366
Ζ. Kristallogr. NCS 217 (2002) 366-368 © by Oldenbourg Wissenschaftsverlag, München
Crystal structure of azido-^^V-dimethylbenzylaiiiine-C^tl^bis(diphenylphosphino)propane-iy>/)]palladium(II), {Pd(C6H4CH2NMe2-C2f)(N3)[(C6H5)2P(CH2)3P(C6H5)2-P^]} E. T. de Almeida1·11, A. M. Santana1, Α. V. de Godoy Netto1, A. E. Mauro1, M. P. Santos™ and R. H. A. Santos*·111
ΠΙ
Instituto de Química-UNESP, Departamento de Química Geral e Inorgánica, Caixa Postal 355, 14800-900, Araraquara, SP, Brazil Universidade Católica de Brasilia, Curso de Química, Caixa Postal 5490, 72030-170 Aguas Claras, Taguatinga, Brasilia, DF, Brazil Universidade de Sâo Paulo, Instituto de Química de Sao Carlos, Depto. de Química e Fisica Molecular, Caixa Postal 780, 13560-970 - Sao Carlos - SP, Brazil
Received April 13,2002, accepted and available on-line July 5,2002; CCDC-No. 1267/843
Abstract C36H38N4P2PCI, monoclinic, P12i/cl (No. 14), a = 9.7373(4) Â, b = 15.909(1) Â, c = 21.690(1) Â, β = 94.650(4)0, V= 3349.0 Â3, Z = 4, RfffF) = 0.033, wRrtiF1) = 0.122, T= 293 K.
Source of material The synthesis and characterization of the title compound has been already described in the literature [1]. It was prepared by the reaction of the dimeric compound Pd(C6H4CH2NMe2-C2^V)(N3)2 with l,3-bis(diphenylphosphino)propane in acetone. Recrystallization from diclhorometane, at room temperature, gave yellow crystals suitable for X-ray analysis.
Discussion Due to the chelating effect, diphosphines ligands enhance the stability of various metals complexes in low oxidation state. These ligands may bridge two metal centers in dinuclear compounds or behave as chelating ligands in the mononuclear ones. This behavior is mainly dependent on the length and nature of the carbon chain between the phosphorus atoms. In addition, there is a correlation between the P-M-P bite angle in diphosphine complexes and their selectivity in several catalytic reactions, such as
hydroformylation, hydrocyanation and cross coupling [2]. Furthermore, the cyclopalladated compounds are successfully employed as anti-tumoral agents [3], liquid crystals [4], nonlinear optical materials [5], among others. The ORTEP representation of the title molecule (50% of probability) is shown in the figure. The palladium atom linked to two P, one C and one Ν atom, has a nearly square planar environment. The propyl group that links the two Ρ atoms and the Pd take the shape of a six-membered ring. The P2-Pd-Pl angle of96.45(3)° and the Pd—C4 bond length of 2.044(3) Ä are similar to those found in the related compounds [2]. The least squares benzyl plane of the dmba (dmba = A^N-dimethylbenzylamine) is perpendicular (89.6(2)°) to the plane defined by the Pd atom and its square planar environment, about the same happens with the phenyl ring defined by the atoms from Clb to C6b (88.4(1)°). The distances Pd—Ρ equal to 2.3461(8) Â and 2.2380(8) À, and the first one is slightly larger than that found for compounds like di-isothiocyanato( 1,3-bis(diphenylphosphino)- propane)palladium(II) (2.241Â) [6], 1,3-bis(diphenylphosphine)propane-P,P)-( 1,10-phenanthroline/V)-(nitromethyl)-palladium(II) hexafluorophosphate (2,333 À and 2,245 Â) [7], bis(u-2-5,10-bis(4-pyridyl)-15,20-diphenylporphyrin)-bis(l ,3-bis(diphenylphosphino)propane)-dipalladium(II) tetrakis(trifluoromethanesulfonate) (2.267 Â, 2.275 Â, 2.276 Â and 2.278 À) [8] and isothiocyanato-thiocyanato-( 1,3-bis(diphenylphosphino)propane-P,P' )-palladium(II) (2.283 Â and 2.256 Â) [9]. The P—C bonds are compatible with the values found in square planar Pd complexes [6-9]. The azido group in the structure is essentially linear with the N1-N2-N3 angle equal to 174.5(5)°.
Table 1. Data collection and handling. Crystal: Wavelength:
μ·
Diffractometer, scan mode:
WtWImcasurcd, /V(Wr/)unique: Criterion for /0bs, N(hkl)gt.
N(param)Kfmoï. Programs:
* Correspondence author (e-mail:
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yellow prism, size 0.13 χ 0.25 χ 0.4 mm Mo Ka radiation (0.71073 Â) 6.8 cm"1 Enraf Nonius TurboCAD4, ω/20 52.6° 7195,6788 /obs>2a(/„bs), 5669 390 SHELXS-97 [10], SHELXL-97 [11]
{Pd(C6H4CH2NMe2-C2)(N3)[(C6H5)2P(CH2)3P(C6H5)2-P,/>']}
367
Table 2. Atomic coordinates and displacement parameters (in  2 ).
Table 2. Continued.
Atom
Site
Atom
Site
H(1 0 H(12) H(21) H(22) H(3I) H(32) H(5) H(6) H(7) H(8) H(101) H(102) H(lll) H(112) H(113) H( 121) H(122) H(123) H(2B)
4e 4e 4e 4e 4e 4e 4e 4e 4e 4e 4e 4e 4e 4e 4e 4e 4e 4e 4e
H(3B) H(4B) H(5B) H(6B) H(8B) H(9B) H(10B) H(11B) H(12B) H(2A) H(3A) H(4A) H(5A) H(6A) H(8A) H(9A) H(10A) H(11A) H( 12A)
4e 4e 4e 4e 4e 4e 4e 4e 4e 4e 4e 4e 4e 4e 4e 4e 4e 4e 4e
0.2000 0.0987 0.0234 0.1517 -0.037 -0.0709 0.4053 0.4352 0.3374 0.2037 0.0525 0.1835 -0.0097 -0.0927 -0.0347 0.2212 0.2176 0.3083 0.3567
0.3876 0.4093 0.2938 0.2426 0.3022 0.2189 0.0935 0.0133 0.0575 0.1758 0.2739 0.3310 0.4147 0.3314 0.3811 0.4221 0.3787 0.3407 0.1226
0.8601 0.8027 0.8605 0.8427 0.7475 0.7816 0.6562 0.5693 0.4733 0.4662 0.5679 0.5753 0.5065 0.4932 0.4386 0.4948 0.4298 0.4860 0.7763
0.052 0.052 0.056 0.056 0.054 0.054 0.064 0.079 0.084 0.080 0.108 0.108 0.265 0.265 0.265 0.212 0.212 0.212 0.060
0.4084 0.2389 0.0120 -0.0424 0.0845 -0.0699 -0.2659 -0.3082 -0.1544 0.2790 0.2872 0.3376 0.3705 0.3558 0.3790 0.5807 0.7839 0.7892 0.5888
0.0095 -0.0789 -0.0561 0.0568 0.0519 0.0087 0.0897 0.2085 0.2533 0.4419 0.5791 0.6867 0.6611 0.5252 0.2842 0.2709 0.3232 0.3918 0.4086
0.8416 0.8687 0.8305 0.7664 0.6385 0.5558 0.5286 0.5811 0.6603 0.6509 0.6154 0.6838 0.7869 0.8240 0.8892 0.9539 0.9234 0.8308 0.7666
0.073 0.074 0.071 0.059 0.073 0.095 0.107 0.105 0.083 0.064 0.089 0.088 0.078 0.063 0.075 0.099 0.093 0.082 0.065
Table 3. Atomic coordinates and displacement parameters (in Â2). Atom
Site
Pd P(l) P(2) N(l) N(2) N(3) N(4) C(l) C(2) C(3) C(4) C(5) C(6) C(7) C(8) C(9) C(10) C(ll) C(12) C(1B) C(2B) C(3B) C(4B) C(5B) C(6B) C(7B) C(8B) C(9B) C(10B) C(11B) C(12B) C(1A) C(2A) C(3A) C(4A) C(5A) C(6A) C(7A) C(8A) C(9A) C(10A) C(11A) C(12A)
4e 4e 4e 4e 4e 4e 4e 4e 4e 4e 4e 4e 4e 4e 4e 4e 4e 4e 4e 4e 4e 4e 4c 4e 4e 4e 4e 4e 4e 4e 4e 4e 4e 4e 4e 4e 4e 4e 4e 4e 4e 4e 4e
X 0.29258(2) 0.30672(8) 0.10682(8) 0.4848(3) 0.5067(4) 0.5400(6) 0.1082(5) 0.1638(3) 0.0861(4) 0.0037(3) 0.2917(3) 0.3662(4) 0.3840(4) 0.3242(5) 0.2462(5) 0.2289(4) 0.1388(7) -0.018(1) 0.224(1) 0.1513(3) 0.2867(3) 0.3176(4) 0.2171(4) 0.0810(4) 0.0486(4) -0.0196(4) 0.0067(4) -0.0862(6) -0.2043(6) -0.2292(5) -0.1372(4) 0.3172(3) 0.2968(4) 0.3028(4) 0.3316(4) 0.3514(4) 0.3434(3) 0.4619(3) 0.4608(4) 0.5823(5) 0.7031(5) 0.7063(4) 0.5862(4)
y 0.26247(2) 0.36115(5) 0.19484(5) 0.3140(2) 0.3252(2) 0.3402(5) 0.3178(3) 0.3677(2) 0.2857(2) 0.2543(2) 0.1850(2) 0.1111(2) 0.0626(3) 0.0887(3) 0.1599(3) 0.2095(2) 0.2866(3) 0.3652(7) 0.3692(5) 0.1020(2) 0.0871(2) 0.0189(3) -0.0337(3) -0.0199(2) 0.0476(2) 0.1578(2) 0.0838(3) 0.0577(3) 0.1067(4) 0.1773(4) 0.2036(3) 0.4688(2) 0.4857(3) 0.5678(3) 0.6320(3) 0.6168(2) 0.5353(2) 0.3494(2) 0.3071(3) 0.2982(4) 0.3297(3) 0.3706(3) 0.3808(2)
ζ
t/n
Un
t/33
0.68897(1) 0.76962(3) 0.71794(4) 0.6628(1) 0.6140(2) 0.5640(2) 0.4892(2) 0.8198(2) 0.8284(2) 0.7698(2) 0.6138(2) 0.6178(2) 0.5659(2) 0.5086(2) 0.5043(2) 0.5563(2) 0.5504(2) 0.4812(5) 0.4736(4) 0.7644(1) 0.7872(2) 0.8264(2) 0.8425(2) 0.8198(2) 0.7812(2) 0.6579(2) 0.6268(2) 0.5775(2) 0.5612(2) 0.5919(2) 0.6397(2) 0.7414(2) 0.6788(2) 0.6575(2) 0.6983(3) 0.7595(2) 0.7817(2) 0.8221(1) 0.8774(2) 0.9160(2) 0.8979(2) 0.8427(2) 0.8042(2)
0.0350(2) 0.0350(4) 0.0324(4) 0.047(2) 0.057(2) 0.131(5) 0.128(4) 0.042(2) 0.045(2) 0.033(2) 0.040(2) 0.046(2) 0.067(3) 0.088(3) 0.087(3) 0.061(2) 0.126(5) 0.24(1) 0.25(1) 0.034(2) 0.035(2) 0.040(2) 0.063(2) 0.053(2) 0.038(2) 0.044(2) 0.063(2) 0.099(4) 0.086(3) 0.079(3) 0.060(2) 0.032(2) 0.046(2) 0.056(2) 0.045(2) 0.041(2) 0.041(2) 0.040(2) 0.058(2) 0.089(4) 0.058(3) 0.044(2) 0.045(2)
0.0329(2) 0.0320(4) 0.0346(4) 0.045(2) 0.063(2) 0.181(7) 0.067(3) 0.039(2) 0.047(2) 0.043(2) 0.037(2) 0.047(2) 0.044(2) 0.056(2) 0.059(2) 0.046(2) 0.078(3) 0.19(1) 0.109(6) 0.038(2) 0.051(2) 0.063(2) 0.048(2) 0.044(2) 0.043(2) 0.050(2) 0.057(2) 0.070(3) 0.098(4) 0.081(3) 0.065(3) 0.037(2) 0.052(2) 0.074(3) 0.041(2) 0.037(2) 0.037(2) 0.036(2) 0.077(3) 0.097(4) 0.086(3) 0.062(3) 0.045(2)
0.0320(1) 0.0323(4) 0.0369(4) 0.039(2) 0.090(3) 0.084(3) 0.052(2) 0.039(2) 0.040(2) 0.051(2) 0.039(2) 0.055(2) 0.073(3) 0.054(2) 0.037(2) 0.036(2) 0.046(2) 0.173(9) 0.139(7) 0.038(2) 0.051(2) 0.064(2) 0.059(2) 0.065(2) 0.055(2) 0.039(2) 0.046(2) 0.050(2) 0.058(3) 0.075(3) 0.062(2) 0.046(2) 0.051(2) 0.077(3) 0.118(4) 0.102(3) 0.066(2) 0.040(2) 0.039(2) 0.040(2) 0.066(3) 0.080(3) 0.061(2)
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Un -0.00536(9) -0.0024(3) -0.0051(3) -0.017(1) -0.013(2) -0.049(4) 0.010(2) 0.001(1) -0.000(2) -0.001(1) -0.006(1) 0.002(2) 0.005(2) -0.010(2) -0.004(2) 0.001(2) 0.044(3) 0.098(9) -0.025(7) -0.002(1) 0.001(2) 0.013(2) 0.011(2) -0.008(2) -0.005(1) -0.015(2) -0.021(2) -0.038(3) -0.030(3) -0.008(3) -0.004(2) 0.000(1) 0.004(2) 0.012(2) 0.005(2) -0.001(2) -0.003(1) 0.005(1) 0.008(2) 0.025(3) 0.020(2) 0.006(2) 0.001(2)
U13 0.00542(9) 0.0030(3) 0.0016(3) 0.014(1) 0.016(2) 0.043(3) -0.013(2) 0.009(1) 0.014(1) 0.006(1) 0.008(1) 0.002(2) 0.019(2) 0.024(2) 0.008(2) 0.008(2) 0.007(3) -0.073(8) 0.056(7) 0.001(1) 0.006(1) -0.003(2) 0.001(2) 0.004(2) -0.003(1) -0.003(1) -0.001(2) 0.006(2) -0.028(2) -0.033(3) -0.013(2) 0.002(1) 0.003(2) 0.011(2) 0.015(2) 0.007(2) -0.002(2) -0.001(1) 0.002(2) -0.012(2) -0.021(2) -0.008(2) -0.001(2)
1/23 -0.00535(8) -0.0044(3) -0.0014(3) -0.013(1) -0.012(2) 0.017(4) 0.015(2) -0.005(1) -0.001(1) -0.001(1) -0.008(1) -0.006(2) -0.016(2) -0.024(2) -0.007(2) -0.002(1) 0.013(2) 0.036(8) 0.040(5) -0.003(1) 0.001(2) 0.003(2) 0.009(2) 0.009(2) 0.007(2) 0.005(1) -0.002(2) -0.008(2) 0.018(3) 0.013(3) 0.009(2) 0.002(1) 0.007(2) 0.033(2) 0.022(2) -0.003(2) -0.006(2) -0.010(1) 0.004(2) -0.003(2) -0.025(2) -0.017(2) -0.003(2)
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{Pd(C6H4CH2NMe2-C2)(N3)[(C6H5)2P(CH2)3P(C6H5)2-P,/"]}
Acknowledgments. This work received partial support from FAPESP, CAPES and CNPq.
References 1. Caires, A. C. F.; De Almeida, E. T.; Mauro, A. E.; Hemerly, J. P; Valentini, S. R.: Sintese e atividade citotóxica de alguns azidociciopaladados estabilizados com ligantes bifosfínicos. Química Nova 22 (1999)329-334. 2. Ma, J. F.; Yamamoto, Y.: Reaction of di-dichloro-bis(N,N-dimethylbenzylamine-C2,A/)dipalladium(II) with diphosphines. Six-membered ring complexes bearing spiro rings. Inorg. Chim. Acta 299 (2000) 164-171. 3. Tusek-Bozic, L. ; Komac, M.; Curie, M.; Lycka, Α.; D'Alpaos, M.; Scarcia, V.; Furlani, Α.: Five-membered [C,N] and [N,0] metallocyclic complexes of palladium(II) with monoalkyl [a-(4-benzeneazoanilino)-AT-benzyl]phosphonates: synthesis, characterization and antitumour activity. Polyhedron 19 (2000) 937-948. 4. Saccomando, D. J.; Black, C.; Cave, G. W. V.; Lydon, D. P.; Rourke, J. P.: Chiral cyclopalladated liquid crystals from amino acids. J. Organomet. Chem. 601 (2000) 305-310. 5. Caruso, U.; Di Matóla, Α.; Panunzi, Β.; Roviello, Α.; Sirigu, Α.: Side chain organometallic polymers containing cyclopalladated potentially second order nonlinear optical active fragments as pendants. Polymer. 42 (2001) 3973-3980.
6. Palenik, G. J.; Mathew, M.; Steffen, W. L.; Beran G.: Di-isothiocyanato-(l,3-bis(diphenylphosphino)propane) palladium(II). J. Am. Chem. Soc. 97 (1975) 1059-1066. 7. Milani, Β.; Corso, G.; Zangrando, E.; Randaccio, L.; Mestroni, G.: 1,3-bis(Dipheny lphosphine)propane-/>,/>)-( 1,10-phenanthroline-ΛΟ(nitromethyl)-palladium(II) hexafluorophosphate acetone solvate. Eur. J. Inorg. Chem. (1999) 2085-2093. 8. Schmitz, M.; Leininger, S.; Fan, J.; Arif, A. M.; Stang P. J.: bis^-2-5,l 0-bis(4-Pyridyl)-15,20-diphenylporphyrin)-bis( 1,3-bis(diphenylphosphino)propane)-di-palladium(II) tetrakis(trifluoromethanesulfonate) ethanol solvate dihydrate. Organometallics 18 (1999) 4817-4824. 9. Paviglianiti, A. J.; Minn, D. J.; Fultz, W. C.; Burmeister, J. L.: Isothiocyanato-thiocyanato-( 1,3-bis(diphenylphosphino)propane-P,/)')-palladium(II) dichloromethane solvate. Inorg. Chim. Acta 159 ( 1989) 65-82. 10. Shelrick, G. M.: SHELXS-97. Program for Crystal Structure Solution, University of Göttingen, Germany 1997. 11. Shelrick, G. M.: SHELXL-97. Program for Crystal Structure Refinement, University of Göttingen, Germany 1997.
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