3031
Chaoyang Dai et al[
ernary\ N\N?!dialkyl species formed by reaction H\ 2[69^ N\ 3[79[ Some loss of solvent of crystallisation
between either bipy or phen and 0\1!dibromoethane occurred accounting for the poor quality analytical
ð6Ł[
Also interesting is the colour of these two
data[ UV!VIS "CH1Cl1#\ 498[7 nm\ o9ꢁ15[
Compound 2 was prepared in an analogous manner
complexes[ All of the mono and bis!picoline adducts and in similar yield using 1\1?!bipyridyl in place of
of 0 and 1 described in Refs[ ð2\ 3Ł are colourless or 0\09!phenanthroline[ X!ray crystallography revealed
very pale yellow in contrast to the red colours seen the presence of CH1Cl1 of crystallisation[
here[ These are presumably charge!transfer tran! C11H05N1B1S3=CH1Cl1 requires C\ 49[89^ H\ 2[24^ N\
sitions from _lled orbitals in the B1"thiocat#1 unit to 4[04)[ Found] C\ 49[54^ H\ 2[04^ N\ 4[94[ The pale
empty pꢀ!orbitals of the bipy or phen ligands[ That the red colour of solutions of 2 in CH1Cl1 were not of a
colours persist in solution indicates that association su.cient intensity to obtain satisfactory solution UV!
between 1 and either bipy or phen is present in solution VIS data[
as well as in the solid state although we were not able
to con_rm this by 0H or 00B NMR studies owing to CHCl2 rather than CH1Cl1[ Analytical data were con!
the very poor solubility of both 2 and 3[ sistent with a 0]0 adduct of 0 and 0\09!phenanthroline
Compound 4 was also prepared similarly but using
As a _nal point\ we note that 0 also forms a red with one molecule of CHCl2 of crystallisation present[
solution in CHCl2 when one equivalent of 0\09!phen! C13H05N1B1O3=CHCl2 requires C\ 44[89^ H 2[19^ N\
anthroline is added\ with red crystals being isolated 4[19)[ Found] C\ 44[94^ H\ 2[99^ N\ 3[34[ UV!VIS
after work!up[ On the basis of the colour of the solu! "CH1Cl1#\ lꢁ314[9 nm\ o9ꢁ439[
tion and solid\ a similar structure to 3 is likely but since
It is important that the 1\1?!bipyridyl and 0\09!
the crystals were not of X!ray quality\ any structural phenanthroline used in these reactions is dry and that
formulation must remain tentative although ana! none of the hydrates are present[ Any traces of water
lytical data were consistent with the formation of a lead to extensive decomposition products\ one of
0]0 adduct albeit as a CHCl2 solvate[
which\ in the reaction which a}orded 4\ was identi_ed
by
X!ray
crystallography
as
the
salt
ðphenHŁ¦ðB"cat#1Ł− ð7Ł[
EXPERIMENTAL
General procedures
X!ray crystallo`raphy
All reactions were performed using standard Sch!
lenk techniques under an atmosphere of dry\ oxygen!
free dinitrogen[ All solvents were distilled from appro!
priate drying agents immediately prior to use "sodium
for toluene and hexanes and CaH1 for CH1Cl1#[
Microanalytical data were obtained at the University
of Bristol and UV!visible spectra were obtained on a
Perkin!Elmer Lambda 1 spectrophotometer[
Compounds 0 and 1 were prepared by the literature
methods ð4Ł[ 1\1?!bipyridyl and 0\09!phenanthroline
were procured commercially but were dried by azeo!
tropic distillation of toluene in a Dean and Stark
apparatus before use[
Crystal data for 2 = CH1Cl1 C12H07B1Cl1N1S3\
Mꢁ432[04\ orthorhombic\ aꢁ05[717"2#\
2
Ä
Ä
bꢁ03[442"2#\ cꢁ19[958"3# A\ Uꢁ3803[8"06# A \
Tꢁ119"0# K\ space group Pna10 "No[ 22#\ Zꢁ7\
mꢁ9[51 mm−0
\ 2951 re~ections measured\ 1364
unique "Rintꢁ9[9869#[ Final R0ꢁ9[9729 for 0738
re~ections I×1s"I#[
X!ray di}raction measurements were made on a
single crystal mounted on a glass _bre with graphite!
Ä
¹
monochromated Mo!Ka X!radiation "lꢁ9[60962 A#
using a Rigaku AFC6S di}ractometer[ Unit cell con!
stants and an orientation matrix were obtained from
a least!squares re_nement using the setting angles of
07 carefully centred re~ections in the range
6[20>³u³00[38>[ Intensity data were collected using
the vÐ1u scan technique[ Azimuthal scans of several
Preparations
ðB1"thiocat#1"phen#Ł "3# A solution of dried 0\09! re~ections indicated no need for an absorption cor!
phenanthroline "9[918 g\ 9[05 mmol# in CH1Cl1 "1 cm2# rection[ Data were integrated using teXsan ð8Ł and
was added to a stirred solution of 1 "9[949 g\ were corrected for Lorentz and polarisation e}ects[
9[05 mmol# in CH1Cl1 "1 cm2# resulting in the immedi! Intensities were weak and collected to only uꢁ19[15>[
ate formation of a red solution[ Addition of an over! The structure was solved by direct methods and
layer of toluene "2 cm2#\ cooling to −29>C and re_ned by full!matrix least squares against F1 for all
subsequent solvent di}usion over a period of two days data with I×−2s"I#[ The structure was solved and
a}orded 3 as dark red "almost black# crystals which re_ned in the acentric space group Pna10 with two
were then washed with hexane "1×1 cm2# "9[978 g\ molecules of 2 and two dichloromethane solvent mol!
73)#[ One of these crystals was used for X!ray crys! ecules per asymmetric unit[ There appears to be a local
tallography which revealed the presence of one mol! pseudo inversion centre between the molecules of 2
ecule of CH1Cl1 and one molecule of toluene per although this does not hold for the solvent molecules
molecule of 3[ C13H05N1B1S3=CH1Cl1=C5H4CH2 and is not a true inversion centre[ Chlorine\ sulphur
requires C\ 47[29^ H\ 3[99^ N\ 3[19)[ Found] C\ 45[09^ and nitrogen atoms were re_ned anisotropically and
Dai, Chaoyang
