Z. Kristallogr. NCS 229 (2014) 391-392 / DOI 10.1515/ncrs-2014-0208
391
© 2014 by Walter de Gruyter Berlin/Boston
Crystal structure of cis-dichloridobis(3-phenylpyridine-"N)platinum(II), C22H18Cl2N2Pt Kwang Ha* Chonnam National University, School of Applied Chemical Engineering, Research Institute of Catalysis, Gwangju 500-757, Republic of Korea Received January 08, 2014, accepted October 06, 2014, available online October 17, 2014, CCDC no. 1267/4197
(–0.71 e Å–3) in the difference Fourier map are located 1.10 Å and 1.01 Å from the Pt1 atom, respectively.
Abstract C22H18Cl2N2Pt, monoclinic, P21/c (no. 14), a = 7.9388(5) Å, b = 13.2988(8) Å, c = 18.951(1) Å, $ = 100.576(1)°, V = 1966.8 Å3, Z = 4, Rgt(F) = 0.0236, wRref(F2) = 0.0596, T = 200 K. Table 1. Data collection and handling. Crystal: Wavelength: #: Diffractometer, scan mode: 2"max: N(hkl)measured, N(hkl)unique: Criterion for Iobs, N(hkl)gt: N(param)refined: Programs:
yellow blocks, size 0.04%0.09%0.10 mm Mo K# radiation (0.71073 Å) 74.15 cm$1 Bruker SMART 1000 CCD, ' and & 52° 11693, 3801 Iobs > 2 !(Iobs), 3332 244 SHELX [6], ORTEP-3 [7], PLATON [8]
Source of material To a solution of K2PtCl4 (0.208 g, 0.50 mmol) and dipicolinic acid (0.085 g, 0.51 mmol) in H2O (20 ml)/MeOH (10 ml) was added 3phenylpyridine (ppy; 0.157 g, 1.0 mmol) and stirred for 24 h at room temperature. The formed precipitate was separated by filtration, washed with H2O and acetone, and dried at 50 °C, to give a yellow powder (0.152 g). Crystals suitable for X-ray diffraction were obtained by slow evaporation from a CH3CN solution. 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) = 1.2Ueq(C). The highest peak (1.90 e Å–3) and the deepest hole
_____________
Discussion This contribution is part of my continuing interest in the structural chemistry of platinum-ppy complexes [1–5]. The title complex cis-[PtCl2(ppy)2] was unexpectedly obtained from the reaction of K 2 PtCl 4 , dipicolinic acid and ppy, whereas the trans[PtCl2(ppy)2] complex was prepared by the reaction of K2PtCl4 and ppy [1]. Both cis- and trans-complexes crystallize in the monoclinic space group P21/c, but the latter has an inversion center on Pt atom. In the title structure, the central Pt(II) ion has a cisCl2N2 square-planar coordination defined by two N atoms from two distinct 3-phenylpyridine ligands and two chlorido ligands. Both, the Pt–N and the Pt–Cl bond lengths are nearly equivalent, respectively, with d(Pt–N) = 2.019(3) and 2.023(3) Å, and d(Pt–Cl) = 2.296(1) and 2.301(1) Å. The dihedral angles between the least-squares plane of the PtCl2N2 coordination unit (maximum deviation = 0.045(1) Å) and the nearly planar pyridine rings are 54.9(1)° (ring N1-C5) and 56.0(1)° (ring N2-C16). In the crystal, the pyridine and phenyl rings of each ligand are twisted by 21.5(2)° (N1-C11) and 33.3(2)° (N2-C22). The complexes are stacked in columns along [100]. In the columns, numerous %!!!% interactions between adjacent six-membered rings are present. For Cg1 (the centroid of ring C6-C11) and Cg1i (symmetry code i: –x,1–y,1–z), the centroid-centroid distance is 3.835(3) Å, the planes are parallel and shifted by 1.829 Å. Intermolecular C–H!!!Cl hydrogen bonds with d(C!!!Cl) = 3.519(4) Å further stabilize the crystal structure. Table 2. Atomic coordinates and displacement parameters (in Å2). Atom
Site
H(1) H(3) H(4) H(5) H(7) H(8) H(9) H(10) H(11) H(12) H(14) H(15) H(16) H(18) H(19) H(20) H(21) H(22)
4e 4e 4e 4e 4e 4e 4e 4e 4e 4e 4e 4e 4e 4e 4e 4e 4e 4e
* e-mail:
[email protected]
Unauthenticated Download Date | 9/24/15 11:13 PM
x 0.0170 0.3339 0.5444 0.4874 $0.1905 $0.4067 $0.3387 $0.0539 0.1633 0.3661 0.0602 $0.1412 $0.0863 0.5780 0.7819 0.6974 0.4094 0.2022
y
z
Uiso
0.2028 0.3668 0.2450 0.1038 0.2794 0.3993 0.5602 0.6047 0.4903 0.1897 0.2712 0.1539 0.0587 0.2359 0.3493 0.4986 0.5346 0.4216
0.4949 0.6407 0.6411 0.5691 0.5280 0.5308 0.5727 0.6099 0.6053 0.3946 0.2099 0.2329 0.3367 0.3350 0.3097 0.2487 0.2133 0.2369
0.033 0.041 0.039 0.036 0.050 0.059 0.061 0.058 0.049 0.033 0.040 0.044 0.037 0.046 0.053 0.051 0.052 0.050
392
C22H18Cl2N2Pt
Table 3. Atomic coordinates and displacement parameters (in Å2). Atom
Site
Pt(1) Cl(1) Cl(2) N(1) N(2) C(1) C(2) C(3) C(4) C(5) C(6) C(7) C(8) C(9) C(10) C(11) C(12) C(13) C(14) C(15) C(16) C(17) C(18) C(19) C(20) C(21) C(22)
4e 4e 4e 4e 4e 4e 4e 4e 4e 4e 4e 4e 4e 4e 4e 4e 4e 4e 4e 4e 4e 4e 4e 4e 4e 4e 4e
x 0.20352(2) 0.1499(1) 0.2874(1) 0.2476(4) 0.1454(4) 0.1251(5) 0.1507(5) 0.3102(5) 0.4351(5) 0.4014(5) 0.0098(5) $0.1611(6) $0.2901(6) $0.2505(7) $0.0820(7) 0.0472(7) 0.2618(5) 0.2368(5) 0.0828(5) $0.0366(5) $0.0035(5) 0.3684(5) 0.5424(6) 0.6635(6) 0.6135(6) 0.4436(7) 0.3202(6)
y 0.02163(1) $0.10899(8) $0.08736(8) 0.1415(2) 0.1163(3) 0.2120(3) 0.2974(3) 0.3089(3) 0.2369(3) 0.1536(3) 0.3718(3) 0.3456(4) 0.4174(4) 0.5125(4) 0.5385(4) 0.4702(3) 0.1833(3) 0.2432(3) 0.2315(3) 0.1623(4) 0.1059(3) 0.3164(3) 0.2963(4) 0.3638(4) 0.4526(4) 0.4735(4) 0.4063(4)
z
U11
U22
U33
0.458873(7) 0.37866(5) 0.55309(5) 0.5254(2) 0.3746(2) 0.5254(2) 0.5682(2) 0.6111(2) 0.6113(2) 0.5685(2) 0.5676(2) 0.5448(2) 0.5467(3) 0.5710(3) 0.5930(3) 0.5908(3) 0.3611(2) 0.3006(2) 0.2522(2) 0.2659(2) 0.3272(2) 0.2881(2) 0.3098(2) 0.2950(3) 0.2588(3) 0.2378(3) 0.2519(2)
0.0257(1) 0.0386(6) 0.0362(5) 0.025(2) 0.025(2) 0.026(2) 0.034(2) 0.038(2) 0.027(2) 0.032(2) 0.037(2) 0.041(3) 0.036(3) 0.060(4) 0.058(3) 0.047(3) 0.029(2) 0.036(2) 0.038(2) 0.030(2) 0.029(2) 0.038(2) 0.042(3) 0.040(3) 0.053(3) 0.062(3) 0.049(3)
0.0228(1) 0.0275(5) 0.0294(6) 0.024(2) 0.031(2) 0.032(2) 0.028(2) 0.031(2) 0.038(3) 0.030(2) 0.032(2) 0.030(3) 0.048(3) 0.046(3) 0.041(3) 0.039(3) 0.027(2) 0.029(2) 0.037(3) 0.045(3) 0.033(2) 0.029(2) 0.031(3) 0.040(3) 0.038(3) 0.033(3) 0.041(3)
0.0202(1) 0.0283(5) 0.0267(5) 0.024(2) 0.019(2) 0.021(2) 0.023(2) 0.032(2) 0.029(2) 0.026(2) 0.027(2) 0.053(3) 0.064(3) 0.048(3) 0.041(3) 0.033(3) 0.025(2) 0.027(2) 0.024(2) 0.030(2) 0.030(2) 0.025(2) 0.042(3) 0.053(3) 0.039(3) 0.035(3) 0.033(2)
Acknowledgments. 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 (2009-0094055).
References 1. Ha, K.: Crystal structure of dichloridobis(3-phenylpyridine-"N)platinum(II), C22H18Cl2N2Pt. Z. Kristallogr. NCS 228 (2013) 311–312. 2. Ha, K.: Crystal structure of dibromido-bis(3-phenylpyridine-"N)platinum(II), PtBr2(C11H9N)2, C22H18Br2N2Pt. Z. Kristallogr. NCS 228 (2013) 103–104. 3. Ha, K.: Crystal structure of diiodido-bis(3-phenylpyridine-"N)platinum(II), PtI2(C11H9N)2, C22H18I2N2Pt. Z. Kristallogr. NCS 228 (2013) 373–374.
U12 0.00013(6) $0.0008(4) 0.0019(4) 0.001(1) 0.003(1) $0.001(2) $0.001(2) $0.005(2) $0.005(2) 0.002(2) 0.004(2) 0.004(2) 0.008(2) 0.026(3) 0.013(2) 0.004(2) 0.001(2) 0.005(2) 0.010(2) 0.003(2) 0.002(2) 0.002(2) 0.001(2) $0.001(2) $0.014(2) 0.000(2) 0.003(2)
U13 0.00201(6) 0.0029(4) 0.0014(4) 0.006(1) 0.003(1) 0.000(2) 0.004(2) 0.004(2) $0.004(2) 0.002(2) 0.006(2) 0.009(2) 0.010(2) 0.012(3) 0.001(2) 0.001(2) 0.002(2) 0.005(2) 0.002(2) $0.004(2) 0.002(2) 0.005(2) 0.006(2) 0.009(2) 0.013(2) 0.008(2) 0.004(2)
U23 0.00023(6) $0.0058(4) 0.0061(4) $0.002(1) $0.000(1) 0.002(2) 0.003(2) $0.007(2) $0.005(2) 0.001(2) 0.005(2) 0.007(2) 0.012(3) 0.004(2) $0.008(2) $0.010(2) $0.001(2) $0.001(2) 0.008(2) 0.000(2) $0.001(2) 0.000(2) $0.001(2) $0.003(2) $0.002(2) 0.009(2) 0.010(2)
4. Ha, K.: Crystal structure of bis(3-phenylpyridine-"N)bis(thiocyanato"S)platinum(II), C24H18N4PtS2. Z. Kristallogr. NCS 228 (2013) 313–314. 5. Ha, K.: Crystal structure of 3-phenylpyridinium pentachloro(3p h e n y lp y ri d i n e -"N )pl at in ate ( IV ) hy dr ate, [C11H10N][PtCl5(C11H9N)]!H2O. Z. Kristallogr. NCS 227 (2012) 12–14. 6. Sheldrick, G. M.: A short history of SHELX. Acta Crystallogr. A64 (2008) 112–122. 7. Farrugia, L. J.: WinGX and ORTEP for Windows: an update. J. Appl. Crystallogr. 45 (2012) 849–854. 8. Spek, A. L.: Structure validation in chemical crystallography. Acta Crystallogr. D65 (2009) 148–155.
Unauthenticated Download Date | 9/24/15 11:13 PM
