metal-organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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ISSN: 2056-9890

(2,2′-Bi­pyridine-κ2N,N′)di­chloridopalladium(II) 1,4-dioxane hemisolvate

aInstituto de Química, Universidad Nacional Autónoma de México, Circuito Exterior, Ciudad Universitaria, Coyoacán, c.p. 04510, México, DF, Mexico
*Correspondence e-mail: carmelacrisostomo@yahoo.com.mx

(Received 8 April 2014; accepted 28 April 2014; online 17 May 2014)

The asymmetric unit of the title compound, [PdCl2(C10H8N2)]·0.5C4H8O2, consists of one PdII complex mol­ecule and a half-mol­ecule of 1,4-dioxane, the complete mol­ecule being generated by inversion symmetry. The PdII atom has an almost square-planar coordination formed by the 2,2′-bi­pyridine ligand and two chloride ligands. Two intra­molecular C—H⋯Cl hydrogen bonds occur. In the crystal, the PdII complex and 1,4-dioxane mol­ecules are connected by C—H⋯O hydrogen bonds, forming a layer parallel to (10-1). Within the layer, weak ππ inter­actions [centroid–centroid distance = 3.817 (4) Å] are observed between the pyridine rings.

Related literature

For related structures, see: Maekawa et al. (1991[Maekawa, M., Munakata, M., Kitagawa, S. & Nakamura, M. (1991). Anal. Sci. 7, 521-522.]); Vicente et al. (1997[Vicente, J., Abad, J. A., Rink, B. & Arellano, M. C. R. (1997). Private communication (refcode PYCXMN02). CCDC, Cambridge, England.]); Kim et al. (2009[Kim, N.-H., Hwang, I.-C. & Ha, K. (2009). Acta Cryst. E65, m615-m616.]). For palladium complexes with chelate ligands, see: Pointillart et al. (2007[Pointillart, F., Train, C., Villain, F., Cartier dit Moulin, C., Gredin, P., Chamoreau, L., Gruselle, M., Aullon, G., Alvarez, S. & Verdaguer, M. (2007). J. Am. Chem. Soc. 129, 1327-1334.]); Pazderski et al. (2006[Pazderski, L., Szlyk, E., Sitkowski, J., Kamienski, B., Kozerski, L., Tousek, J. & Marek, R. (2006). Magn. Reson. Chem. 44, 163-170.]); Ferbinteanu et al. (1998[Ferbinteanu, M., Cimpoesu, F., Andruh, M. & Rochon, F. (1998). Polyhedron, 17, 3671-3679.]). For puckering parameters, see: Cremer & Pople (1975[Cremer, D. & Pople, J. A. (1975). J. Am. Chem. Soc. 97, 1354-1358.]).

[Scheme 1]

Experimental

Crystal data
  • [PdCl(C10H8N2)2]·0.5C4H8O2

  • Mr = 377.54

  • Monoclinic, P 21 /n

  • a = 7.2416 (5) Å

  • b = 14.6215 (10) Å

  • c = 12.9562 (9) Å

  • β = 105.423 (2)°

  • V = 1322.44 (16) Å3

  • Z = 4

  • Mo Kα radiation

  • μ = 1.80 mm−1

  • T = 298 K

  • 0.40 × 0.07 × 0.06 mm

Data collection
  • Bruker APEXII CCD area-detector diffractometer

  • Absorption correction: multi-scan (SADABS; Bruker, 2007[Bruker (2007). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]) Tmin = 0.365, Tmax = 0.906

  • 7244 measured reflections

  • 2414 independent reflections

  • 1813 reflections with I > 2σ(I)

  • Rint = 0.055

Refinement
  • R[F2 > 2σ(F2)] = 0.051

  • wR(F2) = 0.153

  • S = 1.03

  • 2414 reflections

  • 163 parameters

  • H-atom parameters constrained

  • Δρmax = 1.49 e Å−3

  • Δρmin = −1.13 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
C3—H3⋯O1 0.93 2.55 3.471 (9) 170
C5—H5⋯O1i 0.93 2.57 3.464 (8) 163
C9—H9⋯O1 0.93 2.66 3.587 (8) 174
C6—H6⋯Cl2 0.93 2.65 3.239 (7) 122
C12—H12⋯Cl1 0.93 2.65 3.238 (7) 122
Symmetry code: (i) [-x+{\script{1\over 2}}, y-{\script{1\over 2}}, -z+{\script{1\over 2}}].

Data collection: APEX2 (Bruker, 2007[Bruker (2007). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 2007[Bruker (2007). APEX2, SAINT and SADABS. 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: SHELXL2013 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: ORTEP-3 (Farrugia, 2012[Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849-854.]) and SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009[Spek, A. L. (2009). Acta Cryst. D65, 148-155.]).

Supporting information


Comment top

In recent years the use of chelate ligands of the type N—N has been of great interest due to the versatility of its applications. This is particularly true in the case of supramolecular chemistry and crystal engineering, where these kind of chelates are often used as blocking ligands and the study of their metallic derivatives in the solid state has revealed the tremendous importance of non-covalent interactions and advanced the understanding of the reactivity of these species (Pointillart et al., 2007; Pazderski et al., 2006). Complexes of group 10 elements with these ligands often present square planar geometries, and in some cases, they can exhibit interesting dimeric and trimeric structures (Ferbinteanu et al. 1998). The coordination complex [PdCl2(C10H8N2)] has been described before (Maekawa et al., 1991), and as CH2Cl2 solvate (Vicente et al., 1997; Kim et al., 2009). Here, we describe the structure of the title complex and its interaction with 1,4-dioxane as solvate.

The Pd complex crystallizes as 1,4-dioxane solvate and the solvent is determined as a half-molecule in the asymmetric unit; the symmetry operation 1 - x, 1 - y, 1 - z is necessary to generate the whole molecule. The title compound has similar values of bond distances and angles to the previously described CH2Cl2 solvate (Maekawa et al., 1991; Vicente et al., 1997; Kim et al., 2009). According to the Cremer & Pople puckering parameters (Cremer & Pople, 1975), the dioxane molecule has a chair conformation [Q=0.553 (8), θ=180.00 (1)°, ϕ =0°]. In the asymmetric unit, the O atom is bonded to H3—C3 and H9—C9 in a bifurcated fashion (Fig. 1). When the symmetry code (1 - x, 1 - y, 1 - z) is applied, a centrosymmetric structure of Pd complex–1,4-dioxane (2/1) is generated. In addition, the O atom is linked by O···H5—C5(bipy) (Table 1 and Fig. 2). As a result of these interactions, the bipyridine complexes are bonded by a weak ππ stacking interaction [Cg1(N1/C2–C6)···Cg2(N7/C8–C12) 3.817 (4) Å].

Related literature top

For related structures, see: Maekawa et al. (1991); Vicente et al. (1997); Kim et al. (2009). For palladium complexes with chelate ligands, see: Pointillart et al. (2007); Pazderski et al. (2006); Ferbinteanu et al. (1998). For pukering parameters, see: Cremer & Pople (1975).

Experimental top

To a solution of [Pd(MeCN)2Cl2] (0.13 g, 0.638 mmol) in acetone (10 ml), 2,2'-bipyridine (0.1 g, 0.64 mmol) was added under stirring. The resulting orange solution was allowed to react for 2 h under stirring at room temperature. After this time the solution was filtered and the solvent taken off under vacuum to produce a yellow solid of [(bipy)PdCl2]. Crystals suitable for X-ray diffraction experiments were obtained from a dimethylformamide/dioxane solvent system at room temperature. 1H NMR (DMSO-d6): δ 7.83 (t, 1H, CH), 8.38 (t, 1H, CH), 8.60 (d, 1H, CH), 9.14 (d, 1H, CH); 13C{1H}NMR (DMSO-D6): δ 124.3 (s, CH), 127.8 (s, CH), 141.7 (s, CH). 150.1 (s, CH). 156.9 (s, C).

Refinement top

H atoms were included in calculated positions (C—H = 0.97 Å for methylene and C—H = 0.96 Å for aromatic ring), and refined using a riding model with Uiso(H) = 1.2Ueq(C). 4 reflections were omitted from the final refinement.

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 2012) and SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures top
[Figure 1] Fig. 1. The structure of the title compound, the displacement ellipsoids are drawn at the 40% of probability. Only the hydrogen atom involved in intermolecular interaction are drawn.
[Figure 2] Fig. 2. Crystal packing diagram of the title compound. Hydrogen bonds are drawn as dashed lines.
(2,2'-Bipyridine-κ2N,N')dichloridopalladium(II) 1,4-dioxane hemisolvate top
Crystal data top
[PdCl(C10H8N2)2]·0.5C4H8O2F(000) = 744
Mr = 377.54Dx = 1.896 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
a = 7.2416 (5) ÅCell parameters from 4271 reflections
b = 14.6215 (10) Åθ = 2.8–25.4°
c = 12.9562 (9) ŵ = 1.80 mm1
β = 105.423 (2)°T = 298 K
V = 1322.44 (16) Å3Prism, yellow
Z = 40.40 × 0.07 × 0.06 mm
Data collection top
Bruker APEXII CCD area-detector
diffractometer
1813 reflections with I > 2σ(I)
Detector resolution: 0.83 pixels mm-1Rint = 0.055
ω scansθmax = 25.4°, θmin = 2.8°
Absorption correction: multi-scan
(SADABS; Bruker, 2007)
h = 88
Tmin = 0.365, Tmax = 0.906k = 1716
7244 measured reflectionsl = 1415
2414 independent reflections
Refinement top
Refinement on F20 restraints
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.051H-atom parameters constrained
wR(F2) = 0.153 w = 1/[σ2(Fo2) + (0.0933P)2]
where P = (Fo2 + 2Fc2)/3
S = 1.03(Δ/σ)max < 0.001
2414 reflectionsΔρmax = 1.49 e Å3
163 parametersΔρmin = 1.13 e Å3
Crystal data top
[PdCl(C10H8N2)2]·0.5C4H8O2V = 1322.44 (16) Å3
Mr = 377.54Z = 4
Monoclinic, P21/nMo Kα radiation
a = 7.2416 (5) ŵ = 1.80 mm1
b = 14.6215 (10) ÅT = 298 K
c = 12.9562 (9) Å0.40 × 0.07 × 0.06 mm
β = 105.423 (2)°
Data collection top
Bruker APEXII CCD area-detector
diffractometer
2414 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2007)
1813 reflections with I > 2σ(I)
Tmin = 0.365, Tmax = 0.906Rint = 0.055
7244 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0510 restraints
wR(F2) = 0.153H-atom parameters constrained
S = 1.03Δρmax = 1.49 e Å3
2414 reflectionsΔρmin = 1.13 e Å3
163 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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Pd10.16709 (6)0.48172 (3)0.14236 (4)0.0377 (2)
Cl10.1430 (3)0.56553 (14)0.29371 (14)0.0636 (5)
Cl20.0446 (3)0.35687 (14)0.24462 (15)0.0657 (5)
N10.1942 (6)0.4175 (3)0.0003 (4)0.0376 (12)
C20.2757 (9)0.4690 (4)0.0871 (5)0.0387 (15)
C30.3108 (10)0.4325 (5)0.1885 (5)0.0487 (16)
H30.36780.46790.24810.058*
C40.2607 (10)0.3433 (5)0.2008 (6)0.0542 (18)
H40.28400.31790.26880.065*
C50.1779 (9)0.2927 (5)0.1140 (5)0.0512 (17)
H50.14360.23240.12210.061*
C60.1439 (9)0.3305 (5)0.0125 (6)0.0496 (16)
H60.08580.29550.04720.060*
N70.2849 (7)0.5840 (3)0.0419 (4)0.0401 (12)
C80.3249 (8)0.5628 (4)0.0654 (5)0.0382 (14)
C90.4075 (9)0.6253 (5)0.1418 (5)0.0493 (16)
H90.43290.60980.21380.059*
C100.4534 (10)0.7111 (5)0.1131 (6)0.0587 (19)
H100.50920.75410.16500.070*
C110.4154 (10)0.7319 (5)0.0072 (7)0.059 (2)
H110.44610.78940.01390.071*
C120.3315 (9)0.6679 (4)0.0688 (6)0.0468 (16)
H120.30640.68330.14080.056*
O10.4638 (7)0.5658 (4)0.4170 (4)0.0603 (13)
C130.6526 (11)0.5477 (6)0.4826 (6)0.0583 (19)
H13A0.68220.58990.54260.070*
H13B0.74440.55770.44130.070*
C140.6707 (11)0.4527 (6)0.5235 (6)0.062 (2)
H14A0.65040.41050.46370.075*
H14B0.79940.44320.56880.075*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Pd10.0384 (3)0.0347 (4)0.0405 (4)0.00612 (19)0.0114 (2)0.0008 (2)
Cl10.0829 (13)0.0635 (13)0.0483 (10)0.0124 (10)0.0241 (9)0.0100 (9)
Cl20.0785 (12)0.0538 (12)0.0561 (11)0.0033 (9)0.0025 (9)0.0138 (9)
N10.034 (2)0.035 (3)0.047 (3)0.004 (2)0.016 (2)0.000 (2)
C20.038 (3)0.036 (4)0.048 (4)0.006 (3)0.023 (3)0.003 (3)
C30.053 (4)0.054 (5)0.041 (4)0.000 (3)0.017 (3)0.002 (3)
C40.062 (4)0.056 (5)0.050 (4)0.006 (3)0.024 (3)0.008 (4)
C50.058 (4)0.034 (4)0.069 (5)0.000 (3)0.029 (4)0.009 (4)
C60.048 (4)0.041 (4)0.061 (4)0.001 (3)0.018 (3)0.000 (3)
N70.036 (3)0.037 (3)0.051 (3)0.004 (2)0.016 (2)0.002 (3)
C80.034 (3)0.033 (3)0.051 (4)0.000 (3)0.019 (3)0.009 (3)
C90.054 (4)0.046 (4)0.051 (4)0.002 (3)0.020 (3)0.010 (3)
C100.065 (4)0.044 (4)0.070 (5)0.008 (3)0.023 (4)0.025 (4)
C110.055 (4)0.025 (3)0.108 (6)0.002 (3)0.043 (4)0.000 (4)
C120.051 (4)0.034 (4)0.060 (4)0.003 (3)0.022 (3)0.005 (3)
O10.078 (3)0.055 (3)0.052 (3)0.013 (3)0.023 (3)0.013 (3)
C130.066 (5)0.058 (5)0.055 (4)0.007 (4)0.022 (4)0.006 (4)
C140.062 (5)0.062 (5)0.064 (5)0.008 (4)0.018 (4)0.014 (4)
Geometric parameters (Å, º) top
Pd1—N72.017 (5)C8—C91.363 (9)
Pd1—N12.029 (5)C9—C101.374 (10)
Pd1—Cl12.2793 (18)C9—H90.9300
Pd1—Cl22.2912 (19)C10—C111.360 (11)
N1—C61.345 (8)C10—H100.9300
N1—C21.357 (8)C11—C121.376 (9)
C2—C31.377 (9)C11—H110.9300
C2—C81.463 (9)C12—H120.9300
C3—C41.375 (10)O1—C14i1.420 (8)
C3—H30.9300O1—C131.430 (9)
C4—C51.346 (10)C13—C141.479 (11)
C4—H40.9300C13—H13A0.9700
C5—C61.387 (9)C13—H13B0.9700
C5—H50.9300C14—O1i1.420 (8)
C6—H60.9300C14—H14A0.9700
N7—C121.344 (8)C14—H14B0.9700
N7—C81.377 (8)
N7—Pd1—N180.5 (2)C9—C8—C2124.8 (6)
N7—Pd1—Cl194.55 (16)N7—C8—C2114.1 (5)
N1—Pd1—Cl1174.96 (15)C8—C9—C10120.4 (7)
N7—Pd1—Cl2175.00 (15)C8—C9—H9119.8
N1—Pd1—Cl294.89 (15)C10—C9—H9119.8
Cl1—Pd1—Cl290.09 (7)C11—C10—C9118.5 (7)
C6—N1—C2119.6 (5)C11—C10—H10120.7
C6—N1—Pd1125.8 (5)C9—C10—H10120.7
C2—N1—Pd1114.6 (4)C10—C11—C12120.2 (7)
N1—C2—C3120.6 (6)C10—C11—H11119.9
N1—C2—C8115.7 (5)C12—C11—H11119.9
C3—C2—C8123.7 (6)N7—C12—C11121.9 (6)
C4—C3—C2119.4 (6)N7—C12—H12119.0
C4—C3—H3120.3C11—C12—H12119.0
C2—C3—H3120.3C14i—O1—C13109.1 (6)
C5—C4—C3119.8 (7)O1—C13—C14111.5 (6)
C5—C4—H4120.1O1—C13—H13A109.3
C3—C4—H4120.1C14—C13—H13A109.3
C4—C5—C6120.0 (6)O1—C13—H13B109.3
C4—C5—H5120.0C14—C13—H13B109.3
C6—C5—H5120.0H13A—C13—H13B108.0
N1—C6—C5120.6 (6)O1i—C14—C13111.4 (6)
N1—C6—H6119.7O1i—C14—H14A109.3
C5—C6—H6119.7C13—C14—H14A109.3
C12—N7—C8117.8 (5)O1i—C14—H14B109.3
C12—N7—Pd1127.0 (5)C13—C14—H14B109.3
C8—N7—Pd1115.1 (4)H14A—C14—H14B108.0
C9—C8—N7121.1 (6)
Symmetry code: (i) x+1, y+1, z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C3—H3···O10.932.553.471 (9)170
C5—H5···O1ii0.932.573.464 (8)163
C9—H9···O10.932.663.587 (8)174
C6—H6···Cl20.932.653.239 (7)122
C12—H12···Cl10.932.653.238 (7)122
Symmetry code: (ii) x+1/2, y1/2, z+1/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C3—H3···O10.932.553.471 (9)170
C5—H5···O1i0.932.573.464 (8)163
C9—H9···O10.932.663.587 (8)174
C6—H6···Cl20.932.653.239 (7)122
C12—H12···Cl10.932.653.238 (7)122
Symmetry code: (i) x+1/2, y1/2, z+1/2.
 

References

First citationBruker (2007). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.  Google Scholar
First citationCremer, D. & Pople, J. A. (1975). J. Am. Chem. Soc. 97, 1354–1358.  CrossRef CAS Web of Science Google Scholar
First citationFarrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationFerbinteanu, M., Cimpoesu, F., Andruh, M. & Rochon, F. (1998). Polyhedron, 17, 3671–3679.  Web of Science CSD CrossRef CAS Google Scholar
First citationKim, N.-H., Hwang, I.-C. & Ha, K. (2009). Acta Cryst. E65, m615–m616.  Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
First citationMaekawa, M., Munakata, M., Kitagawa, S. & Nakamura, M. (1991). Anal. Sci. 7, 521–522.  CrossRef CAS Web of Science Google Scholar
First citationPazderski, L., Szlyk, E., Sitkowski, J., Kamienski, B., Kozerski, L., Tousek, J. & Marek, R. (2006). Magn. Reson. Chem. 44, 163–170.  Web of Science CrossRef PubMed CAS Google Scholar
First citationPointillart, F., Train, C., Villain, F., Cartier dit Moulin, C., Gredin, P., Chamoreau, L., Gruselle, M., Aullon, G., Alvarez, S. & Verdaguer, M. (2007). J. Am. Chem. Soc. 129, 1327–1334.  Web of Science CSD CrossRef PubMed CAS Google Scholar
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First citationSpek, A. L. (2009). Acta Cryst. D65, 148–155.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationVicente, J., Abad, J. A., Rink, B. & Arellano, M. C. R. (1997). Private communication (refcode PYCXMN02). CCDC, Cambridge, England.  Google Scholar

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