Syntheses, characterization and crystal structures of novel amine adducts of metal saccharinates, orotates and salicylates

Hasan Icbudak, Halis Olmez, Okan Z. Yesilel, Figen Arslan, Pance Naumov, Gligor Jovanovski, Abdul Razak Ibrahim, Anwar Usman, Hoong Kun Fun, Suchada Chantrapromma, Seik Weng Nge

Research output: Contribution to journalArticle

Abstract

Seven novel adducts of ethylenediamine (en), N,N′ -dimethylethylenediamine (dmen) and N, N-dimethylethylenediamine (ndmen) with saccharinate, orotate and salicylate as counter-ions were synthesized and characterized with physico-chemical methods (IR and UV/vis spectroscopy, magnetic susceptibility and thermoanalytical measurements) and X-ray diffraction. Reaction of dmen with tetraaquabis(saccharinato-N)copper(II) dihydrate yielded diaquabis(dmen)copper(II) saccharinate, whereas with the corresponding nickel derivative it afforded bis(dmen)bis(saccharinato-O)nickel(II). In the copper complex the coordinated water and the primary nitrogen end of the donor ligand interact with the saccharinate anion [O1 w⋯O3 = 2.833 (2), N1⋯N2 = 2.992(2) Å]. Adjacent molecules are linked by two more hydrogen bonds into a layer structure. In the nickel compound, the dmen ligand also chelates the metal atom, which is bonded to the carbonyl oxygen of the anionic group. The negatively-charged nitrogen atom of the anion is intramolecularly linked to the dmen [N1⋯N2 = 2.968(2) Å]; hydrogen bonds link the molecules into layers. Under mildly basic conditions, the reaction of orotic acid with cobalt(II) afforded tetraaqua(2,6dioxo-1,2,6-trihydropyrimidine-4-carboxylato-N,O)cobalt(II) hydrate. The complex was oxidatively reacted with en to give a mixed-ligand cobalt(III) adduct which includes both mono- and bisdeprotonated orotate ions. The metal atom in tetraaqua(2,6dioxo-1,2,6-trihydropyrimidine-4-carboxylato-N,O)cobalt(II) hydrate is chelated by the orotato dianion through the carboxyl oxygen and 3-pyrimidyl nitrogen atoms, and its octahedral geometry is completed by four water molecules. The 1-pyrimidyl nitrogen atom engages in hydrogen bonding with the lattice water molecule. The cobalt atom is similarly chelated by the orotato dianion in bis(en)(2,6-dioxo-1,2,6-trihydropyrimidine-4-carboxylato-N,O)cobalt(III) 2,6-dioxo-1,2,3,6-tetrahydropyridimi-dine-4-carboxylate pentahydrate. The copper atom in the five-coordinate aqua(en)orotatocopper(II) monohydrate is chelated by the en ligand, the deprotonated N1 pyrimidine atom and the orotate carboxylate oxygen; the water molecule completes the square-pyramidal coordination. The nickel and copper atoms in bis(en)bis(salicylato-O)nickel(II) and bis(ndmen)bis(salicy-lato-O)copper(II) monomeric octahedral complexes are coordinated by the salicylato monoanion through the carboxylate oxygen in a monodentate fashion and by the en and ndmen molecules through the two amine nitrogen atoms in a bidentate chelating manner. In the copper complex, the carboxylate oxygen atom engages in hydrogen bonding with the lattice water molecule.

Original languageEnglish (US)
Pages (from-to)255-270
Number of pages16
JournalJournal of Molecular Structure
Volume657
Issue number1-3
DOIs
StatePublished - Sep 10 2003

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ethylenediamine
Salicylates
Amines
Crystal structure
Metals
Atoms
Cobalt
Copper
Molecules
Nickel
Nitrogen
Oxygen
Hydrogen bonds
Water
Ligands
Hydrates
Anions
Nickel compounds
Orotic Acid
dimethylethylenediamine

Keywords

  • Amine complexes
  • Coordination
  • Orotate
  • Saccharinate
  • Salicylate

ASJC Scopus subject areas

  • Analytical Chemistry
  • Spectroscopy
  • Organic Chemistry
  • Inorganic Chemistry

Cite this

Syntheses, characterization and crystal structures of novel amine adducts of metal saccharinates, orotates and salicylates. / Icbudak, Hasan; Olmez, Halis; Yesilel, Okan Z.; Arslan, Figen; Naumov, Pance; Jovanovski, Gligor; Ibrahim, Abdul Razak; Usman, Anwar; Fun, Hoong Kun; Chantrapromma, Suchada; Nge, Seik Weng.

In: Journal of Molecular Structure, Vol. 657, No. 1-3, 10.09.2003, p. 255-270.

Research output: Contribution to journalArticle

Icbudak, H, Olmez, H, Yesilel, OZ, Arslan, F, Naumov, P, Jovanovski, G, Ibrahim, AR, Usman, A, Fun, HK, Chantrapromma, S & Nge, SW 2003, 'Syntheses, characterization and crystal structures of novel amine adducts of metal saccharinates, orotates and salicylates', Journal of Molecular Structure, vol. 657, no. 1-3, pp. 255-270. https://doi.org/10.1016/S0022-2860(03)00404-6
Icbudak, Hasan ; Olmez, Halis ; Yesilel, Okan Z. ; Arslan, Figen ; Naumov, Pance ; Jovanovski, Gligor ; Ibrahim, Abdul Razak ; Usman, Anwar ; Fun, Hoong Kun ; Chantrapromma, Suchada ; Nge, Seik Weng. / Syntheses, characterization and crystal structures of novel amine adducts of metal saccharinates, orotates and salicylates. In: Journal of Molecular Structure. 2003 ; Vol. 657, No. 1-3. pp. 255-270.
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abstract = "Seven novel adducts of ethylenediamine (en), N,N′ -dimethylethylenediamine (dmen) and N, N-dimethylethylenediamine (ndmen) with saccharinate, orotate and salicylate as counter-ions were synthesized and characterized with physico-chemical methods (IR and UV/vis spectroscopy, magnetic susceptibility and thermoanalytical measurements) and X-ray diffraction. Reaction of dmen with tetraaquabis(saccharinato-N)copper(II) dihydrate yielded diaquabis(dmen)copper(II) saccharinate, whereas with the corresponding nickel derivative it afforded bis(dmen)bis(saccharinato-O)nickel(II). In the copper complex the coordinated water and the primary nitrogen end of the donor ligand interact with the saccharinate anion [O1 w⋯O3 = 2.833 (2), N1⋯N2 = 2.992(2) {\AA}]. Adjacent molecules are linked by two more hydrogen bonds into a layer structure. In the nickel compound, the dmen ligand also chelates the metal atom, which is bonded to the carbonyl oxygen of the anionic group. The negatively-charged nitrogen atom of the anion is intramolecularly linked to the dmen [N1⋯N2 = 2.968(2) {\AA}]; hydrogen bonds link the molecules into layers. Under mildly basic conditions, the reaction of orotic acid with cobalt(II) afforded tetraaqua(2,6dioxo-1,2,6-trihydropyrimidine-4-carboxylato-N,O)cobalt(II) hydrate. The complex was oxidatively reacted with en to give a mixed-ligand cobalt(III) adduct which includes both mono- and bisdeprotonated orotate ions. The metal atom in tetraaqua(2,6dioxo-1,2,6-trihydropyrimidine-4-carboxylato-N,O)cobalt(II) hydrate is chelated by the orotato dianion through the carboxyl oxygen and 3-pyrimidyl nitrogen atoms, and its octahedral geometry is completed by four water molecules. The 1-pyrimidyl nitrogen atom engages in hydrogen bonding with the lattice water molecule. The cobalt atom is similarly chelated by the orotato dianion in bis(en)(2,6-dioxo-1,2,6-trihydropyrimidine-4-carboxylato-N,O)cobalt(III) 2,6-dioxo-1,2,3,6-tetrahydropyridimi-dine-4-carboxylate pentahydrate. The copper atom in the five-coordinate aqua(en)orotatocopper(II) monohydrate is chelated by the en ligand, the deprotonated N1 pyrimidine atom and the orotate carboxylate oxygen; the water molecule completes the square-pyramidal coordination. The nickel and copper atoms in bis(en)bis(salicylato-O)nickel(II) and bis(ndmen)bis(salicy-lato-O)copper(II) monomeric octahedral complexes are coordinated by the salicylato monoanion through the carboxylate oxygen in a monodentate fashion and by the en and ndmen molecules through the two amine nitrogen atoms in a bidentate chelating manner. In the copper complex, the carboxylate oxygen atom engages in hydrogen bonding with the lattice water molecule.",
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author = "Hasan Icbudak and Halis Olmez and Yesilel, {Okan Z.} and Figen Arslan and Pance Naumov and Gligor Jovanovski and Ibrahim, {Abdul Razak} and Anwar Usman and Fun, {Hoong Kun} and Suchada Chantrapromma and Nge, {Seik Weng}",
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T1 - Syntheses, characterization and crystal structures of novel amine adducts of metal saccharinates, orotates and salicylates

AU - Icbudak, Hasan

AU - Olmez, Halis

AU - Yesilel, Okan Z.

AU - Arslan, Figen

AU - Naumov, Pance

AU - Jovanovski, Gligor

AU - Ibrahim, Abdul Razak

AU - Usman, Anwar

AU - Fun, Hoong Kun

AU - Chantrapromma, Suchada

AU - Nge, Seik Weng

PY - 2003/9/10

Y1 - 2003/9/10

N2 - Seven novel adducts of ethylenediamine (en), N,N′ -dimethylethylenediamine (dmen) and N, N-dimethylethylenediamine (ndmen) with saccharinate, orotate and salicylate as counter-ions were synthesized and characterized with physico-chemical methods (IR and UV/vis spectroscopy, magnetic susceptibility and thermoanalytical measurements) and X-ray diffraction. Reaction of dmen with tetraaquabis(saccharinato-N)copper(II) dihydrate yielded diaquabis(dmen)copper(II) saccharinate, whereas with the corresponding nickel derivative it afforded bis(dmen)bis(saccharinato-O)nickel(II). In the copper complex the coordinated water and the primary nitrogen end of the donor ligand interact with the saccharinate anion [O1 w⋯O3 = 2.833 (2), N1⋯N2 = 2.992(2) Å]. Adjacent molecules are linked by two more hydrogen bonds into a layer structure. In the nickel compound, the dmen ligand also chelates the metal atom, which is bonded to the carbonyl oxygen of the anionic group. The negatively-charged nitrogen atom of the anion is intramolecularly linked to the dmen [N1⋯N2 = 2.968(2) Å]; hydrogen bonds link the molecules into layers. Under mildly basic conditions, the reaction of orotic acid with cobalt(II) afforded tetraaqua(2,6dioxo-1,2,6-trihydropyrimidine-4-carboxylato-N,O)cobalt(II) hydrate. The complex was oxidatively reacted with en to give a mixed-ligand cobalt(III) adduct which includes both mono- and bisdeprotonated orotate ions. The metal atom in tetraaqua(2,6dioxo-1,2,6-trihydropyrimidine-4-carboxylato-N,O)cobalt(II) hydrate is chelated by the orotato dianion through the carboxyl oxygen and 3-pyrimidyl nitrogen atoms, and its octahedral geometry is completed by four water molecules. The 1-pyrimidyl nitrogen atom engages in hydrogen bonding with the lattice water molecule. The cobalt atom is similarly chelated by the orotato dianion in bis(en)(2,6-dioxo-1,2,6-trihydropyrimidine-4-carboxylato-N,O)cobalt(III) 2,6-dioxo-1,2,3,6-tetrahydropyridimi-dine-4-carboxylate pentahydrate. The copper atom in the five-coordinate aqua(en)orotatocopper(II) monohydrate is chelated by the en ligand, the deprotonated N1 pyrimidine atom and the orotate carboxylate oxygen; the water molecule completes the square-pyramidal coordination. The nickel and copper atoms in bis(en)bis(salicylato-O)nickel(II) and bis(ndmen)bis(salicy-lato-O)copper(II) monomeric octahedral complexes are coordinated by the salicylato monoanion through the carboxylate oxygen in a monodentate fashion and by the en and ndmen molecules through the two amine nitrogen atoms in a bidentate chelating manner. In the copper complex, the carboxylate oxygen atom engages in hydrogen bonding with the lattice water molecule.

AB - Seven novel adducts of ethylenediamine (en), N,N′ -dimethylethylenediamine (dmen) and N, N-dimethylethylenediamine (ndmen) with saccharinate, orotate and salicylate as counter-ions were synthesized and characterized with physico-chemical methods (IR and UV/vis spectroscopy, magnetic susceptibility and thermoanalytical measurements) and X-ray diffraction. Reaction of dmen with tetraaquabis(saccharinato-N)copper(II) dihydrate yielded diaquabis(dmen)copper(II) saccharinate, whereas with the corresponding nickel derivative it afforded bis(dmen)bis(saccharinato-O)nickel(II). In the copper complex the coordinated water and the primary nitrogen end of the donor ligand interact with the saccharinate anion [O1 w⋯O3 = 2.833 (2), N1⋯N2 = 2.992(2) Å]. Adjacent molecules are linked by two more hydrogen bonds into a layer structure. In the nickel compound, the dmen ligand also chelates the metal atom, which is bonded to the carbonyl oxygen of the anionic group. The negatively-charged nitrogen atom of the anion is intramolecularly linked to the dmen [N1⋯N2 = 2.968(2) Å]; hydrogen bonds link the molecules into layers. Under mildly basic conditions, the reaction of orotic acid with cobalt(II) afforded tetraaqua(2,6dioxo-1,2,6-trihydropyrimidine-4-carboxylato-N,O)cobalt(II) hydrate. The complex was oxidatively reacted with en to give a mixed-ligand cobalt(III) adduct which includes both mono- and bisdeprotonated orotate ions. The metal atom in tetraaqua(2,6dioxo-1,2,6-trihydropyrimidine-4-carboxylato-N,O)cobalt(II) hydrate is chelated by the orotato dianion through the carboxyl oxygen and 3-pyrimidyl nitrogen atoms, and its octahedral geometry is completed by four water molecules. The 1-pyrimidyl nitrogen atom engages in hydrogen bonding with the lattice water molecule. The cobalt atom is similarly chelated by the orotato dianion in bis(en)(2,6-dioxo-1,2,6-trihydropyrimidine-4-carboxylato-N,O)cobalt(III) 2,6-dioxo-1,2,3,6-tetrahydropyridimi-dine-4-carboxylate pentahydrate. The copper atom in the five-coordinate aqua(en)orotatocopper(II) monohydrate is chelated by the en ligand, the deprotonated N1 pyrimidine atom and the orotate carboxylate oxygen; the water molecule completes the square-pyramidal coordination. The nickel and copper atoms in bis(en)bis(salicylato-O)nickel(II) and bis(ndmen)bis(salicy-lato-O)copper(II) monomeric octahedral complexes are coordinated by the salicylato monoanion through the carboxylate oxygen in a monodentate fashion and by the en and ndmen molecules through the two amine nitrogen atoms in a bidentate chelating manner. In the copper complex, the carboxylate oxygen atom engages in hydrogen bonding with the lattice water molecule.

KW - Amine complexes

KW - Coordination

KW - Orotate

KW - Saccharinate

KW - Salicylate

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