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Acta Cryst. (2007). E63, m1875-m1876    [ doi:10.1107/S1600536807028401 ]

Bis([mu]-4-benzyl-3,5-diphenylpyrazolato-[kappa]2N:N')bis[(4,4'-dimethyl-2,2'-bipyridine-[kappa]2N,N')palladium(II)] bis(hexafluorophosphate) diethyl ether monosolvate monohydrate

H.-P. Huang and L.-X. Liu

Abstract top

In the crystal structure of the title compound, [Pd2(C22H17N2)2(C12H12N2)2](PF6)2·C4H10O·H2O, two Pd(dmbpy) units (dmbpy is 4,4'-dimethyl-2,2'-bipyridine) are bridged by 4-benzyl-3,5-diphenylpyrazolate ligands in an exodentate fashion, which results in a clip-like cavity between the two Pd(dmbpy)Pd planes. A disordered hexafluoridophosphate anion is held in the cavity by an anion-[pi] interaction [P-F...Cg1 = 3.435 (15) Å (Cg1 is the centroid of the Pd-dmbpy chelate ring system) and P-F...Cg2 = 3.187 (15) Å (Cg2 is the centroid of a pyridine ring)]. A crystallographic twofold rotation axis passes through an F atom of the disordered anion and the mid-point of the two Pd atoms. The P and two F atoms of the second anion also lie on a twofold rotation axis, as do the O atom of the diethyl ether and the water O atom. The crystal structure is stabilized by electrostatic forces between the cations and anions, and intermolecular hydrogen bonds involving hexafluoridophosphate anions (C-H...F), the solvent diethyl ether molecules and water molecules (C-H...O).

Comment top

In our previous publictions, we reported a 3,5-diphenylpyrazolate-bridged dinuclear Pd(II) complex having an inorganic anion as the charge-balancing species (Huang et al., 2005 and 2007). Recently, we reported a 4-benzyl substituted 3,5-diphenylpyrazole ligand (Huang et al., 2007). In the present paper, we report the crytal structure of a dinuclear palladium(II) complex based on 4,4'-dimethyl-2,2'-bipyridine (dmbpy) and 4-benzyl-3,5-diphenylpyrazolate (Fig. 1). In the cation, a crystallographic twofold rotation axis passes through F6 and the mid-point of the Pd1—Pd1i atoms (Fig. 1)·The distance of two palladium atoms is 2.9989 (6) Å which are shorter than that of our previous dipalladium complexes (Table 1). The PdII center has a cis-square-planar geometry defined by a N,N'-bidentate pyrazolate ligand and a chelating 4,4'-dimethyl-2,2'-bipyridine ligand. This conformation creates an 'open book' disposition for the square-planar environment of the two Pd atoms. The dihedral angle between the two coordination planes around the Pd atoms is 61.0 (1)°. The two Pd(dmbpy)Pd planes form a cleft with a cavity of approximately 180 Å3. An interesting feature of the structure is the presence of a disordered hexafluorophosphate anion in the clip-like cavity formed by the Pd(dmbpy)Pd1 and Pd(dmbpy)Pdi planes. This disordered hexafluorophosphate anions is generated by a twofold rotation axis and held in the cavity by an anion–π interaction (P2—F8···Cg1 3.435 (15) Å, Cg1 is the centroid of the ring system Pd1, N1, C6, C7, N2; P2—F8···Cg2 3.187 (15) Å, Cg2 is the centroid of the ring system N1, C1, C2, C3, C5, C6). Atoms P1, F3 and F4 of the second anion lie also on a twofold rotation axis (Wyckoff letter a) and is located near the cation by C—H···F intermolecular hydrogen bonds. The compound packs by elestrostatic interactions, C—H···F intermolecular hydrogen bonds between the cations and anions, and C—H···O intermolecular hydrogen bonds between the solvent diethyl ether molecules and water molecules. The non-classical hydrogen bonds that connect cations and anions are detailed in Table 2.

Related literature top

For related literature, see: Flack (1983); Huang et al. (2005); Huang, Wu, Liu & Song (2007); Huang, Wu, Liu & Sun (2007).

Experimental top

A mixture of [4,4'-dimethyl-2,2'-bipyridine]dinitratopalladium (83.0 mg, 0.20 mmol) and 4-benzyl-3,5-diphenylpyrazole (31.0 mg, 0.10 mmol) was dissolved in water (5 ml) and stirred 2 h resulting in a clear yellow solution. To the mixture was added a tenfold excess of potassium hexafluorophosphate, which resulted in the immediate deposition of yellow microcrystals·The crystals were filtered, washed with a minimum amount of cold water and dried under vacuum (quantative yield, of 129.6 mg). Crystals were obtained by the vapor diffusion of diethyl ether into a 1 mM solution of in acetonitrile. 1H NMR (400 MHz, [D3] acetonitrile): δ 2.45 (12H, s, dmbpy-CH3), 4.09 (4H, s, CH2), 6.82 (4H, m, Ph—H), 7.03 (6H, m, Ph—H), 7.20 (4H, d, J=5.9 Hz, dmbpy-H5,5'), 7.26 (8H, t, J = 7.5 Hz, Ph—H), 7.33 (4H, t, J = 7.3 Hz, Ph—H), 7.53 (8H, d, J = 7.5 Hz, Ph—H), 7.77 (4H, d, J = 5.9 Hz, dmbpy-H6,6'), 7.99 (4H, s, dmbpy-H3,3') p.p.m.

Refinement top

The value −0.02 (3) of the Flack parameter (Flack, 1983) indicates the absolute structure of the measured crystal was correctly determined. The water O atoms were refined with anisotropic displacement parameters. The H atoms of water molecules were located in a difference Fourier map and refined as riding, with O—H distances of 0.97 Å and Uiso(H) = 1.2Ueq(O). The aromatic H atoms were constrained to an ideal geometry, with C—H distances of 0.93 Å and Uiso(H) = 1.2Ueq(C). The methyl H atoms were rotated to fit the electron density, with C—H distances of 0.96 Å and Uiso(H) = 1.5Ueq(C). The methylene H atoms were constrained to ideal geometry, with C—H distances of 0.97 Å and Uiso(H) = 1.2Ueq(C). Both PF6− anions and ether molecule were disordered about twofold rotation axis. The largest peak and deepest hole on the final difference Fourier map corresponds to 1.05 and −0.720 e Å−3, and were located 1.15 and 0.16 Å from the F3 and C35 atoms, respectively.

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SMART; data reduction: SAINT-Plus (Bruker, 2001); program(s) used to solve structure: SHELXTL (Sheldrick, 2001); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Figures top
[Figure 1] Fig. 1. A view of the title compound, showing 30% probability displacement ellipsoids and the atom numbering scheme.
[Figure 2] Fig. 2. Crystal packing of the title compound.
Bis(µ-4-benzyl-3,5-diphenylpyrazolato-κ2N:N')bis[(4,4'-\ dimethyl-2,2'-bipyridine-κ2N,N')palladium(II)] bis(hexafluoridophosphate) diethyl ether monosolvate monohydrate top
Crystal data top
[Pd2(C22H17N2)2(C12H12N2)2](PF6)2·C4H10O·H2OZ = 3
Mr = 1582.10F000 = 2412
Trigonal, P3121Dx = 1.444 Mg m−3
Hall symbol: P 31 2"Mo Kα radiation
λ = 0.71073 Å
a = 22.1138 (3) ÅCell parameters from 9974 reflections
b = 22.1138 (3) Åθ = 2.4–27.9º
c = 12.8884 (2) ŵ = 0.62 mm−1
α = 90ºT = 291 (2) K
β = 90ºBlock, yellow
γ = 120º0.48 × 0.42 × 0.36 mm
V = 5458.29 (13) Å3
Data collection top
Bruker SMART CCD area-detector
diffractometer		9007 independent reflections
Radiation source: sealed tube8156 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.028
T = 291(2) Kθmax = 28.3º
φ and ω scansθmin = 1.1º
Absorption correction: multi-scan
(SADABS; Bruker, 2001)		h = −29→29
Tmin = 0.756, Tmax = 0.808k = −29→29
47040 measured reflectionsl = −16→16
Refinement top
Refinement on F2Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: fullH-atom parameters constrained
R[F2 > 2σ(F2)] = 0.045  w = 1/[σ2(Fo2) + (0.0859P)2 + 2.0829P]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.144(Δ/σ)max = 0.001
S = 1.10Δρmax = 1.05 e Å−3
9007 reflectionsΔρmin = −0.74 e Å−3
466 parametersExtinction correction: none
Primary atom site location: structure-invariant direct methodsAbsolute structure: Flack (1983), with 4168 Friedel pairs
Secondary atom site location: difference Fourier mapFlack parameter: −0.02 (3)
Crystal data top
[Pd2(C22H17N2)2(C12H12N2)2](PF6)2·C4H10O·H2Oγ = 120º
Mr = 1582.10V = 5458.29 (13) Å3
Trigonal, P3121Z = 3
a = 22.1138 (3) ÅMo Kα
b = 22.1138 (3) ŵ = 0.62 mm−1
c = 12.8884 (2) ÅT = 291 (2) K
α = 90º0.48 × 0.42 × 0.36 mm
β = 90º
Data collection top
Bruker SMART CCD area-detector
diffractometer		9007 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2001)		8156 reflections with I > 2σ(I)
Tmin = 0.756, Tmax = 0.808Rint = 0.028
47040 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.045H-atom parameters constrained
wR(F2) = 0.144Δρmax = 1.05 e Å−3
S = 1.10Δρmin = −0.74 e Å−3
9007 reflectionsAbsolute structure: Flack (1983), with 4168 Friedel pairs
466 parametersFlack parameter: −0.02 (3)
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*/UeqOcc. (<1)
C10.5436 (3)0.8913 (3)1.0360 (4)0.0499 (10)
H10.52190.91381.06590.060*
C20.5767 (3)0.8665 (3)1.0993 (4)0.0590 (13)
H20.57770.87321.17060.071*
C30.6080 (3)0.8319 (3)1.0572 (4)0.0600 (13)
C40.6420 (5)0.8022 (5)1.1256 (6)0.095 (3)
H4A0.69090.83551.13220.142*
H4B0.63620.76001.09520.142*
H4C0.62060.79211.19290.142*
C50.6071 (3)0.8259 (3)0.9514 (5)0.0577 (12)
H50.62840.80330.92080.069*
C60.5751 (2)0.8527 (2)0.8887 (4)0.0439 (9)
C70.5768 (2)0.8544 (2)0.7752 (4)0.0422 (9)
C80.6115 (3)0.8291 (3)0.7153 (4)0.0525 (11)
H80.63190.80600.74710.063*
C90.6160 (3)0.8379 (3)0.6094 (4)0.0580 (13)
C100.6557 (5)0.8132 (5)0.5452 (6)0.089 (2)
H10A0.63790.76430.55760.133*
H10B0.70420.83890.56370.133*
H10C0.65050.82040.47310.133*
C110.5847 (3)0.8732 (3)0.5659 (4)0.0591 (13)
H110.58700.88090.49470.071*
C120.5500 (3)0.8965 (3)0.6292 (4)0.0508 (11)
H120.52950.92010.59920.061*
C130.4209 (2)0.9453 (2)0.6460 (4)0.0422 (9)
C140.3722 (2)0.8706 (2)0.6242 (4)0.0468 (10)
C150.3780 (3)0.8400 (3)0.5326 (5)0.0652 (14)
H150.41280.86630.48470.078*
C160.3309 (5)0.7694 (4)0.5139 (7)0.084 (2)
H160.33540.74840.45420.101*
C170.2784 (5)0.7310 (3)0.5822 (7)0.088 (2)
H170.24720.68410.56850.106*
C180.2716 (4)0.7611 (4)0.6711 (8)0.086 (2)
H180.23520.73490.71690.103*
C190.3187 (3)0.8307 (3)0.6929 (5)0.0620 (12)
H190.31430.85060.75390.074*
C200.4195 (2)0.9389 (2)1.0197 (4)0.0403 (9)
C210.3762 (2)0.8629 (2)1.0408 (4)0.0455 (10)
C220.3518 (3)0.8147 (3)0.9600 (5)0.0589 (13)
H220.36150.82990.89160.071*
C230.3129 (3)0.7436 (3)0.9820 (6)0.0715 (17)
H230.29710.71160.92780.086*
C240.2976 (3)0.7204 (3)1.0813 (7)0.082 (2)
H240.27040.67281.09440.098*
C250.3214 (3)0.7660 (4)1.1609 (6)0.0725 (18)
H250.31140.74951.22870.087*
C260.3609 (3)0.8374 (3)1.1428 (5)0.0591 (13)
H260.37720.86831.19840.071*
C270.4274 (2)1.0032 (3)0.5939 (3)0.0429 (8)
C280.3809 (3)1.0019 (3)0.5084 (4)0.0528 (11)
H28A0.36420.95870.46990.063*
H28B0.40851.04010.46130.063*
C290.3190 (3)1.0073 (2)0.5424 (4)0.0498 (11)
C300.2880 (3)0.9856 (3)0.6380 (5)0.0644 (14)
H300.30810.96990.68650.077*
C310.2275 (4)0.9864 (5)0.6643 (9)0.096 (3)
H310.20670.96960.72860.115*
C320.1984 (5)1.0118 (6)0.5953 (11)0.117 (4)
H320.15911.01450.61380.140*
C330.2280 (5)1.0335 (5)0.4983 (11)0.108 (4)
H330.20791.04940.45010.130*
C340.2877 (4)1.0314 (3)0.4731 (6)0.0742 (19)
H340.30751.04660.40780.089*
C350.0657 (19)0.0584 (18)0.794 (3)0.282 (17)
H35A0.02560.05640.82770.338*
H35B0.05480.05040.72040.338*
C360.1279 (17)0.1337 (17)0.806 (2)0.267 (14)
H36A0.13420.14620.87820.401*
H36B0.11850.16540.76820.401*
H36C0.16960.13590.77950.401*
F10.5517 (4)1.0008 (4)0.4557 (3)0.1223 (19)
F20.5204 (7)0.9199 (4)0.3331 (6)0.185 (4)
F30.4871 (6)1.00000.33330.220 (9)
F40.6205 (7)1.00000.33330.218 (7)
F50.8020 (4)1.0593 (5)0.8395 (10)0.098 (3)0.50
F60.8550 (5)1.00000.83330.174 (5)
F70.7642 (6)0.9347 (7)0.9591 (14)0.270 (7)
F80.7129 (6)0.9957 (7)0.9187 (15)0.158 (6)0.50
F90.8204 (7)1.0540 (8)0.9732 (17)0.173 (7)0.50
N10.5419 (2)0.8839 (2)0.9324 (3)0.0409 (7)
N20.5449 (2)0.8865 (2)0.7307 (3)0.0405 (7)
N30.46707 (19)0.96654 (19)0.7249 (3)0.0386 (7)
N40.46601 (18)0.96287 (19)0.9408 (3)0.0384 (7)
O10.0732 (17)0.00000.83330.290 (15)
O20.2246 (11)0.2246 (11)1.00000.332 (17)
H2A0.24700.25050.93730.398*
P10.55322 (12)1.00000.33330.0683 (6)
P20.7837 (3)0.9967 (3)0.8965 (6)0.122 (2)0.50
Pd10.500203 (16)0.921712 (16)0.83157 (2)0.03555 (10)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.058 (3)0.064 (3)0.040 (2)0.040 (2)0.004 (2)0.003 (2)
C20.067 (3)0.078 (4)0.046 (3)0.047 (3)0.000 (2)0.009 (3)
C30.069 (3)0.071 (4)0.056 (3)0.047 (3)0.001 (3)0.016 (3)
C40.129 (7)0.135 (7)0.072 (4)0.105 (6)0.011 (5)0.035 (5)
C50.066 (3)0.063 (3)0.066 (3)0.049 (3)0.003 (3)0.008 (3)
C60.042 (2)0.041 (2)0.052 (3)0.0235 (17)0.0037 (19)0.0088 (19)
C70.043 (2)0.042 (2)0.047 (2)0.0253 (17)−0.0012 (19)−0.0018 (18)
C80.055 (3)0.057 (3)0.058 (3)0.038 (2)0.000 (2)−0.005 (2)
C90.056 (3)0.068 (3)0.060 (3)0.038 (3)0.000 (2)−0.013 (2)
C100.104 (6)0.130 (7)0.071 (4)0.088 (6)−0.001 (4)−0.027 (4)
C110.061 (3)0.079 (4)0.048 (3)0.043 (3)0.003 (2)−0.006 (3)
C120.060 (3)0.065 (3)0.042 (2)0.043 (3)0.001 (2)0.001 (2)
C130.0375 (19)0.049 (2)0.042 (2)0.0227 (18)−0.0035 (17)−0.0047 (18)
C140.045 (2)0.043 (2)0.053 (3)0.0231 (18)−0.009 (2)−0.0076 (19)
C150.069 (3)0.066 (3)0.061 (3)0.035 (3)−0.011 (3)−0.020 (3)
C160.103 (5)0.066 (4)0.093 (5)0.050 (4)−0.031 (5)−0.034 (4)
C170.086 (5)0.048 (3)0.125 (7)0.029 (3)−0.038 (5)−0.016 (4)
C180.062 (4)0.050 (3)0.130 (7)0.017 (3)−0.003 (4)0.006 (4)
C190.058 (3)0.051 (3)0.070 (3)0.023 (2)0.002 (3)0.001 (3)
C200.0340 (19)0.044 (2)0.045 (2)0.0209 (17)0.0018 (17)0.0033 (18)
C210.0374 (19)0.048 (2)0.056 (3)0.0251 (19)0.0064 (18)0.008 (2)
C220.054 (3)0.051 (3)0.067 (3)0.024 (2)0.006 (3)0.000 (2)
C230.060 (3)0.046 (3)0.102 (5)0.022 (2)0.007 (3)−0.002 (3)
C240.054 (3)0.051 (3)0.135 (7)0.022 (3)0.015 (4)0.024 (4)
C250.059 (3)0.073 (4)0.083 (5)0.031 (3)0.018 (3)0.039 (4)
C260.051 (2)0.058 (3)0.061 (3)0.023 (2)0.006 (2)0.017 (3)
C270.0407 (19)0.049 (2)0.041 (2)0.0238 (18)−0.0036 (17)−0.0006 (19)
C280.050 (2)0.058 (3)0.044 (3)0.022 (2)−0.007 (2)0.003 (2)
C290.048 (2)0.0312 (18)0.065 (3)0.0159 (17)−0.018 (2)−0.0006 (19)
C300.060 (3)0.062 (3)0.080 (4)0.037 (3)−0.005 (3)0.000 (3)
C310.064 (4)0.087 (5)0.141 (8)0.040 (4)0.008 (4)−0.011 (5)
C320.080 (5)0.103 (7)0.196 (12)0.068 (5)−0.033 (7)−0.033 (8)
C330.095 (6)0.083 (5)0.173 (10)0.064 (5)−0.070 (7)−0.025 (6)
C340.078 (4)0.046 (3)0.098 (5)0.031 (3)−0.036 (4)0.002 (3)
C350.28 (3)0.27 (4)0.29 (3)0.13 (3)0.15 (3)0.00 (3)
C360.27 (3)0.28 (3)0.33 (3)0.20 (3)−0.01 (3)−0.09 (3)
F10.160 (5)0.157 (5)0.047 (2)0.077 (4)−0.004 (3)0.002 (3)
F20.282 (12)0.118 (5)0.138 (6)0.087 (6)0.020 (6)0.015 (5)
F30.197 (9)0.37 (3)0.149 (10)0.186 (14)0.000 (6)0.000 (12)
F40.188 (8)0.30 (2)0.200 (12)0.152 (11)0.013 (7)0.026 (13)
F50.050 (4)0.068 (5)0.160 (10)0.016 (4)0.000 (5)0.007 (5)
F60.110 (5)0.099 (6)0.309 (16)0.049 (3)0.009 (4)0.018 (8)
F70.150 (8)0.208 (11)0.42 (2)0.066 (9)−0.013 (11)0.086 (12)
F80.088 (7)0.095 (8)0.291 (19)0.045 (6)0.021 (9)0.024 (10)
F90.097 (8)0.120 (10)0.28 (2)0.040 (8)0.038 (11)0.061 (12)
N10.0424 (18)0.0435 (18)0.0425 (19)0.0258 (15)0.0024 (16)0.0035 (16)
N20.0427 (18)0.0451 (18)0.0409 (19)0.0273 (15)0.0031 (15)0.0001 (16)
N30.0353 (16)0.0387 (17)0.0426 (19)0.0192 (14)−0.0027 (14)−0.0017 (15)
N40.0343 (16)0.0369 (16)0.046 (2)0.0195 (13)0.0048 (15)0.0013 (15)
O10.29 (3)0.30 (4)0.28 (3)0.15 (2)0.025 (15)0.05 (3)
O20.278 (18)0.278 (18)0.29 (3)0.03 (3)0.056 (16)−0.056 (16)
P10.0776 (11)0.0938 (17)0.0389 (10)0.0469 (8)0.0025 (5)0.0049 (10)
P20.061 (2)0.078 (3)0.219 (7)0.029 (2)0.013 (3)0.010 (4)
Pd10.03531 (15)0.03791 (16)0.03836 (16)0.02200 (12)0.00096 (12)0.00067 (12)
Geometric parameters (Å, °) top
C1—N11.343 (6)C24—H240.9300
C1—C21.378 (7)C25—C261.390 (9)
C1—H10.9300C25—H250.9300
C2—C31.375 (8)C26—H260.9300
C2—H20.9300C27—C20i1.409 (6)
C3—C51.370 (8)C27—C281.497 (6)
C3—C41.506 (7)C28—C291.499 (8)
C4—H4A0.9600C28—H28A0.9700
C4—H4B0.9600C28—H28B0.9700
C4—H4C0.9600C29—C301.375 (9)
C5—C61.388 (6)C29—C341.389 (7)
C5—H50.9300C30—C311.387 (9)
C6—N11.356 (6)C30—H300.9300
C6—C71.464 (7)C31—C321.373 (14)
C7—N21.355 (5)C31—H310.9300
C7—C81.387 (6)C32—C331.382 (16)
C8—C91.375 (8)C32—H320.9300
C8—H80.9300C33—C341.382 (13)
C9—C111.394 (8)C33—H330.9300
C9—C101.495 (8)C34—H340.9300
C10—H10A0.9600C35—O11.47 (4)
C10—H10B0.9600C35—C361.55 (4)
C10—H10C0.9600C35—H35A0.9700
C11—C121.384 (7)C35—H35B0.9700
C11—H110.9300C36—H36A0.9600
C12—N21.321 (6)C36—H36B0.9600
C12—H120.9300C36—H36C0.9600
C13—N31.349 (6)P1—F31.462 (15)
C13—C271.388 (7)P1—F41.489 (15)
C13—C141.480 (6)P1—F21.542 (8)
C14—C191.385 (8)P1—F2ii1.542 (8)
C14—C151.397 (8)P1—F1ii1.577 (4)
C15—C161.398 (10)P1—F11.577 (4)
C15—H150.9300P2—F5i1.425 (13)
C16—C171.362 (12)P2—F51.436 (12)
C16—H160.9300P2—F71.458 (13)
C17—C181.372 (12)P2—F91.49 (2)
C17—H170.9300P2—F81.582 (13)
C18—C191.389 (9)P2—P2i1.634 (15)
C18—H180.9300P2—F61.744 (11)
C19—H190.9300F5—P2i1.425 (12)
C20—N41.352 (6)F6—P2i1.744 (11)
C20—C27i1.409 (6)N1—Pd12.002 (3)
C20—C211.484 (6)N2—Pd12.010 (3)
C21—C221.392 (8)N3—N4i1.352 (5)
C21—C261.403 (7)N3—Pd12.033 (3)
C22—C231.392 (8)N4—N3i1.352 (5)
C22—H220.9300N4—Pd12.017 (3)
C23—C241.356 (11)O1—C35iii1.47 (4)
C23—H230.9300O2—H2A0.9713
C24—C251.348 (12)Pd1—Pd1i2.9989 (6)
N1—C1—C2121.9 (4)C30—C29—C34116.9 (6)
N1—C1—H1119.0C30—C29—C28123.3 (5)
C2—C1—H1119.0C34—C29—C28119.6 (6)
C3—C2—C1120.2 (5)C29—C30—C31122.0 (7)
C3—C2—H2119.9C29—C30—H30119.0
C1—C2—H2119.9C31—C30—H30119.0
C5—C3—C2117.3 (5)C32—C31—C30120.0 (10)
C5—C3—C4121.8 (5)C32—C31—H31120.0
C2—C3—C4120.9 (6)C30—C31—H31120.0
C3—C4—H4A109.5C31—C32—C33119.3 (8)
C3—C4—H4B109.5C31—C32—H32120.4
H4A—C4—H4B109.5C33—C32—H32120.4
C3—C4—H4C109.5C34—C33—C32119.8 (7)
H4A—C4—H4C109.5C34—C33—H33120.1
H4B—C4—H4C109.5C32—C33—H33120.1
C3—C5—C6121.6 (5)C33—C34—C29121.9 (8)
C3—C5—H5119.2C33—C34—H34119.0
C6—C5—H5119.2C29—C34—H34119.0
N1—C6—C5119.8 (5)O1—C35—C36119 (4)
N1—C6—C7114.6 (4)O1—C35—H35A107.7
C5—C6—C7125.5 (4)C36—C35—H35A107.7
N2—C7—C8121.0 (4)O1—C35—H35B107.7
N2—C7—C6115.0 (4)C36—C35—H35B107.7
C8—C7—C6124.0 (4)H35A—C35—H35B107.1
C9—C8—C7120.7 (5)C35—C36—H36A109.5
C9—C8—H8119.7C35—C36—H36B109.5
C7—C8—H8119.7H36A—C36—H36B109.5
C8—C9—C11117.2 (5)C35—C36—H36C109.5
C8—C9—C10120.8 (6)H36A—C36—H36C109.5
C11—C9—C10121.9 (6)H36B—C36—H36C109.5
C9—C10—H10A109.5F3—P1—F4180.000 (4)
C9—C10—H10B109.5F3—P1—F295.9 (5)
H10A—C10—H10B109.5F4—P1—F284.1 (5)
C9—C10—H10C109.5F3—P1—F2ii95.9 (5)
H10A—C10—H10C109.5F4—P1—F2ii84.1 (5)
H10B—C10—H10C109.5F2—P1—F2ii168.1 (10)
C12—C11—C9119.6 (5)F3—P1—F1ii88.5 (3)
C12—C11—H11120.2F4—P1—F1ii91.5 (3)
C9—C11—H11120.2F2—P1—F1ii89.5 (4)
N2—C12—C11122.6 (5)F2ii—P1—F1ii90.8 (4)
N2—C12—H12118.7F3—P1—F188.5 (3)
C11—C12—H12118.7F4—P1—F191.5 (3)
N3—C13—C27109.4 (4)F2—P1—F190.8 (4)
N3—C13—C14122.2 (4)F2ii—P1—F189.5 (4)
C27—C13—C14128.4 (4)F1ii—P1—F1177.0 (6)
C19—C14—C15119.2 (5)F5i—P2—F5105.5 (7)
C19—C14—C13120.1 (5)F5i—P2—F776.7 (8)
C15—C14—C13120.6 (5)F5—P2—F7177.0 (10)
C14—C15—C16119.2 (7)F5i—P2—F9174.8 (8)
C14—C15—H15120.4F5—P2—F975.4 (8)
C16—C15—H15120.4F7—P2—F9102.3 (11)
C17—C16—C15120.8 (7)F5i—P2—F884.6 (8)
C17—C16—H16119.6F5—P2—F884.6 (7)
C15—C16—H16119.6F7—P2—F893.6 (8)
C16—C17—C18120.2 (6)F9—P2—F890.4 (9)
C16—C17—H17119.9F5i—P2—P2i55.5 (6)
C18—C17—H17119.9F5—P2—P2i54.8 (6)
C17—C18—C19120.2 (7)F7—P2—P2i128.0 (10)
C17—C18—H18119.9F9—P2—P2i127.2 (8)
C19—C18—H18119.9F8—P2—P2i100.4 (7)
C14—C19—C18120.3 (6)F5i—P2—F685.0 (5)
C14—C19—H19119.9F5—P2—F684.7 (5)
C18—C19—H19119.9F7—P2—F697.7 (7)
N4—C20—C27i108.2 (4)F9—P2—F6100.2 (6)
N4—C20—C21121.0 (4)F8—P2—F6162.5 (9)
C27i—C20—C21130.7 (4)P2i—P2—F662.1 (3)
C22—C21—C26117.9 (5)P2i—F5—P269.7 (7)
C22—C21—C20120.9 (5)P2i—F6—P255.9 (6)
C26—C21—C20121.1 (5)C1—N1—C6119.0 (4)
C21—C22—C23119.8 (6)C1—N1—Pd1125.9 (3)
C21—C22—H22120.1C6—N1—Pd1115.0 (3)
C23—C22—H22120.1C12—N2—C7118.8 (4)
C24—C23—C22121.0 (7)C12—N2—Pd1126.4 (3)
C24—C23—H23119.5C7—N2—Pd1114.5 (3)
C22—C23—H23119.5C13—N3—N4i108.4 (3)
C25—C24—C23120.4 (6)C13—N3—Pd1137.3 (3)
C25—C24—H24119.8N4i—N3—Pd1114.1 (3)
C23—C24—H24119.8N3i—N4—C20109.0 (3)
C24—C25—C26120.6 (6)N3i—N4—Pd1113.9 (3)
C24—C25—H25119.7C20—N4—Pd1137.0 (3)
C26—C25—H25119.7C35—O1—C35iii113 (4)
C25—C26—C21120.2 (6)H2A—O2—H2Aiv113.3 (1)
C25—C26—H26119.9N1—Pd1—N280.8 (1)
C21—C26—H26119.9N1—Pd1—N495.2 (1)
C13—C27—C20i105.0 (4)N2—Pd1—N4173.5 (2)
C13—C27—C28125.7 (4)N1—Pd1—N3174.7 (2)
C20i—C27—C28129.0 (4)N2—Pd1—N396.8 (1)
C27—C28—C29115.5 (4)N4—Pd1—N386.8 (1)
C27—C28—H28A108.4N1—Pd1—Pd1i110.59 (12)
C29—C28—H28A108.4N2—Pd1—Pd1i110.18 (11)
C27—C28—H28B108.4N4—Pd1—Pd1i66.34 (11)
C29—C28—H28B108.4N3—Pd1—Pd1i65.68 (11)
H28A—C28—H28B107.5
N1—C1—C2—C3−1.2 (10)C30—C29—C34—C33−0.2 (9)
C1—C2—C3—C52.4 (10)C28—C29—C34—C33176.0 (6)
C1—C2—C3—C4−177.7 (7)F5i—P2—F5—P2i−23.9 (8)
C2—C3—C5—C6−0.8 (9)F9—P2—F5—P2i161.4 (7)
C4—C3—C5—C6179.3 (7)F8—P2—F5—P2i−106.8 (8)
C3—C5—C6—N1−2.0 (9)F6—P2—F5—P2i59.4 (4)
C3—C5—C6—C7174.2 (6)F5i—P2—F6—P2i53.3 (5)
N1—C6—C7—N2−0.3 (6)F5—P2—F6—P2i−52.8 (5)
C5—C6—C7—N2−176.6 (5)F7—P2—F6—P2i129.1 (9)
N1—C6—C7—C8176.2 (5)F9—P2—F6—P2i−126.9 (8)
C5—C6—C7—C8−0.2 (8)F8—P2—F6—P2i−0.5 (18)
N2—C7—C8—C91.9 (8)C2—C1—N1—C6−1.7 (8)
C6—C7—C8—C9−174.3 (5)C2—C1—N1—Pd1−176.6 (4)
C7—C8—C9—C110.2 (8)C5—C6—N1—C13.3 (7)
C7—C8—C9—C10177.6 (6)C7—C6—N1—C1−173.3 (4)
C8—C9—C11—C12−1.0 (9)C5—C6—N1—Pd1178.7 (4)
C10—C9—C11—C12−178.4 (6)C7—C6—N1—Pd12.1 (5)
C9—C11—C12—N2−0.3 (9)C11—C12—N2—C72.4 (8)
N3—C13—C14—C1968.4 (6)C11—C12—N2—Pd1176.8 (4)
C27—C13—C14—C19−111.3 (6)C8—C7—N2—C12−3.2 (7)
N3—C13—C14—C15−114.1 (6)C6—C7—N2—C12173.4 (4)
C27—C13—C14—C1566.2 (7)C8—C7—N2—Pd1−178.3 (4)
C19—C14—C15—C16−1.9 (9)C6—C7—N2—Pd1−1.7 (5)
C13—C14—C15—C16−179.4 (6)C27—C13—N3—N4i0.6 (5)
C14—C15—C16—C172.1 (11)C14—C13—N3—N4i−179.1 (4)
C15—C16—C17—C18−0.6 (12)C27—C13—N3—Pd1−173.7 (3)
C16—C17—C18—C19−1.0 (12)C14—C13—N3—Pd16.6 (7)
C15—C14—C19—C180.3 (9)C27i—C20—N4—N3i0.5 (5)
C13—C14—C19—C18177.9 (6)C21—C20—N4—N3i−177.2 (4)
C17—C18—C19—C141.2 (11)C27i—C20—N4—Pd1175.6 (3)
N4—C20—C21—C22−35.4 (7)C21—C20—N4—Pd1−2.0 (7)
C27i—C20—C21—C22147.6 (5)C36—C35—O1—C35iii147 (3)
N4—C20—C21—C26142.2 (5)C1—N1—Pd1—N2172.7 (5)
C27i—C20—C21—C26−34.9 (7)C6—N1—Pd1—N2−2.4 (3)
C26—C21—C22—C230.7 (8)C1—N1—Pd1—N4−2.1 (4)
C20—C21—C22—C23178.3 (5)C6—N1—Pd1—N4−177.2 (3)
C21—C22—C23—C240.7 (9)C1—N1—Pd1—Pd1i64.5 (4)
C22—C23—C24—C25−1.7 (10)C6—N1—Pd1—Pd1i−110.6 (3)
C23—C24—C25—C261.3 (10)C12—N2—Pd1—N1−172.4 (5)
C24—C25—C26—C210.1 (9)C7—N2—Pd1—N12.2 (3)
C22—C21—C26—C25−1.1 (8)C12—N2—Pd1—N32.8 (5)
C20—C21—C26—C25−178.7 (5)C7—N2—Pd1—N3177.4 (3)
N3—C13—C27—C20i−0.3 (5)C12—N2—Pd1—Pd1i−63.7 (4)
C14—C13—C27—C20i179.4 (5)C7—N2—Pd1—Pd1i110.9 (3)
N3—C13—C27—C28−173.6 (4)N3i—N4—Pd1—N1111.1 (3)
C14—C13—C27—C286.1 (8)C20—N4—Pd1—N1−63.9 (5)
C13—C27—C28—C2990.3 (6)N3i—N4—Pd1—N3−63.9 (3)
C20i—C27—C28—C29−81.4 (6)C20—N4—Pd1—N3121.1 (4)
C27—C28—C29—C30−27.2 (7)N3i—N4—Pd1—Pd1i0.9 (2)
C27—C28—C29—C34156.9 (5)C20—N4—Pd1—Pd1i−174.1 (5)
C34—C29—C30—C311.1 (9)C13—N3—Pd1—N265.8 (5)
C28—C29—C30—C31−175.0 (6)N4i—N3—Pd1—N2−108.3 (3)
C29—C30—C31—C32−2.5 (12)C13—N3—Pd1—N4−119.6 (5)
C30—C31—C32—C333.0 (14)N4i—N3—Pd1—N466.3 (3)
C31—C32—C33—C34−2.2 (14)C13—N3—Pd1—Pd1i174.9 (5)
C32—C33—C34—C290.8 (12)N4i—N3—Pd1—Pd1i0.9 (2)
Symmetry codes: (i) x−y+1, −y+2, −z+5/3; (ii) x−y+1, −y+2, −z+2/3; (iii) x−y, −y, −z+5/3; (iv) y, x, −z+2.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C1—H1···F1i0.932.503.228 (8)135
C12—H12···F10.932.443.200 (8)139
C36—H36A···O20.962.453.25 (3)141
C36—H36B···F7v0.962.313.04 (4)133
C36—H36C···F9v0.962.192.95 (3)135
Symmetry codes: (i) x−y+1, −y+2, −z+5/3; (v) −x+y, −x+1, z−1/3.
Table 1
Selected geometric parameters (Å, °) top
N1—Pd12.002 (3)N3—Pd12.033 (3)
N2—Pd12.010 (3)N4—Pd12.017 (3)
N3—N4i1.352 (5)Pd1—Pd1i2.9989 (6)
N4i—N3—Pd1114.1 (3)N1—Pd1—N280.8 (1)
N3i—N4—Pd1113.9 (3)N4—Pd1—N386.8 (1)
Symmetry codes: (i) x−y+1, −y+2, −z+5/3.
Table 2
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C1—H1···F1i0.932.503.228 (8)135
C12—H12···F10.932.443.200 (8)139
C36—H36A···O20.962.453.25 (3)141
C36—H36B···F7ii0.962.313.04 (4)133
C36—H36C···F9ii0.962.192.95 (3)135
Symmetry codes: (i) x−y+1, −y+2, −z+5/3; (ii) −x+y, −x+1, z−1/3.
Acknowledgements top

This work was supported by Renmin University of China.

references
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