[3,3′-Dimesityl-1,1′-(4,5:16,17-dibenzo-3,6,9,12,15,18-hexa­oxaeicosane-1,20-di­yl)diimidazolin-2-yl­idene]dithio­cyanato­palladium(II)

Zhang, X.-Q.; Luo, M.-M.

doi:10.1107/S1600536809014615

metal-organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 65| Part 5| May 2009| Pages m568-m569

doi:10.1107/S1600536809014615

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[3,3′-Dimesityl-1,1′-(4,5:16,17-dibenzo-3,6,9,12,15,18-hexaoxaeicosane-1,20-diyl)diimidazolin-2-ylidene]dithiocyanatopalladium(II)

Xiao-Qin Zhang ^a and Mei-Ming Luo ^a ^*

^aKey Laboratory of Green Chemistry and Technology of the Ministry of Education, College of Chemistry, Sichuan University, Chengdu 610064, People's Republic of China
^*Correspondence e-mail: luomm@scu.edu.cn

(Received 13 April 2009; accepted 20 April 2009; online 25 April 2009)

The coordination geometry of the Pd atom in the title compound, [Pd(SCN)₂(C₄₆H₅₄N₄O₆)], is approximately square-planar. The N-heterocyclic carbene (NHC) metallacrown ether ligand binds to the Pd atom in a trans orientation through the carbene C atoms of the two imidazole rings and generates a 25-membered chelate ring. Two mutually trans S-bound thiocyanate ligands complete the coordination.

Related literature

For N-heterocyclic carbene ligands and their complexes, see: Herrmann (2002 ); Hahn & Jahnke (2008 ). For details of bis-phosphine polyether ligands, see: Alcock et al. (1976 ); Powell et al. (1981 ); Gray et al. (1995 ). For mixed NHC metallacrown ether ligands, see: Nielsen et al. (2003 ); Liu et al. (2007 ); Wang et al. (2005 ). For the use of Pd–NHC complexes in catalysis, see: Herrmann et al. (2002); Kantchev et al. (2007 ). For the synthesis of the ligand precursor, see: Pedersen (1967 ); Haque & Rasmussen (1994 ).

Experimental

Crystal data

[Pd(NCS)₂(C₄₆H₅₄N₄O₆)]
M_r = 981.49
Monoclinic, P 2₁ /n
a = 14.143 (5) Å
b = 19.803 (4) Å
c = 17.101 (3) Å
β = 97.13 (2)°
V = 4753 (2) Å³
Z = 4
Mo Kα radiation
μ = 0.53 mm⁻¹
T = 288 K
0.46 × 0.42 × 0.40 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: spherical (Farrugia, 1999 ) T_min = 0.927, T_max = 0.936
9805 measured reflections
8672 independent reflections
4983 reflections with I > 2σ(I)
R_int = 0.003
3 standard reflections every 300 reflections intensity decay: 1.2%

Refinement

R[F² > 2σ(F²)] = 0.066
wR(F²) = 0.218
S = 1.05
8672 reflections
566 parameters
61 restraints
H-atom parameters constrained
Δρ_max = 0.78 e Å⁻³
Δρ_min = −1.31 e Å⁻³

Table 1
Selected geometric parameters (Å, °)

Pd1—C1	2.040 (6)
Pd1—C35	2.041 (6)
Pd1—S2	2.3211 (18)
Pd1—S1	2.3237 (19)

C1—Pd1—C35	178.6 (3)
C1—Pd1—S2	85.12 (17)
C35—Pd1—S2	95.47 (19)
C1—Pd1—S1	94.03 (17)
C35—Pd1—S1	85.31 (19)
S2—Pd1—S1	176.52 (8)

Data collection: DIFRAC (Gabe et al., 1993 ); cell refinement: DIFRAC; data reduction: DIFRAC; 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: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809014615/sj2617sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809014615/sj2617Isup2.hkl

checkCIF report

Comment top

N-Heterocyclic carbene (NHC) ligands have been found to be interesting substitutes for phosphine ligands and are employed with considerable success in coordination chemistry and various catalytic transformations (Herrmann et al., 2002; Hahn & Jahnke, 2008). Much interest has been devoted to the chemistry of metallacrown ethers formed by the chelation of bis(phosphorus-donor)polyether ligands to transition metals for a number of years (Alcock et al.,1976; Powell et al., 1981; Gray, 1995). Studies on these metallacrown ethers have shown that they can bind hard metal cations and such hard–soft bimetallic complexes are of interest as catalysts for organic reactions. Substitution of phosphine donors by NHCs has led to several examples of mixed NHC metallacrown ether ligands (Nielsen et al., 2003; Liu et al., 2007; Wang et al., 2005). Pd–NHC complexes are known to catalyze a wide range of useful cross-coupling reactions (Herrmann, 2002; Kantchev et al., 2007). However, we were surprised that no Pd–NHC metallacrown ether complexes have been described to date and we present here the first synthesis and crystal structure of the title Pd–NHC metallacrown ether complex.

In the title compound (Fig. 1), a 25-membered Pd–NHC metallacrown ether complex adopting a trans-conformation is formed by a bidentate chelate bis(carbene) ligand with a long flexible linkage and a Pd(II). The coordination geometry at Pd is approximately square planar with the C1–Pd–C35 angle of 178.6 (3)° and the S1–Pd–S2 angle of 178.6 (3)°. The two benzene rings linked with ether oxygen atoms form a dihedral angle of 81.20°. The dihedral angle of the NHC rings is 39.38°.

Related literature top

For N-heterocyclic carbene ligands and their complexes, see: Herrmann (2002); Hahn & Jahnke (2008). For details of bis-phosphine polyether ligands, see: Alcock et al. (1976); Powell et al. (1981); Gray et al. (1995). For mixed NHC metallacrown ether ligands, see: Nielsen et al. (2003); Liu et al. (2007); Wang et al. (2005). For the use of Pd–NHC complexes in catalysis, see: Herrmann et al. (2002); Kantchev et al. (2007). For the synthesis of the ligand precursor, see: Pedersen (1967); Haque & Rasmussen (1994).

Experimental top

A mixture of 1,20-di(1-mesitylimidazolium)-4,5,16,17-dibenzo-3,6,9,12,15,18-hexaoxaeicosane dichloride (83.2 mg, 0.10 mmol) prepared by literature procedures (Pedersen, 1967; Haque & Rasmussen, 1994) and silver(I) oxide (27.6 mg, 0.12 mmol) in 5 ml of CH₂Cl₂ was stirred at room temperature for 2 h. The reaction mixture was filtered and washed with CH₂Cl₂(5 ml × 2). The combined filtrate was reduced to 5 ml under vacuum. [PdCl₂(MeCN)₂] (25.8 mg, 0.10 mmol) in CH₂Cl₂ (3 ml) was added to the resulting solution and stirred at room temperature for 2 h, then KSCN (97 mg, 1 mmol) was added and stirred over night. The reaction mixture was filtered and washed with CH₂Cl₂ (5 ml × 2). The combined solution was evaporated under reduced pressure to leave a raw product, which was purified by flash chromatography on silica gel (CH₂Cl₂) to give a yellow solid. Single crystals suitable for X-ray diffraction were obtained at ambient temperature by slow evaporation of an Et₂O solution over a period of several days.

Computing details top

Data collection: DIFRAC (Gabe et al., 1993); cell refinement: DIFRAC (Gabe et al., 1993); data reduction: DIFRAC (Gabe et al., 1989); 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: SHELXL97 (Sheldrick, 2008).

Figures top

Fig. 1. The molecular structure of the title compound with displacement ellipsoids drawn at the 30% probability level.

[3,3'-Dimesityl-1,1'-(4,5:16,17-dibenzo-3,6,9,12,15,18-hexaoxaeicosane-1,20- diyl)diimidazolin-2-ylidene]dithiocyanatopalladium(II) top

Crystal data top

[Pd(NCS)₂(C₄₆H₅₄N₄O₆)]	F(000) = 2040
M_r = 981.49	D_x = 1.372 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 40 reflections
a = 14.143 (5) Å	θ = 5.0–7.8°
b = 19.803 (4) Å	µ = 0.53 mm⁻¹
c = 17.101 (3) Å	T = 288 K
β = 97.13 (2)°	Block, colourless
V = 4753 (2) Å³	0.46 × 0.42 × 0.40 mm
Z = 4

Data collection top

Enraf–Nonius CAD-4 diffractometer	4983 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.003
Graphite monochromator	θ_max = 25.5°, θ_min = 1.8°
ω/2θ scans	h = −17→16
Absorption correction: for a sphere (Farrugia, 1999)	k = 0→24
T_min = 0.927, T_max = 0.936	l = −7→20
9805 measured reflections	3 standard reflections every 300 reflections
8672 independent reflections	intensity decay: 1.2%

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.066	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.218	H-atom parameters constrained
S = 1.05	w = 1/[σ²(F_o²) + (0.1301P)²] where P = (F_o² + 2F_c²)/3
8672 reflections	(Δ/σ)_max < 0.001
566 parameters	Δρ_max = 0.78 e Å⁻³
61 restraints	Δρ_min = −1.31 e Å⁻³

Crystal data top

[Pd(NCS)₂(C₄₆H₅₄N₄O₆)]	V = 4753 (2) Å³
M_r = 981.49	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 14.143 (5) Å	µ = 0.53 mm⁻¹
b = 19.803 (4) Å	T = 288 K
c = 17.101 (3) Å	0.46 × 0.42 × 0.40 mm
β = 97.13 (2)°

Data collection top

Enraf–Nonius CAD-4 diffractometer	4983 reflections with I > 2σ(I)
Absorption correction: for a sphere (Farrugia, 1999)	R_int = 0.003
T_min = 0.927, T_max = 0.936	3 standard reflections every 300 reflections
9805 measured reflections	intensity decay: 1.2%
8672 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.066	61 restraints
wR(F²) = 0.218	H-atom parameters constrained
S = 1.05	Δρ_max = 0.78 e Å⁻³
8672 reflections	Δρ_min = −1.31 e Å⁻³
566 parameters

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

	x	y	z	U_iso*/U_eq
Pd1	0.57564 (3)	0.29052 (2)	0.23443 (3)	0.04415 (19)
S1	0.64646 (14)	0.18450 (9)	0.24534 (15)	0.0721 (6)
S2	0.50579 (14)	0.39669 (9)	0.23181 (14)	0.0689 (6)
O1	0.7414 (3)	0.4138 (2)	0.4806 (3)	0.0610 (12)
O2	0.6397 (6)	0.4445 (3)	0.5970 (4)	0.122 (3)
O3	0.5875 (5)	0.3396 (5)	0.6878 (7)	0.162 (4)
O4	0.6080 (11)	0.2342 (6)	0.5779 (10)	0.215 (6)
O5	0.5559 (7)	0.1325 (5)	0.4902 (6)	0.159 (4)
O6	0.3911 (4)	0.1529 (3)	0.3957 (4)	0.0852 (17)
N1	0.7502 (4)	0.3790 (3)	0.2186 (3)	0.0541 (14)
N2	0.7516 (4)	0.3414 (3)	0.3370 (3)	0.0482 (13)
N3	0.4200 (4)	0.2032 (3)	0.1410 (3)	0.0505 (13)
N4	0.3804 (4)	0.2329 (3)	0.2526 (3)	0.0574 (14)
N5	0.8391 (6)	0.1955 (4)	0.3031 (7)	0.125 (4)
N6	0.3073 (6)	0.3895 (4)	0.2113 (5)	0.103 (3)
C1	0.7006 (4)	0.3409 (3)	0.2651 (4)	0.0461 (15)
C2	0.8339 (5)	0.4017 (4)	0.2629 (4)	0.066 (2)
H2	0.8808	0.4282	0.2446	0.079*
C3	0.8342 (5)	0.3784 (4)	0.3365 (4)	0.0634 (19)
H3	0.8809	0.3857	0.3790	0.076*
C4	0.7200 (5)	0.3999 (4)	0.1393 (4)	0.0546 (17)
C5	0.7266 (5)	0.3548 (4)	0.0775 (4)	0.064 (2)
C6	0.6955 (6)	0.3780 (5)	0.0023 (5)	0.077 (2)
H6	0.7016	0.3494	−0.0400	0.093*
C7	0.6575 (7)	0.4386 (6)	−0.0131 (6)	0.092 (3)
C8	0.6537 (7)	0.4832 (5)	0.0501 (6)	0.090 (3)
H8	0.6293	0.5264	0.0403	0.108*
C9	0.6852 (5)	0.4645 (4)	0.1264 (5)	0.066 (2)
C10	0.6829 (7)	0.5139 (4)	0.1941 (6)	0.096 (3)
H10A	0.7457	0.5316	0.2091	0.144*
H10B	0.6616	0.4910	0.2382	0.144*
H10C	0.6401	0.5502	0.1778	0.144*
C11	0.6202 (10)	0.4598 (7)	−0.0983 (6)	0.158 (6)
H11A	0.6583	0.4389	−0.1342	0.237*
H11B	0.6239	0.5080	−0.1030	0.237*
H11C	0.5551	0.4457	−0.1106	0.237*
C12	0.7657 (7)	0.2847 (4)	0.0895 (5)	0.087 (3)
H12A	0.7997	0.2808	0.1415	0.131*
H12B	0.8083	0.2755	0.0512	0.131*
H12C	0.7143	0.2527	0.0834	0.131*
C13	0.7204 (5)	0.3113 (4)	0.4082 (4)	0.0572 (17)
H13A	0.7750	0.2935	0.4418	0.069*
H13B	0.6767	0.2744	0.3936	0.069*
C14	0.6710 (5)	0.3653 (4)	0.4527 (4)	0.0599 (18)
H14A	0.6202	0.3865	0.4179	0.072*
H14B	0.6438	0.3452	0.4965	0.072*
C15	0.7069 (5)	0.4784 (4)	0.4864 (5)	0.065 (2)
C16	0.6561 (7)	0.4964 (5)	0.5486 (6)	0.088 (3)
C17	0.6275 (9)	0.5624 (5)	0.5563 (6)	0.107 (4)
H17	0.5935	0.5749	0.5972	0.129*
C18	0.6500 (10)	0.6088 (5)	0.5031 (8)	0.121 (4)
H18	0.6318	0.6535	0.5088	0.145*
C19	0.6984 (8)	0.5921 (5)	0.4413 (7)	0.101 (3)
H19	0.7113	0.6246	0.4049	0.121*
C20	0.7274 (6)	0.5269 (4)	0.4341 (5)	0.077 (2)
H20	0.7616	0.5153	0.3930	0.092*
C21	0.5876 (13)	0.4567 (6)	0.6570 (8)	0.169 (7)
H21A	0.5407	0.4911	0.6399	0.203*
H21B	0.6298	0.4754	0.7007	0.203*
C22	0.5373 (10)	0.3984 (7)	0.6865 (8)	0.147 (6)
H22A	0.5233	0.4083	0.7394	0.176*
H22B	0.4771	0.3924	0.6533	0.176*
C23	0.5281 (11)	0.2759 (8)	0.6820 (15)	0.217 (8)
H23A	0.4685	0.2861	0.6498	0.261*
H23B	0.5128	0.2656	0.7345	0.261*
C24	0.5684 (16)	0.2106 (8)	0.6487 (11)	0.204 (8)
H24A	0.6176	0.1908	0.6864	0.245*
H24B	0.5184	0.1775	0.6353	0.245*
C25	0.6713 (14)	0.1847 (9)	0.5687 (13)	0.204 (8)
H25A	0.6986	0.1710	0.6211	0.245*
H25B	0.7224	0.2051	0.5440	0.245*
C26	0.6442 (11)	0.1235 (9)	0.5252 (12)	0.189 (7)
H26A	0.6871	0.1151	0.4862	0.227*
H26B	0.6467	0.0851	0.5607	0.227*
C27	0.5279 (6)	0.0829 (5)	0.4391 (5)	0.123 (4)
C28	0.4429 (5)	0.0943 (3)	0.3907 (4)	0.084 (3)
C29	0.4052 (6)	0.0443 (5)	0.3388 (4)	0.116 (4)
H29	0.3483	0.0519	0.3065	0.139*
C30	0.4524 (9)	−0.0169 (4)	0.3353 (5)	0.157 (7)
H30	0.4272	−0.0503	0.3006	0.189*
C31	0.5374 (9)	−0.0283 (4)	0.3836 (7)	0.196 (10)
H31	0.5690	−0.0692	0.3813	0.235*
C32	0.5751 (5)	0.0217 (6)	0.4355 (6)	0.172 (8)
H32	0.6320	0.0141	0.4679	0.206*
C33	0.4426 (6)	0.2152 (4)	0.3916 (5)	0.077 (2)
H33A	0.5048	0.2066	0.3753	0.092*
H33B	0.4514	0.2369	0.4428	0.092*
C34	0.3849 (6)	0.2597 (4)	0.3325 (4)	0.068 (2)
H34A	0.3208	0.2639	0.3465	0.082*
H34B	0.4130	0.3044	0.3341	0.082*
C35	0.4510 (4)	0.2390 (3)	0.2064 (4)	0.0489 (15)
C36	0.3311 (5)	0.1766 (4)	0.1479 (5)	0.072 (2)
H36	0.2948	0.1501	0.1106	0.086*
C37	0.3067 (5)	0.1957 (4)	0.2169 (5)	0.073 (2)
H37	0.2501	0.1856	0.2369	0.088*
C38	0.4700 (5)	0.1907 (4)	0.0744 (4)	0.0552 (17)
C39	0.5038 (5)	0.1248 (4)	0.0659 (5)	0.070 (2)
C40	0.5501 (6)	0.1117 (6)	0.0002 (6)	0.093 (3)
H40	0.5730	0.0685	−0.0070	0.111*
C41	0.5629 (6)	0.1605 (7)	−0.0543 (6)	0.096 (3)
C42	0.5268 (6)	0.2250 (5)	−0.0448 (5)	0.078 (3)
H42	0.5340	0.2580	−0.0823	0.094*
C43	0.4801 (5)	0.2409 (4)	0.0200 (5)	0.069 (2)
C44	0.4422 (7)	0.3107 (4)	0.0287 (5)	0.083 (2)
H44A	0.3959	0.3101	0.0653	0.124*
H44B	0.4128	0.3266	−0.0216	0.124*
H44C	0.4936	0.3404	0.0479	0.124*
C45	0.6116 (8)	0.1436 (8)	−0.1273 (7)	0.148 (5)
H45A	0.6633	0.1129	−0.1129	0.222*
H45B	0.6357	0.1843	−0.1480	0.222*
H45C	0.5662	0.1231	−0.1666	0.222*
C46	0.4916 (7)	0.0701 (4)	0.1243 (6)	0.096 (3)
H46A	0.4261	0.0561	0.1188	0.143*
H46B	0.5097	0.0868	0.1767	0.143*
H46C	0.5311	0.0323	0.1148	0.143*
C47	0.7609 (6)	0.1926 (4)	0.2804 (6)	0.072 (2)
C48	0.3883 (6)	0.3909 (4)	0.2185 (6)	0.077 (2)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Pd1	0.0448 (3)	0.0386 (3)	0.0478 (3)	0.0031 (2)	0.0011 (2)	−0.0046 (2)
S1	0.0625 (11)	0.0423 (9)	0.1069 (17)	0.0070 (9)	−0.0080 (11)	−0.0124 (11)
S2	0.0598 (11)	0.0452 (10)	0.0998 (16)	0.0093 (8)	0.0020 (11)	−0.0054 (10)
O1	0.061 (3)	0.060 (3)	0.058 (3)	0.003 (2)	−0.007 (2)	−0.014 (2)
O2	0.202 (8)	0.081 (5)	0.097 (5)	0.047 (5)	0.074 (5)	0.003 (4)
O3	0.082 (5)	0.181 (9)	0.233 (10)	0.009 (6)	0.061 (6)	0.043 (8)
O4	0.212 (13)	0.141 (10)	0.275 (15)	−0.039 (9)	−0.034 (11)	0.012 (11)
O5	0.101 (6)	0.173 (9)	0.191 (10)	−0.005 (6)	−0.031 (6)	0.053 (8)
O6	0.079 (4)	0.089 (4)	0.090 (4)	−0.008 (3)	0.017 (3)	0.022 (3)
N1	0.053 (3)	0.058 (3)	0.053 (3)	−0.004 (3)	0.012 (3)	−0.003 (3)
N2	0.046 (3)	0.050 (3)	0.047 (3)	−0.002 (2)	0.000 (2)	−0.010 (3)
N3	0.052 (3)	0.050 (3)	0.045 (3)	−0.007 (3)	−0.011 (2)	−0.007 (3)
N4	0.048 (3)	0.069 (4)	0.054 (3)	0.000 (3)	0.004 (3)	−0.006 (3)
N5	0.073 (5)	0.075 (5)	0.215 (12)	0.017 (4)	−0.031 (6)	−0.011 (6)
N6	0.070 (5)	0.113 (7)	0.119 (7)	0.017 (5)	−0.014 (5)	−0.009 (5)
C1	0.052 (4)	0.036 (3)	0.050 (4)	0.004 (3)	0.004 (3)	−0.003 (3)
C2	0.044 (4)	0.091 (6)	0.061 (5)	−0.010 (4)	0.002 (3)	−0.006 (4)
C3	0.048 (4)	0.080 (5)	0.060 (5)	−0.003 (4)	−0.001 (3)	−0.012 (4)
C4	0.050 (4)	0.060 (4)	0.054 (4)	0.001 (3)	0.009 (3)	0.009 (3)
C5	0.065 (5)	0.073 (5)	0.057 (5)	0.012 (4)	0.017 (4)	0.000 (4)
C6	0.081 (6)	0.099 (7)	0.053 (5)	0.007 (5)	0.013 (4)	−0.001 (5)
C7	0.092 (7)	0.105 (8)	0.082 (6)	0.009 (6)	0.021 (5)	0.031 (6)
C8	0.092 (6)	0.077 (6)	0.105 (7)	0.013 (5)	0.026 (6)	0.044 (6)
C9	0.068 (5)	0.054 (4)	0.079 (5)	−0.004 (4)	0.017 (4)	0.014 (4)
C10	0.109 (7)	0.055 (5)	0.128 (8)	−0.004 (5)	0.027 (6)	−0.012 (5)
C11	0.170 (12)	0.215 (15)	0.088 (8)	0.022 (11)	0.016 (8)	0.083 (9)
C12	0.109 (7)	0.093 (6)	0.060 (5)	0.039 (5)	0.013 (5)	−0.014 (5)
C13	0.062 (4)	0.061 (4)	0.047 (4)	−0.004 (3)	0.004 (3)	−0.001 (3)
C14	0.065 (4)	0.065 (4)	0.050 (4)	−0.008 (4)	0.008 (3)	−0.002 (4)
C15	0.067 (5)	0.063 (5)	0.061 (5)	0.001 (4)	−0.008 (4)	−0.016 (4)
C16	0.109 (7)	0.078 (6)	0.077 (6)	0.021 (5)	0.013 (5)	−0.001 (5)
C17	0.167 (11)	0.059 (6)	0.097 (7)	0.024 (6)	0.021 (7)	−0.023 (5)
C18	0.162 (12)	0.064 (6)	0.133 (10)	0.014 (7)	0.000 (8)	−0.012 (7)
C19	0.125 (9)	0.061 (6)	0.114 (8)	−0.008 (6)	−0.002 (6)	0.011 (5)
C20	0.085 (6)	0.070 (5)	0.072 (5)	−0.012 (4)	−0.005 (5)	−0.002 (5)
C21	0.28 (2)	0.100 (9)	0.153 (12)	0.040 (11)	0.133 (13)	0.008 (9)
C22	0.132 (11)	0.205 (15)	0.105 (9)	0.057 (11)	0.020 (8)	−0.022 (10)
C23	0.116 (11)	0.191 (16)	0.35 (2)	−0.016 (12)	0.048 (14)	−0.012 (17)
C24	0.29 (2)	0.102 (11)	0.202 (16)	−0.047 (12)	−0.037 (14)	−0.038 (11)
C25	0.185 (16)	0.164 (15)	0.241 (19)	0.015 (14)	−0.060 (14)	0.056 (15)
C26	0.099 (10)	0.193 (16)	0.265 (19)	−0.028 (10)	−0.019 (11)	0.066 (15)
C27	0.087 (8)	0.135 (11)	0.149 (12)	0.011 (8)	0.022 (8)	0.062 (9)
C28	0.094 (7)	0.086 (6)	0.077 (6)	0.006 (5)	0.032 (5)	0.023 (5)
C29	0.171 (11)	0.093 (8)	0.091 (8)	−0.002 (8)	0.048 (8)	0.016 (7)
C30	0.27 (2)	0.095 (10)	0.124 (11)	0.002 (11)	0.109 (13)	0.016 (8)
C31	0.27 (2)	0.198 (19)	0.155 (15)	0.096 (17)	0.153 (16)	0.059 (14)
C32	0.151 (12)	0.198 (16)	0.188 (16)	0.093 (13)	0.101 (12)	0.088 (14)
C33	0.079 (5)	0.092 (6)	0.059 (5)	−0.005 (4)	0.006 (4)	0.004 (4)
C34	0.074 (5)	0.069 (5)	0.063 (5)	0.000 (4)	0.011 (4)	0.001 (4)
C35	0.046 (4)	0.047 (3)	0.051 (4)	0.002 (3)	−0.006 (3)	−0.005 (3)
C36	0.054 (4)	0.083 (6)	0.072 (6)	−0.016 (4)	−0.016 (4)	0.006 (5)
C37	0.045 (4)	0.095 (6)	0.079 (6)	−0.007 (4)	0.003 (4)	0.016 (5)
C38	0.044 (4)	0.066 (4)	0.052 (4)	−0.004 (3)	−0.004 (3)	−0.010 (3)
C39	0.060 (4)	0.067 (5)	0.077 (5)	−0.002 (4)	−0.011 (4)	−0.019 (4)
C40	0.072 (6)	0.105 (7)	0.097 (7)	0.010 (5)	−0.006 (5)	−0.046 (5)
C41	0.054 (5)	0.151 (10)	0.082 (7)	−0.010 (6)	0.002 (5)	−0.050 (6)
C42	0.070 (5)	0.113 (7)	0.049 (5)	−0.021 (5)	−0.002 (4)	−0.001 (5)
C43	0.062 (5)	0.076 (5)	0.069 (5)	−0.015 (4)	0.006 (4)	−0.013 (4)
C44	0.100 (6)	0.084 (5)	0.063 (5)	−0.004 (5)	0.004 (5)	0.007 (5)
C45	0.107 (8)	0.242 (16)	0.103 (9)	−0.004 (10)	0.042 (7)	−0.054 (10)
C46	0.111 (7)	0.058 (5)	0.111 (8)	0.004 (5)	−0.014 (6)	−0.013 (5)
C47	0.068 (5)	0.041 (4)	0.103 (7)	0.015 (4)	−0.003 (5)	−0.007 (4)
C48	0.063 (5)	0.057 (5)	0.112 (7)	0.020 (4)	0.009 (5)	−0.003 (5)

Geometric parameters (Å, º) top

Pd1—C1	2.040 (6)	C16—C17	1.379 (12)
Pd1—C35	2.041 (6)	C17—C18	1.358 (14)
Pd1—S2	2.3211 (18)	C17—H17	0.9300
Pd1—S1	2.3237 (19)	C18—C19	1.369 (15)
S1—C47	1.662 (9)	C18—H18	0.9300
S2—C48	1.653 (9)	C19—C20	1.364 (13)
O1—C15	1.377 (9)	C19—H19	0.9300
O1—C14	1.422 (8)	C20—H20	0.9300
O2—C21	1.357 (12)	C21—C22	1.477 (14)
O2—C16	1.359 (11)	C21—H21A	0.9700
O3—C22	1.362 (12)	C21—H21B	0.9700
O3—C23	1.513 (14)	C22—H22A	0.9700
O4—C25	1.350 (15)	C22—H22B	0.9700
O4—C24	1.472 (15)	C23—C24	1.549 (15)
O5—C26	1.329 (15)	C23—H23A	0.9700
O5—C27	1.341 (11)	C23—H23B	0.9700
O6—C28	1.381 (8)	C24—H24A	0.9700
O6—C33	1.439 (9)	C24—H24B	0.9700
N1—C1	1.354 (8)	C25—C26	1.449 (15)
N1—C2	1.398 (9)	C25—H25A	0.9700
N1—C4	1.431 (8)	C25—H25B	0.9700
N2—C1	1.347 (8)	C26—H26A	0.9700
N2—C3	1.379 (9)	C26—H26B	0.9700
N2—C13	1.472 (8)	C27—C28	1.3900
N3—C35	1.351 (8)	C27—C32	1.3900
N3—C36	1.381 (9)	C28—C29	1.3900
N3—C38	1.435 (8)	C29—C30	1.3900
N4—C35	1.355 (8)	C29—H29	0.9300
N4—C37	1.358 (9)	C30—C31	1.3900
N4—C34	1.459 (9)	C30—H30	0.9300
N5—C47	1.128 (10)	C31—C32	1.3900
N6—C48	1.137 (10)	C31—H31	0.9300
C2—C3	1.342 (10)	C32—H32	0.9300
C2—H2	0.9300	C33—C34	1.503 (10)
C3—H3	0.9300	C33—H33A	0.9700
C4—C9	1.379 (10)	C33—H33B	0.9700
C4—C5	1.395 (10)	C34—H34A	0.9700
C5—C6	1.384 (10)	C34—H34B	0.9700
C5—C12	1.501 (11)	C36—C37	1.325 (11)
C6—C7	1.330 (12)	C36—H36	0.9300
C6—H6	0.9300	C37—H37	0.9300
C7—C8	1.402 (14)	C38—C43	1.382 (11)
C7—C11	1.544 (13)	C38—C39	1.404 (10)
C8—C9	1.375 (12)	C39—C40	1.393 (12)
C8—H8	0.9300	C39—C46	1.498 (12)
C9—C10	1.520 (12)	C40—C41	1.369 (14)
C10—H10A	0.9600	C40—H40	0.9300
C10—H10B	0.9600	C41—C42	1.392 (14)
C10—H10C	0.9600	C41—C45	1.536 (13)
C11—H11A	0.9600	C42—C43	1.394 (11)
C11—H11B	0.9600	C42—H42	0.9300
C11—H11C	0.9600	C43—C44	1.498 (12)
C12—H12A	0.9600	C44—H44A	0.9600
C12—H12B	0.9600	C44—H44B	0.9600
C12—H12C	0.9600	C44—H44C	0.9600
C13—C14	1.530 (9)	C45—H45A	0.9600
C13—H13A	0.9700	C45—H45B	0.9600
C13—H13B	0.9700	C45—H45C	0.9600
C14—H14A	0.9700	C46—H46A	0.9600
C14—H14B	0.9700	C46—H46B	0.9600
C15—C20	1.367 (11)	C46—H46C	0.9600
C15—C16	1.402 (12)

C1—Pd1—C35	178.6 (3)	O3—C22—C21	113.7 (11)
C1—Pd1—S2	85.12 (17)	O3—C22—H22A	108.8
C35—Pd1—S2	95.47 (19)	C21—C22—H22A	108.8
C1—Pd1—S1	94.03 (17)	O3—C22—H22B	108.8
C35—Pd1—S1	85.31 (19)	C21—C22—H22B	108.8
S2—Pd1—S1	176.52 (8)	H22A—C22—H22B	107.7
C47—S1—Pd1	109.4 (3)	O3—C23—C24	119.6 (13)
C48—S2—Pd1	111.0 (3)	O3—C23—H23A	107.4
C15—O1—C14	114.3 (5)	C24—C23—H23A	107.4
C21—O2—C16	118.5 (8)	O3—C23—H23B	107.4
C22—O3—C23	115.4 (10)	C24—C23—H23B	107.4
C25—O4—C24	101.0 (16)	H23A—C23—H23B	107.0
C26—O5—C27	112.3 (13)	O4—C24—C23	103.4 (16)
C28—O6—C33	116.2 (6)	O4—C24—H24A	111.1
C1—N1—C2	109.1 (6)	C23—C24—H24A	111.1
C1—N1—C4	127.0 (6)	O4—C24—H24B	111.1
C2—N1—C4	123.6 (6)	C23—C24—H24B	111.1
C1—N2—C3	110.9 (6)	H24A—C24—H24B	109.0
C1—N2—C13	124.8 (5)	O4—C25—C26	122.0 (17)
C3—N2—C13	124.1 (6)	O4—C25—H25A	106.8
C35—N3—C36	109.6 (6)	C26—C25—H25A	106.8
C35—N3—C38	127.3 (5)	O4—C25—H25B	106.8
C36—N3—C38	123.0 (6)	C26—C25—H25B	106.8
C35—N4—C37	111.5 (6)	H25A—C25—H25B	106.7
C35—N4—C34	124.3 (6)	O5—C26—C25	107.0 (16)
C37—N4—C34	124.1 (6)	O5—C26—H26A	110.3
N2—C1—N1	105.9 (5)	C25—C26—H26A	110.3
N2—C1—Pd1	126.0 (5)	O5—C26—H26B	110.3
N1—C1—Pd1	128.1 (5)	C25—C26—H26B	110.3
C3—C2—N1	107.5 (6)	H26A—C26—H26B	108.6
C3—C2—H2	126.3	O5—C27—C28	115.7 (8)
N1—C2—H2	126.3	O5—C27—C32	124.2 (8)
C2—C3—N2	106.6 (6)	C28—C27—C32	120.0
C2—C3—H3	126.7	O6—C28—C29	118.2 (7)
N2—C3—H3	126.7	O6—C28—C27	121.7 (7)
C9—C4—C5	121.9 (7)	C29—C28—C27	120.0
C9—C4—N1	118.6 (7)	C28—C29—C30	120.0
C5—C4—N1	119.5 (6)	C28—C29—H29	120.0
C6—C5—C4	116.7 (7)	C30—C29—H29	120.0
C6—C5—C12	120.1 (7)	C29—C30—C31	120.0
C4—C5—C12	123.2 (7)	C29—C30—H30	120.0
C7—C6—C5	123.8 (9)	C31—C30—H30	120.0
C7—C6—H6	118.1	C30—C31—C32	120.0
C5—C6—H6	118.1	C30—C31—H31	120.0
C6—C7—C8	118.0 (9)	C32—C31—H31	120.0
C6—C7—C11	121.0 (11)	C31—C32—C27	120.0
C8—C7—C11	121.1 (10)	C31—C32—H32	120.0
C9—C8—C7	121.6 (8)	C27—C32—H32	120.0
C9—C8—H8	119.2	O6—C33—C34	107.4 (7)
C7—C8—H8	119.2	O6—C33—H33A	110.2
C8—C9—C4	118.0 (8)	C34—C33—H33A	110.2
C8—C9—C10	120.9 (8)	O6—C33—H33B	110.2
C4—C9—C10	121.1 (8)	C34—C33—H33B	110.2
C9—C10—H10A	109.5	H33A—C33—H33B	108.5
C9—C10—H10B	109.5	N4—C34—C33	111.9 (7)
H10A—C10—H10B	109.5	N4—C34—H34A	109.2
C9—C10—H10C	109.5	C33—C34—H34A	109.2
H10A—C10—H10C	109.5	N4—C34—H34B	109.2
H10B—C10—H10C	109.5	C33—C34—H34B	109.2
C7—C11—H11A	109.5	H34A—C34—H34B	107.9
C7—C11—H11B	109.5	N3—C35—N4	104.4 (5)
H11A—C11—H11B	109.5	N3—C35—Pd1	129.7 (5)
C7—C11—H11C	109.5	N4—C35—Pd1	125.9 (5)
H11A—C11—H11C	109.5	C37—C36—N3	107.9 (7)
H11B—C11—H11C	109.5	C37—C36—H36	126.0
C5—C12—H12A	109.5	N3—C36—H36	126.0
C5—C12—H12B	109.5	C36—C37—N4	106.6 (7)
H12A—C12—H12B	109.5	C36—C37—H37	126.7
C5—C12—H12C	109.5	N4—C37—H37	126.7
H12A—C12—H12C	109.5	C43—C38—C39	122.3 (7)
H12B—C12—H12C	109.5	C43—C38—N3	120.9 (7)
N2—C13—C14	109.3 (6)	C39—C38—N3	116.8 (7)
N2—C13—H13A	109.8	C40—C39—C38	117.1 (9)
C14—C13—H13A	109.8	C40—C39—C46	120.6 (8)
N2—C13—H13B	109.8	C38—C39—C46	122.3 (7)
C14—C13—H13B	109.8	C41—C40—C39	122.2 (9)
H13A—C13—H13B	108.3	C41—C40—H40	118.9
O1—C14—C13	107.1 (6)	C39—C40—H40	118.9
O1—C14—H14A	110.3	C40—C41—C42	119.1 (8)
C13—C14—H14A	110.3	C40—C41—C45	120.6 (12)
O1—C14—H14B	110.3	C42—C41—C45	120.1 (12)
C13—C14—H14B	110.3	C41—C42—C43	121.1 (9)
H14A—C14—H14B	108.5	C41—C42—H42	119.5
C20—C15—O1	120.0 (7)	C43—C42—H42	119.5
C20—C15—C16	119.1 (8)	C38—C43—C42	118.2 (8)
O1—C15—C16	120.7 (8)	C38—C43—C44	121.9 (7)
O2—C16—C17	125.7 (9)	C42—C43—C44	119.9 (8)
O2—C16—C15	114.4 (8)	C43—C44—H44A	109.5
C17—C16—C15	119.9 (9)	C43—C44—H44B	109.5
C18—C17—C16	118.7 (10)	H44A—C44—H44B	109.5
C18—C17—H17	120.6	C43—C44—H44C	109.5
C16—C17—H17	120.6	H44A—C44—H44C	109.5
C17—C18—C19	122.3 (10)	H44B—C44—H44C	109.5
C17—C18—H18	118.9	C41—C45—H45A	109.5
C19—C18—H18	118.9	C41—C45—H45B	109.5
C20—C19—C18	118.9 (10)	H45A—C45—H45B	109.5
C20—C19—H19	120.5	C41—C45—H45C	109.5
C18—C19—H19	120.5	H45A—C45—H45C	109.5
C19—C20—C15	121.0 (9)	H45B—C45—H45C	109.5
C19—C20—H20	119.5	C39—C46—H46A	109.5
C15—C20—H20	119.5	C39—C46—H46B	109.5
O2—C21—C22	116.6 (11)	H46A—C46—H46B	109.5
O2—C21—H21A	108.1	C39—C46—H46C	109.5
C22—C21—H21A	108.1	H46A—C46—H46C	109.5
O2—C21—H21B	108.1	H46B—C46—H46C	109.5
C22—C21—H21B	108.1	N5—C47—S1	177.2 (8)
H21A—C21—H21B	107.3	N6—C48—S2	176.9 (8)

Experimental details

Crystal data
Chemical formula	[Pd(NCS)₂(C₄₆H₅₄N₄O₆)]
M_r	981.49
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	288
a, b, c (Å)	14.143 (5), 19.803 (4), 17.101 (3)
β (°)	97.13 (2)
V (Å³)	4753 (2)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.53
Crystal size (mm)	0.46 × 0.42 × 0.40

Data collection
Diffractometer	Enraf–Nonius CAD-4 diffractometer
Absorption correction	For a sphere (Farrugia, 1999)
T_min, T_max	0.927, 0.936
No. of measured, independent and observed [I > 2σ(I)] reflections	9805, 8672, 4983
R_int	0.003
(sin θ/λ)_max (Å⁻¹)	0.606

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.066, 0.218, 1.05
No. of reflections	8672
No. of parameters	566
No. of restraints	61
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.78, −1.31

Computer programs: DIFRAC (Gabe et al., 1993), DIFRAC (Gabe et al., 1989), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997).

Selected geometric parameters (Å, º) top

Pd1—C1	2.040 (6)	Pd1—S2	2.3211 (18)
Pd1—C35	2.041 (6)	Pd1—S1	2.3237 (19)

C1—Pd1—C35	178.6 (3)	C1—Pd1—S1	94.03 (17)
C1—Pd1—S2	85.12 (17)	C35—Pd1—S1	85.31 (19)
C35—Pd1—S2	95.47 (19)	S2—Pd1—S1	176.52 (8)

Acknowledgements

Financial support for this work by the Natural Science Foundation of China is gratefully acknowledged.

References

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