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A new monoclinic polymorph of trans-di­chloridodi­pyridine­palladium(II)

aNational Changhua University of Education, Department of Chemistry, Changhua 50058, Taiwan
*Correspondence e-mail: leehm@cc.ncue.edu.tw

(Received 1 October 2008; accepted 15 October 2008; online 22 October 2008)

In the structure of the title compound, [PdCl2(C5H5N)2], the PdII atom is located on an inversion centre and the pyridine rings are coplanar. There is inter­molecular ππ stacking between the pyridyl rings, with a centroid-to-centroid separation of 3.916 (1) Å. The structure is a new polymorph of two previously determined structures [Viossat, Dung & Robert (1993[Viossat, B., Dung, N.-H. & Robert, F. (1993). Acta Cryst. C49, 84-85.]). Acta Cryst. C49, 84–85; Liao & Lee (2006[Liao, C.-Y. & Lee, H. M. (2006). Acta Cryst. E62, m680-m681.]). Acta Cryst. E62, m680–m681].

Related literature

For the other two polymorphs of the title compound, see: Viossat et al. (1993[Viossat, B., Dung, N.-H. & Robert, F. (1993). Acta Cryst. C49, 84-85.]); Liao & Lee (2006[Liao, C.-Y. & Lee, H. M. (2006). Acta Cryst. E62, m680-m681.]).

[Scheme 1]

Experimental

Crystal data
  • [PdCl2(C5H5N)2]

  • Mr = 335.50

  • Monoclinic, P 21 /n

  • a = 3.9159 (2) Å

  • b = 8.7921 (4) Å

  • c = 16.2974 (8) Å

  • β = 90.442 (3)°

  • V = 561.09 (5) Å3

  • Z = 2

  • Mo Kα radiation

  • μ = 2.10 mm−1

  • T = 150 (2) K

  • 0.45 × 0.10 × 0.07 mm

Data collection
  • Bruker SMART APEXII diffractometer

  • Absorption correction: multi-scan (SADABS; Sheldrick, 2003[Sheldrick, G. M. (2003). SADABS. University of Göttingen, Germany.]) Tmin = 0.452, Tmax = 0.867

  • 5861 measured reflections

  • 1445 independent reflections

  • 1314 reflections with I > 2σ

  • Rint = 0.028

Refinement
  • R[F2 > 2σ(F2)] = 0.023

  • wR(F2) = 0.056

  • S = 1.10

  • 1445 reflections

  • 70 parameters

  • H-atom parameters constrained

  • Δρmax = 0.91 e Å−3

  • Δρmin = −1.03 e Å−3

Data collection: APEX2 (Bruker, 2004[Bruker (2004). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 2004[Bruker (2004). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supporting information


Comment top

Two polymorphic forms of the title compound have already been determined (Viossat et al., 1993; Liao & Lee, 2006). The polymorphic form determined by us previously has a plate-like crystal habit (Liao & Lee, 2006). Herein, we present a new polymorphic form of the title compound. This new form has a rod-like habit. The PdII atom, situated at a centre of inversion, has a square-planer coordination geometry with two trans pyridine ligands and two trans chloride ligands (Fig. 1). Similar to the polymorph determined by us previously (Liao & Lee, 2006), in this new polymorphic form the two pyridine rings are co-planar. The co-planariity in these two forms is in sharp contrast to that in the other polymorph in which the the two pyridine planes make an angle of 160.0 (5)° (Viossat et al., 1993).

The crystal packing is distinctly different in the three polymorphs. A view of the packing arrangement for the new polymorphic form is shown in Fig. 2. Intermolecular ππ stacking exists between the pyridyl rings, with centroid–centroid separation 3.916 Å.

Related literature top

For the other two polymorphs of the title compound, see: Viossat et al. (1993); Liao & Lee (2006).

Experimental top

The title compound is commercially available. Crystals were grown by slow diffusion of diethyl ether into a dimethylformamide solution containing the compound. The polymorphic form has a rod-like crystal habit.

Refinement top

All H atoms could be identified in the difference Fourier map, but were positioned geometrically and refined as riding atoms, with C—H = 0.95 Å and Uiso(H) = 1.2Ueq(C).

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. Molecular structure of the title compound, showing 50% displacement ellipsoids for non-H atoms. The H atoms are dipicted by circles of an arbitrary radius. The unlabelled atoms are related to the labelled ones by -x, 1 - y, -z.
[Figure 2] Fig. 2. Packing diagram of the title compound viewed along the a axis.
trans-dichloridodipyridinepalladium(II) top
Crystal data top
[PdCl2(C5H5N)2]F(000) = 328
Mr = 335.50Dx = 1.986 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 4043 reflections
a = 3.9159 (2) Åθ = 2.5–34.2°
b = 8.7921 (4) ŵ = 2.10 mm1
c = 16.2974 (8) ÅT = 150 K
β = 90.442 (3)°Rod, colourless
V = 561.09 (5) Å30.45 × 0.10 × 0.07 mm
Z = 2
Data collection top
Bruker SMART APEXII
diffractometer
1445 independent reflections
Radiation source: fine-focus sealed tube1314 reflections with I > 2σ
Graphite monochromatorRint = 0.028
ω scansθmax = 28.7°, θmin = 2.6°
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
h = 55
Tmin = 0.452, Tmax = 0.867k = 118
5861 measured reflectionsl = 2219
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)] = 0.023Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.056H-atom parameters constrained
S = 1.10 w = 1/[σ2(Fo2) + (0.0105P)2 + 1.3011P]
where P = (Fo2 + 2Fc2)/3
1445 reflections(Δ/σ)max < 0.001
70 parametersΔρmax = 0.91 e Å3
0 restraintsΔρmin = 1.03 e Å3
Crystal data top
[PdCl2(C5H5N)2]V = 561.09 (5) Å3
Mr = 335.50Z = 2
Monoclinic, P21/nMo Kα radiation
a = 3.9159 (2) ŵ = 2.10 mm1
b = 8.7921 (4) ÅT = 150 K
c = 16.2974 (8) Å0.45 × 0.10 × 0.07 mm
β = 90.442 (3)°
Data collection top
Bruker SMART APEXII
diffractometer
1445 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
1314 reflections with I > 2σ
Tmin = 0.452, Tmax = 0.867Rint = 0.028
5861 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0230 restraints
wR(F2) = 0.056H-atom parameters constrained
S = 1.10Δρmax = 0.91 e Å3
1445 reflectionsΔρmin = 1.03 e Å3
70 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
C10.1177 (6)0.6747 (3)0.15154 (15)0.0203 (5)
H10.22530.58330.16900.024*
C20.1019 (7)0.7956 (3)0.20522 (16)0.0249 (5)
H20.19760.78780.25880.030*
C30.0560 (7)0.9288 (3)0.17976 (17)0.0251 (5)
H30.07371.01300.21600.030*
C40.1875 (7)0.9376 (3)0.10081 (18)0.0238 (5)
H40.29131.02880.08170.029*
C50.1655 (6)0.8117 (3)0.05015 (15)0.0194 (5)
H50.25950.81690.00370.023*
Cl10.24377 (16)0.64576 (7)0.10193 (4)0.01983 (13)
N10.0149 (5)0.6822 (2)0.07511 (12)0.0159 (4)
Pd10.00000.50000.00000.01359 (8)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0236 (11)0.0198 (12)0.0174 (11)0.0000 (9)0.0019 (9)0.0002 (9)
C20.0263 (12)0.0314 (14)0.0171 (12)0.0021 (11)0.0009 (10)0.0051 (10)
C30.0272 (13)0.0227 (13)0.0256 (13)0.0032 (11)0.0024 (10)0.0096 (10)
C40.0252 (12)0.0163 (12)0.0298 (14)0.0018 (10)0.0006 (10)0.0020 (10)
C50.0232 (11)0.0170 (11)0.0180 (11)0.0001 (9)0.0011 (9)0.0003 (9)
Cl10.0255 (3)0.0174 (3)0.0167 (3)0.0023 (2)0.0026 (2)0.0009 (2)
N10.0199 (9)0.0140 (9)0.0138 (9)0.0011 (7)0.0000 (7)0.0012 (7)
Pd10.01822 (13)0.01113 (12)0.01142 (12)0.00025 (9)0.00070 (8)0.00068 (8)
Geometric parameters (Å, º) top
C1—N11.347 (3)C4—H40.950
C1—C21.379 (4)C5—N11.344 (3)
C1—H10.950C5—H50.950
C2—C31.386 (4)Cl1—Pd12.3104 (6)
C2—H20.950N1—Pd12.017 (2)
C3—C41.385 (4)Pd1—N1i2.017 (2)
C3—H30.950Pd1—Cl1i2.3104 (6)
C4—C51.384 (4)
N1—C1—C2122.0 (2)N1—C5—C4121.8 (2)
N1—C1—H1119.0N1—C5—H5119.1
C2—C1—H1119.0C4—C5—H5119.1
C1—C2—C3118.9 (2)C5—N1—C1119.1 (2)
C1—C2—H2120.5C5—N1—Pd1120.25 (16)
C3—C2—H2120.5C1—N1—Pd1120.64 (17)
C4—C3—C2119.2 (2)N1i—Pd1—N1180.0
C4—C3—H3120.4N1i—Pd1—Cl189.43 (6)
C2—C3—H3120.4N1—Pd1—Cl190.57 (6)
C5—C4—C3119.0 (2)N1i—Pd1—Cl1i90.57 (6)
C5—C4—H4120.5N1—Pd1—Cl1i89.42 (6)
C3—C4—H4120.5Cl1—Pd1—Cl1i180.0
Symmetry code: (i) x, y+1, z.

Experimental details

Crystal data
Chemical formula[PdCl2(C5H5N)2]
Mr335.50
Crystal system, space groupMonoclinic, P21/n
Temperature (K)150
a, b, c (Å)3.9159 (2), 8.7921 (4), 16.2974 (8)
β (°) 90.442 (3)
V3)561.09 (5)
Z2
Radiation typeMo Kα
µ (mm1)2.10
Crystal size (mm)0.45 × 0.10 × 0.07
Data collection
DiffractometerBruker SMART APEXII
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 2003)
Tmin, Tmax0.452, 0.867
No. of measured, independent and
observed (I > 2σ) reflections
5861, 1445, 1314
Rint0.028
(sin θ/λ)max1)0.675
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.023, 0.056, 1.10
No. of reflections1445
No. of parameters70
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.91, 1.03

Computer programs: APEX2 (Bruker, 2004), SAINT (Bruker, 2004), SHELXTL (Sheldrick, 2008).

 

Acknowledgements

The authors are grateful to the National Science Council of Taiwan for financial support.

References

First citationBruker (2004). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.  Google Scholar
First citationLiao, C.-Y. & Lee, H. M. (2006). Acta Cryst. E62, m680–m681.  Web of Science CSD CrossRef IUCr Journals Google Scholar
First citationSheldrick, G. M. (2003). SADABS. University of Göttingen, Germany.  Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationViossat, B., Dung, N.-H. & Robert, F. (1993). Acta Cryst. C49, 84–85.  CSD CrossRef CAS IUCr Journals Google Scholar

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ISSN: 2056-9890
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