Acta Cryst.(2003). E59, m291±m293 DOI: 10.1107/S1600536803008626 Akira Onodaet al. [PdCl(C33H31N3)]2[PdCl4]4CH2Cl2
m291
metal-organic papers
Acta Crystallographica Section E
Structure Reports Online
ISSN 1600-5368
A distorted square-planar Pd
IIcomplex
with a shortened PdÐCl bond induced
by the bulky terpyridyl ligand 6,6
000000-di-mesityl-2,2
000:6
000,2
000000-terpyridine
Akira Onoda, Keiko Kawakita, Taka-aki Okamura, Hitoshi Yamamoto and Norikazu Ueyama*
Department of Macromolecular Science, Graduate School of Science, Osaka University, Toyonaka, Osaka 560-0043, Japan
Correspondence e-mail: [email protected]
Key indicators
Single-crystal X-ray study T= 200 K
Mean(C±C) = 0.009 AÊ Disorder in solvent or counterion Rfactor = 0.053
wRfactor = 0.144
Data-to-parameter ratio = 17.6
For details of how these key indicators were automatically derived from the article, see http://journals.iucr.org/e.
#2003 International Union of Crystallography Printed in Great Britain ± all rights reserved
The title complex, chloro(6,600-dimesityl-2,20:60,200 -terpyri-dine)palladium(II) tetrachloropalladium(II) dichloromethane tetrasolvate, [PdIICl(dmtpy)]
2[PdIICl4]4CH2Cl2 (dmtpy is
6,600-dimesityl-2,20:60,200-terpyridine, C
33H31N3), was
synthe-sized and the crystal structure of the dichloromethane tetrasolvate has been determined. The complex has a distorted square-planar coordination formed by three N atoms and a chloride ion, the distortion caused by the extremely bulky substituted terpyridyl ligand.
Comment
Design of N-chelating ligands with various bulky substituents is an essential approach in developing N-chelating metal catalysts for polymerization. For example, Brookhart and co-workers have reported highly ef®cient Pd and Ni catalysts with
-diimino ligands for the polymerization of ethylene and
-ole®ns (Johnsonet al., 1995). It has also been reported that control of the bulkiness in pyridine bisimino ligands (3N coordination) contributes to polymerization by their Fe and Co complexes as catalysts (Smallet al., 1998; Britovseket al., 1998). We have synthesized a monochloropalladium complex with a bulky terpyridine ligand, namely 6,600 -dimesityl-2,20:60,200-terpyridine, and determined the effect of the steric hindrance of this ligand, perturbing the metal coordination geometry.
Fig. 1(a) shows the structure of the asymmetric unit of (I). The asymmetric unit consists of one [PdII(dmtpy)]+ cation,
one-half [PdIICl
4]2ÿand two dichloromethane molecules. Fig.
1(b) shows the cation part of the structure. The Pd complex, (I), has a distorted square-planar coordination formed by three N atoms and a chloride ion; the distortion is due to the extremely bulky terpyridyl ligand. The Pd1ÐN21 bond distance [1.953 (4) AÊ] to the central pyridine ring is shorter than those to the pyridine rings on either side [2.0913 (4) and 2.089 (4) AÊ]. The N21ÐPd1ÐCl1 atom lies 0.156 AÊ from the N11ÐN12ÐN31 plane. It has been reported that similar 3N coordination with terpyridine and a chloride gives an almost planar coordination geometry, with similar PdÐN bond distances and an almost linear NÐPdÐCl angle of 193.6
(Intilleet al., 1973). The bulkiness of the dimesityl groups in the 6,600-positions of the terpyridine ligand distorts the square-planar coordination towards a tetrahedral geometry, resulting in shortening of the PdÐCl bond length from 2.331 (1) to 2.286 (1) AÊ. Our ligand design of bulky derivatives of ter-pyridine ligands successfully induces a distortion in the Pd coordination geometry.
Experimental
A solution of Pd(PPh3)4(57.5 mg, 0.05 mmol), mesitylboronic acid
(935 mg, 5.7 mmol), 6,600-dibromo-2,20:60,200-terpyridine (740 mg, 1.9 mmol) and Na3PO4.12H2O (3 g, 7.9 mmol) in a mixture of DME
(18 ml) and H2O (3 ml) was re¯uxed for 20 h under an argon
atmo-sphere. The solution was cooled to room temperature, and the solvent evaporated under reduced pressure. The residue was extracted with benzene, washed with brine and dried over MgSO4. Solvents were
removed under reduced pressure to give a white precipitate, which was collected by ®ltration and washed with hexane. The precipitate was dried in vacuoand recrystallized from toluene to give micro-crystals. Yield 510 mg, 57%. (m.p. 553 K). Spectroscopic analysis:1H
NMR (CDCl3at 298 K): 2.11 (s, 12H), 2.35 (s, 6H), 6.98 (s, 4H), 7.26
(d, 2H), 7.83 (t, 1H), 7.92 (t, 2H), 8.50 (d, 2H), 8.59 (dd, 2H); analysis calculated for C33H31N3: C 84.40, H 6.65, N 8.95%; found: C 84.04, H
6.55, N 8.92%. A solution of dmtpy (15.0 mg, 0.032 mmol) in CH2Cl2
(1.5 ml) was added to a solution of trans-Pd(MeCN)2Cl2 (8.3 mg,
0.032 mmol) in CH2Cl2(1.0 ml) and stirred at room temperature for
20 h to give a yellow precipitate. The yellow powder was washed with pentane and dried in vacuo. The product was recrystallized from dichloromethane/hexane to give crystals suitable for X-ray analysis.
Spectroscopic analysis:1H NMR (CDCl
3at 298 K) 2.18 (s, 12H), 2.23
(s, 6H), 6.78 (s, 4H), 7.39 (2H,d), 8.31 (2H,t), 8.95 (2H,d), 9.00 (1H,
t), 9.21 (2H,d); analysis calculated for C69H68N6Pd3Cl12: C 48.01. H
3.97, N 4.87%; found: C 47.62, H 3.88, N 4.86%.
Crystal data
[PdCl(C33H31N3)]2[PdCl4]4CH2Cl2
Mr= 1810.82
Triclinic,P1 a= 10.6555 (7) AÊ b= 21.3398 (5) AÊ c= 8.5995 (1) AÊ
= 91.2124 (4)
= 100.468 (7)
= 83.566 (7)
V= 1910.75 (14) AÊ3
Z= 1
Dx= 1.574 Mg mÿ3
MoKradiation
Cell parameters from 12443 re¯ections
= 2.3±27.4
= 1.23 mmÿ1
T= 200 K Platelet, orange 0.150.150.05 mm Data collection
Rigaku R-AXIS-RAPID Imaging Plate diffractometer
!scans
Absorption correction: multi-scan (ABSCOR; Higashi, 1995) Tmin= 0.777,Tmax= 0.940
9543 measured re¯ections
8029 independent re¯ections 4933 re¯ections withI> 2(I) Rint= 0.037
max= 27.5
h=ÿ13!13 k=ÿ27!27 l=ÿ11!11 Re®nement
Re®nement onF2
R[F2> 2(F2)] = 0.053
wR(F2) = 0.144
S= 1.00 8029 re¯ections 455 parameters
H atoms treated by a mixture of independent and constrained re®nement
w= 1/[2(F
o2) + (0.078P)2]
whereP= (Fo2+ 2Fc2)/3
(/)max< 0.001
max= 0.53 e AÊÿ3
min=ÿ1.36 e AÊÿ3
Table 1
Selected geometric parameters (AÊ,).
Pd1ÐN21 1.953 (4)
Pd1ÐN31 2.089 (4) Pd1ÐN11Pd1ÐCl1 2.2859 (13)2.091 (4)
N21ÐPd1ÐN31 81.28 (18) N21ÐPd1ÐN11 80.39 (18) N31ÐPd1ÐN11 160.31 (17)
N21ÐPd1ÐCl1 161.42 (14) N31ÐPd1ÐCl1 98.89 (12) N11ÐPd1ÐCl1 100.78 (12)
Figure 2
Space-®lling drawing of the cation of (I). Key: red (Pd), green (Cl) and purple (N).
Figure 1
The H atoms were positioned geometrically and were treated as riding on their parent C atoms, with aromatic CÐH distances of 0.93 AÊ and methyl CÐH distances of 0.96 AÊ. Rotating group re®nement was used for the methyl groups. One dichloromethane molecule is disordered, with distinct positions with partial occu-pancies for Cl atoms. The occuoccu-pancies for the disordered group (Cl21/ Cl22 and Cl31/Cl32) are 0.6315:0.3685. These disordered atoms were re®ned with isotropic displacement parameters.
Data collection: MSC/AFC Diffractometer Control Software
(Molecular Structure Corporation, 1991); cell re®nement:MSC/AFC Diffractometer Control Software; data reduction:TEXSAN (Molec-ular Structure Corporation, 1999); program(s) used to solve structure:
SHELXS97 (Sheldrick, 1997); program(s) used to re®ne structure:
SHELXL97 (Sheldrick, 1997); molecular graphics:TEXSAN and
MERCURY(Brunoet al., 2002); software used to prepare material for publication:TEXSANandMERCURY.
Support of this work by JSPS Fellowships [for AO, grant 2306(1999±2002)] and a Grant-in-Aid for Scienti®c Research
on Priority Area (A) (No. 10146231) from the Ministry of Education, Science, Sports and Culture, Japan, is gratefully acknowledged.
References
Britovsek, G. J. P., Gibson, V. C., Kimberley, B. S., Maddox, P. J., McTavish, S. J., Solan, G. A., White, A. J. P. & Williams, D. J. (1998).Chem. Commun.pp. 849±850.
Bruno, I. J., Cole, J. C., Edgington, P. R., Kessler, M., Macrae, C. F., McCabe, P., Pearson, J. & Taylor, R. (2002).Acta Cryst. B58, 389±397.
Higashi. T. (1995).ABSCOR. Rigaku Corporation, Tokyo, Japan.
Intille, G. M., P¯uger, C. E. & Junior, W. A. B. (1973).Cryst. Struct. Commun.
2, 217±220.
Johnson, L. K., Killiam, C. M., Brookhart, J. (1995).J. Am. Chem. Soc.117, 6414±6415.
Molecular Structure Corpration (1991). MSC/AFC Diffractometer Control Software. MSC, 3200 Forest Drive, The Woodlands, TX 77381, USA. Molecular Structure Corpration (1999).TEXSAN.Version 1.10. MSC, 3200
Research Forest Drive, The Woodlands, TX 77381, USA.
Sheldrick, G. M. (1997). SHELXL97 and SHELXS97. University of GoÈttingen, Germany.
Small, B. L. M., Brookhart, J. & Bennett, A. M. (1998).J. Am. Chem. Soc.120, 4049±4050.
supporting information
Acta Cryst. (2003). E59, m291–m293 [doi:10.1107/S1600536803008626]
A distorted square-planar Pd
IIcomplex with a shortened Pd
—
Cl bond induced
by the bulky terpyridyl ligand 6,6
′′
-dimesityl-2,2
′
:6
′
,2
′′
-terpyridine
Akira Onoda, Keiko Kawakita, Taka-aki Okamura, Hitoshi Yamamoto and Norikazu Ueyama
S1. Comment
Design of N-chelating ligands with various bulky substituents is an essential approach in developing N-chelating metal
catalysis for polymerization. For example, Brookhart and co-workers have reported highly efficient Pd and Ni catalysts
with α-diimino ligands for the polymerization of ethylene and α-olefin (Johnson et al., 1995). It was also reported that
control of the bulkiness in pyridine bisimino ligands (3 N coordination) contributes to polymerization by their Fe and Co
catalysis (Small et al., 1998; Britovsek et al., 1998). We have synthesized a palladium monochloride complex with a
bulky terpyridine ligand, namely 6,6′′-dimesityl-2,2′:6′,2′′-terpyridine and determined the effect of the steric hindrance of
the ligands, which perturbs the metal coordination geometry.
Fig. 1(a) shows the molecular structure. The asymmetric unit consists of one cation of PdII(dmtpy), half of a PdIICl 4
anion and two dichloromethanes. Fig. 1(b) shows the cation part of the structure. Pd complex (I) has a distorted
square-planar coordination formed by three N atoms and a chloride ion because of the extremely bulky terpyridyl ligands. The
Pd1—N21 bond distance [1.953 (4) Å] with the central pyridine ring is shorter than those with the pyridine rings on
either side [2.0913 (4) and 2.089 (4) Å]. The N21—Pd1—Cl1 angle is 161.42 (14)° and the Pd1 ion sits 0.156 Å from the
N11—N12—N31 plane. It has been reported that similar 3 N with terpyridine and a chloride coordination gives an almost
planer coordination geometry, with similar Pd—N bond distances and a linear N—Pd—Cl angle of 193.6° (Intille et al.,
1973). The bulkiness of the dimesityl groups in the 6,6′′-positions the of terpyridine ligands distrupts the square-planar
coordination towards a tetrahedral geometry, that results in shortning of the Pd—Cl bond length from 2.331 (1) to
2.286 (1) Å. Our ligand design of bulky derivatization in terpyridine ligands successfully induces a distortion in Pd
coordination geometry.
S2. Experimental
A solution of Pd(PPh3)4 (57.5 mg, 0.05 mmol), mesitylboronic acid (935 mg, 5.7 mmol),
6,6′′-dibromo-2,2′:6′,2′′-terpyridine (740 mg, 1.9 mmol) and Na3PO4.12H2O (3 g, 7.9 mmol) in a mixture of DME (18 ml) and H2O (3 ml) were
refluxed for 20 h under an argon atmosphere. The solution was cooled to room temperature and the solvent evaporated
under reduced pressure. The residue was extracted with benzene, washed with brine and dried over MgSO4. Solvents
were removed under reduced pressure to give white precipitate, which was collected with filtration and washed with
hexane. The precipitate was dried in vacuo and recrystallized from toluene to give microcrystals. Yield 510 mg, 57%.
(m.p. 553 K). Spectroscopic analysis: 1H NMR (CDCl
3 at 298 K): 2.11 (s, 12H), 2.35 (s, 6H), 6.98 (s, 4H), 7.26 (d, 2H),
7.83 (t, 1H), 7.92 (t, 2H), 8.50 (d, 2H), 8.59 (dd, 2H); analysis calculated for C33H31N3: C 84.40, H 6.65, N 8.95%; found:
C 84.04, H 6.55, N 8.92%. A solution of dmtpy (15.0 mg, 0.032 mmol) in CH2Cl2 (1.5 ml) was added to a solution of
di-supporting information
sup-2
Acta Cryst. (2003). E59, m291–m293
chloromethane/hexane to give crystals suitable for X-ray analysis. Spectroscpic analysis: 1H NMR (CDCl
3 at 298 K) 2.18
(s, 12H), 2.23 (s, 6H), 6.78 (s, 4H), 7.39 (2H, d), 8.31 (2H, t), 8.95 (2H, d), 9.00 (1H, t), 9.21 (2H, d); analysis calculated
for C69H68N6Pd3Cl12: C 48.01. H 3.97, N 4.87%; found: C 47.62, H 3.88, N 4.86%.
S3. Refinement
Data collection and cell refinement: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1991);
[image:5.610.144.463.186.621.2]data reduction: TEXSAN (Molecular Structure Corporation, 1999)
Figure 1
(a) The molecular structure of (I), with 25% probability displacement ellipsoids. Neighboring atoms in the [PdIICl 4]2−
anion are shown for clarity. Atoms C2, Cl121 and Cl122 of the chloroform molecule are disordered and only one set is
shown for clarity. (b) The cation of (I), showing the labeling of non-H atoms and 25% probability displacement
Figure 2
Space-filling drawing of the cation of (I). Key: red (Pd), green (Cl) and purple (N).
(I)
Crystal data
[PdCl(C33H31N3)]2[PdCl4]·4CH2Cl2 Mr = 1810.82
Triclinic, P1 a = 10.6555 (7) Å b = 21.3398 (5) Å c = 8.5995 (1) Å α = 91.21° β = 100.468 (7)° γ = 83.566 (7)° V = 1910.75 (14) Å3
Z = 1 F(000) = 908 Dx = 1.574 Mg m−3
Mo Kα radiation, λ = 0.71069 Å Cell parameters from 12443 reflections θ = 2.3–27.4°
µ = 1.23 mm−1 T = 200 K Platelet, orange 0.15 × 0.15 × 0.05 mm
Data collection
Rigaku R-AXIS-RAPID Imaging Plate diffractometer
Radiation source: fine-focus sealed tube Graphite monochromator
Detector resolution: 10.00 pixels mm-1 ω scans
Absorption correction: multi-scan (ABSCOR; Higashi, 1995) Tmin = 0.777, Tmax = 0.940
9543 measured reflections 8029 independent reflections 4933 reflections with I > 2σ(I) Rint = 0.037
θmax = 27.5°, θmin = 2.1° h = −13→13
supporting information
sup-4
Acta Cryst. (2003). E59, m291–m293 Refinement
Refinement on F2 Least-squares matrix: full R[F2 > 2σ(F2)] = 0.053 wR(F2) = 0.144 S = 1.00 8029 reflections 455 parameters 2 restraints
Primary atom site location: structure-invariant direct methods
Secondary atom site location: difference Fourier map
Hydrogen site location: inferred from neighbouring sites
H atoms treated by a mixture of independent and constrained refinement
w = 1/[σ2(Fo2) + (0.078P)2] where P = (Fo2 + 2Fc2)/3 (Δ/σ)max < 0.001
Δρmax = 0.53 e Å−3 Δρmin = −1.36 e Å−3
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 Occ. (<1)
Pd1 0.36247 (4) 0.190898 (18) 0.51368 (5) 0.04205 (13)
Pd2 1.0000 0.0000 1.0000 0.04568 (16)
Cl1 0.34252 (12) 0.29833 (6) 0.49358 (19) 0.0549 (4)
Cl2 0.92476 (15) −0.03122 (8) 0.7432 (2) 0.0689 (4)
Cl3 0.80997 (13) 0.06468 (7) 0.99641 (19) 0.0596 (4)
Cl11 0.6628 (3) 0.21062 (11) 0.8485 (3) 0.1074 (7)
Cl12 0.7226 (3) 0.33957 (16) 0.8612 (4) 0.1533 (12)
Cl21 0.7376 (14) 0.4774 (5) 0.6671 (13) 0.219 (6) 0.632 (11)
Cl22 0.6860 (13) 0.5227 (3) 0.3693 (8) 0.200 (5) 0.632 (11)
Cl31 0.7697 (14) 0.4826 (7) 0.616 (3) 0.243 (13) 0.368 (11)
Cl32 0.5549 (11) 0.5472 (4) 0.3748 (13) 0.138 (5) 0.368 (11)
N11 0.5380 (4) 0.1671 (2) 0.4393 (5) 0.0459 (10)
N21 0.4055 (4) 0.1057 (2) 0.6002 (6) 0.0496 (11)
N31 0.1908 (4) 0.1810 (2) 0.5907 (5) 0.0474 (11)
C1 0.6037 (7) 0.2902 (4) 0.8339 (10) 0.083 (2)
H32 0.5497 0.2982 0.7283 0.100*
H33 0.5483 0.3001 0.9140 0.100*
C2 0.6980 (19) 0.5429 (11) 0.5590 (16) 0.109 (8) 0.632 (11)
H34 0.6151 0.5644 0.5787 0.205* 0.632 (11)
H35 0.7645 0.5721 0.5878 0.205* 0.632 (11)
C3 0.672 (4) 0.547 (2) 0.538 (5) 0.18 (3) 0.368 (11)
H36 0.6286 0.5649 0.6243 0.117* 0.368 (11)
H37 0.7290 0.5779 0.5171 0.205* 0.368 (11)
C13 0.7223 (5) 0.0877 (3) 0.4840 (7) 0.0575 (15)
H1 0.7659 0.0511 0.5388 0.069*
C14 0.7791 (5) 0.1177 (3) 0.3773 (7) 0.0591 (15)
H2 0.8617 0.1020 0.3574 0.070*
C15 0.7125 (5) 0.1712 (3) 0.3008 (7) 0.0554 (14)
H3 0.7492 0.1917 0.2258 0.068*
C16 0.5927 (5) 0.1954 (3) 0.3319 (6) 0.0475 (12)
C22 0.5287 (5) 0.0793 (2) 0.6075 (6) 0.0464 (13)
C23 0.5722 (6) 0.0257 (3) 0.7002 (7) 0.0583 (15)
H4 0.6577 0.0063 0.7071 0.069*
C24 0.4872 (7) 0.0012 (3) 0.7826 (7) 0.0609 (16)
H5 0.5145 −0.0364 0.8425 0.069*
C25 0.3629 (6) 0.0308 (3) 0.7789 (7) 0.0634 (17)
H6 0.3060 0.0142 0.8364 0.076*
C26 0.3246 (5) 0.0855 (3) 0.6880 (7) 0.0513 (14)
C32 0.2001 (5) 0.1259 (3) 0.6762 (7) 0.0546 (14)
C33 0.1026 (6) 0.1100 (3) 0.7469 (7) 0.0602 (16)
H7 0.1122 0.0716 0.8042 0.073*
C34 −0.0102 (6) 0.1503 (4) 0.7342 (8) 0.075 (2)
H8 −0.0769 0.1415 0.7874 0.089*
C35 −0.0229 (6) 0.2033 (3) 0.6428 (8) 0.0659 (17)
H9 −0.1013 0.2303 0.6283 0.080*
C36 0.0779 (5) 0.2186 (3) 0.5698 (7) 0.0492 (13)
C41 0.5212 (5) 0.2521 (3) 0.2444 (7) 0.0467 (12)
C42 0.5641 (5) 0.3116 (3) 0.2751 (7) 0.0548 (14)
C43 0.4941 (7) 0.3631 (3) 0.1927 (8) 0.0691 (18)
H10 0.5232 0.4035 0.2120 0.083*
C44 0.3830 (7) 0.3576 (4) 0.0830 (9) 0.078 (2)
C45 0.3455 (7) 0.2974 (3) 0.0517 (8) 0.0734 (19)
H11 0.2706 0.2927 −0.0246 0.089*
C46 0.4126 (5) 0.2447 (3) 0.1268 (7) 0.0546 (14)
C47 0.6824 (6) 0.3210 (3) 0.3985 (9) 0.0724 (19)
H12 0.6764 0.3007 0.4976 0.088*
H13 0.6873 0.3663 0.4169 0.088*
H14 0.7595 0.3023 0.3606 0.088*
C48 0.3053 (11) 0.4160 (4) −0.0022 (12) 0.130 (4)
H15 0.2208 0.4227 0.0290 0.150*
H16 0.2945 0.4095 −0.1168 0.150*
H17 0.3512 0.4531 0.0269 0.150*
C49 0.3739 (7) 0.1795 (3) 0.0795 (8) 0.0741 (19)
H18 0.3511 0.1594 0.1704 0.090*
H19 0.4458 0.1537 0.0449 0.090*
H20 0.2998 0.1834 −0.0072 0.090*
C51 0.0520 (5) 0.2740 (3) 0.4578 (6) 0.0486 (13)
C52 0.0319 (5) 0.3350 (3) 0.5200 (7) 0.0535 (14)
C53 −0.0018 (6) 0.3860 (3) 0.4141 (8) 0.0628 (16)
H21 −0.0159 0.4275 0.4539 0.073*
supporting information
sup-6
Acta Cryst. (2003). E59, m291–m293
C55 0.0046 (6) 0.3160 (3) 0.1944 (8) 0.0622 (16)
H22 −0.0043 0.3093 0.0836 0.077*
C56 0.0374 (5) 0.2646 (3) 0.2964 (7) 0.0535 (14)
C57 0.0494 (8) 0.3475 (4) 0.6958 (8) 0.083 (2)
H23 0.1353 0.3294 0.7468 0.097*
H24 −0.0155 0.3281 0.7399 0.097*
H25 0.0399 0.3931 0.7147 0.097*
C58 −0.0559 (9) 0.4319 (4) 0.1361 (11) 0.107 (3)
H26 −0.1296 0.4580 0.1660 0.130*
H27 −0.0800 0.4159 0.0284 0.130*
H28 0.0156 0.4574 0.1404 0.130*
C59 0.0539 (6) 0.1991 (3) 0.2235 (8) 0.0697 (18)
H29 −0.0049 0.1980 0.1218 0.085*
H30 0.0347 0.1678 0.2949 0.085*
H31 0.1426 0.1894 0.2068 0.085*
Atomic displacement parameters (Å2)
U11 U22 U33 U12 U13 U23
Pd1 0.0328 (2) 0.0427 (2) 0.0498 (2) −0.00475 (15) 0.00403 (16) 0.00628 (18)
Pd2 0.0391 (3) 0.0428 (3) 0.0560 (4) 0.0018 (2) 0.0132 (3) 0.0115 (3)
Cl1 0.0418 (7) 0.0444 (7) 0.0806 (10) −0.0025 (5) 0.0168 (7) 0.0079 (7)
Cl2 0.0596 (9) 0.0706 (10) 0.0667 (10) 0.0169 (7) 0.0007 (7) −0.0032 (8)
Cl3 0.0456 (7) 0.0628 (9) 0.0684 (9) 0.0104 (6) 0.0143 (7) 0.0052 (8)
Cl11 0.1268 (19) 0.0978 (15) 0.0898 (15) 0.0162 (13) 0.0173 (13) −0.0090 (12)
Cl12 0.132 (2) 0.152 (3) 0.178 (3) −0.066 (2) 0.001 (2) 0.004 (2)
Cl21 0.410 (18) 0.079 (4) 0.161 (6) −0.005 (7) 0.048 (8) 0.009 (4)
Cl22 0.333 (15) 0.156 (5) 0.143 (5) −0.057 (7) 0.114 (7) −0.010 (4)
Cl31 0.119 (8) 0.068 (6) 0.54 (4) 0.022 (5) 0.074 (14) 0.034 (12)
Cl32 0.142 (9) 0.112 (6) 0.168 (8) −0.044 (6) 0.033 (6) −0.001 (5)
N11 0.039 (2) 0.047 (2) 0.049 (3) −0.0032 (18) 0.0013 (19) −0.004 (2)
N21 0.042 (2) 0.048 (2) 0.056 (3) −0.0093 (19) −0.002 (2) 0.003 (2)
N31 0.041 (2) 0.046 (2) 0.054 (3) −0.0105 (19) 0.001 (2) 0.009 (2)
C1 0.071 (5) 0.090 (5) 0.084 (5) 0.003 (4) 0.010 (4) 0.009 (4)
C2 0.086 (10) 0.077 (13) 0.18 (2) −0.026 (9) 0.043 (11) 0.014 (13)
C3 0.22 (5) 0.11 (3) 0.15 (4) 0.11 (3) −0.05 (3) −0.03 (3)
C12 0.037 (3) 0.046 (3) 0.054 (3) −0.001 (2) −0.003 (2) −0.001 (3)
C13 0.049 (3) 0.053 (3) 0.063 (4) 0.008 (3) −0.002 (3) −0.008 (3)
C14 0.040 (3) 0.072 (4) 0.062 (4) 0.006 (3) 0.009 (3) −0.009 (3)
C15 0.047 (3) 0.067 (4) 0.053 (3) −0.004 (3) 0.012 (3) −0.002 (3)
C16 0.034 (3) 0.057 (3) 0.049 (3) −0.004 (2) 0.005 (2) 0.003 (3)
C22 0.050 (3) 0.040 (3) 0.044 (3) −0.001 (2) −0.003 (2) −0.010 (2)
C23 0.072 (4) 0.044 (3) 0.050 (3) 0.002 (3) −0.006 (3) −0.001 (3)
C24 0.080 (4) 0.044 (3) 0.053 (4) −0.007 (3) −0.003 (3) 0.002 (3)
C25 0.074 (4) 0.060 (4) 0.055 (4) −0.025 (3) −0.003 (3) 0.010 (3)
C26 0.053 (3) 0.046 (3) 0.053 (3) −0.016 (2) 0.000 (3) −0.004 (3)
C32 0.049 (3) 0.064 (4) 0.050 (3) −0.020 (3) −0.004 (3) 0.014 (3)
C34 0.050 (4) 0.106 (5) 0.074 (5) −0.022 (4) 0.011 (3) 0.026 (4)
C35 0.038 (3) 0.085 (5) 0.076 (4) −0.011 (3) 0.007 (3) 0.016 (4)
C36 0.032 (3) 0.060 (3) 0.056 (3) −0.009 (2) 0.007 (2) 0.009 (3)
C41 0.040 (3) 0.050 (3) 0.052 (3) −0.005 (2) 0.014 (2) 0.003 (3)
C42 0.041 (3) 0.062 (4) 0.063 (4) −0.005 (3) 0.015 (3) 0.010 (3)
C43 0.071 (4) 0.055 (4) 0.084 (5) −0.010 (3) 0.018 (4) 0.010 (3)
C44 0.077 (5) 0.074 (5) 0.076 (5) 0.012 (4) 0.007 (4) 0.017 (4)
C45 0.061 (4) 0.084 (5) 0.066 (4) −0.001 (4) −0.008 (3) 0.008 (4)
C46 0.044 (3) 0.064 (4) 0.055 (3) −0.005 (3) 0.006 (3) 0.005 (3)
C47 0.050 (4) 0.074 (4) 0.094 (5) −0.018 (3) 0.011 (3) −0.010 (4)
C48 0.149 (9) 0.086 (6) 0.128 (8) 0.022 (6) −0.031 (7) 0.029 (6)
C49 0.063 (4) 0.093 (5) 0.060 (4) −0.016 (4) −0.011 (3) −0.008 (4)
C51 0.031 (3) 0.064 (3) 0.049 (3) −0.005 (2) 0.003 (2) 0.012 (3)
C52 0.037 (3) 0.063 (4) 0.058 (3) −0.001 (2) 0.005 (2) −0.003 (3)
C53 0.057 (4) 0.045 (3) 0.083 (5) −0.002 (3) 0.006 (3) −0.003 (3)
C54 0.053 (4) 0.081 (5) 0.074 (5) −0.003 (3) 0.008 (3) 0.029 (4)
C55 0.062 (4) 0.068 (4) 0.055 (4) 0.001 (3) 0.012 (3) 0.006 (3)
C56 0.037 (3) 0.062 (4) 0.061 (4) −0.003 (2) 0.008 (3) 0.007 (3)
C57 0.081 (5) 0.091 (5) 0.072 (5) −0.006 (4) 0.007 (4) −0.014 (4)
C58 0.109 (7) 0.092 (6) 0.111 (7) 0.002 (5) 0.000 (5) 0.046 (5)
C59 0.061 (4) 0.074 (4) 0.069 (4) 0.001 (3) 0.004 (3) 0.005 (4)
Geometric parameters (Å, º)
Pd1—N21 1.953 (4) C33—C34 1.386 (9)
Pd1—N31 2.089 (4) C33—H7 0.9500
Pd1—N11 2.091 (4) C34—C35 1.371 (9)
Pd1—Cl1 2.2859 (13) C34—H8 0.9500
Pd2—Cl3 2.3149 (13) C35—C36 1.409 (8)
Pd2—Cl3i 2.3149 (13) C35—H9 0.9500
Pd2—Cl2i 2.3190 (16) C36—C51 1.511 (7)
Pd2—Cl2 2.3190 (16) C41—C42 1.401 (8)
Cl11—C1 1.743 (8) C41—C46 1.413 (8)
Cl12—C1 1.718 (8) C42—C43 1.387 (8)
Cl21—Cl31 0.62 (3) C42—C47 1.522 (8)
Cl21—C2 1.665 (16) C43—C44 1.388 (10)
Cl22—Cl32 1.445 (11) C43—H10 0.9500
Cl22—C2 1.665 (17) C44—C45 1.394 (10)
Cl22—Cl31 2.29 (3) C44—C48 1.537 (10)
Cl31—C3 1.70 (3) C45—C46 1.368 (8)
Cl32—C3 1.70 (3) C45—H11 0.9500
N11—C16 1.362 (7) C46—C49 1.523 (9)
N11—C12 1.389 (6) C47—H12 0.9800
N21—C26 1.355 (7) C47—H13 0.9800
N21—C22 1.360 (7) C47—H14 0.9800
N31—C36 1.354 (7) C48—H15 0.9800
N31—C32 1.385 (7) C48—H16 0.9800
supporting information
sup-8
Acta Cryst. (2003). E59, m291–m293
C1—H33 0.9900 C49—H18 0.9800
C2—H34 0.9900 C49—H19 0.9800
C2—H35 0.9900 C49—H20 0.9800
C3—H36 0.9900 C51—C56 1.381 (8)
C3—H37 0.9900 C51—C52 1.405 (8)
C12—C13 1.380 (8) C52—C53 1.405 (8)
C12—C22 1.477 (8) C52—C57 1.512 (9)
C13—C14 1.390 (9) C53—C54 1.397 (10)
C13—H1 0.9500 C53—H21 0.9500
C14—C15 1.386 (8) C54—C55 1.372 (9)
C14—H2 0.9500 C54—C58 1.536 (9)
C15—C16 1.392 (7) C55—C56 1.393 (8)
C15—H3 0.9500 C55—H22 0.9500
C16—C41 1.494 (7) C56—C59 1.525 (8)
C22—C23 1.394 (7) C57—H23 0.9800
C23—C24 1.397 (9) C57—H24 0.9800
C23—H4 0.9500 C57—H25 0.9800
C24—C25 1.397 (9) C58—H26 0.9800
C24—H5 0.9500 C58—H27 0.9800
C25—C26 1.399 (8) C58—H28 0.9800
C25—H6 0.9500 C59—H29 0.9800
C26—C32 1.487 (8) C59—H30 0.9800
C32—C33 1.372 (8) C59—H31 0.9800
N21—Pd1—N31 81.28 (18) C34—C35—C36 121.4 (6)
N21—Pd1—N11 80.39 (18) C34—C35—H9 119.3
N31—Pd1—N11 160.31 (17) C36—C35—H9 119.3
N21—Pd1—Cl1 161.42 (14) N31—C36—C35 120.1 (5)
N31—Pd1—Cl1 98.89 (12) N31—C36—C51 121.5 (5)
N11—Pd1—Cl1 100.78 (12) C35—C36—C51 118.2 (5)
Cl3—Pd2—Cl3i 180.0 C42—C41—C46 120.3 (5)
Cl3—Pd2—Cl2i 90.50 (5) C42—C41—C16 120.2 (5)
Cl3i—Pd2—Cl2i 89.50 (5) C46—C41—C16 119.4 (5)
Cl3—Pd2—Cl2 89.51 (5) C43—C42—C41 118.4 (6)
Cl3i—Pd2—Cl2 90.50 (5) C43—C42—C47 119.7 (6)
Cl2i—Pd2—Cl2 180.0 C41—C42—C47 121.8 (5)
C16—N11—C12 117.9 (4) C42—C43—C44 122.2 (6)
C16—N11—Pd1 130.5 (3) C42—C43—H10 118.9
C12—N11—Pd1 111.6 (4) C44—C43—H10 118.9
C26—N21—C22 123.3 (5) C43—C44—C45 117.7 (6)
C26—N21—Pd1 116.8 (4) C43—C44—C48 120.8 (7)
C22—N21—Pd1 117.0 (4) C45—C44—C48 121.4 (7)
C36—N31—C32 118.0 (5) C46—C45—C44 122.5 (6)
C36—N31—Pd1 130.9 (4) C46—C45—H11 118.8
C32—N31—Pd1 111.2 (4) C44—C45—H11 118.8
Cl12—C1—Cl11 113.2 (4) C45—C46—C41 118.6 (6)
Cl12—C1—H32 108.9 C45—C46—C49 120.5 (6)
Cl12—C1—H33 108.9 C42—C47—H12 109.5
Cl11—C1—H33 108.9 C42—C47—H13 109.5
H32—C1—H33 107.8 H12—C47—H13 109.5
Cl22—C2—Cl21 108.1 (15) C42—C47—H14 109.5
Cl22—C2—H34 110.1 H12—C47—H14 109.5
Cl21—C2—H34 110.1 H13—C47—H14 109.5
Cl22—C2—H35 110.1 C44—C48—H15 109.5
Cl21—C2—H35 110.1 C44—C48—H16 109.5
H34—C2—H35 108.4 H15—C48—H16 109.5
Cl32—C3—Cl31 126 (3) C44—C48—H17 109.5
Cl32—C3—H36 105.9 H15—C48—H17 109.5
Cl31—C3—H36 105.9 H16—C48—H17 109.5
Cl32—C3—H37 105.9 C46—C49—H18 109.5
Cl31—C3—H37 105.9 C46—C49—H19 109.5
H36—C3—H37 106.2 H18—C49—H19 109.5
C13—C12—N11 122.3 (5) C46—C49—H20 109.5
C13—C12—C22 123.0 (5) H18—C49—H20 109.5
N11—C12—C22 114.7 (4) H19—C49—H20 109.5
C12—C13—C14 119.3 (5) C56—C51—C52 120.6 (5)
C12—C13—H1 120.4 C56—C51—C36 120.5 (5)
C14—C13—H1 120.4 C52—C51—C36 118.6 (5)
C15—C14—C13 118.4 (5) C51—C52—C53 118.4 (5)
C15—C14—H2 120.8 C51—C52—C57 122.2 (6)
C13—C14—H2 120.8 C53—C52—C57 119.4 (6)
C14—C15—C16 121.2 (6) C54—C53—C52 120.8 (6)
C14—C15—H3 119.4 C54—C53—H21 119.6
C16—C15—H3 119.4 C52—C53—H21 119.6
N11—C16—C15 120.7 (5) C55—C54—C53 119.3 (6)
N11—C16—C41 119.2 (4) C55—C54—C58 120.2 (7)
C15—C16—C41 120.0 (5) C53—C54—C58 120.4 (7)
N21—C22—C23 119.1 (6) C54—C55—C56 121.2 (6)
N21—C22—C12 113.9 (5) C54—C55—H22 119.4
C23—C22—C12 127.0 (5) C56—C55—H22 119.4
C22—C23—C24 118.5 (6) C51—C56—C55 119.7 (6)
C22—C23—H4 120.7 C51—C56—C59 122.4 (5)
C24—C23—H4 120.7 C55—C56—C59 117.8 (6)
C25—C24—C23 121.4 (6) C52—C57—H23 109.5
C25—C24—H5 119.3 C52—C57—H24 109.5
C23—C24—H5 119.3 H23—C57—H24 109.5
C24—C25—C26 118.1 (6) C52—C57—H25 109.5
C24—C25—H6 120.9 H23—C57—H25 109.5
C26—C25—H6 120.9 H24—C57—H25 109.5
N21—C26—C25 119.3 (6) C54—C58—H26 109.5
N21—C26—C32 114.2 (5) C54—C58—H27 109.5
C25—C26—C32 126.4 (6) H26—C58—H27 109.5
C33—C32—N31 122.6 (6) C54—C58—H28 109.5
C33—C32—C26 122.3 (5) H26—C58—H28 109.5
supporting information
sup-10
Acta Cryst. (2003). E59, m291–m293
C32—C33—C34 119.5 (6) C56—C59—H29 109.5
C32—C33—H7 120.3 C56—C59—H30 109.5
C34—C33—H7 120.3 H29—C59—H30 109.5
C35—C34—C33 118.3 (6) C56—C59—H31 109.5
C35—C34—H8 120.9 H29—C59—H31 109.5
C33—C34—H8 120.9 H30—C59—H31 109.5
C2—Cl21—Cl31—C3 −7 (2) Pd1—N21—C26—C32 12.7 (6)
C2—Cl21—Cl31—Cl22 −41.0 (16) C24—C25—C26—N21 3.9 (8)
Cl32—Cl22—Cl31—Cl21 14 (4) C24—C25—C26—C32 −176.0 (5)
C2—Cl22—Cl31—Cl21 64 (3) C36—N31—C32—C33 −3.7 (8)
Cl32—Cl22—Cl31—C3 −40 (3) Pd1—N31—C32—C33 176.5 (5)
C2—Cl22—Cl31—C3 9 (3) C36—N31—C32—C26 177.2 (5)
C2—Cl22—Cl32—C3 1 (3) Pd1—N31—C32—C26 −2.6 (6)
Cl31—Cl22—Cl32—C3 31 (2) N21—C26—C32—C33 174.7 (5)
N21—Pd1—N11—C16 166.3 (5) C25—C26—C32—C33 −5.4 (9)
N31—Pd1—N11—C16 144.6 (5) N21—C26—C32—N31 −6.2 (7)
Cl1—Pd1—N11—C16 −32.5 (5) C25—C26—C32—N31 173.7 (5)
N21—Pd1—N11—C12 −10.3 (3) N31—C32—C33—C34 −0.4 (10)
N31—Pd1—N11—C12 −32.0 (7) C26—C32—C33—C34 178.7 (6)
Cl1—Pd1—N11—C12 150.8 (3) C32—C33—C34—C35 3.8 (10)
N31—Pd1—N21—C26 −11.1 (4) C33—C34—C35—C36 −3.3 (10)
N11—Pd1—N21—C26 176.1 (4) C32—N31—C36—C35 4.1 (8)
Cl1—Pd1—N21—C26 80.8 (6) Pd1—N31—C36—C35 −176.1 (4)
N31—Pd1—N21—C22 −172.5 (4) C32—N31—C36—C51 −170.4 (5)
N11—Pd1—N21—C22 14.7 (4) Pd1—N31—C36—C51 9.4 (8)
Cl1—Pd1—N21—C22 −80.5 (6) C34—C35—C36—N31 −0.8 (10)
N21—Pd1—N31—C36 −172.6 (5) C34—C35—C36—C51 173.9 (6)
N11—Pd1—N31—C36 −151.0 (5) N11—C16—C41—C42 110.5 (6)
Cl1—Pd1—N31—C36 26.2 (5) C15—C16—C41—C42 −71.0 (7)
N21—Pd1—N31—C32 7.1 (4) N11—C16—C41—C46 −71.6 (7)
N11—Pd1—N31—C32 28.7 (7) C15—C16—C41—C46 106.9 (6)
Cl1—Pd1—N31—C32 −154.1 (3) C46—C41—C42—C43 2.9 (9)
Cl32—Cl22—C2—Cl21 115.1 (11) C16—C41—C42—C43 −179.2 (5)
Cl31—Cl22—C2—Cl21 −16.7 (11) C46—C41—C42—C47 −178.8 (5)
Cl31—Cl21—C2—Cl22 51 (4) C16—C41—C42—C47 −0.8 (9)
Cl22—Cl32—C3—Cl31 −55 (3) C41—C42—C43—C44 0.7 (10)
Cl21—Cl31—C3—Cl32 −97 (5) C47—C42—C43—C44 −177.6 (7)
Cl22—Cl31—C3—Cl32 41 (2) C42—C43—C44—C45 −2.8 (11)
C16—N11—C12—C13 5.7 (8) C42—C43—C44—C48 178.0 (8)
Pd1—N11—C12—C13 −177.2 (4) C43—C44—C45—C46 1.2 (11)
C16—N11—C12—C22 −172.1 (4) C48—C44—C45—C46 −179.6 (8)
Pd1—N11—C12—C22 5.0 (5) C44—C45—C46—C41 2.3 (10)
N11—C12—C13—C14 −4.1 (8) C44—C45—C46—C49 −175.2 (7)
C22—C12—C13—C14 173.5 (5) C42—C41—C46—C45 −4.4 (9)
C12—C13—C14—C15 0.4 (9) C16—C41—C46—C45 177.7 (6)
C13—C14—C15—C16 1.4 (9) C42—C41—C46—C49 173.1 (6)
Pd1—N11—C16—C15 179.8 (4) N31—C36—C51—C56 68.9 (7)
C12—N11—C16—C41 174.8 (5) C35—C36—C51—C56 −105.7 (7)
Pd1—N11—C16—C41 −1.7 (7) N31—C36—C51—C52 −116.6 (6)
C14—C15—C16—N11 0.3 (9) C35—C36—C51—C52 68.8 (7)
C14—C15—C16—C41 −178.2 (5) C56—C51—C52—C53 −0.7 (8)
C26—N21—C22—C23 5.1 (7) C36—C51—C52—C53 −175.2 (5)
Pd1—N21—C22—C23 165.2 (4) C56—C51—C52—C57 −178.8 (6)
C26—N21—C22—C12 −176.1 (5) C36—C51—C52—C57 6.7 (8)
Pd1—N21—C22—C12 −16.1 (6) C51—C52—C53—C54 −0.1 (9)
C13—C12—C22—N21 −171.3 (5) C57—C52—C53—C54 178.1 (6)
N11—C12—C22—N21 6.5 (6) C52—C53—C54—C55 0.5 (10)
C13—C12—C22—C23 7.3 (9) C52—C53—C54—C58 178.1 (6)
N11—C12—C22—C23 −174.9 (5) C53—C54—C55—C56 −0.1 (10)
N21—C22—C23—C24 −0.1 (8) C58—C54—C55—C56 −177.7 (6)
C12—C22—C23—C24 −178.7 (5) C52—C51—C56—C55 1.1 (8)
C22—C23—C24—C25 −2.7 (8) C36—C51—C56—C55 175.5 (5)
C23—C24—C25—C26 0.9 (9) C52—C51—C56—C59 −178.0 (5)
C22—N21—C26—C25 −7.1 (8) C36—C51—C56—C59 −3.6 (8)
Pd1—N21—C26—C25 −167.2 (4) C54—C55—C56—C51 −0.7 (9)
C22—N21—C26—C32 172.9 (5) C54—C55—C56—C59 178.4 (6)
