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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 PdII 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.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270112045970/sk3458sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270112045970/sk3458Isup2.hkl
Contains datablock I

CCDC reference: 915095

Comment top

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 cyclopropanation, and Heck–Suzuki coupling reactions (Segapelo et al., 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 investigations, with a view to developing less toxic and more selective anticancer drugs. For example, chelating N,N'-bidentate ligands have been viewed as important in preventing trans-labilization and the undesired displacement of the 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 synthesized and crystallized the title compound, namely dichlorido{2-[(2,6-diethylphenyl)iminomethyl]quinoline-N,N'}palladium(II) acetonitrile monosolvate, (I).

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., 2002). It is reasonable to suggest that the cytotoxicity of this 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 view of the molecular structure of (I) is shown in Fig. 1. The PdII atom in (I) is coordinated through the two N atoms of the ligand and two chloride anions, generating a distorted square-planar coordination geometry around the PdII metal centre. The bond angles around Pd1 (Table 1) show significant deviations from 90°, which confirms the distortion of the square-planar geometry. These bond angles are close to those of a similar compound (Motswainyana et al., 2012). The Pd1—Cl bond lengths are in good agreement with the average Pd—Cl bond length of 2.298 (15) Å 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 (Doherty et al., 2002). Atom Cl1 has a short intramolecular contact with H4 (Cl1···H4 = 2.50 Å) and as a result Cl1 deviates more [-1.284 (1) Å] from the best least-squares plane through the quinoline ring than Cl2 [-0.266 Å]. The angle between the quinoline least-squares plane and the plane through atoms C9, C10 and N2 is 9.37 (10)°. This is at the higher end of the range observed in the Cambridge Structural Database (CSD, Version?; Allen, 2002) for 2-iminopyridyl groups involved in dichloridopalladium complexes (0.31–9.65°, 24 hits). The overall r.m.s. deviations are 0.005 and 0.044 Å, 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 [74.5 (3)°] and C11–C16–C19–C20 [80.4 (3)°] torsion angles.

In the crystal packing of (I), ππ interactions between quinoline rings link pairs of molecules into centrosymmetric dimers (Fig. 2), with a Cg1···Cg2i distance of 3.681 (2) Å and a Cg2···Cg2i distance of 3.932 (2) Å [Cg1 and Cg2 are the centroids of the N1/C5–C9 and C1–C6 rings, respectively; symmetry code: (i) -x + 1, -y + 1, -z + 1]. Furthermore, the packing shows a number of weaker contacts of the C—H···π type (C3—H3···Cg3ii = 2.80 Å and C22—H22B···Cg3iii = 2.86 Å; Cg3 is the centroid of the C11–C16 ring; symmetry codes: (ii) -x + 3/2, y - 1/2, -z + 3/2; (iii) x - 1/2, -y + 3/2, z + 1/2].

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. When further analysing the crystal packing, the importance of the presence of acetonitrile becomes clear. Without acetonitrile the unit cell would show four voids of 97 Å3 each, which are now filled by one acetontrile molecule having a molar volume of about 42 Å3. In the packing, the position of this acetonitrile is fixed by two π-interactions: a C22—H22B···π interaction (see above) and a C21N3···Cg2 interaction [N3···Cg2 = 3.793 (3) Å] (Fig. 3). Furthermore, atom N3 interacts with atoms H1 and H3 of a neighbouring molecule [N3···H1iv = 2.66 Å and N3···H3iv = 2.69 Å; symmetry code: (iv) -x, -y + 1, -z + 1]. This bifurcated interaction of the acetonitrile N atom has been observed before in crystal structures (13 hits in the CSD, with N···H contact distances ranging between 2.436 and 2.744 Å). The acetonitrile methyl group interacts with both Cl atoms [H22C···Cl2v = 2.89 Å and H22A···Cl1 = 3.24 Å; symmetry code: (v) x - 1, y, z].

Related literature top

For related literature, see: Allen (2002); Bianchini et al. (2010); Chen et al. (2007); Doherty et al. (2002); Fuertes et al. (2003); Hotze et al. (2002); Ittel et al. (2000); Jung & Lippard (2007); Motswainyana et al. (2011, 2012); Ojwach et al. (2007); Segapelo et al. (2009); Wong & Giandomenico (1999).

Experimental top

All reactions were carried out under an N2 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.

For the preparation of 2-[(2,6-diethylphenyl)iminomethyl]quinoline, 2,6-diethylaniline (0.2972 g, 1.99 mmol) was added dropwise to a solution of quinoline-2-carbaldehyde (0.3130 g, 1.99 mmol) in CH2Cl2 (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 extracted with CH2Cl2 (2 × 10 ml) and dried over anhydrous magnesium sulfate. A red–brown oil was obtained upon evaporation of the solvent (yield 0.5509 g, 96%). Spectroscopic analysis: IR (Nujol, ν, cm-1): 1641 (CN imine), 1596 (CN quinolyl), 1563 (CC quinolyl), 1504 (CC phenyl). Analysis calculated for C20H20N2: C 83.30, H 6.99, N 9.71%; found: C 83.54, H 6.78, N 9.99%.

For the preparation of complex, (I), a solution of dichlorido(cycloocta-1,5-diene)palladium(II), [PdCl2(cod)] (0.0650 g, 0.228 mmol), in CH2Cl2 (5 ml) was added dropwise to a solution of 2-[(2,6-diethylphenyl)iminomethyl]quinoline (0.0640 g, 0.222 mmol) in dry CH2Cl2 (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 Et2O (2 × 10 ml) to obtain a pure yellow solid. Crystals of (I) suitable for X-ray crystallography were grown by slow evaporation from an acetonitrile solution of the complex (yield 0.0848 g, 82%). Spectroscopic analysis: IR (Nujol, ν, cm-1): 1602 (CN imine), 1584 (CN quinolyl), 1563 (CC quinolyl), 1506 (CC phenyl). Analysis calculated for C20H20Cl2N2Pd: C 51.58, H 4.33, N 6.02%; found: C 51.89, H 4.18, N 5.83%.

Refinement top

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 Å (methylene), and with Uiso(H) = 1.2Ueq(C)

Structure description top

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 cyclopropanation, and Heck–Suzuki coupling reactions (Segapelo et al., 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 investigations, with a view to developing less toxic and more selective anticancer drugs. For example, chelating N,N'-bidentate ligands have been viewed as important in preventing trans-labilization and the undesired displacement of the 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 synthesized and crystallized the title compound, namely dichlorido{2-[(2,6-diethylphenyl)iminomethyl]quinoline-N,N'}palladium(II) acetonitrile monosolvate, (I).

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., 2002). It is reasonable to suggest that the cytotoxicity of this 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 view of the molecular structure of (I) is shown in Fig. 1. The PdII atom in (I) is coordinated through the two N atoms of the ligand and two chloride anions, generating a distorted square-planar coordination geometry around the PdII metal centre. The bond angles around Pd1 (Table 1) show significant deviations from 90°, which confirms the distortion of the square-planar geometry. These bond angles are close to those of a similar compound (Motswainyana et al., 2012). The Pd1—Cl bond lengths are in good agreement with the average Pd—Cl bond length of 2.298 (15) Å 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 (Doherty et al., 2002). Atom Cl1 has a short intramolecular contact with H4 (Cl1···H4 = 2.50 Å) and as a result Cl1 deviates more [-1.284 (1) Å] from the best least-squares plane through the quinoline ring than Cl2 [-0.266 Å]. The angle between the quinoline least-squares plane and the plane through atoms C9, C10 and N2 is 9.37 (10)°. This is at the higher end of the range observed in the Cambridge Structural Database (CSD, Version?; Allen, 2002) for 2-iminopyridyl groups involved in dichloridopalladium complexes (0.31–9.65°, 24 hits). The overall r.m.s. deviations are 0.005 and 0.044 Å, 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 [74.5 (3)°] and C11–C16–C19–C20 [80.4 (3)°] torsion angles.

In the crystal packing of (I), ππ interactions between quinoline rings link pairs of molecules into centrosymmetric dimers (Fig. 2), with a Cg1···Cg2i distance of 3.681 (2) Å and a Cg2···Cg2i distance of 3.932 (2) Å [Cg1 and Cg2 are the centroids of the N1/C5–C9 and C1–C6 rings, respectively; symmetry code: (i) -x + 1, -y + 1, -z + 1]. Furthermore, the packing shows a number of weaker contacts of the C—H···π type (C3—H3···Cg3ii = 2.80 Å and C22—H22B···Cg3iii = 2.86 Å; Cg3 is the centroid of the C11–C16 ring; symmetry codes: (ii) -x + 3/2, y - 1/2, -z + 3/2; (iii) x - 1/2, -y + 3/2, z + 1/2].

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. When further analysing the crystal packing, the importance of the presence of acetonitrile becomes clear. Without acetonitrile the unit cell would show four voids of 97 Å3 each, which are now filled by one acetontrile molecule having a molar volume of about 42 Å3. In the packing, the position of this acetonitrile is fixed by two π-interactions: a C22—H22B···π interaction (see above) and a C21N3···Cg2 interaction [N3···Cg2 = 3.793 (3) Å] (Fig. 3). Furthermore, atom N3 interacts with atoms H1 and H3 of a neighbouring molecule [N3···H1iv = 2.66 Å and N3···H3iv = 2.69 Å; symmetry code: (iv) -x, -y + 1, -z + 1]. This bifurcated interaction of the acetonitrile N atom has been observed before in crystal structures (13 hits in the CSD, with N···H contact distances ranging between 2.436 and 2.744 Å). The acetonitrile methyl group interacts with both Cl atoms [H22C···Cl2v = 2.89 Å and H22A···Cl1 = 3.24 Å; symmetry code: (v) x - 1, y, z].

For related literature, see: Allen (2002); Bianchini et al. (2010); Chen et al. (2007); Doherty et al. (2002); Fuertes et al. (2003); Hotze et al. (2002); Ittel et al. (2000); Jung & Lippard (2007); Motswainyana et al. (2011, 2012); Ojwach et al. (2007); Segapelo et al. (2009); Wong & Giandomenico (1999).

Computing details top

Data collection: CrysAlis PRO (Agilent, 2012); cell refinement: CrysAlis PRO (Agilent, 2012); data reduction: CrysAlis PRO (Agilent, 2012); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

Figures top
[Figure 1] Fig. 1. The molecular structure of (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level.
[Figure 2] Fig. 2. ππ 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 Å.
[Figure 3] Fig. 3. The interaction of acetonitrile solvent molecules with neighbouring complex molecules. Dashed lines indicate the various interactions. [Added text OK?] 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).
Dichlorido{2-[(2,6-diethylphenyl)iminomethyl]quinoline- κ2N,N'}palladium(II) acetonitrile monosolvate top
Crystal data top
[PdCl2(C20H20N2)]·C2H3NF(000) = 1024
Mr = 506.73Dx = 1.582 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
a = 7.8874 (3) ÅCell parameters from 5179 reflections
b = 19.3046 (8) Åθ = 2.7–26.3°
c = 14.2966 (7) ŵ = 1.14 mm1
β = 102.164 (4)°T = 100 K
V = 2127.99 (16) Å3Block, yellow
Z = 40.3 × 0.2 × 0.2 mm
Data collection top
Agilent SuperNova (single source at offset, Eos)
diffractometer
4314 independent reflections
Radiation source: SuperNova (Mo) X-ray Source3798 reflections with I > 2σ(I)
Mirror monochromatorRint = 0.036
Detector resolution: 15.9631 pixels mm-1θmax = 26.3°, θmin = 2.7°
ω scansh = 99
Absorption correction: multi-scan
(CrysAlis PRO; Agilent, 2012)
k = 2423
Tmin = 0.971, Tmax = 1.000l = 179
8662 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.030Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.071H-atom parameters constrained
S = 1.03 w = 1/[σ2(Fo2) + (0.0222P)2 + 0.925P]
where P = (Fo2 + 2Fc2)/3
4314 reflections(Δ/σ)max = 0.003
256 parametersΔρmax = 0.39 e Å3
0 restraintsΔρmin = 0.52 e Å3
Crystal data top
[PdCl2(C20H20N2)]·C2H3NV = 2127.99 (16) Å3
Mr = 506.73Z = 4
Monoclinic, P21/nMo Kα radiation
a = 7.8874 (3) ŵ = 1.14 mm1
b = 19.3046 (8) ÅT = 100 K
c = 14.2966 (7) Å0.3 × 0.2 × 0.2 mm
β = 102.164 (4)°
Data collection top
Agilent SuperNova (single source at offset, Eos)
diffractometer
4314 independent reflections
Absorption correction: multi-scan
(CrysAlis PRO; Agilent, 2012)
3798 reflections with I > 2σ(I)
Tmin = 0.971, Tmax = 1.000Rint = 0.036
8662 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0300 restraints
wR(F2) = 0.071H-atom parameters constrained
S = 1.03Δρmax = 0.39 e Å3
4314 reflectionsΔρmin = 0.52 e Å3
256 parameters
Special details top

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.

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) top
xyzUiso*/Ueq
C10.2913 (3)0.46279 (14)0.5574 (2)0.0152 (6)
H10.20000.44320.51360.018*
C20.3898 (3)0.42270 (14)0.6262 (2)0.0151 (6)
H20.36460.37580.62970.018*
C30.5299 (3)0.45173 (14)0.69256 (19)0.0156 (6)
H30.59800.42340.73810.019*
C40.5672 (3)0.52114 (14)0.69081 (19)0.0141 (6)
H40.65910.53960.73550.017*
C50.4663 (3)0.56455 (14)0.62124 (18)0.0112 (5)
C60.3278 (3)0.53484 (14)0.55220 (19)0.0111 (5)
C70.2331 (3)0.57652 (14)0.47949 (19)0.0134 (6)
H70.13830.55850.43640.016*
C80.2815 (3)0.64441 (14)0.47242 (19)0.0131 (6)
H80.22400.67230.42270.016*
C90.4189 (3)0.67081 (14)0.54134 (18)0.0112 (5)
C100.4863 (3)0.74008 (14)0.53032 (18)0.0109 (5)
H100.43270.76880.48060.013*
C110.6937 (3)0.82770 (14)0.57919 (18)0.0106 (5)
C120.6015 (3)0.88821 (14)0.59076 (18)0.0118 (5)
C130.6807 (3)0.95138 (14)0.58095 (19)0.0134 (6)
H130.62220.99220.58810.016*
C140.8450 (3)0.95484 (15)0.56067 (19)0.0155 (6)
H140.89660.99760.55550.019*
C150.9322 (3)0.89411 (14)0.54811 (19)0.0152 (6)
H151.04110.89670.53300.018*
C160.8592 (3)0.82957 (14)0.55772 (18)0.0114 (5)
C170.4237 (3)0.88743 (15)0.61655 (19)0.0145 (6)
H17A0.37070.93270.60350.017*
H17B0.35040.85410.57620.017*
C180.4320 (4)0.86908 (19)0.7209 (2)0.0331 (8)
H18A0.50450.90190.76130.050*
H18B0.47950.82340.73360.050*
H18C0.31740.87040.73370.050*
C190.9507 (3)0.76333 (14)0.54014 (19)0.0145 (6)
H19A0.93180.72840.58570.017*
H19B1.07440.77190.55060.017*
C200.8863 (3)0.73574 (15)0.4385 (2)0.0179 (6)
H20A0.92830.68940.43440.027*
H20B0.92840.76490.39400.027*
H20C0.76180.73560.42350.027*
C210.0756 (4)0.58019 (18)0.7278 (2)0.0274 (7)
C220.1805 (4)0.6129 (2)0.8104 (3)0.0402 (9)
H22A0.30060.60950.80720.060*
H22B0.16240.59030.86730.060*
H22C0.14870.66090.81190.060*
Cl10.71391 (9)0.63912 (3)0.85021 (5)0.01621 (15)
Cl20.89474 (8)0.77099 (3)0.78145 (5)0.01569 (15)
N10.5052 (3)0.63426 (11)0.61660 (15)0.0102 (5)
N20.6208 (3)0.76040 (11)0.59064 (15)0.0098 (5)
N30.0073 (4)0.5546 (2)0.6630 (2)0.0591 (11)
Pd10.68518 (2)0.696873 (10)0.706264 (13)0.00930 (7)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0123 (13)0.0169 (15)0.0167 (14)0.0063 (12)0.0036 (11)0.0054 (12)
C20.0179 (14)0.0097 (14)0.0183 (14)0.0021 (12)0.0055 (11)0.0004 (12)
C30.0195 (14)0.0124 (14)0.0141 (14)0.0006 (12)0.0020 (11)0.0005 (12)
C40.0177 (13)0.0132 (14)0.0098 (13)0.0013 (12)0.0005 (11)0.0005 (11)
C50.0136 (13)0.0099 (13)0.0108 (13)0.0006 (11)0.0044 (10)0.0023 (11)
C60.0090 (12)0.0129 (14)0.0128 (13)0.0001 (11)0.0052 (10)0.0006 (11)
C70.0085 (12)0.0172 (15)0.0137 (13)0.0017 (12)0.0008 (10)0.0039 (12)
C80.0122 (13)0.0152 (15)0.0122 (13)0.0024 (12)0.0033 (10)0.0013 (11)
C90.0118 (12)0.0111 (14)0.0111 (13)0.0021 (12)0.0036 (10)0.0007 (11)
C100.0125 (13)0.0107 (13)0.0091 (13)0.0017 (11)0.0011 (10)0.0010 (11)
C110.0154 (13)0.0097 (13)0.0055 (12)0.0015 (12)0.0007 (10)0.0021 (11)
C120.0123 (12)0.0135 (14)0.0090 (12)0.0005 (11)0.0009 (10)0.0000 (11)
C130.0157 (13)0.0091 (13)0.0142 (14)0.0030 (12)0.0005 (11)0.0007 (11)
C140.0199 (14)0.0117 (14)0.0144 (14)0.0031 (12)0.0022 (11)0.0035 (12)
C150.0131 (13)0.0176 (15)0.0154 (14)0.0016 (12)0.0037 (11)0.0032 (12)
C160.0109 (12)0.0133 (14)0.0086 (12)0.0012 (11)0.0011 (10)0.0004 (11)
C170.0113 (12)0.0142 (14)0.0174 (14)0.0031 (12)0.0020 (11)0.0015 (12)
C180.0312 (17)0.046 (2)0.0255 (18)0.0111 (17)0.0142 (14)0.0063 (17)
C190.0126 (13)0.0154 (15)0.0161 (14)0.0004 (12)0.0044 (11)0.0015 (12)
C200.0167 (14)0.0165 (15)0.0210 (15)0.0016 (12)0.0049 (12)0.0027 (13)
C210.0234 (16)0.0327 (19)0.0268 (17)0.0017 (15)0.0069 (14)0.0080 (16)
C220.0339 (19)0.048 (2)0.033 (2)0.0005 (18)0.0047 (16)0.0149 (18)
Cl10.0254 (3)0.0124 (3)0.0098 (3)0.0033 (3)0.0013 (3)0.0013 (3)
Cl20.0197 (3)0.0127 (3)0.0124 (3)0.0052 (3)0.0018 (3)0.0001 (3)
N10.0104 (10)0.0094 (11)0.0107 (11)0.0002 (9)0.0017 (9)0.0003 (9)
N20.0125 (10)0.0087 (11)0.0094 (11)0.0005 (10)0.0048 (9)0.0003 (9)
N30.0310 (16)0.102 (3)0.045 (2)0.0153 (19)0.0088 (15)0.042 (2)
Pd10.01144 (12)0.00772 (12)0.00791 (11)0.00080 (8)0.00020 (8)0.00001 (8)
Geometric parameters (Å, º) top
C1—H10.9300C14—H140.9300
C1—C21.359 (4)C14—C151.390 (4)
C1—C61.425 (4)C15—H150.9300
C2—H20.9300C15—C161.391 (4)
C2—C31.412 (4)C16—C191.515 (4)
C3—H30.9300C17—H17A0.9700
C3—C41.373 (4)C17—H17B0.9700
C4—H40.9300C17—C181.521 (4)
C4—C51.411 (4)C18—H18A0.9600
C5—C61.429 (3)C18—H18B0.9600
C5—N11.385 (3)C18—H18C0.9600
C6—C71.400 (4)C19—H19A0.9700
C7—H70.9300C19—H19B0.9700
C7—C81.375 (4)C19—C201.530 (4)
C8—H80.9300C20—H20A0.9600
C8—C91.398 (4)C20—H20B0.9600
C9—C101.460 (4)C20—H20C0.9600
C9—N11.345 (3)C21—C221.438 (4)
C10—H100.9300C21—N31.129 (4)
C10—N21.279 (3)C22—H22A0.9600
C11—C121.404 (4)C22—H22B0.9600
C11—C161.403 (4)C22—H22C0.9600
C11—N21.444 (3)Cl1—Pd12.3093 (7)
C12—C131.391 (4)Cl2—Pd12.2773 (7)
C12—C171.523 (4)N1—Pd12.086 (2)
C13—H130.9300N2—Pd12.035 (2)
C13—C141.388 (4)
C2—C1—H1119.9C15—C16—C11117.9 (2)
C2—C1—C6120.2 (2)C15—C16—C19121.2 (2)
C6—C1—H1119.9C12—C17—H17A109.0
C1—C2—H2119.8C12—C17—H17B109.0
C1—C2—C3120.5 (3)H17A—C17—H17B107.8
C3—C2—H2119.8C18—C17—C12112.8 (2)
C2—C3—H3119.5C18—C17—H17A109.0
C4—C3—C2121.0 (3)C18—C17—H17B109.0
C4—C3—H3119.5C17—C18—H18A109.5
C3—C4—H4120.0C17—C18—H18B109.5
C3—C4—C5120.1 (2)C17—C18—H18C109.5
C5—C4—H4120.0H18A—C18—H18B109.5
C4—C5—C6119.0 (2)H18A—C18—H18C109.5
N1—C5—C4120.9 (2)H18B—C18—H18C109.5
N1—C5—C6120.1 (2)C16—C19—H19A109.2
C1—C6—C5119.2 (2)C16—C19—H19B109.2
C7—C6—C1121.2 (2)C16—C19—C20112.1 (2)
C7—C6—C5119.5 (2)H19A—C19—H19B107.9
C6—C7—H7120.3C20—C19—H19A109.2
C8—C7—C6119.3 (2)C20—C19—H19B109.2
C8—C7—H7120.3C19—C20—H20A109.5
C7—C8—H8120.6C19—C20—H20B109.5
C7—C8—C9118.8 (2)C19—C20—H20C109.5
C9—C8—H8120.6H20A—C20—H20B109.5
C8—C9—C10120.2 (2)H20A—C20—H20C109.5
N1—C9—C8124.0 (2)H20B—C20—H20C109.5
N1—C9—C10115.6 (2)N3—C21—C22179.8 (4)
C9—C10—H10120.8C21—C22—H22A109.5
N2—C10—C9118.5 (2)C21—C22—H22B109.5
N2—C10—H10120.8C21—C22—H22C109.5
C12—C11—N2120.4 (2)H22A—C22—H22B109.5
C16—C11—C12122.2 (2)H22A—C22—H22C109.5
C16—C11—N2117.3 (2)H22B—C22—H22C109.5
C11—C12—C17123.1 (2)C5—N1—Pd1131.48 (17)
C13—C12—C11117.6 (2)C9—N1—C5117.9 (2)
C13—C12—C17119.3 (2)C9—N1—Pd1110.57 (17)
C12—C13—H13119.3C10—N2—C11119.5 (2)
C14—C13—C12121.5 (2)C10—N2—Pd1113.10 (18)
C14—C13—H13119.3C11—N2—Pd1126.66 (16)
C13—C14—H14120.1Cl2—Pd1—Cl187.56 (2)
C13—C14—C15119.7 (3)N1—Pd1—Cl1101.20 (6)
C15—C14—H14120.1N1—Pd1—Cl2170.49 (6)
C14—C15—H15119.5N2—Pd1—Cl1167.35 (6)
C14—C15—C16121.1 (2)N2—Pd1—Cl292.11 (6)
C16—C15—H15119.5N2—Pd1—N180.15 (8)
C11—C16—C19120.8 (2)
C1—C2—C3—C41.7 (4)C10—N2—Pd1—Cl2173.06 (18)
C1—C6—C7—C8174.7 (2)C10—N2—Pd1—N112.50 (18)
C2—C1—C6—C51.3 (4)C11—C12—C13—C140.1 (4)
C2—C1—C6—C7177.2 (2)C11—C12—C17—C1874.5 (3)
C2—C3—C4—C50.8 (4)C11—C16—C19—C2080.4 (3)
C3—C4—C5—C61.1 (4)C11—N2—Pd1—Cl185.5 (3)
C3—C4—C5—N1178.1 (2)C11—N2—Pd1—Cl22.8 (2)
C4—C5—C6—C12.2 (4)C11—N2—Pd1—N1177.3 (2)
C4—C5—C6—C7176.3 (2)C12—C11—C16—C150.2 (4)
C4—C5—N1—C9171.4 (2)C12—C11—C16—C19176.5 (2)
C4—C5—N1—Pd16.7 (4)C12—C11—N2—C1067.1 (3)
C5—C6—C7—C83.8 (4)C12—C11—N2—Pd1102.5 (2)
C5—N1—Pd1—Cl126.2 (2)C12—C13—C14—C151.1 (4)
C5—N1—Pd1—N2166.6 (2)C13—C12—C17—C18103.4 (3)
C6—C1—C2—C30.6 (4)C13—C14—C15—C161.5 (4)
C6—C5—N1—C95.5 (3)C14—C15—C16—C110.9 (4)
C6—C5—N1—Pd1176.37 (17)C14—C15—C16—C19177.5 (2)
C6—C7—C8—C93.3 (4)C15—C16—C19—C2096.1 (3)
C7—C8—C9—C10173.2 (2)C16—C11—C12—C130.5 (4)
C7—C8—C9—N11.8 (4)C16—C11—C12—C17178.4 (2)
C8—C9—C10—N2174.5 (2)C16—C11—N2—C10113.8 (3)
C8—C9—N1—C56.2 (4)C16—C11—N2—Pd176.6 (3)
C8—C9—N1—Pd1175.2 (2)C17—C12—C13—C14177.8 (2)
C9—C10—N2—C11177.7 (2)N1—C5—C6—C1179.1 (2)
C9—C10—N2—Pd111.3 (3)N1—C5—C6—C70.6 (4)
C9—N1—Pd1—Cl1155.52 (16)N1—C9—C10—N21.0 (4)
C9—N1—Pd1—N211.68 (17)N2—C11—C12—C13178.5 (2)
C10—C9—N1—C5169.0 (2)N2—C11—C12—C170.7 (4)
C10—C9—N1—Pd19.5 (3)N2—C11—C16—C15178.9 (2)
C10—N2—Pd1—Cl184.8 (3)N2—C11—C16—C194.4 (4)

Experimental details

Crystal data
Chemical formula[PdCl2(C20H20N2)]·C2H3N
Mr506.73
Crystal system, space groupMonoclinic, P21/n
Temperature (K)100
a, b, c (Å)7.8874 (3), 19.3046 (8), 14.2966 (7)
β (°) 102.164 (4)
V3)2127.99 (16)
Z4
Radiation typeMo Kα
µ (mm1)1.14
Crystal size (mm)0.3 × 0.2 × 0.2
Data collection
DiffractometerAgilent SuperNova (single source at offset, Eos)
Absorption correctionMulti-scan
(CrysAlis PRO; Agilent, 2012)
Tmin, Tmax0.971, 1.000
No. of measured, independent and
observed [I > 2σ(I)] reflections
8662, 4314, 3798
Rint0.036
(sin θ/λ)max1)0.624
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.030, 0.071, 1.03
No. of reflections4314
No. of parameters256
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.39, 0.52

Computer programs: CrysAlis PRO (Agilent, 2012), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), OLEX2 (Dolomanov et al., 2009).

Selected geometric parameters (Å, º) top
Cl1—Pd12.3093 (7)N1—Pd12.086 (2)
Cl2—Pd12.2773 (7)N2—Pd12.035 (2)
Cl2—Pd1—Cl187.56 (2)N2—Pd1—Cl1167.35 (6)
N1—Pd1—Cl1101.20 (6)N2—Pd1—Cl292.11 (6)
N1—Pd1—Cl2170.49 (6)N2—Pd1—N180.15 (8)
 

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