Syntheses and crystal structures of the one-dimensional coordination polymers formed by [Ni(cyclam)]2+ cations and 1,3-bis(3-carboxypropyl)tetramethyldisiloxane anions in different degrees of deprotonation

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Abstract
The asymmetric units of the title compounds, namely, catena-poly[[(1,4,8,11-tetraazacyclotetradecane-κ4 N 1,N 4,N 8,N 11)nickel(II)]-μ-1,3-bis(3-carboxylatopropyl)tetramethyldisiloxane-κ2 O:O′], [Ni(C10H24O5Si2)(C12H24N4)] n (I), and catena-poly[[[(1,4,8,11-tetraazacyclotetradecane-κ4 N 1,N 4,N 8,N 11)nickel(II)]-μ-4-({[(3-carboxypropyl)dimethylsilyl]oxy}dimethylsilyl)butanoato-κ2 O:O′] perchlorate], {[Ni(C10H25O5Si2)(C12H24N4)]ClO4} n (II), consist of one (in I) or two crystallographically non-equivalent (in II) centrosymmetric macrocyclic cations and one centrosymmetric dianion (in I) or two centrosymmetric monoanions (in II). In each compound, the metal ion is coordinated by the four secondary N atoms of the macrocyclic ligand, which adopts the most energetically stable trans-III conformation, and the mutually trans O atoms of the carboxylate in a slightly tetragonally distorted trans-NiN4O2 octahedral coordination geometry. The crystals of both types of compounds are composed of parallel polymeric chains of the macrocyclic cations linked by the anions of the acid running along the [101] and [110] directions in I and II, respectively. In I, each polymeric chain is linked to four neighbouring ones by hydrogen bonding between the NH groups of the macrocycle and the carboxylate O atoms, thus forming a three-dimensional supramolecular network. In II, each polymeric chain contacts with only two neighbours, forming hydrogen bonds between the partially protonated carboxylic groups of the bridging ligand. As a result, a lamellar structure is formed with the layers oriented parallel to the (1\overline{1}1) plane.

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