Crystal structure of bis­(2-{1-[(E)-(4-fluoro­benz­yl)imino]­eth­yl}phenolato-κ2N,O)palladium(II)

Mohd Tajuddin, A.; Bahron, H.; Mohd Zaki, H.; Kassim, K.; Chantrapromma, S.

doi:10.1107/S2056989015004405

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ISSN: 2056-9890

Volume 71| Part 4| April 2015| Pages 350-353

doi:10.1107/S2056989015004405

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Crystal structure of bis(2-{1-[(E)-(4-fluorobenzyl)imino]ethyl}phenolato-κ²N,O)palladium(II)

Amalina Mohd Tajuddin,^a Hadariah Bahron,^a,^b ^* Hamizah Mohd Zaki,^a Karimah Kassim ^a,^c and Suchada Chantrapromma ^d ‡

^aFaculty of Applied Sciences, Universiti Teknologi MARA, 40450 Shah Alam, Selangor, Malaysia, ^bDDH CoRe, Universiti Teknologi MARA, 40450 Shah Alam, Selangor, Malaysia, ^cInstitute of Science, Universiti Teknologi MARA, 40450 Shah Alam, Selangor, Malaysia, and ^dDepartment of Chemistry, Faculty of Science, Prince of Songkla University, Hat-Yai, Songkhla 90112, Thailand
^*Correspondence e-mail: hadariah@salam.uitm.edu.my

Edited by J. Simpson, University of Otago, New Zealand (Received 2 February 2015; accepted 3 March 2015; online 11 March 2015)

The asymmetric unit of the title complex, [Pd(C₁₅H₁₃FNO)₂], contains one half of the molecule with the Pd^II cation lying on an inversion centre and is coordinated by the bidentate Schiff base anion. The geometry around the cationic Pd^II centre is distorted square planar, chelated by the imine N- and phenolate O-donor atoms of the two Schiff base ligands. The N- and O-donor atoms of the two ligands are mutually trans, with Pd—N and Pd—O bond lengths of 2.028 (2) and 1.9770 (18) Å, respectively. The fluorophenyl ring is tilted away from the coordination plane and makes a dihedral angle of 66.2 (2)° with the phenolate ring. In the crystal, molecules are linked into chains along the [101] direction by weak C—H⋯O hydrogen bonds. Weak π–π interactions with centroid–centroid distances of 4.079 (2) Å stack the molecules along c.

Keywords: crystal structure; Pd^II complex; NO donors; Schiff base; catalyst activity; hydrogen bonding; π–π interactions.

CCDC reference: 1045879

1. Chemical context

Schiff bases represent one of the most widely utilized classes of ligands in coordination chemistry and the chemistry of Schiff bases is still an area of increasing interest (Canali & Sherrigton, 1999 ). The Pd^II and Ni^II complexes of Schiff bases have attracted much attention as they play important roles in bioinorganic chemistry and may provide the basis for models of active sites of biological systems (Malik et al., 2013 ) or act as catalysts (Shahnaz et al., 2013 ). The title compound, [Pd(C₁₅H₁₃FNO)₂], is related to the previously reported compound bis{2-[(E)-(4-fluorobenzyl)iminomethyl]phenolato-κ²N,O¹}nickel(II) (Mohd Tajuddin et al., 2014 ) in terms of the coordination geometry around the central metal. In this article, we report the synthesis of the title Schiff base–Pd^II complex and its characterization by spectroscopy and elemental analysis. The X-ray structure (Fig. 1), confirms the binding mode of the 4-fluorobenzyl(iminoethyl)phenolate ligand to the Pd^II cation.

Figure 1
The molecular structure of (1), showing 50% probability displacement ellipsoids and the atom-numbering scheme. The labelled atoms are related to the unlabelled atoms of the Schiff base ligands by the symmetry code 1 − x, 2 − y, 2 − z.

The title compound (1) was screened for catalytic activity in the Suzuki cross-coupling reaction between phenylboronic acid and iodobenzene with a catalyst loading of 1 mmol%. The conversion of iodobenzene was found to occur with a yield of 52%.

2. Structural commentary

The asymmetric unit of (1) contains one-half of the molecule with the Pd^II cation lying on an inversion centre and the Schiff base anion acting as an N,O bidentate chelate ligand (Fig. 1). The Pd^II cation binds to the N and the O atoms of two symmetry-related Schiff base ligand such that the N and O atoms are mutually trans. The N₂O₂ donor sets of the two chelating Schiff base ligands in the equatorial plane around Pd1 adopt a slightly distorted square-planar coordination geometry. The Pd1—N1 and Pd1—O1 distances (Table 1) are typical of square-planar Pd^II complexes, and compare well with those observed in other closely related Pd^II complexes (Adrian et al., 2008 ; Bahron et al., 2014 ; Wan Ibrahim & Shamsuddin, 2012 ). The bite angle of the iminomethylphenolate chelate, N1—Pd1—O1 is 88.48 (8)°, which is also similar to that in a related Pd^II complex (Bahron et al., 2014). The ring Pd1/N1/C8/C9/C10/O1 adopts an envelope conformation with Pd1 displaced by 0.270 (2) Å from the plane of the other ring atoms, and with puckering parameters Q = 0.525 (2) Å, θ = 112.8 (3) and φ = 206.9 (3)°. Other bond lengths and angles observed in the structure are also normal. The fluorophenyl ring (C1–C6) makes a dihedral angle of 66.2 (2)° with the phenolate ring (C9–C14).

Table 1
Selected geometric parameters (Å, °)

Pd1—O1	1.9770 (18)	Pd1—N1	2.028 (2)

O1—Pd1—N1	88.48 (8)	O1ⁱ—Pd1—N1	91.52 (8)
Symmetry code: (i) -x+1, -y+2, -z+2.

3. Supramolecular features

In the crystal packing of (1), the molecules are linked into chains along the [101] direction by weak C4—H4A⋯O1 interactions (Fig. 2, Table 2). A weak π–π stacking interaction occurs between the phenolate rings of adjacent complexes (Fig. 3), with a centroid–centroid distance, Cg4⋯Cg4ⁱⁱⁱ, of 4.079 (2) Å [symmetry code: (iii) = 1 − x, 2 − y, 1 − z; Cg4 is the centroid of the C9–C14 ring]. These combine with the C—H⋯O contacts to generate sheets in the ac plane (Fig. 4). These sheets are further stacked along the b-axis direction.

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C4—H4A⋯O1ⁱⁱ	0.93	2.50	3.405 (5)	165
Symmetry code: (ii) -x+2, -y+2, -z+2.

Figure 2
Screw chains of molecules of (1) linked by C—H⋯O interactions (drawn as dashed lines).

Figure 3
π–π contacts for (1) drawn as dotted lines with ring centroids shown as coloured spheres. Cg4 is the centroid of the C9–C14 ring. H atoms are omitted for clarity.

Figure 4
The packing of (1) viewed approximately along the b axis showing molecular sheets of the Pd^II complex. Only H atoms involved in C—H⋯O interactions are shown for clarity.

4. Database survey

Six Pd^II complexes with related Schiff base N₂O₂ donor sets have been reported (Brunner et al., 2000 ; Mehta & Vengurlekar, 2001 ; Bahron et al., 2011 , 2014; Mohd Tajuddin et al., 2012a ; Tsuno et al., 2013 ). However, only three of these Pd^II complexes have closely related Schiff base ligands (Bahron et al., 2011; 2014; Mohd Tajuddin et al., 2012a).

5. Synthesis and crystallization

The ligand, (E)-2-(1-(4-fluorobenzylimino)ethyl)phenol (Mohd Tajuddin et al., 2012b ) (2 mmol, 0.4877 g) was dissolved in CH₃CN (30 mL) in a round-bottomed flask. Palladium(II) acetate (1 mmol, 0.2251 g) was dissolved separately in CH₃CN (20 mL) and was then added into the flask containing the ligand solution. The mixture was stirred and refluxed for 5 h upon which a turmeric yellow solid was formed. The solid was filtered off, washed with ice-cold CH₃CN and air dried at room temperature. The solid product was recrystallized from chloroform, yielding yellow crystals (yield 48.5%). ¹H NMR, ¹³C NMR and IR spectral bands have been studied and agree well with the structure obtained from the values of the CHN analyses and X-ray structure determination.

Melting point 508–510 K. Analytical data for C₃₀H₂₆F₂N₂O₂Pd: C, 60.97; H, 4.43; N, 4.74%; Found: C, 60.81; H, 4.49; N, 4.66%. IR (KBr, cm⁻¹): 1598 ν(C=N), 1319 ν(C—N), 1216 ν(C—O), 1321 ν(CH₃), 556 ν(Pd—N), 450 ν(Pd—O). ¹H NMR (300 MHz, CDCl₃): δ (p.p.m.) 2.32 (s, 3H, C—CH₃), 5.11 (s, 2H, CH₂), 6.53–7.46 (ArC). ¹³C NMR (300 MHz, CDCl₃): δ (p.p.m.) 19.5 (C—CH₃), 54.2 (CH₂), 115.3, 115.6, 121.3, 128.6, 130.2 (ArC), 169.8 (C=N).

The infrared spectrum of (1) exhibits a strong band at 1598 cm⁻¹ assignable to the C=N stretching frequency of the azomethine moiety. Weak bands at 556 and 450 cm⁻¹ attributable to Pd—N and Pd—O vibrations, respectively (Ouf et al., 2010 ), are due to the participation of the nitrogen of the azomethine group and the oxygen of the phenolate ring in the complexation of the palladium(II) centre by the Schiff base ligands. From the NMR results, the free 4-fluorobenzyl(iminoethyl)phenolate ligand shows a multiplet at around 6.80–7.57 p.p.m. assignable to the aromatic protons. A corresponding multiplet appears in almost the same position in the spectrum of the Pd^II complex (compound 1) as that observed by Gupta et al. (2013 ). Singlets for aliphatic methylene (–CH₂) and methyl (–CH₃) protons appear at 5.11 and 2.32 p.p.m., respectively. The ¹³C chemical shift for the imine carbon (C=N) is found at 169.8 p.p.m., agreeing with data reported by Şenol et al. (2011 ).

The title compound was screened for catalytic activity in the Suzuki cross-coupling reaction between phenylboronic acid with iodobenzene. The reaction was carried out under nitrogen at 373 K in dimethylacetamide with a catalyst loading of 1 mmol%. The conversion of iodobenzene was monitored using GC–FID after 24 hours of reaction time. This resulted in a 52% conversion of iodobenzene in the reaction.

6. Refinement

Crystal data, data collection and crystal structure refinement details are summarized in Table 3. All H atoms were positioned geometrically and allowed to ride on their parent atoms, with d(C—H) = 0.93 Å for aromatic, 0.97 Å for CH₂ and 0.96 Å for CH₃ hydrogen atoms. The U_iso values were constrained to be 1.5U_eq of the carrier atom for methyl H atoms and 1.2U_eq for the remaining H atoms. A rotating group model was used for the methyl groups.

Table 3
Experimental details

Crystal data
Chemical formula	[Pd(C₁₅H₁₃FNO)₂]
M_r	590.93
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	296
a, b, c (Å)	7.5924 (5), 21.9212 (14), 9.3475 (5)
β (°)	124.963 (4)
V (Å³)	1274.97 (15)
Z	2
Radiation type	Mo Kα
μ (mm⁻¹)	0.77
Crystal size (mm)	0.50 × 0.25 × 0.25

Data collection
Diffractometer	Bruker APEXII CCD area detector
Absorption correction	Multi-scan (SADABS; Bruker, 2009 )
T_min, T_max	0.699, 0.830
No. of measured, independent and observed [I > 2σ(I)] reflections	38866, 2776, 2720
R_int	0.057
(sin θ/λ)_max (Å⁻¹)	0.639

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.034, 0.073, 1.30
No. of reflections	2776
No. of parameters	170
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.24, −0.48
Computer programs: APEX2 and SAINT (Bruker, 2009), SHELXTL (Sheldrick, 2008 ), PLATON (Spek, 2009 ), Mercury (Macrae et al., 2006 ) and publCIF (Westrip, 2010 ).

Supporting information

CCDC reference: 1045879

Crystal structure: contains datablocks global, I. DOI: 10.1107/S2056989015004405/sj5444sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S2056989015004405/sj5444Isup2.hkl

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: APEX2 (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008), PLATON (Spek, 2009), Mercury (Macrae et al., 2006) and publCIF (Westrip, 2010).

Bis(2-{1-[(E)-(4-fluorobenzyl)imino]ethyl}phenolato-κ²N,O)palladium(II) top

Crystal data top

[Pd(C₁₅H₁₃FNO)₂]	F(000) = 600
M_r = 590.93	D_x = 1.539 Mg m⁻³
Monoclinic, P2₁/c	Melting point = 508–510 K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 7.5924 (5) Å	Cell parameters from 2776 reflections
b = 21.9212 (14) Å	θ = 3.2–27.0°
c = 9.3475 (5) Å	µ = 0.77 mm⁻¹
β = 124.963 (4)°	T = 296 K
V = 1274.97 (15) Å³	Block, yellow
Z = 2	0.50 × 0.25 × 0.25 mm

Data collection top

Bruker APEXII CCD area-detector diffractometer	2776 independent reflections
Radiation source: sealed tube	2720 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.057
φ and ω scans	θ_max = 27.0°, θ_min = 3.2°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −9→9
T_min = 0.699, T_max = 0.830	k = −28→28
38866 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)] = 0.034	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.073	H-atom parameters constrained
S = 1.30	w = 1/[σ²(F_o²) + (0.0086P)² + 1.3994P] where P = (F_o² + 2F_c²)/3
2776 reflections	(Δ/σ)_max < 0.001
170 parameters	Δρ_max = 0.24 e Å⁻³
0 restraints	Δρ_min = −0.48 e Å⁻³

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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	1.0000	1.0000	0.03202 (9)
F1	1.3139 (4)	0.77987 (11)	1.2186 (5)	0.1153 (11)
O1	0.5384 (3)	1.04581 (9)	0.8375 (2)	0.0462 (5)
N1	0.4268 (3)	0.92521 (9)	0.8478 (3)	0.0343 (4)
C1	0.7655 (7)	0.78728 (16)	1.0865 (7)	0.0924 (16)
H1A	0.6670	0.7629	1.0890	0.111*
C2	0.9701 (7)	0.76567 (18)	1.1567 (8)	0.117 (2)
H2A	1.0108	0.7272	1.2078	0.140*
C3	1.1113 (6)	0.80149 (15)	1.1502 (6)	0.0716 (11)
C4	1.0618 (5)	0.85845 (14)	1.0834 (4)	0.0495 (7)
H4A	1.1627	0.8827	1.0839	0.059*
C5	0.8555 (5)	0.87966 (12)	1.0140 (4)	0.0416 (6)
H5	0.8184	0.9188	0.9670	0.050*
C6	0.7048 (5)	0.84467 (12)	1.0125 (4)	0.0411 (6)
C7	0.4795 (5)	0.86633 (12)	0.9399 (4)	0.0429 (6)
H7A	0.3781	0.8358	0.8598	0.051*
H7B	0.4629	0.8702	1.0349	0.051*
C8	0.3497 (4)	0.92650 (12)	0.6831 (4)	0.0382 (6)
C9	0.2963 (4)	0.98338 (13)	0.5855 (3)	0.0381 (6)
C10	0.3929 (4)	1.03958 (13)	0.6678 (3)	0.0390 (6)
C11	0.3352 (6)	1.09165 (15)	0.5625 (4)	0.0527 (7)
H11A	0.3971	1.1289	0.6147	0.063*
C12	0.1898 (6)	1.08905 (16)	0.3845 (4)	0.0578 (8)
H12A	0.1554	1.1243	0.3181	0.069*
C13	0.0945 (5)	1.03431 (17)	0.3037 (4)	0.0551 (8)
H13A	−0.0052	1.0326	0.1833	0.066*
C14	0.1479 (5)	0.98286 (15)	0.4023 (4)	0.0482 (7)
H14A	0.0844	0.9461	0.3468	0.058*
C15	0.3123 (6)	0.86788 (14)	0.5833 (4)	0.0566 (8)
H15A	0.3280	0.8756	0.4900	0.085*
H15B	0.1698	0.8531	0.5359	0.085*
H15C	0.4154	0.8378	0.6608	0.085*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Pd1	0.03017 (15)	0.03263 (14)	0.03135 (14)	−0.00387 (10)	0.01650 (11)	−0.00210 (11)
F1	0.0547 (14)	0.0598 (14)	0.175 (3)	0.0194 (11)	0.0329 (16)	0.0054 (16)
O1	0.0568 (12)	0.0479 (11)	0.0349 (10)	−0.0199 (9)	0.0269 (9)	−0.0048 (8)
N1	0.0332 (11)	0.0332 (10)	0.0370 (11)	−0.0041 (8)	0.0203 (9)	−0.0044 (9)
C1	0.062 (2)	0.0424 (19)	0.143 (4)	−0.0064 (17)	0.041 (3)	0.027 (2)
C2	0.066 (3)	0.042 (2)	0.183 (6)	0.0083 (19)	0.036 (3)	0.038 (3)
C3	0.0486 (19)	0.0420 (17)	0.089 (3)	0.0076 (15)	0.0185 (19)	−0.0048 (17)
C4	0.0444 (16)	0.0509 (17)	0.0489 (17)	0.0005 (13)	0.0242 (14)	−0.0016 (13)
C5	0.0495 (16)	0.0367 (13)	0.0406 (14)	0.0042 (12)	0.0269 (13)	0.0054 (11)
C6	0.0476 (15)	0.0316 (12)	0.0381 (14)	−0.0029 (11)	0.0211 (12)	−0.0027 (11)
C7	0.0504 (16)	0.0328 (13)	0.0514 (16)	−0.0084 (11)	0.0327 (14)	−0.0041 (12)
C8	0.0335 (13)	0.0426 (14)	0.0395 (14)	−0.0059 (11)	0.0215 (12)	−0.0100 (11)
C9	0.0350 (13)	0.0478 (15)	0.0337 (13)	−0.0014 (11)	0.0209 (11)	−0.0032 (11)
C10	0.0424 (14)	0.0460 (15)	0.0363 (14)	−0.0025 (12)	0.0271 (12)	−0.0016 (11)
C11	0.067 (2)	0.0483 (17)	0.0498 (18)	−0.0012 (15)	0.0373 (17)	0.0029 (13)
C12	0.065 (2)	0.062 (2)	0.0513 (18)	0.0141 (16)	0.0365 (17)	0.0169 (16)
C13	0.0447 (17)	0.079 (2)	0.0360 (15)	0.0042 (16)	0.0197 (13)	0.0037 (15)
C14	0.0422 (15)	0.0614 (18)	0.0375 (15)	−0.0046 (13)	0.0208 (13)	−0.0066 (13)
C15	0.070 (2)	0.0485 (17)	0.0523 (18)	−0.0102 (15)	0.0360 (17)	−0.0160 (14)

Geometric parameters (Å, º) top

Pd1—O1	1.9770 (18)	C6—C7	1.510 (4)
Pd1—O1ⁱ	1.9770 (18)	C7—H7A	0.9700
Pd1—N1ⁱ	2.028 (2)	C7—H7B	0.9700
Pd1—N1	2.028 (2)	C8—C9	1.458 (4)
F1—C3	1.369 (4)	C8—C15	1.516 (4)
O1—C10	1.321 (3)	C9—C14	1.411 (4)
N1—C8	1.297 (3)	C9—C10	1.415 (4)
N1—C7	1.474 (3)	C10—C11	1.403 (4)
C1—C2	1.378 (6)	C11—C12	1.373 (5)
C1—C6	1.381 (4)	C11—H11A	0.9300
C1—H1A	0.9300	C12—C13	1.381 (5)
C2—C3	1.358 (6)	C12—H12A	0.9300
C2—H2A	0.9300	C13—C14	1.363 (5)
C3—C4	1.349 (5)	C13—H13A	0.9300
C4—C5	1.387 (4)	C14—H14A	0.9300
C4—H4A	0.9300	C15—H15A	0.9600
C5—C6	1.371 (4)	C15—H15B	0.9600
C5—H5	0.9300	C15—H15C	0.9600

O1—Pd1—O1ⁱ	180.00 (10)	N1—C7—H7B	108.9
O1—Pd1—N1ⁱ	91.52 (8)	C6—C7—H7B	108.9
O1ⁱ—Pd1—N1ⁱ	88.48 (8)	H7A—C7—H7B	107.7
O1—Pd1—N1	88.48 (8)	N1—C8—C9	122.4 (2)
O1ⁱ—Pd1—N1	91.52 (8)	N1—C8—C15	120.7 (3)
N1ⁱ—Pd1—N1	180.000 (1)	C9—C8—C15	116.9 (2)
C10—O1—Pd1	118.68 (16)	C14—C9—C10	118.1 (3)
C8—N1—C7	120.0 (2)	C14—C9—C8	119.6 (3)
C8—N1—Pd1	124.82 (18)	C10—C9—C8	122.2 (2)
C7—N1—Pd1	115.13 (17)	O1—C10—C11	117.9 (3)
C2—C1—C6	120.9 (4)	O1—C10—C9	124.0 (2)
C2—C1—H1A	119.6	C11—C10—C9	118.1 (3)
C6—C1—H1A	119.6	C12—C11—C10	121.8 (3)
C3—C2—C1	118.9 (4)	C12—C11—H11A	119.1
C3—C2—H2A	120.6	C10—C11—H11A	119.1
C1—C2—H2A	120.6	C11—C12—C13	120.3 (3)
C4—C3—C2	122.6 (3)	C11—C12—H12A	119.9
C4—C3—F1	118.5 (4)	C13—C12—H12A	119.9
C2—C3—F1	118.9 (3)	C14—C13—C12	119.3 (3)
C3—C4—C5	117.8 (3)	C14—C13—H13A	120.3
C3—C4—H4A	121.1	C12—C13—H13A	120.3
C5—C4—H4A	121.1	C13—C14—C9	122.4 (3)
C6—C5—C4	121.9 (3)	C13—C14—H14A	118.8
C6—C5—H5	119.0	C9—C14—H14A	118.8
C4—C5—H5	119.0	C8—C15—H15A	109.5
C5—C6—C1	117.9 (3)	C8—C15—H15B	109.5
C5—C6—C7	123.5 (2)	H15A—C15—H15B	109.5
C1—C6—C7	118.6 (3)	C8—C15—H15C	109.5
N1—C7—C6	113.4 (2)	H15A—C15—H15C	109.5
N1—C7—H7A	108.9	H15B—C15—H15C	109.5
C6—C7—H7A	108.9

N1ⁱ—Pd1—O1—C10	−134.7 (2)	Pd1—N1—C8—C9	−3.2 (4)
N1—Pd1—O1—C10	45.3 (2)	C7—N1—C8—C15	0.2 (4)
O1—Pd1—N1—C8	−25.1 (2)	Pd1—N1—C8—C15	176.5 (2)
O1ⁱ—Pd1—N1—C8	154.9 (2)	N1—C8—C9—C14	−157.8 (3)
O1—Pd1—N1—C7	151.39 (18)	C15—C8—C9—C14	22.6 (4)
O1ⁱ—Pd1—N1—C7	−28.61 (18)	N1—C8—C9—C10	24.0 (4)
C6—C1—C2—C3	−0.8 (9)	C15—C8—C9—C10	−155.6 (3)
C1—C2—C3—C4	2.6 (9)	Pd1—O1—C10—C11	141.1 (2)
C1—C2—C3—F1	−179.5 (5)	Pd1—O1—C10—C9	−40.7 (3)
C2—C3—C4—C5	−2.3 (7)	C14—C9—C10—O1	−178.0 (3)
F1—C3—C4—C5	179.8 (3)	C8—C9—C10—O1	0.2 (4)
C3—C4—C5—C6	0.2 (5)	C14—C9—C10—C11	0.2 (4)
C4—C5—C6—C1	1.4 (5)	C8—C9—C10—C11	178.4 (3)
C4—C5—C6—C7	179.4 (3)	O1—C10—C11—C12	178.2 (3)
C2—C1—C6—C5	−1.1 (7)	C9—C10—C11—C12	−0.2 (5)
C2—C1—C6—C7	−179.1 (5)	C10—C11—C12—C13	0.4 (5)
C8—N1—C7—C6	87.6 (3)	C11—C12—C13—C14	−0.7 (5)
Pd1—N1—C7—C6	−89.0 (2)	C12—C13—C14—C9	0.8 (5)
C5—C6—C7—N1	8.3 (4)	C10—C9—C14—C13	−0.6 (4)
C1—C6—C7—N1	−173.7 (3)	C8—C9—C14—C13	−178.8 (3)
C7—N1—C8—C9	−179.5 (2)

Symmetry code: (i) −x+1, −y+2, −z+2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4A···O1ⁱⁱ	0.93	2.50	3.405 (5)	165

Symmetry code: (ii) −x+2, −y+2, −z+2.

Footnotes

‡Additional correspondence author, email: suchada.c@psu.ac.th. Thomson Reuters ResearcherID: A-5085-2009.

Acknowledgements

The authors wish to express their appreciation to the Universiti Teknologi MARA for the research grants Nos. 600-RMI/DANA 5/3/CIFI (1/2014) and 600-RMI/DANA 5/3/PSI (1/2014) and the research facilities. A scholarship from the Universiti Teknologi MARA and the Ministry of Education Malaysia is also gratefully acknowledged.

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