Crystallographic and Spectroscopic Studies of Low-Symmetry Nickel(II) Complexes Possessing Long Nickel-Nitrogen Bonds

A. B.P. Lever; I. M. Walker; K. B. Mertes; A. Jircitano; R. Sheldon; P. J. Mccarthy

doi:10.1021/ic00158a007

Crystallographic and Spectroscopic Studies of Low-Symmetry Nickel(II) Complexes Possessing Long Nickel-Nitrogen Bonds

A. B.P. Lever, I. M. Walker, K. B. Mertes, A. Jircitano, R. Sheldon, P. J. Mccarthy

School of Science (Behrend)

Research output: Contribution to journal › Article › peer-review

51 Scopus citations

Abstract

The X-ray structure of bis(isothiocyanato)bis(N,N-diethylethylenedi_amine)nickel(II), Ni[NH₂C₂H₄N(C₂H₅)₂]₂(NCS)₂, is reported. The complex crystallizes in the triclinic space group P1 with unit cell parameters a = 10.438 (10) A, b = 8.073 (8) Å, c = 14.876 (14) Å, α = 87.2 (8), β - 109.6 (7), γ = 112.8 (8), and 2 = 1. The nickel complexes are six-coordinate and all-trans. There is significant rhombic distortion due to bent NiNCS coordination, short NiNH₂ bonds, and long NiN(C₂H₅)₂ bonds. The single-crystal polarized spectrum of this crystal at 10 K is reported and analyzed in terms of rhombic symmetry. Single-crystal spectroscopic data for [Ni[NH₂CH₂CH₂N(C₂H₅)₂]₂(H₂O)₂]²⁺Cl-₂ and Ni-[(CH₃)₂NCH₂CH₂N(CH₃)₂]₂(NCS)₂ at 10 K are also reported. The data are compared with a range of other nickel complexes of low symmetry where both X-ray and spectroscopic data are available. The angular overlap model (AOM) is used, and it is demonstrated that AOM parameters in this low symmetry parallel those previously encountered for higher symmetries. In particular the use of sterically hindered amines provides a data set in which the Ni-N bond varies from about 208 to 233 pm. The σ-N AOM parameter is shown to correlate with the nickel-nitrogen bond length.

Original language	English (US)
Pages (from-to)	2252-2258
Number of pages	7
Journal	Inorganic chemistry
Volume	22
Issue number	16
DOIs	https://doi.org/10.1021/ic00158a007
State	Published - Aug 1983

All Science Journal Classification (ASJC) codes

Physical and Theoretical Chemistry
Inorganic Chemistry

Access to Document

10.1021/ic00158a007

Cite this

@article{6711aaad561a4790b5b94999f0af9ceb,

title = "Crystallographic and Spectroscopic Studies of Low-Symmetry Nickel(II) Complexes Possessing Long Nickel-Nitrogen Bonds",

abstract = "The X-ray structure of bis(isothiocyanato)bis(N,N-diethylethylenedi_amine)nickel(II), Ni[NH2C2H4N(C2H5)2]2(NCS)2, is reported. The complex crystallizes in the triclinic space group P1 with unit cell parameters a = 10.438 (10) A, b = 8.073 (8) {\AA}, c = 14.876 (14) {\AA}, α = 87.2 (8), β - 109.6 (7), γ = 112.8 (8), and 2 = 1. The nickel complexes are six-coordinate and all-trans. There is significant rhombic distortion due to bent NiNCS coordination, short NiNH2 bonds, and long NiN(C2H5)2 bonds. The single-crystal polarized spectrum of this crystal at 10 K is reported and analyzed in terms of rhombic symmetry. Single-crystal spectroscopic data for [Ni[NH2CH2CH2N(C2H5)2]2(H2O)2]2+Cl-2 and Ni-[(CH3)2NCH2CH2N(CH3)2]2(NCS)2 at 10 K are also reported. The data are compared with a range of other nickel complexes of low symmetry where both X-ray and spectroscopic data are available. The angular overlap model (AOM) is used, and it is demonstrated that AOM parameters in this low symmetry parallel those previously encountered for higher symmetries. In particular the use of sterically hindered amines provides a data set in which the Ni-N bond varies from about 208 to 233 pm. The σ-N AOM parameter is shown to correlate with the nickel-nitrogen bond length.",

author = "Lever, {A. B.P.} and Walker, {I. M.} and Mertes, {K. B.} and A. Jircitano and R. Sheldon and Mccarthy, {P. J.}",

year = "1983",

month = aug,

doi = "10.1021/ic00158a007",

language = "English (US)",

volume = "22",

pages = "2252--2258",

journal = "Inorganic chemistry",

issn = "0020-1669",

publisher = "American Chemical Society",

number = "16",

}

TY - JOUR

T1 - Crystallographic and Spectroscopic Studies of Low-Symmetry Nickel(II) Complexes Possessing Long Nickel-Nitrogen Bonds

AU - Lever, A. B.P.

AU - Walker, I. M.

AU - Mertes, K. B.

AU - Jircitano, A.

AU - Sheldon, R.

AU - Mccarthy, P. J.

PY - 1983/8

Y1 - 1983/8

N2 - The X-ray structure of bis(isothiocyanato)bis(N,N-diethylethylenedi_amine)nickel(II), Ni[NH2C2H4N(C2H5)2]2(NCS)2, is reported. The complex crystallizes in the triclinic space group P1 with unit cell parameters a = 10.438 (10) A, b = 8.073 (8) Å, c = 14.876 (14) Å, α = 87.2 (8), β - 109.6 (7), γ = 112.8 (8), and 2 = 1. The nickel complexes are six-coordinate and all-trans. There is significant rhombic distortion due to bent NiNCS coordination, short NiNH2 bonds, and long NiN(C2H5)2 bonds. The single-crystal polarized spectrum of this crystal at 10 K is reported and analyzed in terms of rhombic symmetry. Single-crystal spectroscopic data for [Ni[NH2CH2CH2N(C2H5)2]2(H2O)2]2+Cl-2 and Ni-[(CH3)2NCH2CH2N(CH3)2]2(NCS)2 at 10 K are also reported. The data are compared with a range of other nickel complexes of low symmetry where both X-ray and spectroscopic data are available. The angular overlap model (AOM) is used, and it is demonstrated that AOM parameters in this low symmetry parallel those previously encountered for higher symmetries. In particular the use of sterically hindered amines provides a data set in which the Ni-N bond varies from about 208 to 233 pm. The σ-N AOM parameter is shown to correlate with the nickel-nitrogen bond length.

AB - The X-ray structure of bis(isothiocyanato)bis(N,N-diethylethylenedi_amine)nickel(II), Ni[NH2C2H4N(C2H5)2]2(NCS)2, is reported. The complex crystallizes in the triclinic space group P1 with unit cell parameters a = 10.438 (10) A, b = 8.073 (8) Å, c = 14.876 (14) Å, α = 87.2 (8), β - 109.6 (7), γ = 112.8 (8), and 2 = 1. The nickel complexes are six-coordinate and all-trans. There is significant rhombic distortion due to bent NiNCS coordination, short NiNH2 bonds, and long NiN(C2H5)2 bonds. The single-crystal polarized spectrum of this crystal at 10 K is reported and analyzed in terms of rhombic symmetry. Single-crystal spectroscopic data for [Ni[NH2CH2CH2N(C2H5)2]2(H2O)2]2+Cl-2 and Ni-[(CH3)2NCH2CH2N(CH3)2]2(NCS)2 at 10 K are also reported. The data are compared with a range of other nickel complexes of low symmetry where both X-ray and spectroscopic data are available. The angular overlap model (AOM) is used, and it is demonstrated that AOM parameters in this low symmetry parallel those previously encountered for higher symmetries. In particular the use of sterically hindered amines provides a data set in which the Ni-N bond varies from about 208 to 233 pm. The σ-N AOM parameter is shown to correlate with the nickel-nitrogen bond length.

UR - http://www.scopus.com/inward/record.url?scp=0000563918&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=0000563918&partnerID=8YFLogxK

U2 - 10.1021/ic00158a007

DO - 10.1021/ic00158a007

M3 - Article

AN - SCOPUS:0000563918

SN - 0020-1669

VL - 22

SP - 2252

EP - 2258

JO - Inorganic chemistry

JF - Inorganic chemistry

IS - 16

ER -

Crystallographic and Spectroscopic Studies of Low-Symmetry Nickel(II) Complexes Possessing Long Nickel-Nitrogen Bonds

Abstract

All Science Journal Classification (ASJC) codes

Access to Document

Other files and links

Fingerprint

Cite this