10.1021/ic970150j.s001
Keith A. Hirsch
Keith A.
Hirsch
Scott R. Wilson
Scott R.
Wilson
Jeffrey S. Moore
Jeffrey S.
Moore
Coordination Networks of 3,3‘-Dicyanodiphenylacetylene and Silver(I) Salts: Structural
Diversity through Changes in Ligand Conformation and Counterion
American Chemical Society
1997
C 6 H 6
oxygen atoms
triflate ions
interpenetrated diamondoid network
sheet structure
transoid conformation
ligand nitrogen atom
CF
interpenetrated sheet structures
DCPA
Counterion Coordination networks
X F 6
1997-07-02 00:00:00
Journal contribution
https://acs.figshare.com/articles/journal_contribution/Coordination_Networks_of_3_3_-Dicyanodiphenylacetylene_and_Silver_I_Salts_Structural_Diversity_through_Changes_in_Ligand_Conformation_and_Counterion/3618462
Coordination networks of 3,3‘-dicyanodiphenylacetylene
(3,3‘-DCPA, <b>1</b>) with silver(I) salts characterized by
single-crystal X-ray analysis are described. Network topology is found to
depend on both the counterion and solvent
employed during crystallization. The conformation adopted by the
ligand varies between planar <i>cisoid</i> and planar
<i>transoid</i>. With silver(I) triflate
(AgCF<sub>3</sub>SO<sub>3</sub>) in benzene, a sheet structure
of composition
[Ag(<b>1</b>)CF<sub>3</sub>SO<sub>3</sub>]C<sub>6</sub>H<sub>6</sub>
(<b>2</b>) forms in which silver(I) is five-coordinate and
bonds to two nitrogen atoms of distinct 3,3‘-DCPA
molecules,
another silver(I) ion, and two oxygen atoms of the triflate ions.
Changing the solvent to toluene produces an
undulating sheet structure of composition
[Ag<sub>2</sub>(<b>1</b>)(CF<sub>3</sub>SO<sub>3</sub>)<sub>2</sub>]
(<b>3</b>) in which silver(I) is six-coordinate, bonding
to
a ligand nitrogen atom, to four oxygen atoms of bridging triflate ions,
and to a neighboring silver(I) ion. In both
triflate structures, 3,3‘-DCPA adopts a <i>transoid</i>
conformation with respect to the positioning of the nitrile
groups.
With silver(I) hexafluorophosphate (AgPF<sub>6</sub>),
silver(I) hexafluoroarsenate (AgAsF<sub>6</sub>), or
silver(I) hexafluoroantimonate (AgSbF<sub>6</sub>), 2-fold interpenetrated sheet structures
[Ag(<b>1</b>)<sub>2</sub>]<i>X</i>F<sub>6</sub>
(<i>X</i> = P (<b>4</b>), As (<b>5</b>), or Sb
(<b>6</b>)) are obtained
in which 3,3‘-DCPA coordinates to tetrahedral silver(I) ions in a
<i>cisoid</i> conformation. In spite of the large
difference
in counterion size, minimal network deformation is observed among these
systems. Interestingly, with silver(I)
perchlorate hydrate (AgClO<sub>4</sub>·<i>x</i>H<sub>2</sub>O,
<i>x</i> ∼ 1), 3,3‘-DCPA coordinates in a <i>transoid</i>
conformation to tetrahedral
silver(I) ions to form the 8-fold interpenetrated diamondoid
network
[Ag(<b>1</b>)<sub>2</sub>]ClO<sub>4</sub>·H<sub>2</sub>O
(<b>7</b>). An analysis of the
packing of these networks is provided, and the results are compared to
complementary systems previously reported
from our study of coordination networks of dinitriles and
silver(I) salts.