Document Type

Article

Publication Date

Winter 1-2014

Abstract

Aqueous reactions of copper(I) cyanide with 1-phenylpiperazine (PhPip) in the presence of KCN produce network compounds having CuCN:PhPip stoichiometries of 1:1, 3:2, and 4:1 depending on the mixing ratio used. In addition to these phases, hydrothermal synthesis yields a 5:3 network. Crystal structures of these four compounds are reported herein. The (CuCN)(PhPip) network (1) forms sheets consisting of Cu centers that coordinate all PhPip via N-H only, and are linked together by mu(3)-cyano bridges. The (CuCN)(3)(PhPip)(2) network (2) exists as a series of dual-chain ladders. All Cu centers are 3-coordinate and half of the PhPip ligands bridge pairs of chains using both N-H and N-Ph, while the other PhPip are only N-H bound. The (CuCN)(5)(PhPip)(3) network (3) forms three independent sets of 1D chains: 2[(CuCN)(PhPip)]center dot(CuCN)(3)(PhPip). Both 2- and 3-coordinate copper atoms are present and all PhPip ligands bond only through N-H. The (CuCN)(4)(PhPip) network (4) forms identical, but orthogonal, interpenetrating sheets consisting of 2- and 3-coordinate CuCN chains linked by bridging PhPip ligands. Pairwise cuprophilic interactions are seen in the 5:3 and 4:1 networks. The 3:2 compound shows visible photoluminescence associated with Cu-CN MLCT. Compound 1 crystallizes in the monoclinic P2(1)/c space group with cell parameters: a = 17.6123(3) , b = 6.89480(10) , c = 8.6154(2) , beta = 96.1460(10), V = 1040.18(3) (3), and Z = 4. Compound 2 crystallizes in the triclinic P - 1 space group with cell parameters: a = 9.93710(10) , b = 10.6359(2) , c = 12.1230(2) , alpha = 105.7110(10), beta = 100.6110(10), gamma = 97.7230(10), V = 1189.11(3) (3), and Z = 2. Compound 3 crystallizes in the monoclinic P2(1)/n space group with cell parameters: a = 15.9018(2) , b = 9.38850(10) , c = 26.1864(3) , beta = 104.5110(10), V = 3784.76(8) (3), and Z = 4. Compound 4 crystallizes in the monoclinic P2(1) space group with cell parameters: a = 13.4773(3) , b = 7.8460(2) , c = 8.5527(2) , beta = 105.1820(10), V = 872.82(4) (3), and Z = 2.

Journal Title

Journal of Chemical Crystallography

DOI

10.1007/s10870-013-0482-2

Volume

44

Issue

1

Journal Article URL

https://link.springer.com/article/10.1007%2Fs10870-013-0482-2

First Page

42

Publisher Statement

This is a post-peer-review, pre-copyedit version of an article published in the Journal of Chemical Crystallography. The final authenticated version is available online at: http://dx.doi.org/10.1007/s10870-013-0482-2.

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