The crystal structure of 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane nickel(II) bisperchlorate at 155 K

doi:10.1016/S0020-1693(00)82213-6

Inorganica Chimica Acta

Volume 111, Issue 1, 2 January 1986, Pages 35-38

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Abstract

The crystal structure of the complex 1, 4, 8, 11-tetramethyl-1,4,8,11-tetraazacyclotetradecane nickel(II) bisperchlorate has been determined by an X-ray diffraction study conducted at 155 K. The monoclinic crystals have the space group Cc with a = 16.960(5), b = 36.651(8), c =18.681(5) Å, β = 112.06° and Z = 20. A combination of Patterson and direct methods were used to solve the structure which was refined by a least squares procedure with R = 0.078 and R_w = 0.079, employing 7242 unique reflections with I ⩾ 2.5 σ(I).

The asymmetric unit consists of five independent complex nickel cations and ten independent perchlorate anions. Of the five nickel centres, three are well resolved and of these, two exhibit a marginal tetrahedral distortion of the square planar arrangement of nitrogen atoms around each nickel centre, whilst the third possesses a slight pyramidally distorted square planar character. An average NiN bond length of 1.96 Å has been observed. This study unambiguously establishes that for each of these cations, the ligand possesses the R, S, R, S conformation with all four methyl groups on the same side of the NiN₄ plane.

References (16)

N. Herron et al.
Inorg. Chim. Acta
(1979)
L. Helm et al.
Inorg. Chim. Acta
(1983)
S. Lincoln et al.
Inorg. Chim. Acta
(1984)
T. Glowiak et al.
Inorg. Chim. Acta
(1978)
F. Wagner et al.
Inorg. Chem.
(1973)
F. Wagner et al.
Inorg. Chem.
(1976)
J. Beattie et al.
Inorg. Chem.
(1985)
P. Moore et al.
J. Chem. Soc., Chem. Commun.
(1983)

There are more references available in the full text version of this article.

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The crystal structure of 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane nickel(II) bisperchlorate at 155 K

Abstract

Inorg. Chim. Acta

Inorg. Chim. Acta

Inorg. Chim. Acta

Inorg. Chim. Acta

Inorg. Chem.

Inorg. Chem.

Inorg. Chem.

J. Chem. Soc., Chem. Commun.