Home Crystal structure of chlorido-(4-chloro-6-(p-tolyl)pyrimidine-κ2C,N)-(triphenylphosphane-κP)palladium(II), C29H23Cl2N2PPd
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Crystal structure of chlorido-(4-chloro-6-(p-tolyl)pyrimidine-κ2C,N)-(triphenylphosphane-κP)palladium(II), C29H23Cl2N2PPd

  • Chen Xu ORCID logo EMAIL logo and Xin-Hua Lou
Published/Copyright: October 23, 2019

Abstract

C29H23Cl2N2PPd, monoclinic, P21/c (no. 14), a = 9.4028(16) Å, b = 30.928(5) Å, c = 9.3071(16) Å, β = 103.222(2)°, V = 2634.8(8) Å3, Z = 4, Rgt(F) = 0.0423, wRref(F2) = 0.1047, T = 296(2) K.

CCDC no.: 1941813

The molecular structure is shown in the figure. Table 1 contains crystallographic data and Table 2 contains the list of the atoms including atomic coordinates and displacement parameters.

Table 1:

Data collection and handling.

Crystal:Brown block
Size:0.33 × 0.25 × 0.18 mm
Wavelength:Mo Kα radiation (0.71073 Å)
μ:0.99 mm−1
Diffractometer, scan mode:CCD, φ and ω
θmax, completeness:25.5°, >99%
N(hkl)measured, N(hkl)unique, Rint:12971, 4900, 0.024
Criterion for Iobs, N(hkl)gt:Iobs > 2 σ(Iobs), 4178
N(param)refined:317
Programs:Bruker [1], SHELX [2]
Table 2:

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2).

AtomxyzUiso*/Ueq
Pd10.70081(3)0.155348(9)0.78562(3)0.04096(12)
Cl10.4003(2)0.34148(6)0.5807(3)0.1416(9)
Cl20.55600(12)0.12064(4)0.57329(11)0.0567(3)
P10.81789(11)0.09272(3)0.86925(10)0.0378(2)
N10.5958(4)0.21451(11)0.7198(4)0.0502(8)
N20.4239(5)0.25952(15)0.5625(5)0.0775(13)
C10.6553(5)0.24902(14)0.8031(5)0.0549(11)
C20.5974(6)0.28981(15)0.7643(7)0.0742(15)
H20.63470.31420.81840.089*
C30.4839(6)0.29268(18)0.6438(7)0.0771(16)
C40.4834(5)0.22157(17)0.6056(6)0.0679(13)
H40.44300.19750.55120.082*
C50.7769(5)0.23830(13)0.9250(5)0.0508(10)
C60.8523(6)0.26962(15)1.0219(6)0.0700(14)
H60.82380.29841.00910.084*
C70.9666(6)0.25862(17)1.1348(6)0.0748(15)
H71.01400.27991.19870.090*
C81.0126(5)0.21647(16)1.1553(5)0.0596(12)
C90.9406(5)0.18524(14)1.0571(5)0.0521(10)
H90.97420.15691.06850.063*
C100.8214(4)0.19453(12)0.9432(4)0.0441(9)
C111.1362(6)0.2036(2)1.2836(6)0.0871(18)
H11A1.20420.22711.30760.131*
H11B1.18520.17871.25680.131*
H11C1.09730.19681.36770.131*
C120.9910(4)0.08706(13)0.8125(4)0.0419(9)
C131.0578(6)0.12305(16)0.7721(5)0.0648(13)
H131.01570.15010.77560.078*
C141.1870(7)0.1194(2)0.7263(7)0.0880(18)
H141.23150.14410.70030.106*
C151.2499(6)0.0801(2)0.7187(6)0.0767(16)
H151.33700.07800.68790.092*
C161.1850(6)0.04388(18)0.7565(5)0.0681(13)
H161.22680.01690.74980.082*
C171.0563(5)0.04720(14)0.8051(5)0.0559(11)
H171.01350.02240.83290.067*
C180.7247(4)0.04154(13)0.8084(4)0.0423(9)
C190.7111(5)0.02755(14)0.6636(5)0.0550(11)
H190.74480.04490.59660.066*
C200.6475(5)−0.01220(15)0.6189(5)0.0648(13)
H200.6397−0.02140.52230.078*
C210.5961(5)−0.03806(16)0.7146(6)0.0682(14)
H210.5544−0.06470.68390.082*
C220.6067(6)−0.02433(16)0.8553(6)0.0710(14)
H220.5712−0.04160.92090.085*
C230.6703(5)0.01538(14)0.9022(5)0.0560(11)
H230.67600.02430.99870.067*
C240.8589(4)0.08700(12)1.0698(4)0.0397(8)
C250.7514(5)0.09895(13)1.1422(5)0.0497(10)
H250.66110.10851.08830.060*
C260.7784(6)0.09669(15)1.2954(5)0.0605(12)
H260.70580.10441.34350.073*
C270.9102(6)0.08330(18)1.3744(5)0.0717(14)
H270.92750.08191.47670.086*
C281.0180(6)0.07181(18)1.3050(5)0.0729(15)
H281.10870.06321.36070.087*
C290.9936(5)0.07287(14)1.1532(5)0.0526(10)
H291.06650.06421.10660.063*

Source of material

The title compound was obtained from the bridge-splitting reaction of the corresponding palladacyclic dimer of 4-chloro-6-p-tolylpyrimidine and PPh3 according to literature [3] and recrystallized from dichloromethane/petroleum ether solution at room temperature.

Experimental details

Hydrogen atoms were added using the riding models implemented in the SHELX system.

Comment

Cyclopalladated complexes are one of the most developed and studied classes of precatalysts because of their structural versatility and easy synthetic accessibility [3], [4], [5], [6], [7], [8]. Among them, a wide variety of phosphines adducts of palladacycles have been successfully used in the coupling reactions [9], [10], [11], [12], [13]. In general, these adducts combine the stability induced by the presence of a palladacycle with the high activity commonly associated with phosphine ligands, and are more active than the corresponding dimeric palladacycles. As a continuation of our interest in the synthesis and application of palladacycles containing halides [3], [14], we report the crystal structure of the title complex.

The single-crystal X-ray analyses shows that the Pd atom is in a slightly distorted square-planar environment, being coordinated by a P atom, the chlorine atom, and the C atom and the nitrogen atom of the pyrimidine ligand. The deviations of the Pd atom from the plane is 0.056 Å. The pyrimidyl and phenyl ring are approximately coplanar, making a dihedral angle of 1.8°, which is less than that of the related free arylpyrimidine ligand [15]. The Pd—P and Pd—N bond lengths of the title complex are similar to those of the related palladacycles [3], [14], [16], [17]. In the crystal there exist weak C—H⋯Cl hydrogen bonds [18], [19], [20], the coordinated chlorine atom forms hydrogen bonds with the adjacent C—H group of the PPh3 ligand (Cl⋯H = 2.849, 2.861 and 2.943 Å). In addition, the chlorine atom in the pyrimidine ring also forms C—H⋯Cl hydrogen bonds with the adjacent C—H group of p-tolylpyrimidyl moiety and PPh3 ligand (Cl⋯H = 2.887 and 2.945 Å), which are attributed to construct the 3D architecture.

Acknowledgements

This work was supported by the high-level introduction of talent research start-up foundation of Jiangsu University of Science and Technology.

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Received: 2019-07-25
Accepted: 2019-09-22
Published Online: 2019-10-23
Published in Print: 2019-12-18

©2019 Chen Xu et al., published by De Gruyter, Berlin/Boston

This work is licensed under the Creative Commons Attribution 4.0 Public License.

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  64. Crystal structure of cyclo[tetra(μ2-cyanido)-tetracyanido-bis(1,4,7,10-tetraazacyclododecane-κ4N,N′,N′′,N′′′)dinickel(II)dipalladium(II)] hexahydrate, C24H52N16Ni2O6Pd2
  65. Crystal structure of (dimethyl sulfoxide)-dioxido-[2-hydroxy-N′-(4-oxo-4-phenylbutan-2-ylidene)benzohydrazidato κ3N,O,O′]molybdenum(VI), C19H20MoN2O6S
  66. Crystal structure of bis(acetylacetonato-κ2O,O′)-(ethanolamine-κ2N,O)copper(II), C14H25CuNO5
  67. Crystal structure of chlorido-diphenyl-(isopropyl(propyl)carbamodithioato-κ2S,S′)tin(IV), C19H24ClNS2Sn
  68. The crystal structure of bis(imidazole-1-yl)methane monohydrate, C7H10N4O
  69. The crystal structure of bis(4-nitroimidazole-1-1yl)methane, C7H6N6O4
  70. Crystal structure of di(naphthalen-2-yl)sulfane, C20H14S
  71. Crystal structure of 3-acetyl-6-bromo-4-hydroxy-2H-chromen-2-one, C11H7BrO4
  72. Crystal structure of N′2,N′6-bis((E)-1-(pyrazin-2-yl)ethylidene)pyridine-2,6-dicarbohydrazide — methanol (1/2), C21H25N9O4
  73. The crystal structure of 3-nitro-4-(p-tolylamino)-2H-chromen-2-one, C16H12N2O4
  74. The crystal structure of 1,2-bis((4-methoxyphenyl)ethynyl)benzene, C24H18O2
  75. Crystal structure of a low-temperature (100 K) polymorph of catena-poly[(μ2-4,4′-bipyridine-κ2N,N′)-bis(O,O′-diethyldithiophosphato-κ1S)zinc(II)], C18H28N2O4P2S4Zn
  76. The pseudosymmetric low temperature polymorph of catena-poly[(μ2-4,4′-bipyridyl-κN,N′)-bis(O,O′-diethyldithiophosphato-κS)-cadmium(II)], {C18H28CdN2O4P2S4}n
  77. Crystal structure of 3-iodophthalic acid, C8H5IO4
  78. The crystal structure of tert-butyl (tert-butoxy(oxo)methyl)(5-bromo-2-fluorophenyl)carbamate, C16H21BrFNO4
  79. The crystal structure of bis(μ2-5,7-dichloroquinolin-8-olato-κ3N,O:O)-tetrakis(5,7-dichloroquinolin-8-olato-κ2N,O)bis(methanol-κ1O)dieuropium(III) — toluene (1/1), C63H39Cl12Eu2N6O8
  80. Crystal structure of dichlorido-(N′-(1-(3-ethylpyrazin-2-yl)ethylidene)-4-methoxybenzohydrazide-κ3N,N′,O)cadmium(II), C16H18N4O2Cl2Cd
  81. A redetermination of the crystal structure of catena-poly[(bis(O,O′-isopropyl dithiophosphato-κ2S,S′)-(μ2-1,2-bis(3-pyridylmethylene)hydrazine-κ2N,N′)cadmium(II)], {C24H38CdN4O4P2S4}n
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