Abstract
The asymmetric unit of the title com-pound, catena-poly[[[(perchlorato-κO)copper(II)]-μ-3-(3-carb-oxy-prop-yl)-1,5,8,12-tetra-aza-3-azonia-cyclo-tetra-decane-κ4 N 1,N 5,N 8,N 12] bis-(per-chlorate)], {[Cu(C13H30N5O2)(ClO4)](ClO4)2} n , (I), consists of a macrocyclic cation, one coordinated per-chlorate anion and two per-chlorate ions as counter-anions. The metal ion is coordinated in a tetra-gonally distorted octa-hedral geometry by the four secondary N atoms of the macrocyclic ligand, the mutually trans O atoms of the per-chlorate anion and the carbonyl O atom of the protonated carb-oxy-lic acid group of a neighbouring cation. The average equatorial Cu-N bond lengths [2.01 (6) Å] are significantly shorter than the axial Cu-O bond lengths [2.379 (8) Å for carboxyl-ate and average 2.62 (7) Å for disordered per-chlorate]. The coordinated macrocyclic ligand in (I) adopts the most energetically favourable trans-III conformation with an equatorial orientation of the substituent at the protonated distal 3-position N atom in a six-membered chelate ring. The coordination of the carb-oxy-lic acid group of the cation to a neighbouring com-plex unit results in the formation of infinite chains running along the b-axis direction, which are cross-linked by N-H⋯O hydrogen bonds between the secondary amine groups of the macrocycle and O atoms of the per-chlorate counter-anions to form sheets lying parallel to the (001) plane. Additionally, the extended structure of (I) is consolidated by numerous intra- and interchain C-H⋯O contacts.
Highlights
The asymmetric unit of the title compound, catena-poly[[[(perchloratoO)copper(II)]--3-(3-carboxypropyl)-1,5,8,12-tetraaza-3-azoniacyclotetradecane-4N1,N5,N8,N12] bis(perchlorate)], {[Cu(C13H30N5O2)(ClO4)](ClO4)2}n, (I), consists of a macrocyclic cation, one coordinated perchlorate anion and two perchlorate ions as counter-anions
The coordination of the carboxylic acid group of the cation to a neighbouring complex unit results in the formation of infinite chains running along the b-axis direction, which are crosslinked by N—HÁ Á ÁO hydrogen bonds between the secondary amine groups of the macrocycle and O atoms of the perchlorate counter-anions to form sheets lying parallel to the (001) plane
E75, 1700–1704 research communications cyclams, as was shown for the NiII and CuII complexes of diazacyclam substituted with 3-carboxypropyl groups (Lu et al, 2005; Ou et al, 2005)
Summary
Because of their exceptionally high thermodynamic stability and kinetic inertness (Melson, 1979; Yatsimirskii & Lampeka, 1985), transition-metal complexes of the macrocycles 1,4,8,11tetraazacyclotetradecane (cyclam), N3,N10-disubstituted 1,3,5,8,10,12-hexaazacyclotetradecane (diazacyclam) and, to a lesser extent, N3-substituted 1,3,5,8,12-pentaazacyclotetradecane (azacyclam) are popular building units for the assembly of metal–organic frameworks (MOFs), demonstrating many promising applications (Lampeka & Tsymbal, 2004; Suh & Moon, 2007; Suh et al, 2012; Stackhouse & Ma, 2018). E75, 1700–1704 research communications cyclams, as was shown for the NiII and CuII complexes of diazacyclam substituted with 3-carboxypropyl groups (Lu et al, 2005; Ou et al, 2005) Such compounds are of particular interest because they can self-polymerize due to the coordination of the donor group of the substituent to the metal ion of another molecule, forming coordination polymers without using additional bridging ligands, the most popular of which are carboxylates (Rao et al, 2004). The methylene group of the substituent at the noncoordinated N3 atom in the six-membered chelate ring is oriented equatorially Such an arrangement of the substituent, in contrast to an axial orientation, is relatively uncommon and only a few examples of such CuII complexes with aza- and diazacyclam ligands have been described so far (Shin et al, 2010, 2012; Tsymbal et al, 2010; Husain et al, 2012; Xia et al, 2014). Bis(perchlorate)], {[Cu(H2L)(ClO4)](ClO4)2}n, which is the first example of azacyclam ligand with a carboxylic acid group
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