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

Laramée, B.; Hanan, G.S.

doi:10.1107/S1600536813032716

metal-organic compounds

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Volume 70| Part 1| January 2014| Page m17

https://doi.org/10.1107/S1600536813032716

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

Baptiste Laramée ^a ^* and Garry S. Hanan ^a

^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

(Received 25 September 2013; accepted 2 December 2013; online 14 December 2013)

The title compound, [PdCl₂(C₄H₄N₂)₂], contains two crystallographically unique complexes; the Pd^II atom lies on an inversion center in both cases. The two pyridazine units bonded to the Pd^II 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

[PdCl₂(C₄H₄N₂)₂]
M_r = 337.48
Triclinic, $[P \overline 1]$
a = 7.9910 (1) Å
b = 8.4273 (1) Å
c = 9.6172 (2) Å
α = 84.614 (1)°
β = 67.682 (1)°
γ = 63.134 (1)°
V = 532.09 (2) Å³
Z = 2
Cu Kα radiation
μ = 18.45 mm⁻¹
T = 150 K
0.08 × 0.06 × 0.06 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.216, T_max = 0.260
13678 measured reflections
1971 independent reflections
1957 reflections with I > 2σ(I)
R_int = 0.018

Refinement

R[F² > 2σ(F²)] = 0.023
wR(F²) = 0.068
S = 1.07
1971 reflections
139 parameters
H-atom parameters constrained
Δρ_max = 0.97 e Å⁻³
Δρ_min = −0.75 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

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⋯Cl2ⁱⁱ	0.95	2.94	3.569 (3)	125
C1—H1⋯Cl2ⁱⁱⁱ	0.95	2.92	3.787 (3)	153
C8—H8⋯Cl1^iv	0.95	2.82	3.529 (3)	132
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.

Data collection: APEX2 (Bruker, 2011 ); cell refinement: 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

Crystal structure: contains datablocks I, New_Global_Publ_Block. DOI: https://doi.org/10.1107/S1600536813032716/nk2214sup1.cif

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

checkCIF report

Comment top

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.

Related literature top

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 top

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).

Structure description top

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.

Computing details top

Data collection: APEX2 (Bruker, 2011); cell refinement: 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).

Figures top

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.

trans-Dichloridobis(pyridazine-κN)palladium(II) top

Crystal data top

[PdCl₂(C₄H₄N₂)₂]	Z = 2
M_r = 337.48	F(000) = 328
Triclinic, P1	D_x = 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

Data collection top

Bruker APEXII CCD diffractometer	1971 independent reflections
Radiation source: fine-focus sealed tube	1957 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.018
φ and ω scans	θ_max = 70.9°, θ_min = 5.0°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −9→9
T_min = 0.216, T_max = 0.260	k = −9→10
13678 measured reflections	l = −11→11

Refinement top

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(F_o²) + (0.0456P)² + 0.8794P] where P = (F_o² + 2F_c²)/3
1971 reflections	(Δ/σ)_max < 0.001
139 parameters	Δρ_max = 0.97 e Å⁻³
0 restraints	Δρ_min = −0.75 e Å⁻³

Crystal data top

[PdCl₂(C₄H₄N₂)₂]	γ = 63.134 (1)°
M_r = 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)°

Data collection top

Bruker APEXII CCD diffractometer	1971 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1957 reflections with I > 2σ(I)
T_min = 0.216, T_max = 0.260	R_int = 0.018
13678 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.023	0 restraints
wR(F²) = 0.068	H-atom parameters constrained
S = 1.07	Δρ_max = 0.97 e Å⁻³
1971 reflections	Δρ_min = −0.75 e Å⁻³
139 parameters

Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
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*

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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.

Hydrogen-bond geometry (Å, º) top

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···Cl2^iv	0.95	2.92	3.787 (3)	153
C8—H8···Cl1^v	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.

Hydrogen-bond geometry (Å, º) top

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···Cl1^iv	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