Bis(tetra-n-butyl­ammonium) bis­(5,6-dicyano­pyrazine-2,3-dithiol­ato-κ2S,S′)palladium(II)

Tomura, M.; Yamashita, Y.

doi:10.1107/S1600536811053402

metal-organic compounds

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ISSN: 2056-9890

Volume 68| Part 1| January 2012| Page m57

doi:10.1107/S1600536811053402

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Bis(tetra-n-butylammonium) bis(5,6-dicyanopyrazine-2,3-dithiolato-κ²S,S′)palladium(II)

Masaaki Tomura ^a ^* and Yoshiro Yamashita ^b

^aInstitute for Molecular Science, Myodaiji, Okazaki 444-8585, Japan, and ^bDepartment of Electronic Chemistry, Interdisciplinary Graduate School of Science and Engineering, Tokyo Institute of Technology, Nagatsuta, Midori-ku, Yokohama 226-8502, Japan
^*Correspondence e-mail: tomura@ims.ac.jp

(Received 3 December 2011; accepted 12 December 2011; online 17 December 2011)

In the title complex, (C₁₆H₃₆N)₂[Pd(C₆N₄S₂)₂], the centrosymmetric dianion is planar, with an r.m.s. deviation of 0.034 (8) Å. The Pd^II atom, lying on an inversion center, has a square-planar coordination geometry, with Pd—S bond lengths of 2.276 (3) and 2.294 (3) Å.

Related literature

For the synthesis of the title complex, see: Tomura et al. (1994 ). For molecular conductors and superconductors based on metal dithiolene complexes, see: Brossard et al. (1986 ); Cassoux et al. (1991 ); Kobayashi et al. (1987 ); Tajima et al. (1993 ); Tanaka et al. (2001 ). For related structures, including the 2,3-dicyano-5,6-dimercaptopyrazine system, see: Belo et al. (1999 , 2004 ); Nomura et al. (2009 ); Rabaça & Almeida (2010 ). For related structures, including the 1,2-dicyano-4,5-dimercaptobenzene system, see: Alves et al. (2004 ). For intermolecular interactions caused by heteroatoms, see: Yamashita & Tomura (1998 ).

Experimental

Crystal data

(C₁₆H₃₆N)₂[Pd(C₆N₄S₂)₂]
M_r = 975.80
Triclinic, $[P \overline 1]$
a = 9.912 (3) Å
b = 10.635 (4) Å
c = 13.286 (4) Å
α = 68.82 (2)°
β = 87.74 (3)°
γ = 80.16 (3)°
V = 1286.3 (8) Å³
Z = 1
Mo Kα radiation
μ = 0.56 mm⁻¹
T = 296 K
0.25 × 0.10 × 0.05 mm

Data collection

Rigaku AFC-7R diffractometer
5102 measured reflections
4835 independent reflections
1751 reflections with I > 2σ(I)
R_int = 0.087
3 standard reflections every 150 reflections intensity decay: 1.0%

Refinement

R[F² > 2σ(F²)] = 0.093
wR(F²) = 0.222
S = 0.98
4835 reflections
272 parameters
H-atom parameters constrained
Δρ_max = 0.39 e Å⁻³
Δρ_min = −0.41 e Å⁻³

Data collection: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1988 $[Molecular Structure Corporation (1988). MSC/AFC Diffractometer Control Software. MSC, The Woodlands, Texas, USA.]$ ); cell refinement: MSC/AFC Diffractometer Control Software; data reduction: TEXSAN (Molecular Structure Corporation & Rigaku, 2000 ); program(s) used to solve structure: SIR97 (Altomare et al., 1999 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ); molecular graphics: PLATON (Spek, 2009 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811053402/hy2494sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811053402/hy2494Isup2.hkl

checkCIF report

Comment top

Metal dithiolene complexes have been widely investigated as molecular conductors and superconductors. Several superconductors (Brossard et al., 1986; Cassoux et al., 1991; Kobayashi et al., 1987; Tajima et al., 1993) and single-component molecular metals (Tanaka et al., 2001) involving dithiolene complexes have been discovered to date. We have synthesized the title palladium dithiolene complex, (I), derived from 2,3-dicyano-5,6-dimercaptopyrazine ligand (Tomura et al., 1994). The ligand is expected to extend the π-conjugation of the complex resulting in decreased Coulombic repulsion (Belo et al., 1999, 2004; Nomura et al., 2009; Rabaça & Almeida, 2010). Intermolecular interactions caused by S···S and S···N heteroatom contacts may increase the dimensionality in the solid state (Yamashita & Tomura, 1998). We report here the molecular and crystal structures of (I).

In the complex (I) the dianion molecule is located on an inversion center. The molecular structure of the dianion is shown in Fig. 1. The dianion is a flat molecule with an r.m.s. deviation of 0.034 (8) Å of fitted atoms from the least-squares plane. The central Pd atom has a square-planar coordination geometry and the Pd1—S1 and Pd1—S2 distances and the S1—Pd1—S2 angle are 2.276 (3), 2.294 (3) Å and 89.39 (10)°, respectively. These values are comparable to those found in bis(tetra-n-butylammonium) bis(4,5-dicyanobenzene-1,2-dithiolato-S,S')palladium(II) complex (Alves et al., 2004). Fig. 2 shows the packing diagram of (I) viewed along the a axis. The dianion molecules form a layered structure with an interlayer distance of 6.5 Å. The tetra-n-butylammonium cations are inserted between the layers.

Related literature top

For the synthesis of the title complex, see: Tomura et al. (1994). For molecular conductors and superconductors based on metal dithiolene complexes, see: Brossard et al. (1986); Cassoux et al. (1991); Kobayashi et al. (1987); Tajima et al. (1993); Tanaka et al. (2001). For related structures, including the 2,3-dicyano-5,6-dimercaptopyrazine system, see: Belo et al. (1999, 2004); Nomura et al. (2009); Rabaça & Almeida (2010). For related structures, including the 1,2-dicyano-4,5-dimercaptobenzene system, see: Alves et al. (2004). For intermolecular interactions caused by heteroatoms, see: Yamashita & Tomura (1998).

Experimental top

The title compound (I) was synthesized according to the literature method (Tomura et al., 1994). Orange crystals of (I) suitable for X-ray analysis were grown from an acetone solution.

Computing details top

Data collection: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1988); cell refinement: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1988); data reduction: TEXSAN (Molecular Structure Corporation & Rigaku, 2000); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the dianion in (I). Displacement ellipsoids are drawn at the 50% probability level. Unlabeled atoms are related to the labeled atoms by -x+2, -y-1, -z.
	Fig. 2. The perspective view of the crystal packing of (I), viewed along the a axis. H atoms have been omitted for clarity.

Bis(tetra-n-butylammonium) bis(5,6-dicyanopyrazine-2,3-dithiolato-κ²S,S')palladium(II) top

Crystal data top

(C₁₆H₃₆N)₂[Pd(C₆N₄S₂)₂]	Z = 1
M_r = 975.80	F(000) = 516
Triclinic, P1	D_x = 1.260 Mg m⁻³
Hall symbol: -P 1	Melting point: 520.5 K
a = 9.912 (3) Å	Mo Kα radiation, λ = 0.7107 Å
b = 10.635 (4) Å	Cell parameters from 24 reflections
c = 13.286 (4) Å	θ = 20.1–22.7°
α = 68.82 (2)°	µ = 0.56 mm⁻¹
β = 87.74 (3)°	T = 296 K
γ = 80.16 (3)°	Needle, orange
V = 1286.3 (8) Å³	0.25 × 0.10 × 0.05 mm

Data collection top

Rigaku AFC-7R diffractometer	R_int = 0.087
Radiation source: rotating anode	θ_max = 27.5°, θ_min = 1.6°
Graphite monochromator	h = −12→11
ω–2θ scans	k = −12→0
5102 measured reflections	l = −15→14
4835 independent reflections	3 standard reflections every 150 reflections
1751 reflections with I > 2σ(I)	intensity decay: 1.0%

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)] = 0.093	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.222	H-atom parameters constrained
S = 0.98	w = 1/[σ²(F_o²) + (0.0782P)²] where P = (F_o² + 2F_c²)/3
4835 reflections	(Δ/σ)_max < 0.001
272 parameters	Δρ_max = 0.39 e Å⁻³
0 restraints	Δρ_min = −0.41 e Å⁻³

Crystal data top

(C₁₆H₃₆N)₂[Pd(C₆N₄S₂)₂]	γ = 80.16 (3)°
M_r = 975.80	V = 1286.3 (8) Å³
Triclinic, P1	Z = 1
a = 9.912 (3) Å	Mo Kα radiation
b = 10.635 (4) Å	µ = 0.56 mm⁻¹
c = 13.286 (4) Å	T = 296 K
α = 68.82 (2)°	0.25 × 0.10 × 0.05 mm
β = 87.74 (3)°

Data collection top

Rigaku AFC-7R diffractometer	R_int = 0.087
5102 measured reflections	3 standard reflections every 150 reflections
4835 independent reflections	intensity decay: 1.0%
1751 reflections with I > 2σ(I)

Refinement top

R[F² > 2σ(F²)] = 0.093	0 restraints
wR(F²) = 0.222	H-atom parameters constrained
S = 0.98	Δρ_max = 0.39 e Å⁻³
4835 reflections	Δρ_min = −0.41 e Å⁻³
272 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	1.0000	0.5000	1.0000	0.0590 (5)
S1	1.0651 (3)	0.7047 (3)	0.9048 (2)	0.0750 (9)
S2	0.7779 (3)	0.5945 (3)	0.9425 (2)	0.0677 (9)
N1	0.9253 (10)	0.9342 (10)	0.7768 (7)	0.063 (2)
N2	0.6744 (9)	0.8402 (11)	0.8066 (8)	0.073 (3)
N3	0.8122 (11)	1.2596 (11)	0.5958 (9)	0.095 (3)
N4	0.4777 (11)	1.1342 (12)	0.6318 (11)	0.127 (5)
N5	0.4587 (7)	0.5033 (8)	0.7369 (6)	0.052 (2)
C1	0.9162 (9)	0.8100 (12)	0.8408 (7)	0.045 (3)
C2	0.7894 (11)	0.7582 (11)	0.8586 (8)	0.060 (3)
C3	0.8115 (12)	1.0150 (12)	0.7253 (9)	0.064 (3)
C4	0.6864 (11)	0.9648 (13)	0.7422 (10)	0.071 (3)
C5	0.8184 (11)	1.1533 (14)	0.6519 (10)	0.069 (3)
C6	0.5674 (13)	1.0600 (13)	0.6803 (10)	0.083 (4)
C7	0.5687 (9)	0.5275 (10)	0.6517 (7)	0.063 (3)
H7A	0.6080	0.4405	0.6458	0.075*
H7B	0.5256	0.5859	0.5825	0.075*
C8	0.6833 (10)	0.5921 (11)	0.6738 (8)	0.073 (3)
H8A	0.7260	0.5351	0.7435	0.087*
H8B	0.6452	0.6807	0.6774	0.087*
C9	0.7918 (11)	0.6105 (11)	0.5879 (8)	0.075 (3)
H9A	0.7503	0.6704	0.5185	0.090*
H9B	0.8284	0.5226	0.5826	0.090*
C10	0.9092 (11)	0.6720 (12)	0.6152 (9)	0.095 (4)
H10A	0.8725	0.7576	0.6229	0.142*
H10B	0.9739	0.6868	0.5581	0.142*
H10C	0.9541	0.6100	0.6815	0.142*
C11	0.3911 (9)	0.6377 (9)	0.7481 (7)	0.054 (3)
H11A	0.3212	0.6181	0.8021	0.065*
H11B	0.4597	0.6734	0.7751	0.065*
C12	0.3266 (12)	0.7474 (11)	0.6475 (9)	0.084 (3)
H12A	0.2521	0.7167	0.6225	0.100*
H12B	0.3938	0.7660	0.5912	0.100*
C13	0.2724 (13)	0.8766 (12)	0.6698 (10)	0.100 (4)
H13A	0.2081	0.8558	0.7281	0.120*
H13B	0.3480	0.9069	0.6936	0.120*
C14	0.2024 (14)	0.9909 (12)	0.5733 (11)	0.129 (5)
H14A	0.2686	1.0215	0.5191	0.193*
H14B	0.1604	1.0655	0.5946	0.193*
H14C	0.1335	0.9589	0.5447	0.193*
C15	0.3575 (9)	0.4356 (10)	0.7003 (7)	0.063 (3)
H15A	0.4077	0.3556	0.6886	0.076*
H15B	0.3173	0.4985	0.6314	0.076*
C16	0.2417 (10)	0.3915 (11)	0.7775 (8)	0.071 (3)
H16A	0.1865	0.4712	0.7863	0.085*
H16B	0.2801	0.3307	0.8477	0.085*
C17	0.1509 (10)	0.3179 (11)	0.7340 (8)	0.075 (3)
H17A	0.1097	0.3800	0.6652	0.090*
H17B	0.2070	0.2405	0.7223	0.090*
C18	0.0388 (11)	0.2682 (13)	0.8123 (10)	0.109 (5)
H18A	0.0793	0.2112	0.8818	0.163*
H18B	−0.0117	0.2167	0.7859	0.163*
H18C	−0.0218	0.3455	0.8188	0.163*
C19	0.5197 (10)	0.4106 (11)	0.8485 (8)	0.063 (3)
H19A	0.5845	0.4567	0.8687	0.076*
H19B	0.4464	0.4019	0.8998	0.076*
C20	0.5915 (11)	0.2686 (11)	0.8611 (8)	0.075 (3)
H20A	0.6722	0.2735	0.8171	0.090*
H20B	0.5309	0.2209	0.8382	0.090*
C21	0.6318 (13)	0.1934 (12)	0.9792 (9)	0.099 (4)
H21A	0.6889	0.2447	1.0014	0.119*
H21B	0.5498	0.1893	1.0217	0.119*
C22	0.7070 (16)	0.0519 (14)	1.0024 (11)	0.144 (6)
H22A	0.6491	−0.0012	0.9846	0.216*
H22B	0.7324	0.0107	1.0777	0.216*
H22C	0.7878	0.0549	0.9600	0.216*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Pd1	0.0540 (9)	0.0755 (11)	0.0521 (8)	−0.0223 (7)	0.0036 (6)	−0.0235 (7)
S1	0.0555 (19)	0.082 (2)	0.081 (2)	−0.0214 (17)	0.0010 (16)	−0.0172 (18)
S2	0.0515 (18)	0.084 (2)	0.0647 (19)	−0.0243 (16)	0.0047 (14)	−0.0173 (17)
N1	0.073 (7)	0.072 (7)	0.059 (6)	−0.019 (6)	0.009 (5)	−0.037 (6)
N2	0.055 (6)	0.071 (7)	0.098 (7)	−0.017 (6)	0.014 (5)	−0.035 (6)
N3	0.108 (9)	0.065 (8)	0.111 (9)	−0.014 (7)	−0.009 (7)	−0.031 (7)
N4	0.071 (8)	0.124 (11)	0.190 (13)	0.012 (7)	−0.055 (8)	−0.069 (9)
N5	0.048 (5)	0.061 (6)	0.051 (5)	−0.009 (4)	0.002 (4)	−0.027 (5)
C1	0.041 (6)	0.078 (8)	0.038 (6)	−0.028 (6)	0.015 (5)	−0.040 (6)
C2	0.050 (7)	0.072 (8)	0.071 (7)	−0.008 (6)	0.009 (6)	−0.042 (7)
C3	0.069 (8)	0.059 (9)	0.074 (8)	−0.011 (7)	0.024 (7)	−0.036 (7)
C4	0.043 (7)	0.063 (9)	0.102 (10)	0.003 (7)	−0.007 (6)	−0.029 (8)
C5	0.062 (8)	0.068 (10)	0.081 (9)	−0.022 (7)	0.006 (6)	−0.028 (8)
C6	0.070 (9)	0.083 (10)	0.103 (10)	−0.022 (8)	−0.006 (8)	−0.038 (8)
C7	0.055 (7)	0.068 (8)	0.055 (6)	−0.003 (6)	0.002 (5)	−0.014 (6)
C8	0.057 (7)	0.084 (9)	0.071 (7)	−0.017 (6)	0.008 (6)	−0.019 (6)
C9	0.081 (8)	0.062 (8)	0.075 (8)	−0.007 (7)	0.017 (6)	−0.019 (6)
C10	0.071 (8)	0.102 (10)	0.097 (9)	−0.031 (8)	0.013 (7)	−0.014 (8)
C11	0.054 (6)	0.048 (7)	0.056 (6)	0.010 (5)	0.007 (5)	−0.023 (6)
C12	0.078 (8)	0.065 (8)	0.101 (10)	0.003 (7)	−0.004 (7)	−0.029 (8)
C13	0.101 (10)	0.072 (10)	0.119 (11)	−0.018 (8)	0.029 (9)	−0.026 (9)
C14	0.143 (13)	0.075 (10)	0.134 (12)	0.028 (9)	−0.015 (10)	−0.016 (10)
C15	0.063 (7)	0.062 (7)	0.064 (7)	−0.015 (6)	−0.012 (6)	−0.019 (6)
C16	0.059 (7)	0.089 (9)	0.068 (7)	−0.011 (7)	0.006 (6)	−0.035 (7)
C17	0.064 (7)	0.087 (9)	0.082 (8)	−0.014 (7)	−0.010 (6)	−0.039 (7)
C18	0.088 (9)	0.138 (12)	0.129 (11)	−0.062 (9)	0.021 (8)	−0.066 (10)
C19	0.056 (7)	0.076 (9)	0.072 (8)	−0.026 (6)	0.007 (6)	−0.038 (7)
C20	0.079 (8)	0.080 (9)	0.072 (8)	−0.013 (7)	−0.005 (6)	−0.033 (7)
C21	0.102 (10)	0.084 (10)	0.094 (10)	0.000 (8)	−0.038 (8)	−0.014 (8)
C22	0.174 (16)	0.094 (12)	0.128 (12)	0.010 (11)	−0.030 (11)	−0.008 (10)

Geometric parameters (Å, º) top

Pd1—S1ⁱ	2.276 (3)	C11—H11B	0.9700
Pd1—S1	2.276 (3)	C12—C13	1.514 (14)
Pd1—S2	2.294 (3)	C12—H12A	0.9700
Pd1—S2ⁱ	2.294 (3)	C12—H12B	0.9700
S1—C1	1.732 (10)	C13—C14	1.503 (15)
S2—C2	1.716 (11)	C13—H13A	0.9700
N1—C1	1.304 (11)	C13—H13B	0.9700
N1—C3	1.336 (12)	C14—H14A	0.9600
N2—C4	1.315 (12)	C14—H14B	0.9600
N2—C2	1.351 (12)	C14—H14C	0.9600
N3—C5	1.100 (12)	C15—C16	1.527 (12)
N4—C6	1.126 (13)	C15—H15A	0.9700
N5—C15	1.516 (10)	C15—H15B	0.9700
N5—C7	1.525 (10)	C16—C17	1.537 (12)
N5—C11	1.527 (10)	C16—H16A	0.9700
N5—C19	1.532 (11)	C16—H16B	0.9700
C1—C2	1.434 (12)	C17—C18	1.519 (13)
C3—C4	1.412 (14)	C17—H17A	0.9700
C3—C5	1.452 (15)	C17—H17B	0.9700
C4—C6	1.469 (16)	C18—H18A	0.9600
C7—C8	1.513 (12)	C18—H18B	0.9600
C7—H7A	0.9700	C18—H18C	0.9600
C7—H7B	0.9700	C19—C20	1.508 (13)
C8—C9	1.520 (12)	C19—H19A	0.9700
C8—H8A	0.9700	C19—H19B	0.9700
C8—H8B	0.9700	C20—C21	1.514 (13)
C9—C10	1.542 (13)	C20—H20A	0.9700
C9—H9A	0.9700	C20—H20B	0.9700
C9—H9B	0.9700	C21—C22	1.488 (15)
C10—H10A	0.9600	C21—H21A	0.9700
C10—H10B	0.9600	C21—H21B	0.9700
C10—H10C	0.9600	C22—H22A	0.9600
C11—C12	1.497 (12)	C22—H22B	0.9600
C11—H11A	0.9700	C22—H22C	0.9600

S1ⁱ—Pd1—S1	180.00 (15)	C11—C12—H12B	109.7
S1ⁱ—Pd1—S2	90.61 (10)	C13—C12—H12B	109.7
S1—Pd1—S2	89.39 (10)	H12A—C12—H12B	108.2
S1ⁱ—Pd1—S2ⁱ	89.39 (10)	C14—C13—C12	113.4 (11)
S1—Pd1—S2ⁱ	90.61 (10)	C14—C13—H13A	108.9
S2—Pd1—S2ⁱ	180.0	C12—C13—H13A	108.9
C1—S1—Pd1	104.8 (4)	C14—C13—H13B	108.9
C2—S2—Pd1	103.6 (4)	C12—C13—H13B	108.9
C1—N1—C3	118.1 (9)	H13A—C13—H13B	107.7
C4—N2—C2	117.0 (9)	C13—C14—H14A	109.5
C15—N5—C7	105.9 (7)	C13—C14—H14B	109.5
C15—N5—C11	112.2 (7)	H14A—C14—H14B	109.5
C7—N5—C11	110.8 (7)	C13—C14—H14C	109.5
C15—N5—C19	110.3 (7)	H14A—C14—H14C	109.5
C7—N5—C19	111.4 (7)	H14B—C14—H14C	109.5
C11—N5—C19	106.3 (7)	N5—C15—C16	115.8 (7)
N1—C1—C2	122.7 (11)	N5—C15—H15A	108.3
N1—C1—S1	117.7 (7)	C16—C15—H15A	108.3
C2—C1—S1	119.6 (9)	N5—C15—H15B	108.3
N2—C2—C1	119.2 (11)	C16—C15—H15B	108.3
N2—C2—S2	118.3 (8)	H15A—C15—H15B	107.4
C1—C2—S2	122.5 (9)	C15—C16—C17	110.7 (8)
N1—C3—C4	119.6 (11)	C15—C16—H16A	109.5
N1—C3—C5	119.5 (10)	C17—C16—H16A	109.5
C4—C3—C5	120.8 (12)	C15—C16—H16B	109.5
N2—C4—C3	123.5 (11)	C17—C16—H16B	109.5
N2—C4—C6	120.8 (10)	H16A—C16—H16B	108.1
C3—C4—C6	115.7 (12)	C18—C17—C16	111.2 (8)
N3—C5—C3	174.2 (13)	C18—C17—H17A	109.4
N4—C6—C4	178.9 (15)	C16—C17—H17A	109.4
C8—C7—N5	114.8 (8)	C18—C17—H17B	109.4
C8—C7—H7A	108.6	C16—C17—H17B	109.4
N5—C7—H7A	108.6	H17A—C17—H17B	108.0
C8—C7—H7B	108.6	C17—C18—H18A	109.5
N5—C7—H7B	108.6	C17—C18—H18B	109.5
H7A—C7—H7B	107.5	H18A—C18—H18B	109.5
C7—C8—C9	112.6 (9)	C17—C18—H18C	109.5
C7—C8—H8A	109.1	H18A—C18—H18C	109.5
C9—C8—H8A	109.1	H18B—C18—H18C	109.5
C7—C8—H8B	109.1	C20—C19—N5	117.6 (8)
C9—C8—H8B	109.1	C20—C19—H19A	107.9
H8A—C8—H8B	107.8	N5—C19—H19A	107.9
C8—C9—C10	111.1 (9)	C20—C19—H19B	107.9
C8—C9—H9A	109.4	N5—C19—H19B	107.9
C10—C9—H9A	109.4	H19A—C19—H19B	107.2
C8—C9—H9B	109.4	C19—C20—C21	107.8 (9)
C10—C9—H9B	109.4	C19—C20—H20A	110.1
H9A—C9—H9B	108.0	C21—C20—H20A	110.1
C9—C10—H10A	109.5	C19—C20—H20B	110.1
C9—C10—H10B	109.5	C21—C20—H20B	110.1
H10A—C10—H10B	109.5	H20A—C20—H20B	108.5
C9—C10—H10C	109.5	C22—C21—C20	113.3 (11)
H10A—C10—H10C	109.5	C22—C21—H21A	108.9
H10B—C10—H10C	109.5	C20—C21—H21A	108.9
C12—C11—N5	116.3 (8)	C22—C21—H21B	108.9
C12—C11—H11A	108.2	C20—C21—H21B	108.9
N5—C11—H11A	108.2	H21A—C21—H21B	107.7
C12—C11—H11B	108.2	C21—C22—H22A	109.5
N5—C11—H11B	108.2	C21—C22—H22B	109.5
H11A—C11—H11B	107.4	H22A—C22—H22B	109.5
C11—C12—C13	110.0 (9)	C21—C22—H22C	109.5
C11—C12—H12A	109.7	H22A—C22—H22C	109.5
C13—C12—H12A	109.7	H22B—C22—H22C	109.5

S2—Pd1—S1—C1	−2.2 (3)	N1—C3—C4—C6	−178.7 (9)
S2ⁱ—Pd1—S1—C1	177.8 (3)	C5—C3—C4—C6	0.8 (15)
S1ⁱ—Pd1—S2—C2	−177.6 (3)	C15—N5—C7—C8	−178.6 (9)
S1—Pd1—S2—C2	2.4 (3)	C11—N5—C7—C8	59.4 (10)
C3—N1—C1—C2	−0.7 (13)	C19—N5—C7—C8	−58.7 (11)
C3—N1—C1—S1	178.5 (7)	N5—C7—C8—C9	178.5 (8)
Pd1—S1—C1—N1	−177.7 (6)	C7—C8—C9—C10	−178.1 (9)
Pd1—S1—C1—C2	1.6 (7)	C15—N5—C11—C12	−60.9 (10)
C4—N2—C2—C1	−0.4 (14)	C7—N5—C11—C12	57.3 (10)
C4—N2—C2—S2	−179.5 (8)	C19—N5—C11—C12	178.5 (8)
N1—C1—C2—N2	0.6 (14)	N5—C11—C12—C13	−176.3 (8)
S1—C1—C2—N2	−178.6 (7)	C11—C12—C13—C14	−178.4 (10)
N1—C1—C2—S2	179.7 (7)	C7—N5—C15—C16	175.8 (8)
S1—C1—C2—S2	0.5 (11)	C11—N5—C15—C16	−63.1 (11)
Pd1—S2—C2—N2	176.8 (7)	C19—N5—C15—C16	55.2 (11)
Pd1—S2—C2—C1	−2.3 (8)	N5—C15—C16—C17	−177.1 (8)
C1—N1—C3—C4	0.6 (14)	C15—C16—C17—C18	177.6 (10)
C1—N1—C3—C5	−178.9 (8)	C15—N5—C19—C20	57.1 (10)
C2—N2—C4—C3	0.3 (16)	C7—N5—C19—C20	−60.2 (11)
C2—N2—C4—C6	178.5 (9)	C11—N5—C19—C20	179.0 (8)
N1—C3—C4—N2	−0.4 (16)	N5—C19—C20—C21	−175.2 (8)
C5—C3—C4—N2	179.2 (10)	C19—C20—C21—C22	−178.6 (11)

Symmetry code: (i) −x+2, −y+1, −z+2.

Experimental details

Crystal data
Chemical formula	(C₁₆H₃₆N)₂[Pd(C₆N₄S₂)₂]
M_r	975.80
Crystal system, space group	Triclinic, P1
Temperature (K)	296
a, b, c (Å)	9.912 (3), 10.635 (4), 13.286 (4)
α, β, γ (°)	68.82 (2), 87.74 (3), 80.16 (3)
V (Å³)	1286.3 (8)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	0.56
Crystal size (mm)	0.25 × 0.10 × 0.05

Data collection
Diffractometer	Rigaku AFC-7R diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	5102, 4835, 1751
R_int	0.087
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.093, 0.222, 0.98
No. of reflections	4835
No. of parameters	272
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.39, −0.41

Computer programs: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1988), TEXSAN (Molecular Structure Corporation & Rigaku, 2000), SIR97 (Altomare et al., 1999), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009).

Acknowledgements

The authors thank the Instrument Center of the Institute for Molecular Science for the X-ray crystallographic analysis.

References

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