Bis{2-[(E)-(4-fluoro­benz­yl)imino­meth­yl]-6-meth­oxy­phenolato}palladium(II)

Hadariah Bahron; Amalina Mohd Tajuddin; Wan Nazihah Wan Ibrahim; Madhukar Hemamalini; Hoong-Kun Fun

doi:10.1107/S1600536811017739

. 2011 May 20;67(Pt 6):m759–m760. doi: 10.1107/S1600536811017739

Bis{2-[(E)-(4-fluorobenzyl)iminomethyl]-6-methoxyphenolato}palladium(II)

Hadariah Bahron ^a, Amalina Mohd Tajuddin ^a, Wan Nazihah Wan Ibrahim ^a, Madhukar Hemamalini ^b, Hoong-Kun Fun ^b,^*,^‡

PMCID: PMC3120330 PMID: 21754647

Abstract

In the title compound, [Pd(C₁₅H₁₃FNO₂)₂], the Pd^II atom is tetracoordinated by two N atoms and two O atoms from the two 2-[(4-fluorobenzyl)iminomethyl]-6-methoxyphenoxy ligands, forming a square-planar geometry. The two N atoms and the two O atoms around the Pd^II atom are trans to each other. The dihedral angle between the two fluoro-substituted benzene rings is 39.03 (6)°. The molecular structure is stabilized by an intramolecular C—H⋯O hydrogen bond. In the crystal, weak intermolecular C—H⋯π interactions occur.

Related literature

For applications of palladium(II)–Schiff base complexes, see: Ali et al. (2002 ▶); Gupta & Sutar (2008 ▶). For related structures, see: Jiang et al. (2008 ▶); Tsai et al. (2009 ▶); Mohd Tajuddin et al. (2010 ▶); Lin et al. (2010 ▶). For the stability of the temperature controller used in the data collection, see: Cosier & Glazer (1986 ▶).

Experimental

Crystal data

[Pd(C₁₅H₁₃FNO₂)₂]
M _r = 622.93
Triclinic,
a = 10.0025 (4) Å
b = 11.0082 (4) Å
c = 12.3152 (4) Å
α = 109.550 (1)°
β = 98.368 (1)°
γ = 90.054 (1)°
V = 1262.45 (8) Å³
Z = 2
Mo Kα radiation
μ = 0.79 mm⁻¹
T = 100 K
0.54 × 0.19 × 0.16 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T _min = 0.677, T _max = 0.885
39095 measured reflections
11056 independent reflections
9774 reflections with I > 2σ(I)
R _int = 0.027

Refinement

R[F ² > 2σ(F ²)] = 0.029
wR(F ²) = 0.081
S = 1.03
11056 reflections
354 parameters
H-atom parameters constrained
Δρ_max = 1.95 e Å⁻³
Δρ_min = −1.72 e Å⁻³

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

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811017739/is2710sup1.cif

e-67-0m759-sup1.cif^{(23KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811017739/is2710Isup2.hkl

e-67-0m759-Isup2.hkl^{(529.7KB, hkl)}

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

Cg1, Cg2, Cg3 and Cg5 are the centroids of the Pd1/N1/O1/C1/C6/C7, Pd1/O2/N2/C16/C21/C22, C1–C6 and C16–C21 rings, respectively.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C29—H29A⋯O1	0.95	2.45	3.2051 (15)	136
C8—H8B⋯Cg2ⁱ	0.99	2.67	3.3882 (13)	130
C15—H15B⋯Cg5ⁱⁱ	0.98	2.71	3.6530 (15)	162
C23—H23A⋯Cg1ⁱⁱ	0.99	2.67	3.3612 (13)	127
C30—H30C⋯Cg3ⁱ	0.98	2.69	3.6146 (16)	158

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

Acknowledgments

HB, AMT, WNWI would like to acknowledge the Ministry of Higher Education of Malaysia for research grant No. 600-RMI/ST/FRGS5/3/Fst(7/2009), Universiti Teknologi MARA and Universiti Sains Malaysia for the facilities. HKF and MH thank the Malaysian Government and Universiti Sains Malaysia for the Research University Grant No. 1001/PFIZIK/811160. MH also thanks Universiti Sains Malaysia for a post-doctoral research fellowship.

supplementary crystallographic information

Comment

Palladium(II)-Schiff base complexes are well-known for their catalytic (Gupta & Sutar, 2008) and biological properties (Ali et al., 2002). Schiff bases containing iminoalkylphenolato groups commonly perform bidentate coordination with metal centres as shown in bis{2-[(E)-benzyliminomethyl]-4,6-dibromophenalato-κ²N,O}cobalt(II) (Jiang et al., 2008) and bis[2-(2H-benzotriazol-2-yl)-4-methyl-phenolato]palladium(II) (Tsai et al., 2009). The title compound, (I), is bis-bidentate (see Fig. 1) and related to the previously reported bis[2-(1-benzyliminoethyl)phenolato]palladium(II) (Mohd Tajuddin et al., 2010) but with different substituents on the iminoalkylphenolato and benzyl moieties.

The geometry around Pd^II atom is tetra-coordinated with a normal square planar environment in which two N atoms and two O atoms are coplanar. The two N atoms and two O atoms around the Pd^II atom are trans to each other. The bond angles of O1—Pd1—N1= 92.57 (4)°, O2—Pd1—N1 = 87.15 (4)°, O1—Pd1—N2 = 87.59 (4)°, O2—Pd1—N2= 92.70 (4)°, N1—Pd1—N2 = 179.85 ° and O1—Pd1—O2 = 179.60 (3) °. The distances between the Pd^II atom and O and N are 1.9717 (9), 1.9727 (9), 2.0194 (10) and 2.0209 (10) Å, respectively. These bond distances and angles are similar to those found in the crystal structure of bis[4-methyl-2- (2H-benzotriazol-2-yl)phenolato]palladium (II) (Tsai et al., 2009; Lin et al., 2010). The dihedral angle between the two fluoro-substituted benzene (C9–C14)/(C24–C29) rings is 39.03 (6)°.

In the crystal structure, (Fig. 2), the molecular packing is stablized by weak C29—H29A···O1 hydrogen bond and C—H···π interactions (Table 1), involving centroids, Cg1 (Pd1/N1/O1/C1/C6/C7), Cg2 (Pd1/O2/N2/C16/C21/C22), Cg3 (C1–C6) and Cg5 (C16–C21).

Experimental

(E)-2-[(4-fluorobenzyl)iminomethyl]-6-methoxyphenol (0.5196 g, 2 mmol) and palladium acetate (0.2249 g, 2 mmol) was each dissolved separately in acetonitrile (5 ml). The two solutions were then mixed and stirred under reflux for 4 hours upon which a brown precipitate was formed. It was isolated by gravity filtration, washed with cold acetonitrile and air dried at room temperature. The solid product was recrystallized from chloroform yielding yellow crystals (yield 97.1%, m.p. 526–529 K). Analytical calculation for C₃₀H₂₆F₂N₂O₄Pd (%): C 57.84, H 4.21, N 4.50. Found (%): C 57.86, H 4.21, N 4.27. IR (cm^-1): ν(C═N) 1616 (s), ν(C–O) 1248 (s), ν(C–H) 2836 (w), ν(C–N) 1328 (m), ν(C–OCH₃) 1084 (m), ν(Pd–O) 581 (w), ν(Pd–N) 495 (w). ¹H NMR (CDCl₃, 300 MHz, p.p.m.): δ = 7.728 (1H, s, HC═N), 7.450–6.492