PMCCPMCCPMCC

Search tips
Search criteria 

Advanced

 
Logo of actaeInternational Union of Crystallographysearchopen accessarticle submissionjournal home pagethis article
 
Acta Crystallogr Sect E Struct Rep Online. 2009 June 1; 65(Pt 6): m619.
Published online 2009 May 7. doi:  10.1107/S1600536809016390
PMCID: PMC2969542

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

Abstract

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.

Related literature

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

An external file that holds a picture, illustration, etc.
Object name is e-65-0m619-scheme1.jpg

Experimental

Crystal data

  • [Pd(C13H10N3O)2]
  • M r = 554.88
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-0m619-efi1.jpg
  • a = 12.9768 (7) Å
  • b = 5.6990 (3) Å
  • c = 15.6035 (8) Å
  • β = 109.287 (3)°
  • V = 1089.19 (10) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 0.89 mm−1
  • T = 295 K
  • 0.20 × 0.10 × 0.08 mm

Data collection

  • Bruker APEXII CCD diffractometer
  • Absorption correction: multi-scan (SADABS; Bruker, 2008 [triangle]) T min = 0.842, T max = 0.932
  • 9857 measured reflections
  • 2690 independent reflections
  • 1959 reflections with I > 2σ(I)
  • R int = 0.104

Refinement

  • R[F 2 > 2σ(F 2)] = 0.031
  • wR(F 2) = 0.066
  • S = 1.03
  • 2690 reflections
  • 161 parameters
  • H-atom parameters constrained
  • Δρmax = 0.42 e Å−3
  • Δρmin = −0.82 e Å−3

Data collection: APEX2 (Bruker, 2008 [triangle]); cell refinement: SAINT (Bruker, 2008 [triangle]); data reduction: SAINT; 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.

Table 1
Selected geometric parameters (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809016390/rk2144sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809016390/rk2144Isup2.hkl

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

Acknowledgments

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).

supplementary crystallographic information

Comment

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.

Experimental

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

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).

Figures

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.
Fig. 2.
Synthesis pass of title compound I.

Crystal data

[Pd(C13H10N3O)2]F(000) = 560
Mr = 554.88Dx = 1.692 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 3862 reflections
a = 12.9768 (7) Åθ = 2.7–28.2°
b = 5.6990 (3) ŵ = 0.89 mm1
c = 15.6035 (8) ÅT = 295 K
β = 109.287 (3)°Columnar, red
V = 1089.19 (10) Å30.20 × 0.10 × 0.08 mm
Z = 2

Data collection

Bruker APEXII CCD diffractometer2690 independent reflections
Radiation source: fine-focus sealed tube1959 reflections with I > 2σ(I)
graphiteRint = 0.104
[var phi] and ω scansθmax = 28.3°, θmin = 1.7°
Absorption correction: multi-scan (SADABS; Bruker, 2008)h = −16→17
Tmin = 0.842, Tmax = 0.932k = −7→7
9857 measured reflectionsl = −20→20

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)] = 0.031Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.066H-atom parameters constrained
S = 1.03w = 1/[σ2(Fo2) + (0.019P)2] where P = (Fo2 + 2Fc2)/3
2690 reflections(Δ/σ)max = 0.002
161 parametersΔρmax = 0.42 e Å3
0 restraintsΔρmin = −0.82 e Å3

Special details

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)

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)

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, °)

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.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: RK2144).

References

  • 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. [PubMed]
  • Lin, C.-S., Lin, C.-H., Huang, J.-H. & Ko, B.-T. (2008). Acta Cryst. E64, m1434. [PMC free article] [PubMed]
  • Peng, Y.-L., Lai, S.-L. & Lin, C.-C. (2008). Macromolecules, 41, 3455–3459.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Yang, H., Khan, M. A. & Nicholas, K. M. (1993). Organometallics, 12, 3485–3494.

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography