Distortion isomers of PtM, Pt2M, PtM2 and PtMM′ (M = non-transition metals) derivatives-structural aspects

2018 ◽  
Vol 0 (0) ◽  
Author(s):  
Milan Melník ◽  
Peter Mikuš
Keyword(s):  
Transition Metals ◽  
Structural Parameters ◽  
Bond Angles ◽  
Bond Lengths ◽  
Metal Atoms ◽  
Independent Molecules ◽  
Structural Aspects

Abstract An analysis of the structural parameters of PtM, Pt2M, PtM2 and PtMM′ (M = non-transition metals) derivatives shows that each complex contains two crystallographically independent molecules within the same crystal. The respective molecules differ by the degrees of distortion and exemplify the distortion isomerism. These are discussed in terms of the coordination with the platinum and the M atoms and the correlations are drawn among the metal atoms, donor atoms, bond lengths and bond angles. A wide variety of non-transition metals (Sn, Ga, In, Tl, Zn, Cd, Hg, Sb) exist, among which the most prevalent is Sn.

Structural aspects of heterotrinuclear Pt2M, PtM2, and PtMM′ complexes – distortion isomers

2018 ◽  
Vol 38 (4) ◽  
pp. 151-162 ◽  
Author(s):  
Milan Melnik ◽  
Peter Mikus ◽  
Andrea Forgacsova ◽  
Maria Bodnar Mikulova
Keyword(s):  
Structural Parameters ◽  
Bond Angles ◽  
Metal Atoms ◽  
Metal Metal ◽  
Coordination Spheres ◽  
Independent Molecules ◽  
Structural Aspects ◽  
Metal Ligand ◽  
Ligand Bond

AbstractIn this review, the structural parameters of 18 heterotrinuclear Pt2M (M=Hg, Zn, Cd, Au, Mn, Ag, Pd), PtM2 (M=Al, Ga, Sb, In, Mo, Fe), PtFeMn, PtHgMn, and PtFeOs types are summarized and analyzed. The Pt atoms are four-, five-, and even six-coordinated, among which the four-coordinated ones are the most common. The M atoms are found to be two- (Hg), three- (Hg), four- (Hg, Sb, In, Ag, Au), and six- (Ga, In, Al, Mo, Mn, Fe, Pd) coordinated and even sandwiched (FeC10). There is a wide variety of donor atoms (ligands) (O+NL, N+CL, NL, CO, CN, CL, Cl, SL, PL, I), which build up the respective inner coordination spheres about the metal atoms. The 17 complexes contain two crystallographically independent molecules within the same crystal, and 1 complex contains four such molecules. In each complex, the respective molecules are differing mostly by the degree of distortion in metal-metal and metal-ligand bond distances and ligand-metal-ligand bond angles, and are examples of distortion isomerism.

Synthesis and Crystal Structures of Three Carboxylate- Bridged Tetranuclear Copper(II) - Lanthanide(III) Complexes of Ph3P+CH2CH2CO2−

1999 ◽  
Vol 52 (10) ◽  
pp. 983 ◽  
Author(s):  
Yang-Yi Yang ◽  
Seik Weng Ng ◽  
Xiao-Ming Chen
Keyword(s):  
Oxygen Atom ◽  
Crystal Structures ◽  
Triclinic Space Group ◽  
Coordination Environment ◽  
Space Group ◽  
Bond Angles ◽  
Bond Lengths ◽  
Metal Atoms ◽  
Apical Site

Three tetranuclear copper(II)–lanthanide(III) complexes of triphenylphosphoniopropionate (Ph3P+CH2CH2CO2−,tppp), namely [Cu2Ln2(tppp)8(H2O)8](ClO4)10·2H 2 O [Ln = EuIII, NdIII or CeIII], were synthesized and characterized by crystallography. The EuIII complex crystallizes in the triclinic space group P1 – with a 16.249(7), b 17.185(11), c 17.807(11) Å, α 69.750(10), β 89.230(10), γ 84.070(10)˚, V 4639(5) Å3, Z 1. In the crystal structures, four tppp ligands bridge a pair of CuII and tetraaquo-EuIII atoms (Cu···Eu 3.527(2) Å) through their µ2-carboxylato ends to form a dinuclear subunit; two of these subunits are additionally linked by one of the CuII -bonded carboxylato oxygen ends, across a centre of inversion, to furnish a dimeric tetranuclear [Cu(tppp)4 Eu(H2O)4]2 species (Cu···Cu 3.323(2) Å). This CuII -bonded oxygen atom occupies the apical site of the square-pyramidal coordination environment of the CuII atom. The EuIII atom is eight-coordinated in a square-antiprismatic geometry. The NdIII and CeIII complexes are isomorphous to the EuIII complex, and only minor differences in bond lengths and bond angles involving the metal atoms are noted.

scholarly journals DFT STUDIES OF STRUCTURAL PARAMETERS, VIBRATIONAL FREQUENCIES AND NMR SPECTRA OF 3-(1H-BENZO[D]IMIDAZOL-1-YL)-N'-(TOSYLOXY)PROPANIMIDAMIDE

2021 ◽  
pp. 15-25
Author(s):  
E.M. Yergaliyeva ◽  
◽  
L.A. Kayukova ◽  
A.V. Vologzhanina ◽  
G.P. Baitursynova ◽  
...  
Keyword(s):  
Nmr Spectra ◽  
Chemical Shifts ◽  
Structural Parameters ◽  
Correlation Coefficients ◽  
Biological Properties ◽  
Vibrational Frequencies ◽  
Substitution Product ◽  
Bond Angles ◽  
Bond Lengths ◽  
B3lyp Level

Amidoxime derivatives have practically valuable biological properties. We have previously obtained new spiropyrazolinium compounds by arylsulfo-chlorination of β-aminopropioamidoximes, but in case of β-(benzimidazol-1-yl)pro-pioamidoxime we have obtained O-substitution product – 3-(1H-benzo[d]imidazol-1-yl)-N'-(tosyloxy)pro-panimidamide. The aim of the work is predicting of structural parameters (bond lengths, bond angles), vibrational frequencies and NMR spectra of 3-(1H-benzo-[d]imidazol-1-yl)-N'-(tosyloxy)propanimidamide. The calculations were performed using Gaussian 09 package. Structural parameters and vibrational frequencies was calculated using DFT (B3LYP/B3PW91/WB97XD)/6-31G(d,p). 1H and 13C NMR was predicted using DFT B3LYP/6-31G(d,p)-GIAO in DMSO. All calculated values are in good agreement with experimental data. The calculated bond lengths and bond angles were compared with results of X-ray structural analysis. The best correlation coefficient was 0.981 (calcu-lations with B3LYP level). For bond angles, the best result was obtained with B3LYP level (0.990). For vibrational frequencies correlation coefficients between the calculated and experimental values were 0.997 (B3LYP), 0.996 (B3PW91) and 0.995 (WB97XD). The most accurate method was used for predic-ting NMR spectrum. The correlation coefficients between the experimental and calculated 1H and 13C chemical shifts were 0.949 and 0.999 respectively.

scholarly journals Crystallographic and structural characterization of heterometallic platinum complexes Part V. Heteropentanuclear complexes

2014 ◽  
Vol 12 (3) ◽  
pp. 283-306 ◽  
Author(s):  
Milan Melník ◽  
Peter Mikuš ◽  
Clive Holloway
Keyword(s):  
Structural Characterization ◽  
Structural Parameters ◽  
Bond Distance ◽  
Platinum Complexes ◽  
Trigonal Bipyramidal ◽  
Metal Atoms ◽  
Independent Molecules

AbstractThis review classifies and analyzes over eighty heteropentanuclear Pt complexes. There are eight types of metal combinations: Pt4M, Pt3M2, Pt2M3, PtM4, Pt3MM′, Pt2M2M′, PtM2M′2 and PtM3M′. The five metal atoms are in a wide variety of arrangements: trigonal-bipyramidal (most common), square-pyramidal, spike-triangular, butterfly, cubane, linear and one unique. Platinum bonds to a variety of triad partner metal atoms, soft, through borderline to hard. The shortest Pt-M bond distances for non-transition and transition M are 2.406(4) Å (M = Ge) and 2.30(1) Å (M = Co). The shortest Pt-Pt bond distance is 2.580(1) Å. Several relationships between the structural parameters were found and are discussed. Several complexes exist in two isomeric forms and others contain two crystallographically independent molecules. Both the isomers as well as independent molecules are examples of distortion isomerism.

Structural aspects of heterooligonuclear platinum clusters – distortion isomers

2019 ◽  
Vol 39 (1) ◽  
pp. 1-12
Author(s):  
Milan Melník ◽  
Peter Mikuš ◽  
Mária Bodnár Mikulová
Keyword(s):  
Metal Bond ◽  
Metal Atoms ◽  
Metal Metal ◽  
Platinum Clusters ◽  
Coordination Spheres ◽  
Independent Molecules ◽  
Structural Aspects

AbstractThis review covers 15 clusters of the compositions Pt3Re2, Pt2Os3, Pt3AgAu, Pt3Ir3, Pt2M4 (M=Ag or Pd), PtM5 [M=Ru (×2) or Os], Pt3Os4, Pt6Au2, Pt2Ru6, Pt3Ru6, Pt2Ru8, and PtAu9. Each of the cluster contains two crystallographically independent molecules that differ mostly by degree of distortion and are classical examples of distortion isomerism. Their structures are very complex. The inner coordination spheres about the metal atoms (Pt and M) are very complex as well. The clusters are rich in metal-metal bond distances with the shortest being 2.573 Å (Pt-Au), 2.615 (Pt-Pt), and 2.673 Å (Ru-Ru).

scholarly journals Crystallographic and structural characterization of heterometallic platinum clusters Part VIII. Heteronona- and heterodecanuclear clusters

2014 ◽  
Vol 13 (1) ◽  
Author(s):  
Milan Melník ◽  
Peter Mikuš ◽  
Clive E. Holloway
Keyword(s):  
Structural Characterization ◽  
Structural Parameters ◽  
Platinum Atom ◽  
Metal Bond ◽  
Metal Atoms ◽  
Metal Metal ◽  
Platinum Clusters ◽  
Metal Composition ◽  
Independent Molecules

AbstractThis review classifies and analyses fifty heteronona- and heterodecanuclear Pt clusters of metal composition: Pt4Ru5, Pt3Ru6, Pt20sr PtRh8, PtAu8; Pt6M4, Pt5M5, Pt4M6, Pt3M2, Pt2M8, PtM9, Pt3Ru6M and PtAu8M. There are nine different heterometals: M = Ru, Au, Ag, Cu, Hg, Os, Rh, Ir and Fe, of which Ru and Au are the most frequent. The clusters crystallize mostly into two crystal classes, monoclinic (74%) and triclinic (18%), and their structures are complex. Three triangular layers of nine metal atoms arranged in the form of a face-shared bioctahedron are common in the series of heterononanuclear clusters. In the series of heterodecanuclear clusters distorted skeletal icosahedrons, where a central platinum atom is surrounded by nine metal atoms, and face (edge) shared (fused) bioctahedral cluster of the metal atoms are the most common. The most frequent ligands are CO and PPh3. The shortest metal-metal bond distances are: 2.540(4) Å (Pt-Fe), 2.580(2) Å (Ru-Ru), 2.584 Å (Pt-Pt) and 2.629(4) Å (Cu-Au). Several relationships between the structural parameters were found and are discussed. Some clusters contain two crystallographically independent molecules within the same crystal and are examples of distortion isomerism.

Structural aspects of heterotetranuclear platinum clusters-distortion isomers

2018 ◽  
Vol 38 (2) ◽  
pp. 77-86 ◽  
Author(s):  
Milan Melník ◽  
Peter Mikuš
Keyword(s):  
Membered Ring ◽  
Metal Atoms ◽  
Platinum Clusters ◽  
Independent Molecules ◽  
Structural Aspects

AbstractThis review includes 16 examples of distortion isomers of heterotetranuclear platinum clusters. The clusters are of the compositions: Pt3Sn, Pt2M2 (M=Au, Ag, W, Mo), and PtM3 (M=Os, Ru, Re). The four metal atoms are found in a distorted tetrahedral core (most common), planar-rhombohedral, spiked-triangular, and eight-membered ring skeleton. There are three pairs (Pt2W2, Pt2Au2, and Pt2Ag2) of clusters and all remainder clusters contain two crystallographically independent molecules within the same crystal. All are classical examples of distortion isomerism. Their structures are analyzed and discussed.

scholarly journals Crystalographic and structural characterization of heterometallic platinum compounds. Part III: heterotrinuclear compounds

2013 ◽  
Vol 11 (6) ◽  
pp. 827-900 ◽  
Author(s):  
Milan Melník ◽  
Peter Mikuš ◽  
Clive Holloway
Keyword(s):  
Structural Characterization ◽  
Structural Parameters ◽  
Bond Distance ◽  
Platinum Complexes ◽  
Review Article ◽  
Platinum Compounds ◽  
Metal Atoms ◽  
Wide Variability ◽  
Independent Molecules

AbstractThis review article includes over three hundred and sixty heterotrinuclear platinum complexes of the composition Pt2M (205 examples), PtM2 (132 examples) and PtMM (24 examples). The heterometals include the non-transition and transition metals. Three metal atoms form a wide variability of frameworks: M3 triangular, dicapped M3 triangular, V shaped M3, M3 linear, five-, six- and seven- metallocycles and unique structures of which triangular and linear are the most common. This has led to a rich chemistry of platinum not only from variability of metals, but also from their framework and stereochemistry. The shortest Pt-M (non-transition) and Pt-M (transition) bonds are 2.315(1) Å for Pt-Ga and 2.4896(9) Å for Pt-Co. The shortest Pt-Pt bond distance is 2.581(1) Å. Two complexes exist in two isomeric forms and several others contain crystallographically independent molecules. All are typical examples of distortion isomerism. Correlations between structural parameters, heterometal and ligand donor atoms are developed and discussed.

The Molecular Structure of 1,3,5,7- Tetra(tert-butyl)-2,4,6,8-tetra(chloro)- borazocine [1]

2009 ◽  
Vol 64 (9) ◽  
pp. 1090-1092 ◽  
Author(s):  
Heinrich Nöth
Keyword(s):  
Molecular Structure ◽  
Standard Deviation ◽  
Unit Cell ◽  
Monoclinic System ◽  
Space Group ◽  
Bond Angles ◽  
Bond Lengths ◽  
Twofold Axis ◽  
Crystallographic Symmetry ◽  
Independent Molecules

The borazocine (ClB=NCMe3)4 crystallizes in the monoclinic system, space group C2/c with Z = 6, i. e. there are two independent molecules in the unit cell. The first molecule has no crystallographic symmetry, while the second molecule is characterized by a twofold axis which generates the (ClB= NCMe3)4 molecule from the fragment (ClB=NCMe3)2. The molecules are tub-shaped showing alternating longer and shorter B-N bonds. Compared with the borazocine (N3B= NCM3)4 the BN bonds of (ClB=NCMe3)4 are on average shorter than those of the azide derivative. Although B-N bond lengths and N-B-N and B-N-B bond angles in both molecules of (ClB=NCMe3)4 are identical within the limits of the standard deviation, the opposite B2N2 planes differ significantly for the two independent molecules.

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