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Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Volume 71| Part 8| August 2015| Pages 919-922
https://doi.org/10.1107/S2056989015013055

Crystal structures of di­iodido­bis­­[(1S,5S)-4-mesityl-1,2,8,8-tetra­methyl-2,4-di­aza­bi­cyclo­[3.2.1]octan-3-yl­­idene-κC3]palladium(IV) and di­chlorido­[(1S,5S)-4-mesityl-1,2,8,8-tetra­methyl-2,4-di­aza­bi­cyclo[3.2.1]octan-3-yl­­idene-κC3](tri­phenyl­phosphane-κP)palladium(IV)

Eduard Rais,a Ulrich Flörkea* and René Wilhelma*

aDepartment Chemie, Universität Paderborn, Warburgerstrasse 100, 33098 Paderborn, Germany
*Correspondence e-mail: ulrich.floerke@upb.de, rene.wilhelm@upb.de

Edited by M. Weil, Vienna University of Technology, Austria (Received 23 June 2015; accepted 7 July 2015; online 11 July 2015)

The mol­ecular structures of the chiral title compounds, [Pd(C19H28N2)2I2], (I), and [Pd(C19H28N2)Cl2(C18H15P)], (II), show a distorted square-planar coordination around the PdII atoms with two halogenide (Hal) ligands each and two N-heterocyclic carbene (NHC) ligands in (I) or one NHC and one tri­phenyl­phosphane ligand in (II). The deviations of the PdII atoms from the L2Hal2 best plane (L = NHC or tri­phenyl­phosphane ligand) are 0.206 (1) Å for (I) and 0.052 (1) Å for (II). The crystal packings exhibit inter­molecular C—H⋯Hal hydrogen bonds.

CCDC references: 1411191; 1411190

Similar articles

1. Chemical context

Six-membered N-heterocyclic carbene (NHC) ligands differ from the extensively reported five-membered analogues in several aspects. As a result of the increased N—C—N angle, the N-substituents exhibit a larger proximity to the metal atom, which can be an advantage for the transfer of chirality from the ligand to the product during a catalytic reaction or for the reductive elimination during the catalytic cycle (Cavallo et al., 2005[Cavallo, L., Correa, A., Costabile, C. & Jacobsen, H. (2005). J. Organomet. Chem. 690, 5407-5413.]). The increased σ-donor ability of six-membered NHC ligands in comparison with their five-membered analogues can be helpful for catalytic applications or for the discovery of new catalytic reactions (Dröge & Glorius, 2010[Dröge, T. & Glorius, F. (2010). Angew. Chem. Int. Ed. 49, 6940-6952.]). Furthermore, NHC–metal complexes are less sensitive to dissociation, oxygen or elevated temperature compared to similar phosphane–metal complexes (Nolan, 2006[Nolan, S. (2006). In N-Heterocyclic Carbenes in Synthesis. Weinheim: Wiley-VCH.]). Notably, (NHC)2Pd complexes are known for their synthetic and catalytic applications (Schneider et al., 2006[Schneider, S. K., Herrmann, W. A. & Herdtweck, E. (2006). J. Mol. Catal. A Chem. 245, 248-254.]; Türkmen & Cetinkaya, 2006[Türkmen, H. & Çetinkaya, B. (2006). J. Organomet. Chem. 691, 3749-3759.]). Structures of related bis­carbene complexes are known from Dunsford & Cavell (2014[Dunsford, J. J. & Cavell, K. J. (2014). Organometallics, 33, 2902-2905.]), Mayr et al. (2004[Mayr, M., Wurst, K., Ongania, K.-H. & Buchmeiser, M. R. (2004). Chem. Eur. J. 10, 1256-1266.]) and Poulten et al. (2014[Poulten, R. C., López, I., Llobet, A., Mahon, M. F. & Whittlesey, M. K. (2014). Inorg. Chem. 53, 7160-7169.]).

We report herein on the syntheses and crystal structures of two N-heterocyclic-carbene (NHC)–Pd complexes {the chiral carbene being [(1S,5S)-4-mesityl-1,2,8,8-tetra­methyl-2,4-di­aza­bicyclo­[3.2.1]octan-3-yl­idene]} with two NHC-ligands in Pd(C19H28N2)I2, (I)[link], and one NHC ligand in Pd(C19H28N2)(C18H15P)Cl2, (II)[link].

2. Structural commentary

The mol­ecular structures of the title compounds, (I)[link] and (II)[link], are shown in Figs. 1[link] and 2[link], respectively. The structure of (I)[link] shows a distorted square-planar coordination environment around the PdII atom by the two N-heterocyclic carbene (NHC) and two iodido ligands. The deviation of the PdII atom from the I2C2 best plane is 0.206 (1) Å. The iodide ligands are trans-arranged and enclose an I—Pd—I angle of 163.275 (13) Å, whereas the C—Pd—C angle measures 178.32 (12)°. Pd—X bond lengths for X = C1, C20, I1, I2 are 2.070 (3), 2.079 (3), 2.6334 (4) and 2.6360 (4) Å, respectively. Other selected X—Pd—X angles are listed in Table 1[link]. The mesityl ring planes make a dihedral angle of 32.7 (2)°.

[Scheme 1]

Table 1
Selected bond angles (°) for (I)[link]

C1—Pd1—I1 91.63 (9) C1—Pd1—I2 89.05 (9)
C20—Pd1—I1 87.63 (8) C20—Pd1—I2 91.23 (9)
[Figure 1]
Figure 1
The mol­ecular structure of (I)[link], with anisotropic displacement ellipsoids drawn at the 50% probability level.
[Figure 2]
Figure 2
The mol­ecular structure of (II)[link], with anisotropic displacement ellipsoids drawn at the 50% probability level.

The structure of (II)[link] also shows the PdII atom to be in a slightly distorted square-planar coordination by one NHC, one phosphine and two chlorido ligands. The deviation of PdII from the PCl2C best plane is only 0.052 (1) Å. The Cl ligands are also trans-arranged and enclose a Cl—Pd—Cl angle of 173.53 (9)° whereas the C—Pd—P angle measures 177.6 (2)°. Pd—X bond lengths for X = C1, P1, Cl1, Cl2 are 2.048 (7), 2.355 (2), 2.309 (2) and 2.311 (2) Å, respectively. Other selected X—Pd—X angles are listed in Table 2[link]. The more pronounced deviation from planarity of the iodido complex is caused by the sterically more demanding iodido and the requirements of the mesityl-NHC ligands, respectively. In general, the NHC ligands in the structures of (I)[link] and (II)[link] exhibit no unexpected geometries.

Table 2
Selected bond angles (°) for (II)[link]

C1—Pd1—Cl1 88.7 (2) Cl1—Pd1—P1 93.58 (7)
C1—Pd1—Cl2 88.6 (2) Cl2—Pd1—P1 89.18 (7)

3. Supra­molecular features

The crystal packing of (I)[link] shows weak inter­molecular C5—H5A⋯I1 hydrogen bonds that link mol­ecules into zigzag chains extending parallel to [100] (Table 3[link] and Fig. 3[link]).

Table 3
Hydrogen-bond geometry (Å, °) for (I)[link]

D—H⋯A D—H H⋯A D⋯A D—H⋯A
C5—H5A⋯I1i 0.99 3.22 4.131 (5) 154
Symmetry code: (i) [x+{\script{1\over 2}}, -y+{\script{3\over 2}}, -z].
[Figure 3]
Figure 3
The crystal packing of (I)[link], viewed approximately along [010], with inter­molecular hydrogen bonds shown as dashed lines. H atoms not involved in the hydrogen bonding have been omitted.

In the crystal packing of (II)[link], inter­molecular C15—H15A⋯Cl2 hydrogen bonds link mol­ecules into endless rows running parallel to [010]. Additionally, an intra­molecular C42—H42A⋯Cl2 bond is present (Table 4[link] and Fig. 4[link]).

Table 4
Hydrogen-bond geometry (Å, °) for (II)[link]

D—H⋯A D—H H⋯A D⋯A D—H⋯A
C42—H42A⋯Cl2 0.95 2.62 3.447 (8) 146
C15—H15A⋯Cl2i 0.95 2.71 3.535 (8) 146
Symmetry code: (i) x, y+1, z.
[Figure 4]
Figure 4
The crystal packing of (II)[link], viewed along [100], with inter­molecular hydrogen bonds shown as dashed lines. H atoms not involved in the hydrogen bonding have been omitted.

4. Synthesis and crystallization

The synthesis of the carbene precursor has been described by Koppenwallner et al. (2015[Koppenwallner, M., Rais, E., Uzarewicz-Baig, M., Tabassum, S., Gilani, M. A. & Wilhelm, R. (2015). Synthesis, 47, 789-800.]). The title compounds (I)[link] and (II)[link] were prepared in similar ways using a stirred solution of (1S,5S)-4-mesityl-1,2,8,8-tetra­methyl-2,4-di­aza­bicyclo-[3.2.1]-oct-2-en-2-ium iodide (0.026 g, 0.063 mmol, 1 eq) and THF (3 ml) for (I)[link] or 0.041 g, 0.099 mmol, 1 eq and 4 ml for (II)[link] in a Schlenk tube. Potassium bis­(tri­methyl­sil­yl)amide dissolved in toluene (139 µl, 0.069 mmol, 1.1 eq, c = 0.5 mol/l) for (I)[link] or 219 µl, 0.109 mmol, 1.1 eq, c = 0.5 mol/l for (II)[link] was added and the mixture stirred for 1 h at room temperature under nitro­gen. After the remaining solid had been removed with a syringe filter, PdI2(PPh3)2 (0.050 g, 0.063 mmol, 1 eq) for (I)[link] or PdCl2(PPh3)2 (0.070 g, 0.099 mmol, 1 eq) for (II)[link] was added to the solution. The mixtures were stirred for 16–20 h under nitro­gen. Subsequently, the solvents were removed under vacuum and the residues washed three times with pentane (3 or 6 ml), dissolved in toluene and then carefully overlayed with pentane. Yellow crystals of Pd(NHC)2I2 (I)[link] and colourless crystals of Pd(NHC)(PPh3)Cl2 (II)[link] suitable for X-ray diffraction were obtained after several days.

5. Refinement details

Crystal data, data collection and structure refinement details are summarized in Table 5[link]. Hydrogen atoms were clearly located from difference Fourier maps and then refined at idealized positions riding on the carbon atoms with Uiso(H) = 1.2U(Ceq) or 1.5U(Ceq) (–CH3) and C—H 0.95–1.00 Å. All CH3 hydrogen atoms were allowed to rotate but not to tip.

Table 5
Experimental details

  (I) (II)
Crystal data
Chemical formula [Pd(C19H28N2)2I2] [Pd(C19H28N2)Cl2(C18H15P)]
Mr 929.07 724.00
Crystal system, space group Orthorhombic, P212121 Monoclinic, P21
Temperature (K) 130 130
a, b, c (Å) 12.2480 (13), 13.3786 (14), 23.465 (2) 10.987 (3), 9.568 (2), 17.211 (4)
α, β, γ (°) 90, 90, 90 90, 107.478 (4), 90
V (Å3) 3845.0 (7) 1725.7 (7)
Z 4 2
Radiation type Mo Kα Mo Kα
μ (mm−1) 2.12 0.77
Crystal size (mm) 0.33 × 0.20 × 0.19 0.48 × 0.20 × 0.01
 
Data collection
Diffractometer Bruker SMART APEX Bruker SMART APEX
Absorption correction Multi-scan (SADABS; Bruker, 2002[Bruker (2002). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]) Multi-scan (SADABS; Bruker, 2002[Bruker (2002). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.])
Tmin, Tmax 0.882, 0.985 0.710, 0.992
No. of measured, independent and observed [I > 2σ(I)] reflections 36757, 9177, 8551 13973, 8099, 6415
Rint 0.047 0.089
(sin θ/λ)max (Å−1) 0.658 0.658
 
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.029, 0.061, 1.01 0.053, 0.113, 0.92
No. of reflections 9177 8099
No. of parameters 414 393
No. of restraints 0 1
H-atom treatment H-atom parameters constrained H-atom parameters constrained
Δρmax, Δρmin (e Å−3) 0.94, −0.33 1.00, −1.60
Absolute structure Flack x determined using 3583 quotients [(I+)−(I−)]/[(I+)+(I−)] (Parsons & Flack, 2004[Parsons, S. & Flack, H. (2004). Acta Cryst. A60, s61.]) Flack x determined using 2367 quotients [(I+)−(I−)]/[(I+)+(I−)] (Parsons & Flack, 2004[Parsons, S. & Flack, H. (2004). Acta Cryst. A60, s61.])
Absolute structure parameter −0.012 (10) −0.02 (4)
Computer programs: SMART and SAINT (Bruker, 2002[Bruker (2002). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]), SHELXL2013 (Sheldrick, 2015[Sheldrick, G. M. (2015). Acta Cryst. C71, 3-8.]), SHELXTL and SHELXL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]) and local programs.

Supporting information

CCDC references: 1411191; 1411190

Crystal structure: contains datablocks I, II, global. DOI: https://doi.org/10.1107/S2056989015013055/wm5179sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989015013055/wm5179Isup2.hkl

Structure factors: contains datablock II. DOI: https://doi.org/10.1107/S2056989015013055/wm5179IIsup3.hkl

checkCIF report


Computing details top

For both compounds, data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT (Bruker, 2002); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2015); molecular graphics: SHELXTL (Sheldrick, 2008). Software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and local programs for (I); SHELXL (Sheldrick, 2008) and local programs for (II).

(I) Diiodidobis[(1S,5S)-4-mesityl-1,2,8,8-tetramethyl-2,4-diazabicyclo[3.2.1]octan-3-ylidene-κC3]palladium(IV) top
Crystal data top
[Pd(C19H28N2)2I2]Dx = 1.605 Mg m−3
Mr = 929.07Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, P212121Cell parameters from 9243 reflections
a = 12.2480 (13) Åθ = 2.2–25.0°
b = 13.3786 (14) ŵ = 2.12 mm−1
c = 23.465 (2) ÅT = 130 K
V = 3845.0 (7) Å3Prism, yellow
Z = 40.33 × 0.20 × 0.19 mm
F(000) = 1856
Data collection top
Bruker SMART APEX
diffractometer		9177 independent reflections
Radiation source: sealed tube8551 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.047
φ and ω scansθmax = 27.9°, θmin = 1.7°
Absorption correction: multi-scan
(SADABS; Bruker, 2002)		h = −16→15
Tmin = 0.882, Tmax = 0.985k = −17→17
36757 measured reflectionsl = −30→30
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.029H-atom parameters constrained
wR(F2) = 0.061 w = 1/[σ2(Fo2) + (0.0269P)2]
where P = (Fo2 + 2Fc2)/3
S = 1.01(Δ/σ)max = 0.002
9177 reflectionsΔρmax = 0.94 e Å−3
414 parametersΔρmin = −0.33 e Å−3
0 restraintsAbsolute structure: Flack x determined using 3583 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons & Flack, 2004)
Primary atom site location: structure-invariant direct methodsAbsolute structure parameter: −0.012 (10)
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
Pd10.30214 (2)0.548524 (17)0.173876 (11)0.01578 (6)
I10.15512 (2)0.628839 (18)0.105990 (10)0.02865 (6)
I20.44142 (2)0.517705 (19)0.257697 (10)0.02955 (6)
N10.4408 (3)0.7055 (2)0.11875 (13)0.0249 (7)
N20.5017 (2)0.54820 (19)0.09716 (11)0.0159 (5)
N30.1463 (2)0.5426 (2)0.27152 (11)0.0186 (6)
N40.1155 (2)0.4141 (2)0.21027 (12)0.0174 (6)
C10.4287 (3)0.6058 (2)0.12539 (14)0.0181 (7)
C20.5186 (3)0.7474 (3)0.07584 (16)0.0249 (8)
C30.6274 (3)0.6914 (3)0.08531 (15)0.0238 (8)
C40.5915 (3)0.5902 (2)0.06160 (15)0.0196 (7)
H4A0.65420.54270.05840.024*
C50.4820 (3)0.7145 (3)0.01587 (16)0.0253 (8)
H5A0.50030.7664−0.01260.030*
H5B0.40230.70270.01500.030*
C60.5446 (3)0.6166 (2)0.00311 (14)0.0217 (7)
H6A0.49480.5637−0.01090.026*
H6B0.60330.6275−0.02520.026*
C70.3834 (4)0.7738 (3)0.15652 (19)0.0381 (11)
H7A0.33860.73550.18340.057*
H7B0.33640.81800.13400.057*
H7C0.43650.81410.17770.057*
C80.5277 (4)0.8621 (3)0.0798 (2)0.0418 (11)
H8A0.45580.89210.07330.063*
H8B0.57900.88630.05090.063*
H8C0.55400.88080.11780.063*
C90.7216 (3)0.7333 (3)0.04938 (17)0.0318 (9)
H9A0.78820.69520.05720.048*
H9B0.73340.80370.05920.048*
H9C0.70320.72780.00890.048*
C100.6640 (4)0.6908 (3)0.14731 (16)0.0353 (10)
H10A0.73320.65440.15060.053*
H10B0.60840.65790.17070.053*
H10C0.67410.75970.16050.053*
C110.4947 (3)0.4403 (2)0.09457 (15)0.0200 (7)
C120.4196 (3)0.3932 (2)0.05859 (15)0.0211 (7)
C130.4284 (3)0.2896 (3)0.05110 (16)0.0278 (8)
H13A0.37840.25700.02640.033*
C140.5072 (4)0.2329 (3)0.07835 (19)0.0335 (10)
C150.5789 (4)0.2819 (3)0.11436 (18)0.0345 (10)
H15A0.63210.24370.13420.041*
C160.5761 (3)0.3846 (3)0.12272 (15)0.0258 (8)
C170.3302 (3)0.4468 (3)0.02708 (15)0.0255 (8)
H17A0.25930.42830.04340.038*
H17B0.33220.4279−0.01320.038*
H17C0.34070.51910.03060.038*
C180.5154 (4)0.1207 (3)0.0700 (2)0.0488 (13)
H18A0.45390.09760.04680.073*
H18B0.51340.08740.10720.073*
H18C0.58410.10470.05070.073*
C190.6615 (3)0.4310 (3)0.16036 (17)0.0330 (9)
H19A0.69370.37950.18480.049*
H19B0.62780.48280.18410.049*
H19C0.71860.46110.13670.049*
C200.1737 (3)0.4952 (2)0.22313 (14)0.0164 (7)
C210.0656 (3)0.4997 (2)0.31324 (14)0.0219 (7)
C22−0.0324 (3)0.4653 (3)0.27739 (15)0.0217 (7)
C230.0239 (3)0.3771 (2)0.24731 (15)0.0217 (7)
H23A−0.02940.33590.22520.026*
C240.0744 (3)0.3173 (3)0.29680 (16)0.0280 (9)
H24A0.13590.27530.28360.034*
H24B0.01930.27430.31560.034*
C250.1140 (3)0.4013 (3)0.33697 (15)0.0281 (9)
H25A0.19470.40440.33740.034*
H25B0.08790.38930.37630.034*
C260.1896 (3)0.6430 (3)0.28286 (17)0.0324 (9)
H26A0.23430.66480.25050.049*
H26B0.23460.64140.31740.049*
H26C0.12890.68980.28820.049*
C270.0374 (3)0.5723 (3)0.36052 (16)0.0305 (9)
H27A0.00710.63360.34400.046*
H27B0.10350.58850.38220.046*
H27C−0.01650.54180.38600.046*
C28−0.1281 (3)0.4260 (3)0.31389 (18)0.0323 (9)
H28A−0.16390.48210.33310.048*
H28B−0.10030.37900.34240.048*
H28C−0.18090.39180.28930.048*
C29−0.0772 (3)0.5471 (3)0.23804 (16)0.0298 (8)
H29A−0.01800.57340.21430.045*
H29B−0.10800.60130.26110.045*
H29C−0.13430.51890.21360.045*
C300.1413 (3)0.3465 (2)0.16380 (14)0.0206 (7)
C310.0680 (3)0.3424 (2)0.11749 (15)0.0233 (8)
C320.0868 (3)0.2706 (3)0.07487 (16)0.0277 (9)
H32A0.04000.26900.04260.033*
C330.1708 (3)0.2025 (3)0.07838 (15)0.0254 (8)
C340.2393 (3)0.2066 (2)0.12488 (15)0.0237 (8)
H34A0.29610.15870.12820.028*
C350.2278 (3)0.2796 (2)0.16770 (15)0.0205 (7)
C36−0.0318 (3)0.4082 (3)0.11195 (18)0.0336 (9)
H36A−0.05040.41600.07160.050*
H36B−0.01640.47390.12850.050*
H36C−0.09310.37730.13210.050*
C370.1862 (4)0.1246 (3)0.03244 (18)0.0391 (10)
H37A0.23630.15030.00340.059*
H37B0.11550.10940.01490.059*
H37C0.21670.06370.04930.059*
C380.3117 (3)0.2797 (3)0.21466 (16)0.0264 (8)
H38A0.29060.32820.24400.040*
H38B0.38310.29810.19890.040*
H38C0.31610.21290.23160.040*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Pd10.01775 (12)0.01382 (10)0.01575 (12)−0.00085 (10)0.00230 (10)0.00026 (10)
I10.02852 (13)0.03119 (12)0.02623 (13)0.00866 (10)0.00307 (11)0.00985 (10)
I20.02637 (12)0.03942 (13)0.02285 (12)−0.00250 (10)−0.00341 (10)0.00155 (10)
N10.0327 (17)0.0148 (13)0.0271 (17)−0.0048 (13)0.0138 (15)−0.0005 (12)
N20.0164 (13)0.0155 (12)0.0159 (14)−0.0031 (11)0.0017 (11)0.0017 (11)
N30.0188 (14)0.0161 (13)0.0210 (15)−0.0025 (12)0.0039 (12)−0.0026 (11)
N40.0202 (15)0.0166 (13)0.0154 (14)−0.0014 (11)0.0031 (12)−0.0006 (11)
C10.0198 (18)0.0160 (15)0.0185 (17)−0.0026 (13)−0.0001 (14)−0.0018 (13)
C20.030 (2)0.0177 (16)0.027 (2)−0.0072 (15)0.0128 (16)0.0010 (15)
C30.022 (2)0.0287 (18)0.0203 (18)−0.0123 (15)0.0009 (15)0.0006 (15)
C40.0160 (17)0.0190 (15)0.0239 (19)−0.0001 (13)0.0061 (14)0.0015 (14)
C50.025 (2)0.0240 (18)0.027 (2)0.0012 (15)−0.0006 (16)0.0084 (15)
C60.026 (2)0.0225 (16)0.0169 (17)−0.0031 (15)0.0004 (15)0.0008 (14)
C70.048 (3)0.0182 (17)0.048 (3)−0.0082 (17)0.025 (2)−0.0108 (17)
C80.056 (3)0.0200 (18)0.049 (3)−0.0101 (19)0.022 (2)−0.0015 (18)
C90.027 (2)0.041 (2)0.028 (2)−0.0195 (17)0.0021 (17)0.0031 (18)
C100.039 (2)0.045 (2)0.022 (2)−0.023 (2)−0.0064 (19)0.0019 (17)
C110.0235 (18)0.0167 (15)0.0199 (18)0.0043 (13)0.0082 (14)0.0002 (13)
C120.0208 (19)0.0214 (17)0.0210 (18)−0.0003 (14)0.0096 (15)−0.0014 (14)
C130.036 (2)0.0202 (17)0.027 (2)−0.0044 (16)0.0127 (18)−0.0043 (15)
C140.047 (3)0.0185 (18)0.035 (2)0.0064 (18)0.017 (2)0.0040 (16)
C150.039 (2)0.0271 (19)0.038 (2)0.0154 (18)0.008 (2)0.0077 (17)
C160.027 (2)0.0271 (18)0.0230 (19)0.0059 (16)0.0067 (15)0.0029 (15)
C170.026 (2)0.0270 (17)0.0238 (19)−0.0057 (16)−0.0012 (15)−0.0055 (15)
C180.077 (4)0.0167 (18)0.052 (3)0.014 (2)0.013 (3)0.0001 (19)
C190.028 (2)0.039 (2)0.032 (2)0.0083 (17)−0.0049 (18)0.0059 (17)
C200.0168 (17)0.0154 (14)0.0170 (16)0.0035 (13)−0.0013 (13)0.0043 (12)
C210.0234 (18)0.0223 (16)0.0200 (18)0.0034 (15)0.0071 (15)0.0047 (14)
C220.0189 (17)0.0215 (17)0.0246 (18)0.0021 (14)0.0073 (14)0.0036 (14)
C230.0230 (18)0.0177 (15)0.0245 (18)−0.0029 (14)0.0080 (15)−0.0016 (15)
C240.035 (2)0.0192 (16)0.030 (2)0.0017 (16)0.0156 (18)0.0035 (15)
C250.037 (2)0.0299 (18)0.0179 (19)0.0077 (16)0.0066 (16)0.0051 (15)
C260.036 (2)0.0238 (18)0.037 (2)−0.0051 (17)0.0133 (19)−0.0104 (16)
C270.037 (2)0.0278 (19)0.026 (2)0.0029 (17)0.0149 (18)−0.0014 (16)
C280.026 (2)0.032 (2)0.039 (2)−0.0007 (16)0.0145 (18)0.0040 (17)
C290.0241 (19)0.0317 (18)0.034 (2)0.0069 (16)0.0005 (17)0.0053 (18)
C300.0258 (19)0.0158 (15)0.0202 (18)−0.0061 (14)0.0043 (15)−0.0022 (13)
C310.0247 (19)0.0241 (17)0.0212 (18)−0.0071 (15)0.0027 (16)0.0010 (14)
C320.033 (2)0.0299 (19)0.0206 (19)−0.0148 (17)−0.0014 (16)−0.0024 (15)
C330.031 (2)0.0255 (17)0.0194 (18)−0.0140 (16)0.0087 (16)−0.0043 (14)
C340.027 (2)0.0179 (16)0.026 (2)−0.0053 (14)0.0080 (16)−0.0013 (14)
C350.0239 (19)0.0185 (15)0.0192 (18)−0.0076 (13)0.0061 (15)0.0003 (14)
C360.028 (2)0.040 (2)0.032 (2)−0.0013 (17)−0.0080 (18)−0.0014 (18)
C370.046 (3)0.037 (2)0.035 (2)−0.014 (2)0.004 (2)−0.0147 (19)
C380.032 (2)0.0250 (17)0.0223 (19)0.0077 (16)0.0029 (16)−0.0007 (15)
Geometric parameters (Å, º) top
Pd1—C12.070 (3)C17—H17B0.9800
Pd1—C202.079 (3)C17—H17C0.9800
Pd1—I12.6334 (4)C18—H18A0.9800
Pd1—I22.6360 (4)C18—H18B0.9800
N1—C11.351 (4)C18—H18C0.9800
N1—C71.454 (5)C19—H19A0.9800
N1—C21.496 (4)C19—H19B0.9800
N2—C11.354 (4)C19—H19C0.9800
N2—C111.448 (4)C21—C271.514 (5)
N2—C41.491 (4)C21—C221.537 (5)
N3—C201.343 (4)C21—C251.548 (5)
N3—C261.468 (4)C22—C291.534 (5)
N3—C211.505 (4)C22—C231.538 (5)
N4—C201.333 (4)C22—C281.544 (5)
N4—C301.451 (4)C23—C241.540 (5)
N4—C231.503 (4)C23—H23A1.0000
C2—C51.541 (5)C24—C251.545 (5)
C2—C81.541 (5)C24—H24A0.9900
C2—C31.545 (5)C24—H24B0.9900
C3—C101.522 (5)C25—H25A0.9900
C3—C41.528 (5)C25—H25B0.9900
C3—C91.535 (5)C26—H26A0.9800
C4—C61.529 (5)C26—H26B0.9800
C4—H4A1.0000C26—H26C0.9800
C5—C61.547 (5)C27—H27A0.9800
C5—H5A0.9900C27—H27B0.9800
C5—H5B0.9900C27—H27C0.9800
C6—H6A0.9900C28—H28A0.9800
C6—H6B0.9900C28—H28B0.9800
C7—H7A0.9800C28—H28C0.9800
C7—H7B0.9800C29—H29A0.9800
C7—H7C0.9800C29—H29B0.9800
C8—H8A0.9800C29—H29C0.9800
C8—H8B0.9800C30—C351.390 (5)
C8—H8C0.9800C30—C311.410 (5)
C9—H9A0.9800C31—C321.406 (5)
C9—H9B0.9800C31—C361.512 (5)
C9—H9C0.9800C32—C331.377 (5)
C10—H10A0.9800C32—H32A0.9500
C10—H10B0.9800C33—C341.377 (5)
C10—H10C0.9800C33—C371.511 (5)
C11—C121.398 (5)C34—C351.408 (5)
C11—C161.409 (5)C34—H34A0.9500
C12—C131.401 (5)C35—C381.507 (5)
C12—C171.503 (5)C36—H36A0.9800
C13—C141.384 (6)C36—H36B0.9800
C13—H13A0.9500C36—H36C0.9800
C14—C151.383 (6)C37—H37A0.9800
C14—C181.517 (5)C37—H37B0.9800
C15—C161.388 (5)C37—H37C0.9800
C15—H15A0.9500C38—H38A0.9800
C16—C191.503 (5)C38—H38B0.9800
C17—H17A0.9800C38—H38C0.9800
C1—Pd1—C20178.32 (12)C14—C18—H18C109.5
C1—Pd1—I191.63 (9)H18A—C18—H18C109.5
C20—Pd1—I187.63 (8)H18B—C18—H18C109.5
C1—Pd1—I289.05 (9)C16—C19—H19A109.5
C20—Pd1—I291.23 (9)C16—C19—H19B109.5
I1—Pd1—I2163.275 (13)H19A—C19—H19B109.5
C1—N1—C7119.8 (3)C16—C19—H19C109.5
C1—N1—C2121.2 (3)H19A—C19—H19C109.5
C7—N1—C2118.9 (3)H19B—C19—H19C109.5
C1—N2—C11123.3 (3)N4—C20—N3116.3 (3)
C1—N2—C4123.1 (3)N4—C20—Pd1123.9 (2)
C11—N2—C4113.3 (3)N3—C20—Pd1119.8 (2)
C20—N3—C26119.7 (3)N3—C21—C27112.4 (3)
C20—N3—C21122.2 (3)N3—C21—C22105.8 (3)
C26—N3—C21117.9 (3)C27—C21—C22114.6 (3)
C20—N4—C30124.1 (3)N3—C21—C25107.9 (3)
C20—N4—C23122.4 (3)C27—C21—C25111.7 (3)
C30—N4—C23113.1 (3)C22—C21—C25103.9 (3)
N1—C1—N2115.7 (3)C29—C22—C21113.3 (3)
N1—C1—Pd1120.7 (2)C29—C22—C23115.6 (3)
N2—C1—Pd1123.5 (2)C21—C22—C2397.5 (3)
N1—C2—C5108.8 (3)C29—C22—C28107.8 (3)
N1—C2—C8112.2 (3)C21—C22—C28113.1 (3)
C5—C2—C8111.2 (3)C23—C22—C28109.5 (3)
N1—C2—C3105.7 (3)N4—C23—C22110.4 (3)
C5—C2—C3104.1 (3)N4—C23—C24107.9 (3)
C8—C2—C3114.3 (3)C22—C23—C24103.4 (3)
C10—C3—C4115.4 (3)N4—C23—H23A111.6
C10—C3—C9107.8 (3)C22—C23—H23A111.6
C4—C3—C9109.9 (3)C24—C23—H23A111.6
C10—C3—C2113.2 (3)C23—C24—C25102.0 (3)
C4—C3—C297.4 (3)C23—C24—H24A111.4
C9—C3—C2113.1 (3)C25—C24—H24A111.4
N2—C4—C3110.0 (3)C23—C24—H24B111.4
N2—C4—C6108.2 (3)C25—C24—H24B111.4
C3—C4—C6103.3 (3)H24A—C24—H24B109.2
N2—C4—H4A111.6C24—C25—C21106.2 (3)
C3—C4—H4A111.6C24—C25—H25A110.5
C6—C4—H4A111.6C21—C25—H25A110.5
C2—C5—C6106.0 (3)C24—C25—H25B110.5
C2—C5—H5A110.5C21—C25—H25B110.5
C6—C5—H5A110.5H25A—C25—H25B108.7
C2—C5—H5B110.5N3—C26—H26A109.5
C6—C5—H5B110.5N3—C26—H26B109.5
H5A—C5—H5B108.7H26A—C26—H26B109.5
C4—C6—C5102.0 (3)N3—C26—H26C109.5
C4—C6—H6A111.4H26A—C26—H26C109.5
C5—C6—H6A111.4H26B—C26—H26C109.5
C4—C6—H6B111.4C21—C27—H27A109.5
C5—C6—H6B111.4C21—C27—H27B109.5
H6A—C6—H6B109.2H27A—C27—H27B109.5
N1—C7—H7A109.5C21—C27—H27C109.5
N1—C7—H7B109.5H27A—C27—H27C109.5
H7A—C7—H7B109.5H27B—C27—H27C109.5
N1—C7—H7C109.5C22—C28—H28A109.5
H7A—C7—H7C109.5C22—C28—H28B109.5
H7B—C7—H7C109.5H28A—C28—H28B109.5
C2—C8—H8A109.5C22—C28—H28C109.5
C2—C8—H8B109.5H28A—C28—H28C109.5
H8A—C8—H8B109.5H28B—C28—H28C109.5
C2—C8—H8C109.5C22—C29—H29A109.5
H8A—C8—H8C109.5C22—C29—H29B109.5
H8B—C8—H8C109.5H29A—C29—H29B109.5
C3—C9—H9A109.5C22—C29—H29C109.5
C3—C9—H9B109.5H29A—C29—H29C109.5
H9A—C9—H9B109.5H29B—C29—H29C109.5
C3—C9—H9C109.5C35—C30—C31120.7 (3)
H9A—C9—H9C109.5C35—C30—N4121.1 (3)
H9B—C9—H9C109.5C31—C30—N4117.7 (3)
C3—C10—H10A109.5C32—C31—C30118.1 (3)
C3—C10—H10B109.5C32—C31—C36118.0 (3)
H10A—C10—H10B109.5C30—C31—C36123.9 (3)
C3—C10—H10C109.5C33—C32—C31122.1 (4)
H10A—C10—H10C109.5C33—C32—H32A118.9
H10B—C10—H10C109.5C31—C32—H32A118.9
C12—C11—C16120.7 (3)C32—C33—C34118.4 (3)
C12—C11—N2120.9 (3)C32—C33—C37120.5 (4)
C16—C11—N2117.7 (3)C34—C33—C37121.1 (4)
C11—C12—C13118.1 (3)C33—C34—C35122.2 (3)
C11—C12—C17124.1 (3)C33—C34—H34A118.9
C13—C12—C17117.8 (3)C35—C34—H34A118.9
C14—C13—C12122.5 (4)C30—C35—C34118.4 (3)
C14—C13—H13A118.7C30—C35—C38124.6 (3)
C12—C13—H13A118.7C34—C35—C38117.0 (3)
C15—C14—C13117.7 (3)C31—C36—H36A109.5
C15—C14—C18120.4 (4)C31—C36—H36B109.5
C13—C14—C18121.9 (4)H36A—C36—H36B109.5
C14—C15—C16122.7 (4)C31—C36—H36C109.5
C14—C15—H15A118.7H36A—C36—H36C109.5
C16—C15—H15A118.7H36B—C36—H36C109.5
C15—C16—C11118.3 (4)C33—C37—H37A109.5
C15—C16—C19118.4 (3)C33—C37—H37B109.5
C11—C16—C19123.3 (3)H37A—C37—H37B109.5
C12—C17—H17A109.5C33—C37—H37C109.5
C12—C17—H17B109.5H37A—C37—H37C109.5
H17A—C17—H17B109.5H37B—C37—H37C109.5
C12—C17—H17C109.5C35—C38—H38A109.5
H17A—C17—H17C109.5C35—C38—H38B109.5
H17B—C17—H17C109.5H38A—C38—H38B109.5
C14—C18—H18A109.5C35—C38—H38C109.5
C14—C18—H18B109.5H38A—C38—H38C109.5
H18A—C18—H18B109.5H38B—C38—H38C109.5
C7—N1—C1—N2−166.4 (3)C30—N4—C20—N3−172.2 (3)
C2—N1—C1—N29.1 (5)C23—N4—C20—N30.3 (4)
C7—N1—C1—Pd115.6 (5)C30—N4—C20—Pd16.8 (4)
C2—N1—C1—Pd1−168.9 (3)C23—N4—C20—Pd1179.3 (2)
C11—N2—C1—N1−173.5 (3)C26—N3—C20—N4−167.2 (3)
C4—N2—C1—N11.0 (5)C21—N3—C20—N48.1 (4)
C11—N2—C1—Pd14.5 (5)C26—N3—C20—Pd113.7 (4)
C4—N2—C1—Pd1179.0 (2)C21—N3—C20—Pd1−170.9 (2)
I1—Pd1—C1—N161.3 (3)I1—Pd1—C20—N479.8 (3)
I2—Pd1—C1—N1−102.0 (3)I2—Pd1—C20—N4−116.9 (3)
I1—Pd1—C1—N2−116.5 (3)I1—Pd1—C20—N3−101.2 (2)
I2—Pd1—C1—N280.2 (3)I2—Pd1—C20—N362.1 (2)
C1—N1—C2—C562.4 (4)C20—N3—C21—C27−172.7 (3)
C7—N1—C2—C5−122.1 (4)C26—N3—C21—C272.7 (4)
C1—N1—C2—C8−174.2 (4)C20—N3—C21—C22−47.0 (4)
C7—N1—C2—C81.4 (5)C26—N3—C21—C22128.4 (3)
C1—N1—C2—C3−48.9 (4)C20—N3—C21—C2563.7 (4)
C7—N1—C2—C3126.6 (4)C26—N3—C21—C25−120.8 (3)
N1—C2—C3—C10−50.4 (4)N3—C21—C22—C29−52.7 (3)
C5—C2—C3—C10−164.9 (3)C27—C21—C22—C2971.7 (4)
C8—C2—C3—C1073.6 (4)C25—C21—C22—C29−166.2 (3)
N1—C2—C3—C471.3 (3)N3—C21—C22—C2369.4 (3)
C5—C2—C3—C4−43.2 (3)C27—C21—C22—C23−166.2 (3)
C8—C2—C3—C4−164.7 (3)C25—C21—C22—C23−44.1 (3)
N1—C2—C3—C9−173.3 (3)N3—C21—C22—C28−175.7 (3)
C5—C2—C3—C972.1 (4)C27—C21—C22—C28−51.3 (4)
C8—C2—C3—C9−49.3 (4)C25—C21—C22—C2870.8 (3)
C1—N2—C4—C330.3 (4)C20—N4—C23—C2231.4 (4)
C11—N2—C4—C3−154.7 (3)C30—N4—C23—C22−155.3 (3)
C1—N2—C4—C6−82.0 (4)C20—N4—C23—C24−80.9 (4)
C11—N2—C4—C693.0 (3)C30—N4—C23—C2492.3 (3)
C10—C3—C4—N256.7 (4)C29—C22—C23—N456.6 (4)
C9—C3—C4—N2178.7 (3)C21—C22—C23—N4−63.8 (3)
C2—C3—C4—N2−63.4 (3)C28—C22—C23—N4178.5 (3)
C10—C3—C4—C6172.0 (3)C29—C22—C23—C24171.8 (3)
C9—C3—C4—C6−65.9 (4)C21—C22—C23—C2451.4 (3)
C2—C3—C4—C652.0 (3)C28—C22—C23—C24−66.3 (4)
N1—C2—C5—C6−92.5 (3)N4—C23—C24—C2578.6 (3)
C8—C2—C5—C6143.4 (3)C22—C23—C24—C25−38.4 (3)
C3—C2—C5—C619.9 (3)C23—C24—C25—C219.8 (4)
N2—C4—C6—C576.3 (3)N3—C21—C25—C24−90.1 (3)
C3—C4—C6—C5−40.3 (3)C27—C21—C25—C24145.9 (3)
C2—C5—C6—C412.0 (3)C22—C21—C25—C2421.9 (4)
C1—N2—C11—C1276.8 (4)C20—N4—C30—C3574.6 (4)
C4—N2—C11—C12−98.3 (4)C23—N4—C30—C35−98.5 (4)
C1—N2—C11—C16−112.5 (4)C20—N4—C30—C31−112.9 (4)
C4—N2—C11—C1672.5 (4)C23—N4—C30—C3174.0 (4)
C16—C11—C12—C13−0.5 (5)C35—C30—C31—C32−1.6 (5)
N2—C11—C12—C13170.0 (3)N4—C30—C31—C32−174.1 (3)
C16—C11—C12—C17179.8 (3)C35—C30—C31—C36176.1 (3)
N2—C11—C12—C17−9.7 (5)N4—C30—C31—C363.6 (5)
C11—C12—C13—C140.8 (5)C30—C31—C32—C332.8 (5)
C17—C12—C13—C14−179.5 (3)C36—C31—C32—C33−175.1 (3)
C12—C13—C14—C150.3 (6)C31—C32—C33—C34−1.1 (5)
C12—C13—C14—C18179.7 (4)C31—C32—C33—C37178.2 (3)
C13—C14—C15—C16−1.7 (6)C32—C33—C34—C35−1.8 (5)
C18—C14—C15—C16178.9 (4)C37—C33—C34—C35178.8 (3)
C14—C15—C16—C112.0 (6)C31—C30—C35—C34−1.1 (5)
C14—C15—C16—C19−176.8 (4)N4—C30—C35—C34171.1 (3)
C12—C11—C16—C15−0.8 (5)C31—C30—C35—C38178.4 (3)
N2—C11—C16—C15−171.6 (3)N4—C30—C35—C38−9.3 (5)
C12—C11—C16—C19177.9 (3)C33—C34—C35—C302.9 (5)
N2—C11—C16—C197.1 (5)C33—C34—C35—C38−176.6 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C5—H5A···I1i0.993.224.131 (5)154
Symmetry code: (i) x+1/2, −y+3/2, −z.
(II) Dichlorido[(1S,5S)-4-mesityl-1,2,8,8-tetramethyl-2,4-diazabicyclo[3.2.1]octan-3-ylidene-κC3](triphenylphosphane-κP)palladium(IV) top
Crystal data top
[Pd(C19H28N2)Cl2(C18H15P)]F(000) = 748
Mr = 724.00Dx = 1.393 Mg m−3
Monoclinic, P21Mo Kα radiation, λ = 0.71073 Å
a = 10.987 (3) ÅCell parameters from 3348 reflections
b = 9.568 (2) Åθ = 2.5–27.0°
c = 17.211 (4) ŵ = 0.77 mm−1
β = 107.478 (4)°T = 130 K
V = 1725.7 (7) Å3Plate, colourless
Z = 20.48 × 0.20 × 0.01 mm
Data collection top
Bruker SMART APEX
diffractometer		8099 independent reflections
Radiation source: sealed tube6415 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.089
φ and ω scansθmax = 27.9°, θmin = 1.2°
Absorption correction: multi-scan
(SADABS; Bruker, 2002)		h = −13→14
Tmin = 0.710, Tmax = 0.992k = −12→12
13973 measured reflectionsl = −22→22
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.053H-atom parameters constrained
wR(F2) = 0.113 w = 1/[σ2(Fo2) + (0.0399P)2]
where P = (Fo2 + 2Fc2)/3
S = 0.92(Δ/σ)max = 0.001
8099 reflectionsΔρmax = 1.00 e Å−3
393 parametersΔρmin = −1.60 e Å−3
1 restraintAbsolute structure: Flack x determined using 2367 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons & Flack, 2004)
Primary atom site location: structure-invariant direct methodsAbsolute structure parameter: −0.02 (4)
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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Pd10.24938 (5)0.19189 (6)0.31693 (3)0.01671 (14)
Cl10.4202 (2)0.3441 (2)0.34508 (12)0.0312 (5)
Cl20.09193 (19)0.0248 (2)0.30106 (12)0.0252 (5)
P10.26931 (18)0.1278 (2)0.18920 (12)0.0185 (4)
N10.2705 (5)0.1616 (7)0.4905 (3)0.0209 (17)
N20.1623 (6)0.3605 (6)0.4351 (3)0.0152 (13)
C10.2245 (6)0.2440 (8)0.4266 (4)0.0168 (16)
C20.3400 (9)0.0354 (10)0.4841 (5)0.032 (2)
H2A0.2954−0.04590.49710.048*
H2B0.42620.04040.52240.048*
H2C0.34520.02650.42850.048*
C30.2468 (6)0.1965 (12)0.5712 (3)0.0183 (13)
C40.3261 (8)0.1040 (9)0.6390 (5)0.0260 (18)
H4A0.30470.00580.62530.039*
H4B0.30820.12720.69000.039*
H4C0.41690.11920.64570.039*
C50.1005 (6)0.1808 (11)0.5580 (4)0.0222 (16)
H5A0.06290.11230.51420.027*
H5B0.08430.14880.60870.027*
C60.0429 (7)0.3274 (9)0.5337 (5)0.0215 (17)
H6A−0.03210.32310.48440.026*
H6B0.01750.37120.57860.026*
C70.1532 (7)0.4064 (8)0.5170 (4)0.0161 (15)
H7A0.14260.50990.51960.019*
C80.2712 (7)0.3541 (8)0.5838 (4)0.0193 (16)
C90.2635 (8)0.4027 (9)0.6674 (4)0.0274 (19)
H9A0.27890.50370.67300.041*
H9B0.32810.35360.71060.041*
H9C0.17850.38190.67190.041*
C100.3999 (7)0.4017 (9)0.5759 (5)0.0240 (18)
H10A0.40890.50280.58470.036*
H10B0.40430.37910.52130.036*
H10C0.46890.35350.61670.036*
C110.0918 (6)0.4438 (8)0.3657 (4)0.0154 (15)
C12−0.0267 (7)0.3981 (8)0.3150 (4)0.0183 (15)
C13−0.0907 (8)0.4853 (9)0.2506 (5)0.0251 (18)
H13A−0.17020.45450.21510.030*
C14−0.0449 (8)0.6143 (9)0.2354 (4)0.0238 (17)
C150.0712 (7)0.6563 (8)0.2895 (4)0.0234 (19)
H15A0.10430.74490.28120.028*
C160.1408 (7)0.5763 (8)0.3545 (5)0.0207 (16)
C17−0.0946 (7)0.2674 (8)0.3277 (5)0.0264 (18)
H17A−0.17200.29270.34150.040*
H17B−0.03820.21260.37230.040*
H17C−0.11760.21160.27760.040*
C18−0.1167 (8)0.7054 (13)0.1664 (5)0.038 (2)
H18A−0.09610.67840.11690.057*
H18B−0.09250.80320.17950.057*
H18C−0.20850.69440.15760.057*
C190.2627 (8)0.6319 (9)0.4105 (5)0.0268 (18)
H19A0.28170.72270.39040.040*
H19B0.33220.56640.41250.040*
H19C0.25420.64310.46520.040*
C210.1114 (7)0.1308 (9)0.1132 (4)0.0212 (16)
C220.0823 (9)0.0484 (10)0.0436 (5)0.032 (2)
H22A0.1436−0.01540.03540.038*
C23−0.0370 (9)0.0598 (11)−0.0140 (5)0.040 (2)
H23A−0.05700.0048−0.06210.048*
C24−0.1263 (8)0.1510 (10)−0.0012 (6)0.040 (3)
H24A−0.20830.1575−0.04010.048*
C25−0.0972 (8)0.2320 (10)0.0672 (5)0.037 (2)
H25A−0.15860.29620.07480.045*
C260.0210 (7)0.2219 (9)0.1257 (5)0.030 (2)
H26A0.03970.27680.17380.035*
C310.3659 (7)0.2364 (8)0.1431 (4)0.0216 (17)
C320.3177 (8)0.3112 (9)0.0720 (5)0.0268 (18)
H32A0.22820.31170.04590.032*
C330.3971 (9)0.3857 (10)0.0379 (5)0.033 (2)
H33A0.36260.4372−0.01100.039*
C340.5277 (9)0.3841 (11)0.0760 (6)0.039 (2)
H34A0.58330.43410.05310.047*
C350.5761 (8)0.3100 (11)0.1468 (6)0.038 (2)
H35A0.66580.30900.17210.046*
C360.4984 (8)0.2372 (9)0.1822 (5)0.032 (2)
H36A0.53360.18840.23190.039*
C410.3339 (7)−0.0452 (9)0.1821 (4)0.0198 (16)
C420.3127 (7)−0.1522 (9)0.2321 (5)0.0258 (18)
H42A0.2665−0.13220.26940.031*
C430.3577 (7)−0.2863 (10)0.2282 (4)0.026 (2)
H43A0.3408−0.35820.26170.032*
C440.4271 (6)−0.3147 (13)0.1755 (4)0.0269 (16)
H44A0.4595−0.40620.17350.032*
C450.4497 (8)−0.2128 (9)0.1261 (5)0.0291 (19)
H45A0.4976−0.23400.08990.035*
C460.4038 (8)−0.0798 (10)0.1283 (5)0.0280 (19)
H46A0.4195−0.01030.09310.034*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Pd10.0131 (2)0.0177 (3)0.0243 (2)−0.0021 (3)0.01319 (18)−0.0018 (3)
Cl10.0278 (11)0.0357 (13)0.0383 (11)−0.0194 (10)0.0222 (9)−0.0155 (10)
Cl20.0216 (10)0.0206 (11)0.0409 (11)−0.0070 (8)0.0206 (9)−0.0044 (9)
P10.0142 (9)0.0201 (10)0.0252 (9)−0.0009 (8)0.0120 (8)−0.0008 (9)
N10.015 (3)0.026 (5)0.026 (3)0.004 (3)0.013 (2)0.003 (3)
N20.014 (3)0.014 (3)0.021 (3)0.000 (3)0.011 (2)−0.001 (2)
C10.008 (3)0.014 (4)0.031 (4)−0.006 (3)0.008 (3)−0.011 (3)
C20.038 (5)0.031 (5)0.033 (4)0.012 (4)0.020 (4)0.000 (4)
C30.016 (3)0.023 (4)0.021 (3)−0.007 (5)0.012 (2)0.001 (5)
C40.022 (4)0.026 (5)0.033 (4)0.006 (4)0.013 (3)0.004 (4)
C50.013 (3)0.025 (4)0.033 (3)−0.001 (4)0.015 (3)0.004 (5)
C60.018 (4)0.025 (5)0.027 (4)−0.001 (3)0.015 (3)−0.001 (3)
C70.013 (3)0.017 (4)0.023 (3)0.002 (3)0.013 (3)−0.006 (3)
C80.016 (4)0.023 (4)0.023 (3)−0.002 (3)0.011 (3)−0.004 (3)
C90.026 (4)0.030 (5)0.029 (4)0.003 (4)0.012 (4)−0.002 (4)
C100.013 (4)0.028 (5)0.033 (4)−0.006 (3)0.009 (3)−0.002 (4)
C110.009 (3)0.019 (4)0.022 (3)−0.002 (3)0.010 (3)−0.005 (3)
C120.012 (3)0.019 (4)0.028 (4)0.000 (3)0.013 (3)−0.004 (3)
C130.016 (4)0.029 (5)0.030 (4)0.005 (3)0.008 (3)−0.003 (4)
C140.029 (4)0.025 (5)0.023 (4)0.003 (4)0.016 (3)0.001 (3)
C150.026 (4)0.017 (5)0.035 (4)0.001 (3)0.020 (3)0.003 (3)
C160.018 (4)0.015 (4)0.034 (4)0.002 (3)0.016 (3)0.000 (3)
C170.016 (4)0.021 (5)0.043 (5)−0.004 (3)0.009 (3)−0.004 (4)
C180.038 (4)0.037 (6)0.040 (4)0.012 (6)0.015 (4)0.008 (5)
C190.028 (4)0.023 (4)0.033 (4)−0.009 (4)0.015 (3)−0.002 (3)
C210.017 (4)0.026 (4)0.024 (4)−0.006 (3)0.011 (3)0.003 (3)
C220.028 (5)0.031 (5)0.033 (4)−0.002 (4)0.006 (4)−0.008 (4)
C230.031 (5)0.045 (6)0.037 (5)−0.003 (5)−0.002 (4)−0.007 (4)
C240.021 (4)0.047 (7)0.047 (5)−0.003 (4)0.000 (4)0.005 (4)
C250.022 (4)0.042 (7)0.050 (5)0.008 (4)0.015 (4)0.007 (4)
C260.023 (4)0.037 (7)0.033 (4)0.000 (4)0.015 (3)0.004 (4)
C310.019 (4)0.021 (4)0.029 (4)−0.001 (3)0.014 (3)−0.002 (3)
C320.024 (4)0.028 (5)0.031 (4)−0.004 (4)0.013 (3)−0.001 (4)
C330.045 (6)0.028 (5)0.034 (4)−0.007 (4)0.025 (4)0.000 (4)
C340.039 (6)0.041 (6)0.050 (5)−0.016 (5)0.032 (5)−0.007 (5)
C350.023 (4)0.049 (6)0.048 (5)−0.014 (4)0.020 (4)−0.005 (5)
C360.021 (4)0.046 (6)0.033 (4)−0.008 (4)0.015 (3)0.001 (4)
C410.010 (3)0.024 (4)0.026 (4)−0.001 (3)0.006 (3)0.000 (3)
C420.020 (4)0.029 (5)0.032 (4)0.002 (4)0.015 (3)−0.001 (4)
C430.025 (4)0.023 (6)0.033 (4)0.002 (4)0.011 (3)0.001 (4)
C440.022 (3)0.026 (4)0.031 (3)0.009 (5)0.006 (3)−0.007 (5)
C450.027 (4)0.031 (5)0.038 (4)0.002 (4)0.022 (4)−0.009 (4)
C460.030 (5)0.026 (5)0.036 (4)0.001 (4)0.021 (4)−0.001 (4)
Geometric parameters (Å, º) top
Pd1—C12.048 (7)C15—C161.381 (11)
Pd1—Cl12.309 (2)C15—H15A0.9500
Pd1—Cl22.311 (2)C16—C191.494 (11)
Pd1—P12.355 (2)C17—H17A0.9800
P1—C411.819 (8)C17—H17B0.9800
P1—C311.827 (7)C17—H17C0.9800
P1—C211.832 (8)C18—H18A0.9800
N1—C11.324 (9)C18—H18B0.9800
N1—C21.450 (10)C18—H18C0.9800
N1—C31.526 (8)C19—H19A0.9800
N2—C11.338 (9)C19—H19B0.9800
N2—C111.452 (9)C19—H19C0.9800
N2—C71.507 (8)C21—C261.386 (11)
C2—H2A0.9800C21—C221.390 (11)
C2—H2B0.9800C22—C231.390 (12)
C2—H2C0.9800C22—H22A0.9500
C3—C41.514 (11)C23—C241.380 (13)
C3—C81.536 (14)C23—H23A0.9500
C3—C51.561 (8)C24—C251.364 (12)
C4—H4A0.9800C24—H24A0.9500
C4—H4B0.9800C25—C261.387 (11)
C4—H4C0.9800C25—H25A0.9500
C5—C61.544 (13)C26—H26A0.9500
C5—H5A0.9900C31—C321.379 (11)
C5—H5B0.9900C31—C361.409 (11)
C6—C71.527 (10)C32—C331.387 (11)
C6—H6A0.9900C32—H32A0.9500
C6—H6B0.9900C33—C341.386 (14)
C7—C81.536 (10)C33—H33A0.9500
C7—H7A1.0000C34—C351.371 (13)
C8—C101.530 (10)C34—H34A0.9500
C8—C91.538 (10)C35—C361.378 (11)
C9—H9A0.9800C35—H35A0.9500
C9—H9B0.9800C36—H36A0.9500
C9—H9C0.9800C41—C421.402 (11)
C10—H10A0.9800C41—C461.409 (11)
C10—H10B0.9800C42—C431.384 (12)
C10—H10C0.9800C42—H42A0.9500
C11—C121.402 (10)C43—C441.377 (10)
C11—C161.413 (10)C43—H43A0.9500
C12—C131.397 (11)C44—C451.365 (13)
C12—C171.505 (11)C44—H44A0.9500
C13—C141.387 (12)C45—C461.373 (12)
C13—H13A0.9500C45—H45A0.9500
C14—C151.394 (11)C46—H46A0.9500
C14—C181.493 (12)
C1—Pd1—Cl188.7 (2)C12—C13—H13A118.1
C1—Pd1—Cl288.6 (2)C13—C14—C15116.2 (7)
Cl1—Pd1—Cl2173.53 (9)C13—C14—C18122.3 (8)
C1—Pd1—P1177.6 (2)C15—C14—C18121.4 (8)
Cl1—Pd1—P193.58 (7)C16—C15—C14123.6 (7)
Cl2—Pd1—P189.18 (7)C16—C15—H15A118.2
C41—P1—C31101.5 (3)C14—C15—H15A118.2
C41—P1—C21105.7 (4)C15—C16—C11117.8 (7)
C31—P1—C21103.3 (3)C15—C16—C19119.7 (7)
C41—P1—Pd1116.6 (2)C11—C16—C19122.4 (7)
C31—P1—Pd1119.1 (2)C12—C17—H17A109.5
C21—P1—Pd1109.2 (2)C12—C17—H17B109.5
C1—N1—C2120.8 (6)H17A—C17—H17B109.5
C1—N1—C3119.9 (6)C12—C17—H17C109.5
C2—N1—C3119.3 (6)H17A—C17—H17C109.5
C1—N2—C11122.0 (6)H17B—C17—H17C109.5
C1—N2—C7121.6 (6)C14—C18—H18A109.5
C11—N2—C7116.2 (6)C14—C18—H18B109.5
N1—C1—N2119.0 (6)H18A—C18—H18B109.5
N1—C1—Pd1119.8 (5)C14—C18—H18C109.5
N2—C1—Pd1121.2 (5)H18A—C18—H18C109.5
N1—C2—H2A109.5H18B—C18—H18C109.5
N1—C2—H2B109.5C16—C19—H19A109.5
H2A—C2—H2B109.5C16—C19—H19B109.5
N1—C2—H2C109.5H19A—C19—H19B109.5
H2A—C2—H2C109.5C16—C19—H19C109.5
H2B—C2—H2C109.5H19A—C19—H19C109.5
C4—C3—N1111.0 (7)H19B—C19—H19C109.5
C4—C3—C8115.4 (6)C26—C21—C22120.0 (7)
N1—C3—C8105.9 (6)C26—C21—P1117.9 (6)
C4—C3—C5112.7 (7)C22—C21—P1122.0 (6)
N1—C3—C5107.2 (5)C21—C22—C23119.6 (9)
C8—C3—C5104.1 (8)C21—C22—H22A120.2
C3—C4—H4A109.5C23—C22—H22A120.2
C3—C4—H4B109.5C24—C23—C22119.9 (8)
H4A—C4—H4B109.5C24—C23—H23A120.0
C3—C4—H4C109.5C22—C23—H23A120.0
H4A—C4—H4C109.5C25—C24—C23120.3 (8)
H4B—C4—H4C109.5C25—C24—H24A119.9
C6—C5—C3105.8 (8)C23—C24—H24A119.9
C6—C5—H5A110.6C24—C25—C26120.8 (8)
C3—C5—H5A110.6C24—C25—H25A119.6
C6—C5—H5B110.6C26—C25—H25A119.6
C3—C5—H5B110.6C21—C26—C25119.3 (8)
H5A—C5—H5B108.7C21—C26—H26A120.3
C7—C6—C5102.5 (6)C25—C26—H26A120.3
C7—C6—H6A111.3C32—C31—C36119.2 (7)
C5—C6—H6A111.3C32—C31—P1124.2 (6)
C7—C6—H6B111.3C36—C31—P1116.6 (6)
C5—C6—H6B111.3C31—C32—C33121.3 (8)
H6A—C6—H6B109.2C31—C32—H32A119.3
N2—C7—C6108.1 (6)C33—C32—H32A119.3
N2—C7—C8109.1 (6)C34—C33—C32119.1 (8)
C6—C7—C8103.7 (6)C34—C33—H33A120.4
N2—C7—H7A111.8C32—C33—H33A120.4
C6—C7—H7A111.8C35—C34—C33119.8 (8)
C8—C7—H7A111.8C35—C34—H34A120.1
C10—C8—C7115.6 (6)C33—C34—H34A120.1
C10—C8—C3113.9 (6)C34—C35—C36121.8 (8)
C7—C8—C398.1 (6)C34—C35—H35A119.1
C10—C8—C9107.8 (6)C36—C35—H35A119.1
C7—C8—C9109.3 (6)C35—C36—C31118.7 (8)
C3—C8—C9111.9 (6)C35—C36—H36A120.6
C8—C9—H9A109.5C31—C36—H36A120.6
C8—C9—H9B109.5C42—C41—C46117.1 (8)
H9A—C9—H9B109.5C42—C41—P1118.9 (6)
C8—C9—H9C109.5C46—C41—P1124.0 (6)
H9A—C9—H9C109.5C43—C42—C41121.3 (7)
H9B—C9—H9C109.5C43—C42—H42A119.3
C8—C10—H10A109.5C41—C42—H42A119.3
C8—C10—H10B109.5C44—C43—C42119.4 (9)
H10A—C10—H10B109.5C44—C43—H43A120.3
C8—C10—H10C109.5C42—C43—H43A120.3
H10A—C10—H10C109.5C45—C44—C43120.7 (10)
H10B—C10—H10C109.5C45—C44—H44A119.6
C12—C11—C16121.0 (7)C43—C44—H44A119.6
C12—C11—N2120.5 (7)C44—C45—C46120.5 (8)
C16—C11—N2118.3 (6)C44—C45—H45A119.8
C13—C12—C11117.4 (7)C46—C45—H45A119.8
C13—C12—C17117.2 (7)C45—C46—C41120.9 (8)
C11—C12—C17125.3 (7)C45—C46—H46A119.5
C14—C13—C12123.8 (8)C41—C46—H46A119.5
C14—C13—H13A118.1
C2—N1—C1—N2−179.2 (7)C13—C14—C15—C161.1 (11)
C3—N1—C1—N22.9 (9)C18—C14—C15—C16179.6 (7)
C2—N1—C1—Pd10.8 (9)C14—C15—C16—C110.9 (11)
C3—N1—C1—Pd1−177.1 (5)C14—C15—C16—C19−178.4 (7)
C11—N2—C1—N1−169.9 (6)C12—C11—C16—C15−3.1 (10)
C7—N2—C1—N15.3 (10)N2—C11—C16—C15−178.2 (6)
C11—N2—C1—Pd110.1 (9)C12—C11—C16—C19176.1 (7)
C7—N2—C1—Pd1−174.7 (5)N2—C11—C16—C191.0 (10)
C1—N1—C3—C4−170.2 (7)C41—P1—C21—C26154.5 (6)
C2—N1—C3—C411.8 (10)C31—P1—C21—C26−99.3 (6)
C1—N1—C3—C8−44.2 (8)Pd1—P1—C21—C2628.4 (7)
C2—N1—C3—C8137.8 (7)C41—P1—C21—C22−27.4 (8)
C1—N1—C3—C566.4 (10)C31—P1—C21—C2278.8 (7)
C2—N1—C3—C5−111.6 (9)Pd1—P1—C21—C22−153.5 (6)
C4—C3—C5—C6145.1 (7)C26—C21—C22—C231.2 (13)
N1—C3—C5—C6−92.5 (8)P1—C21—C22—C23−176.9 (7)
C8—C3—C5—C619.4 (6)C21—C22—C23—C24−1.0 (14)
C3—C5—C6—C711.8 (7)C22—C23—C24—C251.1 (15)
C1—N2—C7—C6−83.3 (8)C23—C24—C25—C26−1.5 (14)
C11—N2—C7—C692.2 (7)C22—C21—C26—C25−1.5 (12)
C1—N2—C7—C828.9 (9)P1—C21—C26—C25176.6 (6)
C11—N2—C7—C8−155.6 (6)C24—C25—C26—C211.7 (13)
C5—C6—C7—N276.6 (7)C41—P1—C31—C32115.9 (7)
C5—C6—C7—C8−39.2 (7)C21—P1—C31—C326.5 (8)
N2—C7—C8—C1057.3 (9)Pd1—P1—C31—C32−114.7 (6)
C6—C7—C8—C10172.4 (6)C41—P1—C31—C36−61.3 (7)
N2—C7—C8—C3−64.2 (6)C21—P1—C31—C36−170.7 (6)
C6—C7—C8—C350.8 (6)Pd1—P1—C31—C3668.1 (7)
N2—C7—C8—C9179.1 (6)C36—C31—C32—C330.7 (12)
C6—C7—C8—C9−65.9 (8)P1—C31—C32—C33−176.4 (7)
C4—C3—C8—C1071.2 (8)C31—C32—C33—C340.3 (13)
N1—C3—C8—C10−51.9 (7)C32—C33—C34—C35−0.4 (14)
C5—C3—C8—C10−164.8 (6)C33—C34—C35—C36−0.6 (15)
C4—C3—C8—C7−166.0 (5)C34—C35—C36—C311.6 (14)
N1—C3—C8—C770.8 (6)C32—C31—C36—C35−1.6 (12)
C5—C3—C8—C7−42.1 (6)P1—C31—C36—C35175.7 (7)
C4—C3—C8—C9−51.3 (8)C31—P1—C41—C42160.9 (6)
N1—C3—C8—C9−174.5 (6)C21—P1—C41—C42−91.5 (6)
C5—C3—C8—C972.7 (7)Pd1—P1—C41—C4230.0 (7)
C1—N2—C11—C1275.1 (8)C31—P1—C41—C46−19.7 (7)
C7—N2—C11—C12−100.3 (8)C21—P1—C41—C4687.8 (7)
C1—N2—C11—C16−109.7 (8)Pd1—P1—C41—C46−150.7 (6)
C7—N2—C11—C1674.8 (8)C46—C41—C42—C43−0.5 (11)
C16—C11—C12—C133.4 (10)P1—C41—C42—C43178.9 (6)
N2—C11—C12—C13178.4 (6)C41—C42—C43—C441.5 (12)
C16—C11—C12—C17−172.3 (7)C42—C43—C44—C45−1.3 (12)
N2—C11—C12—C172.7 (11)C43—C44—C45—C460.2 (13)
C11—C12—C13—C14−1.4 (11)C44—C45—C46—C410.8 (13)
C17—C12—C13—C14174.6 (7)C42—C41—C46—C45−0.6 (12)
C12—C13—C14—C15−0.8 (11)P1—C41—C46—C45−179.9 (7)
C12—C13—C14—C18−179.3 (7)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C42—H42A···Cl20.952.623.447 (8)146
C15—H15A···Cl2i0.952.713.535 (8)146
Symmetry code: (i) x, y+1, z.
 

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ISSN: 2056-9890
Volume 71| Part 8| August 2015| Pages 919-922
https://doi.org/10.1107/S2056989015013055
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