Dichlorido{N-[2-(diphenylphosphanyl)benzylidene]-2-methylaniline} palladium(II) acetonitrile monosolvate

Article abstract of DOI:10.1107/S0108270113002333

The title imino-phosphine compound, [PdCl₂(C₂₆H ₂₂NP)]·CH₃CN, was prepared by reaction of N-[2-(diphenylphosphanyl)benzylidene]-2-methylaniline with dichlorido(cycloocta- 1,5-diene)palladium(II) in dry CH₂C_l2. The Pd^II cation is coordinated by the P and N atoms of the bidentate chelating ligand and by two chloride anions, generating a distorted square-planar coordination geometry. There is a detectable trans influence for the chloride ligands. The methyl group present in this structure has an influence on the crystal packing. Copyright

Full text of DOI:10.1107/S0108270113002333

metal-organic compounds
Acta Crystallographica Section C
Crystal Structure
Communications
human colon (HT-29) cancer cell lines compared with the
reference drug cisplatin. The recorded cytotoxic activities
could be attributed to the higher aqueous solubility of this
palladium(II) complex, which makes it easier to dissociate in
solution, thereby making the compound bio-available (Gao et
al., 2009). The imino–phosphine ligand N-[2-(diphenylphos-
phanyl)benzylidene]-2-methylaniline forms a six-membered
ring around the metal centre, which stabilizes the complex
during biological investigations, probably resulting in the
observed antitumour profiles (Bacchi et al., 2000).
ISSN 0108-2701
Dichlorido{N-[2-(diphenylphos-
phanyl)benzylidene]-2-methylaniline}-
palladium(II) acetonitrile monosolvate
William M. Motswainyana,a Martin O. Onani,a Jeroen
Jacobsb and Luc Van Meerveltb*
aUniversity of the Western Cape, Private Bag X17, Bellville 7535, South Africa, and
bChemistry Department, KU Leuven, Celestijnenlaan 200F, B-3001 Leuven
(Heverlee), Belgium
Correspondence e-mail: luc.vanmeervelt@chem.kuleuven.be
The PdII cation in (I) (Fig. 1) is coordinated by the P and N
atoms of the imino–phosphine ligand and two chloride anions,
generating a distorted square-planar coordination geometry
around the metal centre. The bond angles around Pd1
(Table 1) describe the observed distorted square-planar
geometry, while also indicating some ring strain induced by the
chelating nature of the bidentate ligand. The Pd—C1 bond
lengths (Table 1) are in good agreement with the average
Received 21 January 2013
Accepted 23 January 2013
Online 5 February 2013
The title imino–phosphine compound, [PdCl2(C26H22NP)]Á-
CH3CN, was prepared by reaction of N-[2-(diphenylphos-
phanyl)benzylidene]-2-methylaniline with dichlorido(cyclo-
octa-1,5-diene)palladium(II) in dry CH2Cl2. The PdII cation
is coordinated by the P and N atoms of the bidentate chelating
ligand and by two chloride anions, generating a distorted
square-planar coordination geometry. There is a detectable
trans influence for the chloride ligands. The methyl group
present in this structure has an influence on the crystal
packing.
˚
Pd—Cl bond length of 2.298 (15) A for known palladium(II)
complexes (Allen, 2002; Chiririwa & Muller, 2012). The
average Pd—N and Pd—P bond lengths (Table 1) also
compare well with literature values (Chiririwa & Muller, 2012;
Motswainyana et al., 2012). There is a detectable trans influ-
ence for the chloride anions, since the Pd1—Cl2 bond is
significantly longer than Pd1—Cl1, thus reflecting the stronger
trans influence of the diphenylphosphanyl group compared to
the amine (Doherty et al., 2002). The PdII cation deviates by
Comment
Imino–phosphine complexes have been studied since the early
1990s (Newkome, 1993; Ghilardi et al., 1992). Their prepara-
tion is versatile because a wide range of amines and aldehydes
of varying steric bulk are either available commercially or can
be easily synthesized (Mogorosi et al., 2011; Nobre &
Monteiro, 2009; Pellagati et al., 2005; Newkome, 1993; Ghilardi
et al., 1992; Vaughan et al., 2011; Puri et al., 2011; Doherty et al.,
2002; Onani et al., 2010; Motswainyana et al., 2012). The soft P
atom coordinates strongly to soft metals, while the hard N
atom is weakly coordinated and therefore more easily
displaced, thus allowing hemilability. The hemilability of these
ligands provides a unique reversible protection of coordina-
tion sites, an important property of ligands which leads to
improved catalytic reactions (Ojwach et al., 2007).
˚
0.0026 (3) A from the best least-squares plane through atoms
P1, N1, Cl1 and Cl2. This plane makes an angle of 46.57 (11)ꢀ
with the best least-squares plane through the C2–C7 ring. The
Pd-containing six-membered ring has a screw-boat confor-
Phosphine-based complexes have been less well explored
for their potential to inhibit tumour growth, possibly due to
their susceptibility to oxidation, which makes them very
difficult to handle in air. In our attempt to prepare new imino–
phosphine palladium(II) complexes, which could induce
apoptosis in tumour cells, we synthesized and crystallized the
title compound, (I).
Figure 1
The molecular structure of (I), showing the atom-numbering scheme.
Displacement ellipsoids are drawn at the 50% probability level.
Compound (I) has proved to possess remarkable anti-
proliferative activities against the human breast (MCF-7) and
Acta Cryst. (2013). C69
doi:10.1107/S0108270113002333
# 2013 International Union of Crystallography 1 of 3

metal-organic compounds
mation, with atoms Pd1 and P1 deviating from the plane
through the other four atoms.
Despite the presence of several benzene rings, no ꢀ–ꢀ
interactions are present in (I); only a number of weaker C—
i
˚
HÁ Á Áꢀ contacts are observed [C23—H23Á Á ÁCg1 = 2.84 A and
ii
˚
C26—H26AÁ Á ÁCg2 = 2.93 A; Cg1 and Cg2 are the centroids
of the C2–C7 and C14–C19 rings, respectively; symmetry
3
codes: (i) Àx + , y À , Àz + ; (ii) Àx + , y + , Àz + 32].
1
3
3
1
2
2
2
2
2
The asymmetric unit of (I) contains one acetonitrile solvent
molecule, which was essential during the crystallization
experiments to obtain good quality crystals. Two acetonitrile
3
˚
molecules occupy relatively large voids of 233 A , and there
are four such voids in the unit cell. In the packing, the position
of the acetonitrile is fixed on one side by a C27—H27CÁ Á ÁCl2
interaction [H27CÁ Á ÁCl2iii = 2.70 A; symmetry code: (iii)
˚
Àx + 1, Ày + 2, Àz + 1] and by a weak ꢀ-interaction (C27—
˚
H27BÁ Á ÁCg2 = 3.29 A) (Fig. 2). Furthermore, atom N2 inter-
acts with atoms H11, H16 and H22 of neighbouring molecules
˚
iv
v
vi
˚
[N2Á Á ÁH11 = 2.76 A, N2Á Á ÁH16 = 2.65 A and N2Á Á ÁH22 =
1
˚
2.78 A; symmetry codes: (iv) x, y À 1, z; (v) Àx + 1, y, Àz + 2;
(vi) Àx + 1, Ày + 1, Àz + 1]. Despite these interactions, the
acetonitrile molecules show a slight disorder, as indicated by
the difference Àe3lectron-density map (e.g. peaks of 0.63, 0.46
˚
and À0.52 e A close to acetonitrile).
Figure 3
C—HÁ Á ÁCl interations (dashed lines) in the crystal packing of (I). For
clarity, only H atoms involved in the interactions are shown. [Symmetry
codes: (ii) Àx + 32, y + 21, Àz + 32; (iii) Àx + 1, Ày + 2, Àz + 1; (vii) x, y + 1, z;
1
2
(viii) x, Ày + 2, z + .]
The shortest interactions for both Cl atoms are of the C—
vii
HÁ Á ÁCl type (Fig. 3) [Cl1Á Á ÁH13iii = 2.86 A, Cl1Á Á ÁH17
=
= 2.83 A and
˚
viii
ii
˚
˚
˚
2.75 A, Cl2Á Á ÁH1 = 2.60 A, Cl2Á Á ÁH5
Cl2Á Á ÁH27Ciii = 2.70 A; symmetry codes: (vii) x, y + 1, z; (viii)
˚
x, Ày + 2, z + 12].
The Cambridge Structural Database (CSD, Version 5.34;
Allen, 2002) has 18 structures containing dichlorido-
{[2-(diphenylphosphanyl)benzylidene]amine}palladium(II)
groups. The angle between the best planes through the
benzene ring and the PdCl2NP group range from 27.6 to 62.5ꢀ.
The structure with refcode XUWHIG (Koprowski et al., 2002)
is almost identical to (I), only missing the ortho-methyl group,
but crystallizes in the space group P1. A fit of the Pd complex
from the two structures, excluding the methyl group of (I),
˚
results in an r.m.s. deviation of 0.263 A. As in (I), both Cl
atoms attached to Pd also interact with H—C bonds. However,
the interaction of the Cl atom in XUWHIG equivalent to Cl2
in (I) with the H atom in XUWHIG attached to the C atom
equivalent to C25 in (I) results in the formation of centro-
symmetric dimers in XUWHIG and hence in a different
crystal packing compared to (I).
Figure 2
Experimental
The interaction of the acetonitrile solvent molecules with neighbouring
complex molecules in (I). Dashed lines indicate the various interactions.
The centroid of the C14–C19 ring is indicated by a solid dot (yellow in the
electronic version of the paper). For clarity, only H atoms involved in the
interactions are shown. [Symmetry codes: (iii) Àx + 1, Ày + 2, Àz + 1; (iv)
x, y À 1, z; (v) Àx + 1, y, Àz + 12; (vi) Àx + 1, Ày + 1, Àz + 1.]
All reactions were carried out under a nitrogen atmosphere using a
dual vacuum/nitrogen line and standard Schlenk techniques. Solvents
were dried and purified by heating under reflux and under a nitrogen
atmosphere in the presence of a suitable drying agent.
ꢁ
2 of 3 Motswainyana et al.
[PdCl2(C26H22NP)]ÁC2H3N
Acta Cryst. (2013). C69

metal-organic compounds
Table 1
Selected geometric parameters (A, ).
All H atoms were placed in idealized positions and refined in
ꢀ
˚
˚
riding mode, with C—H = 0.93 (aromatic) or 0.96 A (methyl) and
Uiso(H) = 1.2 or 1.5Ueq(C).
Pd1—Cl1
Pd1—Cl2
2.2770 (7)
2.3664 (7)
Pd1—P1
Pd1—N1
2.2122 (8)
2.049 (2)
Data collection: CrysAlis PRO (Agilent, 2012); cell refinement:
CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to
solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to
refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics:
OLEX2 (Dolomanov et al., 2009); software used to prepare material
for publication: OLEX2.
Cl1—Pd1—Cl2
P1—Pd1—Cl1
P1—Pd1—Cl2
89.95 (3)
91.45 (3)
178.15 (3)
N1—Pd1—Cl1
N1—Pd1—Cl2
N1—Pd1—P1
178.15 (7)
91.61 (7)
87.01 (7)
The authors acknowledge the University of the Western
Cape Senate Research, the South African National Research
Foundation and KU Leuven International Admissions and
Mobility for financial support. The authors also thank the
Hercules Foundation for supporting the purchase of the
diffractometer through project No. AKUL/09/0035.
For the preparation of N-[2-(diphenylphosphanyl)benzylidene]-2-
methylaniline, 2-methylaniline (0.1030 g, 0.961 mmol) was added
dropwise to a solution of 2-(diphenylphosphanyl)benzaldehyde
(0.2790 g, 0.961 mmol) in dry CH2Cl2 (10 ml). Anhydrous magnesium
sulfate (0.5 g) was added to the solution, after which the reaction was
stirred at room temperature for 20 h. The resulting yellow mixture
was filtered to obtain a yellow solution, which gave a yellow oil upon
evaporation of the solvent (yield: 0.2990 g, 82%). IR (Nujol, ꢁ, cmÀ1):
1622 (C N imine), 1593, 1585, 1505 (C C phenyl), 1435 (P—Ph).
Analysis calculated for C26H22NP: C 82.30, H 5.84, N 3.69%; found: C
82.04, H 5.93, N 3.55%.
Supplementary data for this paper are available from the IUCr electronic
archives (Reference: SK3474). Services for accessing these data are
described at the back of the journal.
The preparation of (I) followed the synthetic protocol of
Koprowski et al. (2002), with minor modifications at the precipitation
stage of the product. Crystals of (I) suitable for X-ray crystallographic
analysis were grown by slow evaporation from an acetonitrile solu-
tion of the complex (yield: 0.0697 g, 75%). IR (Nujol, ꢁ, cmÀ1): 1614
(C N imine), 1585, 1560, 1502 (C C phenyl). Analysis calculated
for C26H22Cl2NPPd: C 56.09, H 3.98, N 2.52%; found: C 55.83, H 4.22,
N 2.77%.
References
Agilent (2012). CrysAlis PRO. Agilent Technologies, Yarnton, Oxfordshire,
England.
Allen, F. H. (2002). Acta Cryst. B58, 380–388.
Bacchi, A., Carcelli, M., Costa, M., Fochi, A., Monici, C., Pelagatti, P., Pelizzi,
C., Pelizzi, G. & Roca, L. M. S. (2000). J. Organomet. Chem. 593, 180–191.
Chiririwa, H. & Muller, A. (2012). Acta Cryst. E68, m116–m117.
Doherty, S., Knight, J. G., Scanlam, T. H., Elsegood, M. R. J. & Clegg, W.
(2002). J. Organomet. Chem. 650, 231–248.
Dolomanov, O. V., Bourhis, L. J., Gildea, R. J., Howard, J. A. K. & Puschmann,
H. (2009). J. Appl. Cryst. 42, 339–341.
Gao, E., Liu, C., Zhu, M., Lin, H., Wu, Q. & Liu, L. (2009). Anticancer Agents
Med. Chem. 9, 356–368.
Ghilardi, C. A., Midollini, S., Moneti, S., Orlandini, A. & Scapacci, G. (1992).
J. Chem. Soc. Dalton Trans. pp. 3371–3376.
Koprowski, M., Sebastian, R.-M., Maraval, V., Zablocka, M., Cadierno, V.,
Donnadieu, B., Igau, A., Caminade, A.-M. & Majoral, J.-P. (2002). Organo-
metallics, 21, 4680–4687.
Mogorosi, M. M., Mahamo, T., Moss, J. R., Mapolie, S. F., Slootweg, J. C.,
Lammertsma, K. & Smith, G. S. (2011). J. Organomet. Chem. 696, 3585–
3592.
Crystal data
3
˚
[PdCl2(C26H22NP)]ÁC2H3N
V = 5291.3 (12) A
Z = 8
Mr = 597.77
Monoclinic, C2=c
Mo Kꢃ radiation
ꢄ = 0.98 mmÀ1
T = 100 K
˚
a = 32.350 (3) A
˚
b = 9.9963 (3) A
˚
c = 20.8851 (16) A
0.2 Â 0.2 Â 0.2 mm
ꢂ = 128.423 (13)ꢀ
Motswainyana, W. M., Onani, M. O. & Lalancette, R. A. (2012). Acta Cryst.
E68, m339.
Newkome, G. R. (1993). Chem. Rev. 93, 2067–2089.
Nobre, S. M. & Monteiro, A. L. (2009). J. Mol. Catal. A Chem. 313, 65–73.
Ojwach, S. O., Guzei, I. A., Darkwa, J. & Mapolie, S. F. (2007). Polyhedron, 26,
851–861.
Data collection
Agilent SuperNova diffractometer
(single source at offset, Eos
detector)
Absorption correction: multi-scan
(CrysAlis PRO; Agilent, 2012)
Tmin = 0.983, Tmax = 1.000
10592 measured reflections
5391 independent reflections
4721 reflections with I > 2ꢅ(I)
Rint = 0.025
Onani, M. O., Motswainyana, W. M., Iwuoha, E. I., Darkwa, J. & Lalancette,
R. A. (2010). Acta Cryst. E66, m688.
Pellagati, P., Carcelli, M., Costa, M., Ianelli, S., Pellizi, C. & Rogollino, D.
(2005). J. Mol. Catal. A Chem. 226, 107–110.
Puri, M., Gatard, S., Smith, D. A. & Ozerov, O. V. (2011). Organometallics, 30,
2472–2482.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.
Vaughan, T. F., Koedyk, D. J. & Spencer, J. L. (2011). Organometallics, 30,
5170–5180.
Refinement
R[F2 > 2ꢅ(F2)] = 0.032
wR(F2) = 0.075
S = 1.05
309 parameters
H-atom parameteÀrs3 constrained
˚
Áꢆmax = 0.75 e A
À3
˚
5391 reflections
Áꢆmin = À0.52 e A
ꢁ
Acta Cryst. (2013). C69
Motswainyana et al.
[PdCl2(C26H22NP)]ÁC2H3N 3 of 3

supplementary materials
supplementary materials
Acta Cryst. (2013). C69 [doi:10.1107/S0108270113002333]
Dichlorido{N-[2-(diphenylphosphanyl)benzylidene]-2-methyl-
aniline}palladium(II) acetonitrile monosolvate
William M. Motswainyana, Martin O. Onani, Jeroen Jacobs and Luc Van Meervelt
Dichlorido{N-[2-(diphenylphosphanyl)benzylidene]-2-methylaniline}palladium(II) acetonitrile monosolvate
Crystal data
[PdCl2(C26H22NP)]·C2H3N
Mr = 597.77
F(000) = 2416
Dx = 1.501 Mg m−3
Mo Kα radiation, λ = 0.71073 Å
Cell parameters from 5198 reflections
θ = 2.9–26.3°
Monoclinic, C2/c
a = 32.350 (3) Å
b = 9.9963 (3) Å
c = 20.8851 (16) Å
β = 128.423 (13)°
V = 5291.3 (12) Å3
Z = 8
µ = 0.98 mm−1
T = 100 K
Block, yellow
0.2 × 0.2 × 0.2 mm
Data collection
Agilent SuperNova
Tmin = 0.983, Tmax = 1.000
diffractometer (single source at offset, Eos
detector)
Radiation source: SuperNova (Mo) X-ray
Source
10592 measured reflections
5391 independent reflections
4721 reflections with I > 2σ(I)
Rint = 0.025
Mirror monochromator
Detector resolution: 15.9631 pixels mm-1
ω scans
Absorption correction: multi-scan
(CrysAlis PRO; Agilent, 2012)
θmax = 26.4°, θmin = 2.9°
h = −40→34
k = −12→10
l = −26→25
Refinement
Refinement on F2
Least-squares matrix: full
R[F2 > 2σ(F2)] = 0.032
wR(F2) = 0.075
Secondary atom site location: difference Fourier
map
Hydrogen site location: inferred from
neighbouring sites
S = 1.05
5391 reflections
309 parameters
0 restraints
Primary atom site location: structure-invariant
direct methods
H-atom parameters constrained
w = 1/[σ2(Fo2) + (0.0255P)2 + 11.5559P]
where P = (Fo2 + 2Fc2)/3
(Δ/σ)max = 0.003
Δρmax = 0.75 e Å−3
Δρmin = −0.52 e Å−3
Acta Cryst. (2013). C69
sup-1

supplementary materials
Special details
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full
covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and
torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry.
An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2,
conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used
only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2
are statistically about twice as large as those based on F, and R-factors based on ALL data will be even larger.
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)
x
y
z
Uiso*/Ueq
Pd1
Cl1
Cl2
P1
0.637890 (8)
0.57031 (3)
0.67864 (3)
0.60233 (3)
0.69700 (9)
0.38905 (17)
0.71814 (11)
0.7460
1.06809 (2)
1.21650 (7)
1.15859 (7)
0.98303 (7)
0.9302 (2)
0.4779 (4)
0.8903 (3)
0.8304
0.634944 (12)
0.58060 (4)
0.76645 (4)
0.51296 (4)
0.68102 (13)
0.1631 (3)
0.64898 (17)
0.6799
0.01449 (7)
0.02303 (16)
0.02010 (15)
0.01688 (15)
0.0183 (5)
0.0693 (11)
0.0209 (6)
0.025*
N1
N2
C1
H1
C2
0.70380 (11)
0.65416 (11)
0.64503 (12)
0.6121
0.9276 (3)
0.9765 (3)
1.0060 (3)
1.0377
0.56977 (17)
0.50325 (16)
0.43027 (17)
0.3860
0.0201 (6)
0.0182 (6)
0.0222 (6)
0.027*
C3
C4
H4
C5
0.68440 (12)
0.6781
0.9886 (3)
1.0107
0.42290 (18)
0.3743
0.0266 (7)
0.032*
H5
C6
0.73281 (13)
0.7591
0.9387 (3)
0.9268
0.4874 (2)
0.4822
0.0282 (7)
0.034*
H6
C7
0.74248 (12)
0.7749
0.9062 (3)
0.8700
0.56015 (19)
0.6029
0.0251 (7)
0.030*
H7
C8
0.54572 (11)
0.54967 (12)
0.5818
1.0641 (3)
1.1958 (3)
1.2404
0.42268 (16)
0.40363 (17)
0.4357
0.0198 (6)
0.0243 (6)
0.029*
C9
H9
C10
H10
C11
H11
C12
H12
C13
H13
C14
C15
H15
C16
H16
C17
H17
C18
0.50546 (12)
0.5082
1.2584 (3)
1.3451
0.33696 (18)
0.3237
0.0285 (7)
0.034*
0.45714 (12)
0.4276
1.1941 (3)
1.2377
0.28948 (18)
0.2449
0.0302 (7)
0.036*
0.45293 (13)
0.4205
1.0648 (3)
1.0214
0.30838 (18)
0.2765
0.0304 (7)
0.036*
0.49723 (11)
0.4943
0.9997 (3)
0.9128
0.37519 (17)
0.3880
0.0250 (6)
0.030*
0.58476 (10)
0.59009 (12)
0.6022
0.8086 (3)
0.7175 (3)
0.7464
0.50583 (16)
0.46123 (18)
0.4332
0.0190 (6)
0.0266 (7)
0.032*
0.57752 (12)
0.5813
0.5837 (3)
0.5231
0.4580 (2)
0.4282
0.0305 (7)
0.037*
0.55932 (11)
0.5509
0.5412 (3)
0.4516
0.4995 (2)
0.4977
0.0300 (7)
0.036*
0.55362 (11)
0.6306 (3)
0.54345 (19)
0.0272 (7)
Acta Cryst. (2013). C69
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supplementary materials
H18
C19
0.5415
0.6011
0.5713
0.033*
0.56584 (10)
0.5614
0.7646 (3)
0.8249
0.54659 (17)
0.5758
0.0225 (6)
0.027*
H19
C20
0.71923 (12)
0.68644 (14)
0.6518
0.8740 (3)
0.7899 (3)
0.7735
0.76071 (17)
0.7662 (2)
0.7203
0.0239 (6)
0.0311 (7)
0.037*
C21
H21
C22
0.70622 (14)
0.6857
0.7324 (3)
0.6743
0.8402 (2)
0.8447
0.0330 (8)
0.040*
H22
C23
0.75659 (14)
0.7698
0.7626 (3)
0.7247
0.9067 (2)
0.9568
0.0333 (8)
0.040*
H23
C24
0.78840 (13)
0.8224
0.8462 (3)
0.8643
0.9028 (2)
0.9497
0.0347 (8)
0.042*
H24
C25
0.76964 (13)
0.80273 (13)
0.8274
0.9056 (3)
0.9990 (4)
1.0419
0.82715 (19)
0.8220 (2)
0.8740
0.0299 (7)
0.0422 (9)
0.063*
C26
H26A
H26B
H26C
C27
0.7807
1.0654
0.7811
0.063*
0.8216
0.9506
0.8077
0.063*
0.43269 (18)
0.4461
0.6835 (6)
0.7419
0.2598 (3)
0.2401
0.0827 (17)
0.124*
H27A
H27B
H27C
C28
0.4612
0.6549
0.3143
0.124*
0.4069
0.7302
0.2602
0.124*
0.40812 (17)
0.5665 (5)
0.2063 (3)
0.0509 (11)
Atomic displacement parameters (Å2)
U11
U22
U33
U12
U13
U23
Pd1
Cl1
Cl2
P1
0.01842 (11)
0.0241 (3)
0.0244 (3)
0.0232 (4)
0.0247 (12)
0.085 (3)
0.01280 (11)
0.0242 (4)
0.0203 (3)
0.0133 (3)
0.0167 (12)
0.047 (2)
0.01271 (11)
0.0199 (3)
0.0149 (3)
0.0138 (3)
0.0152 (11)
0.088 (3)
−0.00138 (8)
0.00990 (9)
0.0132 (3)
0.0119 (3)
0.00025 (8)
0.0033 (3)
0.0057 (3)
−0.0019 (3)
−0.0027 (3)
0.0030 (10)
−0.005 (2)
−0.0026 (3)
−0.0001 (3)
0.0034 (10)
0.010 (2)
0.0113 (3)
N1
0.0132 (10)
0.059 (3)
N2
C1
0.0255 (15)
0.0300 (15)
0.0270 (14)
0.0319 (16)
0.0443 (18)
0.0436 (18)
0.0315 (16)
0.0250 (14)
0.0327 (16)
0.0425 (18)
0.0360 (17)
0.0297 (16)
0.0292 (15)
0.0215 (14)
0.0365 (17)
0.0365 (18)
0.0239 (15)
0.0222 (15)
0.0170 (14)
0.0140 (13)
0.0127 (13)
0.0167 (14)
0.0191 (15)
0.0222 (16)
0.0209 (15)
0.0198 (14)
0.0181 (14)
0.0190 (15)
0.0286 (17)
0.0340 (18)
0.0239 (16)
0.0148 (13)
0.0215 (16)
0.0190 (16)
0.0174 (15)
0.0258 (16)
0.0201 (14)
0.0219 (14)
0.0183 (13)
0.0188 (14)
0.0255 (15)
0.0367 (18)
0.0278 (16)
0.0142 (13)
0.0183 (14)
0.0212 (15)
0.0190 (15)
0.0190 (15)
0.0178 (14)
0.0149 (13)
0.0249 (15)
0.0305 (17)
0.0356 (18)
0.0325 (17)
0.0008 (12)
0.0000 (12)
−0.0046 (12)
−0.0067 (13)
−0.0054 (14)
−0.0007 (15)
0.0005 (13)
0.0004 (13)
−0.0020 (13)
0.0021 (14)
0.0066 (15)
−0.0027 (15)
−0.0033 (14)
−0.0029 (12)
−0.0097 (14)
−0.0061 (14)
−0.0053 (13)
−0.0045 (13)
0.0141 (12)
0.0188 (13)
0.0158 (12)
0.0161 (13)
0.0262 (15)
0.0337 (16)
0.0208 (14)
0.0121 (12)
0.0139 (13)
0.0184 (14)
0.0136 (14)
0.0110 (13)
0.0126 (13)
0.0084 (11)
0.0206 (14)
0.0182 (15)
0.0119 (14)
0.0165 (14)
0.0020 (12)
0.0007 (12)
−0.0032 (11)
−0.0030 (12)
−0.0023 (13)
−0.0014 (14)
−0.0009 (13)
−0.0005 (12)
−0.0010 (12)
0.0041 (13)
0.0056 (14)
0.0000 (14)
0.0024 (13)
0.0012 (11)
−0.0053 (13)
−0.0060 (13)
0.0033 (14)
0.0077 (14)
C2
C3
C4
C5
C6
C7
C8
C9
C10
C11
C12
C13
C14
C15
C16
C17
C18
Acta Cryst. (2013). C69
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supplementary materials
C19
C20
C21
C22
C23
C24
C25
C26
C27
C28
0.0187 (14)
0.0359 (16)
0.057 (2)
0.0234 (15)
0.0209 (15)
0.0197 (15)
0.0278 (17)
0.0295 (18)
0.0335 (19)
0.0268 (17)
0.052 (2)
0.0237 (15)
0.0209 (14)
0.0364 (18)
0.0385 (19)
0.0346 (18)
0.0304 (17)
0.0262 (16)
0.0304 (18)
0.056 (3)
−0.0009 (12)
0.0131 (14)
0.0144 (16)
0.0070 (16)
0.0129 (16)
0.0083 (16)
0.0079 (15)
0.0002 (18)
0.019 (3)
0.0123 (12)
0.0207 (14)
0.0385 (17)
0.0337 (17)
0.0332 (17)
0.0147 (15)
0.0192 (15)
0.0141 (15)
0.030 (2)
0.0024 (13)
0.0075 (13)
0.0108 (14)
0.0076 (15)
0.0081 (15)
−0.0006 (15)
0.0049 (14)
0.0054 (18)
−0.028 (3)
0.015 (2)
0.047 (2)
0.050 (2)
0.0313 (17)
0.0364 (17)
0.0329 (18)
0.060 (3)
0.119 (5)
0.056 (3)
0.063 (3)
0.044 (2)
0.019 (2)
0.036 (2)
Geometric parameters (Å, º)
Pd1—Cl1
Pd1—Cl2
Pd1—P1
Pd1—N1
P1—C3
2.2770 (7)
C12—C13
1.393 (4)
2.3664 (7)
2.2122 (8)
2.049 (2)
1.811 (3)
1.809 (3)
1.811 (3)
1.282 (3)
1.454 (3)
1.134 (5)
0.9300
C13—H13
C14—C15
C14—C19
C15—H15
C15—C16
C16—H16
C16—C17
C17—H17
C17—C18
C18—H18
C18—C19
C19—H19
C20—C21
C20—C25
C21—H21
C21—C22
C22—H22
C22—C23
C23—H23
C23—C24
C24—H24
C24—C25
C25—C26
C26—H26A
C26—H26B
C26—H26C
C27—H27A
C27—H27B
C27—H27C
C27—C28
0.9300
1.388 (4)
1.393 (4)
0.9300
P1—C8
1.387 (4)
0.9300
P1—C14
N1—C1
N1—C20
N2—C28
C1—H1
C1—C2
C2—C3
C2—C7
C3—C4
C4—H4
C4—C5
C5—H5
C5—C6
C6—H6
C6—C7
C7—H7
C8—C9
C8—C13
C9—H9
C9—C10
C10—H10
C10—C11
C11—H11
C11—C12
C12—H12
1.383 (4)
0.9300
1.373 (5)
0.9300
1.462 (4)
1.405 (4)
1.402 (4)
1.392 (4)
0.9300
1.386 (4)
0.9300
1.413 (4)
1.368 (4)
0.9300
1.385 (4)
0.9300
1.378 (4)
0.9300
1.376 (4)
0.9300
1.365 (5)
0.9300
1.386 (4)
0.9300
1.367 (5)
0.9300
1.404 (4)
1.387 (4)
0.9300
1.422 (4)
1.474 (5)
0.9600
1.379 (4)
0.9300
0.9600
0.9600
1.383 (4)
0.9300
0.9600
0.9600
1.382 (4)
0.9300
0.9600
1.464 (7)
Cl1—Pd1—Cl2
P1—Pd1—Cl1
P1—Pd1—Cl2
N1—Pd1—Cl1
N1—Pd1—Cl2
89.95 (3)
91.45 (3)
178.15 (3)
178.15 (7)
91.61 (7)
C11—C12—C13
C13—C12—H12
C8—C13—C12
C8—C13—H13
C12—C13—H13
120.0 (3)
120.0
120.1 (3)
120.0
120.0
Acta Cryst. (2013). C69
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supplementary materials
N1—Pd1—P1
C3—P1—Pd1
C3—P1—C14
C8—P1—Pd1
C8—P1—C3
C8—P1—C14
C14—P1—Pd1
C1—N1—Pd1
C1—N1—C20
C20—N1—Pd1
N1—C1—H1
N1—C1—C2
C2—C1—H1
C3—C2—C1
C7—C2—C1
C7—C2—C3
C2—C3—P1
C4—C3—P1
C4—C3—C2
C3—C4—H4
C5—C4—C3
C5—C4—H4
C4—C5—H5
C6—C5—C4
C6—C5—H5
C5—C6—H6
C5—C6—C7
C7—C6—H6
C2—C7—H7
C6—C7—C2
C6—C7—H7
C9—C8—P1
C13—C8—P1
C13—C8—C9
C8—C9—H9
C10—C9—C8
C10—C9—H9
C9—C10—H10
C9—C10—C11
C11—C10—H10
C10—C11—H11
C12—C11—C10
C12—C11—H11
C11—C12—H12
87.01 (7)
106.73 (9)
102.78 (13)
119.56 (9)
107.90 (13)
106.41 (13)
112.13 (9)
127.53 (19)
115.6 (2)
116.78 (17)
116.0
C15—C14—P1
C15—C14—C19
C19—C14—P1
C14—C15—H15
C16—C15—C14
C16—C15—H15
C15—C16—H16
C17—C16—C15
C17—C16—H16
C16—C17—H17
C18—C17—C16
C18—C17—H17
C17—C18—H18
C17—C18—C19
C19—C18—H18
C14—C19—H19
C18—C19—C14
C18—C19—H19
C21—C20—N1
C25—C20—N1
C25—C20—C21
C20—C21—H21
C22—C21—C20
C22—C21—H21
C21—C22—H22
C23—C22—C21
C23—C22—H22
C22—C23—H23
C22—C23—C24
C24—C23—H23
C23—C24—H24
C23—C24—C25
C25—C24—H24
C20—C25—C24
C20—C25—C26
C24—C25—C26
121.6 (2)
119.2 (3)
119.2 (2)
119.7
120.7 (3)
119.7
120.3
119.5 (3)
120.3
119.8
120.3 (3)
119.8
127.9 (3)
116.0
119.7
124.9 (3)
116.1 (3)
119.0 (3)
118.1 (2)
122.3 (2)
119.4 (3)
119.6
120.5 (3)
119.7
120.1
119.8 (3)
120.1
117.4 (3)
120.1 (3)
122.5 (3)
120.3
120.7 (3)
119.6
119.9
119.3 (3)
120.3
120.1 (3)
119.9
120.7
119.9
118.5 (3)
120.7
120.1 (3)
119.9
118.6
119.7
122.8 (3)
118.6
120.5 (3)
119.7
119.9
120.2 (2)
120.0 (2)
119.6 (3)
120.3
120.3 (3)
119.9
116.6 (3)
122.3 (3)
121.1 (3)
119.5 (3)
120.3
H27A—C27—H27B
H27A—C27—H27C
H27B—C27—H27C
C28—C27—H27A
C28—C27—H27B
C28—C27—H27C
N2—C28—C27
109.5
109.5
109.5
109.5
109.5
109.5
178.0 (5)
119.5
120.9 (3)
119.5
120.1
119.8 (3)
120.1
120.0
Pd1—P1—C3—C2
Pd1—P1—C3—C4
Pd1—P1—C8—C9
Pd1—P1—C8—C13
45.0 (2)
C3—P1—C14—C15
C3—P1—C14—C19
C3—C2—C7—C6
C3—C4—C5—C6
−29.3 (3)
150.1 (2)
3.0 (4)
−141.1 (2)
61.7 (3)
−113.7 (2)
1.5 (4)
Acta Cryst. (2013). C69
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supplementary materials
Pd1—P1—C14—C15
Pd1—P1—C14—C19
Pd1—N1—C1—C2
Pd1—N1—C20—C21
Pd1—N1—C20—C25
Cl1—Pd1—P1—C3
Cl1—Pd1—P1—C8
Cl1—Pd1—P1—C14
Cl2—Pd1—N1—C1
Cl2—Pd1—N1—C20
P1—Pd1—N1—C1
P1—Pd1—N1—C20
P1—C3—C4—C5
−143.6 (2)
35.9 (2)
C4—C5—C6—C7
C5—C6—C7—C2
C7—C2—C3—P1
C7—C2—C3—C4
C8—P1—C3—C2
C8—P1—C3—C4
−0.3 (5)
−2.0 (5)
172.3 (2)
−1.8 (4)
174.7 (2)
−11.4 (3)
−3.4 (4)
68.0 (3)
−110.6 (3)
131.11 (10)
8.46 (11)
−117.09 (10)
−140.8 (2)
36.6 (2)
C8—P1—C14—C15
C8—P1—C14—C19
C8—C9—C10—C11
C9—C8—C13—C12
C9—C10—C11—C12
C10—C11—C12—C13
C11—C12—C13—C8
C13—C8—C9—C10
C14—P1—C3—C2
84.0 (3)
−96.6 (2)
1.1 (5)
0.9 (4)
37.9 (2)
−0.6 (5)
0.1 (5)
−144.6 (2)
−174.3 (2)
−176.7 (2)
176.3 (2)
178.6 (2)
−178.2 (2)
−49.93 (11)
−172.58 (13)
61.88 (12)
−23.0 (5)
159.9 (3)
178.7 (3)
−179.9 (3)
1.8 (5)
−0.3 (5)
−1.3 (4)
−73.1 (2)
100.7 (2)
−170.1 (2)
14.5 (3)
0.2 (5)
P1—C8—C9—C10
P1—C8—C13—C12
P1—C14—C15—C16
P1—C14—C19—C18
N1—Pd1—P1—C3
N1—Pd1—P1—C8
N1—Pd1—P1—C14
N1—C1—C2—C3
N1—C1—C2—C7
N1—C20—C21—C22
N1—C20—C25—C24
N1—C20—C25—C26
C1—N1—C20—C21
C1—N1—C20—C25
C1—C2—C3—P1
C14—P1—C3—C4
C14—P1—C8—C9
C14—P1—C8—C13
C14—C15—C16—C17
C15—C14—C19—C18
C15—C16—C17—C18
C16—C17—C18—C19
C17—C18—C19—C14
C19—C14—C15—C16
C20—N1—C1—C2
1.2 (4)
0.1 (5)
0.2 (5)
−0.9 (4)
−0.9 (4)
179.1 (3)
2.2 (5)
−114.3 (3)
67.2 (4)
C20—C21—C22—C23
C21—C20—C25—C24
C21—C20—C25—C26
C21—C22—C23—C24
C22—C23—C24—C25
C23—C24—C25—C20
C23—C24—C25—C26
C25—C20—C21—C22
1.7 (5)
−4.7 (4)
−176.7 (3)
−0.8 (5)
−0.3 (5)
−0.1 (5)
178.2 (3)
−2.7 (5)
C1—C2—C3—C4
C1—C2—C7—C6
C2—C3—C4—C5
C3—P1—C8—C9
−178.7 (3)
−179.8 (3)
−0.5 (4)
−60.4 (3)
124.2 (2)
C3—P1—C8—C13
Acta Cryst. (2013). C69
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