Synthesis and characterization of adducts of bis(O,O′-ditolyl/dibenzyl dithiophosphato)cobalt(II) with pyridine: Crystal structures of [Co{S2P(OC6H4Me-p)2}2(C5H5N)2] a

Article abstract of DOI:10.1016/j.poly.2008.09.025

Bis(O,O′-ditolyl/dibenzyl dithiophosphato)cobalt(II) complexes with pyridine ligands of the type [Co{S₂P(OR)₂}₂(C₅H₅N)₂] (R = o-, m-, p-C₆H₄Me, CH₂Ph) have

Full text of DOI:10.1016/j.poly.2008.09.025

Polyhedron 28 (2009) 85–90
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Polyhedron
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Synthesis and characterization of adducts of bis(O,O0-ditolyl/dibenzyl
dithiophosphato)cobalt(II) with pyridine: Crystal structures of
[Co{S2P(OC6H4Me-p)2}2(C5H5N)2] and [Co{S2P(OC6H4Me-p)2}2(NH3)]
Subhash C. Bajia a, John E. Drake b, Mark E. Light c, Manisha Nirwan a, Sushil K. Pandey d, Raju Ratnani a,
*
a Department of Pure and Applied Chemistry, M.D.S. University, Jaipur Road, Ajmer 305 009, Rajasthan, India
b Department of Chemistry and Biochemistry, University of Windsor, Windsor, Ont., Canada N9B 3P4
c Department of Chemistry, University of Southampton, Highfield, Southampton SO17 1BJ, UK
d Department of Chemistry, Jammu University, Jammu 180 006, India
a r t i c l e i n f o
a b s t r a c t
Bis(O,O0-ditolyl/dibenzyl dithiophosphato)cobalt(II) complexes with pyridine ligands of the type
[Co{S2P(OR)2}2(C5H5N)2] (R = o-, m-, p-C6H4Me, CH2Ph) have been synthesized by the reaction of
CoCl2(C5H5N)2 and the corresponding ammonium salt of O,O0-ditolyl/dibenzyl dithiophosphate in meth-
anol. These newly synthesized adducts were characterized by elemental analysis, IR, UV–Vis spectros-
copy, magnetic susceptibility measurements and single crystal X-ray diffraction. These structures
confirm that in the pyridine complex the geometry around the cobalt metal centre is distorted octahedral,
and in the amine complex it is distorted trigonal bipyramidal.
Article history:
Received 24 July 2008
Accepted 29 September 2008
Available online 17 November 2008
Keywords:
Cobalt(II) complexes
O,O0-Ditolyl/dibenzyl dithiophosphates
Nitrogen base adducts
Crystal structures
Ó 2008 Elsevier Ltd. All rights reserved.
1. Introduction
(O,O0-ditolyl/dibenzyl dithiophosphato)cobalt(II) complexes and a
bis(O,O0-dibenzyl dithiophosphato)cobalt(II) complex. We also re-
The 1,1-dithiolate ligands, viz. O,O0-dialkyl/alkylene dithiophos-
phates, are versatile in nature and coordination complexes with
cobalt have been reported in the literature [1–13]. In these com-
plexes, the dithiophosphate ligand moieties are normally biden-
tate. X-ray crystal structures have been reported for a number of
cobalt compounds with O,O0-dialkyl dithiophosphates including
Co[S2P(OMe)2]3 [14], Co[S2P(i-OPr)2]3 [15], [Co{S2P(OMe)2}2 ꢀ PPh3]
[16], [NMe4][CoCl{S2P(OMe)2}2] [17], Co[S2P(OEt)2]3 ꢀ 1/2H2O [18],
[Co{S2P(OEt)2}2(C5H5N)2] [19], [Co{S2P(OCy)2}2(C5H5N)2] [20] and
[Co{S2P(OEt)2}2(C24H26O2N4)] [21]. Reports on metal complexes
containing O,O0-ditolyl dithiophosphate ligands are relatively few
[22–24]. Recently, we have used O,O0-ditolyl/dibenzyl dithiophos-
phate to examine the influence of bulkier groups on phosphorus
and have reported the syntheses, spectroscopic studies and single
crystal X-ray structures of Ni[S2P(OC6H4CH3-o)2]2 [25], Ni[S2P(OC6
H4CH3-m)2]2 [25], Ni[S2P(OCH2Ph)2]2 [25], [Ni{S2P(OC6H4Me-p)2}2
(N2C10H8)] [26], [Ni{S2P(OC6H4Me-o)2}2(N2C14H12)] ꢀ C6H6 [26]
Me2Sn[S2P(OC6H4Me-o)2]2 [27], Bu2Sn[S2P(OC6H4Me-o)2]2 [27],
Mo2O3[S2P(OC6H4Me-o)2]4 [28], Mo2O3[S2P(OC6H4Me-m)2]4 [28]
and MoO2[S2P(OC6H4Me-p)2]2 [28].
port the single crystal X-ray structures of [Co{S2P(OC6H4Me-
p)2}2(C5H5N)2] and [Co{S2P(OC6H4Me-p)2}2(NH3)].
2. Results and discussion
The reactions of cobalt chloride hexahydrate with ammonium
salts of O,O0- ditolyl dithiophosphates in a 1:2 molar ratio were car-
ried out in methanol. Initially a blue solution of bis(O,O0-ditolyl
dithiophosphato)cobalt(II) was obtained, which soon turned green,
indicating oxidation of Co(II) to Co(III), and finally turned brown.
Various methods were adopted to avoid decomposition, such as
carrying out the reaction in a foil wrapped flask at low temperature,
but all failed, with the solid obtained slowly decomposing into a
brown solid. Attempts were also made to avoid oxidation by carry-
ing out the reactions with CoCl2 ꢀ 6H2O and the sodium salts of the
O,O0-ditolyl dithiophosphates, but these again yielded the oxidized
brown solids. However, the oxidation reactions were comparatively
slow as compared to when the ammonium salts were used. Reac-
tions were also carried out at lower temperature (5 °C), which again
yielded cobalt(III) complexes. However, in one of these attempts
plate-like blue crystals of [Co{S2P(OC6H4Me-p)2}2(NH3)] were iso-
lated, which were relatively stable.
In continuation of this interest, we report here the synthesis,
and spectroscopic characterization of pyridine adducts of bis
An indirect method was used to prepare adducts of bis(O,O0-
ditolyl dithiophosphato)cobalt(II) with pyridine, This route readily
* Corresponding author. Tel.: +91 11 145 2640059.
E-mail address: ratnaniraju@yahoo.co.uk (R. Ratnani).
0277-5387/$ - see front matter Ó 2008 Elsevier Ltd. All rights reserved.
doi:10.1016/j.poly.2008.09.025

86
S.C. Bajia et al. / Polyhedron 28 (2009) 85–90
produced the expected compounds in good yields. Initially, the
blue solid bispyridine cobalt(II) chloride was prepared and then a
stoichiometric amount of ligand was added in situ, to give the pur-
ple pyridine adducts of the (O,O0-ditolyldithiophosphato)cobalt(II)
complexes.
tions of the aromatic ring, indicating the presence of the nitrogen
base donors in the adducts.
2.2. Electronic absorption spectra
The electronic spectra of the pyridine adducts of the bis(O,O0-
ditolyl/dibenzyl dithiophosphato)cobalt(II) complexes and the
bis(O,O0-dibenzyl dithiophosphato)cobalt(II) complex were carried
out in pyridine and CH2Cl2 solvents, respectively. The electronic
CoCl2 ꢀ 6H2O þ 2C5H5N ! CoCl2ðC5H5NÞ2
CoCl2ðC5H5NÞ2 þ 2NH4S2PðORÞ2 ! ½CofS2PðORÞ2g2ðC5H5NÞ2ꢁ
ðR ¼ oꢂ; mꢂ; p ꢂ C6H4Me;CH2PhÞ
spectra suggest
a tetrahedral configuration for [Co{S2P(OCH2
However, the cobalt(II) complex with dibenzyl dithiophosphate
was prepared by the one step stoichiometric reaction of cobalt
chloride hexahydrate with the ammonium salt of dibenzyl dithio-
phosphate in methanol on stirring at room temperature to give a
blue solid product in good yield. This blue solid, on further reaction
with pyridine, gave a purple coloured adduct.
Ph)2}2] which is supported by the presence of a strong absorption
4
band at 613 nm [2]. This band is caused by the 4A2 ! T1ðFÞ tran-
sition whereas, the band at 579 nm is due to the 4A2 ! 4T1ðPÞ tran-
sition. Splitting is also observed in the main band at 613 nm due to
spin–orbital coupling.
In the case of the octahedral adducts, the peaks corresponding
4
4
4
4
4
to the transitions T1gðFÞ ! T1gðPÞ, T1gðFÞ ! A2gðFÞ and T1g
CoCl2 ꢀ 6H2O þ 2NH4S2PðOCH2PhÞ2 ! ½CofS2PðOCH2PhÞ2g2ꢁ
½CofS2PðOCH2PhÞ2g2ꢁ þ 2C5H5N ! ½CofS2PðOCH2PhÞ2g2ðC5H5NÞ2ꢁ
4
ðFÞ ! T2gðFÞ are seen in the ranges 500–524, 574–746 and
1026–1138 nm, respectively. Almost identical electronic transi-
tions for the pyridine adducts of bis(diethyldithiocarbamato)
cobalt(II) [30] and benzathiazole and benzimidazole adducts of
bis(diethyldithiophosphato)cobalt(II) [9] were observed, indicating
an octahedral coordination.
In the case of the O,O0-dibenzyl dithiophosphate cobalt(II) com-
plex, the decomposition rate to the brown coloured cobalt(III)
complex is quite slow, giving enough time to isolate the tetrahe-
dral blue coloured cobalt(II) complex at room temperature. The
fact that the oxidation rate for the bis(O,O0-ditolyl dithiophosph-
ato)cobalt(II) complexes is comparatively fast is probably because
of the electron withdrawing effect due to the conjugation of the to-
lyl moiety which makes the phosphorous have a lower electron
density and in turn withdraw electrons from the sulfur, giving rise
to weaker bonding between the Co and S atoms, which aids the
oxidation of Co(II) to Co(III). This conjugation effect is absent for
the dibenzyl derivative.
2.3. Magnetic measurements
The conclusion about the tetrahedral and octahedral coordina-
tion in the complexes is further supported by the magnetic mo-
ment for [Co{S2P(OCH2Ph)2}2] of 4.34 B.M., as compared with
those of the pyridine adducts which range from 4.87 to 5.0 B.M.
All these pyridine adducts of the bis(O,O0-ditolyl/dibenzyl dith-
iophosphato)cobalt(II) complexes are soluble in common organic
solvents such as benzene, chloroform and acetone. The products
were characterized by elemental analysis, IR, UV–Vis spectroscopy
and magnetic susceptibility measurements, along with the X-ray
crystal structure determination of [Co{S2P(OC6H4Me-p)2}2(C5H5N)2]
and [Co{S2P(OC6H4Me-p)2}2(NH3)].
2.4. Crystal Structures of [Co{S2P(OC6H4Me-p)2}2(C5H5N)2] and
[Co{S2P(OC6H4Me-p)2}2(NH3)]
[Co{S2P(OC6H4Me-p)2}2(C5H5N)2] (3) and [Co{S2P(OC6H4Me-
p)2}2(NH3)] (6) crystallize in the monoclinic space groups P21/c
(centrosymmetric) and P21/n, respectively. The ORTEP diagram of
the molecular structure of 3 in Fig. 1 displays a distorted octahe-
dral geometry with the pyridine molecules occupying trans posi-
tions. In contrast, the ORTEP diagram of the molecular structure
of 6 in Fig. 2 displays distorted trigonal bipyramidal geometry with
N(1), S(1) and S(3) occupying the equatorial plane and S(2) and
S(4) in the axial positions, similar to the structure of [Co{S2P(O-
Me)2}2 ꢀ PPh3] [16], with a phosphine electron donor instead of a
nitrogen base. The Co–N bond distance of (2.162(2) Å) in 3 is essen-
tially the same as that in [Co{S2P(OEt)2}2(C5H5N)2] (2.164(3) Å)
[19], which also has trans Co–N bonds. The shorter Co–N bond
length of 2.052(2) Å in 6, is closer to the average Co–N bond length
of 2.041(7) Å in [Co{S2P(OEt)2}2(C24H26N4O2)] [21] where the Co–N
bonds are cis.
2.1. IR spectra
The relevant assignments of the IR bands (Table 1) have been
made by a comparison with the spectra of the ammonium salts
of the O,O0-ditolyl/dibenzyl dithiophosphates [29] and analogous
adducts of cobalt(II) complexes [9]. The two strong to medium
intensity bands present in the regions 1030–1068 and 897–
993 cmꢂ1 are assigned to
vibrations, respectively. Bands due to
(P–S) or (P–S)symm are observed in the ranges 669–702 and
m
[(P)–O–C] and
m
[P–O–(C)] stretching
(P–S)asymm and
m
(P@S) or
m
m
m
591–602 cmꢂ1. The metal sulfur
m(Co–S) weak bands in the 405–
439 cmꢂ1 region indicate coordination of the dithiophosphate li-
gands through the sulfur atoms. Weak to medium intensity bands
In 6, as is to be expected for a trigonal pyramidal structure, the
Co–Saxial bonds (ave. 2.567(5) Å) are longer than the Co–Sequatorial
bonds (ave. 2.3421(7) Å), as was found in [Co{S2P(OMe)2}2 ꢀ PPh3]
[16]. The longer axial Co–S bonds are accompanied by relatively
shorter S(2)–P(1) and S(4)–P(2) bonds (ave. 1.960(2) Å) than the
due to m
(Co–N) are also seen in the region 351–388 cmꢂ1. Further,
in the case of the pyridine adducts 1–4, additional medium inten-
sity bands in the region 1579–1634 cmꢂ1 are due to the C–N vibra-
Table 1
IR spectral data (cmꢂ1) for the pyridine adducts of the bis(O,O0-ditolyl/dibenzyl dithiophosphato)cobalt(II) complexesa and the bis(dibenzyl dithiophosphato)cobalt(II) complex.
No.
Compound
m
[(P)–O–C]
m[P–O–(C)]
m(P@S)
m(P–S)
m
(Co–S)
m(C–N)
m(Co–N)
1
2
3
4
5
Co[S2P(OC6H4Me-o)2]2(2C5H5N)
Co[S2P(OC6H4Me-m)2]2(2C5H5N)
Co[S2P(OC6H4Me-p)2]2(2C5H5N)
Co[S2P(OC6H5CH2)2]2(2C5H5N)
Co[S2P(OC6H5CH2)2]2
1038s
1039s
1036m
1030s
1068s
915m
945s
897s
990m
993m
669s
690s
688s
702s
697m
601m
591m
599m
602s
439w
414w
428w
405w
402w
1599m
1579m
1596m, 1628m
1597m, 1634m
351w
356w
388w
360w
592m
a Key: s = strong, m = medium, w = weak.

S.C. Bajia et al. / Polyhedron 28 (2009) 85–90
87
Fig. 1. ORTEP plot of the molecule [Co{S2P(OC6H4Me-p)2}2(C5H5N)2]. The non-hydrogen atoms are drawn with 30% probability ellipsoids.
Fig. 2. ORTEP plot of [Co{S2P(OC6H4CH3-p)2}2(NH3)]. The non-hydrogen atoms are drawn with 50% probability ellipsoids.
S(1)–P(1) and S(3)–P(2) bonds (ave. 1.994(9) Å) that accompany
the shorter Co–S equatorial bonds. Similar trends were observed
in [Co{S2P(OMe)2}2 ꢀ PPh3] [16].
moiety is planar (as in pyridine), viz. [Co{S2P(OEt)2}2(C5H5N)2]
[19].
In the octahedral complex 3, there are again two sets of Co–S
When a monodentate coordinating moiety is sterically hin-
dered, 5-coordinated Co(II) adduct formation is seen, viz. [Co-
{S2P(OMe)2}2 ꢀ PPh3] [16], as observed in 6. NH3 is a very small
molecule but it may need considerable space for its coordination
sphere. However, two molecules of monodentate coordinating li-
gands can be attached to Co(II) complexes when the coordinating
bonds, Co(1)–S(1) and Co(1)–S(1)0 (2.5053(8) Å) and Co(1)–S(2)
and Co(1)–S(2)0 (2.5735(8) Å), although the differences are much
smaller. There are no obvious signs of secondary interactions
involving the sulfur atoms to account for the difference, so possibly
it is indicative of a slight tetragonal distortion along the S(2)–
Co(1)–S(2)0 axis; the one with the weakest bonds. The average

88
S.C. Bajia et al. / Polyhedron 28 (2009) 85–90
distance of all four Co–S bonds of 2.54(5) Å is comparable with the
average Co–S distance of 2.52(2) Å reported in [Co{S2P(OEt)2}2
(C5H5N)2] [19].
Found: N, 3.44; S, 15.53; Co 7.22%; UV–Vis electronic absorption
spectral data [kmax., nm(A);
(L molꢂ1)] in 0.008 M pyridine solu-
tion 520(87), 568(80), 632(77), 715(60), 1033(57); leff 5.0 B.M.
e
In 3, not unexpectedly, the longer Co(1)–S(2) bonds, are accom-
panied by relatively shorter S(2)–P(1) bonds (1.970(1) Å) and the
shorter Co(1)–S(1) bonds by longer P(1)–S(1) bonds (1.974(1) Å).
The P–O distances in 3 (ave. 1.599(2) Å), 6 (ave. 1.598(4) Å), [Co-
{S2P(OEt)2}2(C5H5N)2] [19] (ave. 1.593(1) Å) and [Co{S2P(OEt)2}2
(C24H26N4O2)] [21] (ave. 1.596(9) Å) are similar, regardless of their
environment.
3.1.4. [Co{S2P(OCH2C6H5)2}2(C5H5N)2] (4)
Prepared as for [Co{S2P(OC6H4Me-o)2}2(C5H5N)2]. Yield: 0.531 g
(76%); Calc. for C38H38O4N2P2S4Co: N, 3.35; S, 15.35; Co 7.05.
Found: N, 3.29; S, 15.49; Co 7.12%; UV–Vis electronic absorption
spectral data [kmax., nm(A); e
(L molꢂ1)] in 0.0057 M pyridine solu-
tion 500(135), 523(133), 668(98), 1038(114). leff 4.95 B.M.
In 6, the three angles in the equatorial plane, N(1)–Co(1)–S(1),
N(1)–Co(1)–S(3) and S(1)–Co(1)–S(3) of 112.42(6)°, 112.96(6)°
and 134.58(3)°, respectively, sum to exactly 360° as expected.
The S(2)–Co(1)–S(4) angle of 172.23(2)° is not so far from 180°, gi-
ven the planarity of the equatorial bonds and the requirements of
the bite angles of the ligands, S(1)–Co(1)–S(2) and S(3)–Co(1)–S(4)
of 83.88(2)° and 83.48(2)°, respectively In 3, with the three 180°
angles required by symmetry, the S(1)–Co(1)–S(2) and S(1)0–
C(1)–S(2)0 bite angles (80.18(3)°) and the S(1)–Co(1)–S(2)0 and
S(10–Co(1)–S(2)0 (99.82(3)°) inter-ligand angles show the greatest
deviation from 90°, the N–Co–S bond angles in the range of
88.82(6)–91.23(6)° showing only slight variation from a regular
octahedral geometry.
3.1.5. [Co{S2P(OCH2C6H5)2}2] (5)
CoCl2 ꢀ 6H2O (0.289 g, 1.215 mmol) and NH4S2P(OCH2C6H5)2
(0.798 g, 2.437 mmol) were added to toluene (30 mL) and the solu-
tion was stirred for 30 min to give a blue solution which was con-
centrated before the addition of hexane (10 mL). The blue solid
that formed was filtered, washed with hexane and dried in vacuo.
Yield 0.539 g, (66%). Calc. for C28H28O4P2S4Co; S, 18.93; Co, 8.70.
Found: S, 18.64; Co, 8.57%; UV–Vis electronic absorption spectral
data [kmax., nm(A); e
(L molꢂ1)] in 0.01 M in dichloromethane solu-
tion 579(57), 613(55), 635(49), 1043(35); leff 4.34 B.M.
3.2. Crystallography
A purple block crystal of [Co{S2P(OC6H4Me-p)2}2(C5H5N)2] (3),
and a blue block crystal of [Co{S2P(OC6H4Me-p)2}2(NH3)] 6 were
mounted on glass fibres. Data for 3 were collected on a Siemens
SMART System CCD diffractometer with the collection of a hemi-
sphere of data in 1329 frames with 10 s exposure times. Data for
6 were collected on a Bruker-Nonius Kappa CCD area detector dif-
3. Experimental
All chemicals (Emerk) were used after purification and solvents
were dried before use by standard methods. CoCl2(C5H5N)2 was
prepared by the reported method [30]. Literature methods were
used for the preparation of the O,O0-ditolyl dithiophosphoric acids
[29]. O,O0-dibenzyl dithiophosphoric acid was prepared by the
reaction of P2S5 and benzyl alcohol in a 1:4 molar ratio. The ammo-
nium salts of these dithiophosphoric acids were prepared by the
reaction of the parent acids with an equimolar amount of ammonia
in benzene. Cobalt and Sulfur were estimated by pyridine thiocya-
nate and Messenger’s methods, respectively. Electronic spectra
were recorded on a Perkin–Elmer UV–Vis–NIR spectrometer in
pyridine (1–4) and dichloromethane (5). Infrared spectra were re-
corded on a Perkin–Elmer 983G spectrometer as Nujol mulls be-
fractometer, with / and
x scans chosen to give a complete asym-
metric unit. Cell refinements [31] gave cell constants
corresponding to monoclinic cells for both, whose dimensions
Table 2
Crystal data and structure refinements for [Co{S2P(OC6H4Me-p)2}2(C5H5N)2] and
[Co{S2P(OC6H4Me-p)2}2(NH3)].
Empirical formula
Formula weight
Temperature (K)
Wavelength (Å)
Crystal system
Space group
a (Å)
C38H38O4N2P2S4Co C28H31O4N1P2S4Co
835.81
296(2)
694.65
120(2)
tween CsI discs over the range 4000–180 cmꢂ1
.
0.71073
monoclinic
P21/c
0.71073
monoclinic
P21/n
3.1. Preparations
12.215(1)
15.123(2)
11.575(1)
114.573(1)
1944.6(3)
2
9.9460(7)
16.2434(8)
19.610(1)
95.187(7)
3155.2(3)
4
b (Å)
c (Å)
3.1.1. [Co{S2P(OC6H4Me-o)2}2(C5H5N)2] (1)
Typically, CoCl2(C5H5N)2 (0.254 g, 0.882 mmol) was dissolved in
methanol (30 mL) and then a solution of NH4S2P(OC6H4Me-o)2
(0.579 g, 1.825 mmol) in methanol (20 mL) was added, followed
by refluxing for 1 h. The dark-pink precipitate that formed was fil-
tered, washed and dried in vacuo. Yield: 0.644 g (87%); Calc. for
C38H38O4N2P2S4Co: N, 3.35; S, 15.35; Co 7.05. Found: N, 3.40; S,
b (°)
Volume (Å3)
Z
Dcalc (g/cm3)
Absorption coefficient (mmꢂ1
F(000)
1.427
1.462
)
0.780
0.944
866
1436
Crystal size (mm)
h Range for data collection (°)
Index ranges
0.60 ꢃ 0.20 ꢃ 0.20 0.18 ꢃ 0.10 ꢃ 0.08
15.12; Co 6.94%; UV–Vis electronic absorption spectral data [kmax.
,
1.83–25.00
ꢂ14 ꢄ h ꢄ 14,
ꢂ17 ꢄ k ꢄ 17,
ꢂ13 ꢄ l ꢄ 13
18315
3.06–27.48
ꢂ12 ꢄ h ꢄ 12,
ꢂ21 ꢄ k ꢄ 19,
ꢂ25 ꢄ l ꢄ 25
13504
nm(A);
e
(L molꢂ1)] in 0.01 M pyridine solution 525(44), 653(42),
746(25), 915(31), 1126(22); leff 4.91 B.M.
Reflections collected
3.1.2. [Co{S2P(OC6H4Me-m)2}2(C5H5N)2] (2)
Independent reflections (Rint
)
3418 (0.0324)
7184 (0.0383)
Prepared as for [Co{S2P(OC6H4Me-o)2}2(C5H5N)2]. Yield: 0.544 g
(71%); Calc. for C38H38O4N2P2S4Co: N, 3.35; S, 15.35; Co 7.05.
Found: N, 3.23; S, 15.11; Co 7.14%; UV–Vis electronic absorption
Minimum and maximum transmission
Refinement method
0.8595 and 0.6517 0.9283 and 0.8484
full-matrix least-
squares on F2
3418/0/234
full-matrix least-
squares on F2
7184/0/365
spectral data [kmax., nm(A); e
(L molꢂ1)] in 0.004 M pyridine solu-
Data/restraints/parameters
Goodness-of-fit on F2
1.047
0.990
tion 522(155), 574(147), 610(143), 642(135), 1138(120); leff
4.87 B.M.
Final R indices [F2 > 4
r
(F2)]
R1 = 0.0423,
wR2 = 0.1066
R1 = 0.0561,
wR2 = 0.1166
0.386 and ꢂ0.162
R1 = 0.0411,
wR2 = 0.0893
R1 = 0.0771,
wR2 = 0.1014
0.342 and ꢂ0.452
R indices (all data)
3.1.3. [Co{S2P(OC6H4Me-p)2}2(C5H5N)2] (3)
Prepared as for [Co{S2P(OC6H4Me-o)2}2(C5H5N)2]. Yield: 0.531 g
(76%); Calc. for C38H38O4N2P2S4Co: N, 3.35; S, 15.35; Co 7.05.
Largest difference in peak and hole
(e Åꢂ3
)

S.C. Bajia et al. / Polyhedron 28 (2009) 85–90
89
are given in Table 2 along with other experimental parameters. An
absorption correction was applied [32].
are given in Tables 3 and 4 and the molecules are displayed as an
ORTEP diagrams in Figs. 1 and 2, respectively.
The structures were solved by direct methods [33] and were re-
fined using the WINGX version [34] of SHELX-97 [35]. All of the non-
hydrogen atoms were treated anisotropically. Hydrogen atoms
were included in idealized positions with isotropic thermal param-
eters set at 1.2 times that of the carbon atoms to which they were
attached. The final cycle of full-matrix least-squares refinement
was based on 3418 (for 3) and 7184 (for 6) observed reflections,
4. Conclusion
We have prepared and characterized the following complexes,
[Co{S2P(OC6H4Me-p)2}2(C5H5N)2] (R = o-, m-, p-C6H4Me, CH2C6H5)
and Co[S2P(OCH2C6H5)2]2. The IR and UV–Vis spectra and magnetic
moments of these compounds are consistent with the proposed
distorted octahedral structure. The molecular structures of [Co
{S2P(OC6H4Me-p)2}2(C5H5N)2] (3) and [Co{S2P(OC6H4Me-p)2}2-
(NH3)] (6) were determined to have distorted octahedral and dis-
torted trigonal bipyramidal geometries, respectively, around the
central cobalt atom.
2629 with F2 > 4 (F2) for 3 and 4823 with F2 > 4 (F2) for 6 and
r r
234 (for 3) and 365 (for 6) variable parameters, and converged
(the largest parameter shift was 0.001 times its esd).
The structure 6 is pseudo symmetric with a possible higher
symmetry space group of C2/c. However refinement in C2/c leads
to physically less reasonable thermal parameters and the structure
has therefore been left in P21/n. Selected distances and bond angles
Acknowledgements
S.B. and M.N. are grateful to UGC and CSIR, New Delhi, respec-
tively, for financial support. M.E.L. thanks the UK Engineering
and Physical Sciences Council for support of the X-ray facilities at
Southampton University.
Table 3
Bond distances (Å) and angles (°) for [Co{S2P(OC6H4Me-p)2}2(C5H5N)2].a
Co(1)–S(1)
Co(1)–S(2)
Co(1)–N(1)
S(1)–P(1)
P(1)–O(1)
O(1)–C(1)
N(1)–C(15)
2.5053(8)
2.5735(8)
2.162(2)
1.974(1)
1.597(2)
1.399(4)
1.342(3)
Co(1)–S(1)0
Co(1)–S(2)0
Co(1)–N(1)0
S(2)–P(1)
P(1)–O(2)
O(2)–C(8)
N(1)–C(19)
2.5053(8)
2.5735(8)
2.162(2)
1.970(1)
1.600(2)
1.397(3)
1.335(4)
Appendix A. Supplementary data
CCDC 686208 and 686209 contain the supplementary crystallo-
graphic data for [Co{S2P(OC6H4Me-p)2}2(C5H5N)2] and [Co
{S2P(OC6H4Me-p)2}2(NH3)]. These can be obtained free of charge
via http://www.ccdc.cam.ac.uk/conts/retrieving.html, or from the
Cambridge Crystallographic Data Centre, 12 Union Road, Cam-
bridge CB2 2EZ, UK (fax: +44 1223 336033; email: deposit@ccdc.
cam.ac.uk. Supplementary data associated with this article can be
found, in the online version, at doi:10.1016/j.poly.2008.09.025.
N(1)–Co(1)–N(1)0
S(1)–Co(1)–S(1)0
S(1)–Co(1)–S(2)
S(1)–Co(1)–S(2)0
N(1)–Co(1)–S(1)
N(1)–Co(1)–S(1)0
N(1)–Co(1)–S(2)0
N(1)–Co(1)–S(2)
Co(1)–N(1)–C(15)
Co(1)–S(1)–P(1)
S(1)–P(1)–O(1)
S(1)–P(1)–O(2)
S(1)–P(1)–S(2)
180.0
180.0
S(2)–Co(1)–S(2)0
S(1)0–Co(1)–S(2)0
S(1)0–Co(1)–S(2)
N(1)0–Co(1)–S(1)0
N(1)0–Co(1)–S(1)
N(1)0–Co(1)–S(2)
N(1)0–Co(1)–S(2)0
Co(1)–N(1)–C(19)
Co(1)–S(2)–P(1)
S(2)–P(1)–O(2)
S(2)–P(1)–O(1)
O(1)–P(1)–O(2)
P(1)–O(2)–C(8)
180.0
80.18(3)
99.82(3)
88.77(6)
91.23(6)
88.82(6)
91.18(6)
121.7(2)
84.51(4)
113.5(1)
112.3(1)
112.07(5)
127.6(2)
80.18(3)
99.82(3)
88.77(6)
91.23(6)
88.82(6)
91.18(6)
121.2(2)
82.76(4)
113.1(1)
112.4(1)
92.0(1)
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N(1)–Co(1)–S(2)
S(1)–Co(1)–S(2)
S(1)–Co(1)–S(3)
S(2)–Co(1)–S(3)
S(1)–Co(1)–S(2)
Co(1)–S(1)–P(1)
Co(1)–S(2)–P(1)
S(1)–P(1)–S(2)
S(1)–P(1)–O(1)
S(2)–P(1)–O(1)
S(1)–P(1)–O(2)
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O(1)–P(1)–O(2)
P(1)–O(1)–C(1)
P(1)–O(2)–O(8)
112.42(6)
95.37(6)
83.88(2)
134.58(3)
93.60(2)
83.88(2)
84.48(3)
79.37(3)
112.19(4)
111.94(7)
107.90(7)
110.49(7)
114.59(7)
99.01(8)
122.9(2)
121.6(1)
N(1)–Co(1)–S(3)
N(1)–Co(1)–S(4)
S(3)–Co(1)–S(4)
S(2)–Co(1)–S(4)
S(1)–Co(1)–S(4)
S(3)–Co(1)–S(4)
Co(1)–S(3)–P(2)
Co(1)–S(4)–P(2)
S(3)–P(2)–S(4)
S(3)–P(2)–O(3)
S(4)–P(2)–O(3)
S(3)–P(2)–O(4)
S(4)–P(2)–O(4)
O(3)–P(2)–O(4)
P(2)–O(3)–C(15)
P(2)–O(4)–C(22)
112.96(6)
92.40(6)
83.48(2)
172.23(2)
93.02(2)
83.48(2)
84.95(3)
79.69(3)
111.84(4)
112.27(7)
107.87(7)
110.29(8)
114.67(7)
99.29(9)
124.6(2)
121.7(1)

90
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