Journal article
Synthesis, structure, and spectroscopic properties of copper(II) compounds containing nitrogen-sulphur donor ligands; the crystal and molecular structure of aqua[1,7-bis(N-methylbenzimidazol-2′-yl)-2,6-dithiaheptane]copper(II) perchlorate
Dalton Transactions, (7), pp 1349-1356
1984
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Abstract
The linear quadridentate N
2
S
2
donor ligand 1,7-bis(
N
-methylbenzimidazol-2′-yl)-2,6-dithiaheptane (bmdhp) forms mono- and di-hydrate 1 : 1 copper(
II
) complexes which are significantly more stable toward autoreduction than those of the non-methylated analogue. The deep green monohydrate of the perchlorate salt crystallises as the mononuclear aqua-complex, [Cu(bmdhp)(OH
2
)][ClO
4
]
2
, in the monoclinic space group
P
2
1
/
n
, with
Z
= 4,
a
= 18.459(3),
b
= 10.362(2),
c
= 16.365(3)Å, and β= 117.14(1)°. The structure was solved and refined by standard Patterson, Fourier, and least-squares techniques to
R
= 0.047 and
R
′= 0.075 for 3 343 independent reflections with
l
> 2σ(
l
). The compound consists of [Cu(bmdhp)(OH
2
)]
2+
ions and ClO
4
-
counter ions. The co-ordination around copper is intermediate between trigonal bipyramidal and square pyramidal, with Cu-N distances of 1.950(4) and 1.997(4)Å, Cu-O(water) 2.225(4)Å, and Cu-S 2.328(1) and 2.337(1)Å. In the solid state, the perchlorate dihydrate's co-ordination sphere may be a topoisomer of the monohydrate's. A new angular structural parameter, τ, is defined and proposed as an index of trigonality, as a general descriptor of five-co-ordinate centric molecules. By this criterion, the irregular co-ordination geometry of [Cu(bmdhp)(OH
2
)]
2+
in the solid state is described as being 48% along the pathway of distortion from square pyramidal toward trigonal bipyramidal. In the electronic spectrum of the complex, assignment is made of the S(thioether)→ Cu charge-transfer bands by comparison with those of the colourless complex Zn(bmdhp)(OH)(ClO
4
). E.s.r. and ligand-field spectra show that the copper(
II
) compounds adopt a tetragonal structure in donor solvents.
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Details
- Title
- Synthesis, structure, and spectroscopic properties of copper(II) compounds containing nitrogen-sulphur donor ligands; the crystal and molecular structure of aqua[1,7-bis(N-methylbenzimidazol-2′-yl)-2,6-dithiaheptane]copper(II) perchlorate
- Creators
- Anthony W AddisonT. Nageswara RaoJan ReedijkJacobus van RijnGerrit C Verschoor
- Publication Details
- Dalton Transactions, (7), pp 1349-1356
- Publisher
- Royal Society of Chemistry
- Number of pages
- 8
- Resource Type
- Journal article
- Academic Unit
- Chemistry
- Web of Science ID
- WOS:A1984TA65500013
- Scopus ID
- 2-s2.0-37049096497
- Other Identifier
- 991019174281104721
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- Collaboration types
- Domestic collaboration
- International collaboration
- Web of Science research areas
- Chemistry, Inorganic & Nuclear