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ISSN: 2056-9890

trans-Di­chloridobis(quinoline-κN)palladium(II)

aSchool of Applied Chemical Engineering, The Research Institute of Catalysis, Chonnam National University, Gwangju 500-757, Republic of Korea
*Correspondence e-mail: hakwang@chonnam.ac.kr

(Received 20 December 2011; accepted 28 December 2011; online 14 January 2012)

In the title complex, [PdCl2(C9H7N)2], the PdII ion is four-coordinated in an essentially square-planar environment defined by two N atoms from two quinoline ligands and two Cl anions. The Pd atom is located on an inversion centre, and thus the asymmetric unit contains one half of the complex; the PdN2Cl2 unit is exactly planar. The dihedral angle between the PdN2Cl2 unit and quinoline ligand is 85.63 (8)°. In the crystal, the complex mol­ecules are stacked into columns along the b axis. In the columns, several inter­molecular ππ inter­actions between the six-membered rings are present, the shortest ring centroid–centroid distance being 3.764 (3) Å between pyridine rings.

Related literature

For the crystal structure of the related PtII complex cis-[PtCl2(quinoline)2]·0.25DMF, see: Davies et al. (2001[Davies, M. S., Diakos, C. I., Messerle, B. A. & Hambley, T. W. (2001). Inorg. Chem. 40, 3048-3054.]).

[Scheme 1]

Experimental

Crystal data
  • [PdCl2(C9H7N)2]

  • Mr = 435.61

  • Monoclinic, C 2/c

  • a = 16.430 (3) Å

  • b = 7.0050 (11) Å

  • c = 16.118 (2) Å

  • β = 119.532 (3)°

  • V = 1614.0 (4) Å3

  • Z = 4

  • Mo Kα radiation

  • μ = 1.48 mm−1

  • T = 200 K

  • 0.31 × 0.13 × 0.11 mm

Data collection
  • Bruker SMART 1000 CCD diffractometer

  • Absorption correction: multi-scan (SADABS; Bruker, 2000[Bruker (2000). SADABS, SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]) Tmin = 0.869, Tmax = 1.000

  • 4776 measured reflections

  • 1577 independent reflections

  • 1125 reflections with I > 2σ(I)

  • Rint = 0.041

Refinement
  • R[F2 > 2σ(F2)] = 0.040

  • wR(F2) = 0.095

  • S = 1.05

  • 1577 reflections

  • 106 parameters

  • H-atom parameters constrained

  • Δρmax = 1.30 e Å−3

  • Δρmin = −0.40 e Å−3

Table 1
Selected geometric parameters (Å, °)

Pd1—N1 2.035 (4)
Pd1—Cl1 2.2973 (12)
N1—Pd1—Cl1 89.53 (10)

Data collection: SMART (Bruker, 2000[Bruker (2000). SADABS, SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 2000[Bruker (2000). SADABS, SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: ORTEP-3 (Farrugia, 1997[Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565.]) and PLATON (Spek, 2009[Spek, A. L. (2009). Acta Cryst. D65, 148-155.]); software used to prepare material for publication: SHELXL97.

Supporting information


Comment top

In the title complex, [PdCl2(quinoline)2], the PdII ion is four-coordinated in an essentially square-planar environment by two N atoms from two quinoline ligands and two Cl- anions (Fig. 1 and Table 1). The Cl atoms are in trans conformation with respect to each other. By contrast, in the analogous PtII complex [PtCl2(quinoline)2].0.25DMF (DMF = N,N-dimethylformamide), the Cl atoms are in cis conformation (Davies et al., 2001).

The Pd atom is located on an inversion centre, and thus the asymmetric unit contains one half of the complex; the PdN2Cl2 unit is exactly planar. The nearly planar quinoline ligands, with a maximum deviation of 0.015 (4) Å from the least-squares plane, are parallel. The dihedral angle between the PdN2Cl2 unit and quinoline ligand is 85.63 (8)°. The Cl atoms are almost perpendicular to the quinoline planes, with the bond angle <N1—Pd1—Cl1 = 89.53 (10)°. In the crystal, the complex molecules are stacked into columns along the b axis (Fig. 2). In the columns, several intermolecular π-π interactions between the six-membered rings are present, the shortest ring centroid-centroid distance being 3.764 (3) Å between pyridyl rings.

Related literature top

For the crystal structure of the related PtII complex cis-[PtCl2(quinoline)2].0.25DMF, see: Davies et al. (2001).

Experimental top

To a solution of Na2PdCl4 (0.2943 g, 1.000 mmol) in H2O (20 ml) was added quinoline (0.2590 g, 2.005 mmol). The mixture was stirred for 3 h at room temperature. The formed precipitate was separated by filtration, washed with H2O and EtOH, and dried at 50 °C, to give a yellow powder (0.3706 g). Crystals suitable for X-ray analysis were obtained by slow evaporation from its dimethyl sulfoxide (DMSO) solution at 90 °C.

Refinement top

H atoms were positioned geometrically and allowed to ride on their respective parent atoms [C—H = 0.95 Å and Uiso(H) = 1.2Ueq(C)]. The highest peak (1.30 e Å-3) and the deepest hole (-0.40 e Å-3) in the final difference Fourier map were located 1.01 Å and 1.49 Å from the atoms Pd1 and H5, respectively.

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997) and PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. A view of the molecular structure of the title complex, with displacement ellipsoids drawn at the 40% probability level and the atom numbering. Unlabelled atoms are related to the reference atoms by the (-x, 1 - y, -z) symmetry transformation.
[Figure 2] Fig. 2. A view of the unit-cell contents of the title complex, along the a axis.
trans-Dichloridobis(quinoline-κN)palladium(II) top
Crystal data top
[PdCl2(C9H7N)2]F(000) = 864
Mr = 435.61Dx = 1.793 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 1841 reflections
a = 16.430 (3) Åθ = 2.9–25.6°
b = 7.0050 (11) ŵ = 1.48 mm1
c = 16.118 (2) ÅT = 200 K
β = 119.532 (3)°Block, yellow
V = 1614.0 (4) Å30.31 × 0.13 × 0.11 mm
Z = 4
Data collection top
Bruker SMART 1000 CCD
diffractometer
1577 independent reflections
Radiation source: fine-focus sealed tube1125 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.041
ϕ and ω scansθmax = 26.0°, θmin = 2.9°
Absorption correction: multi-scan
(SADABS; Bruker, 2000)
h = 1920
Tmin = 0.869, Tmax = 1.000k = 88
4776 measured reflectionsl = 1819
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)] = 0.040Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.095H-atom parameters constrained
S = 1.05 w = 1/[σ2(Fo2) + (0.0442P)2]
where P = (Fo2 + 2Fc2)/3
1577 reflections(Δ/σ)max < 0.001
106 parametersΔρmax = 1.30 e Å3
0 restraintsΔρmin = 0.40 e Å3
Crystal data top
[PdCl2(C9H7N)2]V = 1614.0 (4) Å3
Mr = 435.61Z = 4
Monoclinic, C2/cMo Kα radiation
a = 16.430 (3) ŵ = 1.48 mm1
b = 7.0050 (11) ÅT = 200 K
c = 16.118 (2) Å0.31 × 0.13 × 0.11 mm
β = 119.532 (3)°
Data collection top
Bruker SMART 1000 CCD
diffractometer
1577 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2000)
1125 reflections with I > 2σ(I)
Tmin = 0.869, Tmax = 1.000Rint = 0.041
4776 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0400 restraints
wR(F2) = 0.095H-atom parameters constrained
S = 1.05Δρmax = 1.30 e Å3
1577 reflectionsΔρmin = 0.40 e Å3
106 parameters
Special details top

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
Pd10.00000.50000.00000.0367 (2)
Cl10.01202 (8)0.3930 (2)0.12827 (8)0.0488 (3)
N10.1092 (2)0.3186 (6)0.0364 (3)0.0381 (9)
C10.0916 (3)0.1476 (7)0.0041 (3)0.0451 (12)
H10.02880.11720.04980.054*
C20.1606 (4)0.0098 (7)0.0169 (4)0.0480 (13)
H20.14490.11060.01420.058*
C30.2514 (4)0.0518 (7)0.0833 (4)0.0490 (14)
H30.29960.03920.09880.059*
C40.2721 (3)0.2324 (7)0.1284 (3)0.0356 (10)
C50.3633 (3)0.2877 (8)0.1971 (3)0.0505 (13)
H50.41340.19970.21620.061*
C60.3806 (4)0.4638 (8)0.2362 (4)0.0519 (14)
H60.44260.49910.28190.062*
C70.3078 (4)0.5939 (9)0.2100 (3)0.0496 (13)
H70.32110.71720.23830.060*
C80.2180 (3)0.5483 (7)0.1448 (3)0.0421 (12)
H80.16920.63840.12830.051*
C90.1979 (3)0.3651 (7)0.1018 (3)0.0373 (11)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Pd10.0248 (3)0.0445 (3)0.0377 (3)0.0052 (2)0.0129 (2)0.0054 (2)
Cl10.0436 (7)0.0605 (9)0.0453 (7)0.0101 (7)0.0243 (6)0.0128 (6)
N10.030 (2)0.041 (2)0.042 (2)0.0018 (18)0.0168 (18)0.0036 (19)
C10.040 (3)0.046 (3)0.050 (3)0.008 (2)0.023 (2)0.002 (2)
C20.065 (4)0.033 (3)0.054 (3)0.003 (3)0.035 (3)0.000 (2)
C30.048 (3)0.047 (3)0.061 (3)0.014 (2)0.033 (3)0.016 (3)
C40.032 (2)0.039 (3)0.040 (3)0.007 (2)0.020 (2)0.008 (2)
C50.037 (3)0.062 (4)0.050 (3)0.010 (3)0.019 (2)0.011 (3)
C60.032 (3)0.071 (4)0.044 (3)0.001 (3)0.012 (2)0.001 (3)
C70.046 (3)0.060 (3)0.041 (3)0.005 (3)0.021 (2)0.008 (3)
C80.035 (3)0.042 (3)0.046 (3)0.001 (2)0.018 (2)0.002 (2)
C90.033 (3)0.043 (3)0.037 (3)0.005 (2)0.018 (2)0.009 (2)
Geometric parameters (Å, º) top
Pd1—N12.035 (4)C3—H30.9500
Pd1—N1i2.035 (4)C4—C51.409 (6)
Pd1—Cl12.2973 (12)C4—C91.421 (6)
Pd1—Cl1i2.2973 (12)C5—C61.350 (7)
N1—C11.326 (6)C5—H50.9500
N1—C91.351 (5)C6—C71.393 (8)
C1—C21.397 (7)C6—H60.9500
C1—H10.9500C7—C81.362 (7)
C2—C31.373 (7)C7—H70.9500
C2—H20.9500C8—C91.418 (7)
C3—C41.414 (6)C8—H80.9500
N1—Pd1—N1i180.0 (2)C5—C4—C3122.9 (4)
N1—Pd1—Cl189.53 (10)C5—C4—C9118.6 (5)
N1i—Pd1—Cl190.47 (10)C3—C4—C9118.4 (4)
N1—Pd1—Cl1i90.47 (10)C6—C5—C4121.0 (5)
N1i—Pd1—Cl1i89.53 (10)C6—C5—H5119.5
Cl1—Pd1—Cl1i180.00 (9)C4—C5—H5119.5
C1—N1—C9119.4 (4)C5—C6—C7120.3 (5)
C1—N1—Pd1118.3 (3)C5—C6—H6119.8
C9—N1—Pd1122.2 (3)C7—C6—H6119.8
N1—C1—C2123.4 (5)C8—C7—C6121.4 (5)
N1—C1—H1118.3C8—C7—H7119.3
C2—C1—H1118.3C6—C7—H7119.3
C3—C2—C1118.7 (5)C7—C8—C9119.5 (5)
C3—C2—H2120.6C7—C8—H8120.3
C1—C2—H2120.6C9—C8—H8120.3
C2—C3—C4119.1 (5)N1—C9—C8120.1 (4)
C2—C3—H3120.4N1—C9—C4120.9 (4)
C4—C3—H3120.4C8—C9—C4119.1 (4)
Cl1—Pd1—N1—C193.7 (3)C5—C6—C7—C80.1 (8)
Cl1i—Pd1—N1—C186.3 (3)C6—C7—C8—C90.6 (8)
Cl1—Pd1—N1—C984.5 (3)C1—N1—C9—C8179.2 (4)
Cl1i—Pd1—N1—C995.5 (3)Pd1—N1—C9—C82.6 (6)
C9—N1—C1—C20.2 (7)C1—N1—C9—C40.7 (6)
Pd1—N1—C1—C2178.5 (3)Pd1—N1—C9—C4177.5 (3)
N1—C1—C2—C30.5 (7)C7—C8—C9—N1179.4 (4)
C1—C2—C3—C40.2 (7)C7—C8—C9—C40.5 (7)
C2—C3—C4—C5179.8 (5)C5—C4—C9—N1179.9 (4)
C2—C3—C4—C91.1 (7)C3—C4—C9—N11.4 (6)
C3—C4—C5—C6177.8 (5)C5—C4—C9—C80.2 (6)
C9—C4—C5—C60.9 (7)C3—C4—C9—C8178.6 (4)
C4—C5—C6—C70.8 (8)
Symmetry code: (i) x, y+1, z.

Experimental details

Crystal data
Chemical formula[PdCl2(C9H7N)2]
Mr435.61
Crystal system, space groupMonoclinic, C2/c
Temperature (K)200
a, b, c (Å)16.430 (3), 7.0050 (11), 16.118 (2)
β (°) 119.532 (3)
V3)1614.0 (4)
Z4
Radiation typeMo Kα
µ (mm1)1.48
Crystal size (mm)0.31 × 0.13 × 0.11
Data collection
DiffractometerBruker SMART 1000 CCD
diffractometer
Absorption correctionMulti-scan
(SADABS; Bruker, 2000)
Tmin, Tmax0.869, 1.000
No. of measured, independent and
observed [I > 2σ(I)] reflections
4776, 1577, 1125
Rint0.041
(sin θ/λ)max1)0.617
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.040, 0.095, 1.05
No. of reflections1577
No. of parameters106
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)1.30, 0.40

Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997) and PLATON (Spek, 2009).

Selected geometric parameters (Å, º) top
Pd1—N12.035 (4)Pd1—Cl12.2973 (12)
N1—Pd1—Cl189.53 (10)
 

Acknowledgements

This work was supported by the Priority Research Centers Program through the National Research Foundation of Korea (NRF) funded by the Ministry of Education, Science and Technology (2010–0029626).

References

First citationBruker (2000). SADABS, SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.  Google Scholar
First citationDavies, M. S., Diakos, C. I., Messerle, B. A. & Hambley, T. W. (2001). Inorg. Chem. 40, 3048–3054.  Web of Science CSD CrossRef PubMed CAS Google Scholar
First citationFarrugia, L. J. (1997). J. Appl. Cryst. 30, 565.  CrossRef IUCr Journals Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationSpek, A. L. (2009). Acta Cryst. D65, 148–155.  Web of Science CrossRef CAS IUCr Journals Google Scholar

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