Palladium(II) mixed-ligand complexes containing 2,2′-bipyridine derivatives and 4-toluenesulfonyl-l-serine: Synthesis, characterization, and crystal structure determination

Article abstract of DOI:10.1080/10426507.2015.1012197

The 4-toluenesulfonyl-L-serine ligand (1), (tsserH₂), was prepared from the reaction of L-serine and 4-toluenesulfonyl chloride in sodium hydroxide solution 1 M. The complexes [Pd(4,4′-dmbipy)(tsser)] (2) and [Pd(5,5′-dmbipy)(tsser)].0.5CH

Full text of DOI:10.1080/10426507.2015.1012197

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Phosphorus, Sulfur, and Silicon and the Related
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Palladium(II) Mixed-Ligand Complexes Containing 2,2'-
Bipyridine Derivaties and 4-Toluenesulfonyl-l-Serine:
Synthesis, Characterizationand Crystal Structure
Determination
a
a
a
b
Ebrahim Mehdipour , Homayoon Bahrami , Shabnam Shamaei , Vahid Amani & Behrouz
c
Notash
a
Department of Chemistry, Faculty of Science, Lorestan University, Khoramabad, Iran.
b
Department of Chemistry, Yadegar-e-Imam Khomeini (RAH) Branch, Islamic Azad University,
Tehran, Iran
c
Click for updates
Department of Chemistry, Shahid Beheshti University, G.C., Evin, Tehran 1983963113, Iran
Accepted author version posted online: 12 Feb 2015.
To cite this article: Ebrahim Mehdipour, Homayoon Bahrami, Shabnam Shamaei, Vahid Amani & Behrouz Notash (2015):
Palladium(II) Mixed-Ligand Complexes Containing 2,2'-Bipyridine Derivaties and 4-Toluenesulfonyl-l-Serine: Synthesis,
Characterizationand Crystal Structure Determination, Phosphorus, Sulfur, and Silicon and the Related Elements, DOI:
10.1080/10426507.2015.1012197
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PALLADIUM(II) MIXED-LIGAND COMPLEXES CONTAINING 2,2'-BIPYRIDINE
DERIVATIES AND 4-TOLUENESULFONYL-L-SERINE: SYNTHESIS,
CHARACTERIZATIONAND CRYSTAL STRUCTURE DETERMINATION
a*
a
a
b
Ebrahim Mehdipour, Homayoon Bahrami, Shabnam Shamaei, Vahid Amani and Behrouz
c
Notash
a
Department of Chemistry, Faculty of Science, Lorestan University, Khoramabad, Iran. e-mail:
e_mehdipour@yahoo.com
b
Department of Chemistry, Yadegar-e-Imam Khomeini (RAH) Branch, Islamic Azad University,
Tehran, Iran
c
Department of Chemistry, Shahid Beheshti University, G.C., Evin, Tehran 1983963113, Iran
Abstract
The 4-toluenesulfonyl-L-serine ligand (1), (tsserH
and 4-toluenesulfonyl chloride in sodium hydroxide solution 1M. The complexes [Pd(4,4'-
dmbipy)(tsser)] (2) and [Pd(5,5'-dmbipy)(tsser)].0.5CH CN (3) (4,4'-dmbipy is 4,4'-dimethyl-
,2'-bipyridine and 5,5'-dmbipy is 5,5'-dimethyl-2,2'-bipyridine) were also prepared from the
reaction of PdCl and 2,2'-bipyridine derivatives with 4-toluenesulfonyl-L-serine ligand in
2
), was prepared from the reaction of L-serine
3
2
2
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mixture of CH
3
CN/CH
3
OH (3:1) and in presence of sodium hydroxide solution 0.5M. These
1
compounds were characterized by elemental analysis, IR, H NMR and UV–Vis spectroscopy
and their structures were studied by single-crystal X-ray diffraction method. The X-ray structure
II
determinations show that in the both complexes, the Pd atoms are four-coordinated in a
distorted square-planar configuration by two N atoms from a bidentate bipyridine ligand and one
2
-
N atom and one O atom from a bidentate tsser ligand.
Keywords Crystal structure; palladium(II) complexes; 4-toluenesulfonyl-L-serine; 4,4'-
dimethyl-2,2'-bipyridine; 5,5'-dimethyl-2,2'-bipyridine
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1
. Introduction
1
-4
Palladium(II) complexes are well-known to show interesting applications in catalysis,
5
-7
8-10
optics and possess antibacterial and antifungal properties.
Palladium(II) complexes have
been also investigated for developing the new antitumor agents because palladium(II) has a
1
1-17
similar coordination mode and chemical properties to platinum(II) complexes.
eight palladium(II) mixed-ligand complexes with formula, [Pd(L)(amino acid)], such as that of
pd(bipy)(Gly)]Cl.4H O, [pd(phen)(Gly)]Cl.4H O and [pd(bpa)(Gly)]Cl.3H O (Gly is glycine,
bipy is 2,2'-bipyridine, phen is 1, 10-phenanthroline and bpa is 2,2'-bipyridylamine), [pd(1,3-
There are only
[
2
2
2
1
7
1
8
dap)(tsser)] (1,3-dap is 1,3-diaminopropane), [pd(1,3-dap)(tsval)] (tsvalH is 4-toluenesulfonyl-
2
1
9
20
L-valine), [pd(tsval)(phen)].2H
2
O, [pd(dab)(tsala)] (dab is 1,4-diaminobutane and tsalaH is
2
2
1
22
4
-toluenesulfonyl-L-alanine), [pd(en)(tsser)] (en is ethylene diamine), have been synthesized
and full characterized by technicals spectroscopy and their structures were studied by single-
crystal X-ray diffraction method. Also, all of these palladium(II) mixed-ligand complexes have
shown significant cytotoxic activities against several human tumor cell lines. We report herein
the synthesis, characterization and crystal structure of the 4-toluenesulfonyl-L-serine ligand (1)
and two [Pd(4,4'-dmbipy)(tsser)] (2) and [Pd(5,5'-dmbipy)(tsser)].0.5CH CN (3) complexes.
3
2
. Results and discussion
2
.1. Synthesis of 1, 2 and 3
1
8
4-Toluenesulfonyl-L-serine (1) was synthesized according to the reported procedure.
Suitable crystals of 1 for X-ray diffraction study were grown by slow evaporation of a 1:1 ratio
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of CH
3
CN/CH
3
OH solution at room temperature over one week. Compounds 2 and 3 were also
and one equivalent of N-N ligand (N-N is
,4'-dimethyl-2,2'-bipyridine in 2 and 5,5'-dimethyl-2,2'-bipyridine in 3) with one equivalent of
-toluenesulfonyl-L-serine ligand in mixture of CH CN/CH OH (3:1) and in presence of sodium
obtained from the reaction one equivalent of PdCl
2
4
4
3
3
hydroxide solution 0.5M. Suitable crystals of 2 and 3 for X-ray diffraction study were grown by
slow evaporation of its solution at room temperature over one week. The synthetic routes of
these compounds are shown in Scheme 1.
2
.2. Description of the molecular structure of 1, 2 and 3
Crystallographic data for 1, 2 and 3 are given in Table 1 and selected bond lengths and angles
are presented in Table 2. The ORTEP view with the numbering scheme for 1 is shown in Figure
. This compound crystallized in orthorhombic P2 space group. As shown in Figure 1, the
1
1
2
2
1 1
carboxylic group and p-toluene ring are in the same side of molecular structure [torsion angle:
C5-S1-N1-C8 = 75.48(18)°]. In this compound, the bond lengths and angles are within normal
2
3
ranges.
In the crystal structure of compound 1, Figure S1 (Supplemental Materials), there is no π-π
interaction between the phenyl rings and intermolecular O-H···O, N-H···O and C-H···O hydrogen
bonds (Table S 1 Supplemental Materials) are effective in the stabilization of the crystal structure
and the formation of the 3D supramolecular compound.
[
[
Insert Figure 1]
Insert Table 1]
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The ORTEP view with the numbering scheme for complex 2, [Pd(4,4'-dmbipy)(tsser)], is
shown in Figure 2. As shown in Figure 2, each palladium(II) cation is four-coordinated in a
distorted square-planar configuration by two N atoms from a bidentate 4,4'-dmbipy ligand and
2
-
one N atom and one O atom from a bidentate tsser anion. The Pd-Nbipy bond lengths are
1
.989(13) and 2.021(14)Å, Pd-Ntsser bond length is 2.014(12)Å and Pd-O bond length is
.007(10)Å (Table 2). The Pd-N and Pd-O bond distances are within the ranges of those for other
2
1
8-22
analogical palladium(II) complexes.
The N1-Pd-N2, N1-Pd-N3, N2-Pd-O3, and N3-Pd-O3
bond angles are 81.1(5), 99.5(5), 96.6(5), and 82.8(5)°, respectively (Table 2). The angle
between planar N1-Pd1-N2 and planar O1-Pd1-N3 is 2.68° which indicates that the Pd1-O3-N3-
N1-N2 plane is slightly distorted. Also, the pyridine rings are slightly distorted from planarity.
The mean planes of rings A (N1/C1-C3/C5-C6), B (N2/C7-C9/C11-C12) and C (Pd1/N1/C6-
C7/N2) make the following dihedral angles with each other: A/B = 7.00, A/C = 5.08 and B/C =
2
.56.
[
[
Insert Table 2]
Insert Figure 2]
In the crystal structure of 2, Figure S 2 (Supplemental Materials), there is no π···π interaction
between the pyridine and phenyl rings, and only intermolecular O-H···O and C-H···O hydrogen
bonds (Table S 1) are effective in the stabilization of the crystal structure and formation of the 3-
D supramolecular assembly.
The crystal structure of 3, [Pd(5,5'-dmbipy)(tsser)].0.5CH
depicted in this Figure, the asymmetric unit of 3 contains one independent [Pd(5,5'-
dmbipy)(tsser)] complex and half no coordinated CH CN molecule. In this complex,
3
CN, is given in Figure 3. As it is
3
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palladium(II) cation is four-coordinated in a distorted square-planar configuration by two N
atoms from a bidentate 5,5'-dmbipy ligand and one N atom and one O atom from a bidentate
2
-
tsser anion. The Pd-Nbipy bond lengths are 2.000(4) and 2.002(4)Å, Pd-Ntsser bond length is
2
.020(4)Å and Pd-O bond length is 1.992(4)Å (Table 2). The Pd-N and Pd-O bond distances are
1
8-22
within the ranges of those for other analogical palladium(II) complexes.
The N1-Pd-N2, N1-
Pd-N3, N2-Pd-O3, and N3-Pd-O3 bond angles are 80.58(17), 102.39(19), 94.38(18), and
2.61(17)°, respectively (Table 2). The angle between planar N1-Pd1-N2 and planar O1-Pd1-N3
8
is 3.55° which indicates that the Pd1-O3-N3-N1-N2 plane is slightly distorted. Also, the pyridine
rings are slightly distorted from planarity. The mean planes of rings A (N1/C1-C2/C4-C6), B
(
N2/C7-C10/C12) and C (Pd1/N1/C6-C7/N2) make the following dihedral angles with each
other: A/B = 5.78, A/C = 3.53 and B/C = 3.24.
[
Insert Figure 3]
In the crystal structures of complex 3, Figure S 3, it seems that the main factors controlling the
packing of the structure are intermolecular O-H···O, C-H···O and C-H···N hydrogen bonds (Table
i
ii
S 1) and π-π interactions between the pyridine and phenyl rings, Cg3···Cg4 and Cg3···Cg5
symmetry codes: (i) -x,2-y,z, (ii) -1/2+x,3/2-y,-z, where Cg3, Cg4 and Cg5 are centroids of the
rings (N1/C1-C2/C4-C6), (N2/C7-C10/C12) and (C14-C19), with centroid-centroid distances of
[
3
2
.816(3) and 3.901(3)Å, respectively].
.3. Spectroscopic characterization of 1, 2 and 3
IR absorptions of 1, 2 and 3 are listed in experimental section. The vibrational bands present at
-
1
3
410 and 3277 cm are assigned to ν(O-H)COOH and ν(N-H), respectively for 1. These bands
disappear for the complexes of 2 and 3, showing that the 4-toluenesulfonyl-L-serine ligand has
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1
8-21
-1
been deprotonated.
The weak absorption bands present in the region 3051 to 2921 cm are
2
4
due to the C-H stretching of phenyl and pyridine rings and methyl groups. In addition, the
-1
25
weak band at 2306 cm in the IR spectrum of 3 has been assigned to ν(C≡N). The strong band
-1
at 1732 cm in the IR spectrum of 1 has been assigned to ν(CO). This band for the free ligand is
shifted to lower frequencies upon coordination in 2 and 3. The strong bands at 1627 and 1641
-1
-1
cm are assigned to νas(COO) and the strong bands at 1375 and 1362 cm are assigned to
ν
ν
s
(COO) for complexes of 2 and 3, respectively. The frequency difference Δν [Δν = νas(COO)-
s
(COO)] is correlated with the coordination mode of a carboxylate ligand. The Δν differences
-1
are 252 and 279 cm for compounds 2 and 3 respectively, which are greater than those of
-1
25-27
sodium acetate (164 cm ), as anticipated for a monodentate mode of the carboxylate ligand.
New bands present in the 260-434 regions are assigned to Pd-Nbipy, Pd-Ntsser and Pd-Otsser
2
5, 28-31
stretching vibrations.
The UV–Vis spectra of dimethyl sulfoxid solutions of title compounds have a broad band in
1
9-21, 32
the region of 258-274 nm, assigned to the ligand π-π* transition.
There is also a broad
1
9-21
band at 304-322 nm for 2 and 3 assigned to the metal-to-ligand charge transfer (MLCT).
1
The H NMR spectra of title compounds in DMSO-d
6
solution are given in Figure 4. As
1
depicted, the H NMR spectrum of 1 exhibited a broad singlet at 12.45 ppm for the –COOH
group and a doublet at 7.91ppm for the –NH group. These signals are absent in the spectra of
compounds 2 and 3, indicating the removal of the –COOH and –NH protons and the formation
of Pd-O and Pd-N bonds. As shown in Figures 3 and 5, the X-ray structures of compounds 2 and
3
show that the half of bipyridine ligands lies down in the diamagnetic protection zone of the
phenyl aromatic ring. Thus, this phenomenon is corroborated with the chemical shifts observed
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1
1
for H13 and H16 in H NMR. The H NMR spectrum of 3 also exhibited a singlet at 2.07 ppm
for the –CH of free acetonitrile.
Insert Figure 4]
3
[
3
. Conclusion
In this work, the 4-toluenesulfonyl-L-serine (1) ligand and two new palladium (II) mixed-
ligand complexes, [Pd(4,4'-dmbipy)(tsser)] (2) and [Pd(5,5'-dmbipy)(tsser)].0.5CH CN (3), have
3
been synthesized. All of these compounds were characterized by elemental analysis, IR, UV-Vis
1
and H NMR spectroscopy and their structures were studied by single-crystal X-ray
crystallography. In the crystal structure of compound 1, intermolecular O-H···O, N-H···O and C-
H···O hydrogen bonds, in compound 2, intermolecular O-H···O and C-H···O hydrogen bonds and
in compound 3, π-π interactions and intermolecular O-H···O, C-H···O and C-H···N hydrogen
bonds are effective in the stabilization of the crystal structures and the formation of the 3D
supramolecular compounds.
4
4
. Experimental
.1. Physical measurements and materials
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-1
All chemicals were purchased from Merck and Aldrich. Infrared spectra (4000–250 cm ) of
solid samples were taken as 1% dispersion in CsI pellets using a Shimadzu-470 spectrometer.
NMR was recorded on a Bruker AC-300 spectrometer for protons at 300.13 MHz in DMSO-d .
6
Melting points were obtained on a Kofler Heizbank Rechart type 7841 melting point apparatus.
Elemental analysis was performed using a Heraeus CHN–O Rapid analyzer. UV-Vis spectra
were recorded on a Shimadzu 2100 spectrometer using a 1 cm path length cell DMSO at room
temperature.
4
.2. Crystal structure determination and refinement
The X-ray diffraction measurements were made on a STOE IPDS-II diffractometer with
graphite monochromated Mo-Kα radiation. For tsserH
dimensions 0.50×0.20×0.15 mm, for [Pd(4,4'-dmbipy)(tsser)] (2), a yellow plate crystal with
dimensions 0.12×0.08×0.08 mm and for [Pd(5,5'-dmbipy)(tsser)].0.5CH CN (3), a yellow plate
2
(1), a colorless plate crystal with
3
crystal with dimensions 0.45×0.40×0.25 mm were mounted on glass fibers and used for data
collection. Cell constants and an orientation matrix for data collection were obtained by the least-
squares refinement of the diffraction data from 2952 for 1, 4614 for 2 and 3923 for 3 unique
reflections. Data were collected at 120(2) K for 1-3 to a maximum 2θ value of 58.30 for 1, 58.32
for 2 and 50.00° for 3 in a series of ω scans in 1° oscillations and then integrated using the Stoe
3
3
X-AREA software package. The numerical absorption coefficients, µ, for Mo-Kα radiation are
-1
-1
-1
0
.291 mm for 1, 0.997 mm for 2 and 0.952 mm for 3. The numerical absorption correction
3
4
35
was applied using the X-RED and X-SHAPE software packages. The data were corrected for
Lorentz and Polarizing effects. The structures were solved by direct methods and subsequent
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2
differences Fourier maps and then refined on F by a full-matrix least-squares procedure using
3
6
anisotropic displacement parameters. All hydrogen atoms for 1, 2, 3 and 4 were added at ideal
positions and constrained to ride on their parent atoms, with Uiso(H) = 1.2Ueq. Atomic factors are
3
7
from the International Tables for X-ray Crystallography. All refinements were performed using
3
8
the X-STEP32 crystallographic software package.
Full crystallographic details are deposited with the Cambridge Structural Database (CCDC
No 1012724 for complex 1, 1012725 for complex 2 and 1012726 for complex 3). Copies of the
data can be obtained free of charge on application to CCDC, 12 Union Road, Cambridge
CB21EZ, UK.
4
4
.3. Synthesis of compounds
.3.1. Synthesis of 4-toluenesulfonyl-L-serine (tsserH ) (1)
2
1
8
4-Toluenesulfonyl-L-serine was prepared according to the procedure described previously.
(
for synthesis details, please see Supplemental Materials)
4
.3.2. Synthesis of [Pd(4,4'-dmbipy)(tsser)] (2)
A suspension of PdCl (0.09 g, 0.5 mmol) in CH
C, to give a orange solution. Then 4,4'-dimethyl-2,2'-bipyridine (0.10 g, 0.5 mmol) in CH
10 mL) was added and the mixture stirred at 70 °C. After 10 min a mixture of 4-
toluenesulfonyl-L-serine (0.13 g, 0.5 mmol) in CH OH (20 mL) and NaOH (2 mL, 0.50 M in
water solution, 1.0 mmol) was added and the contents refluxed for 3 h. The solution was filtered
2
3
CN (50 mL) was stirred and warmed to 70
CN
°
3
(
3
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and allowed to crystallize at room temperature, whereupon yellow plate crystals were formed
-1
after one week (yield 0.21 g, 76.7%, m.p. 258 °C). IR (CsI, Cm ): 3042m, 2945m, 2922m,
1
3
8
627s, 1421m, 1375s, 1265m, 1134m, 1088s, 980m, 906m, 809m, 667m, 584m, 530m, 434m,
1
88m, 309m, 260m. Uv-Vis. λmax (DMSO, nm): 261, 304 and 314. H NMR (DMSO-d
6
, ppm):
.85 (d, J = 5.7 Hz, 1H, 4,4'-dmbipy), 8.47 (s, 1H, 4,4'-dmbipy), 8.41 (s, 1H, 4,4'-dmbipy), 8.10
(
d, J = 5.7 Hz, 1H, 4,4'-dmbipy), 7.93 (d, J = 7.8 Hz, 2H, ArH, tsser), 7.65-7.60 (m, 2H, 4,4'-
dmbipy), 7.27 (d, J = 7.8 Hz, 2H, ArH, tsser), 4.89 (s, 1 H, OH, tsser), 3.83-3.76 (m,1H, CH,
tsser), 3.61-3.51 (m, 2H, CH , tsser), 2.53 (s, 6 H, CH , 4,4'-dmbipy), 2.34 (s, 3 H, CH , tsser).
Elemental analysis Calcd (%) for 2, C22 PdS: C, 48.22; H, 4.20; N, 7.67. Found: C,
2
3
3
H
23
N
3
O
5
4
7.91; H, 4.18; N, 7.63.
4
.3.3. Synthesis of [Pd(5,5'-dmbipy)(tsser)].0.5CH
The complex of 3 was prepared according to the procedure of complex 2 except using 5,5'-
dimethyl-2,2'-bipyridine instead of 4,4'-dimethyl-2,2'-bipyridine in mixture of CH CN (60 mL)
3
CN (3)
3
and MeOH (20 mL). Yellow plate single crystals of 3 suitable for X-ray analysis were obtained
by slow evaporation of the solvent after one week (yield 0.22 g, 77.4%, m.p. 246 °C). IR (CsI,
-1
Cm ): 3051m, 2921m, 2306w, 1641s, 1514m, 1362s, 1141m, 1029s, 985m, 943m, 837m, 716m,
6
68m, 612m, 576m, 527m, 422m, 347m, 279m, 261m. Uv-Vis. λmax (DMSO, nm): 262 and 322.
1
H NMR (DMSO-d
.39 (d, J = 8.4 Hz, 1H, 5,5'-dmbipy), 8.16 (t, 2H, 5,5'-dmbipy), 8.04 (s, 1H, 5,5'-dmbipy), 7.92
d, J = 7.5 Hz, 2H, ArH in tsser), 7.29 (d, J = 7.5 Hz, 2H, ArH in tsser), 4.95 (s, 1 H, OH in
tsser), 3.85-3.82 (m,1H, CH in tsser), 3.63-3.56 (m, 2H, CH in tsser), 2.45 (s, 3 H, CH in 5,5'-
6
, ppm): 8.85 (s, 1H, 5,5'-dmbipy), 8.45 (d, J = 8.4 Hz, 1H, 5,5'-dmbipy),
8
(
2
3
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dmbipy), 2.41 (s, 3 H, CH
3
in 5,5'-dmbipy), 2.34 (s, 3 H, CH
3
in tsser), 2.07 (s, 1.5H, CH in
CH CN). Elemental analysis Calcd (%) for 3, C23
3
H
24.5
N
3.5
O
5
PdS: C, 48.59; H, 4.31; N, 8.62.
Found: C, 48.21; H, 4.28; N, 8.55.
Acknowledgments
We would like to thank the University of Lorestan for financial support.
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Table 1 Crystallographic and structure refinement data for 1–3
1
2
3
Formula
C
10
H13NO
5
S
C
22 23
H N
3 5
O PdS
C
23 24.5
H N
3.5
O PdS
5
Formula weight
Temperature /K
Wavelength λ /Å
Crystal system
Space Group
259.28
120(2)
0.71073
547.90
120(2)
0.71073
Triclinic
Pı
568.43
120(2)
0.71073
Orthorhombic
P2
Orthorhombic
P2
1
2
1
2
1
1
2 2
1
3
Crystal size /mm
0.11×0.10×0.09 0.12×0.08×0.08 0.45×0.40×0.25
a /Å
b /Å
c /Å
α /°
β /°
γ /°
4.9036(10)
9.7072(19)
24.168(5)
90
90
90
1150.4(4)
4
1.497
6.0595(12)
9.975(2)
10.170(2)
113.39(3)
101.57(3)
96.62(3)
539.6(3)
1
11.974(2)
17.892(4)
10.592(2)
90
90
90
2269.2(8)
2
1.664
3
Volume / Å
Z
Density (calc.) /g cm
-
1
1.686
θ ranges for data collection
2.69-29.15
544
0.291
2.42-29.16
278
0.997
-8≤ h ≤ 8
-12 ≤ k ≤ 13
-13≤ l ≤ 13
5960
2.57-25.00
1156
0.952
-14≤ h ≤ 12
-21 ≤ k ≤ 18
-12≤ l ≤ 11
7014
F(000)
Absorption coefficient mm
Index ranges
-
1
-5≤ h ≤ 6
-
-
11 ≤ k ≤ 13
27≤ l ≤ 33
Data collected
5147
Unique data (Rint
)
2952, 0.0364
167, 0
0.0398, 0.0825
0.0472, 0.0854
1.007
4614, 0.0934
268, 3
0.0614, 0.1176
0.0810, 0.1360
1.007
3923, 0.0444
313, 0
0.0333, 0.0838
0.0391, 0.0983
1.126
Parameters, restrains
a
Final R
Final R
1
, wR
, wR
2
(Obs. data)
(All data)
a
1
2
2
Goodness of fit on F (S)
-
3
Largest diff peak and hole /e.Å
0.369, -0.302
0.822, -0.789
0.973, -0.401
a
2
2 2
2 2 1/2
R
1
= Σ||F
o
|-|F
c
||/Σ|F
o
|, wR
2
= [Σ(w(F
o
-F
c
) )/Σw(F
o
) ]
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Table 2 Bond distances (Å) and bond angles (°) for 1-3
1
S1-N1
S1-C5
O3-C9
O4-C9
N1-C8
C8-C9
C8-C10
1.6206(18)
1.764(2)
1.204(3)
1.319(3)
1.459(3)
1.519(3)
1.529(3)
N1-S1-C5
C8-N1-S1
N1-C8-C9
N1-C8-C10
C9-C8-C10
O3-C9-O4
O3-C9-C8
O4-C9-C8
109.79(10)
120.32(15)
111.49(17)
109.54(17)
109.76(17)
125.9(2)
124.4(2)
109.68(18)
2
Pd1-O3
Pd1-N1
Pd1-N2
Pd1-N3
S1-N3
S1-C19
O3-C21
O4-C21
N3-C20
C20-C21
O3-Pd1-N1
O3-Pd1-N3
O3-Pd1-N2
2.007(10)
1.989(13)
2.021(14)
2.014(12)
1.625(13)
1.776(9)
1.268(16)
1.232(13)
1.489(16)
1.528(15)
177.7(6)
82.8(5)
N1-Pd1-N3
N1-Pd1-N2
N3-Pd1-N2
C21-O3-Pd1
C20-N3-Pd1
S1-N3-Pd1
N3-S1-C19
N3-C20-C22
N3-C20-C21
O3-C21-C20
O4-C21-O3
N3-C20-C22
99.5(5)
81.1(5)
177.3(7)
114.2(8)
106.6(8)
117.8(7)
102.7(5)
109.2(9)
109.9(9)
117.0(10)
124.6(10)
109.2(9)
96.6(5)
3
Pd1-O3
Pd1-N1
Pd1-N2
Pd1-N3
S1-N3
S1-C19
O3-C22
O4-C22
C20-C22
N3-C20
O3-Pd1-N2
O3-Pd1-N1
O3-Pd1-N3
1.992(4)
2.002(4)
2.000(4)
2.020(4)
1.600(4(
1.783(6(
1.308(7(
1.220(7(
1.529(7)
1.483(7)
94.38(18)
173.87(17)
82.61(17)
N2-Pd1-N3
N1-Pd1-N3
N2-Pd1-N1
C22-O3-Pd1
C20-N3-Pd1
S1-N3-Pd1
N3-S1-C19
N3-C20-C21
N3-C20-C22
O4-C22-O3
O3-C22-C20
N3-C20-C21
176.9(2)
102.39(19)
80.58(17)
115.3(3)
108.0(3)
124.6(3)
104.2(2)
107.9(4)
110.2(4)
122.3(5)
115.6(4)
107.9(4)
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Figure 1 The labeled diagram of 4-toluenesulfonyl-L-serine (1). Thermal ellipsoids are at 50%
probability level.
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Figure 2 The labeled diagram of [Pd(4,4'-dmbipy)(tsser)] (2). Thermal ellipsoids are at 50%
probability level.
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Figure 3 The labeled diagram of [Pd(5,5'-dmbipy)(tsser)] (3). Thermal ellipsoids are at 50%
probability level.
1
Figure 4 The H NMR spectra of compounds 1, 2 and 3 in DMSO-d
6
.
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Scheme 1. The preparation method of compounds 1-3.
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