Crystal structure of (bis(2 pyridyl)imido)chloropalladium(II), PdCl(C12H8N3O2) Kwang Ha* Chonnam National University, School of Applied Chemical Engineering, Research Institute of Catalysis, Gwangju 5[.]
Z Kristallogr NCS 225 (2010) 789-790 / DOI 10.1524/ncrs.2010.0347 789 © by Oldenbourg Wissenschaftsverlag, München Crystal structure of (bis(2-pyridyl)imido)chloropalladium(II), PdCl(C12H8N3O2) Kwang Ha* Chonnam National University, School of Applied Chemical Engineering, Research Institute of Catalysis, Gwangju 500-757, Republic of Korea Received October 9, 2010, accepted and available on-line October 23, 2010; CCDC no 1267/3234 analysis were obtained by slow evaporation from a dimethyl sulfoxide solution at 80 °C Experimental details Hydrogen atoms were positioned geometrically and allowed to ride on their parent atoms with d(C—H) = 0.95 Å and Uiso(H) = 1.2 Ueq(C) The highest peak (0.45 e·Å–3) and the deepest hole (–0.77 e·Å–3) in the difference Fourier map are located 1.30 and 0.67 Å apart the atoms C2 and Pd1, respectively Abstract C12H8ClN3O2Pd, orthorhombic, Pbcn (no 60), a = 11.962(1) Å, b = 14.179(1) Å, c = 6.9203(7) Å, V = 1173.8 Å3, Z = 4, Rgt(F) = 0.024, wRref(F2) = 0.070, T = 200 K Source of material To a solution of Na2PdCl4 (0.4414 g, 1.5 mmol) in H2O (40 ml) was added 2,4,6-tris(2-pyridyl)-1,3,5-triazine (tptz, 0.1561 g, 0.5 mmol; C18H12N6), and the mixture was stirred at room temperature for h The precipitate was then separated by filtration, washed with water and acetone, and dried at 50 °C to give an orange powder (0.3199 g) Crystals suitable for X-ray diffraction Discussion The title complex [PdCl(C12H8N3O2)] was unexpectedly prepared by the reaction of K2PdCl4 with tptz It seems that either the tptz ligand decomposed into the bis(2-pyridyl)imide (C12H9N3O2, N-picolinoylpicolinamide) molecule or the anion arised from the imide by the Pd(II)-assisted hydrolysis The hydrolysis phenomenon of the tptz molecule by Cu(II) ion was previously reported and the formed Cu(II)-imido complex [Cu(C12H8N3O2)(tptz)](CF3SO3) was characterized by the X-ray structure analysis [1] In the title complex, the Pd(II) ion is four-coordinated in a distorted square-planar manner by three N atoms from the imide anionic ligand and the chloride ion (figure, top) The complex is located on a two-fold rotation axis running in the [010] direction and passing through the Pd1, Cl1 and N1 atoms Thus the asymmetric unit contains one half of the formula unit The tight N1–Pd1–N2 chelate angle of 81.75(6)° contributes to the distortion of the square-planar geometry and results in non-linear trans arrangement of the N2–Pd1–N2i bond (symmetry code i: 1–x,y,½–z; ∠N2–Pd1–N2i = 163.5(1)°) The bond length d(Pd1—N1imide) = 1.962(3) Å is slightly shorter than the d(Pd1—N2pyridine) = 2.026(2) Å In the crystal structure, the nearly planar complexes are arranged in a V-shaped packing pattern and stacked in columns along [001] (figure, bottom) When viewed down the c axis, the successive complexes are stacked in the opposite direction with the Pd···Pd distance of 3.5875(4) Å In the columns, several intermolecular - interactions between adjacent pyridine rings are present The shortest distance between Cg1 (the centroid of ring N2-C6) and Cg1ii (symmetry code ii: x,–y,–½+z) is 4.167(2) Å, and the dihedral angle between the ring planes is 9° Moreover, there are intermolecular C–H···O hydrogen bonds with d(C···O) = 3.092(3) Å _ * e-mail: hakwang@chonnam.ac.kr Unauthenticated Download Date | 2/21/17 10:43 AM 790 PdCl(C12H8N3O2) Table Data collection and handling Table Atomic coordinates and displacement parameters (in Å2) Crystal: Wavelength: : Diffractometer, scan mode: 2,max: N(hkl)measured, N(hkl)unique: Criterion for Iobs, N(hkl)gt: N(param)refined: Programs: Atom Site x H(3) H(4) H(5) H(6) 8d 8d 8d 8d 0.1874 0.0455 0.0892 0.2721 orange stick, size 0.15 × 0.19 × 0.22 mm Mo Kα radiation (0.71073 Å) 18.08 cm−1 Bruker SMART 1000 CCD, #/% 56.54° 7672, 1440 Iobs > )(Iobs), 1053 88 SHELXS-97, SHELXL-97 [2], ORTEP-III [3], PLATON [4] y 0.2411 0.1282 −0.0313 −0.0753 z Uiso 0.1065 0.0722 0.1184 0.1869 0.037 0.039 0.037 0.032 Table Atomic coordinates and displacement parameters (in Å2) Atom Site Pd(1) Cl(1) O(1) N(1) N(2) C(1) C(2) C(3) C(4) C(5) C(6) 4c 4c 8d 4c 8d 8d 8d 8d 8d 8d 8d x ½ ½ 0.3900(2) ½ 0.3363(2) 0.4037(2) 0.3104(2) 0.2035(2) 0.1197(2) 0.1458(2) 0.2547(2) y 0.03340(2) −0.13040(6) 0.3001(1) 0.1718(2) 0.0539(2) 0.2162(2) 0.1469(2) 0.1760(2) 0.1095(2) 0.0154(2) −0.0104(2) z ¼ ¼ 0.1631(3) ¼ 0.1878(3) 0.1906(4) 0.1643(4) 0.1222(4) 0.1028(4) 0.1289(4) 0.1703(4) U11 U22 U33 U12 0.0209(2) 0.0331(5) 0.030(1) 0.024(2) 0.023(1) 0.025(1) 0.025(1) 0.026(2) 0.027(2) 0.026(2) 0.031(2) 0.0135(2) 0.0150(4) 0.0174(9) 0.014(1) 0.020(1) 0.021(1) 0.019(1) 0.025(1) 0.032(2) 0.031(2) 0.019(1) 0.0241(2) 0.0336(5) 0.063(2) 0.031(2) 0.023(1) 0.032(2) 0.029(2) 0.040(2) 0.040(2) 0.035(2) 0.031(2) 0 0.0033(8) −0.0008(9) 0.002(1) 0.000(1) 0.004(1) 0.002(1) −0.006(1) −0.004(1) U13 0.0010(1) 0.0005(4) −0.002(1) −0.001(1) 0.001(1) 0.002(1) 0.002(1) 0.000(1) −0.003(1) −0.002(1) −0.001(1) U23 0 0.004(1) 0.0009(9) 0.000(1) 0.002(1) 0.002(1) −0.000(1) 0.001(1) 0.002(1) Acknowledgment This work was supported by Priority Research Centers Program through the National Research Foundation of Korea (NRF) funded by the Ministry of Education, Science and Technology (grant no 20090094056) References Faus, J.; Julve, M.; Amigó, J M.; Debaerdemaeker, T.: Copper(II)assisted hydrolysis of 2,4,6-tris(2-pyridyl)-1,3,5-triazine Part Crystal structures of [bis(2-pyridylcarbonyl)amido](pyridine-2-carboxamide)copper(II) trifluoromethanesulphonate and [bis(2-pyridylcarbonyl)amido][2,4,6-tris(2-pyridyl)-1,3,5-triazine]copper(II) trifluoromethanesulphonate J Chem Soc., Dalton Trans (1989) 1681-1687 Sheldrick, G M.: A short history of SHELX Acta Crystallogr A64 (2008) 112-122 Farrugia, L J.: ORTEP-3 for Windows - a version of ORTEP-III with a Graphical User Interface (GUI) J Appl Crystallogr 30 (1997) 565 Spek, A L.: Single-crystal structure validation with the program PLATON J Appl Crystallogr 36 (2003) 7-13 Unauthenticated Download Date | 2/21/17 10:43 AM ... 0.030(1) 0. 024 (2) 0. 023 (1) 0. 025 (1) 0. 025 (1) 0. 026 (2) 0. 027 (2) 0. 026 (2) 0.031 (2) 0.0135 (2) 0.0150(4) 0.0174(9) 0.014(1) 0. 020 (1) 0. 021 (1) 0.019(1) 0. 025 (1) 0.0 32( 2) 0.031 (2) 0.019(1) 0. 024 1 (2) 0.0336(5)... 0.1718 (2) 0.0539 (2) 0 .21 62( 2) 0.1469 (2) 0.1760 (2) 0.1095 (2) 0.0154 (2) −0.0104 (2) z ¼ ¼ 0.1631(3) ¼ 0.1878(3) 0.1906(4) 0.1643(4) 0. 122 2(4) 0.1 028 (4) 0. 128 9(4) 0.1703(4) U11 U 22 U33 U 12 0. 020 9 (2) ... hydrolysis of 2, 4,6-tris (2- pyridyl) -1,3,5-triazine Part Crystal structures of [bis( 2- pyridylcarbonyl)amido](pyridine -2- carboxamide)copper (II) trifluoromethanesulphonate and [bis( 2- pyridylcarbonyl)amido] [2, 4,6-tris (2- pyridyl) -1,3,5-triazine]copper (II)