metal-organic compounds
trans-Dichloridobis(pyridazine-κN)palladium(II)
aDépartement de Chimie, Université de Montréal, Pavillon J.-A. Bombardier, 5155 Decelles Avenue, Montréal, Québec, H3T 2B1, Canada
*Correspondence e-mail: baptiste.laramee-milette@umontreal.ca
The title compound, [PdCl2(C4H4N2)2], contains two crystallographically unique complexes; the PdII atom lies on an inversion center in both cases. The two pyridazine units bonded to the PdII atom are thus coplanar although dihedral angles within each complex are different. In one complex, the angle between the ring plane and Pd—Cl bond is almost perpendicular [89.4 (1)°], while the other is tilted with an angle of 60.0 (1)°. In the crystal, weak C⋯H—N hydrogen bonds and C⋯H—Cl interactions connect the two independent complex molecules.
CCDC reference: 974817
Related literature
For related pyridazine copper, nickel, silver and rhenium metal complexes, see: Otieno et al. (1995); Cano et al. (2000); Degtyarenko et al. (2008) and Raimondi et al. (2012), respectively.
Experimental
Crystal data
|
Data collection: APEX2 (Bruker, 2011); cell SAINT (Bruker, 2011); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: publCIF (Westrip, 2010).
Supporting information
CCDC reference: 974817
https://doi.org/10.1107/S1600536813032716/nk2214sup1.cif
contains datablocks I, New_Global_Publ_Block. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536813032716/nk2214Isup2.hkl
Supporting information file. DOI: https://doi.org/10.1107/S1600536813032716/nk2214Isup3.cdx
trans-bis(chloro)-bis(pyridazine-κN)palladium(II). Pyridazine (0.12 mg, 0.0015 mmol) is added into a nitromethane solution (1.0 mL) of PdCl2(MeCN)2 (0.39 mg, 0.0015 mmol), and heated to 80 °C for 12 hours. After 3 hours, a yellow precipitate started to form. The precipitate was isolated by filtration and redissolved in a minimum amount of dimethyl sulfoxide. Clear bronze crystals were obtained by slow diffusion of THF into the DMSO solution over 2 weeks. 1H NMR (400 MHz, CD3NO2) delta ppm 9.15-9.13 (t, J=3.5 Hz. 4 H) 8.80 (t, J=3.2 Hz, 4 H).
H atoms were positioned geometrically (C—H 0.95 Å) and included in the
in the riding model approximation; their temperature displacement parameters were set to 1.2 times the equivalent isotropic temperature factors of the parent site.In the present work, a square planar trans-bis(chloro)-bis(pyridazine-κN) palladium(II) metal complex has been synthesized. Similar metal complexes are already known in coordination polymer chemistry (Degtyarenko et al., 2008)).
The molecular structure of the title compound is illustrated in Fig. 1, where two molecules are found in the
The bond distances are unexceptional. In one complex the plane of the pyridazyl ring is perpendicular with respect to the Cl–Pd–Cl axis, while in the second molecules the ring is slightly tilted with an angle of 60 (1)°, which may be due to the presence of weak hydrogen bonds.For related pyridazine copper, nickel, silver and rhenium metal complexes, see: Otieno et al. (1995); Cano et al. (2000); Degtyarenko et al. (2008) and Raimondi et al. (2012), respectively.
Data collection: APEX2 (Bruker, 2011); cell
SAINT (Bruker, 2011); data reduction: SAINT (Bruker , 2011); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: publCIF (Westrip, 2010).Fig. 1. The molecular structure of trans-bis(chloro)-bis(pyridazine-κN)palladium(II), with atom labels and displacement ellipsoids drawn at the 80% probability level. The two halves of both complexes are related by inversion symmetry. |
[PdCl2(C4H4N2)2] | Z = 2 |
Mr = 337.48 | F(000) = 328 |
Triclinic, P1 | Dx = 2.106 Mg m−3 |
Hall symbol: -P 1 | Cu Kα radiation, λ = 1.54178 Å |
a = 7.9910 (1) Å | Cell parameters from 9992 reflections |
b = 8.4273 (1) Å | θ = 5.9–70.9° |
c = 9.6172 (2) Å | µ = 18.45 mm−1 |
α = 84.614 (1)° | T = 150 K |
β = 67.682 (1)° | Block, brown |
γ = 63.134 (1)° | 0.08 × 0.06 × 0.06 mm |
V = 532.09 (2) Å3 |
Bruker APEXII CCD diffractometer | 1971 independent reflections |
Radiation source: fine-focus sealed tube | 1957 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.018 |
φ and ω scans | θmax = 70.9°, θmin = 5.0° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −9→9 |
Tmin = 0.216, Tmax = 0.260 | k = −9→10 |
13678 measured reflections | l = −11→11 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.023 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.068 | H-atom parameters constrained |
S = 1.07 | w = 1/[σ2(Fo2) + (0.0456P)2 + 0.8794P] where P = (Fo2 + 2Fc2)/3 |
1971 reflections | (Δ/σ)max < 0.001 |
139 parameters | Δρmax = 0.97 e Å−3 |
0 restraints | Δρmin = −0.75 e Å−3 |
[PdCl2(C4H4N2)2] | γ = 63.134 (1)° |
Mr = 337.48 | V = 532.09 (2) Å3 |
Triclinic, P1 | Z = 2 |
a = 7.9910 (1) Å | Cu Kα radiation |
b = 8.4273 (1) Å | µ = 18.45 mm−1 |
c = 9.6172 (2) Å | T = 150 K |
α = 84.614 (1)° | 0.08 × 0.06 × 0.06 mm |
β = 67.682 (1)° |
Bruker APEXII CCD diffractometer | 1971 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 1957 reflections with I > 2σ(I) |
Tmin = 0.216, Tmax = 0.260 | Rint = 0.018 |
13678 measured reflections |
R[F2 > 2σ(F2)] = 0.023 | 0 restraints |
wR(F2) = 0.068 | H-atom parameters constrained |
S = 1.07 | Δρmax = 0.97 e Å−3 |
1971 reflections | Δρmin = −0.75 e Å−3 |
139 parameters |
Experimental. X-ray crystallographic data for I were collected from a single-crystal sample, which was mounted on a loop fiber. Data were collected using a Bruker Platform diffractometer, equipped with a Bruker SMART 4 K Charged-Coupled Device (CCD) Area Detector using the program APEX2 and a Nonius FR591 rotating anode equiped with a Montel 200 optics The crystal-to-detector distance was 5.0 cm, and the data collection was carried out in 512 x 512 pixel mode. The initial unit-cell parameters were determined by a least-squares fit of the angular setting of strong reflections, collected by a 10.0 degree scan in 33 frames over four different parts of the reciprocal space (132 frames total). One complete sphere of data was collected, to better than 0.80 Å resolution. |
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. |
x | y | z | Uiso*/Ueq | ||
Pd1 | 0.5000 | 0.5000 | 1.0000 | 0.01106 (11) | |
Cl1 | 0.18605 (9) | 0.51044 (8) | 1.13317 (7) | 0.01691 (15) | |
N1 | 0.3652 (3) | 0.7675 (3) | 1.0036 (3) | 0.0132 (5) | |
N2 | 0.3068 (3) | 0.8322 (3) | 0.8878 (3) | 0.0170 (5) | |
C1 | 0.2179 (4) | 1.0087 (4) | 0.8859 (3) | 0.0162 (5) | |
H1 | 0.1750 | 1.0556 | 0.8050 | 0.019* | |
C2 | 0.1834 (4) | 1.1295 (4) | 0.9954 (3) | 0.0171 (6) | |
H2 | 0.1207 | 1.2548 | 0.9892 | 0.021* | |
C3 | 0.2440 (4) | 1.0592 (4) | 1.1123 (3) | 0.0186 (6) | |
H3 | 0.2238 | 1.1347 | 1.1906 | 0.022* | |
C4 | 0.3358 (4) | 0.8747 (4) | 1.1130 (3) | 0.0166 (5) | |
H4 | 0.3785 | 0.8237 | 1.1932 | 0.020* | |
Pd2 | 0.5000 | 0.0000 | 0.5000 | 0.01214 (11) | |
Cl2 | 0.20050 (9) | 0.03267 (8) | 0.49612 (7) | 0.01848 (16) | |
N3 | 0.3747 (3) | 0.2644 (3) | 0.5494 (3) | 0.0141 (5) | |
N4 | 0.3653 (3) | 0.3203 (3) | 0.6799 (3) | 0.0169 (5) | |
C5 | 0.2860 (4) | 0.4951 (4) | 0.7117 (3) | 0.0175 (5) | |
H5 | 0.2774 | 0.5357 | 0.8042 | 0.021* | |
C6 | 0.2145 (4) | 0.6235 (4) | 0.6188 (4) | 0.0191 (6) | |
H6 | 0.1618 | 0.7473 | 0.6452 | 0.023* | |
C7 | 0.2239 (4) | 0.5624 (4) | 0.4878 (3) | 0.0196 (6) | |
H7 | 0.1769 | 0.6429 | 0.4197 | 0.023* | |
C8 | 0.3034 (4) | 0.3806 (4) | 0.4574 (3) | 0.0156 (5) | |
H8 | 0.3078 | 0.3366 | 0.3680 | 0.019* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Pd1 | 0.01260 (16) | 0.00575 (16) | 0.01452 (16) | −0.00218 (11) | −0.00736 (11) | 0.00139 (10) |
Cl1 | 0.0152 (3) | 0.0133 (3) | 0.0216 (3) | −0.0055 (2) | −0.0080 (2) | 0.0037 (2) |
N1 | 0.0136 (10) | 0.0093 (11) | 0.0164 (11) | −0.0043 (9) | −0.0067 (9) | 0.0027 (9) |
N2 | 0.0188 (11) | 0.0152 (12) | 0.0160 (11) | −0.0060 (9) | −0.0078 (9) | 0.0023 (9) |
C1 | 0.0147 (12) | 0.0135 (13) | 0.0184 (12) | −0.0041 (10) | −0.0077 (10) | 0.0048 (10) |
C2 | 0.0139 (13) | 0.0115 (14) | 0.0226 (14) | −0.0038 (11) | −0.0063 (11) | 0.0029 (11) |
C3 | 0.0201 (14) | 0.0147 (15) | 0.0219 (14) | −0.0060 (11) | −0.0105 (11) | −0.0007 (11) |
C4 | 0.0187 (13) | 0.0126 (13) | 0.0194 (13) | −0.0050 (11) | −0.0108 (11) | 0.0018 (11) |
Pd2 | 0.01237 (16) | 0.00725 (17) | 0.01663 (16) | −0.00237 (11) | −0.00801 (11) | 0.00169 (11) |
Cl2 | 0.0156 (3) | 0.0139 (3) | 0.0278 (3) | −0.0051 (2) | −0.0121 (3) | 0.0025 (2) |
N3 | 0.0125 (10) | 0.0092 (11) | 0.0197 (12) | −0.0032 (9) | −0.0069 (9) | 0.0000 (9) |
N4 | 0.0168 (11) | 0.0162 (12) | 0.0179 (11) | −0.0063 (9) | −0.0082 (9) | 0.0022 (9) |
C5 | 0.0157 (12) | 0.0131 (13) | 0.0214 (13) | −0.0040 (10) | −0.0065 (11) | −0.0039 (10) |
C6 | 0.0143 (13) | 0.0102 (14) | 0.0266 (14) | −0.0031 (11) | −0.0041 (11) | −0.0006 (11) |
C7 | 0.0164 (13) | 0.0173 (15) | 0.0214 (14) | −0.0048 (11) | −0.0077 (11) | 0.0048 (12) |
C8 | 0.0157 (12) | 0.0135 (13) | 0.0169 (12) | −0.0043 (10) | −0.0085 (10) | 0.0025 (10) |
Pd1—N1 | 2.009 (2) | Pd2—N3 | 2.003 (2) |
Pd1—N1i | 2.009 (2) | Pd2—N3ii | 2.004 (2) |
Pd1—Cl1 | 2.3072 (6) | Pd2—Cl2 | 2.2969 (6) |
Pd1—Cl1i | 2.3073 (6) | Pd2—Cl2ii | 2.2969 (6) |
N1—C4 | 1.333 (4) | N3—C8 | 1.335 (4) |
N1—N2 | 1.344 (3) | N3—N4 | 1.346 (3) |
N2—C1 | 1.329 (4) | N4—C5 | 1.327 (3) |
C1—C2 | 1.396 (4) | C5—C6 | 1.393 (4) |
C1—H1 | 0.9500 | C5—H5 | 0.9500 |
C2—C3 | 1.370 (4) | C6—C7 | 1.369 (4) |
C2—H2 | 0.9500 | C6—H6 | 0.9500 |
C3—C4 | 1.388 (4) | C7—C8 | 1.377 (4) |
C3—H3 | 0.9500 | C7—H7 | 0.9500 |
C4—H4 | 0.9500 | C8—H8 | 0.9500 |
N1—Pd1—N1i | 180.0 | N3—Pd2—N3ii | 180.000 (1) |
N1—Pd1—Cl1 | 89.26 (7) | N3—Pd2—Cl2 | 89.44 (7) |
N1i—Pd1—Cl1 | 90.74 (7) | N3ii—Pd2—Cl2 | 90.56 (7) |
N1—Pd1—Cl1i | 90.74 (7) | N3—Pd2—Cl2ii | 90.56 (7) |
N1i—Pd1—Cl1i | 89.26 (7) | N3ii—Pd2—Cl2ii | 89.44 (7) |
Cl1—Pd1—Cl1i | 179.999 (1) | Cl2—Pd2—Cl2ii | 180.0 |
C4—N1—N2 | 121.9 (2) | C8—N3—N4 | 121.2 (2) |
C4—N1—Pd1 | 122.5 (2) | C8—N3—Pd2 | 121.78 (19) |
N2—N1—Pd1 | 115.63 (17) | N4—N3—Pd2 | 117.00 (18) |
C1—N2—N1 | 117.4 (2) | C5—N4—N3 | 117.2 (2) |
N2—C1—C2 | 124.2 (3) | N4—C5—C6 | 124.6 (3) |
N2—C1—H1 | 117.9 | N4—C5—H5 | 117.7 |
C2—C1—H1 | 117.9 | C6—C5—H5 | 117.7 |
C3—C2—C1 | 117.0 (3) | C7—C6—C5 | 116.8 (3) |
C3—C2—H2 | 121.5 | C7—C6—H6 | 121.6 |
C1—C2—H2 | 121.5 | C5—C6—H6 | 121.6 |
C2—C3—C4 | 118.1 (3) | C6—C7—C8 | 118.1 (3) |
C2—C3—H3 | 120.9 | C6—C7—H7 | 121.0 |
C4—C3—H3 | 120.9 | C8—C7—H7 | 121.0 |
N1—C4—C3 | 121.5 (3) | N3—C8—C7 | 122.1 (3) |
N1—C4—H4 | 119.3 | N3—C8—H8 | 118.9 |
C3—C4—H4 | 119.3 | C7—C8—H8 | 118.9 |
N1i—Pd1—N1—C4 | 37 (100) | N3ii—Pd2—N3—C8 | −88 (32) |
Cl1—Pd1—N1—C4 | 90.8 (2) | Cl2—Pd2—N3—C8 | −60.0 (2) |
Cl1i—Pd1—N1—C4 | −89.2 (2) | Cl2ii—Pd2—N3—C8 | 120.0 (2) |
N1i—Pd1—N1—N2 | −143 (100) | N3ii—Pd2—N3—N4 | 92 (32) |
Cl1—Pd1—N1—N2 | −89.38 (18) | Cl2—Pd2—N3—N4 | 120.08 (18) |
Cl1i—Pd1—N1—N2 | 90.62 (18) | Cl2ii—Pd2—N3—N4 | −59.92 (18) |
C4—N1—N2—C1 | 0.1 (4) | C8—N3—N4—C5 | −1.2 (4) |
Pd1—N1—N2—C1 | −179.70 (18) | Pd2—N3—N4—C5 | 178.73 (18) |
N1—N2—C1—C2 | 0.5 (4) | N3—N4—C5—C6 | −0.7 (4) |
N2—C1—C2—C3 | −0.8 (4) | N4—C5—C6—C7 | 1.5 (4) |
C1—C2—C3—C4 | 0.4 (4) | C5—C6—C7—C8 | −0.4 (4) |
N2—N1—C4—C3 | −0.4 (4) | N4—N3—C8—C7 | 2.4 (4) |
Pd1—N1—C4—C3 | 179.4 (2) | Pd2—N3—C8—C7 | −177.6 (2) |
C2—C3—C4—N1 | 0.1 (4) | C6—C7—C8—N3 | −1.5 (4) |
Symmetry codes: (i) −x+1, −y+1, −z+2; (ii) −x+1, −y, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
C4—H4···N4i | 0.95 | 2.55 | 3.438 (3) | 155 |
C3—H3···Cl2iii | 0.95 | 2.94 | 3.569 (3) | 125 |
C1—H1···Cl2iv | 0.95 | 2.92 | 3.787 (3) | 153 |
C8—H8···Cl1v | 0.95 | 2.82 | 3.529 (3) | 132 |
Symmetry codes: (i) −x+1, −y+1, −z+2; (iii) x, y+1, z+1; (iv) x, y+1, z; (v) x, y, z−1. |
D—H···A | D—H | H···A | D···A | D—H···A |
C4—H4···N4i | 0.95 | 2.55 | 3.438 (3) | 155.0 |
C3—H3···Cl2ii | 0.95 | 2.94 | 3.569 (3) | 124.6 |
C1—H1···Cl2iii | 0.95 | 2.92 | 3.787 (3) | 152.7 |
C8—H8···Cl1iv | 0.95 | 2.82 | 3.529 (3) | 132.1 |
Symmetry codes: (i) −x+1, −y+1, −z+2; (ii) x, y+1, z+1; (iii) x, y+1, z; (iv) x, y, z−1. |
Acknowledgements
The authors thank the Department of Chemistry of the Université de Montréal for access to the CCD facility. We thank Thierry Maris for useful crystallographic discussions. We are grateful to the Université de Montréal for financial assistance.
References
Bruker (2011). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Cano, J., De Munno, G., Lloret, F. & Julve, M. (2000). Inorg. Chem. 39, 1611–1614. Web of Science CSD CrossRef PubMed CAS Google Scholar
Degtyarenko, A. S., Solntsev, P. V., Krautscheid, H., Rusanov, E. B., Chernega, A. N. & Domasevitch, K. V. (2008). New J. Chem. 32, 1910–1918. Web of Science CSD CrossRef CAS Google Scholar
Otieno, T., Rettig, S. J., Thompson, R. C. & Trotter, J. (1995). Inorg. Chem. 34, 1718–1725. CSD CrossRef CAS Web of Science Google Scholar
Raimondi, A., Panigati, M., Maggioni, D., D'Alfonso, L., Mercandelli, P., Mussini, P. & D'Alfonso, G. (2012). Inorg. Chem. 51, 2966–2975. Web of Science CSD CrossRef CAS PubMed Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals 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.
In the present work, a square planar trans-bis(chloro)-bis(pyridazine-κN) palladium(II) metal complex has been synthesized. Similar metal complexes are already known in coordination polymer chemistry (Degtyarenko et al., 2008)).
The molecular structure of the title compound is illustrated in Fig. 1, where two molecules are found in the asymmetric unit. The bond distances are unexceptional. In one complex the plane of the pyridazyl ring is perpendicular with respect to the Cl–Pd–Cl axis, while in the second molecules the ring is slightly tilted with an angle of 60 (1)°, which may be due to the presence of weak hydrogen bonds.