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Acta Crystallogr Sect E Struct Rep Online. 2010 September 1; 66(Pt 9): m1100.
Published online 2010 August 18. doi:  10.1107/S1600536810031375
PMCID: PMC3007840

Bis{2-[1-(benzyl­imino)­eth­yl]phenolato}palladium(II)

Abstract

In the title compound, [Pd(C15H14NO)2], the Pd atom lies on an inversion center and is coordinated by two ligand mol­ecules through the O and N atoms in a bidentate manner, forming a slightly distorted square-planar geometry. The dihedral angle between the two benzene rings in the ligand is 76.53 (19)°. The mol­ecular packing is stablized by C—H(...)O and C—H(...)π inter­actions.

Related literature

For the catalytic activity of palladium(II)–Schiff base complexes, see: Gupta & Sutar (2008 [triangle]); Lai et al. (2005 [triangle]) and for their anti­tumor activity, see: Garoufis et al. (2008 [triangle]). For related structures, see: Adrian et al. (2008 [triangle]); Wan Nazihah Wan Ibrahim et al. (2008 [triangle]); Chen & Xia (2009 [triangle]). For bond-length data, see: Allen et al. (2002 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-66-m1100-scheme1.jpg

Experimental

Crystal data

  • [Pd(C15H14NO)2]
  • M r = 554.94
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-m1100-efi1.jpg
  • a = 11.188 (2) Å
  • b = 9.4460 (17) Å
  • c = 11.984 (2) Å
  • β = 110.558 (4)°
  • V = 1185.8 (4) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 0.81 mm−1
  • T = 298 K
  • 0.28 × 0.20 × 0.12 mm

Data collection

  • Bruker SMART APEX CCD area-detector diffractometer
  • Absorption correction: multi-scan (SADABS; Bruker, 2000 [triangle]) T min = 0.804, T max = 0.908
  • 6420 measured reflections
  • 2177 independent reflections
  • 1939 reflections with I > 2σ(I)
  • R int = 0.038

Refinement

  • R[F 2 > 2σ(F 2)] = 0.036
  • wR(F 2) = 0.109
  • S = 1.18
  • 2177 reflections
  • 161 parameters
  • H-atom parameters constrained
  • Δρmax = 0.88 e Å−3
  • Δρmin = −0.98 e Å−3

Data collection: SMART (Bruker, 2000 [triangle]); cell refinement: SAINT (Bruker, 2000 [triangle]); data reduction: SAINT (Bruker, 2000 [triangle]); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: SHELXTL (Sheldrick, 2008 [triangle]); software used to prepare material for publication: SHELXTL (Sheldrick, 2008 [triangle]), PARST (Nardelli, 1995 [triangle]) and PLATON (Spek, 2009 [triangle]).

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810031375/pv2311sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810031375/pv2311Isup2.hkl

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

Acknowledgments

Thanks are gratefully extended to The Ministry of Higher Education of Malaysia, Universiti Teknologi MARA and Universiti Kebangsaan Malaysia for the research grants Nos. 600-RMI/ST/FRGS 5/3/Fst(7/2009) and UKM-OUP-BTT-28/2007.

supplementary crystallographic information

Comment

The palladium- Schiff bases complexes have found various applications expecially as catalyst (Gupta & Sutar, 2008; Lai et al., 2005) and antitumors activity (Garoufis et al., 2008). The title compound is analogous to the previously reported complex, {2,2'-[(2,2-dimethylpropane-1,3-diyl)-bis (nitrilomethylidyne)]diphenolato}-palladium(II) ethanol hemisolvate (Wan Nazihah Wan Ibrahim et al., 2008) in terms of the geometry around the central palladium atom.

In the title molecule (Fig. 1), the palladium atom lies on an inversion center and is coordinated to two ligand molecules through the oxygen and nitrogen atoms in a bidentate manner to form a perfect square planar geometry. The bond distances and bond angles in the title complex are normal (Allen et al., 2002). The Pd1—O and Pd1—N bond lengths of 1.981 (2) and 2.039 (2)Å, respectively, in a square planar geometry are typical of square planar Pd(II) of Schiff bases (Adrian et al., 2008). The dihedral angle between the benzene rings is 76.5 (2)°. The molecule is stabilized by C—H..π (C8—H8B···Cg3, C8—H8C···Cg4 and C13H-13 A···Cg3) interactions (Table 1).

Experimental

The ligand, 2-hydroxyacetophenonebenzylimine, (1.1271 g, 5 mmol) was dissolved in hot ethanol (20 ml) in a round-bottomed flask. Palladium(II) acetate (0.5618 g, 2.5 mmol) was dissolved separately in hot ethanol (40 ml) and added into the flask containing the ligand solution. The mixture was stirred and refluxed for 5 h upon which green precipitate was formed. It was isolated by gravity filtration, washed with cold ethanol and air dried at room temperature. The solid product was recrystallized from chloroform yielding yellow crystals. Yield 87.80%; m.p. 529–530 K.

Refinement

The H atoms were positioned geometrically with C—H = 0.97, 96 and 0.93 Å for methyl, methylene and aromatic groups, respectively, and constrained to ride on their parent atoms with Uiso(H) = 1.5(methyl) or 1.2(methylene and aromatic) × Ueq(C). The highest peak and deepest hole are located at 0.90 Å from Pd1 atom.

Figures

Fig. 1.
The molecular structure of the title complex with displacement ellipsods drawn at the 50% probability level.

Crystal data

[Pd(C15H14NO)2]F(000) = 568
Mr = 554.94Dx = 1.554 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 4170 reflections
a = 11.188 (2) Åθ = 2.1–25.5°
b = 9.4460 (17) ŵ = 0.81 mm1
c = 11.984 (2) ÅT = 298 K
β = 110.558 (4)°Block, yellow
V = 1185.8 (4) Å30.28 × 0.20 × 0.12 mm
Z = 2

Data collection

Bruker SMART APEX CCD area-detector diffractometer2177 independent reflections
Radiation source: fine-focus sealed tube1939 reflections with I > 2/s(I)
graphiteRint = 0.038
Detector resolution: 83.66 pixels mm-1θmax = 25.5°, θmin = 2.1°
ω scanh = −13→13
Absorption correction: multi-scan (SADABS; Bruker, 2000)k = −11→11
Tmin = 0.804, Tmax = 0.908l = −14→11
6420 measured reflections

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.036Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.109H-atom parameters constrained
S = 1.18w = 1/[σ2(Fo2) + (0.0502P)2 + 0.7043P] where P = (Fo2 + 2Fc2)/3
2177 reflections(Δ/σ)max < 0.001
161 parametersΔρmax = 0.88 e Å3
0 restraintsΔρmin = −0.98 e Å3

Special details

Experimental. Analytical calculation for C30H28N2O2Pd: C,64.93; H,5.09; N,5.05. Found: C,64.58; H,4.97; N,4.94. IR (cm-1): v(C=N) 1586, v(C—O) 1323, v(C—H) 2977, v(C—N) 1355, v(Pd—O) 695, v(Pd—N) 476.
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)

xyzUiso*/Ueq
Pd10.50000.50000.00000.02879 (16)
O10.4462 (2)0.5912 (3)0.1236 (2)0.0409 (6)
N10.6541 (2)0.6317 (3)0.0459 (2)0.0323 (6)
C10.5319 (3)0.6226 (3)0.2285 (3)0.0335 (7)
C20.4944 (3)0.6076 (4)0.3284 (3)0.0422 (8)
H2A0.41280.57480.31780.051*
C30.5765 (4)0.6406 (4)0.4419 (3)0.0468 (9)
H3A0.55030.62910.50690.056*
C40.6971 (4)0.6906 (4)0.4583 (4)0.0498 (10)
H4A0.75290.71160.53460.060*
C50.7346 (3)0.7095 (4)0.3632 (4)0.0428 (9)
H5A0.81560.74580.37600.051*
C60.6551 (3)0.6758 (3)0.2454 (3)0.0326 (7)
C70.7007 (3)0.6991 (3)0.1464 (3)0.0335 (7)
C80.8047 (4)0.8088 (4)0.1658 (4)0.0437 (9)
H8A0.79610.85290.09120.066*
H8B0.88670.76380.19770.066*
H8C0.79740.87930.22080.066*
C90.7070 (3)0.6577 (3)−0.0483 (3)0.0347 (7)
H9A0.69930.5717−0.09450.042*
H9B0.79720.6790−0.01140.042*
C100.6432 (3)0.7774 (3)−0.1320 (3)0.0321 (7)
C110.5685 (3)0.8786 (4)−0.1050 (3)0.0423 (8)
H11A0.55410.8737−0.03330.051*
C120.5149 (5)0.9877 (4)−0.1846 (5)0.0554 (12)
H12A0.46461.0553−0.16570.066*
C130.5354 (6)0.9965 (4)−0.2906 (5)0.0569 (13)
H13A0.49981.0701−0.34320.068*
C140.6090 (4)0.8957 (4)−0.3186 (4)0.0531 (10)
H14A0.62310.9007−0.39050.064*
C150.6619 (3)0.7873 (4)−0.2398 (3)0.0438 (9)
H15A0.71120.7193−0.25950.053*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Pd10.0270 (2)0.0261 (2)0.0302 (3)−0.00145 (11)0.00621 (17)0.00023 (12)
O10.0325 (12)0.0481 (14)0.0402 (14)−0.0030 (10)0.0104 (11)−0.0108 (11)
N10.0297 (13)0.0273 (13)0.0396 (16)0.0003 (11)0.0116 (12)0.0024 (12)
C10.0351 (16)0.0236 (15)0.039 (2)0.0035 (13)0.0098 (15)−0.0020 (14)
C20.0437 (19)0.0346 (18)0.053 (2)−0.0016 (15)0.0227 (18)−0.0025 (16)
C30.057 (2)0.049 (2)0.036 (2)0.0019 (18)0.0177 (18)−0.0037 (17)
C40.053 (2)0.054 (2)0.034 (2)0.0033 (18)0.0051 (18)−0.0084 (18)
C50.0366 (18)0.041 (2)0.046 (2)0.0004 (15)0.0083 (17)−0.0055 (17)
C60.0357 (16)0.0268 (16)0.0317 (18)0.0023 (13)0.0074 (14)−0.0005 (13)
C70.0301 (16)0.0257 (15)0.038 (2)0.0009 (13)0.0041 (14)0.0009 (14)
C80.0424 (19)0.0353 (19)0.050 (2)−0.0090 (15)0.0115 (18)−0.0001 (17)
C90.0300 (16)0.0345 (17)0.040 (2)−0.0021 (13)0.0133 (15)−0.0002 (14)
C100.0320 (16)0.0330 (16)0.0305 (18)−0.0065 (13)0.0099 (14)−0.0012 (14)
C110.053 (2)0.043 (2)0.0287 (19)0.0076 (16)0.0111 (16)0.0007 (16)
C120.074 (3)0.040 (2)0.052 (3)0.0167 (18)0.021 (3)0.0026 (17)
C130.076 (4)0.038 (2)0.051 (3)0.0001 (17)0.016 (3)0.0121 (16)
C140.072 (3)0.051 (2)0.043 (2)−0.010 (2)0.029 (2)0.0042 (18)
C150.050 (2)0.043 (2)0.046 (2)−0.0010 (16)0.0268 (18)−0.0005 (17)

Geometric parameters (Å, °)

Pd1—O11.981 (2)C7—C81.514 (4)
Pd1—O1i1.981 (2)C8—H8A0.9600
Pd1—N1i2.039 (3)C8—H8B0.9600
Pd1—N12.039 (3)C8—H8C0.9600
O1—C11.319 (4)C9—C101.514 (5)
N1—C71.299 (4)C9—H9A0.9700
N1—C91.468 (4)C9—H9B0.9700
C1—C21.407 (5)C10—C111.380 (5)
C1—C61.414 (4)C10—C151.382 (5)
C2—C31.384 (5)C11—C121.389 (6)
C2—H2A0.9300C11—H11A0.9300
C3—C41.377 (5)C12—C131.371 (8)
C3—H3A0.9300C12—H12A0.9300
C4—C51.357 (6)C13—C141.375 (6)
C4—H4A0.9300C13—H13A0.9300
C5—C61.415 (5)C14—C151.377 (6)
C5—H5A0.9300C14—H14A0.9300
C6—C71.463 (5)C15—H15A0.9300
O1—Pd1—O1i180.00 (8)C7—C8—H8A109.5
O1—Pd1—N1i90.97 (10)C7—C8—H8B109.5
O1i—Pd1—N1i89.03 (10)H8A—C8—H8B109.5
O1—Pd1—N189.03 (10)C7—C8—H8C109.5
O1i—Pd1—N190.97 (10)H8A—C8—H8C109.5
N1i—Pd1—N1180.00 (11)H8B—C8—H8C109.5
C1—O1—Pd1120.0 (2)N1—C9—C10114.3 (3)
C7—N1—C9119.5 (3)N1—C9—H9A108.7
C7—N1—Pd1125.1 (2)C10—C9—H9A108.7
C9—N1—Pd1115.2 (2)N1—C9—H9B108.7
O1—C1—C2117.0 (3)C10—C9—H9B108.7
O1—C1—C6124.2 (3)H9A—C9—H9B107.6
C2—C1—C6118.7 (3)C11—C10—C15118.3 (3)
C3—C2—C1121.4 (3)C11—C10—C9123.0 (3)
C3—C2—H2A119.3C15—C10—C9118.6 (3)
C1—C2—H2A119.3C10—C11—C12120.3 (4)
C4—C3—C2119.7 (3)C10—C11—H11A119.9
C4—C3—H3A120.1C12—C11—H11A119.9
C2—C3—H3A120.1C13—C12—C11120.5 (4)
C5—C4—C3120.1 (4)C13—C12—H12A119.7
C5—C4—H4A119.9C11—C12—H12A119.7
C3—C4—H4A119.9C12—C13—C14119.6 (4)
C4—C5—C6122.4 (4)C12—C13—H13A120.2
C4—C5—H5A118.8C14—C13—H13A120.2
C6—C5—H5A118.8C13—C14—C15119.8 (4)
C1—C6—C5117.6 (3)C13—C14—H14A120.1
C1—C6—C7122.5 (3)C15—C14—H14A120.1
C5—C6—C7119.9 (3)C14—C15—C10121.4 (3)
N1—C7—C6122.5 (3)C14—C15—H15A119.3
N1—C7—C8120.9 (3)C10—C15—H15A119.3
C6—C7—C8116.5 (3)
O1i—Pd1—O1—C1−151 (100)C4—C5—C6—C7179.6 (3)
N1i—Pd1—O1—C1138.5 (2)C9—N1—C7—C6−178.3 (3)
N1—Pd1—O1—C1−41.5 (2)Pd1—N1—C7—C66.9 (4)
O1—Pd1—N1—C720.0 (3)C9—N1—C7—C82.7 (4)
O1i—Pd1—N1—C7−160.0 (3)Pd1—N1—C7—C8−172.1 (2)
N1i—Pd1—N1—C7156 (100)C1—C6—C7—N1−24.1 (5)
O1—Pd1—N1—C9−155.0 (2)C5—C6—C7—N1157.2 (3)
O1i—Pd1—N1—C925.0 (2)C1—C6—C7—C8155.0 (3)
N1i—Pd1—N1—C9−19 (100)C5—C6—C7—C8−23.7 (5)
Pd1—O1—C1—C2−144.1 (2)C7—N1—C9—C10−89.1 (3)
Pd1—O1—C1—C638.9 (4)Pd1—N1—C9—C1086.1 (3)
O1—C1—C2—C3−178.7 (3)N1—C9—C10—C1117.5 (4)
C6—C1—C2—C3−1.5 (5)N1—C9—C10—C15−163.5 (3)
C1—C2—C3—C40.7 (6)C15—C10—C11—C12−0.5 (6)
C2—C3—C4—C51.0 (6)C9—C10—C11—C12178.6 (4)
C3—C4—C5—C6−1.8 (6)C10—C11—C12—C13−0.1 (7)
O1—C1—C6—C5177.7 (3)C11—C12—C13—C140.5 (8)
C2—C1—C6—C50.7 (4)C12—C13—C14—C15−0.3 (7)
O1—C1—C6—C7−1.0 (5)C13—C14—C15—C10−0.3 (6)
C2—C1—C6—C7−178.0 (3)C11—C10—C15—C140.7 (5)
C4—C5—C6—C10.9 (5)C9—C10—C15—C14−178.4 (3)

Symmetry codes: (i) −x+1, −y+1, −z.

Hydrogen-bond geometry (Å, °)

Cg3 and Cg4 are the centroids of the ???? and ???? rings, respectively.
D—H···AD—HH···AD···AD—H···A
C9—H9A···O1i0.972.182.862 (4)127
C11—H11A···N10.932.582.900 (5)101
C8—H8B···Cg4ii0.962.573.523 (5)172
C13—H13A···Cg3iii0.932.873.626 (5)139

Symmetry codes: (i) −x+1, −y+1, −z; (ii) x−1/2, −y+1/2, z−1/2; (iii) −x+1, −y+2, −z.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: PV2311).

References

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  • Lai, Y. C., Chen, H. Y., Hung, W. C., Lin, C. C. & Hong, F. E. (2005). Tetrahedron, 61, 9484–9489.
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