Crystal structure of [N,N′-bis­(4-methyl­phen­yl)-1,2-di­phenyl­ethane-1,2-di­imine-κ2 N,N′]di­chlorido­palladium(II) methanol monosolvate

Alfredo Peñaloza; Frank R Fronczek; Ralph Isovitsch

doi:10.1107/S2056989015014851

. 2015 Aug 15;71(Pt 9):m164–m165. doi: 10.1107/S2056989015014851

Crystal structure of [N,N′-bis(4-methylphenyl)-1,2-diphenylethane-1,2-diimine-κ² N,N′]dichloridopalladium(II) methanol monosolvate

Alfredo Peñaloza ^a, Frank R Fronczek ^b, Ralph Isovitsch ^a,^*

PMCID: PMC4555432 PMID: 26396867

Abstract

The title compound, [PdCl₂(C₂₈H₂₄N₂)]·CH₃OH, was prepared from the reaction of PdCl₂(DMSO)₂ (DMSO is dimethyl sulfoxide) and N,N′-bis(4-methylphenyl)-1,2-diphenylethane-1,2-diimine in methanol. The chelating diimine core of the title compound deviates slightly from planarity, with an N—C—C—N torsion angle of 5.3 (3)°. Delocalization in the diimine core is indicated by N—C and C—C bonds that are, respectively, longer and shorter than those found in related nonchelating diimines. The distorted square-planar coordination environment around the Pd^II atom is manifested as bond angles that are smaller and larger than 90°, and palladacycle torsion angles of −173.22 (16) and 167.06 (16)°. These deviations are attributed to the small bite angle of 79.13 (8)° of the diimine chelate. The crystal packing exhibits weak intermolecular hydrogen-bonding interactions involving aromatic H atoms, Cl atoms and intercalated methanol solvent molecules, defining layers parallel to (010).

Keywords: crystal structure, palladium(II) dichlorido diimine complex, polymerization catalyst

Related literature

Palladium(II) diimiine complexes have been widely used as polymerization catalysts for α-olefins (Johnson et al., 1995 ▸; Popeney & Guan, 2005 ▸) and are prepared easily by the reaction of PdCl₂(DMSO)₂ with the diimine of choice (Kubota et al., 2013 ▸; Ettedgui & Neumann, 2009 ▸; Price et al., 1972 ▸). For structural information about related palladium(II) diimine complexes, see: Kubota et al. (2013 ▸); Comerlato et al. (2001 ▸); Dyakonenko et al. (2015 ▸). For structures of other diimines, see: Wang et al. (2012 ▸); Zhao et al. (2015 ▸).

Experimental

Crystal data

[PdCl₂(C₂₈H₂₄N₂)]·CH₄O
M _r = 597.83
Triclinic,
a = 8.8213 (3) Å
b = 12.3364 (3) Å
c = 12.7697 (4) Å
α = 108.992 (2)°
β = 93.900 (3)°
γ = 92.457 (3)°
V = 1307.83 (7) Å³
Z = 2
Mo Kα radiation
μ = 0.94 mm⁻¹
T = 90 K
0.18 × 0.10 × 0.06 mm

Data collection

Bruker Kappa APEXII DUO CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2014 ▸) T _min = 0.831, T _max = 0.946
12258 measured reflections
5965 independent reflections
5026 reflections with I > 2σ(I)
R _int = 0.032

Refinement

R[F ² > 2σ(F ²)] = 0.031
wR(F ²) = 0.066
S = 1.02
5965 reflections
322 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.57 e Å⁻³
Δρ_min = −0.64 e Å⁻³

Data collection: APEX2 (Bruker, 2014 ▸); cell refinement: SAINT (Bruker, 2014 ▸); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▸); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▸); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ▸); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablock(s) I, New_Global_Publ_Block. DOI: 10.1107/S2056989015014851/wm5193sup1.cif

e-71-0m164-sup1.cif^{(31.9KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015014851/wm5193Isup2.hkl

e-71-0m164-Isup2.hkl^{(292KB, hkl)}

Supporting information file. DOI: 10.1107/S2056989015014851/wm5193sup3.pdf

e-71-0m164-sup3.pdf^{(40KB, pdf)}

Click here for additional data file.^{(1.5MB, tif)}

. DOI: 10.1107/S2056989015014851/wm5193fig1.tif

The molecular components of the title compound. Displacement ellipsoids are represented at the 50% probability level.

Click here for additional data file.^{(2.2MB, tif)}

. DOI: 10.1107/S2056989015014851/wm5193fig2.tif

Crystal packing in the title compound, with intermolecular hydrogen bonding emphasized as dashed lines.

Click here for additional data file.^{(1.5MB, tif)}

. DOI: 10.1107/S2056989015014851/wm5193fig3.tif

Crystal packing in the title compound as viewed along [100].

CCDC reference: 1417572

Additional supporting information: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (, ).

DHA	DH	HA	D A	DHA
O1H10HCl2	0.83(2)	2.36(2)	3.161(2)	163(3)
C17H17Cl2ⁱ	0.95	2.80	3.708(3)	161
C21H21O1ⁱⁱ	0.95	2.48	3.275(3)	141

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Symmetry codes: (i) Inline graphic ; (ii) .

Acknowledgments

Whittier College is acknowledged for the funds that supported this research. Tammy Le is acknowledged for obtaining the UV–Vis spectrum of the title compound. The upgrade of the diffractometer was made possible by grant No. LEQSF(2011–2012)-ENH-TR-01, administered by the Louisiana Board of Regents.

supplementary crystallographic information

S1. Synthesis and crystallization

0.086 g (0.257 mmol, 1 eq.) of PdCl₂(DMSO)₂ and 0.100 g (0.257 mmol, 1 eq.) of N,N'-di(4-methylphenyl)-1,2-diphenylethane-1,2-diimine were combined with 10 ml of methanol and stirred for 1.5 hours at room temperature. The orange precipitate that formed was collected via vacuum filtration, washed well with water and then air-dried giving 0.0363 g (25%) of the title compound. Slow evaporation of the reaction mixture gave X-ray quality crystals of the title compound. MP: > 532 K. IR (KCl): 3135, 2922, 1514 cm^-1. UV-Vis (λ nm (ε)): 242 (41,200), 264 (34,800), 317 (17,800). TLC (alumina, ethanol): R_f = 0.59.

S2. Refinement

H atoms were placed in idealized positions, guided by difference maps, with C—H bond lengths in the range 0.95-0.98 Å, with U_iso(H) = 1.2U_eq(C) of the attached atom (1.5 for methyl), and thereafter treated as riding. A torsional parameter was refined for each methyl group. The H atom of the methanol solvent molecule was refined with O—H = 0.85 Å and U_iso(H) = 1.5U_eq(O).