Novel Layered 2D and Triply Interpenetrating 3D Cobalt-Functionalized Diaza-12-crown Based Coordination Polymers: Synthesis, Structure, and Magnetic Properties

Two novel coordination polymers with formulas CoL1·3H2O [1, L1 =
3,3′-((1,7-dioxa-4,10-diazacyclododecane-4,10-diyl)­bis­(methylene)
dibenzenecarboxylate] and Co2L2(H2O)2·2­(H2O) [2, L2 = 5,5′-((1,7-dioxa-4,10-diazacyclododecane-4,10-diyl)­bis­(methylene))
diisophthalate] were synthesized, where one Co­(II) ion coordinates
the crown-4 moiety of the ligand. Compound 1 crystallizes
in the space group C2 as an infinite two-dimensional
chiral layered coordination network with a tetragonal 44 sql net topology. The structural unit consists of the
coordinated Co­(II) ion and the deprotonated ligand. The Co­(II) ion
is 6-coordinate with two nitrogen atoms and two oxygen atoms of the
crown 1,7-diaza-12-crown-4, and two carboxylate oxygen atoms from
neighboring ligands, and exhibits a highly distorted octahedral geometry.
Compound 2 crystallizes in the monoclinic space group P21/n as a triply interpenetrating
3D network with the uncommon sqc528/dmd system, the first
coordination polymer with a 3-fold interpenetrating dmd topology.
It exhibits two distinct Co­(II) ions. One is in the center of the
crown-4 along with two cis-coordinated water molecules
in a highly distorted octahedral geometry; the other is 4-coordinate
with tetrahedral geometry and a node in the framework. Weak antiferromagnetic
interactions exist between the cobalt centers in both compounds.

成功合成了两种新颖的配位聚合物，其化学式分别为CoL1·3H2O（其中L1 = 3,3′-((1,7-二氧-4,10-二氮杂环癸烷-4,10-二基)双(亚甲基)二苯甲酸酯]）和Co2L2(H2O)2·2(H2O)（其中L2 = 5,5′-((1,7-二氧-4,10-二氮杂环癸烷-4,10-二基)双(亚甲基)对苯二甲酸酯]）。在这些化合物中，一个钴(II)离子与配体中的冠-4基团进行配位。化合物1以C2空间群结晶，形成一个无限延伸的二维手性层状配位网络，具有正方44型sql网络拓扑结构。其结构单元由配位的钴(II)离子和去质子的配体构成。钴(II)离子以6配位形式存在，其中包含冠1,7-二氮杂12-冠-4的两个氮原子和两个氧原子，以及邻近配体的两个羧酸氧原子，并展现出高度扭曲的八面体几何形状。化合物2以单斜空间群P21/n结晶，形成一种三重穿插的3D网络，具有不常见的sqc528/dmd系统，这是首个具有3重穿插dmd拓扑结构的配位聚合物。它表现出两种不同的钴(II)离子。一个位于冠-4中心，与两个在高度扭曲的八面体几何形状中顺式配位的水分子一起；另一个以4配位形式存在，具有四面体几何形状和框架中的节点。两种化合物中的钴中心之间存在弱反铁磁性相互作用。