TY - JOUR
T1 - Coordination geometries of bis(4-amino-3-alkyl-1,2,4-triazole-5-thione) complexes of first-row transition metals
T2 - Crystal structures of complexes with propyl and hydrogen in the 3-position. Relationship to the 3-methyl and 3-ethyl analogs
AU - McCarrick, Robert M.
AU - Eltzroth, Martin J.
AU - Squattrito, Philip J.
N1 - Funding Information:
We thank Dennis Anderson for assistance with collection and interpretation of the NMR spectra. The Herbert H. and Grace A. Dow Foundation, The Dow Chemical Company Foundation, and Central Michigan University provided funds for the establishment of the CMU X-Ray Crystallography Laboratory. This work was partially supported by a grant from the Faculty Research and Creative Endeavors Committee of Central Michigan University.
PY - 2000/12/22
Y1 - 2000/12/22
N2 - A series of bis bidentate complexes of 4-amino-3-propyl-1,2,4-triazole-5-thione, SN4C5H10 (apt, 1) of the divalent ions Fe, Co, Ni, and Zn has been crystallized by direct combination of the ligand and metal nitrate or perchlorate hydrate salt in ethanol. The structures were determined by single-crystal X-ray diffraction techniques. In all the complexes, the triazole bonds to the metal ion through the amine and thione substituents on the five-membered ring. [Fe(apt)2(H2O)2] (ClO4)2 (2) has the like-ligands trans to each other. The Fe-N distances (2.259(5) Å) are elongated relative to the Fe-O bond lengths (2.092(5) Å). The compounds [Co(apt)2(H2O)2] (NO3)2·2H2O (3), [Ni(apt)2(H2O)2] (NO3)2·2H2O (4), and [Zn(apt)2(H2O)2] (NO3)2·2H2O (5) are isostructural, with the water molecules cis to each other and the triazole ligands positioned with the amine groups cis and S atoms trans. A series of complexes of 4-amino-1,2,4-triazole-5-thione (aht, 6) of divalent Mn, Co, and Zn has also been crystallized by similar means and structurally characterized. [Mn(aht)2(H2O)2] (ClO4)2 (7) has the ligands arranged as in 3, though with a non-centrosymmetric packing (space group C2). The cis Mn-N distances are significantly longer (2.377(2) Å) than the Mn-O distances (2.160(2) Å). [Co(aht)2(H2O)2] (ClO4)2 (8) possesses the trans geometry found in 2, though with comparable Co-N and Co-O bond lengths (2.175(3) and 2.082(3) Å). [Zn(aht)2(H2O)2] (ClO4)2 (9) is isostructural with 7. These structures are compared with those of two recently reported series of 4-amino-3-alkyl-1,2,4-triazole-5-thione complexes (alkyl = methyl and ethyl) in order to gauge the effect of the alkyl group on the coordination behavior of the triazole ligand towards the divalent first-row transition metals.
AB - A series of bis bidentate complexes of 4-amino-3-propyl-1,2,4-triazole-5-thione, SN4C5H10 (apt, 1) of the divalent ions Fe, Co, Ni, and Zn has been crystallized by direct combination of the ligand and metal nitrate or perchlorate hydrate salt in ethanol. The structures were determined by single-crystal X-ray diffraction techniques. In all the complexes, the triazole bonds to the metal ion through the amine and thione substituents on the five-membered ring. [Fe(apt)2(H2O)2] (ClO4)2 (2) has the like-ligands trans to each other. The Fe-N distances (2.259(5) Å) are elongated relative to the Fe-O bond lengths (2.092(5) Å). The compounds [Co(apt)2(H2O)2] (NO3)2·2H2O (3), [Ni(apt)2(H2O)2] (NO3)2·2H2O (4), and [Zn(apt)2(H2O)2] (NO3)2·2H2O (5) are isostructural, with the water molecules cis to each other and the triazole ligands positioned with the amine groups cis and S atoms trans. A series of complexes of 4-amino-1,2,4-triazole-5-thione (aht, 6) of divalent Mn, Co, and Zn has also been crystallized by similar means and structurally characterized. [Mn(aht)2(H2O)2] (ClO4)2 (7) has the ligands arranged as in 3, though with a non-centrosymmetric packing (space group C2). The cis Mn-N distances are significantly longer (2.377(2) Å) than the Mn-O distances (2.160(2) Å). [Co(aht)2(H2O)2] (ClO4)2 (8) possesses the trans geometry found in 2, though with comparable Co-N and Co-O bond lengths (2.175(3) and 2.082(3) Å). [Zn(aht)2(H2O)2] (ClO4)2 (9) is isostructural with 7. These structures are compared with those of two recently reported series of 4-amino-3-alkyl-1,2,4-triazole-5-thione complexes (alkyl = methyl and ethyl) in order to gauge the effect of the alkyl group on the coordination behavior of the triazole ligand towards the divalent first-row transition metals.
KW - Crystal structures
KW - Transition metal complexes
KW - Triazole complexes
UR - http://www.scopus.com/inward/record.url?scp=0034704095&partnerID=8YFLogxK
U2 - 10.1016/S0020-1693(00)00314-5
DO - 10.1016/S0020-1693(00)00314-5
M3 - Article
AN - SCOPUS:0034704095
SN - 0020-1693
VL - 311
SP - 95
EP - 105
JO - Inorganica Chimica Acta
JF - Inorganica Chimica Acta
IS - 1-2
ER -