TY - JOUR
T1 - Synthesis, structure and bonding of cadmium(II) thiocyanate systems featuring nitrogen based ligands of different denticity
AU - Banerjee, Suparna
AU - Wu, Biao
AU - Lassahn, Paul G.
AU - Janiak, Christoph
AU - Ghosh, Ashutosh
PY - 2005/2/10
Y1 - 2005/2/10
N2 - Complexes catena-[di(4-amino-pyridine)di(μ-S,N-thiocyanato)cadmium(II)], ∞1 [Cd(μ-SCN)2(L1) 2] (1), catena-[{(1-pyridine-2-yl-ethylene)-hydrazine}di(μ-S,N- thiocyanato)cadmium(II)], ∞1[Cd(μ-SCN) 2(L2)] (2), and di-μ-S,N-thiocyanatobis{(N,N-diethyl- N′-(1-pyridine-2-yl-ethylidene)-ethane-1,2-diamine)(N-thiocyanato) cadmium(II)}, [Cd(NCS)(μ-SCN)(L3)]2 (3) have been synthesized by reacting cadmium acetate/NH4SCN with 4-amino-pyridine (L1), C5H4N-C(CH3)=NNH2 (L2), and C5H4N-C(CH3)=N-CH 2-CH2-N(C2H5)2 (L 3), respectively, in methanol. Characterization by single-crystal X-ray crystallography shows that in compounds 1 and 2 the cadmium atoms have a 4N2S-hexa-coordination sphere, exhibiting pseudo-octahedral geometry. The cadmium atoms are bridged by two thiocyanate ions generating 1-D polymeric chains. Compound 3 is a centrosymmetric dimeric complex, with the cadmium atom pseudo octahedrally surrounded by a 5N1S coordination sphere. In compound 1 the crystal packing is controlled mainly by interchain N-H⋯N and C-H⋯π interactions between the aminopyridine moieties, whereas in complexes 2 and 3 π-stacking interactions between the pyridyl planes stabilize the interchain or intermolecular packing, respectively. Thiocyanate and pyridylimine chelation to metal center is also scrutinized with EHMO analysis.
AB - Complexes catena-[di(4-amino-pyridine)di(μ-S,N-thiocyanato)cadmium(II)], ∞1 [Cd(μ-SCN)2(L1) 2] (1), catena-[{(1-pyridine-2-yl-ethylene)-hydrazine}di(μ-S,N- thiocyanato)cadmium(II)], ∞1[Cd(μ-SCN) 2(L2)] (2), and di-μ-S,N-thiocyanatobis{(N,N-diethyl- N′-(1-pyridine-2-yl-ethylidene)-ethane-1,2-diamine)(N-thiocyanato) cadmium(II)}, [Cd(NCS)(μ-SCN)(L3)]2 (3) have been synthesized by reacting cadmium acetate/NH4SCN with 4-amino-pyridine (L1), C5H4N-C(CH3)=NNH2 (L2), and C5H4N-C(CH3)=N-CH 2-CH2-N(C2H5)2 (L 3), respectively, in methanol. Characterization by single-crystal X-ray crystallography shows that in compounds 1 and 2 the cadmium atoms have a 4N2S-hexa-coordination sphere, exhibiting pseudo-octahedral geometry. The cadmium atoms are bridged by two thiocyanate ions generating 1-D polymeric chains. Compound 3 is a centrosymmetric dimeric complex, with the cadmium atom pseudo octahedrally surrounded by a 5N1S coordination sphere. In compound 1 the crystal packing is controlled mainly by interchain N-H⋯N and C-H⋯π interactions between the aminopyridine moieties, whereas in complexes 2 and 3 π-stacking interactions between the pyridyl planes stabilize the interchain or intermolecular packing, respectively. Thiocyanate and pyridylimine chelation to metal center is also scrutinized with EHMO analysis.
KW - Bonding
KW - Cadmium(II)
KW - Coordination polymers
KW - Schiff bases
KW - Thiocyanate
UR - http://www.scopus.com/inward/record.url?scp=11144297225&partnerID=8YFLogxK
U2 - 10.1016/j.ica.2004.07.048
DO - 10.1016/j.ica.2004.07.048
M3 - Article
AN - SCOPUS:11144297225
SN - 0020-1693
VL - 358
SP - 535
EP - 544
JO - Inorganica Chimica Acta
JF - Inorganica Chimica Acta
IS - 3
ER -