2339
S[ Pal et al[
full matrix least!square re_nement coverged at R to
Synthesis of the complexes
9[942[ Crystallographic data and additional details
ðNi"DSALPTP#Ł"0#] A solution of NiCl1[5H1O regarding data collected and re_nement are given in
"9[13 g\ 0 mmol# or Ni"ClO3#1[5H1O "9[22 g\ 0 mmol# Table 0[
in methanol "19 cm2# was added to a stirring solution
of the ligand "9[38 g\ 0 mmol# in chloroform "19 cm2#
Structure description
and the mixture was stirred for 0 h[ A few drops of
5"N# NH2 was then added to the mixture[ The mixture
The compound ðNi"DSALPTX#Ł crystallises in the
was further stirred for 37 h[ Red precipitate separated
P101010 space group with four molecules in general
out which was recrystallised from methanol "yields]
position[ The ligand binds the Ni"II# acceptor centre
64)#[
in a distorted octahedral pattern[ The square base of
ðNi"DSALPTX#Ł "1#] This complex was prepared
the octahedron is de_ned by the O"A#\ S"B#\ S"A# and
by the same procedure as above by taking NiCl1[5H1O
O"B# atoms with two nitrogen N"A# and N"B# in the
"9[13 g\ 0 mmol# as the starting metal salt and
two apical positions[ Selected bond lengths and bond
H1DSALPTX "9[45 g\ 0 mmol# as the ligand\ with a
angles are given in Table 1 and a few selected torsion
few drops of 5"N# NH2[ The complex was recrys!
angles are listed in Table 2[ The two phenolate oxygen
tallised from methanol with an yield of about 69)[
and thioether sulphur donors occupy cis!positions of
Ni"ClO3#1[5H1O readily reacts with the ligand in the
the distorted square plane de_ned by O"A#ÐO"B#Ð
same ratio in absence of NH2 to give the same orange!
S"A# and S"B# with the Ni"II# ion centrally placed on
red product[ It was recrystallised from methanol "yield
it with a mean deviation of −9[901"1#A[ The bite
64)#[
Physical measurements
Table 0[ Crystal data and structure re_nement for ðNi"D!
Physical measurements were done as reported in
our earlier communications ð0\ 1Ł[ Electrochemical
SALPTX#Ł "1#
data were collected with a BAS CV!16 and a BAS
model X!Y recorder at 187 K[ The electrodes used
were ~at platinum disc working electrode\ Pt wire Formula weight
Identi_cation code
Empirical formula
"1#
C23H15N1NiO1S1
506[39
Temperature
Wavelength
Crystal system
Space group
Unit cell dimensions
182"1# K
0[43076 A
Orthorhombic
P101010
a ꢁ 02[9749"09# A
a ꢁ 89>
auxiliary electrode and a Ag:AgCl reference electrode[
Crystal structure determination of ðNi"DSALPTX#Ł "1#
Ä
X!ray data were collected in Enraf!Nonius!CAD!3
di}ractometer for a crystal mounted on top of a glass
_bre[ The unit cell parameters were determined from
a least!square re_nement of 06 high angle re~ections[
Ä
b ꢁ 03[0049"09# A
b ꢁ 89>
c ꢁ 04[141"2# A
Ä
g ꢁ 89>
1706[9"5# A
2
Ä
The three intensity controlled re~ections "!2 0!1\ 2!0! Volume
Z
3
1\ !3!2!3# checked every hour\ showed no signi_cant
variations "29[4)#[ The intensities were corrected for
Lorentz!polarisation e}ects and an empirical absorp!
tion correction was also made ð7Ł[ A total of 2149
unique re~ections measured contained 2007 with
Fo − 3s"Fo#[ The structure was solved by direct
methods using the program\ SHELXS!75 ð8Ł which
revealed the positions of all the non!hydrogen atoms[
The program SHELXL!82 ð09Ł was used to re_ne the
Density "calculated#
Absorption coe.cient
F"999#
0[345 gm:cm2
1[548 mm−0
0179
Crystal size
9[19×9[19×9[14 mm
3[16 to 63[80>
Theta range for
data collection
Index ranges
9 ¾ h ¾ 05\ 9 ¾ k ¾ 06\
9 ¾ l ¾ 08
2149
Re~ections collected
structure[ Re_nement on F using anisotropic dis! Unique re~ections
2149
2007
Fo − 3s"Fo#
placement parameters for all non!hydrogen atoms was
performed[ Positions of 00 hydrogen atoms were
located from the di}erence Fourier map[ The other
03 residual hydrogen atoms were placed in their cal!
culated positions with a temperature factor 0[1 times
the Ueq[ of the parent atom to which it is attached[
Coordinates of the 00 hydrogen atoms and their iso!
tropic temperature factors were re_ned[ Figure 0
shows thermal ellipsoid of the molecule\ excluding the
hydrogen atoms for the clarity of the _gure[ The _nal
Re_nement method
Full!matrix least!squares
on F
2149:9:304
9[181
Data:restraints:parameters
Goodness!of!_t on Fo
Final R indices
R ꢁ 9[9416
ðFo × 1s"Fo#Ł
R indices "all data#
Extinction coe.cient
Largest di}[ peak and hole
R ꢁ 9[9432
9[9907"2#
0[912 and −9[588 e[ Aý−2
Pal, Shefali
