Preparation and crystallographic characterization of Pd(II) complexes containing imidobis(diphenylthiophosphinato) ligand

Article abstract of DOI:10.1016/j.poly.2007.05.007

The reactions of PdCI₂(L-L) [L-L = Ph₂PCH₂PPh₂(dppm), Ph₂PCH₂CH₂PPh₂(dppe) and Ph₂PCH₂CH₂CH₂PPh₂(dppp)] with equ

Full text of DOI:10.1016/j.poly.2007.05.007

Polyhedron 26 (2007) 4114–4118
www.elsevier.com/locate/poly
Preparation and crystallographic characterization of Pd(II)
complexes containing imidobis(diphenylthiophosphinato) ligand
a
a,
b
_
Selmin Yanar , Sevil Irißsli *, Orhan Buyukgungo¨r
¨ ¨
¨
a
_
Department of Inorganic Chemistry, Faculty of Science, Ege University, 35100 Bornova-Izmir, Turkey
b
Department of Physics, Ondokuz Mayıs University, TR-55139, Samsun, Turkey
Received 1 February 2007; accepted 4 May 2007
Available online 22 May 2007
Abstract
The reactions of PdCI2(L-L) [L-L = Ph2PCH2PPh2(dppm), Ph2PCH2CH2PPh2(dppe) and Ph2PCH2CH2CH2PPh2(dppp)] with equiv-
alent amount of (Ph2P(S)NHP(S)Ph2)(dppaS2) gave the complexes [Pd(L-L)(dppaS2-H)]ClO4 [L-L = dppm (1), dppe (2), dppp (3)]. The
different synthetic route was used for complex 2 by using of Pd(dppe)Cl2 and K[N(PSPh2)2] as starting materials (2a). All of these com-
plexes have been characterized 31P{1H} NMR, IR and elemental analyses. The complexes 2, 2a and 3 were crystallographically charac-
terized. The coordination geometry around the Pd atoms in these complexes distorted square planar. Six membered dppaS2-H rings are
twist boat conformations in three complexes.
ꢀ 2007 Elsevier Ltd. All rights reserved.
Keywords: Palladium complexes; X-ray crystal structures; Phosphines; Phosphine complexes; Diphosphines; Chalcogenide ligands
1. Introduction
form six-membered inorganic (carbon-free) chelate rings
2 and seldom act as bridging ligands [6].
Ligands with mixed donor sets have attracted much
interesting especially in recent years [1]. One particular
class that has received widespread attention is hemilabile
ligands in which both ‘‘soft’’ (e.g. P) and ‘‘hard’’ (e.g. N
or O) donor centres are present [2,3]. The hard donor site
coordinates only weakly to a late transition-metal centre
and can readily be displaced by other ligands. This prop-
erty has been extensively exploited in catalysis [4]. The
iminobis(diphenylphosphinechalcogenide) ligands may be
considered to be main group analogues of acetylacetone
[5]. Dichalcogenoimidodiphosphinato anions [R2P(E)–N–
P(E)R2]ꢀ (E = O, S, Se), derived from iminobis(diphenyl-
phosphinechalcogenide) ligands, are versatile ligands, with
a strong tendency to from inorganic (carbon-free) chelate
rings. All dichalcogenoimidodisphosphinates 1 tend to
With differing donor properties of the atoms (O, S or Se)
at the two ends of the diphosphazene fragment, the com-
parison of the structures and properties of various dic-
halcogenoimidodiphosphinato ligand becomes interesting
[6]. Gabor Balazs et al. have reported the reaction between
Li[HN(X)PR2] and R02P(Y)Cl in a benzene/n-hexane
mixture to give white crystalline solids of (XPPh2)-
[YP(OEt)2]NH (X, Y = O, S) [7].
As a result a number of complexes have been described.
The reaction of Cu(PPh)3NO3 with K[Ph2P(Se)–N–
P(Se)Ph2] has been reported by Novasad [6]. Martin B.
Smith has reported a number of Pd(II) and Pt(II) com-
plexes with the ligands Ph2PNHP(O)Ph2, [Ph2PNP(O)-
Ph2]ꢀ or [Ph2P(E)NP(O)Ph2]ꢀ (E = S or Se) [8]. It has been
reported heterofunctional ligands of the type R2PNHP(O)-
R2 [9,10] and [R2P(E)NP(O)R2]ꢀ (E = S or Se; R = Ph)
[11–13] and their coordination chemistry to catalytically
useful metals. Manganese compounds of the type
Mn[(XPR2)(YPR02)N]2 (X, Y = O, S; R, R0 = Me, Ph) were
*
Corresponding author. Tel.: +90 232 3884000 2454; fax: +90 232
3888264.
_
E-mail address: irislisevil@hotmail.com (S. Irißsli).
0277-5387/$ - see front matter ꢀ 2007 Elsevier Ltd. All rights reserved.
doi:10.1016/j.poly.2007.05.007

S. Yanar et al. / Polyhedron 26 (2007) 4114–4118
4115
prepared by metathesis reactions between MnCl2 Æ 4H2O
and the alkaline salt of the corresponding ligand by Szekely
et al. [14].
presence of strong absorptions in the regions 1150–
1170 cmꢀ1, assigned to the tas(P2NH) stretching vibrations,
indicate that the dppaS2 ligand is coordinated to the palla-
dium center in the deprotonated form [6]. In K[N(PP2S)2]
salt, which is prepared to obtain [Pd(dppe)(dppaS2-
H)]CIO4 2a by different method, tas(P2N) vibration is at
1171.2 cmꢀ1. This absorption is at 1146.7 cmꢀ1 in complex
2a. Analytical data of four complexes are in accordance
with the proposed formulation.
In complexes 1, 2, 3 and 2a, the resonance due to the
diphosphines (dppm, dppe, dppp) phosphorus atoms
appear at –42.25, 72.06, 11.35 and 69.55 ppm, respectively.
It has been seen that the signals of chelate dppm and dppe
ligands are shifted to the downfield related to the starting
complexes [Pd(L-L)Cl2] (L-L = dppm, dppe), but dppp
ligand is shifted to the upfield on relative to the starting
complex, Pd(dppp)Cl2. Phosphorus chemical shifts of
dppaS2-H are 36.16, 38.67 and 37.63 ppm in complexes 1,
2 and 3, respectively.
N
R
R
R
R
N
R
R
R
R
P
P
E
P
E
P
E
E
M
2
1
In this study, we are reporting the preparation of
cationic palladium(II) complexes containing [Ph2P(S)-
NP(S)Ph2]ꢀ [disulfideimidodiphosphinato] of the type
[Pd(L-L)(dppaS2-H)]ClO4 [L-L = dppm (1), dppe (2), dppp
(3)]. Complex 2 was also synthesized 2a by using of
Pd(dppe)Cl2 and K[N(PSPh2)2] as starting materials. All of
these complexes have been characterized 31P{1H} NMR,
IR and elemental analyses. Complex 2 was recrystallized
from acetone/hexane, complex 3 was recrystallized from ace-
tone/diethyl ether and complex 2a was recrystallized from
dichloromethane/diethyl ether for X-ray crystallography.
In 31P{1H} NMR of pottassium salt, K[N(PP2S)2], there
is a shifted at 38.69 ppm. This resonance is at 38.65 ppm in
complex 2a and is suitable with value of the complex 2.
Solid state structures of complexes 2, 2a, and 3 were deter-
mined by single crystal X-ray diffraction. Complex 2 was
recrystallized from acetone/hexane and includes one mole-
cule acetone, complex 2a was recrystallized from CH2Cl2/
diethyl ether and has one molecule CH2Cl2. Complex 3
was recrystallized from acetone/diethyl ether and includes
one molecule acetone. The perspective view of complexes
2, 2a and 3 are given in Figs. 1–3, respectively. The selected
bond distances and angles are listed in Table. 1. Complexes
2 and 2a are monoclinic and complex 3 is triclinic crystal sys-
tems. The solvent (CH3)2CO and CH2Cl2 lie in the lattice on
non-bonded molecules in the complexes 2 and 3, respec-
tively. All of the data for complex 2 and 2a are similar. Pal-
ladium atoms in every complex are distorted square planar
environments with from P(3)Pd(1)S(1) and P(4)Pd(1)S(2)
are 168.90(4)ꢁ and 169.99(4)ꢁ for complex 2, 170.66(3)ꢁ and
170.92(3)ꢁ for complex 2a and 171.57(2)ꢁ and 173.96(2)ꢁ
for complex 3. The bite angles of iminobis(diphenylphos-
phine sulfide) in complexes 2 and 2a [102.94(3)ꢁ and
102.69(3)ꢁ) are different from complex 3 (98.82(2)ꢁ]. This dif-
ference can be explained by diphosphine bite angle
[P(4)Pd(1)P(3); 84.85(4)ꢁ for complex 2 and 84.61(3)ꢁ for
complex 2a and 91.62(2)ꢁ for complex 3]. These values are
comparable with the complexes [Pd(dppaS2-H)2] [5].
2. Results and discussion
Previous works have demonstrated that the imin-
obis(phosphinechalcogenide) ligands can be deprotonated
to afford coordinated dichalcogenoimidodiphosphinato
anions by the reaction of metal–halides or starting com-
plexes containing metal–halide bonds [15]. The starting
complexes, Pd(L-L)Cl2 (L-L = dppm, dppe, dppp) and
K[N(PP2S)2] were synthesized according to the literature
(see Section 2). 31P{1H} NMR spectra of these compounds
only a singlet dP values are ꢀ51.17, 67.67, 13.64 and
36.70 ppm, respectively. [Pd(L-L)(dppaS2-H)]ClO4 com-
plexes (1, 2, 3) were prepared by the mixing of solution
of Pd(L-L)Cl2 complexes in CH2Cl2 and dppaS2 ligand
and NaClO4 Æ H2O salt in (CH3)2CO. Another method
was used to prepared [Pd(dppe)(dppaS2-H)]ClO4 (2a). In
this method, the solution of K[N(PP2S)2] salt in CH3OH
was added solution of Pd(dppe)Cl2 in CH2Cl2 as a molar
ratio 1:1 in the presence of NaClO4 Æ H2O salt.
Solid state IR spectra of the complexes (1–3) showed the
characteristic absorption of P@S group at 570.0, 573.0 and
570.0 cmꢀ1. These absorptions are shifted to the lower fre-
quencies according to the free ligand, dppaS2, absorption
which is at 612.9 cmꢀ1. This shows that the ligand is coor-
dinating to Pd(II) center via S donor atoms in the com-
Pd–S bond lengths are slightly different from each other.
˚
Pd(1)–S(1) and Pd(1)–S(2) are 2.3933(10) and 2.4114(10) A
˚
for complex 2; 2.3853(9) and 2.4110(9) A for complex 2a;
˚
2.4017(6) and 2.3674(6) A for complex 3. These are compa-
rable with the literature values [16].
ꢀ
plexes. ClO4 group vibrations give rise to two bonds in
In complex 3, six membered dppp chelate ring has chair
conformation with Pd(1)P(3)C(13)C(14) and Pd(1)P(4)-
C(15)C(14) torsion angles of ꢀ44.4(3)ꢁ and 60.2(2)ꢁ, respec-
tively, and with Pd(1) and C(14) atoms are located at
1100 and 620 cmꢀ1 region. IR spectra of free acid, dppaS2,
exhibits absorption of medium intensity at 2630.8 cmꢀ1 and
very strong absorption at 922.0 cmꢀ1 which were assigned
to t(N–H) stretching vibration and tas(P2NH) stretching
vibration, respectively. In IR spectra of complexes 1, 2, 3,
˚
˚
ꢀ0.6932(21) A below and 0.7342(45) A above the plane
defined by the atoms P(3)–P(4)–C(13)–C(15).

4116
S. Yanar et al. / Polyhedron 26 (2007) 4114–4118
Fig. 1. The perspective view of 2 (20% thermal probability). Hydrogen
atoms, anions and solvent molecule are omitted for clarity.
Fig. 3. The perspective view of 3 (20% thermal probability). Hydrogen
atoms, anions and solvent molecule are omitted for clarity.
Table 1
˚
Selected bond angles (ꢁ) and distances (A) for [Pd(dppe)(dppaS2-H)]-
(ClO4) Æ (CH3)2CO (2), [Pd(dppe)(dppaS2-H)](ClO4) Æ CH2Cl2 (2a) and
[Pd(dppp)(dppaS2-H)](ClO4) Æ (CH3)2CO (3)
2
2a
3
Bond distances
Pd(1)–S(1)
Pd(1)–S(2)
P(1)–S(1)
P(2)–S(2)
Pd(1)–P(3)
Pd(1)–P(4)
2.3933(10)
2.4114(10)
2.0184(14)
2.0170(15)
2.2667(10)
2.2622(11)
2.3853(9)
2.4110(9)
2.0165(11)
2.0239(12)
2.2616(9)
2.2614(9)
2.4017(6)
2.3674(6)
2.0304(9)
2.0152(9)
2.2915(6)
2.2819(6)
Bond angles
S(1)–Pd(1)–S(2)
P(4)–Pd(1)–S(2)
P(3)–Pd(1)–P(4)
P(3)–Pd(1)–S(1)
P(3)–Pd(1)–S(2)
P(4)–Pd(1)–S(1)
102.69(3)
169.99(4)
84.85(4)
168.90(4)
88.13(3)
84.72(4)
102.94(3)
170.92(3)
84.61(3)
170.66(3)
86.39(3)
86.06(3)
98.82(2)
173.96(2)
91.62(2)
171.57(2)
84.50(2)
85.66(2)
Fig. 2. The perspective view of 2a (20% thermal probability). Hydrogen
atoms, anions and solvent molecule are omitted for clarity.
As a result, three new complexes have been synthesized.
Two different synthetic route was used for one of them and
their structures were determined by spectroscopic methods.
Six membered dppaS2-H rings are twist boat conforma-
tions in three complexes and are very similar to that
observed related platinum analogue [Pt(PEt3)2{Ph2P(S)-
NHP(S)Ph2}]PF6 in the literature [17].
3. Experimental
PNP bond angles are 122.41(19)ꢁ, 120.74(17)ꢁ and
121.47(13)ꢁ, respectively. These angles show the sp2 charac-
ter at the nitrogen atoms [5].
Solvents were dried according to the methods given in
the literature and were purified under inert conditions
[18]. All synthesis were carried using standard Schlenk tube
techniques under inert atmosphere.
dppm, dppe, dppp, NaCIO4 Æ H2O and acetone were
purchased from Merck Chemical; dichloromethane, tolu-
ene, methanol, hexane and diethylether were purchased
from Lab-Scan. The starting complexes, [PdCl2(COD)]
(COD = 1,5-cyclooctadiene) [19], which is used for prepar-
˚
P–S bond lengths are 2.0184(14) and 2.0170(15) A for
˚
complex 2; 2.0165(11) and 2.0239(12) A for complex 2a
˚
and 2.0304(9) and 2.0152(9) A for complex 3. P–S bond
distances, as expected, are longer than the analogous
P@S distances in the sulfur compounds and are suitable
with the similar compounds in the literature [6,7,14].

S. Yanar et al. / Polyhedron 26 (2007) 4114–4118
4117
ing the [PdCI2(L-L)] complexes [L-L = dppm (Ph2PCH2-
PPh2), dppe (Ph2PCH2CH2PPh2), dppp (Ph2PCH2CH2-
CH2PPh2)] [20], dppa (Ph2PNHPPh2) and dppaS2
(Ph2P(S)NHP(S)Ph2) were synthesized according to the
method given in the literature [21].
diethyl ether (1:3 v/v) to give yellow crystals. Yield
0.08 g, 41.9%. Data for 1: 31P{1H} NMR (DMSO):
ꢀ42.30 ppm (s), 36.18 ppm (s). Selected IR data (KBr):
m(PS) 570.0 cmꢀ1, 1098.5 (s) and 622.7 (m) cmꢀ1 (ClO4ꢀ).
Anal. Calc. for C49H42NClO4P4PdS2: C, 56.65; H, 4.04;
S, 6.17; N, 1.34. Found: C, 56.12; H, 4.16; S, 5.80; N,
1.65%.
31P{1H} NMR spectra were recorded on Varian AS
400+Mercury instruments, chemical shifts, in ppm, related
to external 85% H3PO4. Coupling constants are in Hz. IR
spectra were recorded from 4000 to 400 cmꢀ1 with a Per-
kin–Elmer 100 FT-IR instrument. Melting points were
determined by Electrothermal melting point detection
apparatus. Elemental analyses were performed by the
3.1.2. [Pd(dppe)(dppaS2-H)](ClO4)2 (2)
[PdCl2(dppe)] (0.17 mmol, 0.10 g), dppaS2 (0.17 mmol,
0.08 g) were placed together in 30 mL CH2CI2 and stirred.
The solution of NaClO4 Æ H2O (0.71 mmol, 0.10 g) in
20 mL acetone was added dropwise to the stirring solution.
After 24 h, the solution was removed in vacuo. The solid
was dissolved in CH2CI2 and then it was filtered through cel-
ite to separate NaCI. After the resulting solution was
removed in vacuo this complex was obtained as a cream solid
and it was recrystallized from acetone/hexane. (1:3 v/v).
Yield 0.07 g, 40%. Data for 2: 31P{1H} NMR (DMSO):
72.13 ppm (s), 38.76 ppm (s). Selected IR data (KBr): m(PS)
573.0 cmꢀ1, 1098.5 (s) and 622.7 (m) cmꢀ1 (ClO4ꢀ). Anal.
Calc. for C50H44NClO4P4PdS2: C, 57.04; H, 4.21; S, 6.09;
N, 1.33. Found: C, 56.44; H, 4.15; S, 5.53; N, 1.76%.
_
¨
TUBITAK-Ankara Test and Analyse Laboratories. There
is potential explosion hazard arising from the use of perchl-
orates in the presence of organic material, so quantities
should be kept small and heating (especially to dryness)
avoided.
3.1. Method I
3.1.1. [Pd(dppm)(dppaS2-H)](ClO4) (1)
PdCl2(dppm) (0.18 mmol, 0.10 g) and dppaS2
(0.18 mmol, 0.08 g) were placed in 30 mL CH2Cl2and stir-
red. The solution of NaClO4 Æ H2O (0.71 mmol, 0.10 g) in
20 mL acetone was added dropwise to the stirring solution.
Stirring was continued for 24 h at room temperature. After
that, the solution was removed in vacuo. Yellow solid was
dissolved in CH2CI2 and then it was filtered through celite
in order to separate NaCI. The solution was removed in
vacuo again. Complex 1 was recrystallized from acetone/
3.1.3. [Pd(dppp)(dppaS2-H)](ClO4)2 (3)
This complex was obtained as a yellow solid, in a
manner similar to
1
and
2
from [PdCl2(dppp)]
(0.17 mmol, 0.10 g), dppaS2 (0.17 mmol, 0.08 g) and
NaClO4 Æ H2O (0.71 mmol, 0.10 g). Yellow crystals, suit-
able for X-ray analysis, were obtained by slow diffusion
Table 2
Crystal data, data collection and structure-refinement parameters for complex 2, 2a and 3
Empirical formula
2
2a
3
C
50H44NClO4P4PdS2 Æ (CH3)2CO
C50H44NClO4P4PdS2 Æ CH2Cl2
C51H46NClO4P4PdS2 Æ (CH3)2CO
Color
light yellow
0.750 · 0.333 · 0.070
monoclinic
colorless
yellow
0.640 · 0.440 · 0.330
triclinic
Crystal size (mm)
Crystal system
Space group
0.560 · 0.353 · 0.190
monoclinic
P21/c
ꢀ
P21/c
P1
Unit cell dimensions
˚
a (A)
17.2474(8)
11.1817(4)
27.3800(12)
90.00
98.217(4)
90.00
5226.2(4)
4
1.412
13.2643(6)
27.6872(8)
15.3404(7)
90.00
111.568(3)
90.00
5239.3(4)
4
1.442
11.0367(5)
13.1618(6)
20.6186(9)
73.135(3)
77.898(4)
68.038(3)
2641.0(2)
2
˚
b (A)
˚
c (A)
a (ꢁ)
b (ꢁ)
c (ꢁ)
3
˚
Volume (A )
Z
Dcalc (Mg mꢀ3
)
1.414
Formula weight
Absorption coefficient (mmꢀ1
F (000)
1110.79
0.656
2280
1137.64
0.753
2320
1124.82
0.650
1156
)
Index ranges
ꢀ20 6 h 6 20,
ꢀ13 6 k 6 13,
ꢀ32 6 l 6 32
1.50–25.03
9164
ꢀ15 6 h 6 15,
ꢀ32 6 k6 32,
ꢀ18 6 l 6 18
1.47–25.04
9190
ꢀ12 6 h 6 13,
ꢀ16 6 k 6 16,
ꢀ25 6 l 6 25
1.72–26.00
10375
h Range (ꢁ)
Number of data measured
Number of data with [I > 2r(I)]
R1 [I > 2r(I)]
5612
0.0413
7266
0.0397
8827
0.0339
WR2 [I > 2r(I)]
0.0714
0.1117
0.0933

4118
S. Yanar et al. / Polyhedron 26 (2007) 4114–4118
of diethylether into a acetone solution of 3. (1:3 v/v).
Yield 0.09 g, 50.5%. Data for 3: 31P{1H} NMR (DMSO):
11.39 ppm (s), 37.67 ppm (s). Selected IR data (KBr):
m(PS) 570.0 cmꢀ1, 1098.5 (s) and 622.7 (m) cmꢀ1 (ClO4ꢀ).
Anal. Calc. for C51H46NClO4P4PdS2: C, 57.42; H, 4.31 ;
S, 6.01; N, 1.31. Found: C, 56.25; H, 4.41; S, 5.20; N,
1.50%.
graphic Data Centre, 12 Union Road, Cambridge CB2
1EZ, UK; fax: (+44) 1223-336-033; or e-mail:
deposit@ccdc.cam.ac.uk.
Acknowledgements
The authors acknowledge the Faculty of Arts and Sci-
ences, Ondokuz Mayis University, Turkey, for the use of
the STOE IPDS II diffractometer (purchased under Grant
F.279 of the University Research Fund).
3.2. Method II
3.2.1. [Pd(dppe)(dppaS2-H)](ClO4)2 (2a)
dppaS2 (0.45 mmol, 0.2 g) and KOBut (0.45 mmol,
0.05 g) were stirred in diethyl ether and K[N(SPPh2)2]
synthesized.
References
[1] K.K. Hii, Thornton-Pett, A. Jutand, R.P. Tooze, Organometallics 18
(1999) 1887.
K[N(SPPh2)2] (0.17 mmol, 0.085 g) in 5 mL methanol
and NaClO4 Æ H2O (0.71 mmol, 0.10 g) in 2 mL methanol
was added to PdCl2dppe (0.17 mmol, 0.1 g) in 15 mL
CH2Cl2. After 24 h, the solvent was removed in vacuo.
Complex 2a was recrystallized from CH2Cl2/diethyl ether
(1:3 v/v). Yield 0.11 g, 58.08%. Data for 2a: 31P{1H}
NMR (CDCl3): 69.5 ppm (s), 38.6 ppm (s). Selected IR
data (KBr): m(PS) 576.0 cmꢀ1, 1093.7 (s) and 623.1
(m) cmꢀ1 (ClO4ꢀ). Anal. Calc. for C50H44NClO4P4PdS2:
C, 57.04; H, 4.21; S, 6.09; N, 1.33. Found: C, 56.09; H,
4.38; S, 5.5; N, 1.65%.
[2] G.R. Newkome, Chem. Rev. 93 (1993) 2067.
[3] A. Bader, E. Lindner, Coord. Chem. Rev. 108 (1991) 27.
[4] N.J. Hovestad, E.B. Eggeling, H.J. Heidbuchel, J.T.B.H. Jastrzebski,
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U. Kragl, W. Keim, D. Vogt, G. van Koten, Angew. Chem. Int. Ed.
Engl. 38 (1999) 1655.
[5] P. Bhattacharyya, J. Novasad, J. Phillips, A.M.Z. Slawin, D.J.
Williams, J.D. Woollins, J. Chem. Soc. Dalton Trans. (1995) 1607.
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Haiduc, M. Watanabe, J.D. Woollins, Inorg. Chim. Acta 290 (1999)
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[7] G. Balazs, J.E. Drake, C. Silvestru, I. Haiduc, Inorg. Chim. Acta 287
(1999) 61.
[8] M.B. Smith, A.M.Z. Slawin, Inorg. Chim. Acta 299 (2000) 172.
[9] P. Bhattacharyya, A.M.Z. Slawin, M.B. Smith, J.D. Woollins, Inorg.
Chem. 35 (1996) 3675.
3.2.2. X-ray crystallographic study of 2, 2a and 3
The intensity data of the complexes 2, 2a and 3 were col-
lected using a STOE IPDS 2 diffractometer with graphite-
monochromated Mo Ka radiation (k = 0.71073) at
296 K. Details of crystal data, data collection, structure
solution and refinement are given in Table 2. Data collec-
tion: Stoe X-AREA [22]. Cell refinement: Stoe X-AREA
[22]. Data reduction: Stoe X-RED [22]. The structure was
solved by direct-methods using SHELXS-97 [23] and aniso-
tropic displacement parameters were applied to non-hydro-
gen atoms in a full-matrix least-squares refinement based
on F2 using SHELXL-97 [24]. All hydrogen atoms were
included using a riding model. Molecular drawings were
obtained using ORTEP-III [25].
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_
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4. Supplementary material
CCDC 622361, 622362 and 622363 contains the
supplementary crystallographic data for C50H44NClO4-
P4PdS2 Æ (CH3)2CO, C50H44NClO4P4PdS2 Æ CH2Cl2 and
C51H46NClO4P4PdS2 Æ (CH3)2CO respectively. These data
can be obtained free of charge via http://www.ccdc.ac.uk/
conts/retrieving.html, or from the Cambridge Crystallo-
[23] G.M. Sheldrick, Acta Cryst. A46 (1990) 467.
[24] G.M. Sheldrick, SHELXL-97, University of Go¨ttingen, Germany, 1997.
[25] M.N. Burnett, C.K. Johnson, OrtepIII. Report ORNL-6895. OAK
Ridge National Laboratory, Tennessee, USA, 1996.