New palladium complexes with phosphino- and phosphinitopyridine ligands

Article abstract of DOI:10.1107/S0108270106001296

Three new palladium complexes containing a difunctional P,N-chelate, namely tris(chloro{[1-methyl-1-(6-methyl-2-pyridyl)ethoxy]diphenylphospine- κ²N,P}methylpalladium(II)chloroform solvate, 3[Pd(CH ₃)Cl(C₂₁H₂₂NOP)]·CHCl₃, (III), dichloro[2-(2,6-dimethylphenyl)-6-(diphenylphosphinomethyl)pyridine- κ²N,P]palladium(II), [PdCl₂(C₂₆H ₂₄NP)], (IV), and chloro[2-(2,6-dimethylphenyl)-6- (diphenylphosphinomethyl)pyridine-κ²N,P]methylpalladium(II), [Pd(CH₃)Cl(C₂₆H₂₄NP)], (V), are reported. Geometric data and the conformations of the ligands around the metal centers, as well as slight distortions of the Pd coordination environments from idealized square-planar geometry, are discussed and compared with the situations in related compounds. Non-conventional hydrogen-bond interactions (C - H...Cl) have been found in all three complexes. Compound (III) is the first six-membered chloro-methyl-phosphinite P,N-type Pd^II complex to be structurally characterized.

Full text of DOI:10.1107/S0108270106001296

metal-organic compounds
Acta Crystallographica Section C
Crystal Structure
Communications
therein; Speiser et al., 2004, 2004a,b). We have recently
reported the synthesis of the ligands [1-methyl-1-(6-methyl-2-
pyridyl)ethoxy]diphenylphospine, (I) (Speiser et al., 2004),
and 2-(2,6-dimethylphenyl)-6-(diphenylphosphinomethyl)py-
ridine, (II) (Speiser et al., 2004a), and investigated the catalytic
properties of their [NiCl2(P,N)] complexes (P,N = P,N-
chelating ligand) for ethylene oligomerization. Owing to the
paramagnetism of these NiII compounds, it was felt desirable
to prepare analogous PdII complexes amenable to NMR
studies in solution. For comparison, we have selected
complexes of the type [PdCl2(P,N)], for which the PdÐCl
distances should provide direct evidence of the respective
trans in¯uences of the P- and N-donor functions, and of the
type [PdCl(CH3)(P,N)], since the stoichiometric or catalytic
insertion of small molecules (such as CO or ole®ns) into the
PdÐCH3 ꢁ bond is very much in¯uenced by the nature of the
donor group situated in the trans position. The new Pd
complexes (III)±(V) have been synthesized, and their struc-
tural features are analyzed and, in the case of (III), compared
with the Ni analog (Speiser et al., 2004).
ISSN 0108-2701
New palladium complexes with
phosphino- and phosphinitopyridine
ligands
Magno Agostinho,a Andrei Banu,a Pierre Braunstein,a*
Richard Welterb and Xavier Morisea
a
Â
Laboratoire de Chimie de Coordination, UMR CNRS 7177, Universite Louis Pasteur,
4 rue Blaise Pascal, 67070 Strasbourg Cedex, France, and bLaboratoire DECMET,
Â
UMR CNRS 7177, Universite Louis Pasteur, 4 rue Blaise Pascal, 67070 Strasbourg
Cedex, France
Correspondence e-mail: braunst@chimie.u-strasbg.fr
Received 17 October 2005
Accepted 11 January 2006
Online 11 February 2006
Three new palladium complexes containing a difunctional
P,N-chelate, namely tris(chloro{[1-methyl-1-(6-methyl-2-pyri-
dyl)ethoxy]diphenylphospine-ꢀ2N,P}methylpalladium(II)
chloroform solvate, 3[Pd(CH3)Cl(C21H22NOP)]ÁCHCl3, (III),
dichloro[2-(2,6-dimethylphenyl)-6-(diphenylphosphinometh-
yl)pyridine-ꢀ2N,P]palladium(II), [PdCl2(C26H24NP)], (IV),
and chloro[2-(2,6-dimethylphenyl)-6-(diphenylphosphino-
methyl)pyridine-ꢀ2N,P]methylpalladium(II), [Pd(CH3)Cl-
(C26H24NP)], (V), are reported. Geometric data and the
conformations of the ligands around the metal centers, as well
as slight distortions of the Pd coordination environments from
idealized square-planar geometry, are discussed and compared
with the situations in related compounds. Non-conventional
hydrogen-bond interactions (CÐHÁ Á ÁCl) have been found in
all three complexes. Compound (III) is the ®rst six-membered
chloro±methyl±phosphinite P,N-type PdII complex to be
structurally characterized.
Comment
Ligands containing at least two chemically different donor
functions and able to chelate a metal center are of consider-
able interest since they provide a way to in¯uence selectively
the bonding and/or reactivity of the other ligands, in particular
those in trans positions (Braunstein & Naud, 2001). This
concept has been successfully applied to ligands containing a
P,O- or a P,N-donor set (Braunstein & Naud, 2001; Slone et
al., 1999).
Phosphinito- and phosphinopyridine ligands ®nd wide-
spread applications in the coordination chemistry of transition
metals (Newkome, 1993, and references therein; Chen et al.,
2003a) and in homogeneous catalysis (Agbossou et al., 1998,
and references therein; Espinet & Soulantica, 1999, and
references therein; Bianchini & Meli, 2002, and references
therein; Chen et al., 2003b; Braunstein, 2004, and references
Despite the relevance of Pd complexes featuring these types
of P,N-donor ligands in the catalytic alternating copolymer-
ization of ole®ns and CO, as well as in other CÐC coupling
reactions, (III) is the ®rst six-membered chloro±methyl±
phosphinite P,N-type palladium(II) complex to be structurally
characterized. Other groups have reported six-membered
chloro±methyl±Pd complexes with iminophosphine (van den
Beuken et al., 1998; Song et al., 2002; Reddy et al., 2002;
Spek, 2003) and 1-(dimethylamino)-8-(diphenylphosphino)-
naphthalene ligands (Dekker et al., 1992). Recently, Chen et al.
(2003b) reported the ®rst structurally characterized ®ve-
membered chloro±methyl±phosphinopyridine-based PdII
complex. Other ®ve-membered chloro±methyl complexes
Acta Cryst. (2006). C62, m81±m86
DOI: 10.1107/S0108270106001296
# 2006 International Union of Crystallography m81

metal-organic compounds
Figure 1
The P,N-chelate conformations of molecules A±C in (III), showing the atomic labeling. Displacement ellipsoids are drawn at the 50% probability level.
H atoms and CH groups of phenyl rings have been omitted for clarity.
containing 2-(2-pyridyl)phosphaalkenes (van der Sluis et al.,
1997), 2-(2-pyridyl)phospholes (Sauthier et al., 2002), imino-
phosphines (Coleman et al., 2001; Reddy et al., 2001, 2002;
Doherty et al., 2002; Daugulis & Brookhart, 2002) and phos-
phinooxazoline (Apfelbacher et al., 2003) P,N-donor ligands
have also been reported.
The structure of (III) shows that the asymmetric unit
contains three very similar but crystallographically different
molecules (A±C), together with a chloroform solvent mol-
ecule. Although the geometric data are as expected for the
three molecules (Table 1), examination reveals (Fig. 1) that
the P,N-chelate in molecules A and C has approximately the
same conformation, whereas in B the pyridine ring has a
different orientation with respect to the PdÐN axis. This is
con®rmed by the torsion-angle values, which are similar for A
Figure 2
and C [Cl1ÐPd1ÐN1ÐC9 = 55.9 (3)ꢀ and Cl3ÐPd3ÐN3Ð
C53 = 61.6 (3)ꢀ, respectively], whereas for B the Cl2ÐPd2Ð
N2ÐC31 angle is 51.3 (3)ꢀ. The symmetry-equivalent asym-
metric units contain enantiomers of molecules A, B and C with
opposite torsion angles.
A view of the roof-like conformation formed by the ligand folding along
the Pd1Á Á ÁC2 hinge in the structure of molecule A of (III). Displacement
ellipsoids are drawn at the 50% probability level and H atoms have been
omitted for clarity.
Analysis of molecule A shows a folding of the ligand along
the Pd1Á Á ÁC2 hinge, creating a roof-like conformation, which
generates a niche limited by a phenyl group (Fig. 2). This
conformation is similar to the [NiCl2(P,N)] analog (Speiser et
al., 2004) for which the Ni coordination geometry was slightly
distorted square planar. The Pd atom is almost in the mean
plane passing through atoms Cl1, C1, N1 and P1 [the deviation
Ê
of the Pd atom is 0.0390 (3) A], and the sum of the bond
angles around the Pd atom is 360.56ꢀ. Although the distance
from the metal atom to the corresponding plane in the
Ê
analogous Ni complex [0.03 (1) A] is similar to that for Pd, the
sum of the bond angles around the Ni center is larger
(365.22ꢀ), indicating a slight distortion toward tetrahedral for
the Ni coordination (Speiser et al., 2004). Molecules B and C
are almost identical to A and therefore will not be discussed
further.
In the ligands of complexes (IV) (Fig. 3) and (V) (Fig. 4),
the geometric data (Tables 2 and 3) are similar and in the
expected ranges; the only marked difference between these
two structures concerns the PdÐN distance, which is larger in
Figure 3
A view of (IV), showing the atomic labeling. Displacement ellipsoids are
drawn at the 50% probability level and H atoms have been omitted for
clarity.
Ê
Ê
(V) [2.286 (3) A] than in (IV) [2.098 (2) A]. The aromatic
ꢁ
m82 Agostinho et al.
3[Pd(CH3)Cl(C21H22NOP)]ÁCHCl3 and [PdClX(C26H24NP)] (X = Cl and CH3)
Acta Cryst. (2006). C62, m81±m86

metal-organic compounds
substituent at the 6-position is oriented nearly perpendicular
to the pyridine ring, as evidenced by the N1ÐC6ÐC7ÐC12
torsion angles [70.3 (3)ꢀ for (IV) and 78.9 (4)ꢀ for (V)].
In (IV), the PdÐCl bond distance trans to the P atom is
longer than that trans to the N atom, which is consistent with
the respective trans in¯uences of the P- and N-donor atoms
(Hartley, 1973). The methyl group in (III) and (V) is cis to the
P atom, which is in agreement with the fact that the donor
groups with the largest trans in¯uence avoid being mutually
trans to one another. This is consistent with complexes of the
type [Pd(CH3)Cl(P,N)] (Apfelbacher et al., 2003; Chen et al.,
2003b; Coleman et al., 2001; Daugulis & Brookhart, 2002).
The P,N-chelate bite angle [81.74 (5)ꢀ for (IV) and
78.92 (8)ꢀ for (V)] is in accordance with that of other ®ve-
membered P,N-chelates [82.5 (2)ꢀ; Perera et al., 1995]. As
Figure 6
Part of the crystal structure of (IV), showing the CÐHÁ Á ÁCl interactions
(viewed down the c axis). (The symmetry code is as in Table 4.)
Figure 4
A view of (V), showing the atomic labeling. Displacement ellipsoids are
drawn at the 50% probability level and H atoms have been omitted for
clarity.
Figure 5
Figure 7
Part of the crystal structure of (III), showing the CÐHÁ Á ÁCl interactions
Part of the crystal structure of (V), showing the CÐHÁ Á ÁCl interaction
(viewed down the a axis). (The symmetry code is as in Table 4.)
(viewed down the c axis). (The symmetry code is as in Table 4.)
ꢁ
Acta Cryst. (2006). C62, m81±m86
Agostinho et al.
3[Pd(CH3)Cl(C21H22NOP)]ÁCHCl3 and [PdClX(C26H24NP)] (X = Cl and CH3) m83

metal-organic compounds
expected, on increasing in size from this ®ve-membered
chelate ring to a six-membered ring as in (III), the
chelate bite angle increases by 4±5ꢀ [84.03 (8)ꢀ for mole-
cule A in (III)].
(C23ÐH23Á Á ÁCl1ii; Fig. 7). In both cases, these interactions
result in in®nite one-dimensional chains of molecules along
(100).
From a packing viewpoint, the crystal structure of (III) can
be described in term of pseudo-slabs stacked along (001).
These slabs, interconnected by van der Waals contacts, are
constituted by a succession of A, B and C moieties, as de®ned
above (Fig. 1), with chloroform solvent molecules located
between these slabs (Fig. 8). For (IV) and (V) (Fig. 9), the bc
and ac projections show that the molecular moieties are placed
along pseudo-slabs, with these slabs connected via van der
Waals contacts, but speci®cally through the organic part of the
corresponding molecules.
Although no classical intermolecular hydrogen bonds were
detected in (III)±(V), signi®cant non-conventional CÐHÁ Á ÁCl
hydrogen bonds are present and these constitute structure-
directing elements. Compound (III) has an interaction invol-
ving the Cl atom on the Pd metal center of molecule A and a
phenyl H atom of a neighboring A molecule (C13Ð
H13Á Á ÁCl1i; all symmetry codes as in Table 4; Fig. 5). Another
interaction of this type is observed between the H atom of the
chloroform solvent molecule and the Cl atom from the
palladium metal center of molecule B (C67ÐH67Á Á ÁCl2ii).
Furthermore, molecules A and C have an intramolecular
interaction between a phenyl H atom and the O atom adjacent
to the P atom (C22ÐH22Á Á ÁO1 and C66ÐH66Á Á ÁO3), and
®nally in molecule B an interaction involves the H atoms of
the pyridine methyl group and the Pd-bound Cl atom (C32Ð
H32Á Á ÁCl2). In (IV), an interaction exists between a Pd-bound
Cl atom and a pyridine H atom (C4ÐH4Á Á ÁCl2ii) (Fig. 6). A
similar interaction occurs in (V) involving a phenyl H atom
Experimental
All solvents were dried and distilled under N2 using common tech-
niques unless otherwise stated. [Pd(CH3)Cl(COD)] and [PdCl2-
(COD)] (COD is 1,5-cyclooctadiene, C8H12) were prepared according
to literature methods (Rulke et al., 1993; Ladipo & Anderson, 1994;
Chatt et al., 1957), as were ligands (I) and (II) (Speiser et al., 2004,
2004a). Compound (III) was synthesized by the addition of solid
[Pd(CH3)Cl(COD)] (0.391 g, 1.475 mmol) to a solution of (I)
(0.545 g, 1.623 mmol) in CH2Cl2 (20 ml); the resulting yellow mixture
was stirred for 2 h at room temperature. The solvent was evaporated
under reduced pressure and the white residue was washed with
diethyl ether (2 Â 10 ml) and pentane (1 Â 10 ml). The product was
dried under vacuum overnight, and (III) was obtained as a white
solid. Crystals of (III) suitable for X-ray diffraction were obtained by
slow diffusion of pentane into a CHCl3 solution of (III) (yield 0.442 g,
0.897 mmol, 61%). Compound (IV) was obtained using a procedure
similar to that described for (III), using (II) (0.615 g, 1.612 mmol) and
[PdCl2(COD)] (0.460 g, 1.612 mmol), and was obtained as a yellow±
white solid. Crystals of (IV) suitable for X-ray diffraction were
obtained by slow diffusion of pentane into a CH2Cl2 solution of (IV)
(yield 0.595 g, 1.064 mmol, 66%). Compound (V) was obtained using
a procedure similar to that described above for the preparation of
(III), using (II) (0.588 g, 1.541 mmol) and [Pd(CH3)Cl(COD)]
(0.408 g, 1.541 mmol), and was obtained as a yellow±white solid.
Crystals of (V) suitable for X-ray diffraction were obtained by slow
diffusion of pentane into a CH2Cl2 solution of this complex (yield
0.463 g, 0.859 mmol, 56%).
Figure 8
A view of the packing for complex (III) (viewed down the a axis).
Figure 9
A view of the packing for complexes (IV) (left; viewed down the a axis) and (V) (right; viewed down the b axis).
ꢁ
m84 Agostinho et al.
3[Pd(CH3)Cl(C21H22NOP)]ÁCHCl3 and [PdClX(C26H24NP)] (X = Cl and CH3)
Acta Cryst. (2006). C62, m81±m86

metal-organic compounds
Re®nement
Re®nement on F2
Compound (III)
w = 1/[ꢁ2(F2o) + (0.0331P)2
+ 0.3488P]
Crystal data
R[F2 > 2ꢁ(F2)] = 0.031
wR(F2) = 0.078
S = 1.00
3
where P = (F2o + 2Fc2)/3
(Á/ꢁ)max = 0.001
3[Pd(CH3)Cl(C21H22NOP)]ÁCHCl3
Dx = 1.526 Mg m
Mo Kꢃ radiation
Mr = 1596.12
Monoclinic, P21=c
3
Ê
5587 re¯ections
280 parameters
H-atom parameters constrained
Áꢆmax = 0.49 e A
Cell parameters from 53191
re¯ections
3
Ê
0.80 e A
Ê
Ê
Áꢆmin
=
a = 14.628 (1) A
b = 28.573 (5) A
ꢄ = 1.0±30.0ꢀ
1
Ê
c = 17.324 (2) A
ꢅ = 1.11 mm
T = 173 (2) K
ꢂ = 106.39 (5)ꢀ
Ê
V = 6947 (2) A
Z = 4
3
Table 2
Selected geometric parameters (A, ) for (IV).
Prism, yellow
0.13 Â 0.10 Â 0.08 mm
ꢀ
Ê
Data collection
Pd1ÐCl1
Pd1ÐCl2
Pd1ÐP1
Pd1ÐN1
2.3747 (12)
2.2749 (13)
2.2093 (11)
2.098 (2)
P1ÐC1
N1ÐC2
C1ÐC2
1.826 (3)
1.369 (3)
1.506 (3)
Nonius KappaCCD diffractometer
! scans
58356 measured re¯ections
20304 independent re¯ections
13997 re¯ections with I > 2ꢁ(I)
Rint = 0.067
ꢄmax = 30.0ꢀ
h = 20 ! 20
k = 40 ! 37
l = 20 ! 24
N1ÐPd1ÐP1
N1ÐPd1ÐCl2
P1ÐPd1ÐCl2
81.74 (5)
171.99 (5)
90.52 (3)
N1ÐPd1ÐCl1
P1ÐPd1ÐCl1
Cl2ÐPd1ÐCl1
96.05 (5)
167.92 (2)
91.95 (3)
Re®nement
Re®nement on F2
R[F2 > 2ꢁ(F2)] = 0.059
wR(F2) = 0.123
S = 1.09
20304 re¯ections
766 parameters
H-atom parameters constrained
w = 1/[ꢁ2(F2o) + (0.05P)2]
where P = (F2o + 2Fc2)/3
(Á/ꢁ)max < 0.001
Compound V
3
Ê
Áꢆmax = 0.69 e A
3
Crystal data
Ê
0.88 e A
Áꢆmin
=
[Pd(CH3)Cl(C26H24NP)]
Mr = 538.32
Mo Kꢃ radiation
Cell parameters from 23164
re¯ections
Monoclinic, P21=n
Table 1
Selected geometric parameters (A, ) for (III).
a = 11.507 (1) A
ꢄ = 1.0±30.0ꢀ
ꢅ = 0.97 mm
T = 173 (2) K
Ê
Ê
ꢀ
Ê
1
b = 12.011 (2) A
Ê
c = 17.490 (2) A
Pd1ÐCl1
Pd1ÐP1
Pd1ÐN1
Pd1ÐC1
Pd2ÐCl2
Pd2ÐP2
Pd2ÐN2
Pd2ÐC23
2.3838 (10)
2.1650 (9)
2.205 (3)
Pd3ÐCl3
Pd3ÐP3
Pd3ÐN3
Pd3ÐC45
P1ÐO1
2.3929 (12)
2.1725 (13)
2.200 (3)
2.034 (4)
1.611 (2)
1.608 (2)
1.617 (2)
ꢂ = 99.92 (5)ꢀ
V = 2381.2 (6) A
Prism, yellow
0.10 Â 0.08 Â 0.06 mm
3
Ê
Z = 4
Dx = 1.502 Mg m
2.038 (4)
3
2.4047 (10)
2.1717 (10)
2.193 (3)
P2ÐO2
P3ÐO3
Data collection
2.050 (4)
Nonius KappaCCD diffractometer
! scans
6838 measured re¯ections
6837 independent re¯ections
4250 re¯ections with I > 2ꢁ(I)
Rint = 0.045
ꢄmax = 30.0ꢀ
h = 16 ! 15
k = 0 ! 16
l = 0 ! 24
C1ÐPd1ÐP1
C1ÐPd1ÐN1
P1ÐPd1ÐN1
C1ÐPd1ÐCl1
P1ÐPd1ÐCl1
N1ÐPd1ÐCl1
C23ÐPd2ÐP2
C23ÐPd2ÐN2
P2ÐPd2ÐN2
91.45 (12)
173.65 (14)
84.03 (8)
90.20 (12)
172.09 (4)
94.87 (8)
93.23 (12)
176.97 (13)
83.76 (8)
C23ÐPd2ÐCl2
P2ÐPd2ÐCl2
N2ÐPd2ÐCl2
C45ÐPd3ÐP3
C45ÐPd3ÐN3
P3ÐPd3ÐN3
C45ÐPd3ÐCl3
P3ÐPd3ÐCl3
N3ÐPd3ÐCl3
88.48 (12)
175.46 (4)
94.50 (8)
91.45 (12)
174.34 (14)
84.71 (8)
90.38 (12)
168.49 (4)
94.21 (9)
Table 3
Selected geometric parameters (A, ) for V.
ꢀ
Ê
Pd1ÐCl1
Pd1ÐP1
Pd1ÐN1
Pd1ÐC27
2.3681 (14)
2.189 (2)
2.286 (3)
2.042 (4)
P1ÐC1
N1ÐC2
C1ÐC2
1.823 (4)
1.356 (4)
1.510 (5)
C27ÐPd1ÐP1
C27ÐPd1ÐN1
P1ÐPd1ÐN1
91.64 (11)
170.52 (11)
78.92 (8)
C27ÐPd1ÐCl1
P1ÐPd1ÐCl1
N1ÐPd1ÐCl1
88.40 (11)
173.30 (4)
101.07 (8)
Compound (IV)
Crystal data
[PdCl2(C26H24NP)]
Mr = 558.73
Triclinic, P1
Z = 2
Dx = 1.566 Mg m
Mo Kꢃ radiation
3
Table 4
Hydrogen-bond parameters (A, ) for compounds (III)±(V).
Ê
ꢀ
Ê
a = 10.151 (1) A
Cell parameters from 7840
re¯ections
Ê
b = 11.461 (1) A
c = 12.106 (2) A
ꢄ = 1.0±27.9ꢀ
ꢅ = 1.09 mm
T = 173 (2) K
Ê
Compound
(III)
DÐHÁ Á ÁA
DÐH
HÁ Á ÁA
DÁ Á ÁA
DÐHÁ Á ÁA
1
ꢃ = 95.40 (5)ꢀ
ꢂ = 109.93 (5)ꢀ
ꢇ = 112.23 (5)ꢀ
C13ÐH13Á Á ÁCl1i
C22ÐH22Á Á ÁO1
C32ÐH32Á Á ÁCl2
C66ÐH66Á Á ÁO3
C67ÐH67Á Á ÁCl2ii
0.95
0.95
0.98
0.95
1.00
2.74
2.56
2.68
2.53
2.56
3.630 (4)
2.975 (5)
3.449 (4)
2.909 (5)
3.523 (4)
156
107
136
104
161
Prism, yellow±orange
0.13 Â 0.10 Â 0.08 mm
3
Ê
V = 1184.7 (9) A
Data collection
Nonius KappaCCD diffractometer
! scans
14956 measured re¯ections
5587 independent re¯ections
4878 re¯ections with I > 2ꢁ(I)
Rint = 0.033
ꢄmax = 27.8ꢀ
h = 13 ! 13
k = 14 ! 15
l = 15 ! 15
(IV)
(V)
C4ÐH4Á Á ÁCl2ii
C23ÐH23Á Á ÁCl1ii
0.95
0.95
2.73
2.83
3.410 (4)
3.750 (4)
130
164
Symmetry codes: (i) x; y ‡ 1=2; z 1=2; (ii) x ‡ 1; y; z.
ꢁ
Acta Cryst. (2006). C62, m81±m86
Agostinho et al.
3[Pd(CH3)Cl(C21H22NOP)]ÁCHCl3 and [PdClX(C26H24NP)] (X = Cl and CH3) m85

metal-organic compounds
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Sweet, pp. 307±326. New York: Academic Press.
Re®nement
Re®nement on F2
R[F2 > 2ꢁ(F2)] = 0.055
wR(F2) = 0.112
S = 0.91
6837 re¯ections
280 parameters
H-atom parameters constrained
w = 1/[ꢁ2(F2o)]
where P = (F2o + 2Fc2)/3
(Á/ꢁ)max < 0.001
3
Ê
Áꢆmax = 0.72 e A
3
Ê
0.63 e A
Áꢆmin
=
The rotational orientations of the methyl groups were re®ned
using the circular Fourier method available in SHELXL97 (Shel-
drick, 1997). All H atoms were treated as riding, with CÐH distances
Ê
ranging from 0.95 to 1.00 A and Uiso(H) values equal to 1.5 (methyl H
atoms) or 1.2 (all other H atoms) times Ueq(C).
For all compounds, data collection: COLLECT (Nonius, 1998); cell
re®nement: DENZO (Otwinowski & Minor, 1997); data reduction:
DENZO; program(s) used to solve structure: SHELXS97 (Sheldrick,
1997); program(s) used to re®ne structure: SHELXL97 (Sheldrick,
1997); molecular graphics: PLATON98 (Spek, 1998); software used
to prepare material for publication: SHELXL97.
Perera, S. D., Shaw, B. L. & Thornton-Pett, M. (1995). Inorg. Chim. Acta, 236,
7±12.
Reddy, K. R., Surekha, K., Lee, G.-H., Peng, S.-M., Chen, J.-T. & Liu, S.-T.
(2001). Organometallics, 20, 1292±1299.
Á
The authors thank the CNRS, the Ministere de la
Recherche (Paris), the Institut FrancËais du Petrole (IFP) and
the Europeen Commission (Palladium Network HPRN-CT-
2002-00196 and COST program) for support.
Reddy, K. R., Tsai, W.-W., Surekha, K., Lee, G.-H., Peng, S.-M., Chen, J.-T. &
Liu, S.-T. (2002). J. Chem. Soc. Dalton Trans. pp. 1776±1782.
Rulke, R. E., Ernsting, J. M., Spek, A. L., Elsevier, C. J., van Leeuwen,
P. W. N. M. & Vrieze, K. (1993). Inorg. Chem. 32, 5769±5778.
Sauthier, M., Leca, F., Toupet, L. & Reau, R. (2002). Organometallics, 21,
1591±1602.
Â
Supplementary data for this paper are available from the IUCr electronic
archives (Reference: GG1299). Services for accessing these data are
described at the back of the journal.
Sheldrick, G. M. (1997). SHELXL97 and SHELXS97. University of
È
Gottingen, Germany.
Slone, C. S., Weinberger, D. A. & Mirkin, C. A. (1999). Prog. Inorg. Chem. 48,
233±350.
Sluis, M. van der, Beverwijk, V., Termaten, A., Gavrilova, E., Bickelhaupt, F.,
Kooijman, H., Veldman, N. & Spek, A. L. (1997). Organometallics, 16, 1144±
1152.
Song, H.-B., Zhang, Z.-Z. & Mak, T. C. W. (2002). Polyhedron, 21, 1043±
1050.
Speiser, F., Braunstein, P. & Saussine, L. (2004a). Organometallics, 23, 2633±
2640.
Speiser, F., Braunstein, P. & Saussine, L. (2004b). Organometallics, 23, 2625±
2632.
Speiser, F., Braunstein, P., Saussine, L. & Welter, R. (2004). Inorg. Chem. 43,
1649±1658.
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Spek, A. L. (2003). Acta Cryst. E59, m97±m98.
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ꢁ
m86 Agostinho et al.
3[Pd(CH3)Cl(C21H22NOP)]ÁCHCl3 and [PdClX(C26H24NP)] (X = Cl and CH3)
Acta Cryst. (2006). C62, m81±m86