supplementary materials


bg2480 scheme

Acta Cryst. (2012). E68, m1419-m1420    [ doi:10.1107/S1600536812043589 ]

trans-Iodido(pyrazinyl-[kappa]C2)bis(triphenylphosphane-[kappa]P)palladium(II)

Y.-J. Tu, H.-F. Wang, G.-H. Lee, K.-H. Yih and X.-Y. Tang

Abstract top

There are two independent molecules with similar configurations in the asymmetric unit of the title complex, [Pd(C4H3N2)I(C18H15P)2]. In each molecule, the geometry around the Pd atom is distorted square-planar, with the Pd atom displaced by 0.0549 (12) and 0.0734 (13) Å from the least-squares plane of the I-P-P-C atoms. The PPh3 ligands are in trans positions, with P-Pd-P angles of 173.12 (4) and 170.29 (4)°, while the pyrazinyl ligands and I atoms, also trans to each other, form C-Pd-I angles of 179.38 (12) and 178.44 (12)°. In the crystal, C-H...[pi] interactions occur, resulting in a three-dimensional supramolecular architecture.

Comment top

Processes leading to the formation of C—C bonds and cathalized by Palladium complexes are among the most important reactions in organic synthesis (Dobrzynski & Angelici, 1975). Intramolecular reductive elimination of the Pd—N binuclear complex [Pd(µ-C9H6N)(µ-dppm)]2(Cl)2 yielding the organic compound 2,2'-biquinoline has been reported (Chin et al., 1988). A pyridyl-bridged palladium complex was reported as an effective precatalyst for the Suzuki cross-coupling reactions of a variety organoboronic acids and aryl bromides (Beeby, et al., 2004). Pyrazinyl nickel complexes have been used to as a catalyst for C—C coupling reactions (Steffen et al., 2005), but to our knowledge, no pyrazinyl palladium crystal structure has been described.

For the synthesis of the pyrazinyl title compound, complex [Pd(PPh3)4] was used to react with 2-iodopyrazine in dichloromethane at room temperature. As a result, a two triphenylphosphine displaced complex [Pd(I)(C4H3N2)(PPh3)2] was isolated with 98% yield. The X-ray crystal structure analysis has been carried out to provide structural parameters.

The molecular structure (with two independent molecules) is shown in Fig. 1. There are small difference in bond distances (in the range of 0.001–0.027 Å) and bond angles (in the range of 0.05–0.7.46°) between them, mainly around the metal atoms. The palladium atom has a distorted square planar geometry, while being displaced by 0.0549 (12) Å (0.0734 (13) Å) from the least-squares plane Angles around the Pd center lay within ± 2.79° of 90°. The average Pd—C1(C41) bond distance, 1.998 (4) Å, is longer than reported PdII-carbon(carbonyl) distances, and similar to those of Pd—C(carbene) distances (Cardin et al., 1972). The PPh3 ligands are in trans position: P—Pd—P(av), 171.71 (4)°, while the pyrazinyl ligand and iodine atom, also trans to each other, present a C—Pd—I(av) of 178.91 (12)°. The phosphorus atoms approach tetrahedral geometry as expected, with a maximun deviation from idealized tetrahedral geometry for C5—P1—Pd = 119.13 (14)°. The average Pd—N1(N(3) bond distance of 2.899 (4) Å indicates no bonding interaction between the nitrogen atom and palladium metal atom. Within the pyrazinyl ligand itself, the geometry is consistent with a significant partial double bond character in the C—C and C—N bond. The C—N(av) bond distances (1.321 (5), 1.353 (6) Å) are typical for a C—N bond having partial double bond character and are certainly much shorter than a normal C—N (1.47 Å) single bond. The average Pd—C (1.998 Å), Pd—P (2.3375, 2.3255 Å) and Pd—I (2.7007 Å) coordination lengths of (I) are in agreement with reported values (Yih et al., 2009).

There are five C—H···π intermolecular hydrogen bond interactions (Fig. 2 and Table 1) and intramolecular π-π interactions (Fig. 1). The pyrazinyl ligand (N1, N2, C1 > C4) and two phenyl rings (C5 > C10 and C29 > C34) from the trans triphenylphosphanes respectively are nearly parallel, with intercentroid distances of 3.564 (3) and 3.677 (3) Å, and a shortest inter-ring distance of 3.120 (2) and 3,317 (2) Å. A similar effect is observed in the remaining molecule, where the intercentroid distances between the pyrazinyl ligand (N3, N4, C41 > C44) and the phenyl rings (C45 > C50 and C69 > C74) are 3.716 (3) and 3.446 (3) Å, with a shortest inter-ring distance of 3.225 (2) and 3,119 (2) Å.

Related literature top

For reactions in organic synthesis that form C—C bonds, see: Steffen et al. (2005); Beeby et al. (2004); Chin et al. (1988); Dobrzynski & Angelici (1975). For Pd—C(carbene) bond lengths, see: Cardin et al. (1972) and for Pd—I bond lengths, see: Yih et al. (2009). For intramolecular ππ interaction, see: Bustos et al. (2006). For a Pd–pyrimidinyl complex, see: Wang et al. (2011)

Experimental top

The synthesis of the title compound (I) was carried out as follows. CH2Cl2 (20 ml) was added to a flask (100 ml) containing Pd(PPh3)4 (1.155 g, 1.0 mmol) and 2-iodiopyrazine (0.248 g, 1.2 mmol) at ambient temperature. The mixture was stirred for about 10 min. The solvent was concentrated to 10 ml, and 20 ml of diethyl ether was added to the solution. The pale-yellow solids were formed which were isolated by filtration (G4), washed with n-hexane (2 x 10 ml) and subsequently dried under vacuum yielding 0.82 g (98%) of [Pd(PPh3)2(C4H3N2)I], (I).

Refinement top

H atoms were positioned geometrically and refined using a riding model, with C—H = 0.95 Å and with Uiso(H) = 1.2 times Ueq(C).

Computing details top

Data collection: SMART (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP in SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The molecular structure of (I), showing the atom-numbering scheme and the 50% probability displacement ellipsoids. Dashed lines represent the π-π interactions.
[Figure 2] Fig. 2. The molecular structure of (I), showing the intermolecular C—H···π hydrogen bond interactions.
(I) top
Crystal data top
[Pd(C4H3N2)I(C18H15P)2]F(000) = 3328
Mr = 836.92Dx = 1.601 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 4895 reflections
a = 21.5786 (9) Åθ = 2.2–25.3°
b = 19.8596 (9) ŵ = 1.55 mm1
c = 16.9192 (8) ÅT = 150 K
β = 106.6952 (11)°Block, colorless
V = 6945.0 (5) Å30.27 × 0.20 × 0.16 mm
Z = 8
Data collection top
Bruker SMART APEX CCD area-detector
diffractometer
15924 independent reflections
Radiation source: fine-focus sealed tube11520 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.055
ω scansθmax = 27.5°, θmin = 1.0°
Absorption correction: multi-scan
(SADABS; Bruker, 2001)
h = 2818
Tmin = 0.680, Tmax = 0.790k = 2522
40984 measured reflectionsl = 2121
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.048Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.101H-atom parameters constrained
S = 1.04 w = 1/[σ2(Fo2) + (0.033P)2 + 0.398P]
where P = (Fo2 + 2Fc2)/3
15924 reflections(Δ/σ)max = 0.003
829 parametersΔρmax = 1.35 e Å3
0 restraintsΔρmin = 0.55 e Å3
Crystal data top
[Pd(C4H3N2)I(C18H15P)2]V = 6945.0 (5) Å3
Mr = 836.92Z = 8
Monoclinic, P21/cMo Kα radiation
a = 21.5786 (9) ŵ = 1.55 mm1
b = 19.8596 (9) ÅT = 150 K
c = 16.9192 (8) Å0.27 × 0.20 × 0.16 mm
β = 106.6952 (11)°
Data collection top
Bruker SMART APEX CCD area-detector
diffractometer
15924 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2001)
11520 reflections with I > 2σ(I)
Tmin = 0.680, Tmax = 0.790Rint = 0.055
40984 measured reflectionsθmax = 27.5°
Refinement top
R[F2 > 2σ(F2)] = 0.048H-atom parameters constrained
wR(F2) = 0.101Δρmax = 1.35 e Å3
S = 1.04Δρmin = 0.55 e Å3
15924 reflectionsAbsolute structure: ?
829 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'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 > σ(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) top
xyzUiso*/Ueq
Pd10.146035 (15)0.406204 (16)0.895828 (18)0.01645 (8)
I10.089411 (14)0.285212 (15)0.898708 (18)0.02538 (8)
P10.23255 (5)0.37985 (6)1.01093 (6)0.0168 (2)
P20.05913 (5)0.44510 (6)0.78820 (7)0.0195 (2)
N10.17522 (18)0.54643 (19)0.9394 (2)0.0253 (9)
N20.25835 (19)0.5641 (2)0.8410 (2)0.0319 (10)
C10.18713 (19)0.4964 (2)0.8938 (2)0.0193 (9)
C20.2052 (2)0.6052 (2)0.9359 (3)0.0298 (11)
H20.19790.64210.96800.036*
C30.2459 (2)0.6137 (2)0.8876 (3)0.0339 (12)
H30.26590.65620.88720.041*
C40.2281 (2)0.5069 (2)0.8446 (3)0.0242 (10)
H40.23470.47060.81140.029*
C50.2836 (2)0.4508 (2)1.0597 (3)0.0214 (10)
C60.3266 (2)0.4770 (2)1.0200 (3)0.0255 (10)
H60.33280.45490.97310.031*
C70.3607 (2)0.5359 (2)1.0495 (3)0.0357 (13)
H70.38980.55391.02230.043*
C80.3524 (3)0.5679 (3)1.1180 (3)0.0419 (14)
H80.37540.60821.13770.050*
C90.3109 (3)0.5415 (3)1.1574 (3)0.0415 (14)
H90.30580.56331.20510.050*
C100.2760 (2)0.4833 (2)1.1288 (3)0.0314 (11)
H100.24700.46581.15650.038*
C110.2050 (2)0.3462 (2)1.0950 (2)0.0181 (9)
C120.1520 (2)0.3765 (2)1.1116 (3)0.0278 (11)
H120.12950.41171.07700.033*
C130.1320 (2)0.3558 (2)1.1782 (3)0.0309 (11)
H130.09670.37791.19010.037*
C140.1626 (2)0.3036 (2)1.2273 (3)0.0304 (12)
H140.14840.28971.27290.036*
C150.2141 (2)0.2713 (2)1.2104 (3)0.0310 (12)
H150.23440.23431.24330.037*
C160.2363 (2)0.2931 (2)1.1448 (3)0.0236 (10)
H160.27250.27181.13410.028*
C170.2913 (2)0.3187 (2)0.9962 (2)0.0197 (9)
C180.2746 (2)0.2741 (2)0.9303 (3)0.0252 (10)
H180.23270.27580.89210.030*
C190.3193 (2)0.2269 (2)0.9201 (3)0.0320 (12)
H190.30780.19660.87480.038*
C200.3802 (2)0.2238 (2)0.9754 (3)0.0321 (12)
H200.41040.19140.96800.038*
C210.3972 (2)0.2672 (2)1.0407 (3)0.0285 (11)
H210.43920.26501.07870.034*
C220.3530 (2)0.3145 (2)1.0515 (3)0.0261 (10)
H220.36500.34441.09720.031*
C230.0450 (2)0.4064 (2)0.6870 (2)0.0206 (9)
C240.0775 (2)0.3482 (2)0.6767 (3)0.0274 (11)
H240.10540.32620.72330.033*
C250.0692 (2)0.3222 (2)0.5983 (3)0.0279 (11)
H250.09180.28250.59180.034*
C260.0291 (2)0.3527 (2)0.5299 (3)0.0309 (11)
H260.02380.33410.47660.037*
C270.0038 (2)0.4113 (3)0.5392 (3)0.0311 (12)
H270.03170.43290.49220.037*
C280.0044 (2)0.4376 (2)0.6168 (3)0.0262 (10)
H280.01790.47760.62290.031*
C290.0602 (2)0.5342 (2)0.7604 (3)0.0228 (10)
C300.0258 (2)0.5822 (2)0.7892 (3)0.0315 (12)
H300.00060.56930.82450.038*
C310.0279 (2)0.6497 (3)0.7667 (4)0.0439 (14)
H310.00390.68280.78590.053*
C320.0657 (3)0.6677 (3)0.7156 (4)0.0460 (15)
H320.06680.71330.69910.055*
C330.1010 (2)0.6209 (3)0.6892 (3)0.0378 (13)
H330.12770.63400.65590.045*
C340.0982 (2)0.5543 (2)0.7106 (3)0.0310 (11)
H340.12250.52170.69120.037*
C350.0150 (2)0.4370 (2)0.8193 (3)0.0212 (10)
C360.0760 (2)0.4286 (2)0.7642 (3)0.0320 (12)
H360.08080.42560.70670.038*
C370.1299 (2)0.4245 (3)0.7925 (3)0.0398 (14)
H370.17140.41860.75430.048*
C380.1241 (2)0.4289 (2)0.8757 (3)0.0339 (12)
H380.16130.42580.89480.041*
C390.0640 (2)0.4378 (2)0.9306 (3)0.0340 (12)
H390.05980.44190.98790.041*
C400.0094 (2)0.4408 (2)0.9030 (3)0.0291 (11)
H400.03210.44560.94170.035*
Pd20.348046 (15)0.592426 (16)0.622033 (18)0.01642 (8)
I20.406173 (15)0.713311 (15)0.626859 (18)0.02865 (8)
P30.42975 (5)0.55229 (6)0.73396 (7)0.0190 (2)
P40.27144 (6)0.61773 (6)0.49785 (7)0.0207 (3)
N30.32016 (18)0.45176 (18)0.5822 (2)0.0247 (9)
N40.21891 (19)0.4440 (2)0.6553 (2)0.0313 (10)
C410.3031 (2)0.5044 (2)0.6191 (2)0.0176 (9)
C420.2857 (2)0.3946 (2)0.5807 (3)0.0306 (11)
H420.29670.35550.55530.037*
C430.2350 (2)0.3918 (2)0.6152 (3)0.0334 (12)
H430.21070.35130.61040.040*
C440.2532 (2)0.4990 (2)0.6557 (3)0.0240 (10)
H440.24320.53760.68290.029*
C450.4259 (2)0.4636 (2)0.7618 (2)0.0206 (9)
C460.4659 (2)0.4140 (2)0.7458 (3)0.0302 (11)
H460.49950.42580.72240.036*
C470.4572 (2)0.3475 (2)0.7640 (3)0.0368 (12)
H470.48440.31370.75220.044*
C480.4096 (2)0.3298 (2)0.7987 (3)0.0339 (12)
H480.40390.28400.81110.041*
C490.3701 (3)0.3784 (3)0.8156 (3)0.0344 (12)
H490.33690.36610.83960.041*
C500.3784 (2)0.4451 (2)0.7979 (2)0.0249 (10)
H500.35130.47860.81060.030*
C510.4455 (2)0.5931 (2)0.8343 (2)0.0190 (9)
C520.4094 (2)0.6479 (2)0.8460 (3)0.0252 (10)
H520.37640.66570.80090.030*
C530.4213 (2)0.6768 (2)0.9234 (3)0.0278 (11)
H530.39660.71460.93110.033*
C540.4686 (2)0.6513 (2)0.9892 (3)0.0260 (10)
H540.47640.67131.04210.031*
C550.5049 (2)0.5964 (2)0.9783 (3)0.0273 (11)
H550.53780.57891.02370.033*
C560.4931 (2)0.5671 (2)0.9016 (3)0.0240 (10)
H560.51760.52910.89440.029*
C570.5029 (2)0.5600 (2)0.7017 (3)0.0220 (10)
C580.5026 (2)0.5306 (2)0.6273 (3)0.0334 (12)
H580.46620.50530.59680.040*
C590.5559 (2)0.5383 (2)0.5973 (3)0.0369 (13)
H590.55570.51780.54650.044*
C600.6084 (2)0.5750 (3)0.6400 (3)0.0349 (12)
H600.64460.58010.61930.042*
C610.6082 (2)0.6047 (3)0.7135 (3)0.0402 (13)
H610.64450.63050.74330.048*
C620.5558 (2)0.5974 (3)0.7447 (3)0.0362 (12)
H620.55630.61800.79550.043*
C630.3096 (2)0.6476 (2)0.4213 (3)0.0266 (11)
C640.2779 (3)0.6866 (3)0.3541 (3)0.0487 (16)
H640.23540.70270.34800.058*
C650.3104 (4)0.7020 (3)0.2948 (3)0.062 (2)
H650.28920.72830.24800.074*
C660.3709 (4)0.6800 (3)0.3034 (4)0.065 (2)
H660.39180.69110.26270.077*
C670.4028 (4)0.6415 (3)0.3702 (4)0.062 (2)
H670.44560.62610.37620.074*
C680.3716 (3)0.6258 (3)0.4285 (3)0.0420 (14)
H680.39340.59910.47480.050*
C690.2243 (2)0.5458 (2)0.4453 (3)0.0244 (10)
C700.2445 (2)0.5079 (2)0.3884 (3)0.0293 (11)
H700.28040.52230.37090.035*
C710.2121 (3)0.4490 (2)0.3572 (3)0.0362 (12)
H710.22490.42420.31650.043*
C720.1617 (2)0.4261 (3)0.3847 (3)0.0363 (13)
H720.14110.38480.36440.044*
C730.1411 (2)0.4625 (2)0.4409 (3)0.0313 (11)
H730.10580.44690.45910.038*
C740.1723 (2)0.5227 (2)0.4716 (3)0.0270 (11)
H740.15810.54820.51060.032*
C750.2096 (2)0.6772 (2)0.5041 (3)0.0263 (11)
C760.2169 (2)0.7142 (2)0.5748 (3)0.0320 (11)
H760.25560.71010.61880.038*
C770.1684 (3)0.7577 (3)0.5833 (4)0.0449 (14)
H770.17430.78310.63250.054*
C780.1129 (3)0.7634 (3)0.5207 (4)0.0504 (17)
H780.07940.79210.52720.061*
C790.1040 (3)0.7285 (3)0.4484 (4)0.0503 (16)
H790.06530.73400.40470.060*
C800.1521 (2)0.6850 (2)0.4392 (3)0.0405 (13)
H800.14620.66060.38930.049*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Pd10.01639 (17)0.01662 (18)0.01584 (16)0.00067 (13)0.00386 (13)0.00095 (13)
I10.02899 (17)0.02145 (17)0.02611 (16)0.00769 (13)0.00859 (13)0.00107 (12)
P10.0177 (6)0.0164 (6)0.0164 (5)0.0003 (5)0.0049 (4)0.0006 (4)
P20.0185 (6)0.0211 (6)0.0179 (5)0.0031 (5)0.0037 (5)0.0004 (5)
N10.026 (2)0.025 (2)0.027 (2)0.0014 (17)0.0101 (17)0.0026 (17)
N20.032 (2)0.034 (3)0.033 (2)0.010 (2)0.0145 (19)0.0015 (19)
C10.014 (2)0.024 (3)0.018 (2)0.0027 (18)0.0016 (17)0.0060 (18)
C20.030 (3)0.019 (3)0.042 (3)0.005 (2)0.012 (2)0.008 (2)
C30.041 (3)0.020 (3)0.043 (3)0.005 (2)0.016 (3)0.004 (2)
C40.025 (2)0.025 (3)0.026 (2)0.003 (2)0.013 (2)0.0016 (19)
C50.022 (2)0.017 (2)0.022 (2)0.0007 (19)0.0012 (19)0.0017 (18)
C60.024 (3)0.020 (3)0.032 (3)0.002 (2)0.007 (2)0.003 (2)
C70.021 (3)0.029 (3)0.055 (3)0.007 (2)0.008 (2)0.011 (3)
C80.040 (3)0.024 (3)0.054 (4)0.009 (2)0.002 (3)0.003 (3)
C90.049 (4)0.027 (3)0.043 (3)0.004 (3)0.005 (3)0.011 (2)
C100.035 (3)0.024 (3)0.033 (3)0.003 (2)0.006 (2)0.003 (2)
C110.020 (2)0.020 (2)0.015 (2)0.0062 (18)0.0066 (17)0.0005 (17)
C120.026 (3)0.031 (3)0.026 (2)0.001 (2)0.007 (2)0.004 (2)
C130.033 (3)0.038 (3)0.028 (3)0.003 (2)0.017 (2)0.003 (2)
C140.046 (3)0.028 (3)0.022 (2)0.013 (2)0.017 (2)0.007 (2)
C150.048 (3)0.020 (3)0.022 (2)0.009 (2)0.007 (2)0.0019 (19)
C160.031 (3)0.021 (3)0.020 (2)0.004 (2)0.0088 (19)0.0005 (18)
C170.020 (2)0.021 (2)0.021 (2)0.0027 (19)0.0111 (18)0.0019 (18)
C180.025 (3)0.025 (3)0.026 (2)0.000 (2)0.008 (2)0.0002 (19)
C190.036 (3)0.031 (3)0.029 (3)0.005 (2)0.010 (2)0.006 (2)
C200.034 (3)0.022 (3)0.044 (3)0.010 (2)0.019 (2)0.006 (2)
C210.020 (2)0.028 (3)0.036 (3)0.000 (2)0.006 (2)0.004 (2)
C220.022 (3)0.022 (3)0.032 (3)0.003 (2)0.003 (2)0.004 (2)
C230.020 (2)0.025 (3)0.017 (2)0.0019 (19)0.0054 (18)0.0005 (18)
C240.029 (3)0.028 (3)0.024 (2)0.004 (2)0.005 (2)0.003 (2)
C250.025 (3)0.032 (3)0.026 (2)0.007 (2)0.007 (2)0.001 (2)
C260.031 (3)0.041 (3)0.023 (2)0.004 (2)0.010 (2)0.003 (2)
C270.028 (3)0.043 (3)0.020 (2)0.001 (2)0.002 (2)0.007 (2)
C280.022 (2)0.029 (3)0.029 (3)0.005 (2)0.008 (2)0.001 (2)
C290.018 (2)0.023 (3)0.024 (2)0.0015 (19)0.0011 (18)0.0039 (18)
C300.025 (3)0.028 (3)0.043 (3)0.004 (2)0.012 (2)0.001 (2)
C310.032 (3)0.028 (3)0.069 (4)0.010 (2)0.011 (3)0.002 (3)
C320.039 (3)0.030 (3)0.062 (4)0.006 (3)0.004 (3)0.016 (3)
C330.037 (3)0.034 (3)0.041 (3)0.004 (2)0.008 (2)0.013 (2)
C340.031 (3)0.030 (3)0.029 (3)0.002 (2)0.005 (2)0.004 (2)
C350.020 (2)0.020 (2)0.024 (2)0.0007 (19)0.0077 (19)0.0015 (18)
C360.028 (3)0.041 (3)0.025 (2)0.005 (2)0.005 (2)0.006 (2)
C370.021 (3)0.056 (4)0.039 (3)0.004 (2)0.004 (2)0.012 (3)
C380.033 (3)0.028 (3)0.046 (3)0.002 (2)0.020 (3)0.005 (2)
C390.045 (3)0.033 (3)0.029 (3)0.003 (2)0.019 (2)0.004 (2)
C400.021 (3)0.039 (3)0.027 (2)0.002 (2)0.007 (2)0.007 (2)
Pd20.01819 (17)0.01557 (18)0.01483 (15)0.00133 (14)0.00368 (13)0.00039 (13)
I20.03742 (19)0.02015 (17)0.02770 (16)0.01020 (14)0.00826 (14)0.00112 (12)
P30.0172 (6)0.0191 (6)0.0185 (5)0.0013 (5)0.0018 (5)0.0001 (4)
P40.0252 (6)0.0162 (6)0.0185 (6)0.0011 (5)0.0028 (5)0.0007 (4)
N30.030 (2)0.019 (2)0.025 (2)0.0029 (17)0.0068 (17)0.0002 (16)
N40.034 (2)0.029 (2)0.032 (2)0.0095 (19)0.0102 (19)0.0030 (18)
C410.020 (2)0.016 (2)0.014 (2)0.0028 (18)0.0014 (17)0.0031 (16)
C420.046 (3)0.015 (3)0.028 (3)0.000 (2)0.006 (2)0.0018 (19)
C430.040 (3)0.024 (3)0.032 (3)0.012 (2)0.002 (2)0.007 (2)
C440.028 (3)0.025 (3)0.020 (2)0.002 (2)0.0084 (19)0.0039 (19)
C450.022 (2)0.018 (2)0.018 (2)0.0000 (19)0.0003 (18)0.0004 (17)
C460.027 (3)0.024 (3)0.039 (3)0.003 (2)0.009 (2)0.006 (2)
C470.039 (3)0.026 (3)0.042 (3)0.012 (2)0.008 (3)0.003 (2)
C480.041 (3)0.022 (3)0.033 (3)0.001 (2)0.002 (2)0.004 (2)
C490.041 (3)0.034 (3)0.026 (3)0.009 (2)0.007 (2)0.002 (2)
C500.031 (3)0.026 (3)0.017 (2)0.001 (2)0.0050 (19)0.0016 (18)
C510.020 (2)0.017 (2)0.018 (2)0.0002 (18)0.0029 (17)0.0016 (17)
C520.024 (3)0.024 (3)0.026 (2)0.002 (2)0.004 (2)0.0033 (19)
C530.037 (3)0.021 (3)0.026 (2)0.003 (2)0.012 (2)0.002 (2)
C540.029 (3)0.030 (3)0.020 (2)0.005 (2)0.008 (2)0.0019 (19)
C550.025 (3)0.033 (3)0.021 (2)0.002 (2)0.0024 (19)0.007 (2)
C560.021 (2)0.024 (3)0.027 (2)0.003 (2)0.006 (2)0.0034 (19)
C570.017 (2)0.023 (3)0.025 (2)0.0007 (19)0.0046 (19)0.0010 (19)
C580.029 (3)0.036 (3)0.037 (3)0.003 (2)0.013 (2)0.008 (2)
C590.043 (3)0.035 (3)0.040 (3)0.002 (3)0.024 (3)0.008 (2)
C600.024 (3)0.036 (3)0.049 (3)0.003 (2)0.017 (2)0.011 (2)
C610.028 (3)0.051 (4)0.040 (3)0.013 (3)0.007 (2)0.003 (3)
C620.033 (3)0.046 (3)0.028 (3)0.012 (3)0.007 (2)0.004 (2)
C630.042 (3)0.019 (2)0.017 (2)0.008 (2)0.006 (2)0.0005 (18)
C640.068 (4)0.044 (4)0.025 (3)0.028 (3)0.002 (3)0.009 (2)
C650.098 (6)0.051 (4)0.024 (3)0.046 (4)0.001 (3)0.005 (3)
C660.123 (7)0.049 (4)0.034 (3)0.044 (4)0.041 (4)0.018 (3)
C670.104 (6)0.035 (4)0.072 (5)0.011 (4)0.066 (4)0.012 (3)
C680.068 (4)0.026 (3)0.043 (3)0.001 (3)0.034 (3)0.001 (2)
C690.027 (3)0.022 (3)0.019 (2)0.001 (2)0.0001 (19)0.0010 (18)
C700.033 (3)0.029 (3)0.023 (2)0.003 (2)0.003 (2)0.003 (2)
C710.047 (3)0.029 (3)0.031 (3)0.003 (3)0.009 (2)0.011 (2)
C720.040 (3)0.024 (3)0.037 (3)0.010 (2)0.001 (2)0.004 (2)
C730.026 (3)0.028 (3)0.036 (3)0.002 (2)0.003 (2)0.004 (2)
C740.026 (3)0.024 (3)0.027 (2)0.002 (2)0.002 (2)0.001 (2)
C750.022 (2)0.015 (2)0.038 (3)0.0052 (19)0.001 (2)0.001 (2)
C760.033 (3)0.024 (3)0.041 (3)0.001 (2)0.013 (2)0.002 (2)
C770.050 (4)0.029 (3)0.062 (4)0.007 (3)0.027 (3)0.000 (3)
C780.038 (3)0.022 (3)0.098 (5)0.007 (3)0.029 (4)0.013 (3)
C790.030 (3)0.032 (4)0.079 (5)0.002 (3)0.000 (3)0.015 (3)
C800.036 (3)0.020 (3)0.056 (3)0.001 (2)0.003 (3)0.005 (2)
Geometric parameters (Å, º) top
Pd1—C12.003 (4)Pd2—C411.992 (4)
Pd1—P12.3373 (11)Pd2—P42.3246 (12)
Pd1—P22.3383 (11)Pd2—P32.3263 (11)
Pd1—I12.7025 (4)Pd2—I22.6990 (4)
P1—C111.820 (4)P3—C571.819 (4)
P1—C171.823 (4)P3—C511.823 (4)
P1—C51.832 (4)P3—C451.832 (4)
P2—C231.821 (4)P4—C751.807 (5)
P2—C351.829 (4)P4—C631.822 (5)
P2—C291.833 (4)P4—C691.829 (4)
N1—C11.328 (5)N3—C411.324 (5)
N1—C21.344 (6)N3—C421.353 (6)
N2—C41.321 (5)N4—C441.319 (5)
N2—C31.335 (6)N4—C431.338 (6)
C1—C41.394 (5)C41—C441.391 (6)
C2—C31.372 (6)C42—C431.382 (7)
C2—H20.9500C42—H420.9500
C3—H30.9500C43—H430.9500
C4—H40.9500C44—H440.9500
C5—C101.386 (6)C45—C501.384 (6)
C5—C61.393 (6)C45—C461.387 (6)
C6—C71.394 (6)C46—C471.382 (6)
C6—H60.9500C46—H460.9500
C7—C81.378 (7)C47—C481.368 (7)
C7—H70.9500C47—H470.9500
C8—C91.364 (7)C48—C491.371 (7)
C8—H80.9500C48—H480.9500
C9—C101.390 (6)C49—C501.382 (6)
C9—H90.9500C49—H490.9500
C10—H100.9500C50—H500.9500
C11—C121.389 (6)C51—C521.386 (6)
C11—C161.397 (6)C51—C561.395 (6)
C12—C131.379 (6)C52—C531.385 (6)
C12—H120.9500C52—H520.9500
C13—C141.373 (6)C53—C541.372 (6)
C13—H130.9500C53—H530.9500
C14—C151.382 (7)C54—C551.386 (6)
C14—H140.9500C54—H540.9500
C15—C161.397 (6)C55—C561.377 (6)
C15—H150.9500C55—H550.9500
C16—H160.9500C56—H560.9500
C17—C181.388 (6)C57—C621.380 (6)
C17—C221.393 (6)C57—C581.387 (6)
C18—C191.389 (6)C58—C591.391 (6)
C18—H180.9500C58—H580.9500
C19—C201.377 (7)C59—C601.366 (7)
C19—H190.9500C59—H590.9500
C20—C211.366 (6)C60—C611.377 (7)
C20—H200.9500C60—H600.9500
C21—C221.388 (6)C61—C621.386 (6)
C21—H210.9500C61—H610.9500
C22—H220.9500C62—H620.9500
C23—C241.389 (6)C63—C681.378 (7)
C23—C281.401 (6)C63—C641.383 (6)
C24—C251.385 (6)C64—C651.412 (8)
C24—H240.9500C64—H640.9500
C25—C261.371 (6)C65—C661.344 (9)
C25—H250.9500C65—H650.9500
C26—C271.396 (6)C66—C671.375 (9)
C26—H260.9500C66—H660.9500
C27—C281.377 (6)C67—C681.382 (7)
C27—H270.9500C67—H670.9500
C28—H280.9500C68—H680.9500
C29—C301.380 (6)C69—C701.386 (6)
C29—C341.392 (6)C69—C741.398 (6)
C30—C311.398 (7)C70—C711.387 (6)
C30—H300.9500C70—H700.9500
C31—C321.396 (7)C71—C721.378 (7)
C31—H310.9500C71—H710.9500
C32—C331.357 (7)C72—C731.367 (7)
C32—H320.9500C72—H720.9500
C33—C341.376 (6)C73—C741.397 (6)
C33—H330.9500C73—H730.9500
C34—H340.9500C74—H740.9500
C35—C401.388 (6)C75—C761.375 (6)
C35—C361.388 (6)C75—C801.409 (6)
C36—C371.381 (6)C76—C771.394 (6)
C36—H360.9500C76—H760.9500
C37—C381.380 (7)C77—C781.357 (8)
C37—H370.9500C77—H770.9500
C38—C391.372 (7)C78—C791.372 (8)
C38—H380.9500C78—H780.9500
C39—C401.388 (6)C79—C801.393 (7)
C39—H390.9500C79—H790.9500
C40—H400.9500C80—H800.9500
C1—Pd1—P187.86 (12)C41—Pd2—P487.27 (12)
C1—Pd1—P287.21 (12)C41—Pd2—P388.26 (12)
P1—Pd1—P2173.12 (4)P4—Pd2—P3170.29 (4)
C1—Pd1—I1179.38 (12)C41—Pd2—I2178.44 (12)
P1—Pd1—I192.46 (3)P4—Pd2—I292.22 (3)
P2—Pd1—I192.42 (3)P3—Pd2—I292.47 (3)
C11—P1—C17105.01 (19)C57—P3—C51107.2 (2)
C11—P1—C5102.72 (19)C57—P3—C45105.4 (2)
C17—P1—C5102.8 (2)C51—P3—C45101.44 (19)
C11—P1—Pd1111.78 (14)C57—P3—Pd2104.32 (14)
C17—P1—Pd1117.08 (14)C51—P3—Pd2120.03 (14)
C5—P1—Pd1115.82 (14)C45—P3—Pd2117.31 (14)
C23—P2—C35108.0 (2)C75—P4—C63108.7 (2)
C23—P2—C29100.2 (2)C75—P4—C69102.8 (2)
C35—P2—C29103.6 (2)C63—P4—C69102.2 (2)
C23—P2—Pd1118.23 (14)C75—P4—Pd2115.70 (16)
C35—P2—Pd1108.57 (14)C63—P4—Pd2111.34 (16)
C29—P2—Pd1116.91 (14)C69—P4—Pd2114.98 (14)
C1—N1—C2116.7 (4)C41—N3—C42116.5 (4)
C4—N2—C3114.9 (4)C44—N4—C43114.6 (4)
N1—C1—C4119.8 (4)N3—C41—C44120.3 (4)
N1—C1—Pd1119.9 (3)N3—C41—Pd2120.4 (3)
C4—C1—Pd1120.3 (3)C44—C41—Pd2119.3 (3)
N1—C2—C3122.1 (4)N3—C42—C43121.6 (4)
N1—C2—H2119.0N3—C42—H42119.2
C3—C2—H2119.0C43—C42—H42119.2
N2—C3—C2122.3 (4)N4—C43—C42122.4 (4)
N2—C3—H3118.9N4—C43—H43118.8
C2—C3—H3118.9C42—C43—H43118.8
N2—C4—C1124.3 (4)N4—C44—C41124.5 (4)
N2—C4—H4117.8N4—C44—H44117.7
C1—C4—H4117.8C41—C44—H44117.7
C10—C5—C6119.3 (4)C50—C45—C46118.7 (4)
C10—C5—P1122.4 (4)C50—C45—P3117.5 (3)
C6—C5—P1117.9 (3)C46—C45—P3123.8 (3)
C5—C6—C7119.8 (4)C47—C46—C45120.2 (5)
C5—C6—H6120.1C47—C46—H46119.9
C7—C6—H6120.1C45—C46—H46119.9
C8—C7—C6120.4 (5)C48—C47—C46120.5 (5)
C8—C7—H7119.8C48—C47—H47119.7
C6—C7—H7119.8C46—C47—H47119.7
C9—C8—C7119.6 (5)C47—C48—C49119.9 (5)
C9—C8—H8120.2C47—C48—H48120.1
C7—C8—H8120.2C49—C48—H48120.1
C8—C9—C10121.1 (5)C48—C49—C50120.1 (5)
C8—C9—H9119.5C48—C49—H49120.0
C10—C9—H9119.5C50—C49—H49120.0
C5—C10—C9119.8 (5)C49—C50—C45120.6 (4)
C5—C10—H10120.1C49—C50—H50119.7
C9—C10—H10120.1C45—C50—H50119.7
C12—C11—C16119.3 (4)C52—C51—C56119.1 (4)
C12—C11—P1118.1 (3)C52—C51—P3121.4 (3)
C16—C11—P1122.5 (3)C56—C51—P3119.5 (3)
C13—C12—C11120.3 (4)C53—C52—C51120.1 (4)
C13—C12—H12119.9C53—C52—H52119.9
C11—C12—H12119.9C51—C52—H52119.9
C14—C13—C12120.7 (4)C54—C53—C52120.4 (4)
C14—C13—H13119.7C54—C53—H53119.8
C12—C13—H13119.7C52—C53—H53119.8
C13—C14—C15120.0 (4)C53—C54—C55120.0 (4)
C13—C14—H14120.0C53—C54—H54120.0
C15—C14—H14120.0C55—C54—H54120.0
C14—C15—C16120.0 (4)C56—C55—C54119.9 (4)
C14—C15—H15120.0C56—C55—H55120.0
C16—C15—H15120.0C54—C55—H55120.0
C15—C16—C11119.7 (4)C55—C56—C51120.4 (4)
C15—C16—H16120.2C55—C56—H56119.8
C11—C16—H16120.2C51—C56—H56119.8
C18—C17—C22118.6 (4)C62—C57—C58119.5 (4)
C18—C17—P1120.3 (3)C62—C57—P3123.0 (4)
C22—C17—P1121.1 (3)C58—C57—P3117.3 (4)
C17—C18—C19120.0 (4)C57—C58—C59119.7 (5)
C17—C18—H18120.0C57—C58—H58120.2
C19—C18—H18120.0C59—C58—H58120.2
C20—C19—C18120.5 (4)C60—C59—C58120.8 (5)
C20—C19—H19119.8C60—C59—H59119.6
C18—C19—H19119.8C58—C59—H59119.6
C21—C20—C19120.2 (4)C59—C60—C61119.3 (5)
C21—C20—H20119.9C59—C60—H60120.4
C19—C20—H20119.9C61—C60—H60120.4
C20—C21—C22119.9 (4)C60—C61—C62120.9 (5)
C20—C21—H21120.1C60—C61—H61119.6
C22—C21—H21120.1C62—C61—H61119.6
C21—C22—C17120.9 (4)C57—C62—C61119.8 (5)
C21—C22—H22119.6C57—C62—H62120.1
C17—C22—H22119.6C61—C62—H62120.1
C24—C23—C28118.5 (4)C68—C63—C64119.1 (5)
C24—C23—P2121.0 (3)C68—C63—P4117.3 (4)
C28—C23—P2120.3 (3)C64—C63—P4123.4 (4)
C25—C24—C23120.0 (4)C63—C64—C65118.4 (6)
C25—C24—H24120.0C63—C64—H64120.8
C23—C24—H24120.0C65—C64—H64120.8
C26—C25—C24121.3 (4)C66—C65—C64121.2 (6)
C26—C25—H25119.3C66—C65—H65119.4
C24—C25—H25119.3C64—C65—H65119.4
C25—C26—C27119.4 (4)C65—C66—C67120.7 (6)
C25—C26—H26120.3C65—C66—H66119.6
C27—C26—H26120.3C67—C66—H66119.6
C28—C27—C26119.6 (4)C66—C67—C68118.7 (6)
C28—C27—H27120.2C66—C67—H67120.6
C26—C27—H27120.2C68—C67—H67120.6
C27—C28—C23121.2 (4)C63—C68—C67121.7 (6)
C27—C28—H28119.4C63—C68—H68119.1
C23—C28—H28119.4C67—C68—H68119.1
C30—C29—C34119.1 (4)C70—C69—C74118.9 (4)
C30—C29—P2121.9 (4)C70—C69—P4121.3 (4)
C34—C29—P2119.0 (4)C74—C69—P4119.1 (3)
C29—C30—C31120.2 (5)C69—C70—C71119.8 (5)
C29—C30—H30119.9C69—C70—H70120.1
C31—C30—H30119.9C71—C70—H70120.1
C32—C31—C30119.0 (5)C72—C71—C70120.7 (5)
C32—C31—H31120.5C72—C71—H71119.6
C30—C31—H31120.5C70—C71—H71119.6
C33—C32—C31120.8 (5)C73—C72—C71120.4 (5)
C33—C32—H32119.6C73—C72—H72119.8
C31—C32—H32119.6C71—C72—H72119.8
C32—C33—C34120.0 (5)C72—C73—C74119.5 (5)
C32—C33—H33120.0C72—C73—H73120.3
C34—C33—H33120.0C74—C73—H73120.3
C33—C34—C29120.8 (5)C73—C74—C69120.6 (4)
C33—C34—H34119.6C73—C74—H74119.7
C29—C34—H34119.6C69—C74—H74119.7
C40—C35—C36118.6 (4)C76—C75—C80118.3 (5)
C40—C35—P2117.5 (3)C76—C75—P4119.9 (4)
C36—C35—P2123.8 (3)C80—C75—P4121.7 (4)
C37—C36—C35120.3 (4)C75—C76—C77121.3 (5)
C37—C36—H36119.8C75—C76—H76119.4
C35—C36—H36119.8C77—C76—H76119.4
C38—C37—C36120.8 (5)C78—C77—C76119.5 (5)
C38—C37—H37119.6C78—C77—H77120.2
C36—C37—H37119.6C76—C77—H77120.2
C39—C38—C37119.3 (5)C77—C78—C79121.3 (5)
C39—C38—H38120.3C77—C78—H78119.4
C37—C38—H38120.3C79—C78—H78119.4
C38—C39—C40120.4 (4)C78—C79—C80119.7 (5)
C38—C39—H39119.8C78—C79—H79120.1
C40—C39—H39119.8C80—C79—H79120.1
C35—C40—C39120.5 (4)C79—C80—C75119.9 (5)
C35—C40—H40119.7C79—C80—H80120.0
C39—C40—H40119.7C75—C80—H80120.0
Hydrogen-bond geometry (Å, º) top
Cg1, Cg2, Cg3, Cg4 and Cg5 are the centroids of the C11–C16, C17–C22, C51–C56, C63–C68 and C75–C80 rings, respectively.
D—H···AD—HH···AD···AD—H···A
C2—H2···Cg5i0.952.993.898 (5)160
C7—H7···Cg30.953.003.930 (5)168
C25—H25···Cg1ii0.952.913.769 (5)151
C42—H42···Cg2ii0.953.003.944 (5)176
C53—H53···Cg4i0.952.803.617 (5)145
Symmetry codes: (i) x, y+3/2, z+1/2; (ii) x, y+1/2, z1/2.
Hydrogen-bond geometry (Å, º) top
Cg1, Cg2, Cg3, Cg4 and Cg5 are the centroids of the C11–C16, C17–C22, C51–C56, C63–C68 and C75–C80 rings, respectively.
D—H···AD—HH···AD···AD—H···A
C2—H2···Cg5i0.952.993.898 (5)160
C7—H7···Cg30.953.003.930 (5)168
C25—H25···Cg1ii0.952.913.769 (5)151
C42—H42···Cg2ii0.953.003.944 (5)176
C53—H53···Cg4i0.952.803.617 (5)145
Symmetry codes: (i) x, y+3/2, z+1/2; (ii) x, y+1/2, z1/2.
Acknowledgements top

We thank the National Science Council of the Republic of China for financial support (NSC101–2113-M-241–001-MY3).

references
References top

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