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

Gutiérrez Márquez, R.A.; Crisóstomo-Lucas, C.; Morales-Morales, D.; Hernández-Ortega, S.

doi:10.1107/S1600536814009507

metal-organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 70| Part 6| June 2014| Page m218

doi:10.1107/S1600536814009507

Open

access

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

Ricardo Alfredo Gutiérrez Márquez,^a Carmela Crisóstomo-Lucas,^a ^* David Morales-Morales ^a and Simón Hernández-Ortega ^a

^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 Pd^II complex molecule and a half-molecule of 1,4-dioxane, the complete molecule being generated by inversion symmetry. The Pd^II 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 Pd^II 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 π–π interactions [centroid–centroid distance = 3.817 (4) Å] are observed between the pyridine rings.

CCDC reference: 999627

Related literature

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 puckering parameters, see: Cremer & Pople (1975 ).

Experimental

Crystal data

[PdCl(C₁₀H₈N₂)₂]·0.5C₄H₈O₂
M_r = 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 ) T_min = 0.365, T_max = 0.906
7244 measured reflections
2414 independent reflections
1813 reflections with I > 2σ(I)
R_int = 0.055

Refinement

R[F² > 2σ(F²)] = 0.051
wR(F²) = 0.153
S = 1.03
2414 reflections
163 parameters
H-atom parameters constrained
Δρ_max = 1.49 e Å⁻³
Δρ_min = −1.13 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	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); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT; 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; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 ).

Supporting information

CCDC reference: 999627

Crystal structure: contains datablocks I, New_Global_publ_block. DOI: 10.1107/S1600536814009507/is5358sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536814009507/is5358Isup2.hkl

checkCIF report

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 π–π 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).

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

	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.
	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]·0.5C₄H₈O₂	F(000) = 744
M_r = 377.54	D_x = 1.896 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
a = 7.2416 (5) Å	Cell parameters from 4271 reflections
b = 14.6215 (10) Å	θ = 2.8–25.4°
c = 12.9562 (9) Å	µ = 1.80 mm⁻¹
β = 105.423 (2)°	T = 298 K
V = 1322.44 (16) Å³	Prism, yellow
Z = 4	0.40 × 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^-1	R_int = 0.055
ω scans	θ_max = 25.4°, θ_min = 2.8°
Absorption correction: multi-scan (SADABS; Bruker, 2007)	h = −8→8
T_min = 0.365, T_max = 0.906	k = −17→16
7244 measured reflections	l = −14→15
2414 independent reflections

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.051	H-atom parameters constrained
wR(F²) = 0.153	w = 1/[σ²(F_o²) + (0.0933P)²] where P = (F_o² + 2F_c²)/3
S = 1.03	(Δ/σ)_max < 0.001
2414 reflections	Δρ_max = 1.49 e Å⁻³
163 parameters	Δρ_min = −1.13 e Å⁻³

Crystal data top

[PdCl(C₁₀H₈N₂)₂]·0.5C₄H₈O₂	V = 1322.44 (16) Å³
M_r = 377.54	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 7.2416 (5) Å	µ = 1.80 mm⁻¹
b = 14.6215 (10) Å	T = 298 K
c = 12.9562 (9) Å	0.40 × 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)
T_min = 0.365, T_max = 0.906	R_int = 0.055
7244 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.051	0 restraints
wR(F²) = 0.153	H-atom parameters constrained
S = 1.03	Δρ_max = 1.49 e Å⁻³
2414 reflections	Δρ_min = −1.13 e Å⁻³
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

	x	y	z	U_iso*/U_eq
Pd1	0.16709 (6)	0.48172 (3)	−0.14236 (4)	0.0377 (2)
Cl1	0.1430 (3)	0.56553 (14)	−0.29371 (14)	0.0636 (5)
Cl2	0.0446 (3)	0.35687 (14)	−0.24462 (15)	0.0657 (5)
N1	0.1942 (6)	0.4175 (3)	−0.0003 (4)	0.0376 (12)
C2	0.2757 (9)	0.4690 (4)	0.0871 (5)	0.0387 (15)
C3	0.3108 (10)	0.4325 (5)	0.1885 (5)	0.0487 (16)
H3	0.3678	0.4679	0.2481	0.058*
C4	0.2607 (10)	0.3433 (5)	0.2008 (6)	0.0542 (18)
H4	0.2840	0.3179	0.2688	0.065*
C5	0.1779 (9)	0.2927 (5)	0.1140 (5)	0.0512 (17)
H5	0.1436	0.2324	0.1221	0.061*
C6	0.1439 (9)	0.3305 (5)	0.0125 (6)	0.0496 (16)
H6	0.0858	0.2955	−0.0472	0.060*
N7	0.2849 (7)	0.5840 (3)	−0.0419 (4)	0.0401 (12)
C8	0.3249 (8)	0.5628 (4)	0.0654 (5)	0.0382 (14)
C9	0.4075 (9)	0.6253 (5)	0.1418 (5)	0.0493 (16)
H9	0.4329	0.6098	0.2138	0.059*
C10	0.4534 (10)	0.7111 (5)	0.1131 (6)	0.0587 (19)
H10	0.5092	0.7541	0.1650	0.070*
C11	0.4154 (10)	0.7319 (5)	0.0072 (7)	0.059 (2)
H11	0.4461	0.7894	−0.0139	0.071*
C12	0.3315 (9)	0.6679 (4)	−0.0688 (6)	0.0468 (16)
H12	0.3064	0.6833	−0.1408	0.056*
O1	0.4638 (7)	0.5658 (4)	0.4170 (4)	0.0603 (13)
C13	0.6526 (11)	0.5477 (6)	0.4826 (6)	0.0583 (19)
H13A	0.6822	0.5899	0.5426	0.070*
H13B	0.7444	0.5577	0.4413	0.070*
C14	0.6707 (11)	0.4527 (6)	0.5235 (6)	0.062 (2)
H14A	0.6504	0.4105	0.4637	0.075*
H14B	0.7994	0.4432	0.5688	0.075*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Pd1	0.0384 (3)	0.0347 (4)	0.0405 (4)	0.00612 (19)	0.0114 (2)	−0.0008 (2)
Cl1	0.0829 (13)	0.0635 (13)	0.0483 (10)	0.0124 (10)	0.0241 (9)	0.0100 (9)
Cl2	0.0785 (12)	0.0538 (12)	0.0561 (11)	−0.0033 (9)	0.0025 (9)	−0.0138 (9)
N1	0.034 (2)	0.035 (3)	0.047 (3)	0.004 (2)	0.016 (2)	0.000 (2)
C2	0.038 (3)	0.036 (4)	0.048 (4)	0.006 (3)	0.023 (3)	−0.003 (3)
C3	0.053 (4)	0.054 (5)	0.041 (4)	0.000 (3)	0.017 (3)	0.002 (3)
C4	0.062 (4)	0.056 (5)	0.050 (4)	0.006 (3)	0.024 (3)	0.008 (4)
C5	0.058 (4)	0.034 (4)	0.069 (5)	0.000 (3)	0.029 (4)	0.009 (4)
C6	0.048 (4)	0.041 (4)	0.061 (4)	0.001 (3)	0.018 (3)	0.000 (3)
N7	0.036 (3)	0.037 (3)	0.051 (3)	0.004 (2)	0.016 (2)	−0.002 (3)
C8	0.034 (3)	0.033 (3)	0.051 (4)	0.000 (3)	0.019 (3)	−0.009 (3)
C9	0.054 (4)	0.046 (4)	0.051 (4)	−0.002 (3)	0.020 (3)	−0.010 (3)
C10	0.065 (4)	0.044 (4)	0.070 (5)	−0.008 (3)	0.023 (4)	−0.025 (4)
C11	0.055 (4)	0.025 (3)	0.108 (6)	0.002 (3)	0.043 (4)	0.000 (4)
C12	0.051 (4)	0.034 (4)	0.060 (4)	0.003 (3)	0.022 (3)	0.005 (3)
O1	0.078 (3)	0.055 (3)	0.052 (3)	0.013 (3)	0.023 (3)	0.013 (3)
C13	0.066 (5)	0.058 (5)	0.055 (4)	−0.007 (4)	0.022 (4)	−0.006 (4)
C14	0.062 (5)	0.062 (5)	0.064 (5)	0.008 (4)	0.018 (4)	0.014 (4)

Geometric parameters (Å, º) top

Pd1—N7	2.017 (5)	C8—C9	1.363 (9)
Pd1—N1	2.029 (5)	C9—C10	1.374 (10)
Pd1—Cl1	2.2793 (18)	C9—H9	0.9300
Pd1—Cl2	2.2912 (19)	C10—C11	1.360 (11)
N1—C6	1.345 (8)	C10—H10	0.9300
N1—C2	1.357 (8)	C11—C12	1.376 (9)
C2—C3	1.377 (9)	C11—H11	0.9300
C2—C8	1.463 (9)	C12—H12	0.9300
C3—C4	1.375 (10)	O1—C14ⁱ	1.420 (8)
C3—H3	0.9300	O1—C13	1.430 (9)
C4—C5	1.346 (10)	C13—C14	1.479 (11)
C4—H4	0.9300	C13—H13A	0.9700
C5—C6	1.387 (9)	C13—H13B	0.9700
C5—H5	0.9300	C14—O1ⁱ	1.420 (8)
C6—H6	0.9300	C14—H14A	0.9700
N7—C12	1.344 (8)	C14—H14B	0.9700
N7—C8	1.377 (8)

N7—Pd1—N1	80.5 (2)	C9—C8—C2	124.8 (6)
N7—Pd1—Cl1	94.55 (16)	N7—C8—C2	114.1 (5)
N1—Pd1—Cl1	174.96 (15)	C8—C9—C10	120.4 (7)
N7—Pd1—Cl2	175.00 (15)	C8—C9—H9	119.8
N1—Pd1—Cl2	94.89 (15)	C10—C9—H9	119.8
Cl1—Pd1—Cl2	90.09 (7)	C11—C10—C9	118.5 (7)
C6—N1—C2	119.6 (5)	C11—C10—H10	120.7
C6—N1—Pd1	125.8 (5)	C9—C10—H10	120.7
C2—N1—Pd1	114.6 (4)	C10—C11—C12	120.2 (7)
N1—C2—C3	120.6 (6)	C10—C11—H11	119.9
N1—C2—C8	115.7 (5)	C12—C11—H11	119.9
C3—C2—C8	123.7 (6)	N7—C12—C11	121.9 (6)
C4—C3—C2	119.4 (6)	N7—C12—H12	119.0
C4—C3—H3	120.3	C11—C12—H12	119.0
C2—C3—H3	120.3	C14ⁱ—O1—C13	109.1 (6)
C5—C4—C3	119.8 (7)	O1—C13—C14	111.5 (6)
C5—C4—H4	120.1	O1—C13—H13A	109.3
C3—C4—H4	120.1	C14—C13—H13A	109.3
C4—C5—C6	120.0 (6)	O1—C13—H13B	109.3
C4—C5—H5	120.0	C14—C13—H13B	109.3
C6—C5—H5	120.0	H13A—C13—H13B	108.0
N1—C6—C5	120.6 (6)	O1ⁱ—C14—C13	111.4 (6)
N1—C6—H6	119.7	O1ⁱ—C14—H14A	109.3
C5—C6—H6	119.7	C13—C14—H14A	109.3
C12—N7—C8	117.8 (5)	O1ⁱ—C14—H14B	109.3
C12—N7—Pd1	127.0 (5)	C13—C14—H14B	109.3
C8—N7—Pd1	115.1 (4)	H14A—C14—H14B	108.0
C9—C8—N7	121.1 (6)

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···O1	0.93	2.55	3.471 (9)	170
C5—H5···O1ⁱⁱ	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: (ii) −x+1/2, y−1/2, −z+1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	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+1/2, y−1/2, −z+1/2.

References

Bruker (2007). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Cremer, D. & Pople, J. A. (1975). J. Am. Chem. Soc. 97, 1354–1358. CrossRef CAS Web of Science Google Scholar
Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854. Web of Science CrossRef CAS IUCr Journals Google Scholar
Ferbinteanu, M., Cimpoesu, F., Andruh, M. & Rochon, F. (1998). Polyhedron, 17, 3671–3679. Web of Science CSD CrossRef CAS Google Scholar
Kim, N.-H., Hwang, I.-C. & Ha, K. (2009). Acta Cryst. E65, m615–m616. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Maekawa, M., Munakata, M., Kitagawa, S. & Nakamura, M. (1991). Anal. Sci. 7, 521–522. CrossRef CAS Web of Science Google Scholar
Pazderski, 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
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. Web of Science CSD CrossRef PubMed CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar
Vicente, J., Abad, J. A., Rink, B. & Arellano, M. C. R. (1997). Private communication (refcode PYCXMN02). CCDC, Cambridge, England. Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 70| Part 6| June 2014| Page m218

doi:10.1107/S1600536814009507

Open

access