xxiii πανελληνιο ÏƒÏ Î½ÎµÎ´ÏÎ¹Î¿ Ï†Ï ÏƒÎ¹ÎºÎ·Ï‚ στερεας καταστασης & επιστημης ...

Crystal Structure of a new Supramolecular Copper(I) complex (μ-isothiocyanato)-(2-
pyridinecarboxaldehydebenzoylhydrazonato)Copper(I)
Paschalidis Damianos G. 1 , Batistakis Chrysostomos 2 , Gan Yu 3 , Cardin Christine J. 3 , Kavounis A. Constantinos 2*
1 Aristoteles University of Thessaloniki, Chemistry Department 54124 Thessaloniki Greece
2 Aristoteles University of Thessaloniki School of Science, Physics Department 54 124 Thessaloniki Greece
3 School of Chemistry University of Reading Whiteknights Reading RG6 6AD England
Abstract
In the present work we report the crystal structure of the new supramolecular compound (μ-isothiocyanato)-(2-
pyridinecarboxaldehydebenzoylhydrazonato)Copper(I). Crystals of the complex are monoclinic, space group P 2 1 /n and cell
constants a = 8.8370(10) Å, b = 15.625(2) Å, c = 10.3660(10) Å, β = 103.362(12) o and Z = 4. The copper atom is fivecoordinated
in distorted tetragonal pyramidal arrangement. Thiocyanato and isothiocyanato ligands are bridging to the Cu(II)
atoms forming an infinite one dimension chain.
Introduction
The research in supramolecular complexes has been rapidly expanding [1]. One aspect is their fascinating structural
diversity. Another aspect is their potential applications as functional materials in catalysis and magnetism. As part of our
work on hydrazone complexes we report here the crystal structure of a new copper –hydrazone supramolecular complex.
Experimental
Single crystals of copper complex were prepared by placing a 0.5M solution of copper (I) chloride and 1 M
ammoniunm thiocyanate in one arm of a narrow U-tube and an ethanolic 0.5M solution of picolinaldehyde benzoylhydrazone
and 0.5 M tetrabutylammonium hydroxide in the other arm. Suitable crystals with well formed faces appeared after few
hours.
Results and discussion
The presence of a NCS-Cu bridge that connects the crystallographic asymmetric unit to its adjacent forming a
continuous chain through the whole crystal. This is caused by the bidentate ligand NCS which is N-bonded to the metal ion
Cu. The copper atom is five-coordinated in distorted tetragonal pyramidal arrangement. As shown by the clinographic
projection of Fig. 1, the Cu environment involves three nitrogen atoms and an oxygen atom at the base and a sulfur atom in
apical position. Four of the atoms of the base of the pyramid namely the O, Cu, N2 and N3 form a very good least squares
plane from which the N4 deviates by 0.5988(0.0030) Ǻ and the S atom is in the apex at a distance of 2.8465(0.0012) Ǻ . If
we consider the plane formed by the four atoms N2, N3, N4 and O then the Cu atom deviates from their plane by
0.2075(0.0008) Ǻ towards the apex. The two five membered rings involving Cu [Cu, O, C7, N1,N2 and Cu,N3, C9, C8, N2]
form a dihedral angle of 2.44 degrees and the latter of these form a dihedral angle with the pyridine ring to which is attached
of 1.10 degrees. The six-membered ring formed by the atoms C1, C2, C3, C4, C5 and C6 forms a dihedral angle of 3.31
degrees with the three rings plane of the rest molecule. The whole hydrazone molecule forms a least squares plane with an
rms deviation of fitted atoms of 0.0398 Ǻ , from which the N4 atom deviates by 0.6969(0.0024) Ǻ and the S atom is
2.8000(0.0012) Ǻ away.
Table 1. Crystallographic Data
Formula
C 14 H 10 Cu N 4 O S
Fw 345.86
Crystal system
monoclinic
space group P 2 1 /n
a (Å) 8.8370(10)
b (Å) 15.625(2)
c (Å) 10.3660(10)
α (deg) 90.00
β (deg) 103.362(12)
γ (deg) 90.00
V (Å 3 ) 1392.6(3)
Z 4
T (°C) 20
λ (Å) 0.70930
ρ calcd (g cm -3 ) 1.650
R1 0.0291
wR2 0.0745
number of reflns collected 8755
number of inepednent reflns 3048
number of observed reflns
2392 [I>2σ(I)]
θ
2.40