Dipotassium tetra­kis­(thio­cyanato-κS)palladate(II)–(2,2′-bipyrimidine-κ2N1,N1′)bis­(thio­cyanato-κS)palladium(II) (1/2)

Ha, K.

doi:10.1107/S1600536812015383

metal-organic compounds

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ISSN: 2056-9890

Volume 68| Part 5| May 2012| Pages m616-m617

doi:10.1107/S1600536812015383

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Dipotassium tetrakis(thiocyanato-κS)palladate(II)–(2,2′-bipyrimidine-κ²N¹,N^1′)bis(thiocyanato-κS)palladium(II) (1/2)

Kwang Ha ^a ^*

^aSchool of Applied Chemical Engineering, The Research Institute of Catalysis, Chonnam National University, Gwangju 500-757, Republic of Korea
^*Correspondence e-mail: hakwang@chonnam.ac.kr

(Received 3 April 2012; accepted 8 April 2012; online 18 April 2012)

The asymmetric unit of the title compound, K₂[Pd(NCS)₄]·2[Pd(NCS)₂(C₈H₆N₄)], contains two crystallographically independent half-molecules of the anionic Pd^II complex, two K⁺ cations and two independent neutral Pd^II complexes; an inversion centre is located at the centroid of each anionic complex. In the anionic complexes, each Pd^II ion is four-coordinated in an almost regular square-planar environment by four S atoms from four SCN⁻ anions, and the PdS₄ unit is exactly planar. In the neutral complexes, the Pd^II ion has a slightly distorted square-planar coordination environment defined by two pyrimidine N atoms derived from a chelating 2,2′-bipyrimidine ligand and two mutually cis S atoms from two SCN⁻ anions. Both 2,2′-bipyrimidine ligands are almost planar [dihedral angle between the rings = 3.98 (16) and 4.57 (17)°] and also chelate to a potassium ion from their other two N atoms. In the crystal, the K⁺ ions interact with various S and N atoms of the ligands, forming a three-dimensional polymeric network, in which the shortest K⋯K contacts between the KN₇S polyhedra are 4.4389 (17) and 4.4966 (18) Å. Intra- and intermolecular C—H⋯S and C—H⋯N hydrogen bonds are also observed.

Related literature

For the crystal structure of K₂[Pd(SCN)₄], see: Mawby & Pringle (1972 ); Ha (2010 ).

Experimental

Crystal data

K₂[Pd(NCS)₄]·2[Pd(NCS)₂(C₈H₆N₄)]
M_r = 1178.38
Monoclinic, P 2₁ /c
a = 15.9625 (7) Å
b = 10.9700 (5) Å
c = 21.6801 (9) Å
β = 94.104 (1)°
V = 3786.6 (3) Å³
Z = 4
Mo Kα radiation
μ = 2.12 mm⁻¹
T = 200 K
0.28 × 0.24 × 0.18 mm

Data collection

Bruker SMART 1000 CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2000 ) T_min = 0.854, T_max = 1.000
22881 measured reflections
7371 independent reflections
5722 reflections with I > 2σ(I)
R_int = 0.030

Refinement

R[F² > 2σ(F²)] = 0.030
wR(F²) = 0.080
S = 1.08
7371 reflections
481 parameters
H-atom parameters constrained
Δρ_max = 0.65 e Å⁻³
Δρ_min = −0.59 e Å⁻³

Table 1
Selected bond lengths (Å)

Pd1—N1	2.074 (3)
Pd1—N4	2.070 (3)
Pd1—S1	2.2945 (11)
Pd1—S2	2.3077 (11)
Pd2—N7	2.059 (3)
Pd2—N10	2.069 (3)
Pd2—S3ⁱ	2.2958 (10)
Pd2—S4	2.2829 (11)
Pd3—S5	2.3388 (9)
Pd3—S6	2.3314 (9)
Pd4—S7	2.3157 (10)
Pd4—S8	2.3419 (10)
Symmetry code: (i) $[-x, y-{\script{1\over 2}}, -z-{\script{1\over 2}}]$ .

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C1—H1⋯S1	0.95	2.77	3.334 (4)	119
C1—H1⋯N11ⁱⁱ	0.95	2.45	3.134 (5)	128
C6—H6⋯S7ⁱⁱⁱ	0.95	2.76	3.457 (4)	131
C8—H8⋯S2	0.95	2.77	3.321 (4)	118
C11—H11⋯S3ⁱ	0.95	2.82	3.371 (4)	118
C11—H11⋯N6^iv	0.95	2.63	3.315 (5)	130
C13—H13⋯N15^v	0.95	2.61	3.376 (5)	138
C16—H16⋯S6ⁱⁱ	0.95	2.83	3.640 (4)	144
C18—H18⋯S4	0.95	2.71	3.276 (4)	119
Symmetry codes: (i) $[-x, y-{\script{1\over 2}}, -z-{\script{1\over 2}}]$ ; (ii) -x+1, -y+1, -z; (iii) x, y-1, z; (iv) -x, -y+1, -z; (v) -x, -y+2, -z.

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablock global. DOI: 10.1107/S1600536812015383/hb6728sup1.cif

checkCIF report

Comment top

The title compound, K₂[Pd(SCN)₄].2[Pd(SCN)₂(bpym)] (bpym = 2,2'-bipyrimidine), was unexpected obtained from the reaction of Na₂PdCl₄ with KSCN and bpym. The asymmetric unit contains two crystallographically independent half-molecules of the anionic Pd^II complex [Pd(SCN)₄]^2-, two K⁺ cations and two independent neutral Pd^II complexes [Pd(SCN)₂(bpym)]; an inversion centre is located at the centroid of each anionic complex (Fig. 1). The crystal structure of K₂[Pd(SCN)₄] has been investigated previously (Mawby & Pringle, 1972; Ha, 2010).

In the anionic complexes, each Pd^II ion is four-coordinated in an essentially square-planar environment by four S atoms from four SCN^- anions, and the PdS₄ unit is exactly planar. The two complexes are chemically identical, but slightly different in geometry. The Pd—S bond lengths are roughly equal [Pd—S: 2.3157 (10)–2.3419 (10) Å] (Table 1). The thiocyanato ligands are almost linear displaying S—C—N bond angles of 174.8 (4)°–178.1 (4)°, and the S atoms coordinate to the Pd atom with the nearly tetrahedral Pd—S—C bond angles of 106.57 (13)°–110.44 (13)°.

In the two neutral complexes, each Pd^II ion has a slightly distorted square-planar coordination environment defined by two pyrimidine N atoms derived from a chelating bpym ligand and two mutually cis S atoms from two SCN^- anions. The complexes are fairly different in geometry, because the coordination modes of the anions are significantly different. The two thiocyanato ligands are located on the same side of the PdS₂N₂ unit plane in the complex with Pd1, whereas in the other complex with Pd2, the ligands lie on the opposite sides of the PdS₂N₂ unit. But, the Pd—N and Pd—S bond lengths are nearly equivalent, respectively [Pd—N = 2.059 (3)–2.074 (3) Å; Pd—S = 2.2829 (11)–2.3077 (11) Å] (Table 1). The bpym ligands are slightly inclined to the least-squares plane of the PdS₂N₂ unit [maximum deviation = 0.090 (1) Å], making dihedral angles of 9.55 (9)° in the complex with Pd1 and 7.28 (7)° in the complex with Pd2.

In the crystal structure, the K⁺ ions interact with the various S and N atoms of the ligands with the distances of K···S = 3.6081 (13) Å and 3.6692 (13) Å, and K···N = 2.806 (3)–3.370 (5) Å, forming a three-dimensional polymeric network, and the short K···K contacts are present [4.4389 (17) Å and 4.4966 (18) Å]. Intra- and intramolecular C—H···S and C—H···N hydrogen bonds are also observed (Table 2).

Related literature top

For the crystal structure of K₂[Pd(SCN)₄], see: Mawby & Pringle (1972); Ha (2010).

Experimental top

To a solution of Na₂PdCl₄ (0.1478 g, 0.502 mmol) in MeOH (30 ml) were added KSCN (0.5358 g, 5.513 mmol) and 2,2'-bipyrimidine (0.0819 g, 0.518 mmol), and refluxed for 3 h. The formed precipitate was separated by filtration and washed with H₂O and acetone, and dried at 50 °C, to give a pale red powder (0.1095 g). Red blocks were obtained by slow evaporation from a CH₃CN solution.

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

Fig. 1. A structure detail of the title compound, with displacement ellipsoids drawn at the 30% probability level for non-H atoms. Unlabelled atoms are generated by the application of the inversion centres.

Dipotassium tetrakis(thiocyanato-κS)palladate(II)– (2,2'-bipyrimidine-κ²N¹,N^1')bis(thiocyanato- κS)palladium(II) (1/2) top

Crystal data top

K₂[Pd(NCS)₄]·2[Pd(NCS)₂(C₈H₆N₄)]	F(000) = 2288
M_r = 1178.38	D_x = 2.067 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 5010 reflections
a = 15.9625 (7) Å	θ = 2.5–26.0°
b = 10.9700 (5) Å	µ = 2.12 mm⁻¹
c = 21.6801 (9) Å	T = 200 K
β = 94.104 (1)°	Block, red
V = 3786.6 (3) Å³	0.28 × 0.24 × 0.18 mm
Z = 4

Data collection top

Bruker SMART 1000 CCD diffractometer	7371 independent reflections
Radiation source: fine-focus sealed tube	5722 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.030
ϕ and ω scans	θ_max = 26.0°, θ_min = 1.3°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −18→19
T_min = 0.854, T_max = 1.000	k = −12→13
22881 measured reflections	l = −25→26

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)] = 0.030	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.080	H-atom parameters constrained
S = 1.08	w = 1/[σ²(F_o²) + (0.0336P)² + 1.0988P] where P = (F_o² + 2F_c²)/3
7371 reflections	(Δ/σ)_max = 0.001
481 parameters	Δρ_max = 0.65 e Å⁻³
0 restraints	Δρ_min = −0.59 e Å⁻³

Crystal data top

K₂[Pd(NCS)₄]·2[Pd(NCS)₂(C₈H₆N₄)]	V = 3786.6 (3) Å³
M_r = 1178.38	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 15.9625 (7) Å	µ = 2.12 mm⁻¹
b = 10.9700 (5) Å	T = 200 K
c = 21.6801 (9) Å	0.28 × 0.24 × 0.18 mm
β = 94.104 (1)°

Data collection top

Bruker SMART 1000 CCD diffractometer	7371 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2000)	5722 reflections with I > 2σ(I)
T_min = 0.854, T_max = 1.000	R_int = 0.030
22881 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.030	0 restraints
wR(F²) = 0.080	H-atom parameters constrained
S = 1.08	Δρ_max = 0.65 e Å⁻³
7371 reflections	Δρ_min = −0.59 e Å⁻³
481 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	0.482313 (18)	0.51068 (2)	0.188694 (12)	0.03065 (9)
Pd2	−0.014348 (18)	−0.00967 (2)	−0.182524 (12)	0.02913 (8)
Pd3	0.5000	0.5000	0.0000	0.02538 (10)
Pd4	0.0000	1.0000	0.0000	0.02620 (10)
K1	0.42675 (5)	0.96456 (8)	0.08137 (4)	0.0397 (2)
K2	0.09465 (6)	0.52691 (8)	−0.07076 (4)	0.0426 (2)
S1	0.59836 (7)	0.62463 (10)	0.21959 (5)	0.0483 (3)
S2	0.39550 (7)	0.62960 (10)	0.24449 (5)	0.0498 (3)
S3	0.13902 (6)	0.40429 (9)	−0.28031 (5)	0.0412 (2)
S4	0.05796 (7)	−0.17773 (10)	−0.21091 (5)	0.0515 (3)
S5	0.41359 (6)	0.64489 (9)	0.04273 (5)	0.0376 (2)
S6	0.61598 (6)	0.62728 (9)	0.01879 (5)	0.0396 (2)
S7	0.11212 (6)	1.12966 (9)	0.02391 (5)	0.0448 (3)
S8	0.09601 (6)	0.84561 (9)	−0.01933 (5)	0.0405 (2)
N1	0.55052 (17)	0.3754 (2)	0.14802 (12)	0.0263 (6)
N2	0.53434 (18)	0.1777 (3)	0.10408 (12)	0.0312 (7)
N3	0.36456 (18)	0.1932 (3)	0.11846 (13)	0.0330 (7)
N4	0.38671 (18)	0.3913 (3)	0.16051 (12)	0.0302 (7)
N5	0.5592 (2)	0.8652 (3)	0.18054 (17)	0.0528 (9)
N6	0.3527 (2)	0.8499 (4)	0.18235 (19)	0.0607 (11)
N7	−0.06619 (17)	0.1506 (3)	−0.15385 (12)	0.0280 (6)
N8	−0.02642 (18)	0.3475 (3)	−0.11603 (13)	0.0347 (7)
N9	0.13917 (19)	0.2811 (3)	−0.12042 (14)	0.0381 (8)
N10	0.09353 (18)	0.0838 (3)	−0.15250 (13)	0.0320 (7)
N11	0.17991 (19)	0.5602 (3)	−0.17926 (16)	0.0460 (9)
N12	−0.0430 (3)	−0.3800 (4)	−0.1863 (2)	0.0694 (12)
N13	0.2462 (2)	0.5816 (3)	0.00536 (17)	0.0509 (9)
N14	0.5701 (2)	0.8743 (3)	0.02917 (15)	0.0427 (8)
N15	0.0555 (2)	1.3726 (3)	0.03105 (16)	0.0469 (9)
N16	0.2599 (2)	0.9214 (3)	0.02070 (17)	0.0516 (9)
C1	0.6330 (2)	0.3698 (4)	0.14158 (16)	0.0353 (9)
H1	0.6675	0.4368	0.1549	0.042*
C2	0.6693 (2)	0.2698 (3)	0.11627 (16)	0.0355 (9)
H2	0.7280	0.2661	0.1118	0.043*
C3	0.6171 (2)	0.1759 (4)	0.09784 (16)	0.0372 (9)
H3	0.6407	0.1062	0.0798	0.045*
C4	0.5048 (2)	0.2778 (3)	0.12903 (14)	0.0268 (8)
C5	0.4131 (2)	0.2861 (3)	0.13633 (14)	0.0272 (8)
C6	0.2825 (2)	0.2081 (4)	0.12340 (17)	0.0402 (10)
H6	0.2458	0.1427	0.1117	0.048*
C7	0.2488 (2)	0.3139 (4)	0.14461 (18)	0.0441 (10)
H7	0.1899	0.3243	0.1459	0.053*
C8	0.3038 (2)	0.4030 (4)	0.16362 (17)	0.0398 (9)
H8	0.2825	0.4764	0.1797	0.048*
C9	0.5728 (2)	0.7657 (4)	0.19553 (18)	0.0411 (10)
C10	0.3729 (2)	0.7573 (4)	0.20423 (18)	0.0405 (10)
C11	−0.1472 (2)	0.1804 (3)	−0.15213 (16)	0.0329 (8)
H11	−0.1894	0.1226	−0.1647	0.039*
C12	−0.1702 (2)	0.2942 (3)	−0.13225 (16)	0.0370 (9)
H12	−0.2277	0.3157	−0.1307	0.044*
C13	−0.1075 (2)	0.3756 (3)	−0.11476 (17)	0.0378 (9)
H13	−0.1225	0.4546	−0.1013	0.045*
C14	−0.0094 (2)	0.2372 (3)	−0.13530 (15)	0.0293 (8)
C15	0.0802 (2)	0.2000 (3)	−0.13587 (15)	0.0309 (8)
C16	0.2179 (2)	0.2413 (4)	−0.12183 (19)	0.0487 (11)
H16	0.2624	0.2973	−0.1126	0.058*
C17	0.2379 (3)	0.1234 (4)	−0.1360 (2)	0.0517 (11)
H17	0.2946	0.0969	−0.1352	0.062*
C18	0.1730 (2)	0.0461 (4)	−0.15129 (19)	0.0445 (10)
H18	0.1846	−0.0363	−0.1613	0.053*
C19	0.1617 (2)	0.4984 (3)	−0.22118 (18)	0.0342 (9)
C20	−0.0035 (3)	−0.2959 (4)	−0.19531 (18)	0.0452 (10)
C21	0.3143 (2)	0.6055 (3)	0.02093 (17)	0.0379 (9)
C22	0.5851 (2)	0.7726 (4)	0.02536 (16)	0.0328 (8)
C23	0.0761 (2)	1.2729 (4)	0.02831 (17)	0.0362 (9)
C24	0.1932 (2)	0.8932 (3)	0.00439 (17)	0.0373 (9)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Pd1	0.03478 (17)	0.02747 (16)	0.02909 (15)	−0.00023 (12)	−0.00199 (12)	−0.00338 (12)
Pd2	0.03272 (16)	0.02533 (16)	0.02903 (15)	−0.00017 (12)	0.00016 (12)	−0.00167 (12)
Pd3	0.0290 (2)	0.0225 (2)	0.02406 (19)	0.00083 (15)	−0.00188 (15)	0.00014 (15)
Pd4	0.0283 (2)	0.0216 (2)	0.0280 (2)	−0.00027 (15)	−0.00313 (16)	0.00051 (16)
K1	0.0359 (5)	0.0320 (5)	0.0517 (5)	−0.0038 (4)	0.0055 (4)	−0.0031 (4)
K2	0.0389 (5)	0.0381 (5)	0.0512 (5)	−0.0072 (4)	0.0072 (4)	−0.0074 (4)
S1	0.0455 (6)	0.0389 (6)	0.0580 (7)	−0.0035 (5)	−0.0140 (5)	−0.0123 (5)
S2	0.0631 (7)	0.0439 (6)	0.0430 (6)	0.0079 (5)	0.0090 (5)	−0.0079 (5)
S3	0.0449 (6)	0.0334 (6)	0.0442 (6)	0.0121 (4)	−0.0041 (5)	−0.0023 (5)
S4	0.0507 (7)	0.0383 (6)	0.0668 (7)	0.0042 (5)	0.0134 (6)	−0.0161 (6)
S5	0.0363 (5)	0.0318 (5)	0.0449 (5)	0.0030 (4)	0.0035 (4)	−0.0079 (4)
S6	0.0338 (5)	0.0279 (5)	0.0558 (6)	−0.0010 (4)	−0.0051 (5)	−0.0041 (5)
S7	0.0336 (6)	0.0276 (5)	0.0713 (7)	−0.0023 (4)	−0.0106 (5)	−0.0040 (5)
S8	0.0338 (5)	0.0302 (5)	0.0568 (6)	0.0030 (4)	−0.0014 (5)	−0.0082 (5)
N1	0.0283 (16)	0.0246 (16)	0.0259 (14)	−0.0013 (12)	0.0002 (12)	−0.0035 (12)
N2	0.0306 (17)	0.0335 (18)	0.0294 (15)	−0.0005 (13)	0.0008 (13)	−0.0028 (14)
N3	0.0296 (17)	0.0369 (18)	0.0322 (16)	−0.0059 (14)	−0.0009 (13)	−0.0015 (14)
N4	0.0325 (17)	0.0305 (17)	0.0273 (15)	0.0023 (13)	0.0005 (13)	0.0041 (13)
N5	0.050 (2)	0.047 (2)	0.061 (2)	−0.0081 (19)	0.0080 (18)	−0.003 (2)
N6	0.035 (2)	0.054 (3)	0.092 (3)	−0.0003 (18)	−0.0020 (19)	0.028 (2)
N7	0.0288 (16)	0.0247 (16)	0.0302 (15)	−0.0014 (12)	−0.0001 (13)	0.0008 (13)
N8	0.0339 (18)	0.0308 (18)	0.0386 (17)	−0.0005 (14)	−0.0028 (14)	−0.0057 (14)
N9	0.0316 (18)	0.0382 (19)	0.0435 (18)	−0.0095 (15)	−0.0049 (14)	0.0035 (15)
N10	0.0316 (17)	0.0307 (18)	0.0333 (16)	−0.0012 (13)	0.0003 (13)	0.0021 (14)
N11	0.0307 (19)	0.051 (2)	0.055 (2)	0.0003 (16)	−0.0048 (16)	−0.0065 (19)
N12	0.079 (3)	0.041 (2)	0.092 (3)	0.017 (2)	0.035 (2)	0.011 (2)
N13	0.036 (2)	0.046 (2)	0.072 (2)	0.0018 (17)	0.0105 (18)	−0.0076 (19)
N14	0.046 (2)	0.034 (2)	0.0476 (19)	−0.0019 (16)	0.0009 (16)	−0.0057 (16)
N15	0.049 (2)	0.030 (2)	0.061 (2)	−0.0015 (16)	−0.0027 (17)	−0.0088 (17)
N16	0.032 (2)	0.045 (2)	0.078 (3)	0.0001 (16)	0.0049 (18)	−0.001 (2)
C1	0.031 (2)	0.040 (2)	0.034 (2)	−0.0060 (17)	−0.0021 (16)	0.0059 (17)
C2	0.030 (2)	0.042 (2)	0.034 (2)	0.0014 (17)	0.0050 (16)	0.0010 (18)
C3	0.033 (2)	0.042 (2)	0.037 (2)	0.0028 (18)	0.0042 (17)	−0.0032 (18)
C4	0.0296 (19)	0.030 (2)	0.0202 (17)	−0.0024 (15)	−0.0009 (14)	0.0026 (15)
C5	0.0303 (19)	0.030 (2)	0.0211 (17)	−0.0024 (16)	−0.0013 (14)	0.0025 (15)
C6	0.031 (2)	0.047 (3)	0.042 (2)	−0.0082 (18)	−0.0003 (17)	0.0030 (19)
C7	0.021 (2)	0.053 (3)	0.058 (3)	−0.0011 (18)	0.0021 (18)	0.006 (2)
C8	0.030 (2)	0.042 (2)	0.048 (2)	0.0082 (18)	0.0075 (18)	0.005 (2)
C9	0.034 (2)	0.050 (3)	0.040 (2)	−0.0090 (19)	0.0030 (17)	−0.014 (2)
C10	0.035 (2)	0.046 (3)	0.040 (2)	−0.0071 (19)	0.0047 (18)	−0.013 (2)
C11	0.031 (2)	0.031 (2)	0.037 (2)	−0.0038 (16)	0.0000 (16)	−0.0005 (17)
C12	0.035 (2)	0.036 (2)	0.039 (2)	0.0056 (17)	0.0010 (17)	−0.0055 (18)
C13	0.043 (2)	0.027 (2)	0.043 (2)	0.0051 (17)	−0.0013 (18)	−0.0066 (18)
C14	0.031 (2)	0.028 (2)	0.0278 (18)	−0.0038 (16)	0.0001 (15)	0.0011 (16)
C15	0.033 (2)	0.031 (2)	0.0280 (19)	−0.0020 (16)	−0.0033 (15)	0.0037 (16)
C16	0.032 (2)	0.058 (3)	0.055 (3)	−0.012 (2)	−0.0032 (19)	0.008 (2)
C17	0.029 (2)	0.054 (3)	0.071 (3)	0.002 (2)	0.000 (2)	0.009 (2)
C18	0.030 (2)	0.044 (2)	0.059 (3)	0.0055 (18)	0.0024 (19)	−0.002 (2)
C19	0.0235 (19)	0.035 (2)	0.044 (2)	0.0031 (16)	0.0012 (17)	0.0090 (19)
C20	0.059 (3)	0.039 (3)	0.039 (2)	0.017 (2)	0.013 (2)	0.001 (2)
C21	0.037 (2)	0.034 (2)	0.044 (2)	0.0084 (18)	0.0138 (19)	0.0008 (19)
C22	0.034 (2)	0.036 (2)	0.0283 (19)	−0.0049 (17)	−0.0007 (16)	−0.0011 (17)
C23	0.038 (2)	0.032 (2)	0.037 (2)	−0.0063 (17)	−0.0045 (17)	−0.0057 (18)
C24	0.040 (2)	0.031 (2)	0.042 (2)	0.0073 (18)	0.0102 (18)	0.0034 (18)

Geometric parameters (Å, º) top

Pd1—N1	2.074 (3)	N3—C5	1.321 (4)
Pd1—N4	2.070 (3)	N3—C6	1.331 (4)
Pd1—S1	2.2945 (11)	N3—K1^vi	2.835 (3)
Pd1—S2	2.3077 (11)	N4—C8	1.336 (4)
Pd2—N7	2.059 (3)	N4—C5	1.348 (4)
Pd2—N10	2.069 (3)	N5—C9	1.155 (5)
Pd2—S3ⁱ	2.2958 (10)	N6—C10	1.158 (5)
Pd2—S4	2.2829 (11)	N7—C11	1.337 (4)
Pd3—S5ⁱⁱ	2.3388 (9)	N7—C14	1.354 (4)
Pd3—S5	2.3388 (9)	N8—C14	1.315 (4)
Pd3—S6ⁱⁱ	2.3314 (9)	N8—C13	1.333 (4)
Pd3—S6	2.3314 (9)	N9—C15	1.321 (4)
Pd4—S7ⁱⁱⁱ	2.3157 (10)	N9—C16	1.333 (5)
Pd4—S7	2.3157 (10)	N10—C18	1.333 (5)
Pd4—S8ⁱⁱⁱ	2.3419 (10)	N10—C15	1.346 (4)
Pd4—S8	2.3419 (10)	N11—C19	1.154 (5)
K1—N14	2.806 (3)	N12—C20	1.142 (5)
K1—N3^iv	2.835 (3)	N12—K2^vi	3.370 (5)
K1—N6	2.853 (4)	N13—C21	1.146 (5)
K1—N2^iv	2.922 (3)	N14—C22	1.145 (5)
K1—N16	2.923 (4)	N14—K1^v	2.981 (3)
K1—N14^v	2.981 (3)	N15—C23	1.144 (5)
K1—N5	3.103 (4)	N15—K2ⁱⁱⁱ	2.827 (4)
K1—S5	3.6081 (13)	N15—K2^iv	2.886 (4)
K1—K1^v	4.4389 (17)	N16—C24	1.141 (5)
K2—N11	2.824 (4)	C1—C2	1.373 (5)
K2—N15ⁱⁱⁱ	2.827 (4)	C1—H1	0.9500
K2—N8	2.881 (3)	C2—C3	1.366 (5)
K2—N15^vi	2.886 (4)	C2—H2	0.9500
K2—N13	2.892 (4)	C3—H3	0.9500
K2—N9	3.008 (3)	C4—C5	1.486 (5)
K2—N12^iv	3.370 (5)	C6—C7	1.373 (5)
K2—S8	3.6692 (13)	C6—H6	0.9500
K2—K2^vii	4.4966 (18)	C7—C8	1.358 (5)
S1—C9	1.674 (5)	C7—H7	0.9500
S2—C10	1.676 (5)	C8—H8	0.9500
S3—C19	1.666 (4)	C11—C12	1.379 (5)
S3—Pd2^viii	2.2958 (10)	C11—H11	0.9500
S4—C20	1.675 (5)	C12—C13	1.375 (5)
S5—C21	1.677 (4)	C12—H12	0.9500
S6—C22	1.678 (4)	C13—H13	0.9500
S7—C23	1.679 (4)	C14—C15	1.487 (5)
S8—C24	1.683 (4)	C16—C17	1.372 (6)
N1—C1	1.336 (4)	C16—H16	0.9500
N1—C4	1.344 (4)	C17—C18	1.361 (6)
N2—C4	1.325 (4)	C17—H17	0.9500
N2—C3	1.338 (4)	C18—H18	0.9500
N2—K1^vi	2.922 (3)

N4—Pd1—N1	79.65 (11)	C10—S2—Pd1	108.31 (14)
N4—Pd1—S1	173.55 (8)	C19—S3—Pd2^viii	98.67 (13)
N1—Pd1—S1	94.39 (8)	C20—S4—Pd2	104.84 (14)
N4—Pd1—S2	93.13 (8)	C21—S5—Pd3	106.57 (13)
N1—Pd1—S2	168.65 (8)	C21—S5—K1	110.74 (13)
S1—Pd1—S2	92.38 (4)	Pd3—S5—K1	136.58 (4)
N7—Pd2—N10	79.94 (11)	C22—S6—Pd3	110.44 (13)
N7—Pd2—S4	173.34 (8)	C23—S7—Pd4	108.97 (13)
N10—Pd2—S4	93.40 (9)	C24—S8—Pd4	108.78 (13)
N7—Pd2—S3ⁱ	95.74 (8)	C24—S8—K2	111.96 (13)
N10—Pd2—S3ⁱ	174.43 (8)	Pd4—S8—K2	138.91 (4)
S4—Pd2—S3ⁱ	90.90 (4)	C1—N1—C4	116.7 (3)
S6ⁱⁱ—Pd3—S6	180.00 (5)	C1—N1—Pd1	128.9 (2)
S6ⁱⁱ—Pd3—S5ⁱⁱ	90.42 (3)	C4—N1—Pd1	114.2 (2)
S6—Pd3—S5ⁱⁱ	89.58 (3)	C4—N2—C3	115.8 (3)
S6ⁱⁱ—Pd3—S5	89.58 (3)	C4—N2—K1^vi	120.7 (2)
S6—Pd3—S5	90.42 (3)	C3—N2—K1^vi	123.0 (2)
S5ⁱⁱ—Pd3—S5	180.00 (6)	C5—N3—C6	116.2 (3)
S7ⁱⁱⁱ—Pd4—S7	180.00 (6)	C5—N3—K1^vi	123.7 (2)
S7ⁱⁱⁱ—Pd4—S8ⁱⁱⁱ	88.80 (3)	C6—N3—K1^vi	119.8 (2)
S7—Pd4—S8ⁱⁱⁱ	91.20 (3)	C8—N4—C5	116.1 (3)
S7ⁱⁱⁱ—Pd4—S8	91.20 (3)	C8—N4—Pd1	129.5 (3)
S7—Pd4—S8	88.80 (4)	C5—N4—Pd1	114.3 (2)
S8ⁱⁱⁱ—Pd4—S8	180.00 (5)	C9—N5—K1	129.2 (3)
N14—K1—N3^iv	137.64 (9)	C10—N6—K1	125.6 (3)
N14—K1—N6	123.28 (11)	C11—N7—C14	116.7 (3)
N3^iv—K1—N6	89.98 (10)	C11—N7—Pd2	128.9 (2)
N14—K1—N2^iv	82.17 (9)	C14—N7—Pd2	114.4 (2)
N3^iv—K1—N2^iv	57.16 (8)	C14—N8—C13	116.3 (3)
N6—K1—N2^iv	119.60 (10)	C14—N8—K2	126.0 (2)
N14—K1—N16	120.30 (10)	C13—N8—K2	117.6 (2)
N3^iv—K1—N16	86.83 (9)	C15—N9—C16	115.5 (3)
N6—K1—N16	81.96 (10)	C15—N9—K2	120.8 (2)
N2^iv—K1—N16	135.31 (10)	C16—N9—K2	123.3 (3)
N14—K1—N14^v	79.86 (10)	C18—N10—C15	117.2 (3)
N3^iv—K1—N14^v	74.32 (9)	C18—N10—Pd2	128.5 (3)
N6—K1—N14^v	155.48 (10)	C15—N10—Pd2	114.2 (2)
N2^iv—K1—N14^v	67.52 (8)	C19—N11—K2	118.1 (3)
N16—K1—N14^v	78.53 (10)	C20—N12—K2^vi	91.9 (3)
N14—K1—N5	67.69 (10)	C21—N13—K2	162.4 (3)
N3^iv—K1—N5	110.45 (9)	C22—N14—K1	123.6 (3)
N6—K1—N5	67.21 (10)	C22—N14—K1^v	120.3 (3)
N2^iv—K1—N5	78.54 (9)	K1—N14—K1^v	100.14 (10)
N16—K1—N5	143.95 (10)	C23—N15—K2ⁱⁱⁱ	129.9 (3)
N14^v—K1—N5	135.69 (9)	C23—N15—K2^iv	116.2 (3)
N14—K1—S5	66.36 (7)	K2ⁱⁱⁱ—N15—K2^iv	103.82 (11)
N3^iv—K1—S5	155.51 (7)	C24—N16—K1	169.6 (3)
N6—K1—S5	74.30 (9)	N1—C1—C2	121.7 (3)
N2^iv—K1—S5	147.20 (7)	N1—C1—H1	119.2
N16—K1—S5	72.67 (7)	C2—C1—H1	119.2
N14^v—K1—S5	113.18 (7)	C3—C2—C1	117.0 (3)
N5—K1—S5	81.08 (7)	C3—C2—H2	121.5
N14—K1—K1^v	41.39 (7)	C1—C2—H2	121.5
N3^iv—K1—K1^v	106.59 (7)	N2—C3—C2	123.0 (4)
N6—K1—K1^v	163.30 (9)	N2—C3—H3	118.5
N2^iv—K1—K1^v	69.94 (6)	C2—C3—H3	118.5
N16—K1—K1^v	100.68 (8)	N2—C4—N1	125.7 (3)
N14^v—K1—K1^v	38.47 (7)	N2—C4—C5	118.4 (3)
N5—K1—K1^v	103.93 (7)	N1—C4—C5	115.8 (3)
S5—K1—K1^v	90.63 (3)	N3—C5—N4	125.5 (3)
N11—K2—N15ⁱⁱⁱ	132.28 (10)	N3—C5—C4	118.9 (3)
N11—K2—N8	98.97 (9)	N4—C5—C4	115.6 (3)
N15ⁱⁱⁱ—K2—N8	78.92 (9)	N3—C6—C7	122.8 (4)
N11—K2—N15^vi	148.93 (10)	N3—C6—H6	118.6
N15ⁱⁱⁱ—K2—N15^vi	76.18 (11)	C7—C6—H6	118.6
N8—K2—N15^vi	71.51 (9)	C8—C7—C6	116.7 (4)
N11—K2—N13	90.88 (10)	C8—C7—H7	121.6
N15ⁱⁱⁱ—K2—N13	115.96 (10)	C6—C7—H7	121.6
N8—K2—N13	148.14 (10)	N4—C8—C7	122.5 (4)
N15^vi—K2—N13	84.46 (10)	N4—C8—H8	118.8
N11—K2—N9	71.18 (9)	C7—C8—H8	118.8
N15ⁱⁱⁱ—K2—N9	133.30 (9)	N5—C9—S1	176.3 (4)
N8—K2—N9	55.62 (8)	N6—C10—S2	172.0 (4)
N15^vi—K2—N9	79.48 (9)	N7—C11—C12	120.6 (3)
N13—K2—N9	100.43 (9)	N7—C11—H11	119.7
N11—K2—N12^iv	70.69 (9)	C12—C11—H11	119.7
N15ⁱⁱⁱ—K2—N12^iv	65.57 (10)	C13—C12—C11	118.0 (3)
N8—K2—N12^iv	64.42 (10)	C13—C12—H12	121.0
N15^vi—K2—N12^iv	125.51 (10)	C11—C12—H12	121.0
N13—K2—N12^iv	146.66 (11)	N8—C13—C12	122.2 (3)
N9—K2—N12^iv	99.44 (9)	N8—C13—H13	118.9
N11—K2—C19	16.81 (8)	C12—C13—H13	118.9
N15ⁱⁱⁱ—K2—C19	129.62 (9)	N8—C14—N7	126.1 (3)
N8—K2—C19	82.22 (9)	N8—C14—C15	118.4 (3)
N15^vi—K2—C19	138.92 (9)	N7—C14—C15	115.4 (3)
N13—K2—C19	104.47 (9)	N9—C15—N10	125.6 (3)
N9—K2—C19	59.54 (8)	N9—C15—C14	118.8 (3)
N12^iv—K2—C19	64.12 (9)	N10—C15—C14	115.6 (3)
N11—K2—S8	97.90 (8)	N9—C16—C17	123.2 (4)
N15ⁱⁱⁱ—K2—S8	61.49 (7)	N9—C16—H16	118.4
N8—K2—S8	138.05 (7)	C17—C16—H16	118.4
N15^vi—K2—S8	108.87 (7)	C18—C17—C16	117.2 (4)
N13—K2—S8	69.04 (7)	C18—C17—H17	121.4
N9—K2—S8	165.17 (7)	C16—C17—H17	121.4
N12^iv—K2—S8	85.78 (7)	N10—C18—C17	121.2 (4)
C19—K2—S8	111.77 (7)	N10—C18—H18	119.4
N11—K2—K2^vii	166.57 (8)	C17—C18—H18	119.4
N15ⁱⁱⁱ—K2—K2^vii	38.55 (7)	N11—C19—S3	177.2 (4)
N8—K2—K2^vii	71.07 (6)	N11—C19—K2	45.1 (2)
N15^vi—K2—K2^vii	37.63 (7)	S3—C19—K2	134.80 (17)
N13—K2—K2^vii	102.31 (8)	N12—C20—S4	176.7 (4)
N9—K2—K2^vii	108.30 (7)	N13—C21—S5	178.1 (4)
N12^iv—K2—K2^vii	96.47 (7)	N14—C22—S6	174.8 (4)
C19—K2—K2^vii	152.22 (7)	N15—C23—S7	176.6 (4)
S8—K2—K2^vii	84.69 (3)	N16—C24—S8	177.7 (4)
C9—S1—Pd1	103.83 (14)

N1—Pd1—S1—C9	130.92 (16)	S4—Pd2—N10—C15	173.9 (2)
S2—Pd1—S1—C9	−58.20 (15)	N15ⁱⁱⁱ—K2—N11—C19	−88.3 (3)
N4—Pd1—S2—C10	−104.11 (16)	N8—K2—N11—C19	−5.2 (3)
N1—Pd1—S2—C10	−154.2 (4)	N15^vi—K2—N11—C19	63.7 (4)
S1—Pd1—S2—C10	79.23 (14)	N13—K2—N11—C19	144.4 (3)
N10—Pd2—S4—C20	145.08 (17)	N9—K2—N11—C19	43.7 (3)
S3ⁱ—Pd2—S4—C20	−38.46 (16)	N12^iv—K2—N11—C19	−64.0 (3)
S6ⁱⁱ—Pd3—S5—C21	−15.44 (14)	S8—K2—N11—C19	−146.6 (3)
S6—Pd3—S5—C21	164.56 (14)	K2^vii—K2—N11—C19	−46.4 (6)
S6ⁱⁱ—Pd3—S5—K1	−163.85 (6)	N11—K2—N13—C21	−1.9 (10)
S6—Pd3—S5—K1	16.15 (6)	N15ⁱⁱⁱ—K2—N13—C21	−141.0 (10)
N14—K1—S5—C21	−147.04 (16)	N8—K2—N13—C21	106.8 (10)
N3^iv—K1—S5—C21	22.9 (2)	N15^vi—K2—N13—C21	147.3 (10)
N6—K1—S5—C21	74.78 (16)	N9—K2—N13—C21	69.1 (10)
N2^iv—K1—S5—C21	−164.47 (17)	N12^iv—K2—N13—C21	−56.5 (11)
N16—K1—S5—C21	−11.52 (16)	C19—K2—N13—C21	8.1 (11)
N14^v—K1—S5—C21	−80.41 (16)	S8—K2—N13—C21	−100.0 (10)
N5—K1—S5—C21	143.48 (16)	K2^vii—K2—N13—C21	−179.3 (10)
K1^v—K1—S5—C21	−112.52 (14)	N3^iv—K1—N14—C22	170.0 (3)
N14—K1—S5—Pd3	0.49 (9)	N6—K1—N14—C22	34.0 (4)
N3^iv—K1—S5—Pd3	170.47 (15)	N2^iv—K1—N14—C22	154.4 (3)
N6—K1—S5—Pd3	−137.68 (9)	N16—K1—N14—C22	−67.0 (4)
N2^iv—K1—S5—Pd3	−16.93 (14)	N14^v—K1—N14—C22	−137.2 (4)
N16—K1—S5—Pd3	136.02 (9)	N5—K1—N14—C22	73.6 (3)
N14^v—K1—S5—Pd3	67.13 (9)	S5—K1—N14—C22	−16.2 (3)
N5—K1—S5—Pd3	−68.98 (9)	K1^v—K1—N14—C22	−137.2 (4)
K1^v—K1—S5—Pd3	35.02 (6)	N3^iv—K1—N14—K1^v	−52.87 (16)
S5ⁱⁱ—Pd3—S6—C22	157.74 (14)	N6—K1—N14—K1^v	171.15 (11)
S5—Pd3—S6—C22	−22.26 (14)	N2^iv—K1—N14—K1^v	−68.44 (9)
S8—Pd4—S7—C23	168.18 (15)	N16—K1—N14—K1^v	70.22 (13)
S7ⁱⁱⁱ—Pd4—S8—C24	−170.46 (14)	N14^v—K1—N14—K1^v	0.0
S7—Pd4—S8—C24	9.54 (14)	N5—K1—N14—K1^v	−149.21 (12)
S7ⁱⁱⁱ—Pd4—S8—K2	1.77 (7)	S5—K1—N14—K1^v	120.99 (9)
S7—Pd4—S8—K2	−178.23 (7)	N14—K1—N16—C24	110.1 (18)
N11—K2—S8—C24	−69.23 (16)	N3^iv—K1—N16—C24	−104.3 (18)
N15ⁱⁱⁱ—K2—S8—C24	156.54 (17)	N6—K1—N16—C24	−13.9 (18)
N8—K2—S8—C24	177.82 (17)	N2^iv—K1—N16—C24	−138.4 (17)
N15^vi—K2—S8—C24	94.77 (16)	N5—K1—N16—C24	16.9 (19)
N13—K2—S8—C24	18.67 (16)	S5—K1—N16—C24	62.1 (18)
N9—K2—S8—C24	−27.7 (3)	K1^v—K1—N16—C24	149.4 (18)
N12^iv—K2—S8—C24	−139.05 (16)	C4—N1—C1—C2	0.6 (5)
C19—K2—S8—C24	−79.09 (16)	Pd1—N1—C1—C2	176.4 (2)
K2^vii—K2—S8—C24	124.04 (14)	N1—C1—C2—C3	0.0 (5)
N11—K2—S8—Pd4	118.71 (9)	C4—N2—C3—C2	0.6 (5)
N15ⁱⁱⁱ—K2—S8—Pd4	−15.52 (10)	K1^vi—N2—C3—C2	−170.9 (3)
N8—K2—S8—Pd4	5.76 (13)	C1—C2—C3—N2	−0.7 (5)
N15^vi—K2—S8—Pd4	−77.29 (10)	C3—N2—C4—N1	0.1 (5)
N13—K2—S8—Pd4	−153.39 (10)	K1^vi—N2—C4—N1	171.9 (2)
N9—K2—S8—Pd4	160.2 (2)	C3—N2—C4—C5	179.1 (3)
N12^iv—K2—S8—Pd4	48.89 (9)	K1^vi—N2—C4—C5	−9.1 (4)
C19—K2—S8—Pd4	108.84 (9)	C1—N1—C4—N2	−0.7 (5)
K2^vii—K2—S8—Pd4	−48.03 (7)	Pd1—N1—C4—N2	−177.1 (3)
N4—Pd1—N1—C1	179.1 (3)	C1—N1—C4—C5	−179.7 (3)
S1—Pd1—N1—C1	−3.3 (3)	Pd1—N1—C4—C5	3.9 (4)
S2—Pd1—N1—C1	−129.7 (4)	C6—N3—C5—N4	2.2 (5)
N4—Pd1—N1—C4	−5.0 (2)	K1^vi—N3—C5—N4	−172.4 (2)
S1—Pd1—N1—C4	172.5 (2)	C6—N3—C5—C4	−176.9 (3)
S2—Pd1—N1—C4	46.1 (5)	K1^vi—N3—C5—C4	8.5 (4)
N1—Pd1—N4—C8	−175.6 (3)	C8—N4—C5—N3	−3.3 (5)
S2—Pd1—N4—C8	13.3 (3)	Pd1—N4—C5—N3	175.9 (3)
N1—Pd1—N4—C5	5.4 (2)	C8—N4—C5—C4	175.9 (3)
S2—Pd1—N4—C5	−165.8 (2)	Pd1—N4—C5—C4	−5.0 (3)
N14—K1—N5—C9	−80.2 (4)	N2—C4—C5—N3	0.8 (5)
N3^iv—K1—N5—C9	145.5 (4)	N1—C4—C5—N3	179.9 (3)
N6—K1—N5—C9	64.5 (4)	N2—C4—C5—N4	−178.4 (3)
N2^iv—K1—N5—C9	−166.3 (4)	N1—C4—C5—N4	0.7 (4)
N16—K1—N5—C9	31.1 (5)	C5—N3—C6—C7	1.2 (5)
N14^v—K1—N5—C9	−126.3 (4)	K1^vi—N3—C6—C7	176.0 (3)
S5—K1—N5—C9	−12.2 (4)	N3—C6—C7—C8	−3.1 (6)
K1^v—K1—N5—C9	−100.6 (4)	C5—N4—C8—C7	1.0 (5)
N14—K1—N6—C10	−6.0 (4)	Pd1—N4—C8—C7	−178.0 (3)
N3^iv—K1—N6—C10	−158.1 (4)	C6—C7—C8—N4	1.9 (6)
N2^iv—K1—N6—C10	−106.7 (4)	C14—N7—C11—C12	0.0 (5)
N16—K1—N6—C10	115.1 (4)	Pd2—N7—C11—C12	−178.9 (3)
N14^v—K1—N6—C10	152.6 (3)	N7—C11—C12—C13	0.4 (5)
N5—K1—N6—C10	−45.8 (4)	C14—N8—C13—C12	0.3 (5)
S5—K1—N6—C10	41.0 (4)	K2—N8—C13—C12	−176.5 (3)
K1^v—K1—N6—C10	14.7 (6)	C11—C12—C13—N8	−0.6 (6)
N10—Pd2—N7—C11	−176.4 (3)	C13—N8—C14—N7	0.1 (5)
S3ⁱ—Pd2—N7—C11	7.2 (3)	K2—N8—C14—N7	176.7 (2)
N10—Pd2—N7—C14	4.7 (2)	C13—N8—C14—C15	−178.3 (3)
S3ⁱ—Pd2—N7—C14	−171.7 (2)	K2—N8—C14—C15	−1.7 (4)
N11—K2—N8—C14	63.2 (3)	C11—N7—C14—N8	−0.3 (5)
N15ⁱⁱⁱ—K2—N8—C14	−165.3 (3)	Pd2—N7—C14—N8	178.8 (3)
N15^vi—K2—N8—C14	−86.3 (3)	C11—N7—C14—C15	178.2 (3)
N13—K2—N8—C14	−43.3 (4)	Pd2—N7—C14—C15	−2.8 (4)
N9—K2—N8—C14	3.4 (3)	C16—N9—C15—N10	−0.1 (5)
N12^iv—K2—N8—C14	126.6 (3)	K2—N9—C15—N10	−172.9 (2)
C19—K2—N8—C14	61.7 (3)	C16—N9—C15—C14	179.8 (3)
S8—K2—N8—C14	175.7 (2)	K2—N9—C15—C14	7.1 (4)
K2^vii—K2—N8—C14	−126.1 (3)	C18—N10—C15—N9	2.4 (5)
N11—K2—N8—C13	−120.3 (3)	Pd2—N10—C15—N9	−173.7 (3)
N15ⁱⁱⁱ—K2—N8—C13	11.2 (3)	C18—N10—C15—C14	−177.6 (3)
N15^vi—K2—N8—C13	90.2 (3)	Pd2—N10—C15—C14	6.4 (4)
N13—K2—N8—C13	133.2 (3)	N8—C14—C15—N9	−3.8 (5)
N9—K2—N8—C13	180.0 (3)	N7—C14—C15—N9	177.7 (3)
N12^iv—K2—N8—C13	−56.8 (3)	N8—C14—C15—N10	176.1 (3)
C19—K2—N8—C13	−121.8 (3)	N7—C14—C15—N10	−2.4 (4)
S8—K2—N8—C13	−7.7 (3)	C15—N9—C16—C17	−2.3 (6)
K2^vii—K2—N8—C13	50.4 (2)	K2—N9—C16—C17	170.3 (3)
N11—K2—N9—C15	−121.0 (3)	N9—C16—C17—C18	2.3 (7)
N15ⁱⁱⁱ—K2—N9—C15	10.0 (3)	C15—N10—C18—C17	−2.3 (6)
N8—K2—N9—C15	−5.3 (2)	Pd2—N10—C18—C17	173.1 (3)
N15^vi—K2—N9—C15	69.4 (3)	C16—C17—C18—N10	0.1 (6)
N13—K2—N9—C15	151.7 (3)	Pd2^viii—S3—C19—K2	79.2 (2)
N12^iv—K2—N9—C15	−55.2 (3)	N15ⁱⁱⁱ—K2—C19—N11	106.2 (3)
C19—K2—N9—C15	−107.6 (3)	N8—K2—C19—N11	174.8 (3)
S8—K2—N9—C15	−164.9 (2)	N15^vi—K2—C19—N11	−135.2 (3)
K2^vii—K2—N9—C15	44.9 (3)	N13—K2—C19—N11	−36.9 (3)
N11—K2—N9—C16	66.8 (3)	N9—K2—C19—N11	−130.7 (3)
N15ⁱⁱⁱ—K2—N9—C16	−162.2 (3)	N12^iv—K2—C19—N11	109.5 (3)
N8—K2—N9—C16	−177.5 (3)	S8—K2—C19—N11	35.9 (3)
N15^vi—K2—N9—C16	−102.8 (3)	K2^vii—K2—C19—N11	158.9 (3)
N13—K2—N9—C16	−20.5 (3)	N11—K2—C19—S3	176.0 (5)
N12^iv—K2—N9—C16	132.6 (3)	N15ⁱⁱⁱ—K2—C19—S3	−77.8 (3)
C19—K2—N9—C16	80.2 (3)	N8—K2—C19—S3	−9.2 (2)
S8—K2—N9—C16	22.9 (5)	N15^vi—K2—C19—S3	40.8 (3)
K2^vii—K2—N9—C16	−127.3 (3)	N13—K2—C19—S3	139.1 (2)
N7—Pd2—N10—C18	178.4 (3)	N9—K2—C19—S3	45.3 (2)
S4—Pd2—N10—C18	−1.6 (3)	N12^iv—K2—C19—S3	−74.5 (2)
N7—Pd2—N10—C15	−6.1 (2)	S8—K2—C19—S3	−148.1 (2)

Symmetry codes: (i) −x, y−1/2, −z−1/2; (ii) −x+1, −y+1, −z; (iii) −x, −y+2, −z; (iv) x, y+1, z; (v) −x+1, −y+2, −z; (vi) x, y−1, z; (vii) −x, −y+1, −z; (viii) −x, y+1/2, −z−1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1···S1	0.95	2.77	3.334 (4)	119
C1—H1···N11ⁱⁱ	0.95	2.45	3.134 (5)	128
C6—H6···S7^vi	0.95	2.76	3.457 (4)	131
C8—H8···S2	0.95	2.77	3.321 (4)	118
C11—H11···S3ⁱ	0.95	2.82	3.371 (4)	118
C11—H11···N6^vii	0.95	2.63	3.315 (5)	130
C13—H13···N15ⁱⁱⁱ	0.95	2.61	3.376 (5)	138
C16—H16···S6ⁱⁱ	0.95	2.83	3.640 (4)	144
C18—H18···S4	0.95	2.71	3.276 (4)	119

Symmetry codes: (i) −x, y−1/2, −z−1/2; (ii) −x+1, −y+1, −z; (iii) −x, −y+2, −z; (vi) x, y−1, z; (vii) −x, −y+1, −z.

Experimental details

Crystal data
Chemical formula	K₂[Pd(NCS)₄]·2[Pd(NCS)₂(C₈H₆N₄)]
M_r	1178.38
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	200
a, b, c (Å)	15.9625 (7), 10.9700 (5), 21.6801 (9)
β (°)	94.104 (1)
V (Å³)	3786.6 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	2.12
Crystal size (mm)	0.28 × 0.24 × 0.18

Data collection
Diffractometer	Bruker SMART 1000 CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2000)
T_min, T_max	0.854, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	22881, 7371, 5722
R_int	0.030
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.030, 0.080, 1.08
No. of reflections	7371
No. of parameters	481
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.65, −0.59

Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997).

Selected bond lengths (Å) top

Pd1—N1	2.074 (3)	Pd2—S3ⁱ	2.2958 (10)
Pd1—N4	2.070 (3)	Pd2—S4	2.2829 (11)
Pd1—S1	2.2945 (11)	Pd3—S5	2.3388 (9)
Pd1—S2	2.3077 (11)	Pd3—S6	2.3314 (9)
Pd2—N7	2.059 (3)	Pd4—S7	2.3157 (10)
Pd2—N10	2.069 (3)	Pd4—S8	2.3419 (10)

Symmetry code: (i) −x, y−1/2, −z−1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1···S1	0.95	2.77	3.334 (4)	119
C1—H1···N11ⁱⁱ	0.95	2.45	3.134 (5)	128
C6—H6···S7ⁱⁱⁱ	0.95	2.76	3.457 (4)	131
C8—H8···S2	0.95	2.77	3.321 (4)	118
C11—H11···S3ⁱ	0.95	2.82	3.371 (4)	118
C11—H11···N6^iv	0.95	2.63	3.315 (5)	130
C13—H13···N15^v	0.95	2.61	3.376 (5)	138
C16—H16···S6ⁱⁱ	0.95	2.83	3.640 (4)	144
C18—H18···S4	0.95	2.71	3.276 (4)	119

Symmetry codes: (i) −x, y−1/2, −z−1/2; (ii) −x+1, −y+1, −z; (iii) x, y−1, z; (iv) −x, −y+1, −z; (v) −x, −y+2, −z.

Acknowledgements

This work was supported by the Priority Research Centers Program through the National Research Foundation of Korea (NRF) funded by the Ministry of Education, Science and Technology (2011–0030747).

References

Bruker (2000). SADABS, SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Ha, K. (2010). Z. Kristallogr. New Cryst. Struct. 225, 619–620. CAS Google Scholar
Mawby, A. & Pringle, G. E. (1972). J. Inorg. Nucl. Chem. 34, 2213–2217. CrossRef CAS Web of Science Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar

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