Structural Control of Copper(I) Coordination Polymers: Construction of One-, Two-, and Three-Dimensional Frameworks of Tetrahedral Copper(I) Ions Bridged by Dicyanobenzene Derivatives

With the use of three dicyanobenzene derivatives as bridging
ligands, four copper(I) coordination polymers,
[Cu(dchq)2](ClO4)(Me2CO)2
(1; dchq = 1,2-dicyanohydroquinone),
[Cu(ipn)2](PF6)(Me2CO)
(2; ipn = 1,3-dicyanobenzene), and
[Cu(dmtpn)2](X)(dmtpn)(THF)
(3a (X = BF4), 3b (X =
ClO4); dmtpn = 2,5-dimethylterephthalonitrile) were synthesized and characterized.
Single-crystal X-ray analyses revealed that all
copper(I) ions in these complexes have tetrahedral geometry and
are coordinated by four ligands which also
coordinate to the next copper ions, resulting in the formation of
coordination polymer compounds. The polymer
framework of 1 consists of one-dimensional chains that run
along the a-axis direction and weakly interact
with
each other through π−π interactions between the dchq molecules
and through hydrogen bonding. 2 has a two-dimensional sheet with a square arrangement of copper(I) ions.
Stacking of the square lattice in the c-axis
direction
forms cavities in which the acetone molecules and
PF6- anions are incorporated. Both
3a and 3b are isostructural
and have triply interpenetrated three-dimensional diamond-like
frameworks with π−π stacking columns of
alternately coordinated and uncoordinated dmtpn molecules. It is
demonstrated that the dimensionality of the
polymer structures can be successfully controlled by the relative
positions of two CN groups in the bridging
ligands. Crystallographic data are as follows.
1: 
C22H20CuClN4O10,
monoclinic, C2/c, a = 19.514(2)
Å, b =
10.526(2) Å, c = 12.276(1) Å, β =
96.839(8)°, Z = 4. 2: 
C19H14CuF6N4OP,
orthorhombic, P212121,
a = 12.743(2) Å, b = 15.026(3) Å, c =
11.362(2) Å, Z = 4. 3a: 
C34H32BCuF4N6O,
monoclinic, Cc, a = 9.599(3) Å, b
=
27.298(5) Å, c = 13.367(3) Å, β =
105.45(2)°, Z = 4. 3b: 
C34H32ClCuN6O5,
monoclinic, Cc, a = 9.590(7)
Å,
b = 27.429(3) Å, c = 13.416(4) Å,
β = 105.80(3)°, Z = 4.