Synthesis, spectroscopic characterization and X-ray single crystal structures of trans-bis[4-methoxyphenyl (3-methylbutyl) dithiophosphinato] nickel(II) and bis [4-methoxyphenyl (3-methylbutyl) dithiophosphinato]cobalt(II) complexes

Article abstract of DOI:10.1007/s11243-010-9341-6

Thionation of 3-methylbutylmagnesium bromide with Lawesson's Reagent (LR) gave 4-methoxyphenyl (3-methylbutyl)dithiophosphinic acid (DTPA), and the latter was converted to the ammonium salt (NH₄L = Ammonium 4-methoxyphenyl (3-methylbutyl) dithi

Full text of DOI:10.1007/s11243-010-9341-6

Transition Met Chem (2010) 35:399–405
DOI 10.1007/s11243-010-9341-6
Synthesis, spectroscopic characterization and X-ray single crystal
structures of trans-bis[4-methoxyphenyl (3-methylbutyl)
dithiophosphinato] nickel(II) and bis [4-methoxyphenyl
(3-methylbutyl) dithiophosphinato]cobalt(II) complexes
Ertu g˘ rul Gazi Sa g˘ lam
•
Omer C¸ elik •
¨
Hamza Yılmaz
•
_
Semra Ide
Received: 2 September 2009 / Accepted: 9 February 2010 / Published online: 27 February 2010
Springer Science+Business Media B.V. 2010
ꢀ
Abstract Thionation of 3-methylbutylmagnesium bro-
mide with Lawesson’s Reagent (LR) gave 4-methoxyphenyl
stable chelate complexes; consequently, these sulfur
ligands are suitable for solvent extraction of metals [1–3].
An example of such dithiophosphinates, known as CYA-
NEX 301, has found use in industry for metal extraction
[4–6]. Some of these complexes have antitumor activity
and are therefore the subject of chemotherapy studies [7].
Although there are several reports on the chemistry of
symmetric dithiophosphinic acid complexes, studies on
dithiophosphinic acids bearing different R groups are rather
rare.
(
3-methylbutyl)dithiophosphinic acid (DTPA), and the latter
was converted to the ammonium salt (NH L = Ammonium
4
4
-methoxyphenyl (3-methylbutyl) dithiophosphinate). The
complex, trans–bis[4-methoxyphenyl(3–methylbutyl) dith-
iophosphinato] nickel(II) [NiL ], was prepared by the reaction
2
of NH L with NiCl .6H O in EtOH. Bis [4-methoxyphenyl
4
2
2
(
3-methylbutyl) dithiophosphinato]cobalt(II) [(CoL ) ] was
2 2
also prepared in the same way. The structures of the com-
plexes have been characterized by elemental analysis, FTIR,
In this study, the reaction of Lawesson’s Reagent (LR)
with 3-methylbutylmagnesium bromide, subsequent salt
formation of the product (NH L) with NH , and new Ni(II)
1
13
31
H, C, P NMR and X-ray diffraction. The single crystal
X-ray structures of [NiL ] and [(CoL ) ] show that the nickel
2
2 2
4
3
-
complex is square planar while the cobalt counterpart has
tetrahedral coordination with a dimeric structure. Bond
lengths, angles, torsion angles and dihedral angles are cor-
related to the structures and also compared with the literature
data on similar compounds.
and Co(II) complexes of the L anion have been investi-
gated (Scheme 1). The compounds were characterized by
1
13
31
elemental analyses, H, C, P NMR and FTIR spectral
data. The magnetic susceptibilities of the complexes were
measured. The crystal structures of [NiL ] and [(CoL ) ]
2
2 2
were confirmed by X-ray crystallography.
Introduction
Experimental
-
The dithiophosphinate (DTP) anions [R PS ] can act as
2
2
bidentate ligands with many transition metals to form
Analytical-grade LR and 1-bromo-3-methylbutane were
purchased from Across and used without further purification.
Benzene, diethyl ether, methanol, ethanol, NiCl .6H O and
E. G. Sa g˘ lam ꢀ H. Yılmaz (&)
2
2
Department of Chemistry, Faculty of Science,
University of Ankara, Tando g˘ an, 06100 Ankara, Turkey
e-mail: hyilmaz@science.ankara.edu.tr
CoCl .6H O were purchased from Merck. All solvents were
2 2
dried and distilled before use. Magnetic susceptibilities were
determined on a Sherwood Scientific Magnetic susceptibil-
ity Balance (Model MK1) at room temperature (25 ꢁC).
Melting points were measured on a Gallenkamp apparatus
¨
O. C¸ elik
Department of Physics, Faculty of Sciences and Art,
Harran University, 63300 S¸ anlıurfa, Turkey
1
13
31
using a capillary tube. NMR spectra ( H, C and P) were
recorded at 400 MHz on a Bruker DPX FT-NMR spec-
_
S. Ide
trometer in D O and CDCl . SiMe was used as the internal
2
Department of Physics Engineering, Faculty of Engineering,
Hacettepe University, 06800 Beytepe-Ankara, Turkey
3
4
1 13
standard for H and C NMR; 85% H PO was employed as
3
4
123

4
00
Transition Met Chem (2010) 35:399–405
Scheme 1 Synthesis of NH
4
L
S
O
SH
CH3
P
H3C
+
S
S
S
H /H O
2
H3C
O
P
P
+
2
2
O
S
MgBr
- 2 MgBrOH
LR
DTPA
S
S
+
SH
S NH4
P
P
H3C
H3C
+
NH 3
O
O
DTPA
4
NH L
3
an external standard for P NMR. IR spectra were
1
cooled and hydrolyzed with 5% H SO (200 mL). The
2 4
recorded on a Mattson 1000 FTIR spectrophotometer (400–
ether layer was separated, the aqueous phase was extracted
several times with ether, and the combined ether layers
were dried over Na SO and evaporated under vacuum.
-
,000 cm ) in KBr pellets (1%w/w) and are reported in
1
4
-
1
cm units. Microanalyses were performed using a LECO
CHNS-932 C elemental analyzer.
2
4
The oily residue, dithiophosphinic acid, DTPA was taken
into dry benzene, the solution was cooled with in an ice-
salt bath, and dry ammonia was passed through the cooled
solution. The precipitated white solid was filtered off and
dried in a vacuum desiccator. Yield: 1,43 g (49%). M.P.
X-ray studies
Suitable single crystals of sizes 0.25 9 0.20 9 0.15 mm
for [NiL ] and 0.40 9 0.20 9 0.20 mm for [(CoL ) ] were
-
1
183–184 ꢁC. Anal. Calcd. for C H NOPS (291,4 g mol ):
2
2 2
12 22
2
selected for X-ray diffraction. The intensity data were
collected at room temperature on an Enraf–Nonius CAD4
C, 49.5; H, 7.6; N, 4.8; S, 22.0; found: C, 49.7; H, 8.0;
1
N, 4.8; S, 22.1. H NMR (ppm in D O): d = 0.60
2
3
3
diffractometer using graphite-monochromated Mo K radi-
a
(d, J = 6 Hz, 6H, CH–(CH ) ), 1.30 (m, J = 7 Hz,
HH 3 2 HH
˚
ation (k = 0.71073 A) [8]. Data were corrected for Lorenz
1H, C–CH), 1.20 (m, 2H, CH –CH ), 2.06 (m, 2H,
2 2
4
P–CH ), 3.70 (s, 3H, Ar–OCH ), 6.88 (dd, J = 1.7 Hz,
and polarization effects, and an absorption correction was
made using psi.scan after obtaining the complete struc-
tural model. The intensity data were collected by x - 2h
scan mode within 4.40ꢁ B 2h B 45.52ꢁ for -17 B h B 0,
2
3
PH
3
3
JHH = 8.6 Hz, 2H, Ar–Hmeta), 7.85 (dd, J = 12.6 Hz,
PH
3
13
JHH = 8.6 Hz, 2H, Ar–Horto). C NMR (ppm in D O):
2
3
d = 22.0 (s, CH–(CH ) ), 33.1 (d, j
= 4.1 Hz, C–CH),
P–C
3
2
2
28.5 (d, jP–C = 17.0 Hz, CH –CH ), 42.6 (d, j
0
B k B 12, -17 B l B 18 in the monoclinic crystal sys-
=
P–C
2
2
tem for [NiL ] and 4.60ꢁ B 2h B 52.58ꢁ for -14 B h B 0,
56.4 Hz, P–CH –CH ), 56.1 (s, CH O–Ar), 113.9 (d,
2
2
2
3
3
-
15 B k B 13, -16 B l B 15 in the triclinic crystal sys-
JP–C = 13.2 Hz, =CH–CH=CH–P), 163.9 (s, CH O–C),
3
2
132.4 (d, J
1
= 12.3 Hz, –CH=CH–P), 131.6 (d, J
tem for [(CoL ) ]. The structures were solved by direct
2
=
P–C
2
P–C
3
1
methods using SHELXS 97 and refined by full-matrix least
squares SHELXL 97 [9]. All non-hydrogen atoms were
refined anisotropically. Hydrogen atoms were treated by a
riding model. ORTEP III plotting program was used for
molecular graphics [10].
74 Hz, –CH=CH–P). P NMR (ppm in D O): d = 66.37.
2
Preparation of [NiL2]
A solution of NiCl .6H O (0.08 g, 0.3 mmol) in methanol
2
2
(10 mL) was added to a solution of NH L (0.2 g,
4
Preparation of NH4L
0.6 mmol) in the same solvent (25 mL). The mixture was
heated gently. The resulting solution was left to stand
overnight to obtain needle-like crystals. The dark blue
crystalline solid was filtered off and recrystallized
from ethanol. Yield: 0.17 g (% 85). M.P. 133–134 ꢁC.
leff = Diamagnetic. Anal. Calcd. for C H NiO P S
NH L was prepared in accordance with the literature pub-
4
lished for related compounds [11]. All the procedures that
follow were performed under argon atmosphere. A sus-
pension of LR (2 g, 4.9 mmol) in diethyl ether (200 mL)
was stirred and cooled in ice while an etheral solution of
isobutyl magnesium bromide (1.59 g, 9.9 mmol) was
added. The mixture was heated under reflux for 1 h, then
24
36
2 2 4
-
1
(605,4 g mol ): C, 47.6; H, 6.0; S, 21.2; found: C, 47.5;
1
H, 5.7; S, 21.5. H NMR (ppm in CDCl ): d = 0.60
3
3
(d, J = 6 Hz, 6H, CH–(CH ) ), 1.63 (m, 2H, C–CH),
3
HH
3 2
1
23

Transition Met Chem (2010) 35:399–405
401
1
.60 (m, 2H, CH –CH ), 2.20 (m, 2H, P–CH ), 3.78 (s, 3H,
2 2 2
9
3
Ar–OCH ), 7.00 (d, J = 7.5 Hz, 2H, Ar–Hmeta), 7.70
3
3
2
7
3
PH
S
P
3
dd, J = 12.7 Hz, J = 8.7 Hz, 2H, Ar–Horto).
3
13
(
C
5
8
PH
HH
4
1
CH O
NMR (ppm in CDCl ): d = 22.0 (s, CH–(CH ) ), 31.0
3
3
3 2
6
9'
2
s, C–CH), 29.2 (d, jP–C = 15.7 Hz, CH –CH ), 40.1
(
S NH4
2
2
' 2'
(
d, jP–C = 43.7 Hz, P–CH –CH –), 161.9 (s, CH O–C),
2 2 3
3
5
6.2 (s, CH O–Ar), 115.2 (d, JP–C = 15.0 Hz, =CH–
3
4
Fig. 1 Numbering scheme for NH L
2
CH=CH–P), 131.9 (d, JP–C = 14.0 Hz, –CH=CH–P),
1
31.1 (d, J
31
1
= 70.1 Hz, –CH=CH–P). P NMR (ppm
P–C
in CDCl ): d = 90.00.
2.06 ppm is assigned to the CH protons at position 6. This
2
3
multiplet does not give any indication that the phosphorus
center is chiral, which implies that the two sulfur atoms are
chemically equivalent in solution. The signal at 3.7 ppm
Preparation of [(CoL ) ]
2
2
A solution of CoCl .6H O (0.08 g, 0.3 mmol) in ethanol
2
reflects the presence of the OCH group, while the signals
3
2
(
10 mL) was added to a solution of NH L (0.2 g, 0.6 mmol)
4
at 6.88 and 7.85 ppm, both of which are doublets of dou-
in the same solvent (25 mL). The mixture was heated gently.
The solution was kept overnight 21 ꢁC, whereupon the
complex precipitated as a green crystalline solid, which was
filtered off and recrystallized from ethanol. Yield: 0.18 g (%
blets, belong to the phenolic protons. The signal of the
?
NH4 protons appears to be been overlapped with the H O
2
signals, as expected.
1
The H NMR features of the complex [NiL ] are
2
9
0). M.P. 188–190 ꢁC. leff = 4.11 B.M. Anal. Calcd. for
essentially the same as those of free NH L, except that the
4
-
C H Co O P S (1,211,4 g mol ): C, 47.6; H, 6.0; S,
1
4
8
72
2 4 4 8
resonances are shifted downfield, which may be the result
of solvent change (from D O to CDCl ) as well as the
2
1.2; found: C, 47.6; H, 5.4; S, 22.0.
2
3
2
?
Single crystals of both complexes suitable for X-ray
bonding to Ni
.
analysis were obtained by recrystallization from ethanol.
The complex [(CoL ) ] is paramagnetic, and the ambi-
2
2
ent temperature NMR spectrum is so complicated as to
make it awkward to comment on.
1
The C NMR spectrum of NH L displays nine distinct
3
Results and discussion
4
signals, as expected from the structure. The signal at
0
Spectroscopic data
22 ppm is due to the CH carbons at positions 9 and 9
3
(Fig. 1) and the one at 28.5 ppm to the CH carbon at
2
Selected IR data for the compounds NH L, [NiL ] and
4
position 7. This signal is split by 17 Hz through two-bond
coupling to P. The doublet at 33.1 ppm is assigned to the
2
[
(CoL ) ] are listed in Table 1. The characteristic asym-
2 2
3
1
metric and symmetric mP=S bands are observed at 596–619
and 518–546, respectively. Characteristic m bands are
observed at 3,171 and 3,111 cm for NH L; these bands
carbon at position 8. A three-bond P-coupling of 4.1 Hz
is observable here. The doublet at 42.6 ppm belongs to the
N–H
-
1
4
CH carbon at positions 6. The splitting here is 56.4 Hz,
2
are absent in the spectra of the two complexes, confirming
?
the exclusion of the NH4 ion.
reflecting an interaction of normal order for one-bond
coupling.
1
The principle features of the H NMR spectra assign-
The singlet at 56.1 ppm is due to the OCH carbon, and
3
ments being made on the bases of the numbering scheme
given in Fig. 1 are as follows: The doublet at 0.6 ppm is
the doublet at 113.9 ppm to the aromatic carbons at posi-
tion 3. The three-bond splitting of 13.2 Hz conforms with
the literature values for similar structures [12–15]. The
ipso-carbon at position 1 gives rise to a doublet signal at
around 131.6 ppm. The downfield member of the doublet
appears to be overlapped with the doublet signal of C2. The
C2 signal at 132.4 ppm is a doublet with coupling of
12.3 Hz, which is comparable with similar structures
assigned to the CH protons at 9 and 9’. The multiplet at
3
around 1.2 ppm is attributed to the CH protons of the
2
position 7. The general appearance of the multiplet reflects
a partly superimposed doublet of triplets, as expected. The
neighboring multiplet at 1.3 ppm belongs to the methine
proton of the isopropyl group, while the multiplet at
Table 1 Selected FTIR data
(
-
cm ) for the compounds
1
Compound
NH
m
(as,s) (P S)
m(N–H)
m(C=C)
m(C–H)aliph
m(C–H)arom
4
L
619; 544
596; 546
610; 518
3,171; 3,111
1,592; 1,496
2,955; 2,868; 2,839
2,955; 2,926; 2,839
2,955; 2,895; 2,868
3,010
3,008
3,026
[
NiL
2
]
–
–
1,592; 1,498
[
2
(CoL )
2
]
1,591; 1,498; 1,459
123

4
02
Transition Met Chem (2010) 35:399–405
[
16–18]. The signal at 160.0 ppm belongs to the C4 ipso-
carbon and is unsplit as expected.
1
The C NMR spectrum of [NiL ] displays essentially
3
2
the same features as NH L. [(CoL ) ] is paramagnetic, and
4
2 2
13
its C NMR spectrum is not commented on.
3
The proton de-coupled P NMR spectra of NH L and
1
4
[
NiL ] show singlets at 66.37 and 90.00 ppm, respectively.
2
X-ray crystal structures
Crystal and experimental data are given in Table 2 for the
compounds [NiL ] and [(CoL ) ].
2
2 2
An ORTEP III diagram and numbering scheme for
[
NiL ] is shown in Fig. 2. The crystal structure reveals that
2
the central Ni atom is four-coordinate, with the two
-
0
crystallographically independent L anions acting as S,S -
bidentate ligands. The alkyl substituents of the two phos-
phinate anions are in trans-configuration with respect to the
2
Fig. 2 ORTEP III diagram of [NiL ] with thermal ellipsoids at 50%
probability level
Table 2 Crystal and experimental data for [NiL
2
] and [(CoL
2 2
) ]
Compound
[NiL
2
]
[(CoL
2 2
) ]
central coordination plane. The central coordination
geometry is slightly distorted square planar, with the dis-
Formula
C
24
H
36NiO
605.44
Monoclinic
P2 /a (14)
2
P
S
2 4
48 2 4 4 8
C H72Co O P S
Formula weight
Crystal system
Space group
1,211.36
Triclinic
P - 1
˚
˚
tances S1–S2 and S3–S4 being 3.125 A and 3.218 A,
respectively. The torsion angle S1–S2–S3–S4 is 0.1ꢁ,
supporting the nearly perfect planar coordination. Other
torsion angles, namely Ni–S2–P1–S1 (0.6ꢁ) and Ni–S3–
P2–S4 (0.0ꢁ), are also strong indications of the near co-
planarity of the two four-membered chelate rings. The
dihedral angle between the two ring-planes is measured to
be 0.55(6)ꢁ. The deviation from coplanarity can be attrib-
uted to packing effects. P1 shows a slight deviation of
1
Unit cell dimensions
˚
a (A)
15.8616(12)
11.5704(18)
17.110(2)
90.000
11.3566(13)
12.487(3)
12.9779(12)
74.349(9)
68.082(8)
63.545(10)
1,516.7(4)
2
˚
b (A)
˚
c (A)
a (ꢁ)
b (ꢁ)
c (ꢁ)
107.700(9)
90.000
˚
0.0134 A from the coordination plane. The angle between
3
˚
V (A )
2,991.5(7)
4
the two phenyl planes is 69.6(3)ꢁ. The bond lengths, Ni–
S1, Ni–S2, Ni–S3 and Ni–S4, are 2.238(3), 2.244(2),
Z
˚
2.224(2) and 2.225(3) A, respectively. These values are
Calculated density
-
1.34
1.33
1
)
(
g cm
comparable to the literature values reported for similar
structures as shown in Table 3 [19–22]. The phosphorus
atoms have an essentially tetrahedral geometry.
Absorption coefficient
(
1.054
0.965
-
mm )
1
Crystal size (mm)
h(max) (ꢁ)
Reflexions measured
0.25 9 0.20 9 0.15 0.40 9 0.20 9 0.20
The average P–S and P–C bond lengths are 2.011(3) and
˚
.802(3) A, respectively. Apparently, the molecular
22.76
4,003
3,838
0.0505
1,767
26.29
6,010
5,723
0.0203
3,634
1
geometry is affected by the C6–H1ꢀꢀꢀS1 intramolecular
Unique reflexions
˚
hydrogen bond, the bond lengths being 0.930 A (D H) and
…
R
int
˚
2
.858(3) A (H–A). The angle A–HꢀꢀꢀD is 115.3(7)ꢁ, and the
Reflexions with
2
…
˚
distance A D is 3.362(12) A .
2
F [ 2r(F )
Number of parameters
Figure 3 shows the ORTEP III diagram of the complete
complex molecule, [(CoL ) ] with 50% probability level
298
271
2
2
2
2
R
1
1
[F [ 2r(F )]
(all data)
0.052
0.198
0.147
0.973
0.051
0.111
0.153
1.000
ellipsoids. The most important bond lengths, angles and
torsion angles are listed in Table 4. In Fig. 4, are given
three planes around the central coordination sphere. The
molecule is a discrete dimer. The catenation is mediated by
two dithiophosphinato groups as monodentate ligands to
one Co atom with the remaining sulfur atoms being
R
2
wR (all data)
GOOF, S
Difference peak
˚
and hole (e A
0.401 and -0.322 0.870 and -0.527
-
3
)
1
23

Transition Met Chem (2010) 35:399–405
403
Table 3 Selected geometric
parameters for [NiL
similar structures
˚
Ni–S (A)
˚
P–S (A)
˚
P–C (A)
Compound
S–Ni (ꢁ)
S–P–S (ꢁ)
Literature
2
] and
I
2.232(2)
2.170(2)
2.226(9)
2.222(8)
2.241(5)
88.17(9)
87.64(6)
88.34(3)
88.14(3)
87.7(2)
2.011(3)
2.015(2)
2.006(1)
1.994(1)
2.004(6)
101.07(14)
99.66(7)
No data
1.802(3)
1.784(4)
1,787(3)
1.782(3)
1.828(19)
Present study
[19]
II
III
IV
V
[20]
100.57(4)
101.6(3)
[21]
[22]
Table 4 continued
NiL
[
2
]
2 2
[(CoL ) ]
S4–Ni–S3
S4–Ni–S1
S3–Ni–S1
S4–Ni–S2
S3–Ni–S2
S1–Ni–S2
P1–S2–Ni
P1–S1–Ni
C8–P1–C1
C8–P1–S1
C1–P1–S1
C8–P1–S2
C1–P1–S2
S1–P1–S2
C18–P2–C13
S3–P2–S4
P2–S3–Ni
P2–S4–Ni
87.93(9)
S1–Co–S3
122.09(5)
130.73(5)
103.34(4)
85.99(4)
91.57(9)
S1–Co–S4
179.40(10)
179.87(12)
92.10(9)
S3–Co–S4
S1–Co–S2
S3–Co–S2
100.86(4)
104.43(5)
80.86(5)
88.40(9)
S4–Co–S2
84.63(11)
84.96(11)
105.9(4)
P1–S2–Co
P2–S4–Co
111.46(5)
103.1(2)
C1–P1–C8
113.1(3)
C1–P1–S2
113.00(1)
111.6(2)
111.9(3)
C8–P1–S2
111.5(3)
C1–P1–S1
111.59(1)
109.22(2)
108.28(7)
83.72(5)
112.6(3)
C8–P1–S1
Fig. 3 ORTEP III drawing of the complete molecule and atom-
labeling scheme for [(CoL
probability level
102.01(14)
106.5(4)
S2–P1–S1
2 2
) ] with thermal ellipsoids at 50%
P1–S1–Co
100.12(14)
86.00(11)
85.95(11)
C4–O1–C7
116.7(4)
C13–P2–C20
C13–P2–S4
C20–P2–S4
S1–Co–S2–P1
S3–Co–S2–P1
S4–Co–S2–P1
S1–Co–S4–P2
S3–Co–S4–P2
S2–Co–S4–P2
Co–S2–P1–C1
Co–S2–P1–C8
Co–S2–P1–S1
C1–P1–S1–Co
C8–P1–S1–Co
S2–P1–S1–Co
S3–Co–S1–P1
S4–Co–S1–P1
S2–Co–S1–P1
Co–S4–P2–C13
Co–S4–P2–C20
106.8(3)
˚
113.12(1)
105.8(2)
Table 4 Selected bond lengths (A), bond and torsion angles (ꢁ) for
complexes [NiL
2 2 2
] and [(CoL ) ]
S4–Ni–S2–P1
S3–Ni–S2–P1
S1–Ni–S2–P1
S4–Ni–S1–P1
S3–Ni–S1–P1
S2–Ni–S1–P1
Ni–S1–P1–C8
Ni–S1–P1–C1
Ni–S1–P1–S2
Ni–S2–P1–C8
Ni–S2–P1–S1
S4–Ni–S3–P2
S1–Ni–S3–P2
S2–Ni–S3–P2
C18–P2–S4–Ni
C13–P2–S4–Ni
S3–P2–S4–Ni
S1–Ni–S4–P2
S1–S2–S3–S4
-76(51)
-179.2(1)
0.50(13)
179.4(1)
145(1)
7.38(5)
[
NiL
2
]
2 2
[(CoL ) ]
-114.54(6)
138.48(5)
-4.75(9)
152.87(6)
-102.00(6)
-133.06(2)
111.30(2)
-8.93(6)
134.33(2)
-112.3(2)
9.36(7)
Ni–S1
Ni–S2
Ni–S4
Ni–S3
S1–S2
S2–S3
S1–P1
S2–P1
P1–C8
P1–C1
P2–C18
P2–C13
P2–S3
P2–S4
O2–C21
O2–C24
O1–C4
O1–C7
2.238(3)
2.244(2)
2.224(2)
2.225(3)
3.125
Co–S1
Co–S2
Co–S3
Co–S4
P1–S1
P1–S2
P2–S4
P1–C1
P1–C8
2.321(1)
2.449(1)
2.328(1)
2.357(1)
2.018(2)
1.998(2)
2.018(2)
1.791(4)
1.834(5)
1.789(4)
1.826(5)
1.363(5)
1.431(6)
1.355(5)
1.447(6)
-0.5(1)
120.4(4)
-120.0(3)
0.58(14)
-121.6(4)
-0.6(1)
0.04(1)
3.218
2.007(3)
2.014(3)
1.801(8)
1.812(10)
1.788(10)
1.804(8)
2.012(3)
2.016(3)
1.370(11)
1.436(10)
1.368(12)
1.424(11)
P2–C13
P2–C20
O2–C16
O2–C19
O1–C4
O1–C7
34(11)
93.06(6)
179.9(1)
-119.2(3)
121.1(3)
0.04(1)
-112.88(6)
-7.25(5)
43.46(2)
160.0(2)
-179.7(1)
0.1(1)
123

4
04
Transition Met Chem (2010) 35:399–405
sulfur atoms to give a slightly distorted tetrahedral
arrangement. The inter-ion chelate bite is certainly
˚
responsible for the rather short Co–Co distance of 3.952 A.
The Co–S1, Co–S2, Co–S3 and Co–S4 bond lengths are
˚
2
.321(1), 2.449(1), 2.328(1) and 2.357(1) A, respectively.
0
0
In the Co chelate geometry, each S3–S4 –S3 –S4, P2–Co–
0
0
0
0
P2 –Co and Co–S4–Co –S4 atom group forms planes, as
shown in Fig. 4a–c. The two sulfur and two carbon atoms
around the phosphorus atoms are of essentially tetrahedral
configuration. The P1–S1, P1–S2 and P2–S4 bond lengths
˚
are 2.018(2), 1.998(2) and 2.018(2) A, respectively, and
P1–C1, P1–C8, P2–C13 and P2–C20 are 1.791(4),
˚
1.834(5), 1.789(4) and 1.826(5) A, respectively. Remark-
ably, the P–C bonds attaching the methoxyphenyl moiety
are shorter than the P–C bonds attaching the aliphatic
moiety. This may—at least partly—be due to the electron
delocalization on the phenyl rings. The dihedral angle
between the Co–S1–S2 and P1–S1–S2 planes is 12.44(6)ꢁ.
In addition, the dihedral angle between the two phenyl
rings (with C1 and C13) is 27.84(15)ꢁ. Other compounds of
similar structures, namely, chelates of Cd, Zn, Hg and Au
with dithiophosphinates, compare well with these findings
[
23–25].
The hydrogen bond molecular geometry data for the
complexes are given in Table 5. The molecular geometry is
obviously affected by the four C–HꢀꢀꢀS intramolecular, as
well as two C–HꢀꢀꢀO intermolecular hydrogen bond
interactions.
Conclusion
Three new compounds, NH L, [NiL ] and [(CoL ) ], have
2 2
4
2
been synthesized. The ammonium salt has been charac-
terized by elemental analysis and spectroscopy. The com-
plexes were investigated by X-ray single crystal methods
as well as elemental analysis and spectroscopy. The
Fig. 4 ORTEP III drawing of some planes of the chelate geometry
for [(CoL ] with thermal ellipsoids at 50% probability
2 2
)
attached to the second Co atom, and vice versa. By the
dimerization via a crystallographic center of symmetry, a
puckered eight-membered ring is formed that has a chair
structure of [(CoL ) ] comprises a dimer with an eight-
2 2
membered metallocyclic ring formed by chelating and
bridging of ligands and has a ‘chair’ conformation. Both
complexes are stable at room temperature for at least a
period of 11 months.
0
conformation [formed by the atoms Co, S3, S4, P2, Co ,
0
0
0
S3 , S4 , P2 ]. The cobalt atoms are coordinated by four
Table 5 Hydrogen bonding
˚
Compound
D–HꢀꢀꢀA
D–H
HꢀꢀꢀA
DꢀꢀꢀA
D–HꢀꢀꢀA
geometry (A, ꢁ) for [NiL
(CoL
2
] and
[
2
)
2
]
i
i
i
[
NiL
2
]
C6–H1ꢀꢀꢀS1
C6–H6ꢀꢀꢀS1
C2–H2ꢀꢀꢀS2
0.930
0.930
0.930
0.970
0.960
0.960
0.930
2.858(3)
2.954(2)
2.982(2)
2.893(1)
2.651(3)
2.707(4)
2.819(2)
3.362(12)
3.417(6)
3.426(7)
3.451(9)
3.428(8)
3.409(8)
3.329(6)
115.3(7)
112.3(3)
110.9(4)
117.6(4)
138.3(4)
130.4(4)
115.6(3)
[
2 2
(CoL ) ]
i
C21–H21AꢀꢀꢀS4
iib
C7–H7AꢀꢀꢀO2
iib
Symmetry codes: (i) x, y, z; (iib)
C19–H19Aꢀꢀꢀ O1
-
-
x ? 2, -y ? 1, -z ? 1; (iiib)
x ? 1, -y, -z ? 1
iiib
C18–H18ꢀꢀꢀ S3
1
23

Transition Met Chem (2010) 35:399–405
405
Supplementary material
11. Diemert K, Kuchen W (1977) Phosphorus Sulfur Silicon Relat
Elem 3(2):131–136
1
2. Przychodzen W (2004) Phosphorus Sulfur Silicon 179:1621–
633
Crystallographic data have been deposited at the Cambridge
Crystallographic Data Center (CCDC) under the deposition
numbers 743998 for [NiL ] and 743997 for [(CoL ) ].
1
13. Shabana R, Osman FH, Atrees SS (1993) Tetrahedron
49(6):1271–1282
1
2
2 2
4. Ramirez RG, Toscano RA, Silverstu C, Haiduc I (1996) Poly-
hedron 15(21):3857–3867
5. Karaku s¸ M, Yilmaz H (2006) Rus J Coord Chem 32(6):437–443
6. Casas JS, Garcia-Tasende MS, Sanches A, Sordo J, Vazquez-
Lopez EM, Castellano EE, Zukerman-Schpector J (1994) Inorg
Chim Acta 219:115–119
Acknowledgments Financial assistance from Ankara University
Research and Development Fund (grant number DPT-2002-K-
1
1
1
20130-5) is gratefully acknowledged.
1
1
7. Klaehn JR, Peterman DR, Harrup MK, Tillotson RD, Luther TA,
Law JD, Daniels LM (2008) Inorg Chim Acta 361:2522–2532
8. Mansfield NE, Coles MP, Hitchcock PB (2008) Phosphorus
Sulfur Silicon 183:2685–2702
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