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Acta Cryst. (2009). E65, m619    [ doi:10.1107/S1600536809016390 ]

Bis[2-(2H-benzotriazol-2-yl)-4-methylphenolato]palladium(II)

C.-Y. Tsai, C.-H. Lin and B.-T. Ko

Abstract top

In the title complex, [Pd(C13H10N3O)2], the PdII atom is tetracoordinated by two N atoms and two O atoms from two bidentate 2-(2H-benzotriazol-2-yl)-4-methylphenolate ligands, forming a square-planar environment. The asymmetric unit contains one half molecule in which the Pd atom lies on a centre of symmetry.

Comment top

During the last 2 decades, the synthesis and characterization of polypeptides is an interesting research field that received considerable attentions. The chemical synthesis of high molecular weight poly(α-peptides) can be accomplished by the ring-opening polymerization of α-amino acid N-carboxyanhydride (α-NCA) initiated by suitable initiators/catalysts. Among these initiators/catalysts, the Ni, Co, Fe, Pd, Pt, Ru, Ir, and Al complexes modified by adequate ligands have been shown to be active initiators/catalysts for NCA polymerization (Kricheldorf, 2006). In particular, Deming, (1997), reported that Schiff base ligand containing primary amine complexes of Co, Ni, Pd, and Cu metal ion could efficiently catalyze polymerizations of γ-benzyl L-glutamate N-carboxyanhydride (Glu-NCA) to achieve poly(γ-benzyl L-glutamate). Recently, Peng et al., 2008, has also reported the Pt complex supported by amido-sulfonamidate ligand and this complex has been demonstrated as efficient initiators for living ROP of α-NCA. Most recently, we have successfully synthesized and structural characterized a N,N',O-tridentate Schiff base of Cu(II) complex (Lin et al., 2008). We report herein the synthesis and crystal structure of N,O-bidentate benzotriazol-phenolate ligands incorporated PdII complex (I), a potential catalyst for chemical synthesis of poly(peptides) (Scheme 1).

The solid structure of (I) reveals a monomeric PdII complex (Fig. 1) containing two six-member rings coordinated from these two N,O-bidentate benzotriazol-phenolate ligands. It was found that the asymmetric unit has one half of molecule in which the Pd atom lies on a centre of symmetry. The Pd 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 Pd atom are trans to each other with bond angle of O–Pd–N1 of 91.74 (7)°. The distances between the Pd atom and O and N1 are 1.9676 (15)Å, 1.9986 (18)Å, respectively. These bond distances of Pd–O and Pd–N1 are around 0.1 Å shorter to those found in the other Schiff base PdII complexes (Yang et al.,1993). The bond distance of imine bond, C7–N1 of the benzotriazol group is 1.359 (3)Å and is 0.01Å longer than the other imine bond, C12–N3 (1.348 (3)Å). This is probably due to the existing coordination bond of the former nitrogen, N1.

Related literature top

For background information, see: Deming (1997); Kricheldorf (2006); Lin et al. (2008); Peng et al. (2008). For related structures: see: Yang et al., (1993).

Experimental top

The title complex was synthesized by the following procedures (Fig. 2): 2-(2H-benzotriazol-2-yl)-4-methylphenol (0.45 g, 2.0 mmol) and Pd(OAc)2 (0.22 g, 1.0 mmol) was stirred at ambient temperature in THF (25 ml) for 12 h during which a red-orange precipitate formed (yield: 75%). The resulting solids were crystallized from CH2Cl2 solution to yield red crystals. Anal. calcd for C26H20N6O2Pd: C, 56.28; H, 3.63; N, 15.15%. Found: C, 56.13; H, 3.79; N, 15.46%.

Refinement top

The H atoms were placed in idealized positions and constrained to ride on their parent atoms, with C–H = 0.93 and 0.96Å with Uiso(H) = 1.2 and 1.5Ueq(C).

Computing details top

Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); 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: SHELXTL (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. A view of the title molecule I with the atom numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. H atoms are presented as a small spheres of arbitrary radius. Symmetry code: (i) 2-x, -y, 1-z.
[Figure 2] Fig. 2. Synthesis pass of title compound I.
Bis[2-(2H-benzotriazol-2-yl)-4-methylphenolato]palladium(II) top
Crystal data top
[Pd(C13H10N3O)2]F000 = 560
Mr = 554.88Dx = 1.692 Mg m−3
Monoclinic, P21/cMo Kα radiation
λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 3862 reflections
a = 12.9768 (7) Åθ = 2.7–28.2º
b = 5.6990 (3) ŵ = 0.89 mm−1
c = 15.6035 (8) ÅT = 295 K
β = 109.287 (3)ºColumnar, red
V = 1089.19 (10) Å30.20 × 0.10 × 0.08 mm
Z = 2
Data collection top
Bruker APEXII CCD
diffractometer		2690 independent reflections
Radiation source: fine-focus sealed tube1959 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.104
T = 295 Kθmax = 28.3º
φ and ω scansθmin = 1.7º
Absorption correction: multi-scan
(SADABS; Bruker, 2008)		h = −16→17
Tmin = 0.842, Tmax = 0.932k = −7→7
9857 measured reflectionsl = −20→20
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.031H-atom parameters constrained
wR(F2) = 0.066  w = 1/[σ2(Fo2) + (0.019P)2]
where P = (Fo2 + 2Fc2)/3
S = 1.03(Δ/σ)max = 0.002
2690 reflectionsΔρmax = 0.42 e Å−3
161 parametersΔρmin = −0.82 e Å−3
Primary atom site location: structure-invariant direct methodsExtinction correction: none
Crystal data top
[Pd(C13H10N3O)2]V = 1089.19 (10) Å3
Mr = 554.88Z = 2
Monoclinic, P21/cMo Kα
a = 12.9768 (7) ŵ = 0.89 mm−1
b = 5.6990 (3) ÅT = 295 K
c = 15.6035 (8) Å0.20 × 0.10 × 0.08 mm
β = 109.287 (3)º
Data collection top
Bruker APEXII CCD
diffractometer		2690 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2008)		1959 reflections with I > 2σ(I)
Tmin = 0.842, Tmax = 0.932Rint = 0.104
9857 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.031161 parameters
wR(F2) = 0.066H-atom parameters constrained
S = 1.03Δρmax = 0.42 e Å−3
2690 reflectionsΔρmin = −0.82 e Å−3
Special details top

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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
xyzUiso*/Ueq
Pd1.00000.00000.50000.02562 (9)
O0.98900 (13)0.1401 (3)0.38204 (11)0.0359 (4)
N10.84675 (14)−0.1144 (3)0.44409 (13)0.0284 (4)
N20.76972 (15)−0.0006 (3)0.37741 (13)0.0270 (4)
N30.66977 (16)−0.0858 (3)0.35839 (14)0.0328 (5)
C10.89890 (19)0.2481 (4)0.33261 (16)0.0309 (5)
C20.79138 (18)0.1917 (4)0.32782 (15)0.0280 (5)
C30.70175 (19)0.3162 (4)0.27150 (16)0.0324 (5)
H3B0.63190.27360.26980.039*
C40.7139 (2)0.4982 (4)0.21906 (17)0.0352 (5)
C50.8191 (2)0.5568 (4)0.22219 (18)0.0406 (7)
H5A0.82930.68050.18700.049*
C60.9083 (2)0.4351 (4)0.27641 (18)0.0392 (6)
H6A0.97730.47750.27600.047*
C70.79189 (19)−0.2925 (4)0.46805 (16)0.0301 (5)
C80.8287 (2)−0.4786 (4)0.52925 (18)0.0375 (6)
H8A0.9021−0.49800.56300.045*
C90.7499 (2)−0.6305 (4)0.53637 (18)0.0429 (7)
H9A0.7707−0.75590.57660.051*
C100.6391 (2)−0.6036 (5)0.48527 (19)0.0463 (7)
H10A0.5890−0.71070.49330.056*
C110.6026 (2)−0.4273 (4)0.4248 (2)0.0408 (6)
H11A0.5291−0.41160.39080.049*
C120.68220 (19)−0.2680 (4)0.41576 (17)0.0328 (5)
C130.6164 (2)0.6324 (5)0.15814 (19)0.0511 (7)
H13A0.55140.58030.16900.077*
H13B0.60940.60490.09580.077*
H13C0.62660.79710.17110.077*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Pd0.01933 (15)0.02899 (11)0.02833 (15)0.00099 (10)0.00758 (11)0.00236 (11)
O0.0225 (9)0.0518 (10)0.0342 (10)0.0034 (7)0.0102 (8)0.0126 (8)
N10.0228 (11)0.0311 (9)0.0307 (11)0.0003 (8)0.0080 (9)0.0017 (8)
N20.0196 (10)0.0309 (8)0.0289 (11)−0.0003 (8)0.0057 (9)−0.0005 (9)
N30.0215 (12)0.0359 (9)0.0387 (12)−0.0033 (8)0.0070 (10)−0.0023 (9)
C10.0281 (14)0.0388 (11)0.0259 (13)−0.0002 (10)0.0089 (11)−0.0002 (10)
C20.0285 (14)0.0302 (10)0.0255 (13)−0.0014 (9)0.0090 (11)−0.0011 (9)
C30.0254 (14)0.0373 (11)0.0332 (14)0.0034 (9)0.0079 (12)−0.0021 (10)
C40.0361 (15)0.0391 (11)0.0264 (13)0.0074 (11)0.0049 (11)0.0006 (11)
C50.0445 (18)0.0419 (14)0.0335 (15)−0.0010 (10)0.0107 (14)0.0095 (10)
C60.0302 (15)0.0493 (13)0.0368 (16)−0.0050 (10)0.0093 (13)0.0086 (11)
C70.0287 (14)0.0312 (10)0.0320 (14)−0.0044 (9)0.0124 (12)−0.0045 (9)
C80.0385 (16)0.0358 (12)0.0359 (15)−0.0038 (10)0.0093 (13)0.0021 (11)
C90.057 (2)0.0341 (12)0.0400 (16)−0.0080 (11)0.0194 (15)0.0011 (11)
C100.053 (2)0.0425 (13)0.0505 (19)−0.0198 (13)0.0266 (16)−0.0053 (13)
C110.0329 (16)0.0444 (12)0.0467 (18)−0.0132 (11)0.0154 (14)−0.0069 (12)
C120.0284 (14)0.0349 (11)0.0365 (14)−0.0046 (9)0.0124 (12)−0.0067 (10)
C130.0457 (18)0.0549 (16)0.0448 (18)0.0142 (13)0.0041 (15)0.0105 (13)
Geometric parameters (Å, °) top
Pd—Oi1.9676 (15)C5—C61.375 (4)
Pd—O1.9677 (15)C5—H5A0.9300
Pd—N11.9986 (18)C6—H6A0.9300
Pd—N1i1.9986 (18)C7—C121.394 (3)
O—C11.321 (3)C7—C81.401 (3)
N1—N21.347 (3)C8—C91.372 (3)
N1—C71.361 (3)C8—H8A0.9300
N2—N31.324 (3)C9—C101.403 (4)
N2—C21.422 (3)C9—H9A0.9300
N3—C121.346 (3)C10—C111.353 (4)
C1—C21.410 (3)C10—H10A0.9300
C1—C61.410 (3)C11—C121.417 (3)
C2—C31.398 (3)C11—H11A0.9300
C3—C41.362 (3)C13—H13A0.9600
C3—H3B0.9300C13—H13B0.9600
C4—C51.391 (4)C13—H13C0.9600
C4—C131.515 (3)
Oi—Pd—O180.0C4—C5—H5A119.4
Oi—Pd—N191.74 (7)C5—C6—C1122.4 (2)
O—Pd—N188.26 (7)C5—C6—H6A118.8
Oi—Pd—N1i88.27 (7)C1—C6—H6A118.8
O—Pd—N1i91.73 (7)N1—C7—C12106.86 (19)
N1—Pd—N1i180.0N1—C7—C8131.3 (2)
C1—O—Pd120.80 (13)C12—C7—C8121.8 (2)
N2—N1—C7104.42 (18)C9—C8—C7115.9 (3)
N2—N1—Pd123.90 (14)C9—C8—H8A122.0
C7—N1—Pd131.19 (16)C7—C8—H8A122.0
N3—N2—N1114.76 (18)C8—C9—C10122.4 (2)
N3—N2—C2121.06 (19)C8—C9—H9A118.8
N1—N2—C2124.15 (18)C10—C9—H9A118.8
N2—N3—C12103.9 (2)C11—C10—C9122.3 (2)
O—C1—C2126.5 (2)C11—C10—H10A118.8
O—C1—C6118.3 (2)C9—C10—H10A118.8
C2—C1—C6115.3 (2)C10—C11—C12116.5 (3)
C3—C2—C1121.4 (2)C10—C11—H11A121.7
C3—C2—N2117.4 (2)C12—C11—H11A121.7
C1—C2—N2121.1 (2)N3—C12—C7110.0 (2)
C4—C3—C2121.8 (2)N3—C12—C11129.0 (2)
C4—C3—H3B119.1C7—C12—C11121.0 (2)
C2—C3—H3B119.1C4—C13—H13A109.5
C3—C4—C5117.9 (2)C4—C13—H13B109.5
C3—C4—C13121.6 (2)H13A—C13—H13B109.5
C5—C4—C13120.5 (2)C4—C13—H13C109.5
C6—C5—C4121.2 (2)H13A—C13—H13C109.5
C6—C5—H5A119.4H13B—C13—H13C109.5
Symmetry codes: (i) −x+2, −y, −z+1.
Table 1
Selected geometric parameters (Å, °) top
Pd—Oi1.9676 (15)Pd—N11.9986 (18)
Oi—Pd—O180.0O—Pd—N188.26 (7)
Oi—Pd—N191.74 (7)N1—Pd—N1i180.0
Symmetry codes: (i) −x+2, −y, −z+1.
Acknowledgements top

The authors gratefully acknowledge financial support in part from the National Science Council, Taiwan (grant No. NSC97-2113-M-033-005-MY2) and in part from the project of the specific research fields in the Chung Yuan Christian University, Taiwan (grant No. CYCU-97-CR-CH).

references
References top

Bruker (2008). APEX2, SADABS and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.

Deming, T. J. (1997). J. Am. Chem. Soc. 119, 2759–2760.

Kricheldorf, H. R. (2006). Angew. Chem. Int. Ed. 45, 5752–5784.

Lin, C.-S., Lin, C.-H., Huang, J.-H. & Ko, B.-T. (2008). Acta Cryst. E64, m1434.

Peng, Y.-L., Lai, S.-L. & Lin, C.-C. (2008). Macromolecules, 41, 3455–3459.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.

Yang, H., Khan, M. A. & Nicholas, K. M. (1993). Organometallics, 12, 3485–3494.