Journal of the Chemical Society, Dalton Transactions p. 13 - 22 (1981)
Update date:2022-08-11
Topics:
Boyd, Peter D. W.
Mitra, Samaresh
Raston, Colin L.
Rowbottom, Graham L.
White, Allan H.
The magnetic susceptibilities of a series of copper(II) dialkyldithiocarbamates have been measured over the range 4-290 K, the alkyl groups being methyl, ethyl, isopropyl, and n-butyl.Contrary to a previous report of strong ferromagnetic interaction in the diethyl derivative, we find no evidence of any significant exchange interaction in this compound.The dimethyl and di-isopropyl analogues show weak antiferromagnetic interactions.Only the di-n-butyl derivative in the dialkyl series shows evidence of strong magnetic exchange interaction but of an antiferromagnetic nature; this effect is peculiar to the phase recrystallized from chloroform-light petroleum (α), the phase obtained from chloroform-ethanol (β) showing no such interaction.To seek the origin of the exchange interaction in the α derivative, its crystal structure has been determined by single-crystal X-ray diffraction methods at 295 K and refined by least squares to a residual 0.032 for 1976 'observed' reflections.Crystals are triclinic, P1, a=15.29(1), b=9.963(7), c=9.243(7) Angstroem, α=67.94(7), β=82.92(7), γ=71.55(7) deg, and Z=2.The copper environment is the usual pseudo-square-planar array of four sulphur atoms from two bidentate ligands (a long fifth interaction a) the bridging geometry in the 'dimer' and (b) the proximity to the 'dimer' sulphur ligands of sulphur atoms from neighbouring dimers at ca. 3.8 Angstroem.The likely relative importance of these two features in determining the origin of the antiferromagnetic coupling is discussed.The structure of the β phase has also been determined, the final residual being 0.036 for 1324 'observed' reflections.Crystals are monoclinic, P21/n, a= 14.593(5), b= 7.840(2), c= 10.822(5) Angstroem, β= 101.55(3) deg, and Z= 2.The molecules are located with the copper atoms on crystallographic centres of symmetry, and the only significant intermolecular interactions observed are S<*>H contacts.The CuS4 entity is planar with
Baoding City Light Industry And Textiles Imp.& Exp. Corp. Chemical Department.
Contact:86-312-3262436
Address:NO.658 CHAOYANG SOUTH STREET,BAODING CITY HEBEI CHINA
AllyChem Co., Ltd., Dalian, China（BBChem）
Contact:+86-411-62313318/62313328
Address:No.5 of Jinbin Road, Jinzhou New District, Dalian City, Liaoning Province, P.R.China
Wuhan Kemi-Works Chemical Co., Ltd
website:http://www.kemiworks.com
Contact:86-27-85736489
Address:Rm. 1503, No. 164, Jianghan North Rd., Wuhan, 430022 China
Jiangsu Hualun Chemical Industry Co., Ltd
website:http://www.hualunchem.com
Contact:+86-0514-86464168 86507985
Address:39# Middle Renmin Road, Dinghuo Town
LinHai Cina Chemical Co., LTD.
Contact:0576-85580989
Address:Pharma-chem zone,Duqiao,Linhai,Zhejiang,China
Doi:10.1016/S0040-4039(00)85657-9
(1982)Doi:10.1021/ja01158a074
(1950)Doi:10.1021/acs.orglett.5b00252
(2015)Doi:10.1016/j.dyepig.2017.03.009
(2017)Doi:10.1246/bcsj.48.3718
(1975)Doi:10.1002/jhet.3845
(2020)
