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Synthesis and Crystal Structures of Nickel(II) and Copper(II) Complexes of Meso‐3,6,6,9‐Tetramethyl‐4,8‐Diazaundecane‐2,10‐Dione Dioxime
Author(s) -
Fun HoongKun,
Lee TsongJen,
Tahirov Tahir,
Lu TianHuey,
Luh Hung,
Chung ChungSun
Publication year - 1993
Publication title -
journal of the chinese chemical society
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.329
H-Index - 45
eISSN - 2192-6549
pISSN - 0009-4536
DOI - 10.1002/jccs.199300068
Subject(s) - chemistry , intramolecular force , crystallography , nickel , copper , square pyramid , crystal structure , hydrogen bond , bond length , thiocyanate , ion , oxime , square pyramidal molecular geometry , stereochemistry , molecule , inorganic chemistry , medicinal chemistry , organic chemistry
Abstract The nickel(II) and copper(II) complexes of meso ‐3,6,6,9‐tetramethyl‐4,8‐diazaundecane‐2,10‐dione dioxime ( meso ‐HM‐PAO) have an intramolecular hydrogen bond between cis oxime groups. [Cu( meso ‐HM‐PAO‐H)(H 2 O)](NCS) crystallizes in space group P2 1 /n with a = 7.692(1), b = 12.028(2), c=20.235(3) Å, β=93.03(1)°, Z = 4 and Dc=1.46 g/cm 3 . The final R value for this complex was 0.034 for 2223 observed reflections with I ≥ 2.5σ (I). The Cu(II) coordination is a distorted square pyramid. The Cu(II) ion is five‐coorinated with the diazadioxime N atoms equatorial and water O atom axial. The Cu(II) is 0.12 Å from the equatorial plane towards the hydrate. The equatorial Cu‐N distances span a narrow range, 1.953(3)‐1.999(3) Å. The axial Cu‐O distance is 2.314(3) Å. The thiocyanate group is almost linear. The intramolecular O ⃛O hydrogen bond length is 2.479(4) Å. [Ni( meso ‐HM‐PAO‐H)](ClO 4 ) crystallizes in space group P2 1 /c with a = 14.774(3), b = 12.752(3), c = 20.035(4) Å, β = 92.94(3)°, Z = 8 and Dc = 1.51 g/cm 3 . The final R value for the complex was 0.053 for 4794 observed reflections with F ≥ 4σ (F). The coordination about Ni(II) is a slightly distorted square plane. The Ni(II) ion is 0.0673(7) Å from the best plane of the four donor nitrogen atoms away from the perchlorate ion. The Ni‐N distances span a narrow range 1.863(4)‐1.927(4) Å. There are two molecules per asymmetrical unit resulting in eight molecules being packed in an unit cell; they are bound together by van der Waals interactions. The O‐H ⃛O bonds of these complexes give characteristic infrared absorptions as well as chemical shift of the 1 H NMR signal (Ni complex).