ChemInform Abstract: CRYSTAL STRUCTURE AND POLARIZED ELECTRONIC SPECTRUM OF μ-HYDROXO-BIS(PENTAAMINECHROMIUM(III)) CHLORIDE DIHYDRATE

1977 ◽  
Vol 8 (40) ◽  
pp. no-no
Author(s):  
P. ENGEL ◽  
H. U. GUEDEL
2017 ◽  
Vol 73 (8) ◽  
pp. 620-624 ◽  
Author(s):  
Katherine M. Van Heuvelen ◽  
Isabell Lee ◽  
Katherine Arriola ◽  
Rilke Griffin ◽  
Christopher Ye ◽  
...  

The tetraazamacrocyclic ligand 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane (TMC) has been used to bind a variety of first-row transition metals but to date the crystal structure of the cobalt(II) complex has been missing from this series. The missing cobalt complex chlorido(1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane-κ4 N)cobalt(II) chloride dihydrate, [CoCl(C14H32N4)]Cl·2H2O or [CoIICl(TMC)]Cl·2H2O, crystallizes as a purple crystal. This species adopts a distorted square-pyramidal geometry in which the TMC ligand assumes the trans-I configuration and the chloride ion binds in the syn-methyl pocket of the ligand. The CoII ion adopts an S = 3 \over 2 spin state, as measured by the Evans NMR method, and UV–visible spectroscopic studies indicate that the title hydrated salt is stable in solution. Density functional theory (DFT) studies reveal that the geometric parameters of [CoIICl(TMC)]Cl·2H2O are sensitive to the cobalt spin state and correctly predict a change in spin state upon a minor perturbation to the ligand environment.


Author(s):  
Bougar Sarr ◽  
Abdou Mbaye ◽  
Cheikh Abdoul Khadir Diop ◽  
Mamadou Sidibe ◽  
Yoann Rousselin

The organic–inorganic title salt, (C6H16N)2[Sn(C2O4)2Cl2] or ( i Pr2NH2)2[Sn(C2O4)2Cl2], was obtained by reacting bis(diisopropylammonium) oxalate with tin(IV) chloride dihydrate in methanol. The SnIV atom is coordinated by two chelating oxalate ligands and two chloride ions in cis positions, giving rise to an [Sn(C2O4)2Cl2]2− anion (point group symmetry 2), with the SnIV atom in a slightly distorted octahedral coordination. The cohesion of the crystal structure is ensured by the formation of N—H...O hydrogen bonding between (iPr2NH2)+ cations and [SnCl2(C2O4)2]2− anions. This gives rise to an infinite chain structure extending parallel to [101]. The main inter-chain interactions are van der Waals forces. The electronic spectrum of the title compound displays only one high intensity band in the UV region assignable to ligand–metal ion charge-transfer (LMCT) transitions. An IR spectrum was also recorded and is discussed.


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