443
F[A[ Mautner\ M[A[S[ Goher : Polyhedron 07 "0888# 442Ð448
1[0[ Preparation of complexes
about 49 mW[ Electronic spectra of complexes were
obtained for solids mulled in Nujol using a Varian Cary!
4 double beam spectrophotometer[ The emission spectra
of the solid samples were obtained using a Aminco Bow!
man 1 apparatus[ The apparatus was calibrated for solid
sample measurements by using an authentic compound[
The experimental procedures and instruments used for
other measurements are as described previously ð8Ł[
CuI"3!Bzpy#] this complex was prepared by mixing
Cu"NO2#1 = 2H1O and 3!Bzpy in a 0]5 molar ratio in ace!
tone followed by addition of L"¦#!ascorbic acid with
several drops of water[ Upon addition of KI "0]0 molar
ratio with respect to copper# dissolved in the least amount
of water some yellow 0]0 complex was precipitated[ The
_nal heterogeneous mixture was boiled for ca[ 19 min\
and then _ltered[ The red _ltrate was allowed to stand
over night to deposit red needles!like crystals of the
complex[
1[4[ X!ray crystal structure analysis
A modi_ed STOE four circle di}ractometer was used
for single crystal X!ray measurements[ Orientation
matrix and lattice parameters were obtained by least!
squares re_nement of the di}raction data[ Data were
collected at 187"1# K\ using graphite crystalÐmono!chro!
1[1[ ð"3!bezoylpyridine#1HŁ = I "0#
Upon addition of an aqueous solution of KI to an
aqueous solution of Cu"NO2#1 = 2H1O in the presence of
L"¦#!ascorbic acid a white precipitate of copper"I# iodide
if formed[ Solid KI was then added until a clear solution
was obtained[ To this solution\ an excess amount of 3!
Bzpy "four folds with respect to copper# in acetone was
added upon which the solution turns yellow[ This solu!
tion was allowed to stand in a test tube[ After several
days a colorless solid of the organic ligand was obtained
and _ltered o}[ The _ltrate was allowed to stand over two
more days to deposite yellow crystals of the compound[
Ä
matized MoKa radiation "lꢁ9[60958 A# and the v!scan
technique[ The intensities were corrected for Lorentz!
polarization e}ects and for absorption[ Crystallographic
data are given in Table 1[
The structure was solved by direct methods and sub!
sequent Fourier analysis[ Anisotropic displacement par!
ameters were applied to nonhydrogen atoms in full!
matrix least!squares re_nements based on F1[ The hydro!
gen atoms were assigned with common isotropic dis!
placement factors and included in the _nal re_nement
cycles by use of geometrical restraints[ Analytical
expressions of neutral atom scattering factors were
employed and anomalous dispersion corrections were
incorporated[ The program DIFABS ð09Ł and the
SHELXT:PC ð00Ł program package were used for com!
putations[ Selected bond distances and bond angles are
given in Table 3[ Additional material consisting of frac!
tional atomic coordinates\ displacement parameters\
observed and calculated structure factors and a complete
lists of bond distances and angles has been deposited with
the Editor[
1[2[ CuX"2!Bzpy#\ XꢀCl\ Br\ I\ CN and SCN
These complexes were prepared by one of the following
general procedures
0[ An aqueous solution of Cu"NO2#1 = 2H1O "3 mmol#
was mixed with KX or NaX\ followed by the addition
of L"¦#!ascorbic acid[ An ethanolic solution of the 2!
benzoylpyridine ligand "09 mmol# was then added and
the mixture stirred for ca 04 min[ The _nal mixture
was allowed to stand over several hours or days until
a crystalline product separated[
1[ A boiled ethanolic solution of 2!benzoylpyridine
"09 mmol# was mixed with Cu"NO2#1 = 2H1O "3 mmol#
in ethanol and the subsequent addition of L"¦#!asc!
orbic acid resulted in a clear yellow to orange solution[
To this solution an aqueous solution of KX was added
dropwise and the mixture was boiled for several
minutes and allowed to stand over several hours to
produce the complex[
2[ Results and discussion
The results of the preparation of the complexes given
in Table 0 suggest that 2!benzoylpyridine behaves very
similar to ethyl nicotinate ð01Ł and forms only 0]0 com!
plexes with CuX\ for XꢁCl\ Br\ I\ CN and SCN\ whereas
the copper"I# perchlorate\ nitrate and azide complexes
are too easily oxidized to be isolated[ In a previous paper
we reported that 3!benzoylpyridine forms 0]0 complexes
with copper"I# halides and pseudohalides and 0]1 with
the nitrate and perchlorate\ and described the crystal
structure of the 0]0 chloride complex ð8Ł[ However\ when
we tried to prepare crystals suitable for X!ray di}raction
of the corresponding yellow 0]0 copper"I# iodide complex
we isolated a new red complex formulated as Cu"3!
Bzpy#I\ in addition to a yellow crystalline compound
formulated as ð"3!benzoylpyridine#1HŁ I[
Elemental analysis results of the isolated complexes are
given in Table 0[
1[3[ Physical measurements
The IR spectra of solid samples were measured as KBr
pellets using a Bruker FTIR spectrophotometer[ Raman
spectra were obtained using a Perkin!Elmer System 1999
NIR FT!Raman spectrometer[ The laser power was
Mautner, Franz A.
