The crystal and molecular structure of bis(2,4-dithiobiureto)nickel(II) diperchlorate–ethanol, Ni(HDTB)₂(ClO₄)₂.EtOH

Abstract

DERIVED BY R1, Rz, AND R, REFINEMENTS atomic site is only partially occupied, but the partial occupancy is not recognized, and refinement is carried out in the usual way in both RI and R2 with unit weights in each case. The temperature parameters found were too large to be reasonable for the halogen atom in question, and larger for R2 than for RI. As pointed out by another referee, this suggests that deliberately carrying out two refinements with different weighting schemes might reveal the presence of significant but unsuspected defects in the model or systematic errors in the measurements.I am indebted to Professor R. A. Young and Dr W. C. Hamilton for helpful discussions during the Kyoto Congress, and to Professor H. E. Daniels for the calculations of (n 1/2) for small n. l am grateful to Professor Sukeaki Hosoya for the invitation to work at the Institute for Solid State Physics, and to the Royal Society for a travel and subsistence grant. In the press. SHOEMAKER, D. P. (1968). Acta Cryst. A24, 136-142. SUDARSANAN, K., W1LSON, A. J. C. & YOUNG, R. A. (1972).Acta Cryst. A28, S151. Acta Cryst. (1973). B29, 1490The Crystal and Molecular Structure of Bis-(2,4-dithiobiureto)nickel(II) Diperchlorate-Ethanol, Ni(HDTB)2(CIO4)z. EtOH BY ANNA P1GNEDOLI, GIORGIO PEYRONEL AND LUCIANO ANTOLINIIstituto di Chimica Generale e Inorganica, University of Modena, 41100 Modena, Italy (Received 22 January 1973 ; accepted 20 February 1973) The crystal structure was determined by Patterson and Fourier methods and refined by least-squares calculations using counter data (1363 reflexions), with anisotropic temperature factors for non-hydrogen atoms and positional parameters for hydrogen atoms, to a final R = 0.075. The crystals are monoclinic, space group P2Jc, a = 4.990 (6), b = 20.026 ( 11 ), c = 19-713 (9) A, fl = 93-70 (5) °, Z = 4. The structure consists of four equivalent layers per unit cell, parallel to the xz plane, each containing the four constituents Ni(HDTB)2.2CIO4. EtOH of the asymmetric and stoichiometric unit. The nickel atom is planar-coordinated to four sulphur atoms. In the cationic complex Ni(HDTB)Z, + the interatomic distances and angles are very similar to those of the neutral complex Ni(DTB)2, except that the S-C and C-N bond distances are respectively shorter and longer, and the bond angles S-C-N (terminal) and N(terminai)-C-N(central) are respectively higher and lower than in the neutral complex. Average bond distances: Ni-S = 2.162, S-C = 1.645, C-N(central)= 1.38, C-N(terminal)= 1.37 A. The perchlorate ions (average Cl-O = 1.40 A) and the ethanol molecule (C-C= 1.53, C-O = 1-41 A) are linked to each other and to the complex molecules by several intermolecular hydrogen bonds. Each central NH group of the complex is linked to an oxygen atom of the perchlorate ions by the shortest observed hydrogen bonds (O.--H distances = 1.86 and 1.88 A). Another eleven intermolecular hydrogen bonds have O.• • H distances of 2.09-2.48 A, and seven intramolecular hydrogen bonds have N.• • H distances of 2.23-2.51 A. Introd...

Biomimetic polyorganosiloxanes: model compounds for new materials

“…The metal is itself square planar with Ni-S distances [Ni-S(1) 2.1466(9), Ni-S(2) 2.1671( 9) Å] consistent with those in the two other nickel dithiobiurets reported previously [2.150-2.168 Å]. 38,39 The two biuret ligands are not coplanar but form a flattened chair conformation about the metal. The pattern of hydrogen bonds between biuret and thymine shows two strong NH⋯O and a weaker NH⋯N interaction, 32 as has been observed by others in the complex between dithiobiuret and uracil, 38 despite the general preference for thymine to form just two hydrogen bond interactions with its partner.…”

The crystal and molecular structure of tetraethylammonium bis(2,3-quinoxalinedithiolato)nickelate(II) dihydrate, [(C2H5)4N]2[C6H4N2C2S2]2NiII.2H2O

“…The Ni-S distances (2.17 A) agree well with those observed for the neutral Ni(DTB)2 complex (2-17 A) (Pignedoli, Peyronel & Antolini, 1972) and for the Ni(HDTB)~ ÷ cation (average 2.16 .~) (Pignedoli, Peyronel & Antolini, 1973). The inter-chelate S-S distances (3.01 ,~) are well within the range postulated by Steifel, Dori & Gray (1967) as indicative of some residual S-S inter-chelate bonding.…”

“…In previous work we determined the crystal structures of some nickel(II) complexes with thio-amidic ligands: the neutral complex Ni(II)bis-(N,N'-di-n-propyldithiocarbamate), Ni-(DPDTC)2 (Peyronel & Pignedoli, 1967) with a fourmembered ring, the neutral complex Ni(DTB)2 in the bis-(2,4-dithiobiureto)nickel(II)-glycol compound (Pignedoli, Peyronel & Antolini, 1972) and the cationic complex Ni(HDTB) 2+ in the bis-(2,4-dithiobiureto)-nickel(II)-diperchlorate-ethanol compound (Pignedoll, Peyronel & Antolini, 1973) both having a sixmembered ring. We were therefore interested in determining the structure of the bis-(2,3-quinoxalinedithiolato)nickelate(lI) anion, Ni(qdt) 2-, having a five-membered ring and we chose for this study the tetraethylammonium salt, less cumbersome than the tetrabutylammonium salt.…”

Thiocarbonyl Pseudohalides – The Curious Case of Thiocarbonyl Dithiocyanate

“…It is the first crystal structure of this type of complex, since only dithiobiuret derivative complexes are known. [37][38][39][40][41][42] The nickel atom in 4 is coordinated in a square planar geometry by four sulfur atoms (see Figure 8). The ligand backbone is tilted out of the coordination plane by 22°.…”

“…NiÀ S distances are ranging from 2.165(5) Å to 2.169(7) Å, which is comparable to literature known complexes. [37][38][39][40][41][42]…”