Synthesis, crystal structure, magnetic properties and cyclic voltammetry of the unsymmetric (μ-oxalato)-[N,N′,N″,N‴-tetrakis-(2-pyridylmethyl)-1,4,8, 11-tetraazacyclotetra-decane]dicobalt(II) perchlorate trihydrate
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1999
Authors
Sovilj, Sofija P.Vučković, Gordana
Babić-Samardžija, Ksenija

Matsumoto, N.
Jovanović, Vladislava M.

Mrozinski, J.
Article (Published version)

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A new dinuclear cobalt(II) complex, [Co2(ox)tpmc](ClO4)2 3H2O, (tpmc = N, N′, N″, N″′-tetrakis(2-pyridylmethyl)-1, 4, 8, 11-tetraazacyclotetradecane, ox2 -oxalate ion), has been synthesized and its crystal structure solved by single crystal X-ray diffraction studies. It crystallizes in the monoclinic system, space group P21, with a = 97558(8) A, b = 21.455(2) A, c - 21.241(2) A, β=100.069(8)°, V=4391.0(8) A3, Z =4,R = 0.083, Rw = 0.086. Its structure consists of two dinuclear, crystallographically unique molecules in which the oxalate ion bridges two cobalt(II) ions unsymmetrically. E:ach cobalt is hexa-coordinated with four macrocyclic nitrogens and two oxygens in an octahedral arrangement of an “em” coordination of a macrocyclic ligand. The third oxygen is simultaneously bonded to both cobalt ions and the last one remains uncoordinated, which is the unique way of oxalato ion coordination. Intramolecular antiferromagnetic coupling between the two cobalt(II) ions is observed and yielde...d J = -9.3 an−1, g - 5.64 and g = 1.21. The variable temperature (4.2-192 K) inagiietic susceptibility nieasureinents are interpreted on the basis of the spin lamiltonian H 25/9JSASB + goβHz(SAZ - SBZ). Cyclic voltanllnetiy suggests that the complex is electrochcmically stable up to the potential of the cobalt reduction.
Keywords:
Magnetic properties / dinuclear complex / X-ray difraction / antiferromagnetic coupling / Cyclic voltanllnetiySource:
Synthesis and Reactivity in Inorganic and Metal-Organic Chemistry, 1999, 29, 5, 785-803Publisher:
- Taylor and Francis
Funding / projects:
- Ministry of Science and Technology of Republic of Serbia
- Polish State Commitee for Scientific Research (Project No. 3T09A06308)
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Institution/Community
IHTMTY - JOUR AU - Sovilj, Sofija P. AU - Vučković, Gordana AU - Babić-Samardžija, Ksenija AU - Matsumoto, N. AU - Jovanović, Vladislava M. AU - Mrozinski, J. PY - 1999 UR - https://cer.ihtm.bg.ac.rs/handle/123456789/3672 AB - A new dinuclear cobalt(II) complex, [Co2(ox)tpmc](ClO4)2 3H2O, (tpmc = N, N′, N″, N″′-tetrakis(2-pyridylmethyl)-1, 4, 8, 11-tetraazacyclotetradecane, ox2 -oxalate ion), has been synthesized and its crystal structure solved by single crystal X-ray diffraction studies. It crystallizes in the monoclinic system, space group P21, with a = 97558(8) A, b = 21.455(2) A, c - 21.241(2) A, β=100.069(8)°, V=4391.0(8) A3, Z =4,R = 0.083, Rw = 0.086. Its structure consists of two dinuclear, crystallographically unique molecules in which the oxalate ion bridges two cobalt(II) ions unsymmetrically. E:ach cobalt is hexa-coordinated with four macrocyclic nitrogens and two oxygens in an octahedral arrangement of an “em” coordination of a macrocyclic ligand. The third oxygen is simultaneously bonded to both cobalt ions and the last one remains uncoordinated, which is the unique way of oxalato ion coordination. Intramolecular antiferromagnetic coupling between the two cobalt(II) ions is observed and yielded J = -9.3 an−1, g - 5.64 and g = 1.21. The variable temperature (4.2-192 K) inagiietic susceptibility nieasureinents are interpreted on the basis of the spin lamiltonian H 25/9JSASB + goβHz(SAZ - SBZ). Cyclic voltanllnetiy suggests that the complex is electrochcmically stable up to the potential of the cobalt reduction. PB - Taylor and Francis T2 - Synthesis and Reactivity in Inorganic and Metal-Organic Chemistry T1 - Synthesis, crystal structure, magnetic properties and cyclic voltammetry of the unsymmetric (μ-oxalato)-[N,N′,N″,N‴-tetrakis-(2-pyridylmethyl)-1,4,8, 11-tetraazacyclotetra-decane]dicobalt(II) perchlorate trihydrate VL - 29 IS - 5 SP - 785 EP - 803 DO - 10.1080/00945719909349487 ER -
@article{ author = "Sovilj, Sofija P. and Vučković, Gordana and Babić-Samardžija, Ksenija and Matsumoto, N. and Jovanović, Vladislava M. and Mrozinski, J.", year = "1999", abstract = "A new dinuclear cobalt(II) complex, [Co2(ox)tpmc](ClO4)2 3H2O, (tpmc = N, N′, N″, N″′-tetrakis(2-pyridylmethyl)-1, 4, 8, 11-tetraazacyclotetradecane, ox2 -oxalate ion), has been synthesized and its crystal structure solved by single crystal X-ray diffraction studies. It crystallizes in the monoclinic system, space group P21, with a = 97558(8) A, b = 21.455(2) A, c - 21.241(2) A, β=100.069(8)°, V=4391.0(8) A3, Z =4,R = 0.083, Rw = 0.086. Its structure consists of two dinuclear, crystallographically unique molecules in which the oxalate ion bridges two cobalt(II) ions unsymmetrically. E:ach cobalt is hexa-coordinated with four macrocyclic nitrogens and two oxygens in an octahedral arrangement of an “em” coordination of a macrocyclic ligand. The third oxygen is simultaneously bonded to both cobalt ions and the last one remains uncoordinated, which is the unique way of oxalato ion coordination. Intramolecular antiferromagnetic coupling between the two cobalt(II) ions is observed and yielded J = -9.3 an−1, g - 5.64 and g = 1.21. The variable temperature (4.2-192 K) inagiietic susceptibility nieasureinents are interpreted on the basis of the spin lamiltonian H 25/9JSASB + goβHz(SAZ - SBZ). Cyclic voltanllnetiy suggests that the complex is electrochcmically stable up to the potential of the cobalt reduction.", publisher = "Taylor and Francis", journal = "Synthesis and Reactivity in Inorganic and Metal-Organic Chemistry", title = "Synthesis, crystal structure, magnetic properties and cyclic voltammetry of the unsymmetric (μ-oxalato)-[N,N′,N″,N‴-tetrakis-(2-pyridylmethyl)-1,4,8, 11-tetraazacyclotetra-decane]dicobalt(II) perchlorate trihydrate", volume = "29", number = "5", pages = "785-803", doi = "10.1080/00945719909349487" }
Sovilj, S. P., Vučković, G., Babić-Samardžija, K., Matsumoto, N., Jovanović, V. M.,& Mrozinski, J.. (1999). Synthesis, crystal structure, magnetic properties and cyclic voltammetry of the unsymmetric (μ-oxalato)-[N,N′,N″,N‴-tetrakis-(2-pyridylmethyl)-1,4,8, 11-tetraazacyclotetra-decane]dicobalt(II) perchlorate trihydrate. in Synthesis and Reactivity in Inorganic and Metal-Organic Chemistry Taylor and Francis., 29(5), 785-803. https://doi.org/10.1080/00945719909349487
Sovilj SP, Vučković G, Babić-Samardžija K, Matsumoto N, Jovanović VM, Mrozinski J. Synthesis, crystal structure, magnetic properties and cyclic voltammetry of the unsymmetric (μ-oxalato)-[N,N′,N″,N‴-tetrakis-(2-pyridylmethyl)-1,4,8, 11-tetraazacyclotetra-decane]dicobalt(II) perchlorate trihydrate. in Synthesis and Reactivity in Inorganic and Metal-Organic Chemistry. 1999;29(5):785-803. doi:10.1080/00945719909349487 .
Sovilj, Sofija P., Vučković, Gordana, Babić-Samardžija, Ksenija, Matsumoto, N., Jovanović, Vladislava M., Mrozinski, J., "Synthesis, crystal structure, magnetic properties and cyclic voltammetry of the unsymmetric (μ-oxalato)-[N,N′,N″,N‴-tetrakis-(2-pyridylmethyl)-1,4,8, 11-tetraazacyclotetra-decane]dicobalt(II) perchlorate trihydrate" in Synthesis and Reactivity in Inorganic and Metal-Organic Chemistry, 29, no. 5 (1999):785-803, https://doi.org/10.1080/00945719909349487 . .