Binuclear metal(II) complexes of 1,3-diphenyltriazene : The crystal and molecular structures of the nickel(II), palladium(II) and copper(II) derivatives

1975 ◽  
Vol 28 (11) ◽  
pp. 2377 ◽  
Author(s):  
M Corbett ◽  
BF Hoskins ◽  
NJ McLeod ◽  
BP O'Day
Keyword(s):  
Least Squares Method ◽  
Fourier Method ◽  
Molecular Structures ◽  
Cell Parameters ◽  
Crystal And Molecular Structures ◽  
Metal Atoms ◽  
Metal Metal ◽  
Structure Determinations ◽  
Metal Derivatives ◽  
Binuclear Metal

The crystal and molecular structures have been determined, by single-crystal X-ray methods, for each of the isomorphous set of divalent binuclear metal derivatives of 1,3-diphenyltriazene, abbreviated as dptH, [M(dpt)2]2 where M = Ni, Pd, and Cu. The crystals are composed of discrete molecular units, of composition M2(dpt)4, which have a syn-syn structure analogous to that of copper(II) acetate monohydrate with pairs of closely separated metal atoms held together by the terminal nitrogen atoms of four ligand groups in such a way that the environment of each metal atom is almost square-planar. The interatomic distances between the pairs of metal atoms, 2.395(3), 2563(1), and 2.441(2) Ǻ for the Ni, Pd, and Cu compounds, are strongly suggestive of metal-metal bonding. The two N4-planes are almost parallel but the two sets of coordinating nitrogen atoms are twisted markedly from the eclipsed configuration, the average angle of rotation being about 15°. Crystals of each complex are triclinic with space group P 1. The unit cell parameters in the order of a, b, c, α, β, and γ are 10.335(3), 15.84(1), 13.546(3)& 100.48(5), 94.47(2), 102.57(3)° for Ni2(dpt)4; 10.486(1), 15.791(2), 13.751(1)Ǻ, 99.48(1), 93.61(1), 104.37(1)° for Pd2(dpt)4; 10.373(3), 15.916(5), 13.612(3) Ǻ, 99.51(2), 94.85(3), 102.33(2)° for Cu2(dpt)4. The structure of the nickel complex was solved by the Patterson-Fourier method and the atomic parameters found for this structure were used as the basis of the structure determinations of the isomorphous copper and palladium compounds. All three structures were refined by a block-diagonal least-squares method using 3300 (photographic data) 4065 (counter) and 2753 (counter) independent non-zero terms for the nickel(II), palladium(II) and copper(II) compounds respectively, converging with R values 0.13 (isotropic), 0.056 (anisotropic) and 0.069 (isotropic) respectively.

Metal derivatives of thiosemicarbazones: crystal and molecular structures of mono- and di-nuclear copper(I) complexes with N1-substituted thiosemicarbazones

2009 ◽  
Vol 62 (11) ◽  
pp. 1754-1765 ◽  
Author(s):  
Tarlok S. Lobana ◽  
Poonam Kumari ◽  
Alfonso Castineiras ◽  
Ray J. Butcher
Keyword(s):  
Molecular Structures ◽  
Crystal And Molecular Structures ◽  
Metal Derivatives ◽  
Derivatives Of

Isoelectronic molecules with triple bonds to metal atoms (M = Mo, W): crystal and molecular structures of tri-tert-butoxytungsten ethylidyne and nitride

1983 ◽  
Vol 22 (20) ◽  
pp. 2903-2906 ◽  
Author(s):  
Malcolm H. Chisholm ◽  
David M. Hoffman ◽  
John C. Huffman
Keyword(s):  
Molecular Structures ◽  
Triple Bonds ◽  
Crystal And Molecular Structures ◽  
Metal Atoms ◽  
Isoelectronic Molecules

Arsenic(III), Antimony (III) and Bismuth(III) Thiobenzoates: Crystal and Molecular Structures of M(SOCR)3 and PhSb(SOCPh)2

1998 ◽  
Vol 53 (12) ◽  
pp. 1475-1482 ◽  
Author(s):  
Prit Singh ◽  
Sudha Singh ◽  
Vishnu D. Gupta ◽  
Heinrich Nöth
Keyword(s):  
Crystal Structure ◽  
Molecular Structures ◽  
X Ray ◽  
Crystal And Molecular Structures ◽  
Covalently Bonded ◽  
Bismuth Complex ◽  
Group 15 ◽  
Structure Determinations ◽  
Trigonal Pyramid ◽  
Trigonal Prisms

Abstract Tris-thiobenzoates, Arsenic, Antimony, Bismuth Tris-thiobenzoates of arsenic, antimony and bismuth, M(SOCR)3 have been obtained from their oxides and characterized. In the X-ray crystal structure determinations of these, the group 15 atom and the three covalently bonded sulfur atoms are found to constitute a trigonal pyramid, the central atoms lie at a C3 axis. In the bismuth complex the thiobenzoate ligand tends to chelate. However, three comparatively short intermolecular M···S interactions are significant features for these molecules resulting in stacking of trigonal prisms providing an essentially six coordinate environment around arsenic and antimony and a nine-coordinate one for bismuth. The structure of PhSb(SOCPh)2 can be considered

Crystal and Molecular Structures of Some Alkynyl - Group 9/Group 11 Complexes [M2m4(C2R)8(PPh3)2] (M = Rh, Ir; m = Cu, Ag; R = Ph, Fc (Ir/Cu only))

2003 ◽  
Vol 56 (5) ◽  
pp. 509 ◽  
Author(s):  
Michael I. Bruce ◽  
Natasha N. Zaitseva ◽  
Brian W. Skelton ◽  
Neil Somers ◽  
Allan H. White
Keyword(s):  
Molecular Structures ◽  
Major Contributor ◽  
Crystal And Molecular Structures ◽  
Metal Atoms ◽  
Bonding Mode

The crystal and molecular structures of five complexes [M2m4(C≡ CR)8(PPh3)2] (M = Rh, Ir; m = Cu, Ag; R = Ph, Fc (Ir/Cu only)) are described. Each consists of an approximately octahedral arrangement of the six metal atoms, with atoms M occupying opposite apical positions and atoms m forming an approximate plane. Four alkynyl groups are σ-bonded to each M. Two of these, one from each M, also interact by an asymmetric π-bonding mode with each atom m. Each M is also coordinated to one PPh3 ligand. The M–m distances range between 2.7698(9) and 3.2050(9) Å, although average values fall within the tight ranges 2.86(8) and 2.90(5) (m = Cu) or 3.06(5), 3.09(9) Å (m = Ag). Formally non-bonding M ··· M distances range between 4.1511(8) and 4.654(1) Å, while the shorter m ··· m separations range between 2.659(1) and 2.918(2) Å, which suggests that only weak intermetallic bonding exists. Both the geometries of these complexes and their intense colours suggest that the M2m4 cluster formulation is a major contributor to the structure, rather than a more simplistic, formally zwitterionic assemblage of two [M(C≡ CR)4(PPh3)]2− centres held together by the four m+ cations.

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