10.1021/acs.cgd.5b00989.s001
Love Karan Rana
Love Karan
Rana
Sanyog Sharma
Sanyog
Sharma
Geeta Hundal
Geeta
Hundal
First Report on
Crystal Engineering of Hg(II) Halides
with Fully Substituted 3,4-Pyridinedicarboxamides: Generation of Two-Dimensional
Coordination Polymers and Linear Zig-Zag Chains of Mercury Metal Ions
American Chemical Society
2016
noncovalent
dimer
Hg
2 D CP
HgCl
interaction
ligand L 1.
halide bridged 2 D structure
coordination polymers
Mercury Metal IonsTwo
complex
LP
2016-01-06 00:00:00
Journal contribution
https://acs.figshare.com/articles/journal_contribution/First_Report_on_Crystal_Engineering_of_Hg_II_Halides_with_Fully_Substituted_3_4_Pyridinedicarboxamides_Generation_of_Two_Dimensional_Coordination_Polymers_and_Linear_Zig_Zag_Chains_of_Mercury_Metal_Ions/2091280
Two new ligands <i>N</i>,<i>N</i>,<i>N</i>′,<i>N</i>′-tetraisopropyl/tetraisobutyl-3,4-pyridinedicarboxamide <b>L1</b>–<b>L2</b> and six of their Hg(II)X<sub>2</sub> complexes (where X = Cl<sup>–</sup>, Br<sup>–</sup>, and I<sup>–</sup>) have been synthesized and characterized.
Single crystal X-ray structures of three complexes of <b>L1</b> (<b>1</b>–<b>3</b>) with HgCl<sub>2</sub>/Br<sub>2</sub>/I<sub>2</sub> and two complexes of <b>L2</b> (<b>4</b>–<b>5</b>) with HgCl<sub>2</sub>/Br<sub>2</sub> show that these are two-dimensional (2D) coordination polymers,
with three different (one new) topologies and five coordinated Hg(II)
ions, in square pyramidal coordination. Complex <b>6</b>, of <b>L2</b> with HgI<sub>2</sub>, is a dimer with a four coordinated
tetrahedral Hg(II) ion. The ligands behave as two- or three-connecting
linkers for forming coordination polymers (CPs) but only one-connector
in the dimer. Various types of hydrogen bonding and other noncovalent
interactions have been calculated, analyzed, and discussed for all
the complexes and the ligand <b>L1</b>. Although the large size
and soft character of iodide coupled with the steric effects of large
isobutyl groups are mainly responsible for a change in the primary
structure of <b>6</b>, a significant role of the semilocalized
LP···π and C–H···O noncovalent
interactions into this has also been found. The latter transform this
dimer into a stable 2D hydrogen-bonded network instead of a coordination
polymer. The unique halide bridged 2D structure of <b>1</b> forms
one-dimensional zig-zag chains of metal ions owing to the mercurophilic
interactions. Weaker interactions of the same kind further extend
along the basic skeleton of 2D CP and are facilitated by LP···π,
strong C–H···Cl and C–H···N(py)
interactions.