The dithiooxalate-bridged complex [Cr(C2O2S2)3(NiL) 3][ClO4]3 (L = racemic 5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane): Synthesis, crystal structure and magnetism

Minoru Mitsumi, Hisashi Okawa, Hiroshi Sakiyama, Masaaki Ohba, Naohide Matsumoto, Tsutomu Kurisaki, Hisanobu Wakita

Research output: Contribution to journalArticle

38 Citations (Scopus)

Abstract

The reaction of KCa[Cr(C2O2S2)3]·6H 2O (C2O2S2 = dithiooxalate) and [NiL][ClO4]2 (L = racemic 5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane) in the 1:3 molar ratio gave a chromium(III)trinickel(II) complex [Cr(C2O2S2)3(NiL) 3][ClO4]3. It crystallizes with two dimethylformamide and two PriOH molecules in the monoclinic space group C2/c, with a = 31.51(1), b = 17.447(6), c = 19.05(1) Å, β = 112.75(4)° and Z = 4. The complex has a CrNi3 core bridged by dithiooxalate groups which bond through sulfur atoms to the Cr and through oxygen atoms to the Ni. The Cr⋯Ni separation is 5.959(5)-5.999(6) Å. The CrS6 entity shows a distortion to a trigonal-prismatic geometry. Each nickel ion assumes a pseudo-octahedral geometry with two oxygen atoms of the C2O2S2 group and four nitrogen atoms of L in a folded form. Cryomagnetic studies (4.2-300 K) revealed a ferromagnetic spin-exchange interaction between the CrIII and NiII (J = +5.9 cm-1 based on ℋ = -2ΣJijŜiŜj).

Original languageEnglish
Pages (from-to)2991-2995
Number of pages5
JournalJournal of the Chemical Society, Dalton Transactions
Issue number20
DOIs
Publication statusPublished - Dec 1 1993

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Magnetism
Crystal structure
Atoms
Oxygen
Dimethylformamide
Geometry
Exchange interactions
Chromium
Nickel
Sulfur
Nitrogen
Ions
Molecules
perchlorate
cyclam

All Science Journal Classification (ASJC) codes

  • Chemistry(all)

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The dithiooxalate-bridged complex [Cr(C2O2S2)3(NiL) 3][ClO4]3 (L = racemic 5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane) : Synthesis, crystal structure and magnetism. / Mitsumi, Minoru; Okawa, Hisashi; Sakiyama, Hiroshi; Ohba, Masaaki; Matsumoto, Naohide; Kurisaki, Tsutomu; Wakita, Hisanobu.

In: Journal of the Chemical Society, Dalton Transactions, No. 20, 01.12.1993, p. 2991-2995.

Research output: Contribution to journalArticle

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title = "The dithiooxalate-bridged complex [Cr(C2O2S2)3(NiL) 3][ClO4]3 (L = racemic 5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane): Synthesis, crystal structure and magnetism",
abstract = "The reaction of KCa[Cr(C2O2S2)3]·6H 2O (C2O2S2 = dithiooxalate) and [NiL][ClO4]2 (L = racemic 5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane) in the 1:3 molar ratio gave a chromium(III)trinickel(II) complex [Cr(C2O2S2)3(NiL) 3][ClO4]3. It crystallizes with two dimethylformamide and two PriOH molecules in the monoclinic space group C2/c, with a = 31.51(1), b = 17.447(6), c = 19.05(1) {\AA}, β = 112.75(4)° and Z = 4. The complex has a CrNi3 core bridged by dithiooxalate groups which bond through sulfur atoms to the Cr and through oxygen atoms to the Ni. The Cr⋯Ni separation is 5.959(5)-5.999(6) {\AA}. The CrS6 entity shows a distortion to a trigonal-prismatic geometry. Each nickel ion assumes a pseudo-octahedral geometry with two oxygen atoms of the C2O2S2 group and four nitrogen atoms of L in a folded form. Cryomagnetic studies (4.2-300 K) revealed a ferromagnetic spin-exchange interaction between the CrIII and NiII (J = +5.9 cm-1 based on ℋ = -2ΣJijŜiŜj).",
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T1 - The dithiooxalate-bridged complex [Cr(C2O2S2)3(NiL) 3][ClO4]3 (L = racemic 5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane)

T2 - Synthesis, crystal structure and magnetism

AU - Mitsumi, Minoru

AU - Okawa, Hisashi

AU - Sakiyama, Hiroshi

AU - Ohba, Masaaki

AU - Matsumoto, Naohide

AU - Kurisaki, Tsutomu

AU - Wakita, Hisanobu

PY - 1993/12/1

Y1 - 1993/12/1

N2 - The reaction of KCa[Cr(C2O2S2)3]·6H 2O (C2O2S2 = dithiooxalate) and [NiL][ClO4]2 (L = racemic 5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane) in the 1:3 molar ratio gave a chromium(III)trinickel(II) complex [Cr(C2O2S2)3(NiL) 3][ClO4]3. It crystallizes with two dimethylformamide and two PriOH molecules in the monoclinic space group C2/c, with a = 31.51(1), b = 17.447(6), c = 19.05(1) Å, β = 112.75(4)° and Z = 4. The complex has a CrNi3 core bridged by dithiooxalate groups which bond through sulfur atoms to the Cr and through oxygen atoms to the Ni. The Cr⋯Ni separation is 5.959(5)-5.999(6) Å. The CrS6 entity shows a distortion to a trigonal-prismatic geometry. Each nickel ion assumes a pseudo-octahedral geometry with two oxygen atoms of the C2O2S2 group and four nitrogen atoms of L in a folded form. Cryomagnetic studies (4.2-300 K) revealed a ferromagnetic spin-exchange interaction between the CrIII and NiII (J = +5.9 cm-1 based on ℋ = -2ΣJijŜiŜj).

AB - The reaction of KCa[Cr(C2O2S2)3]·6H 2O (C2O2S2 = dithiooxalate) and [NiL][ClO4]2 (L = racemic 5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane) in the 1:3 molar ratio gave a chromium(III)trinickel(II) complex [Cr(C2O2S2)3(NiL) 3][ClO4]3. It crystallizes with two dimethylformamide and two PriOH molecules in the monoclinic space group C2/c, with a = 31.51(1), b = 17.447(6), c = 19.05(1) Å, β = 112.75(4)° and Z = 4. The complex has a CrNi3 core bridged by dithiooxalate groups which bond through sulfur atoms to the Cr and through oxygen atoms to the Ni. The Cr⋯Ni separation is 5.959(5)-5.999(6) Å. The CrS6 entity shows a distortion to a trigonal-prismatic geometry. Each nickel ion assumes a pseudo-octahedral geometry with two oxygen atoms of the C2O2S2 group and four nitrogen atoms of L in a folded form. Cryomagnetic studies (4.2-300 K) revealed a ferromagnetic spin-exchange interaction between the CrIII and NiII (J = +5.9 cm-1 based on ℋ = -2ΣJijŜiŜj).

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