The crystal and molecular structure of bis(dithiobiureto)nickel(II)

Luth, H.; Hall, E. A.; Spofford, W. A.; Amma, E. L.

doi:10.1039/c2969000520b

Cited by 22 publications

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“…The Ni-S bond distances, the intrachelate and interchelate S-Ni-S angles and S-S distances (Tables 2, 3, 5) are very close to those observed in the neutral complex in both the Ni(DTB)2 and Ni(DTB)z.glycol structures. The interchelate S-S distance of about 2.9 A in both the neutral and the cationic complexes is well within the range of 3.04-3.17 A postulated by Steifel, Dori & Gray (1967) as indicative of some residual S-S bonding; this shorter distance was considered by Luth, Hall, Spofford & Amma (1969) as significant and led them to conclude that in Ni(DTB)2 there is some residual S-S interchelate bonding. This residual bonding could be at least partially responsible for the almost identical structure of the NiS4 group in both the neutral and the cationic Ni(dithiobiureto)2 complexes.…”

Section: Resultsmentioning

confidence: 93%

“…It generally acts as a uninegative donor in neutral solution or as a neutral donor in acidic solution. The crystal and molecular structure of its square planar neutral complexes Pd(DTB)z (Girling & Aroma, 1968) and Ni(DTB)2 (Luth, Hall, Spofford & Amma, 1969) showed an S, S coordination of the ligand to the metal. The crystal structure of the addition compound Ni(DTB)2.glycol (Pignedoli, Peyronel & Antolini, 1972) showed several hydrogen bonds between the glycol and the complex molecules having a definite influence on their molecular structures.…”

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

Pignedoli¹,

Peyronel²,

Antolini³

1973

Acta Crystallogr B Struct Sci

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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...

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Section: Resultsmentioning

confidence: 93%

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confidence: 99%

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

Pignedoli¹,

Peyronel²,

Antolini³

1973

Acta Crystallogr B Struct Sci

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“…( 6)]. Results for K-edge transition energies of heavier elements are presented in Table 2, including molecules containing third-row elements Si, P, S, and Cl, along with a few organometallic complexes containing a 3d transition metal, [101][102][103][104] as shown in Fig. 2.…”

Section: B Benchmarking Core Excitation Energiesmentioning

confidence: 99%

A new parameterization of the DFT/CIS method with applications to core-level spectroscopy

Mandal,

Berquist,

Herbert

2024

Preprint

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Time-dependent density functional theory (TD-DFT) within a restricted excitation space is an efficient means to compute core-level excitation energies, using only a small subset of the occupied orbitals. However, core-to-valence excitation energies are significantly underestimated when standard exchange-correlation functionals are used, which is partly traceable to systemic issues with TD-DFT's description of Rydberg and charge-transfer excited states. To mitigate this, we have implemented an empirically modified combination of configuration interaction with single substitutions (CIS) based on Kohn-Sham orbitals, which is known as "DFT/CIS". This semi-empirical approach is well-suited for simulating x-ray near-edge spectra, as it contains sufficient exact exchange to model charge-transfer excitations yet retains DFT's low-cost description of dynamical electron correlation. Empirical corrections to the matrix elements enable semi-quantitative simulation of near-edge x-ray spectra without the need for significant a posteriori shifts; this should be useful in complex molecules and materials with multiple overlapping x-ray edges. Parameter optimization for use with a specific range-separated hybrid functional makes this a black-box method intended for both core and valence spectroscopy. Results herein demonstrate that realistic K-edge absorption and emission spectra can be obtained for second- and third-row elements and 3d transition metals, with promising results for L-edge spectra as well. DFT/CIS calculations require absolute shifts that are considerably smaller than what is typical in TD-DFT.

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The Stereochemistry of Bis‐Chelate Metal(II) Complexes

Holm

O'connor

1971

Progress in Inorganic Chemistry

221

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The crystal and molecular structure of bis(dithiobiureto)nickel(II)

Cited by 22 publications

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

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

A new parameterization of the DFT/CIS method with applications to core-level spectroscopy

The Stereochemistry of Bis‐Chelate Metal(II) Complexes

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The crystal and molecular structure of bis(dithiobiureto)nickel(II)

Cited by 22 publications

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

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

A new parameterization of the DFT/CIS method with applications to core-level spectroscopy

The Stereochemistry of Bis‐Chelate Metal(II) Complexes

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

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