Synthesis and structural characterization of Pd(II) complexes containing 2,6-bis[(dimethylamino)methyl]-4-methylphenolate ligand

Article abstract of DOI:10.1016/j.ica.2011.01.098

Treatment of 2,6-bis[(dimethylamino)methyl]-4-methylphenol (1) with [Pd(PhCN)₂Cl₂] in a 1:1 molar ratio gives the mononuclear Pd(II) complex [PdCl₂(OC₆H₂(CH ₂NMe₂)-2-Me-4-(CH₂NHMe₂)-6)] (2) containing one ligand with an ammonium hydrogen atom, which forms a bifurcated hydrogen bonding to the phenoxy oxygen and the chlorine atoms, as shown by the single crystal X-ray diffraction study. The reaction between the lithium salt of 1 and [Pd(COD)Cl₂] gives the mononuclear Pd(II) complex [Pd(OC ₆H₂(CH₂NMe₂)₂-2,6-Me-4) ₂] (3). The X-ray structure of 3 showed the presence of two ligands coordinated to one palladium metal center in a trans fashion with two dangling dimethylamine groups. The yield of the complex 3 was improved by carrying out the reaction between [Pd(OAc)₂] and 1 in acetone. The solid state structures of the complexes 2 and 3 were confirmed by ¹H, ¹³C, HETCOR NMR, IR and elemental analysis methods. The ¹H NMR spectra of 2 and 3 showed two different chemical shifts corresponding to the coordinated and uncoordinated amine groups of the ligand. No decoalescence of signals for the chelate ring puckering process was observed in variable-temperature NMR spectra.

Full text of DOI:10.1016/j.ica.2011.01.098

Inorganica Chimica Acta 372 (2011) 412–416
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Note
Synthesis and structural characterization of Pd(II) complexes containing
2,6-bis[(dimethylamino)methyl]-4-methylphenolate ligand
⇑
Debasish Ghorai, Ganesan Mani
Department of Chemistry, Indian Institute of Technology, Kharagpur 721 302, India
a r t i c l e i n f o
a b s t r a c t
Article history:
Available online 4 February 2011
Treatment of 2,6-bis[(dimethylamino)methyl]-4-methylphenol (1) with [Pd(PhCN)2Cl2] in a 1:1 molar
ratio gives the mononuclear Pd(II) complex [PdCl2(OC6H2(CH2NMe2)-2-Me-4-(CH2NHMe2)-6)] (2)
containing one ligand with an ammonium hydrogen atom, which forms a bifurcated hydrogen bonding
to the phenoxy oxygen and the chlorine atoms, as shown by the single crystal X-ray diffraction study.
The reaction between the lithium salt of 1 and [Pd(COD)Cl2] gives the mononuclear Pd(II) complex
[Pd(OC6H2(CH2NMe2)2-2,6-Me-4)2] (3). The X-ray structure of 3 showed the presence of two ligands coor-
dinated to one palladium metal center in a trans fashion with two dangling dimethylamine groups. The
yield of the complex 3 was improved by carrying out the reaction between [Pd(OAc)2] and 1 in acetone.
The solid state structures of the complexes 2 and 3 were confirmed by 1H, 13C, HETCOR NMR, IR and ele-
mental analysis methods. The 1H NMR spectra of 2 and 3 showed two different chemical shifts corre-
sponding to the coordinated and uncoordinated amine groups of the ligand. No decoalescence of
signals for the chelate ring puckering process was observed in variable-temperature NMR spectra.
Ó 2011 Elsevier B.V. All rights reserved.
Dedicated to Professor S.S. Krishnamurthy
on the occasion of his 70th birthday.
Keywords:
Palladium(II) complexes
Bifurcated hydrogen bond
O,N chelation
Aminophenolate ligand
Metallo-ligand
1. Introduction
2. Experimental
2,6-Bis[(dimethylamino)methyl]-4-methylphenol 1 is a versa-
tile, an easy-to-synthesize and a bis-chelating phenoxy ligand. As
it has an acidic phenolic proton, it can coordinate to a metal center
as a monoanionic–monodentate, bidentate and bridging ligand and
stabilizes metal complexes in various oxidation states [1].
2.1. General procedures
Solvents were distilled before use by following standard proce-
dures. All reactions and manipulations were carried out under
nitrogen atmosphere using standard Schlenk line techniques. 1H
NMR (200 and 400 MHz) and 13C NMR (51.3 and 102.6 MHz)
spectra were recorded on Bruker ACF200 and AV400 spectrome-
ters. Chemical shifts are referenced with respect to the chemical
shift of the residual proton present in the deuterated solvents. FTIR
spectra were recorded using Perkin-Elmer spectrophotometer RX-
1. The [Pd(PhCN)2Cl2] [6], [Pd(COD)Cl2] [7] and 2,6-bis[(dimethyl-
amino)methyl]-4-methylphenol [8] were prepared according to
the literature procedures. Other chemicals were obtained from
commercial sources and used without further purification.
N
OH
N
1
The steric and electronic nature of this aminophenolate ligand
can readily be changed to fine tune the property of its complex,
which is often used as a catalyst for reactions such as ring-opening
metathesis polymerization of 2-norbornene [2], lactide polymeri-
zation [3] and the hydrolysis of b-lactam substrates [4]. van Koten
and co-workers reported vanadium complexes of 1 which are cat-
alysts for the polymerization of a-olefins [5]. Here, we first report
the synthesis and the structural characterization of new Pd(II)
complexes of 1.
2.2. Synthesis of complex [PdCl2(OC6H2(CH2NMe2)-2-Me-4-
(CH2NHMe2)-6)] (2)
To a CH2Cl2 solution of 2,6-bis[(dimethylamino)methyl]-4-
methylphenol (0.0145 g, 0.065 mmol), [PdCl2(PhCN)2] (0.025 g,
0.065 mmol) was added at room temperature. The resulting solu-
tion was refluxed for 4 h to give a red color solution. The solution
was cooled to room temperature and then concentrated to ꢀ2 mL,
to which diethyl ether (20 mL) was added to give orange-red pre-
cipitate of 2. The precipitate was filtered, washed with diethyl
ether and then dried under vacuum. Yield: 0.022 g, 84%. 2 was
⇑
Corresponding author. Tel.: +91 3222 282320; fax: +91 3222 282252.
E-mail address: gmani@chem.iitkgp.ernet.in (G. Mani).
0020-1693/$ - see front matter Ó 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.ica.2011.01.098

D. Ghorai, G. Mani / Inorganica Chimica Acta 372 (2011) 412–416
413
crystallized from dichloromethane solution upon layering with
3. Results and discussion
diethyl ether. mp 70 °C (decomposed). 1H NMR (CDCl3): d (ppm),
2.12 (s, 3H, Ph-CH3), 2.62 (s, 6H, coordinated NMe2), 2.89 (d, 6H,
3J(H,H) = 4.8 Hz, HN+Me2), 2.95 (s, 2H, coordinated Me2NCH2),
4.11 (d, 2H, 3J(H,H) = 5.2 Hz, Me2N+HCH2), 6.81 (s, 1H, Ph), 6.89
(s, 1H, Ph), 10.22 (br s, 1H, NH). 13C NMR (CDCl3): d (ppm) 20.4
(Ph-CH3), 42.7 (HN+Me2), 50.8 (coordinated NMe2), 60.5 (CH2N+H),
63.3 (coordinated CH2NMe2), 117.6 (Ph), 125.9 (Ph), 126.9 (Ph),
3.1. Synthesis and spectroscopic characterization of the palladium(II)
complexes
The Pd(II) complex 2 was synthesized by the reaction between
an equimolar amount of the ligand 1 and [Pd(PhCN)2Cl2] in 84%
yield (Scheme 1). 2 is an orange solid that is soluble in solvents
such as CH2Cl2, CHCl3 and THF. The structure of this complex 2
was first established by single crystal X-ray diffraction study which
was then confirmed by NMR, IR and elemental analysis methods.
The 1H NMR spectrum of 2 displays two sets of resonances for
the coordinated and the protonated (dimethylamino)methyl
groups. The NMe2 methyl groups and the benzylic protons of the
protonated amine group show doublets at d 2.89 and 4.11 ppm,
respectively, due to the coupling with N+H proton, which resonates
as a broad singlet at d 10.22 ppm. The chemical shift assignments
are based on the HETCOR spectrum of 2 (see Supplementary data).
In addition, the 1H NMR spectrum of 2 shows a considerable
change in the chemical shift of other protons of the ligand with re-
spect to the 1H NMR spectrum of the free ligand and their inte-
grated intensities are in accord with the structure. The presence
of NH group is further confirmed by the stretching frequency ob-
131.5 (Ph), 132.3 (Ph), 161.1 (Ph). IR (KBr, m
, cmÀ1): 3440 (br, m,
NH), 3015 (m), 2918 (m), 2843 (m), 1720 (w), 1636 (w), 1468
(vs), 1266 (s), 1101 (m), 1018 (w), 839 (w), 798 (m), 593 (w),
527 (w). Anal. Calc. for C13H22N2OPdCl2 (399.63): C, 39.07; H,
5.55; N, 7.01. Found: C, 38.24; H, 5.33; N, 6.58%.
2.3. Synthesis of complex [Pd(OC6H2(CH2NMe2)2-2,6-Me-4)2] (3)
2.3.1. Method a
To a solution of 1 (0.099 g, 0.44 mmol) in acetone, [Pd(OAc)2]
(0.05 g, 0.22 mmol) was added and stirred at room temperature
for 24 h, resulting in a yellow–orange solution. The solvent was re-
moved under vacuum and the resultant residue was extracted with
petroleum ether (10 mL) two times. The solvent was removed
again to give 3 (0.1 g, 0.18 mmol, 82% yield). A solution of 3 in ace-
tone/hexane (1:2 v/v) mixture was allowed to stand for the slow
evaporation and crystals of 3 formed after 5 days.
served at 3440 cmÀ1
.
Variable-temperature NMR study of the puckered six mem-
bered chelate ring has been reported for W and B complexes of 1
[1a,h]. To detect the formation of the conformers resulting from
the ring-flipping process variable-temperature 1H NMR spectra of
2 in CD2Cl2 were recorded. When the temperature is reduced from
the room temperature to À80 °C with 10 °C incremental reductions
the signals due to the benzylic and the NMe2 methyl groups are
broadened without decoalescence (see Supplementary data). This
indicates a fast exchange going on between the conformers result-
ing from the puckering of the six membered chelate ring on the
NMR time scale even at À80 °C.
2.3.2. Method b
To a solution of 1 (0.31 g, 1.4 mmol) in diethyl ether (50 mL) at
À78 °C, nBuLi (0.9 mL, 1.6 M, hexanes solution) was added with
stirring. The solution was brought slowly to room temperature.
After stirring for 1 h, [Pd(COD)Cl2] (0.2 g, 0.7 mmol) was added
and stirred for additional 12 h. The solvent was removed under
vacuum and the residue was extracted with petroleum ether
(30 mL) to give yellow–orange solution. The solution was concen-
trated to ꢀ15 mL and left at room temperature for seven days to
give needle shaped yellow colored crystals of 3 (0.127 g, 33%).
mp 165 °C (decomposed). 1H NMR (CDCl3): d (ppm) 2.15 (s, 6H,
PhCH3), 2.19 (s, 12H, dangling NMe2), 2.63 (s, 12H, coordinated
NMe2), 3.24 (s, 4H, coordinated CH2), 3.33 (s, 4H, dangling CH2),
6.62 (s, 2H, Ph), 6.92 (s, 2H, Ph). 13C NMR (CDCl3): d (ppm) 20.4
(PhCH3), 45.6 (dangling NMe2), 48.4 (coordinated NMe2), 59.3 (dan-
gling CH2), 64.5 (coordinated CH2), 123.5 (Ph), 124.2 (Ph), 126.7
When the ligand 1 is treated with [Pd(OAc)2] in acetone at room
temperature the mononuclear Pd(II) complex 3 is formed in 82%
yield. This complex is formed by substituting both the acetate an-
ions of [Pd(OAc)2] with the anions of the ligand, resulting in the
concomitant formation of acetic acid. The complex 3 was also ob-
tained in 33% crystalline yield when two equivalents of the lithium
salt of the ligand, which was generated in situ by the addition of
nBuLi to a solution of 1 in diethylether, is treated with one equiva-
lent of [Pd(COD)Cl2] (Scheme 2).
The complex 3 was characterized by both spectroscopic and X-
ray methods. In the 1H NMR spectrum, 3 shows two distinctive
chemical shifts for the NMe2 and the benzylic groups, as shown
by 2, and its chemical shifts are assigned based on the HETCOR
spectrum of 3 (see Supplementary data). The resonances due to
the other protons of the complex are also changed on comparison
with that of the free ligand and their integrated intensities are
matching each other, which confirm the observed solid state struc-
ture (see below). Since 3 has dangling (dimethylamino)methyl
groups and coordinated arms the 1H NMR of 3 was recorded for
(Ph), 129.7 (Ph), 132.2 (Ph), 161.8 (Ph). IR (Nujol, m
, cmÀ1): 2807
(m), 2758 (m), 1607 (w), 1364 (w), 1316 (w), 1264 (m), 1145
(w), 1092 (w), 1024 (m), 979 (w), 877 (w), 846 (w), 807 (m) 627
(w), 548 (w). Anal. Calc. for C26H42N4O2Pd (549.04): C, 56.87; H,
7.71; N, 10.21. Found: C, 57.01; H, 7.64; N, 9.99%.
2.4. X-ray crystallography
Single crystal X-ray diffraction data collections were performed
using Bruker-APEX-II CCD diffractometer with graphite monochro-
mated Mo K
a radiation (k = 0.71073 Å). The crystals were glued
onto the tip of glass fibers using Wembley’s Quickfix. The unit cell
parameters were determined by using three matrices each consists
of 12 frames of reflections and then the data were collected with a
set up of 10 seconds per frame for every 0.5°. The structures were
solved by direct methods, which successfully located most of the
non-hydrogen atoms. Subsequently, least square refinement was
carried out on F2 using SHELXL-97 [9] (WinGX version) to locate
the remaining non-hydrogen atoms. All non-hydrogen atoms were
refined anisotropically. All hydrogen atoms except H2 attached to
N2 were fixed on calculated positions using riding models and
were refined isotropically. The hydrogen atom attached to N2
was located in difference map and refined isotropically with ther-
mal parameter equivalent to 1.2 times that of N2.
CH2Cl2
[PdCl2(PhCN)2]
4 h, 50 o
C
N
O
N
H
N
OH
N
Pd
1
Cl
Cl
2
Scheme 1. Synthesis of [PdCl2(OC6H2(CH2NMe2)-2-Me-4-(CH2NHMe2)-6)] (2).

414
D. Ghorai, G. Mani / Inorganica Chimica Acta 372 (2011) 412–416
Cl2–H2–O1 (75.78°) equals to 359.79°, indicating the efficacy of a
bifurcated hydrogen bond [10].
The zwitterionic form with its bifurcated hydrogen bond is
probably formed by the abstraction of proton from the acidic OH
group of the ligand. Similar structures containing the zwitterionic
form of 2,6-bis[(dimethylamino)methyl]-4-methylphenol 1 with
a bifurcated hydrogen bond have been reported for Zn and V metal
complexes [1f,11]. The geometry around the Pd(II) metal center is a
distorted square planar with O(1)–Pd–Cl(1) and N(1)–Pd–Cl(2) an-
gles of 174.90(5)° and 176.59(8)°, respectively. Owing to the pres-
ence of less bulky groups on N2 the average C–N–C bond angle
around the protonated amine nitrogen atom N2 is higher
(112.2°) than that (109.5°) found at N1 which is bonded to Pd me-
tal. The Pd–N1 distance (2.060 Å) is shorter than that reported for
an analogous sp3 nitrogen coordinated Pd(II) complexes (2.1037,
2.092 and 2.110 Å) containing five membered chelate rings [12].
The bite angle of the ligand (O(1)–Pd–N(1) = 92.20°) is higher than
the bite angles (82.00° and 81.94°) reported for these Pd(II) com-
plexes. But the Pd–N1 distance is longer than that reported for a
Pd(II) complex containing sp2 coordinated nitrogen atom [13].
The Pd–O1 distance (2.0106) is slightly longer than that reported
(1.987 and 1.974 Å) for the Pd(II) complexes [14,15].
(i) 2 nBuLi, Et2O, -78 o
C
2
N
N
O
N
N
(ii) [Pd(COD)Cl2] , rt
Pd
OH
O
N
N
1
[Pd(OAc)2], Acetone, rt
- 2AcOH
3
Scheme 2. Synthesis of [Pd(OC6H2(CH2NMe2)2-2,6-Me-4)2] (3).
every 10 °C increase from room temperature to 60 °C to check
whether there is an exchange between them. The elevated temper-
ature spectra appeared the same as the room temperature one,
indicating no exchange between the coordinated and the free
(dimethylamino)methyl groups at the Pd metal center and the rig-
idness of the Pd–N bond on the NMR time scale, as reported for the
tungsten complex [1a]. Variable-temperature 1H NMR spectra (see
Supplementary data) show the broadening of signals and no deco-
alescence, indicating the ring-flipping process does not slow down
even at À60 °C in CDCl3 on the NMR time scale.
3.2.2. Complex 3
The complex 3 crystallizes in C2/c space group and one half of
the molecule is present in the asymmetric unit with the Pd metal
at the inversion center. The crystal structure of 3 is shown in
Fig. 2. Crystallographic refinement data, and selected bond length
and bond angles are given in Tables 1 and 4, respectively.
The X-ray structure reveals that two phenolate ligands are coor-
dinated to one Pd(II) metal center. Each ligand uses one of its NMe2
nitrogen atoms and the phenoxide oxygen atom to form a six
membered chelate ring which is puckered; the other (dimethyl-
amino)methyl arm is dangling and away that reduces steric inter-
actions. The geometry around the Pd metal center is distorted
square planar, as shown by the bond angles. The two coordinated
oxygen atoms are trans to each other, as are the two nitrogen
atoms, probably owing to the steric hindrance of the (dimethyl-
amino)methyl groups. As described for the structure of 2, the Pd–
N distance (2.082(5) Å) is shorter than that found in the reported
Pd(II) complexes [12]. The Pd–O bond distance (2.021(4) Å) is
slightly longer than that found in the complex 2 and in other Pd(II)
complexes [14,15].
The used diaminophenoloate ligand is a bulky aryloxy ligand
and there can be a repulsion between the lone pairs on the oxygen
atom and the filled metal d orbitals. This can cause the oxygen
atom to adopt sp2 hybridization, as shown by the angles (C9–
O1–Pd = 118.68° for 2 and C10–O1–Pd1 = 117.3° for 3) and the
puckering of the chelate rings observed in both complexes. As a re-
sult the lone pair on the oxygen atom becomes increasingly suit-
able for forming hydrogen bond with the protonated amine
hydrogen atom (Fig. 1) and the Pd–O bond distances of both com-
plexes are longer. Since Pd(II) metal has filled d orbitals and is
bonded to two hard donors (O, N) the lone pairs on the chlorine
3.2. Crystal structure analyses
3.2.1. Complex 2
The molecular structure of 2 is shown in Fig. 1. Crystallographic
refinement data, and selected bond lengths and bond angles are gi-
ven in Tables 1–3, respectively. The X-ray structure reveals that
one ligand 1 as a zwitterionic form is coordinated through its N
and O atoms to the Pd(II) metal center, forming a six membered
chelate ring which is puckered. The protonated amine group (N2)
acts as a bifurcated donor and forms a bifurcated hydrogen bond
with the coordinated oxygen atom (O1) and chloride atom (Cl2)
of the Pd(II) metal center. The N2–O1 distance is considerably
shorter than the sum of the van der walls radii (3.07 Å), while
the N2–Cl2 distance is only slightly lower than the sum of the
van der waals radii (3.30 Å). The hydrogen atom sits in the plane
formed by N2, O1 and Cl2 atoms and the sum of the angles of
N(2)-H(2)ÁÁÁO(1) (140.38°), N(2)-H(2)ÁÁÁCl(2) (143.63°) and
atom (Cl2) rather involved in hydrogen bond than does act as
p-
donor ligand. This is reflected in the bond distances; the Pd–Cl2
is longler (2.3125(6) Å) than the Pd–Cl1 distance (2.2975(7) Å)
[16].
In conclusion, two new mononuclear Pd(II) complexes of 2,6-
bis[(dimethylamino)methyl]-4-methylphenol ligand are synthe-
sized and structurally characterized. Owing to a fast exchange
the conformers resulting from the ring-flipping process could not
be detected by variable-temperature NMR studies for both the
complexes. Catalytic properties of these Pd(II) complexes are under
investigation. In addition the complex 3 contains two uncoordi-
Fig. 1. Molecular structure of 2. The thermal ellipsoids are drawn at the 50%
probability level.

D. Ghorai, G. Mani / Inorganica Chimica Acta 372 (2011) 412–416
415
Table 1
Crystal data and details of the structure refinement for 2 and 3.
Table 4
Selected bond lengths (Å) and bond angles (°) for 3.
2
3
Pd(1)–O(1)
Pd(1)–N(1)
O(1)–C(10)
N(1)–C(3)
C(4)–C(3)
2.021(4)
2.082(5)
1.327(8)
1.479(8)
1.507(8)
1.509(9)
1.461(8)
O(1)–Pd(1)–N(1)
O(1i)1–Pd(1)–O(1)
C(10)–O(1)–Pd(1)
C(3)–N(1)–Pd(1)
C(10)–C(4)–C(3)
N(1)–C(3)–C(4)
92.65(18)
180.0(3)
117.3(3)
112.5(3)
117.2(6)
115.3(5)
122.6(5)
119.1(6)
Empirical formula
Formula weight
Radiation (Å)
T (K)
C
13H22Cl2N2OPd
C26H42N4O2Pd
549.04
0.7107
293(2)
monoclinic
red needle
C2/c
399.63
0.7107
293(2)
monoclinic
red needle
C2/c
C(11)–C(9)
C(11)–N(2)
Crystal system
Color and shape
Space group
a (Å)
b (Å)
c (Å)
O(1)–C(10)–C(4)
C(10)–C(9)–C(11)
18.6557(7)
15.4400(5)
13.9569(5)
90
17.767(8)
17.659(8)
9.602(4)
90
nated amine groups which could be used to build heteronuclear
complexes.
a
(°)
b (°)
110.4050(10)
90
3767.9(2)
8
1.409
1.263
117.090(5)
90
2682(2)
4
1.36
0.72
c
(°)
V (Å3)
Acknowledgements
Z
Dcalcd (mg mÀ3
)
l
(Mo K
F(0 0 0)
Crystal size (mm)
Total/unique number of reflections 27 895, 5980
a
) (mmÀ1
)
We thank the CSIR and DST for support and for the X-ray and
NMR facilities. We thank Dr. G.P.A. Yap, Department of Chemistry
and Biochemistry, University of Delaware, and Prof. Kumar Bira-
dha, Department of Chemistry, IIT-Kharagpur for their help with
the X-ray structures. We also thank Dr. Swadhin Mandal, Indian
Institute of Science Education and Research, Kolkata for X-ray data
collection.
1616
1152
0.46 Â 0.12 Â 0.10 0.38 Â 0.02 Â 0.02
14 113, 2840
0.1475
0.0646, 0.1571
0.1131, 0.1907
Rint
R1, wR2
0.0255
0.0346, 0.0923
0.0501, 0.0983
0.807 and À0.454 1.486 and À2.119
R1, wR2 (all data)
Largest different peak and hole
(e ÅÀ3
)
Appendix A. Supplementary material
CCDC 794416 and 794417 contains the supplementary crystal-
lographic data for 2 and 3, respectively. These data can be obtained
free of charge from The Cambridge Crystallographic Data Centre
via www.ccdc.cam.ac.uk/data_request/cif. Supplementary data
associated with this article can be found, in the online version, at
doi:10.1016/j.ica.2011.01.098.
Table 2
Hydrogen bonds distances (Å) and angles (°) in the structure of 2.
D–HÁÁÁA
d(D–H)
d(HÁÁÁA)
d(DÁÁÁA)
<(DHA)
N(2)–H(2)ÁÁÁO(1)
N(2)–H(2)ÁÁÁCl(2)
0.73(3)
0.73(3)
2.08(3)
2.63(3)
2.688(2)
3.248(2)
140(3)
144(3)
References
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Table 3
Selected bond lengths (Å) and bond angles (°) for 2.
(b) P.A. van der Schaaf, E. Wissing, J. Boersma, W.J.J. Smeets, A.L. Spek, G. van
Koten, Organometalics 12 (1993) 3624;
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Pd–O(1)
2.0106(14)
2.060(2)
2.2975(7)
2.3125(6)
1.340(3)
1.500(4)
1.493(3)
92.20(9)
174.90(5)
84.82(4)
91.91(8)
N(1)–Pd–Cl(2)
176.59(8)
91.16(3)
118.68(12)
110.4(2)
111.08(18)
106.9(2)
111.2(3)
107.7(3)
109.6(2)
111.55(19)
112.5(2)
112.66(19)
Pd–N(1)
Pd–Cl(1)
Cl(1) –Pd–Cl(2)
C(9)–O(1)–Pd
Pd–Cl(2)
C(1)–N(1)–Pd
O(1)–C(9)
C(3)–N(1)–Pd
N(1)–C(3)
C(2)–N(1)–Pd
N(2)–C(11)
O(1)–Pd–N(1)
O(1)–Pd–Cl(1)
O(1)–Pd–Cl(2)
N(1)–Pd–Cl(1)
C(1)–N(1)–C(2)
C(1)–N(1)–C(3)
C(3)–N(1)–C(2)
C(12)–N(2)–C(13)
C(12)–N(2)–C(11)
C(13)–N(2)–C(11)
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