The new coordination compounds [CuCl2(C5H14N2)(2)]center dot 4 H2O (1) and [Co(CO3)(C5H14N2)(2)] Cl center dot H2O (2) (C5H14N2 = 2,2-dimethylpropyldiamine) were synthesized under solvothermal conditions. Compound 1 crystallizes in the monoclinic space group P2(1)/n with a = 6.2175(4), b = 27.4152(17), c = 11.7975(8) angstrom, beta = 97.702(8)degrees, V = 1992.8(2) angstrom(3), Z = 4 and 2 in the monoclinic space group P2(1)/c with a = 11.5913(8), b = 22.4797(12), c = 7.3655(5) angstrom, beta = 96.760(8)degrees, V = 1905.9(2) angstrom(3), Z = 4. In 1 the Cu2+ cation is octahedrally coordinated by two bidentate 2,2-dimethylpropyldiamine molecules in the basal plane and two Cl anions located at the apices. The Cu-Cl bond lengths are very unsymmetrical which is caused by the significantly different hydrogen bonding interactions of the two Cl anions. The H2O molecules are joined by strong H center dot center dot center dot O interactions generating a (H2O)(10) decamer which are fused to form a wavy water layer. The layer displays a new and hitherto never observed H2O layer motif which may be described as L10(6). In 2 the Co2+ cation is surrounded by two bidentate amine molecules and a bidentate CO32 anion which was formed in situ by CO2 uptake from the atmosphere. N-H, O and Cl are involved in an extended hydrogen bonding networks leading to the formation of layers which are arranged generating channels along [001] which are occupied by water molecules. Thermal investigations of both compounds exhibit complex decomposition patterns and successive emission of the constituents. The optical band gaps of 3.79 for 1 and 3.48 eV for 2 confirm that both compounds are isolators. (C) 2011 Elsevier B.V. All rights reserved.