Dichlorido{2-[(2,6-diethylphenyl)iminomethyl]quinoline-κ2 N,N′}palladium(II) acetonitrile monosolvate

Article abstract of DOI:10.1107/S0108270112045970

The title complex, [PdCl2(C20H20N2)]·CH3CN, was synthesized by the reaction of 2-[(2,6-diethylphenyl)iminomethyl]quinoline with dichlorido(cycloocta-1,5-diene)palladium(II) in dry CH2Cl2. The Pd^II ion is coordinated by two N atoms of the bidentate quinoline ligand and by two chloride anions, generating a distorted square-planar coordination geometry around the metal centre. There is a detectable trans influence for the chloride ligands. The crystal packing is characterized by π-π stacking between the quinoline rings. The use of acetonitrile as the crystallization solvent was essential for obtaining good-quality crystals.

Full text of DOI:10.1107/S0108270112045970

metal-organic compounds
Acta Crystallographica Section C
Crystal Structure
Communications
Compound (I) exhibits growth-inhibitory activities against
human breast (MCF-7) and human colon (HT-29) cancer cell
lines which are superior to the reference compound, cisplatin,
therefore underlining the importance of steric congestion in
preventing an axial approach to the coordinated metal atom
and permitting high selectivity to DNA binding (Hotze et al.,
ISSN 0108-2701
Dichlorido{2-[(2,6-diethylphenyl)-
iminomethyl]quinoline-j N,N }-
palladium(II) acetonitrile monosolvate
2
002). It is reasonable to suggest that the cytotoxicity of this
2
0
compound is derived from DNA binding when considering the
proposed mechanism of action of cisplatin, because the
compound is square-planar with metal–chloride bonds in the
cis positions (Fuertes et al., 2003; Jung & Lippard, 2007).
a
a
William M. Motswainyana, Martin O. Onani, Jeroen
b
b
Jacobs and Luc Van Meervelt *
a
Chemistry Department, University of the Western Cape, Private Bag X17, Bellville
b
7
535, South Africa, and Chemistry Department, KU Leuven, Celestijnenlaan 200F,
B-3001 Leuven (Heverlee), Belgium
Correspondence e-mail: luc.vanmeervelt@chem.kuleuven.be
Received 5 November 2012
Accepted 7 November 2012
Online 14 November 2012
A view of the molecular structure of (I) is shown in Fig. 1.
II
The Pd atom is coordinated by the two N atoms of the
The title complex, [PdCl (C H N )]ꢀCH CN, was synthesized
2
20 20
2
3
2-[(2,6-diethylphenyl)iminomethyl]quinoline ligand and by
two chloride anions, generating a distorted square-planar
II
coordination geometry around the Pd metal centre. The
by the reaction of 2-[(2,6-diethylphenyl)iminomethyl]quino-
line with dichlorido(cycloocta-1,5-diene)palladium(II) in dry
II
CH Cl . The Pd ion is coordinated by two N atoms of the
2
2
bond angles around Pd1 (Table 1) show significant deviations
ꢁ
bidentate quinoline ligand and by two chloride anions,
generating a distorted square-planar coordination geometry
around the metal centre. There is a detectable trans influence
for the chloride ligands. The crystal packing is characterized
by ꢀ–ꢀ stacking between the quinoline rings. The use of
acetonitrile as the crystallization solvent was essential for
obtaining good-quality crystals.
from 90 , which confirms the distortion of the square-planar
geometry. These angles are close to those of a similar com-
pound (Motswainyana et al., 2012). The Pd1—Cl bond lengths
(Table 1) are in good agreement with the average Pd—Cl bond
˚
length of 2.298 (15) A for known palladium complexes (Chen
et al., 2007; Allen, 2002). There is a detectable trans influence
for the chloride ligands since the Pd1—Cl1 bond is slightly
longer than Pd1—Cl2, thus reflecting the stronger trans
influence of the quinoline group compared with the secondary
amine group (Doherty et al., 2002). Atom Cl1 has a short
Comment
Imino-quinoline ligands coordinate as neutral bidentate
species when they react with labile transition metal precursors
to form air-stable complexes, which show hemilability due to
the weakly coordinating N atoms (Segapelo et al., 2009). These
complexes could be investigated in various applications, such
as olefin oligomerization, polymerization and cyclopropan-
ation, and Heck–Suzuki coupling reactions (Segapelo et al.,
˚
intramolecular contact with atom H4 (Cl1ꢀ ꢀ ꢀH4 = 2.50 A) and
˚
as a result Cl1 deviates more [1.284 (1) A] from the best least-
squares plane through the quinoline ring than Cl2
˚
[0.003 (1) A]. The angle between the quinoline least-squares
plane and the plane through atoms C9, C10 and N2 is
2009; Ojwach et al., 2007; Bianchini et al., 2010; Ittel et al., 2000;
Motswainyana et al., 2011). Besides their preferred use in
various catalytic applications, palladium(II) complexes with
N-donor ligands have been explored in biological investiga-
tions with a view to developing less toxic and more selective
0
anticancer drugs. For example, chelating N,N -bidentate
ligands have been viewed as important in preventing trans-
labilization and the undesired displacement of ligands by
biomolecules (Wong & Giandomenico, 1999). In our study of
sterically hindered imino-quinoline palladium(II) complexes
which could exert cytotoxicity on tumour cells, we have now
synthesized and crystallized the title compound, namely
dichlorido{2-[(2,6-diethylphenyl)iminomethyl]quinoline-
Figure 1
The molecular structure of (I), showing the atom-numbering scheme.
Displacement ellipsoids are drawn at the 50% probability level for non-H
atoms.
2
0
ꢁ
N,N }palladium(II) acetonitrile monosolvate, (I).
m356 # 2012 International Union of Crystallography
doi:10.1107/S0108270112045970
Acta Cryst. (2012). C68, m356–m358

metal-organic compounds
Figure 3
The interaction of acetonitrile solvent molecules with neighbouring
complex molecules. Dashed lines indicate the various interactions. The
centroid of the C1–C6 ring is indicated by a solid dot (red in the electronic
version of the paper) and the centroid of the C11–C16 ring is indicated by
a hollow dot (yellow).
Figure 2
–ꢀ interactions (dashed lines) between quinoline rings in (I). The
centroid of the C1–C6 ring is indicated by a hollow dot (yellow in the
electronic version of the paper) and the centroid of the N1/C5–C9 ring is
˚
indicated by a solid dot (red). Distances are in A.
ꢀ
iv
atoms H1 and H3 of a neighbouring molecule [N3ꢀ ꢀ ꢀH1 =
iv
˚
˚
2.66 A and N3ꢀ ꢀ ꢀH3 = 2.69 A; symmetry code: (iv) ꢂx, ꢂy + 1,
ꢂz + 1]. This bifurcated interaction of the acetonitrile N atom
has been observed before in crystal structures (13 hits in the
ꢁ
9.37 (10) . This is at the higher end of the range observed in
the Cambridge Structural Database (CSD, Version 5.33; Allen,
CSD, with Nꢀ ꢀ ꢀH contact distances ranging between 2.436 and
˚
.744 A). The acetonitrile methyl group interacts with both Cl
2
2002) for 2-iminopyridyl groups involved in dichlor-
idopalladium complexes (0.31–9.65 , 24 hits). The overall
v
˚
˚
atoms [H22Cꢀ ꢀ ꢀCl2 = 2.89 A and H22Aꢀ ꢀ ꢀCl1 = 3.24 A;
symmetry code: (v) x ꢂ 1, y, z].
ꢁ
˚
r.m.s. deviations are 0.005 and 0.044 A, respectively, for the
benzene and quinoline rings; the angle between the least-
ꢁ
squares planes is 65.54 (10) . The two ethyl groups are situated
on different sides of the benzene plane but show similar
conformations, as indicated by the C11—C12—C17—C18
Experimental
2
All reactions were carried out under an N atmosphere using a dual
vacuum/nitrogen line and standard Schlenk techniques. Solvents
were dried and purified by heating under reflux under an N2
atmosphere in the presence of a suitable drying agent.
ꢁ
ꢁ
[
74.5 (3) ] and C11—C16—C19—C20 [80.4 (3) ] torsion
angles.
In the crystal packing of (I), ꢀ–ꢀ interactions between
quinoline rings link pairs of molecules into centrosymmetric
For the preparation of 2-[(2,6-diethylphenyl)iminomethyl]quino-
line, 2,6-diethylaniline (0.2972 g, 1.99 mmol) was added dropwise to a
i
2 2
solution of quinoline-2-carbaldehyde (0.3130 g, 1.99 mmol) in CH Cl
˚
dimers (Fig. 2), with a Cg1ꢀ ꢀ ꢀCg2 distance of 3.681 (2) A and
i
(10 ml). The reaction was stirred at room temperature for 10 h and a
crude product was obtained after evaporation of the solvent. The
product was washed with water (10 ml), and the organic material
˚
a Cg2ꢀ ꢀ ꢀCg2 distance of 3.932 (2) A [Cg1 and Cg2 are the
centroids of the N1/C5–C9 and C1–C6 rings, respectively;
symmetry code: (i) ꢂx + 1, ꢂy + 1, ꢂz + 1]. Furthermore, the
packing shows a number of weaker contacts of the C—Hꢀ ꢀ ꢀꢀ
extracted with CH Cl
magnesium sulfate. A red–brown oil was obtained upon evaporation
2
2
(2 ꢃ 10 ml) and dried over anhydrous
ii
iii
˚
type (C3—H3ꢀ ꢀ ꢀCg3 = 2.80 A and C22—H22Bꢀ ꢀ ꢀCg3
=
ꢂ1
of the solvent (yield 0.5509 g, 96%). IR (Nujol, ꢂ, cm ): 1641 (C
imine), 1596 (C N quinolyl), 1563 (C C quinolyl), 1504 (C
N
C
˚
.86 A; Cg3 is the centroid of the C11–C16 ring; symmetry
2
3
1
3
1
3
1
codes: (ii) ꢂx + , y ꢂ , ꢂz + ; (iii) x ꢂ , ꢂy + , z + ].
20 20 2
phenyl). Analysis calculated for C H N : C 83.30, H 6.99, N 9.71%;
2
2
2
2
2
2
During the crystallization experiments, it became clear that
the presence of acetonitrile in the crystallization solution was
essential. For example, when using dichloromethane as solvent
the quality of the crystals was not good enough to obtain an
accurate structure determination. On further analysis of the
crystal packing, the importance of the presence of acetonitrile
becomes clear. Without acetonitrile the unit cell would show
found: C 83.54, H 6.78, N 9.99%.
For the preparation of complex (I), a solution of dichlorido(cyclo-
octa-1,5-diene)palladium(II), [PdCl (cod)] (0.0650 g, 0.228 mmol), in
CH Cl (5 ml) was added dropwise to a solution of 2-[(2,6-diethyl-
phenyl)iminomethyl]quinoline(0.0640 g, 0.222 mmol) in dry CH Cl
10 ml). The yellow solution was refluxed for 4 h, resulting in the
formation of a yellow precipitate. The precipitate was filtered off and
washed with Et
2
2
2
2
2
(
2
O (2 ꢃ 10 ml) to obtain a pure yellow solid, (I).
3
˚
four voids of 97 A each, which are here filled by one aceto-
3
nitrile molecule having a molar volume of about 42 A . In the
Crystals of (I) suitable for X-ray crystallography were grown by slow
evaporation from an acetonitrile solution of the complex (yield
˚
packing, the position of this acetonitrile molecule is fixed by
two ꢀ-interactions, viz. a C22—H22Bꢀ ꢀ ꢀꢀ interaction (see
ꢂ1
0.0848 g, 82%). IR (Nujol, ꢂ, cm ): 1602 (C N imine), 1584 (C
N
quinolyl), 1563 (C C quinolyl), 1506 (C C phenyl). Analysis
calculated for C H Cl N Pd: C 51.58, H 4.33, N 6.02%; found: C
51.89, H 4.18, N 5.83%.
above) and a C21 N3ꢀ ꢀ ꢀCg2 interaction [N3ꢀ ꢀ ꢀCg2 =
2
0
20
2
2
˚
.793 (3) A] (Fig. 3). Furthermore, atom N3 interacts with
3
ꢄ
Acta Cryst. (2012). C68, m356–m358
Motswainyana et al.
[PdCl
2
(C20
H
20
N
2
2 3
)]ꢀC H N
m357

metal-organic compounds
Table 1
Selected geometric parameters (A, ).
OLEX2 (Dolomanov et al., 2009); software used to prepare material
for publication: OLEX2.
˚
ꢁ
Cl1—Pd1
Cl2—Pd1
2.3093 (7)
2.2773 (7)
N1—Pd1
N2—Pd1
2.086 (2)
2.035 (2)
The authors acknowledge the University of the Western
Cape Senate Research, the National Research Foundation
and KU Leuven International Admissions and Mobility for
financial support. The authors thank the Hercules Foundation
for supporting the purchase of the diffractometer through
project No. AKUL/09/0035.
Cl2—Pd1—Cl1
N1—Pd1—Cl1
N1—Pd1—Cl2
87.56 (2)
101.20 (6)
170.49 (6)
N2—Pd1—Cl1
N2—Pd1—Cl2
N2—Pd1—N1
167.35 (6)
92.11 (6)
80.15 (8)
Crystal data
Supplementary data for this paper are available from the IUCr electronic
archives (Reference: SK3458). Services for accessing these data are
described at the back of the journal.
˚
3
[PdCl (C20H
2 20
N
2
)]ꢀC
2 3
H N
V = 2127.99 (16) A
Z = 4
M
r
= 506.73
Monoclinic, P2 =n
˚
a = 7.8874 (3) A
b = 19.3046 (8) A
˚
c = 14.2966 (7) A
Mo Kꢄ radiation
1
ꢂ1
ꢅ = 1.14 mm
T = 100 K
˚
0.3 ꢃ 0.2 ꢃ 0.2 mm
References
ꢁ
ꢃ = 102.164 (4)
Agilent (2012). CrysAlis PRO. Agilent Technologies, Yarnton, Oxfordshire,
England.
Allen, F. H. (2002). Acta Cryst. B58, 380–388.
Data collection
Agilent SuperNova diffractometer
single source at offset, Eos
detector)
Absorption correction: multi-scan
(CrysAlis PRO; Agilent, 2012)
8662 measured reflections
4314 independent reflections
3798 reflections with I > 2ꢆ(I)
Bianchini, C., Giambastiani, G., Luconi, L. & Meli, A. (2010). Coord. Chem.
Rev. 254, 431–455.
Chen, W., Xi, C. & Wu, Y. (2007). J. Organomet. Chem. 692, 4381–4388.
Doherty, S., Knight, J. G., Scanlam, T. H., Elsegood, M. R. J. & Clegg, W.
(2002). J. Organomet. Chem. 650, 231–248.
(
Rint = 0.036
T
min = 0.971, Tmax = 1.000
Dolomanov, O. V., Bourhis, L. J., Gildea, R. J., Howard, J. A. K. & Puschmann,
H. (2009). J. Appl. Cryst. 42, 339–341.
Fuertes, M. A., Alonso, C. & Perez, J. M. (2003). Chem. Rev. 103, 645–662.
Hotze, A. C. G., Chen, Y., Hambley, T. W., Parsons, S., Kratochwil, N. A.,
Parkison, J. A., Munk, V. P. & Sadler, P. J. (2002). Eur. J. Inorg. Chem. pp.
Refinement
2
2
R[F > 2ꢆ(F )] = 0.030
wR(F ) = 0.071
256 parameters
H-atom parameters constrained
2
1035–1039.
˚
ꢂ3
Áꢇmax = 0.39 e A
S = 1.03
4314 reflections
Ittel, S. D., Johnson, L. K. & Brookhart, M. (2000). Chem. Rev. 100, 1169–1203.
Jung, Y. & Lippard, S. J. (2007). Chem. Rev. 107, 1387–1407.
Motswainyana, W. M., Ojwach, S. O., Onani, M. O., Iwuoha, E. I. & Darkwa, J.
Áꢇmin = ꢂ0.52 e A˚
ꢂ3
(
2011). Polyhedron, 30, 2574–2580.
All H atoms were placed in idealized positions and refined in
˚
riding mode, with C—H = 0.93 (aromatic), 0.96 (methyl) or 0.97 A
Motswainyana, W. M., Onani, M. O. & Madiehe, A. M. (2012). Acta Cryst. E68,
m380.
Ojwach, S. O., Guzei, I. A., Darkwa, J. & Mapolie, S. F. (2007). Polyhedron, 26,
(methylene), and with Uiso(H) = 1.2 or 1.5Ueq(C)
8
51–861.
Segapelo, T. V., Guzei, I. A., Spencer, L. C., Van Zyl, W. E. & Darkwa, J.
2009). Inorg. Chim. Acta, 362, 3314–3324.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.
Wong, E. & Giandomenico, M. (1999). Chem. Rev. 99, 2451–2466.
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:
(
ꢄ
m358 Motswainyana et al.
2 20
[PdCl (C20H N
2
2 3
)]ꢀC H N
Acta Cryst. (2012). C68, m356–m358

supplementary materials
supplementary materials
Acta Cryst. (2012). C68, m356–m358 [doi:10.1107/S0108270112045970]
2
Dichlorido{2-[(2,6-diethylphenyl)iminomethyl]quinoline-κ N,N′}palladium(II)
acetonitrile monosolvate
William M. Motswainyana, Martin O. Onani, Jeroen Jacobs and Luc Van Meervelt
2
Dichlorido{2-[(2,6-diethylphenyl)iminomethyl]quinoline- κ N,N′}palladium(II) acetonitrile monosolvate
Crystal data
[
M
PdCl
= 506.73
Monoclinic, P2
2
(C20
H
20
N
2
)]·C
2 3
H N
F(000) = 1024
= 1.582 Mg m
−3
r
D
x
1
/n
Mo Kα radiation, λ = 0.71073 Å
Cell parameters from 5179 reflections
θ = 2.7–26.3°
a = 7.8874 (3) Å
b = 19.3046 (8) Å
c = 14.2966 (7) Å
β = 102.164 (4)°
V = 2127.99 (16) Å
Z = 4
−1
µ = 1.14 mm
T = 100 K
3
Block, yellow
0.3 × 0.2 × 0.2 mm
Data collection
Agilent SuperNova (single source at offset, Eos)
diffractometer
Radiation source: SuperNova (Mo) X-ray
Source
Tmin = 0.971, Tmax = 1.000
8662 measured reflections
4314 independent reflections
3798 reflections with I > 2σ(I)
Mirror monochromator
Detector resolution: 15.9631 pixels mm
ω scans
R
int = 0.036
-1
θmax = 26.3°, θmin = 2.7°
h = −9→9
k = −24→23
l = −17→9
Absorption correction: multi-scan
(
CrysAlis PRO; Agilent, 2012)
Refinement
2
Refinement on F
Secondary atom site location: difference Fourier
map
Hydrogen site location: inferred from
neighbouring sites
Least-squares matrix: full
R[F > 2σ(F )] = 0.030
2
2
2
wR(F ) = 0.071
S = 1.03
H-atom parameters constrained
2
2
2
4
2
0
314 reflections
56 parameters
restraints
w = 1/[σ (F
where P = (F
o
) + (0.0222P) + 0.925P]
2
2
o
+ 2F )/3
c
(Δ/σ)max = 0.003
Δρmax = 0.39 e Å
Δρmin = −0.52 e Å
−
3
Primary atom site location: structure-invariant
direct methods
−
3
Acta Cryst. (2012). C68, m356–m358
sup-1

supplementary materials
Special details
Experimental. Absorption correction: CrysAlisPro, Agilent Technologies, Version 1.171.36.20, Empirical absorption
correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.
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.
2
2
Refinement. Refinement of F against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F ,
2
2
2
conventional R-factors R are based on F, with F set to zero for negative F . The threshold expression of F > σ(F ) is used
only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F
2
are statistically about twice as large as those based on F, and R-factors based on ALL data will be even larger.
2
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å )
x
y
z
Uiso*/Ueq
C1
0.2913 (3)
0.2000
0.46279 (14)
0.4432
0.5574 (2)
0.5136
0.0152 (6)
0.018*
H1
C2
0.3898 (3)
0.3646
0.42270 (14)
0.3758
0.6262 (2)
0.6297
0.0151 (6)
0.018*
H2
C3
0.5299 (3)
0.5980
0.45173 (14)
0.4234
0.69256 (19)
0.7381
0.0156 (6)
0.019*
H3
C4
0.5672 (3)
0.6591
0.52114 (14)
0.5396
0.69081 (19)
0.7355
0.0141 (6)
0.017*
H4
C5
0.4663 (3)
0.3278 (3)
0.2331 (3)
0.1383
0.56455 (14)
0.53484 (14)
0.57652 (14)
0.5585
0.62124 (18)
0.55220 (19)
0.47949 (19)
0.4364
0.0112 (5)
0.0111 (5)
0.0134 (6)
0.016*
C6
C7
H7
C8
0.2815 (3)
0.2240
0.64441 (14)
0.6723
0.47242 (19)
0.4227
0.0131 (6)
0.016*
H8
C9
0.4189 (3)
0.4863 (3)
0.4327
0.67081 (14)
0.74008 (14)
0.7688
0.54134 (18)
0.53032 (18)
0.4806
0.0112 (5)
0.0109 (5)
0.013*
C10
H10
C11
C12
C13
H13
C14
H14
C15
H15
C16
C17
H17A
H17B
C18
H18A
H18B
H18C
C19
H19A
0.6937 (3)
0.6015 (3)
0.6807 (3)
0.6222
0.82770 (14)
0.88821 (14)
0.95138 (14)
0.9922
0.57919 (18)
0.59076 (18)
0.58095 (19)
0.5881
0.0106 (5)
0.0118 (5)
0.0134 (6)
0.016*
0.8450 (3)
0.8966
0.95484 (15)
0.9976
0.56067 (19)
0.5555
0.0155 (6)
0.019*
0.9322 (3)
1.0411
0.89411 (14)
0.8967
0.54811 (19)
0.5330
0.0152 (6)
0.018*
0.8592 (3)
0.4237 (3)
0.3707
0.82957 (14)
0.88743 (15)
0.9327
0.55772 (18)
0.61655 (19)
0.6035
0.0114 (5)
0.0145 (6)
0.017*
0.3504
0.8541
0.5762
0.017*
0.4320 (4)
0.5045
0.86908 (19)
0.9019
0.7209 (2)
0.7613
0.0331 (8)
0.050*
0.4795
0.8234
0.7336
0.050*
0.3174
0.8704
0.7337
0.050*
0.9507 (3)
0.9318
0.76333 (14)
0.7284
0.54014 (19)
0.5857
0.0145 (6)
0.017*
Acta Cryst. (2012). C68, m356–m358
sup-2

supplementary materials
H19B
C20
1.0744
0.7719
0.5506
0.017*
0.8863 (3)
0.9283
0.73574 (15)
0.6894
0.4385 (2)
0.4344
0.0179 (6)
0.027*
H20A
H20B
H20C
C21
0.9284
0.7649
0.3940
0.027*
0.7618
0.7356
0.4235
0.027*
0.0756 (4)
0.1805 (4)
0.3006
0.58019 (18)
0.6129 (2)
0.6095
0.7278 (2)
0.8104 (3)
0.8072
0.0274 (7)
0.0402 (9)
0.060*
C22
H22A
H22B
H22C
Cl1
0.1624
0.5903
0.8673
0.060*
0.1487
0.6609
0.8119
0.060*
0.71391 (9)
0.89474 (8)
0.5052 (3)
0.6208 (3)
−0.0073 (4)
0.68518 (2)
0.63912 (3)
0.77099 (3)
0.63426 (11)
0.76040 (11)
0.5546 (2)
0.696873 (10)
0.85021 (5)
0.78145 (5)
0.61660 (15)
0.59064 (15)
0.6630 (2)
0.706264 (13)
0.01621 (15)
0.01569 (15)
0.0102 (5)
0.0098 (5)
0.0591 (11)
0.00930 (7)
Cl2
N1
N2
N3
Pd1
2
Atomic displacement parameters (Å )
11
22
33
12
13
23
U
U
U
U
U
U
C1
0.0123 (13)
0.0179 (14)
0.0195 (14)
0.0177 (13)
0.0136 (13)
0.0090 (12)
0.0085 (12)
0.0122 (13)
0.0118 (12)
0.0125 (13)
0.0154 (13)
0.0123 (12)
0.0157 (13)
0.0199 (14)
0.0131 (13)
0.0109 (12)
0.0113 (12)
0.0312 (17)
0.0126 (13)
0.0167 (14)
0.0234 (16)
0.0339 (19)
0.0254 (3)
0.0169 (15)
0.0097 (14)
0.0124 (14)
0.0132 (14)
0.0099 (13)
0.0129 (14)
0.0172 (15)
0.0152 (15)
0.0111 (14)
0.0107 (13)
0.0097 (13)
0.0135 (14)
0.0091 (13)
0.0117 (14)
0.0176 (15)
0.0133 (14)
0.0142 (14)
0.046 (2)
0.0167 (14)
0.0183 (14)
0.0141 (14)
0.0098 (13)
0.0108 (13)
0.0128 (13)
0.0137 (13)
0.0122 (13)
0.0111 (13)
0.0091 (13)
0.0055 (12)
0.0090 (12)
0.0142 (14)
0.0144 (14)
0.0154 (14)
0.0086 (12)
0.0174 (14)
0.0255 (18)
0.0161 (14)
0.0210 (15)
0.0268 (17)
0.033 (2)
−0.0063 (12)
−0.0021 (12)
−0.0006 (12)
0.0013 (12)
−0.0006 (11)
0.0001 (11)
−0.0017 (12)
0.0024 (12)
0.0021 (12)
0.0017 (11)
−0.0015 (12)
−0.0005 (11)
0.0030 (12)
−0.0031 (12)
−0.0016 (12)
0.0012 (11)
0.0031 (12)
0.0111 (17)
−0.0004 (12)
0.0016 (12)
0.0017 (15)
0.0005 (18)
−0.0033 (3)
−0.0052 (3)
−0.0002 (9)
0.0005 (10)
−0.0153 (19)
−0.00080 (8)
0.0036 (11)
0.0055 (11)
0.0020 (11)
−0.0005 (11)
0.0044 (10)
0.0052 (10)
0.0008 (10)
0.0033 (10)
0.0036 (10)
0.0011 (10)
−0.0007 (10)
0.0009 (10)
0.0005 (11)
0.0022 (11)
0.0037 (11)
−0.0011 (10)
0.0020 (11)
0.0142 (14)
0.0044 (11)
0.0049 (12)
0.0069 (14)
−0.0047 (16)
0.0013 (3)
−0.0054 (12)
−0.0004 (12)
−0.0005 (12)
−0.0005 (11)
−0.0023 (11)
−0.0006 (11)
−0.0039 (12)
0.0013 (11)
0.0007 (11)
0.0010 (11)
0.0021 (11)
0.0000 (11)
0.0007 (11)
0.0035 (12)
0.0032 (12)
0.0004 (11)
−0.0015 (12)
0.0063 (17)
0.0015 (12)
−0.0027 (13)
−0.0080 (16)
−0.0149 (18)
0.0013 (3)
C2
C3
C4
C5
C6
C7
C8
C9
C10
C11
C12
C13
C14
C15
C16
C17
C18
C19
C20
C21
C22
Cl1
Cl2
N1
0.0154 (15)
0.0165 (15)
0.0327 (19)
0.048 (2)
0.0124 (3)
0.0127 (3)
0.0094 (11)
0.0087 (11)
0.102 (3)
0.0098 (3)
0.0124 (3)
0.0107 (11)
0.0094 (11)
0.045 (2)
0.0197 (3)
−0.0018 (3)
0.0017 (9)
0.0001 (3)
0.0104 (10)
0.0125 (10)
0.0310 (16)
0.01144 (12)
−0.0003 (9)
−0.0003 (9)
−0.042 (2)
N2
0.0048 (9)
N3
0.0088 (15)
0.00020 (8)
Pd1
0.00772 (12)
0.00791 (11)
0.00001 (8)
Acta Cryst. (2012). C68, m356–m358
sup-3

supplementary materials
Geometric parameters (Å, º)
C1—H1
C1—C2
0.9300
C14—H14
C14—C15
C15—H15
C15—C16
C16—C19
C17—H17A
C17—H17B
C17—C18
C18—H18A
C18—H18B
C18—H18C
C19—H19A
C19—H19B
C19—C20
C20—H20A
C20—H20B
C20—H20C
C21—C22
C21—N3
0.9300
1.359 (4)
1.425 (4)
0.9300
1.390 (4)
0.9300
C1—C6
C2—H2
C2—C3
C3—H3
C3—C4
C4—H4
C4—C5
C5—C6
C5—N1
C6—C7
1.391 (4)
1.515 (4)
0.9700
1.412 (4)
0.9300
1.373 (4)
0.9300
0.9700
1.521 (4)
0.9600
1.411 (4)
1.429 (3)
1.385 (3)
1.400 (4)
0.9300
0.9600
0.9600
0.9700
C7—H7
C7—C8
C8—H8
C8—C9
0.9700
1.375 (4)
0.9300
1.530 (4)
0.9600
1.398 (4)
1.460 (4)
1.345 (3)
0.9300
0.9600
C9—C10
C9—N1
C10—H10
C10—N2
C11—C12
C11—C16
C11—N2
C12—C13
C12—C17
C13—H13
C13—C14
0.9600
1.438 (4)
1.129 (4)
0.9600
1.279 (3)
1.404 (4)
1.403 (4)
1.444 (3)
1.391 (4)
1.523 (4)
0.9300
C22—H22A
C22—H22B
C22—H22C
Cl1—Pd1
0.9600
0.9600
2.3093 (7)
2.2773 (7)
2.086 (2)
2.035 (2)
Cl2—Pd1
N1—Pd1
N2—Pd1
1.388 (4)
C2—C1—H1
C2—C1—C6
C6—C1—H1
C1—C2—H2
C1—C2—C3
C3—C2—H2
C2—C3—H3
C4—C3—C2
C4—C3—H3
C3—C4—H4
C3—C4—C5
C5—C4—H4
C4—C5—C6
N1—C5—C4
N1—C5—C6
C1—C6—C5
C7—C6—C1
C7—C6—C5
C6—C7—H7
C8—C7—C6
119.9
C15—C16—C11
C15—C16—C19
C12—C17—H17A
C12—C17—H17B
117.9 (2)
121.2 (2)
109.0
120.2 (2)
119.9
119.8
109.0
120.5 (3)
119.8
H17A—C17—H17B
C18—C17—C12
107.8
112.8 (2)
109.0
109.0
109.5
109.5
109.5
109.5
109.5
109.5
109.2
109.2
112.1 (2)
107.9
109.2
109.2
119.5
C18—C17—H17A
C18—C17—H17B
C17—C18—H18A
C17—C18—H18B
C17—C18—H18C
H18A—C18—H18B
H18A—C18—H18C
H18B—C18—H18C
C16—C19—H19A
C16—C19—H19B
C16—C19—C20
121.0 (3)
119.5
120.0
120.1 (2)
120.0
119.0 (2)
120.9 (2)
120.1 (2)
119.2 (2)
121.2 (2)
119.5 (2)
120.3
H19A—C19—H19B
C20—C19—H19A
C20—C19—H19B
119.3 (2)
Acta Cryst. (2012). C68, m356–m358
sup-4

supplementary materials
C8—C7—H7
120.3
C19—C20—H20A
C19—C20—H20B
C19—C20—H20C
109.5
109.5
109.5
C7—C8—H8
120.6
C7—C8—C9
118.8 (2)
120.6
C9—C8—H8
H20A—C20—H20B
H20A—C20—H20C
H20B—C20—H20C
N3—C21—C22
C21—C22—H22A
C21—C22—H22B
C21—C22—H22C
H22A—C22—H22B
H22A—C22—H22C
H22B—C22—H22C
C5—N1—Pd1
109.5
C8—C9—C10
N1—C9—C8
120.2 (2)
124.0 (2)
115.6 (2)
120.8
109.5
109.5
N1—C9—C10
C9—C10—H10
N2—C10—C9
N2—C10—H10
C12—C11—N2
C16—C11—C12
C16—C11—N2
C11—C12—C17
C13—C12—C11
C13—C12—C17
C12—C13—H13
C14—C13—C12
C14—C13—H13
C13—C14—H14
C13—C14—C15
C15—C14—H14
C14—C15—H15
C14—C15—C16
C16—C15—H15
C11—C16—C19
179.8 (4)
109.5
118.5 (2)
120.8
109.5
109.5
120.4 (2)
122.2 (2)
117.3 (2)
123.1 (2)
117.6 (2)
119.3 (2)
119.3
109.5
109.5
109.5
131.48 (17)
117.9 (2)
110.57 (17)
119.5 (2)
113.10 (18)
126.66 (16)
87.56 (2)
101.20 (6)
170.49 (6)
167.35 (6)
92.11 (6)
80.15 (8)
C9—N1—C5
C9—N1—Pd1
C10—N2—C11
C10—N2—Pd1
C11—N2—Pd1
Cl2—Pd1—Cl1
N1—Pd1—Cl1
121.5 (2)
119.3
120.1
119.7 (3)
120.1
N1—Pd1—Cl2
119.5
N2—Pd1—Cl1
121.1 (2)
119.5
N2—Pd1—Cl2
N2—Pd1—N1
120.8 (2)
C1—C2—C3—C4
C1—C6—C7—C8
C2—C1—C6—C5
C2—C1—C6—C7
C2—C3—C4—C5
C3—C4—C5—C6
C3—C4—C5—N1
C4—C5—C6—C1
C4—C5—C6—C7
C4—C5—N1—C9
C4—C5—N1—Pd1
C5—C6—C7—C8
C5—N1—Pd1—Cl1
C5—N1—Pd1—N2
C6—C1—C2—C3
C6—C5—N1—C9
C6—C5—N1—Pd1
C6—C7—C8—C9
C7—C8—C9—C10
C7—C8—C9—N1
C8—C9—C10—N2
C8—C9—N1—C5
1.7 (4)
C10—N2—Pd1—Cl2
C10—N2—Pd1—N1
C11—C12—C13—C14
C11—C12—C17—C18
C11—C16—C19—C20
C11—N2—Pd1—Cl1
C11—N2—Pd1—Cl2
C11—N2—Pd1—N1
C12—C11—C16—C15
C12—C11—C16—C19
C12—C11—N2—C10
C12—C11—N2—Pd1
C12—C13—C14—C15
C13—C12—C17—C18
C13—C14—C15—C16
C14—C15—C16—C11
C14—C15—C16—C19
C15—C16—C19—C20
C16—C11—C12—C13
C16—C11—C12—C17
C16—C11—N2—C10
C16—C11—N2—Pd1
−173.06 (18)
12.50 (18)
−0.1 (4)
−174.7 (2)
−1.3 (4)
177.2 (2)
−0.8 (4)
−1.1 (4)
−178.1 (2)
2.2 (4)
74.5 (3)
80.4 (3)
85.5 (3)
−2.8 (2)
−177.3 (2)
0.2 (4)
−176.3 (2)
171.4 (2)
−6.7 (4)
3.8 (4)
−176.5 (2)
67.1 (3)
−102.5 (2)
1.1 (4)
−26.2 (2)
166.6 (2)
−0.6 (4)
−5.5 (3)
176.37 (17)
−3.3 (4)
173.2 (2)
−1.8 (4)
−174.5 (2)
6.2 (4)
−103.4 (3)
−1.5 (4)
0.9 (4)
177.5 (2)
−96.1 (3)
−0.5 (4)
−178.4 (2)
−113.8 (3)
76.6 (3)
Acta Cryst. (2012). C68, m356–m358
sup-5

supplementary materials
C8—C9—N1—Pd1
C9—C10—N2—C11
C9—C10—N2—Pd1
C9—N1—Pd1—Cl1
C9—N1—Pd1—N2
C10—C9—N1—C5
C10—C9—N1—Pd1
C10—N2—Pd1—Cl1
−175.2 (2)
177.7 (2)
−11.3 (3)
155.52 (16)
−11.68 (17)
−169.0 (2)
9.5 (3)
C17—C12—C13—C14
177.8 (2)
179.1 (2)
0.6 (4)
N1—C5—C6—C1
N1—C5—C6—C7
N1—C9—C10—N2
N2—C11—C12—C13
N2—C11—C12—C17
N2—C11—C16—C15
N2—C11—C16—C19
1.0 (4)
178.5 (2)
0.7 (4)
−178.9 (2)
4.4 (4)
−84.8 (3)
Acta Cryst. (2012). C68, m356–m358
sup-6