactions in the crystal structure by the method of molecular Voronoi-Dirichlet polyhedra (MMVDP) are presented.     

The crystal and molecular structures of aqua(1,4,7,10,13-pentaazacyclopentadecane)nickel(II) nitrate perchlorate [Ni[15]aneN5·H H2O](NO3)(ClO4) and (1,5,9,13,17-pentaazacycloeicosane)-nikel(II) nitrate hydrate [Ni[20]aneN5](NO3)2·H2O

Summary The structures of Ni^II complexes of the macrocyclic ligands 1,4,7,10,13-pentaazacyclopentadecane, [15]aneN₅ and 1,5,9,13,17-pentaazacycloeicosane, [20]aneN₅ have been determined. [Ni(C₁₀H₂₅N₅)H₂O]-(NO₃)(ClO₄) monoclinic, space group P2₁/n,a=8.265(3)Å,b=6.201(6)Å,c=13.672(4)Å, =93.35(3)°· 2394 unique reflections were used in the structure determination and the refinement proceeded to an R value of 0.045. The ligand is coordinated to the metalvia all five nitrogens in theracemic conformation and a water molecule completes the coordination sphere of the metal ion. The complex cation shows considerable distortion from octahedral geometry which may rationalise the unusual spectroscopic properties and the low enthalpy of formation of the complex cation. [Ni(C₁₅H₃₅N₅)](NO₃)₂·H₂O monoclinic, space group P2₁/n,a=15.437(9)Å,b=9.573(6)Å,c=15.942(8)Å, =109.24(4)°. 2715 unique observed reflections were used in the structure refinement which proceeded to an R value of 0.035. The five nitrogens of the macrocycle are bound to Ni(II) in a distorted square pyramidal coordination geometry. The Ni^II lies 0.35Å above the basal plane of the four nitrogen atoms.     

Crystal structure of a novel complex [Co(3,3′-bpbc)(H2O)3]·H2O

A novel coordination polymer constructed with [Co(3,3′-bpbc)(H₂O)₃]·H₂O(I) (3,3′-bpbc = 2,2′-bipyridine-3,3′-dicarboxylic acid) is successfully synthesized at room temperature and characterized by elemental analysis and IR spectra. The crystal structure of the complex is determined by single crystal X-ray diffraction. The unit cell parameters for complex I are: a = 9.9606(11) Å, b = 9.2552(10) Å, c = 16.0258(17) Å, β = 96.731(0)°, V = 1467.2(3) ų, Z = 4, space group P2(1)/n. In the crystal, the cobalt(II) ion adopts a hexa-coordinate environment, and the structure units aggregate together to give birth to infinite 1D chains. The 2D and 3D framework is constructed via intermolecular hydrogen bonds.     

Synthesis,Crystal Structure and Vibrational Spectroscopy of NH4[Co(NH3)5(H2O)][B4O5(OH)4]2·6H2O

A novel hydrated cobalt tetraborate complex NH₄[Co(NH₃)₅(H₂O)][B₄O₅(OH)₄]₂·6H₂O, was synthesized by the reaction of NH₄‐borate aqueous with CoCl₂ and its structure was determined by single crystal X‐ray diffraction. The crystal system of this complex is orthorhombic, the space group is Pnma, and the unit cell parameters are a=1.2901(2) nm, b=1.6817(3) nm, c=1.1368(2) nm, α=β=γ=90°, V=2.4742(8) nm³, and Z=4. This compound contains infinite borate layers constructed from [B₄O₅(OH)₄]^2? units via hydrogen bonds. The adjacent polyborate anion layers are further linked together with the octahedral [Co(NH₃)₅(H₂O)]³⁺ groups through hydrogen bonds to form 3D framework. The groups and guest water molecules are deposited in the empty space of this framework and interact with the layers by extensive hydrogen bonds. Infrared and Raman spectra (4000–400 cm^?1) of NH₄[Co(NH₃)₅(H₂O)][B₄O₅(OH)₄]₂·6H₂O were recorded at room temperature and analyzed. Fundamental vibrational modes were identified and band assignments were made. The middle band observed at 575 cm^?1 in Raman spectrum is the pulse vibration of [B₄O₅(OH)₄]^2?.     

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...     

Syntheses,crystal structures and antibacterial activities of [Cu2(C11H11NO5S)2(H2O)4] · 5H2O and [Ni2(C11H11NO5S)2(H2O)4] · 2H2O

The binuclear complexes [Cu₂L₂(H₂O)₄] · 5H₂O (1) and [Ni₂L₂(H₂O)₄] · 2H₂O (2) (where L = C₁₁H₁₁NO₅S, H ₂ L = 2-[(3-formyl-5-methyl-2-hydroxy-benzylidene)-amino]ethanesulfonic acid) have been synthesized and characterized by IR, elemental analysis and X-ray diffraction. The crystals belong to the monoclinic system, space group P2₁/c. Complex 1: a = 16.8902(12), b = 11.2829(6), c = 17.4249(11) Å; β = 106.709(4)°; S = 1.131; V = 3180.5(3) ų; Z = 4; D _Calcd = 1.729 g cm^?3; F(000) = 1712; μ = 1.554 mm^?1; R ₁ = 0.0519, wR ₂ = 0.1349; complex 2: a = 11.399(2), b = 19.985(3), c = 7.3694(10) Å; β = 108.664(7)°; S = 1.157; V = 1590.6(4) ų; Z = 2; D _Calcd = 1.604 g cm^?3; F(000) = 800; μ = 1.388 mm^?1; R ₁ = 0.1859, wR ₂ = 0.4346. The geometry around each metal(II) center can be described as slightly distorted octahedral. Water-sulfonic clusters and (H₂O)₄ water clusters can be observed for 1 from the crystal packing diagram, while cavity and offset face-to-face π–π stacking can be observed for 2. The complexes have been tested for the antibacterial activities which show antibacterial activities of 1 for β-hemolytic streptococcus, Staphylococcus aureus and Escherichia coli, and the antibacterial activity of 2 only for β-hemolytic streptococcus.     

Crystal structure and thermal properties of [Pt(NH3)5Cl][ReCl6]Cl·H2O

The crystal structure of double complex salt [Pt(NH₃)₅Cl][ReCl₆]Cl·H₂O is determined. Crystallographic characteristics are: a = 23.9502(4) Å, b = 7.5963(1) Å, c = 8.9016(2) Å, V = 1619.49(5) ų, space group Pnma, Z = 4, d _x = 3.150 g/cm³. The packing of structural fragments is studied. It is shown that on heating the salt in a helium atmosphere up to 840 °C a mixture of two solid solutions of fcc Pt_0.90Re_0.10 and hcp Pt_0.25Re_0.75 forms.     

XPS study of the electronic structure of heterometallic complexes [Fe2MO(O2CCH3)6(H2O)3] · 3H2O (M = Co,Ni)

Heterometallic compounds of general formula [Fe ₂ ^III M^IIO(O₂CR)₆(H₂O)₃] · 3H₂O (R = CH₃, M = Co, Ni; R = CCl₃, M = Co, Ni) have been studied by XPS. The compounds have been identified as high-spin complexes with metal atoms in oxidation states M(II) and M(III). Analysis of the XPS data revealed the tendency of the XPS pattern and magnetic parameters of molecules to change with a change in the electronic nature of metal atoms. The assignment is based on the degree of covalence of the M-O bond. In chloro-substituted heterocomplexes, electron density delocalization on the metal atoms with metal-to-ligand charge transfer through three bonds (M-O-C-C) is observed. The substitution in terminal groups leads to the change in the electron density distribution between the carboxylate and terminal groups.     

[Co(Phen)2(H2O)2](HL)NO3·3H2O的合成及晶体结构

在水溶液中,以邻菲咯啉、丁二酸与硝酸钴为原料合成了一个新的超分子化合物[Co(Phen)2(H2O)2].(HL).(NO3).3H2O,并经元素分析、IR、X射线单晶衍射分析进行了结构表征.结构分析表明,晶体属三斜晶系,P1-空间群,a=0.968 0(2)nm,b=1.370(3)nm,c=1.394 9(3)nm,α=61.714(3)°,β=71.495(4)°,γ=79.575(4)°,V=1.543 7 nm3,Z=2,ρ=1.481 g/cm3,C28H31CoN5O12,Mr=688.51,F(000)=714 andμ=0.627 mm-1,7 754个独立衍射点中,5 428个可观察点满足I≥2σ(I),R1=0.074 5,wR2=0.210 7.晶体中[Co(Phen)2(H2O)2]2+通过π-π相互作用堆积成二维层状结构,层间通过氢键作用构成三维超分子.     

Crystal structure and single crystal EPR of (NH4)2(15-crown-5)3[Cu(mnt)2] and (NH4)2(benzo-15-crown-5)4[Cu(mnt)2]·0.5H2O

The X-ray crystal structures of (NH4)2(15-crown-5)3[Cu(mnt)2] (1) and (NH4)2(benzo-15-crown-5)4- [Cu(mnt)2]·0.5H2O (2) were determined. Two single crystals are composed of distinct structures of ammonium-crown ether supramolecular cation and [Cu(mnt)2]2- anion. The triple-decker dication in complex 1 and a sandwich dimmer in complex 2 were observed. X-Band EPR studies on the single crystals of both complex 1 and complex 2 have been carried out at room temperature, which revealed that complex 2 showed a perfect hyperfine structure of Cu whereas that of complex 1 could not be observed. The principal values and direction cosines of the principal axes of the g and A tensors were computed by a least-squares fitting procedure. The spin density of Cu(Ⅱ) was estimated according to the principal values of the A tensors and compared well with the results calculated based on DFT method.     

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.     

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).     

Crystal,molecular, and electronic structure of carboxylate [Fe3O(CH3COO)6(H2O)3]NO3·4H2O

Results of X-ray structural analysis, IR spectroscopy, and quantum chemical study of the [Fe₃O(CH₃COO)₆(H₂O)₃]NO₃·4H₂O complex are reported. The crystal belongs to the monoclinic system with a=15.688(3), b=11.767(2), c=15.318(4) Å, γ=92.54(3)^o, space group P2₁/a, R=0.078. The molecule has a trinuclear structure: three iron atoms occupy the vertices of an equilateral, triangle with an Fe−Fe distance of 3.29 Å and are bonded by the μ₃-oxo and μ-CH₃COO⁻ (O,O′) ligands. To each iron atom, one water molecule is coordinated. Using the obtained values of populations on 3d AO of Fe (d _xy ^1.34 ; d _xz ^1.39 ; d _yz ^1.46 ; ; ) and charges on oxygen atoms (O _c ^−0.5 ; O _ac ^−0.31 ; O _w ^−0.31 ), we estimated the values of isomeric shift and quadrupole splitting (0.75 and 0.70 mm/sec, respectively; these are close to the experimental values of 0.75 and 0.58 mm/sec, (300 K)). Institute of Chemistry, Moldovian Academy of Sciences. Moldovian State University. Institute of Applied Physics, Moldovian Academy of Sciences. Translated fromZhurnal Strukturnoi Khimii., Vol. 35, No. 2, pp. 112–120, March–April, 1994. Translated by T. Yudanova     

THE CRYSTAL AND MOLECULAR STRUCTURES OF TWO DERIVATIVES OF WERNER'S HEXOL CLUSTER CATION: [Co{(OH)2Co(NH3)4}3](NO3)5 (OH) · 4H2O(I) AND [Co{(OH)2Co(NH3)4}3](NO3)6 · 2H2O(II)

Abstract

Crystals of compound (I) and (II) are black in reflected light and brown‐ black in transmitted light. The ¹H-nmr of the cations of (I), recorded in D⁶-DMSO, show peaks, relative to the ¹H of D⁶-DMSO, at + 0.46 ppm(rel. int. = 3); + 0.85 ppm(rel. int. = 1.2); + 1.80 ppm (rel. int. = 3); and ?4.18 ppm(rel. int. = 1). The magnetic susceptibility of (I) is C′_m (293.18 K) = 588.45×10^?6 c.g.s. units, which corresponds to a m _eff = 0.295 B.M. per Co ion; however, the small shifts and sharp ¹H-nmr lines in the DMSO spectrum preclude the presence of paramagnetic clusters. Cyclic voltametry of the cation present in (I) shows highly distorted, irreversible, oxidation and reduction waves which indicate the lack of stability of any oxidized or reduced form ‐ a fact which accords with the sharp lines of the NMR spectra; e.g., no stable paramagnetic species are present in (I).

Compound (I), M.W. = 941.24, crystallizes in P2₁/n (No. 14), with cell constants a = 11.789(2), b = 13.855(2), c = 21.534(3) Å, β = 91.94(1)° V = 3515.44 Å ³, d (meas; z = 4) = 1.778 gm-cm^?3. A total of 4705 data were collected in the range 4° ≤ 2θ ≤ 50°. They were corrected for absorption (μ = 19.562 cm^?1; rel. trans. coeff. range = 0.8642 to 0.9997); of these, 2623 were unique and had l ≥ 3σ(l). The structure was solved by direct methods, none of the hydrogens of the amine ligands were found experimentally at sensible positions; thus, they were left out. Refinement of the heavy atoms (anisotropic) led to final residuals of R(F) = 0.0637 and 0.0771.

Compound (II), M.W. = 950.20, crystallizes in space group P1 (bar; No. 2), with cell constants a = 12.858(3), b = 12.475(2), c = 12.114(2) Å, α = 96.63(1), β = 91.94(1) and γ = 61.71(2)° V = 1615.68 Å ³, d(meas; z = 2) = 1.953 gm-cm^?3. A total of 5657 data were collected in the range 4° ≤ 2θ ≤ 50°. They were corrected for absorption (μ = 21.301 cm^?1; rel. trans. coeff. range = 0.7372 to 0.9998); of these, 4456 were unique and had l ≥ 3σ (l). The structure was solved by direct methods, the majority of the hydrogens of the amine ligands were found experimentally at sensible positions, the rest were calculated at idealized positions (N═H = 0.95 Å). The hydrogens of the OH ligands were located experimentally in a final difference Fourier map. Refinement of the heavy atoms (anisotropic) with fixed hydrogens (B = 5.00 A? ²) led to final residuals of R(F) = 0.0348 and 0.0440.

Precisely as visualized by Werner, the hexol cations consist of a central Co(III) cation surrounded by three {Co(NH₃)₄(OH)₂]¹⁺ ligands. IN (I), the O═Col═O angles are acute (av. value = 82.97°), as expected from the electrostatic repulsion of the Co(III) central cation and the monopositive ligands surrounding it. Consequently, the Co… Co distances the long (2.896, 2.888 and 2.889 A?) and the the av. Co═O═Co angles are 97.43°. The remaining portions of the cation and anions are as expected from standard values; i.e., Co═O═1.90–1.95 and Co═N = 1.95–2.00 A?. In (II), the Col═O═Co angles are also obtuse (av. value = 97.87°), as expected from the electrostatic repulsion of the Co(III) central cation, and the Co… Co distances are equally long (2.881, 2.876 and 2.874 A?; on average, 2.877 A?).