Bis[S-benzyl-3-(4-n-octyloxybenzyl­idene)dithio­carbazato-[kappa]²N³,S']palladium(II)

In the title compound, [Pd(C₂₃H₂₉N₂OS₂)₂], the Pd^II atom displays the expected square-planar coordination geometry. However, the trans configuration, which allows the Pd^II atom to be located on a crystallographic inversion centre, is unusual with respect to the cis arrangement found in analogous Pd complexes comprising similar N,S-chelating ligands.

S1. Comment

Metal chelates of S-alkyl/arylesters of dithiocarbazate (SBDTC) and their Schiff bases have attracted the interest of researchers for their coordination chemistry and also for their potential use as anticancer compounds (How et al. 2008; Crouse et al., 2004; Tarafder et al., 2002, 2001; Ali et al., 1992). As a continuation of our interest in N,S-donor ligands and their complexes, we have isolated a novel Schiff base of SBDTC, benzyl-3-[(4-n-octyloxyphenyl)methylene]dithiocarbazate, and its bis(bidentate) palladium(II) complex, the title compound, (I).

The structure of (I) shows the Pd^II ion in the expected square-planar donor environment (Fig. 1), with the metal on a centre of inversion and the asymmetric unit therefore constituted by half of the molecule. Each of the ligands is coordinated to the metal as a bidentate chelating agent bonding via the thiolate S and azomethine N atoms, yielding two five-membered chelate rings. The Pd—N and Pd—S bond lengths (Table 1) are sligthly shorter and longer, respectively, than those observed in Pd complexes containing bis-chelating dithiocarbazato-N,S ligands, which fall in the ranges 2.067–2.111 and 2.253–2.268 Å, respectively, as retrieved from the Cambridge Structural Database (CSD, Version 5.31 of November 2009; Allen, 2002). Inside the C—N—N—C group, the bond distances follow the trend found in the other Pd complexes retrieved, indicating that C9—N1 and N2—C1 are double bonds and N1—N2 is a single bond. As described in the Experimental section, the octyloxyl chain is disordered over two positions, leading to absolute O1—C17—C18—C19 torsion angles of 66.6 (14) and 162.7 (17)° for the two arrangements, corresponding to synclinal and antiperiplanar conformations, respectively. The former is close to that found in the octyloxybenzaldehyde thiosemicarbazone ligand (Islam et al., 2010).

A key interest in bis(N,S-bidentate) complexes of Ni triad metals is the adoption of cis versus trans geometries. A CSD search for the fragment M[SC(S)NN]₂ (where M = Ni, Pd or Pt) indicates that Ni complexes with chelating dithiocarbazato-N,S groups adopt either a cis (12 entries) or a trans geometry (12 entries) with equal probability. By contrast, five out of six Pd complexes have a cis configuration, while all five Pt complexes adopt a trans arrangement. The unique reported Pd complex with a trans geometry is notable in that the S-benzyldithiocarbazate ligand has an NH₂ group (Tampouris et al. 2007) as the coordinating N atom, rather than an alkyl- or alkylidene-substituted N atom.

Although the Pd and Pt dithiocarbazate complexes are fewer in number, there is a fair indication that these metals prefer a cis (Pd) or a trans (Pt) geometry, although it should be noted that a broader search of Pd complexes of bis(bidentate) ligands with N—C—C—S (nine cis versus five trans) or N—N—C—S (10 cis versus 17 trans) linkages shows no clear preference. Thus, we can say that (I) represents a rare example of a bis(dithiocarbazato)palladium(II) ion in a trans-planar coordination geometry (see second scheme), likely assumed in order to avoid steric clashes between the substituents on the ligand. The (ferrocenyl)ethylidene (Duan et al., 1998) and diazafluorene–dithiocarbazate (Zhou et al., 2007) derivatives, which have bulky groups on the ligand and a cis configuration, appear to be stabilized by intramolecular stacking interactions between the cyclopentadienyl planes from different Fe atoms and between the diazafluorene rings, respectively. Since no stacking interaction between phenyl rings is detected in (I), intermolecular packing forces favouring the trans geometry appear to be excluded. In the absence of such effects, the stabilization of one configuration over the other may result from the different trans influence exerted by the N and S atoms, induced by the electronic and steric effects of substituent groups on the ligand, which lead to different Pd—N and Pd—S bond energies.

S2. Experimental

The title compound was prepared by adding a solution of palladium chloride (0.04 g, 0.25 mmol) in methanol (60 ml) to the hot solution of benzyl 3-(4-n-octyloxybenzylidene)dithiocarbazate (0.21 g, 0.5 mmol) in ethanol (20 ml). The resulting solution was kept under reflux for 30 min, after which time a brick-red precipitate appeared. The compound was filtered off, washed with hot ethanol, and recrystallized from a mixture of chloroform and ethanol (20:10 v/v) (yield 0.1 g, 40%; m.p. 417 K). In an attempt to grow single crystals, the product was dissolved in a solution of chloroform and toluene (20:5 v/v) and allowed to stand at room temperature. Red microcrystals unsuitable for X-ray study were obtained after 7 d. The compound was then dissolved in a mixture of chloroform and acetone (30:30 v/v) and allowed to stand at room temperature. Very fine flat orange–red crystals of (I) were obtained after 12 d that proved usable for analysis.

S3. Refinement

The octyloxy chain proved to be highly disordered. The part of the chain immediately attached to the arene ring (atoms O1 and C16–C18) was split over two positions, with refined occupancies of 0.568 (8):0.432 (8) and restraints on displacement parameters and bond distances (Sheldrick, 2008). The disordered non-H atoms at lower occupancy were treated isotropically. H atoms were included at calculated positions, with C—H = 0.93 (aromatic) or 0.97Å (alkyl), and with U_iso(H) = 1.2U_eq(C).

Computing details

Data collection: XPRESS (MacScience, 2002); cell refinement: DENZO (Otwinowski & Minor, 1997); data reduction: DENZO and SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures

Fig. 1. The molecular structure of (I), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level. For clarity, only one conformation of the disordered alkyl chain is shown. [Symmetry code: (i) -x, -y + 1, -z.]

Bis[S-benzyl-3-(4-n-octyloxybenzylidene)dithiocarbazato- κ²N³,S']palladium(II)

Crystal data

[Pd(C23H29N2OS2)2]	F(000) = 976
Mr = 933.60	Dx = 1.298 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 16.586 (4) Å	Cell parameters from 258 reflections
b = 14.082 (3) Å	θ = 2.4–23.1°
c = 10.507 (2) Å	µ = 0.60 mm^−1
β = 103.22 (3)°	T = 293 K
V = 2389.0 (8) Å^3	Plate, orange
Z = 2	0.40 × 0.35 × 0.12 mm

Data collection

Enraf–Nonius DIP1030 image-plate diffractometer	4042 independent reflections
Radiation source: fine-focus sealed tube	1977 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.060
laser scanner	θmax = 25.0°, θmin = 2.5°
Absorption correction: part of the refinement model (ΔF) (Parkin et al., 1995)	h = −19→19
Tmin = 0.742, Tmax = 0.932	k = −16→16
27894 measured reflections	l = −12→12

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.036	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.083	H-atom parameters constrained
S = 0.77	w = 1/[σ^2(Fo^2) + (0.0296P)^2] where P = (Fo^2 + 2Fc^2)/3
4042 reflections	(Δ/σ)max < 0.001
277 parameters	Δρmax = 0.22 e Å^−3
60 restraints	Δρmin = −0.27 e Å^−3

Special details

Experimental. Absorption correction:- Parkin S, Moezzi B & Hope H, (1995) J. Appl. Cryst. 28, 53–56 Quadratic fit to sin(theta)/lambda - 18 parameters

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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.

Some atoms in the alkyl chain (O1/C16/C17/C18) were refined over two positions. C19—C23 show abnormally high displacement parameters due to the disorder, and all these atoms were refined with anisotropic displacement parameters, with a positive definite thermal tensor. The phenyl group shows a libration motion, while the ipso carbon atom C3 appears more stable.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
Pd1	0.0000	0.5000	0.0000	0.07133 (17)
S1	0.06976 (8)	0.36189 (7)	−0.01275 (9)	0.0895 (4)
S2	0.18528 (8)	0.26015 (8)	0.19090 (10)	0.0958 (4)
N1	0.05344 (19)	0.4883 (2)	0.1939 (3)	0.0693 (8)
N2	0.1090 (2)	0.4152 (2)	0.2412 (3)	0.0728 (9)
C1	0.1183 (2)	0.3565 (3)	0.1517 (3)	0.0737 (11)
C2	0.2379 (3)	0.2837 (3)	0.3569 (3)	0.0928 (13)
H2A	0.2496	0.3511	0.3678	0.111*
H2B	0.2026	0.2659	0.4150	0.111*
C3	0.3173 (4)	0.2288 (4)	0.3920 (4)	0.1002 (15)
C4	0.3827 (6)	0.2573 (5)	0.3463 (9)	0.198 (3)
H4	0.3773	0.3107	0.2929	0.238*
C5	0.4594 (6)	0.2086 (7)	0.3766 (11)	0.227 (4)
H5	0.5032	0.2242	0.3391	0.272*
C6	0.4636 (7)	0.1397 (9)	0.4618 (10)	0.216 (5)
H6	0.5162	0.1162	0.4983	0.259*
C7	0.4000 (8)	0.0991 (7)	0.5026 (8)	0.237 (6)
H7	0.4050	0.0431	0.5506	0.284*
C8	0.3239 (5)	0.1512 (5)	0.4642 (6)	0.188 (3)
H8	0.2776	0.1294	0.4912	0.225*
C9	0.0403 (2)	0.5473 (3)	0.2838 (3)	0.0738 (11)
H9	0.0010	0.5935	0.2512	0.089*
C10	0.0740 (3)	0.5552 (3)	0.4224 (3)	0.0746 (11)
C11	0.1285 (3)	0.4936 (3)	0.5022 (3)	0.0908 (12)
H11	0.1463	0.4393	0.4662	0.109*
C12	0.1565 (3)	0.5114 (3)	0.6328 (4)	0.0960 (13)
H12	0.1930	0.4690	0.6842	0.115*
C13	0.1319 (3)	0.5902 (4)	0.6890 (4)	0.0931 (14)
C14	0.0750 (3)	0.6510 (3)	0.6135 (4)	0.1031 (15)
H14	0.0555	0.7035	0.6511	0.124*
C15	0.0478 (3)	0.6330 (3)	0.4823 (4)	0.0952 (14)
H15	0.0103	0.6748	0.4318	0.114*
O1	0.1739 (5)	0.5983 (5)	0.8183 (6)	0.097 (3)	0.568 (8)
C16	0.1559 (6)	0.6823 (6)	0.8853 (8)	0.109 (4)	0.568 (8)
H16A	0.1034	0.6759	0.9103	0.130*	0.568 (8)
H16B	0.1539	0.7380	0.8304	0.130*	0.568 (8)
C17	0.2294 (7)	0.6897 (9)	1.0096 (10)	0.157 (5)	0.568 (8)
H17A	0.2807	0.6904	0.9802	0.189*	0.568 (8)
H17B	0.2250	0.7505	1.0508	0.189*	0.568 (8)
C18	0.2360 (13)	0.6168 (13)	1.1084 (11)	0.197 (7)	0.568 (8)
H18A	0.2518	0.5578	1.0730	0.236*	0.568 (8)
H18B	0.1817	0.6072	1.1262	0.236*	0.568 (8)
C19	0.2992 (6)	0.6372 (7)	1.2413 (9)	0.228 (4)	0.568 (8)
H19A	0.3508	0.6553	1.2194	0.274*
H19B	0.2791	0.6931	1.2781	0.274*
O1A	0.1424 (8)	0.6269 (10)	0.8161 (14)	0.118 (5)*	0.432 (8)
C16A	0.2028 (7)	0.5754 (8)	0.8983 (12)	0.104 (5)*	0.432 (8)
H16C	0.2557	0.5813	0.8744	0.125*	0.432 (8)
H16D	0.1880	0.5087	0.8986	0.125*	0.432 (8)
C17A	0.2050 (9)	0.6246 (11)	1.0383 (13)	0.103 (5)*	0.432 (8)
H17C	0.2039	0.6934	1.0325	0.123*	0.432 (8)
H17D	0.1601	0.6028	1.0759	0.123*	0.432 (8)
C18A	0.2883 (14)	0.588 (2)	1.113 (2)	0.283 (19)*	0.432 (8)
H18C	0.2875	0.5196	1.1240	0.340*	0.432 (8)
H18D	0.3320	0.6049	1.0701	0.340*	0.432 (8)
C19A	0.2992 (6)	0.6372 (7)	1.2413 (9)	0.228 (4)	0.432 (8)
C20	0.3193 (9)	0.5721 (7)	1.3412 (13)	0.277 (5)
H20A	0.3500	0.5214	1.3112	0.332*
H20B	0.2679	0.5446	1.3530	0.332*
C21	0.3670 (10)	0.6013 (10)	1.4704 (17)	0.368 (11)
H21A	0.3384	0.6521	1.5043	0.442*
H21B	0.4211	0.6244	1.4642	0.442*
C22	0.3763 (10)	0.5173 (13)	1.5595 (19)	0.394 (11)
H22A	0.3232	0.4887	1.5600	0.472*
H22B	0.4126	0.4697	1.5359	0.472*
C23	0.4108 (8)	0.5586 (10)	1.6761 (13)	0.376 (10)
H23A	0.4651	0.5815	1.6747	0.564*
H23B	0.4148	0.5128	1.7449	0.564*
H23C	0.3769	0.6108	1.6910	0.564*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Pd1	0.0805 (3)	0.0726 (3)	0.0607 (2)	−0.0011 (3)	0.0158 (2)	0.0009 (2)
S1	0.1121 (10)	0.0856 (8)	0.0662 (6)	0.0168 (7)	0.0112 (6)	−0.0039 (5)
S2	0.1229 (11)	0.0881 (8)	0.0727 (7)	0.0259 (8)	0.0146 (6)	−0.0007 (6)
N1	0.073 (2)	0.070 (2)	0.0635 (17)	−0.002 (2)	0.0132 (15)	−0.0026 (17)
N2	0.083 (3)	0.071 (2)	0.0651 (19)	0.008 (2)	0.0174 (17)	0.0033 (17)
C1	0.079 (3)	0.072 (3)	0.071 (2)	−0.001 (2)	0.018 (2)	0.003 (2)
C2	0.097 (4)	0.099 (3)	0.081 (3)	0.016 (3)	0.015 (2)	0.004 (2)
C3	0.111 (5)	0.095 (4)	0.092 (3)	0.023 (4)	0.019 (3)	−0.001 (3)
C4	0.110 (6)	0.146 (6)	0.335 (10)	0.031 (5)	0.044 (7)	0.049 (6)
C5	0.136 (8)	0.200 (9)	0.347 (12)	−0.003 (7)	0.059 (8)	0.010 (8)
C6	0.177 (10)	0.243 (11)	0.195 (9)	0.072 (8)	−0.022 (7)	0.033 (8)
C7	0.324 (15)	0.238 (11)	0.177 (7)	0.169 (11)	0.117 (8)	0.088 (6)
C8	0.246 (9)	0.193 (7)	0.151 (5)	0.136 (6)	0.103 (5)	0.078 (5)
C9	0.076 (3)	0.074 (2)	0.069 (2)	0.004 (2)	0.014 (2)	0.004 (2)
C10	0.083 (3)	0.078 (3)	0.063 (2)	−0.001 (2)	0.017 (2)	−0.005 (2)
C11	0.105 (3)	0.101 (3)	0.065 (2)	0.011 (3)	0.016 (2)	−0.005 (2)
C12	0.114 (4)	0.104 (3)	0.061 (2)	0.011 (3)	0.004 (2)	0.000 (3)
C13	0.121 (4)	0.095 (4)	0.063 (3)	−0.014 (3)	0.022 (3)	−0.017 (3)
C14	0.143 (5)	0.086 (3)	0.079 (3)	0.010 (3)	0.022 (3)	−0.017 (3)
C15	0.115 (4)	0.093 (3)	0.076 (3)	0.012 (3)	0.020 (3)	−0.009 (2)
O1	0.116 (6)	0.114 (6)	0.051 (4)	0.022 (5)	−0.002 (4)	−0.025 (3)
C16	0.145 (9)	0.098 (7)	0.075 (5)	0.009 (6)	0.009 (5)	−0.025 (5)
C17	0.205 (12)	0.166 (10)	0.119 (8)	−0.037 (9)	0.074 (8)	−0.054 (7)
C18	0.257 (16)	0.230 (14)	0.115 (9)	−0.125 (12)	0.069 (10)	−0.077 (9)
C19	0.222 (8)	0.264 (9)	0.170 (7)	−0.022 (7)	−0.013 (6)	−0.025 (7)
C19A	0.222 (8)	0.264 (9)	0.170 (7)	−0.022 (7)	−0.013 (6)	−0.025 (7)
C20	0.328 (14)	0.224 (10)	0.305 (12)	−0.063 (10)	0.124 (11)	−0.014 (10)
C21	0.291 (15)	0.301 (16)	0.393 (19)	−0.080 (12)	−0.167 (14)	0.053 (13)
C22	0.210 (15)	0.49 (3)	0.47 (3)	−0.066 (18)	0.064 (17)	−0.14 (2)
C23	0.319 (17)	0.45 (2)	0.295 (15)	−0.132 (14)	−0.066 (12)	0.067 (14)

Geometric parameters (Å, º)

Pd1—N1^i	2.034 (3)	C14—H14	0.9300
Pd1—N1	2.034 (3)	C15—H15	0.9300
Pd1—S1^i	2.2825 (11)	O1—C16	1.442 (11)
Pd1—S1	2.2825 (11)	C16—C17	1.572 (11)
S1—C1	1.732 (4)	C16—H16A	0.9700
S2—C1	1.743 (4)	C16—H16B	0.9700
S2—C2	1.794 (4)	C17—C18	1.447 (14)
N1—C9	1.312 (4)	C17—H17A	0.9700
N1—N2	1.396 (4)	C17—H17B	0.9700
N2—C1	1.287 (4)	C18—C19	1.568 (13)
C2—C3	1.499 (6)	C18—H18A	0.9700
C2—H2A	0.9700	C18—H18B	0.9700
C2—H2B	0.9700	C19—C20	1.376 (9)
C3—C8	1.321 (7)	C19—H19A	0.9700
C3—C4	1.343 (8)	C19—H19B	0.9700
C4—C5	1.416 (9)	O1A—C16A	1.372 (14)
C4—H4	0.9300	C16A—C17A	1.619 (14)
C5—C6	1.310 (10)	C16A—H16C	0.9700
C5—H5	0.9300	C16A—H16D	0.9700
C6—C7	1.353 (11)	C17A—C18A	1.516 (18)
C6—H6	0.9300	C17A—H17C	0.9700
C7—C8	1.434 (10)	C17A—H17D	0.9700
C7—H7	0.9300	C18A—H18C	0.9700
C8—H8	0.9300	C18A—H18D	0.9700
C9—C10	1.440 (5)	C20—C21	1.465 (13)
C9—H9	0.9300	C20—H20A	0.9700
C10—C15	1.382 (5)	C20—H20B	0.9700
C10—C11	1.387 (5)	C21—C22	1.495 (16)
C11—C12	1.368 (5)	C21—H21A	0.9700
C11—H11	0.9300	C21—H21B	0.9700
C12—C13	1.363 (5)	C22—C23	1.359 (13)
C12—H12	0.9300	C22—H22A	0.9700
C13—C14	1.382 (6)	C22—H22B	0.9700
C13—O1	1.383 (8)	C23—H23A	0.9600
C13—O1A	1.405 (14)	C23—H23B	0.9600
C14—C15	1.372 (5)	C23—H23C	0.9600
N1^i—Pd1—N1	180.0	C14—C15—H15	118.7
N1^i—Pd1—S1^i	83.08 (10)	C10—C15—H15	118.7
N1—Pd1—S1^i	96.92 (10)	C13—O1—C16	115.7 (7)
N1^i—Pd1—S1	96.92 (10)	O1—C16—C17	104.6 (7)
N1—Pd1—S1	83.08 (10)	O1—C16—H16A	110.8
S1^i—Pd1—S1	180.0	C17—C16—H16A	110.8
C1—S1—Pd1	96.01 (13)	O1—C16—H16B	110.8
C1—S2—C2	103.20 (19)	C17—C16—H16B	110.8
C9—N1—N2	114.5 (3)	H16A—C16—H16B	108.9
C9—N1—Pd1	124.3 (3)	C18—C17—C16	117.8 (12)
N2—N1—Pd1	121.1 (2)	C18—C17—H17A	107.9
C1—N2—N1	113.1 (3)	C16—C17—H17A	107.9
N2—C1—S1	126.5 (3)	C18—C17—H17B	107.9
N2—C1—S2	120.2 (3)	C16—C17—H17B	107.9
S1—C1—S2	113.3 (2)	H17A—C17—H17B	107.2
C3—C2—S2	110.4 (3)	C17—C18—C19	115.7 (12)
C3—C2—H2A	109.6	C17—C18—H18A	108.3
S2—C2—H2A	109.6	C19—C18—H18A	108.3
C3—C2—H2B	109.6	C17—C18—H18B	108.3
S2—C2—H2B	109.6	C19—C18—H18B	108.3
H2A—C2—H2B	108.1	H18A—C18—H18B	107.4
C8—C3—C4	119.0 (6)	C20—C19—C18	123.6 (11)
C8—C3—C2	121.4 (6)	C20—C19—H19A	106.4
C4—C3—C2	119.6 (6)	C18—C19—H19A	106.4
C3—C4—C5	122.1 (8)	C20—C19—H19B	106.4
C3—C4—H4	118.9	C18—C19—H19B	106.4
C5—C4—H4	118.9	H19A—C19—H19B	106.5
C6—C5—C4	114.7 (10)	C16A—O1A—C13	108.5 (11)
C6—C5—H5	122.7	O1A—C16A—C17A	101.9 (10)
C4—C5—H5	122.7	O1A—C16A—H16C	111.4
C5—C6—C7	127.2 (12)	C17A—C16A—H16C	111.4
C5—C6—H6	116.4	O1A—C16A—H16D	111.4
C7—C6—H6	116.4	C17A—C16A—H16D	111.4
C6—C7—C8	113.2 (9)	H16C—C16A—H16D	109.2
C6—C7—H7	123.4	C18A—C17A—C16A	99.0 (11)
C8—C7—H7	123.4	C18A—C17A—H17C	112.0
C3—C8—C7	122.5 (7)	C16A—C17A—H17C	112.0
C3—C8—H8	118.8	C18A—C17A—H17D	112.0
C7—C8—H8	118.8	C16A—C17A—H17D	112.0
N1—C9—C10	133.4 (4)	H17C—C17A—H17D	109.7
N1—C9—H9	113.3	C17A—C18A—H18C	111.2
C10—C9—H9	113.3	C17A—C18A—H18D	111.2
C15—C10—C11	116.7 (3)	H18C—C18A—H18D	109.1
C15—C10—C9	115.6 (4)	C19—C20—C21	120.3 (11)
C11—C10—C9	127.7 (4)	C19—C20—H20A	107.2
C12—C11—C10	121.1 (4)	C21—C20—H20A	107.2
C12—C11—H11	119.4	C19—C20—H20B	107.2
C10—C11—H11	119.4	C21—C20—H20B	107.2
C13—C12—C11	121.1 (4)	H20A—C20—H20B	106.9
C13—C12—H12	119.4	C20—C21—C22	108.3 (14)
C11—C12—H12	119.4	C20—C21—H21A	110.0
C12—C13—C14	119.3 (4)	C22—C21—H21A	110.0
C12—C13—O1	111.1 (5)	C20—C21—H21B	110.0
C14—C13—O1	129.6 (5)	C22—C21—H21B	110.0
C12—C13—O1A	136.6 (6)	H21A—C21—H21B	108.4
C14—C13—O1A	103.7 (6)	C23—C22—C21	100.8 (17)
O1—C13—O1A	27.2 (5)	C23—C22—H22A	111.6
C15—C14—C13	119.1 (4)	C21—C22—H22A	111.6
C15—C14—H14	120.5	C23—C22—H22B	111.6
C13—C14—H14	120.5	C21—C22—H22B	111.6
C14—C15—C10	122.6 (4)	H22A—C22—H22B	109.4
N1^i—Pd1—S1—C1	177.41 (15)	N1—C9—C10—C15	175.4 (4)
N1—Pd1—S1—C1	−2.59 (15)	N1—C9—C10—C11	−5.4 (7)
S1^i—Pd1—S1—C1	−123 (18)	C15—C10—C11—C12	−2.0 (6)
N1^i—Pd1—N1—C9	175 (100)	C9—C10—C11—C12	178.8 (4)
S1^i—Pd1—N1—C9	2.9 (3)	C10—C11—C12—C13	−0.1 (7)
S1—Pd1—N1—C9	−177.1 (3)	C11—C12—C13—C14	2.7 (7)
N1^i—Pd1—N1—N2	−5 (100)	C11—C12—C13—O1	−174.2 (5)
S1^i—Pd1—N1—N2	−176.4 (2)	C11—C12—C13—O1A	174.4 (10)
S1—Pd1—N1—N2	3.6 (2)	C12—C13—C14—C15	−3.1 (7)
C9—N1—N2—C1	177.5 (3)	O1—C13—C14—C15	173.0 (6)
Pd1—N1—N2—C1	−3.1 (4)	O1A—C13—C14—C15	−177.3 (7)
N1—N2—C1—S1	0.0 (5)	C13—C14—C15—C10	1.1 (7)
N1—N2—C1—S2	179.9 (2)	C11—C10—C15—C14	1.5 (6)
Pd1—S1—C1—N2	2.3 (4)	C9—C10—C15—C14	−179.3 (4)
Pd1—S1—C1—S2	−177.53 (18)	C12—C13—O1—C16	176.7 (6)
C2—S2—C1—N2	−9.0 (4)	C14—C13—O1—C16	0.3 (10)
C2—S2—C1—S1	170.9 (2)	O1A—C13—O1—C16	−20.5 (15)
C1—S2—C2—C3	−160.0 (4)	C13—O1—C16—C17	−162.7 (8)
S2—C2—C3—C8	−103.1 (5)	O1—C16—C17—C18	−66.6 (14)
S2—C2—C3—C4	74.9 (6)	C16—C17—C18—C19	−168.8 (11)
C8—C3—C4—C5	−2.2 (12)	C17—C18—C19—C20	−173.5 (13)
C2—C3—C4—C5	179.7 (7)	C12—C13—O1A—C16A	11.8 (17)
C3—C4—C5—C6	−6.1 (14)	C14—C13—O1A—C16A	−175.6 (9)
C4—C5—C6—C7	14.0 (18)	O1—C13—O1A—C16A	−12.0 (11)
C5—C6—C7—C8	−12.3 (18)	C13—O1A—C16A—C17A	−178.6 (10)
C4—C3—C8—C7	4.0 (11)	O1A—C16A—C17A—C18A	−162.7 (17)
C2—C3—C8—C7	−178.0 (6)	C18—C19—C20—C21	−169.0 (15)
C6—C7—C8—C3	2.5 (14)	C19—C20—C21—C22	177.7 (13)
N2—N1—C9—C10	3.2 (6)	C20—C21—C22—C23	−172.1 (13)
Pd1—N1—C9—C10	−176.2 (3)

Symmetry code: (i) −x, −y+1, −z.