TY - JOUR
T1 - Solid State Structural Variations in Copper(II) Complexes of Open-Chain and Macrocyclic Malonamide-Derived Ligands
AU - Gavrish, Sergey P.
AU - Lampeka, Yaroslaw D.
AU - Lightfoot, Philip
AU - Arion, Vladimir B.
AU - Keppler, Bernhard K.
AU - Wozniak, Krzysztof
PY - 2012/9
Y1 - 2012/9
N2 - An analysis of the molecular structure of the copper(II) complexes with open-chain and macrocyclic malonamide-derived tetradentate ligands based on single crystal X-ray diffraction study of four copper(II) complexes [CuL1(H2O)]center dot 4H(2)O, [CuL2(H2O)], [CuL3(H2O)], and [CuL4(H2O)] (H2L1 = 1,4,8,11-tetraazaundecane-S,7-dione, H2L2 = 13-methyl-13-nitro-1,4,8,11-tetraazacyclotetradecane-5,7-dione, H2L3 = 1,4,8,11-tetraazacyclotetradecane-5,7-dione, and H2L4 = 1,4,8,11-tetraazacyclotridecane-5,7-dione) as well as on published data regarding related compounds revealed that the violations of planarity of the metal-amide fragments are due almost exclusively to the deviation of the copper(II) ion from the amide plane. Both the deviation of the copper(II) ion from the amide plane and the angle between amide planes in the 6-membered malonamide ring are strongly affected by substituents with minimal values observed in the complexes of unsubstituted ligands. The deviation of the copper(II) ion from the basal plane of donor atoms was shown to relate to the sum of bite angles around the copper(II) ion and roughly correlates to Cu-L-ax distances when apical ligands are present. The crystals of the macrocyclic complexes CuL2 to CulL(4) are built up from similar corrugated layers in which metal complex molecules are linked in a "head-to-tail" manner via NH center dot center dot center dot O=C hydrogen bonds. In contrast, [CuL1(H2O)]center dot 4H(2)O has a lamellar crystal structure in which the layers built up of [CuL1(H2O)] units alternate with sheets formed by water molecules.
AB - An analysis of the molecular structure of the copper(II) complexes with open-chain and macrocyclic malonamide-derived tetradentate ligands based on single crystal X-ray diffraction study of four copper(II) complexes [CuL1(H2O)]center dot 4H(2)O, [CuL2(H2O)], [CuL3(H2O)], and [CuL4(H2O)] (H2L1 = 1,4,8,11-tetraazaundecane-S,7-dione, H2L2 = 13-methyl-13-nitro-1,4,8,11-tetraazacyclotetradecane-5,7-dione, H2L3 = 1,4,8,11-tetraazacyclotetradecane-5,7-dione, and H2L4 = 1,4,8,11-tetraazacyclotridecane-5,7-dione) as well as on published data regarding related compounds revealed that the violations of planarity of the metal-amide fragments are due almost exclusively to the deviation of the copper(II) ion from the amide plane. Both the deviation of the copper(II) ion from the amide plane and the angle between amide planes in the 6-membered malonamide ring are strongly affected by substituents with minimal values observed in the complexes of unsubstituted ligands. The deviation of the copper(II) ion from the basal plane of donor atoms was shown to relate to the sum of bite angles around the copper(II) ion and roughly correlates to Cu-L-ax distances when apical ligands are present. The crystals of the macrocyclic complexes CuL2 to CulL(4) are built up from similar corrugated layers in which metal complex molecules are linked in a "head-to-tail" manner via NH center dot center dot center dot O=C hydrogen bonds. In contrast, [CuL1(H2O)]center dot 4H(2)O has a lamellar crystal structure in which the layers built up of [CuL1(H2O)] units alternate with sheets formed by water molecules.
U2 - 10.1021/cg300554r
DO - 10.1021/cg300554r
M3 - Article
SN - 1528-7483
VL - 12
SP - 4388
EP - 4396
JO - Crystal Growth & Design
JF - Crystal Growth & Design
IS - 9
ER -