Bis(tetra-n-butyl-ammonium) bis-(5,6-dicyano-pyrazine-2,3-dithiol-ato-κS,S')palladium(II).

In the title complex, (C(16)H(36)N)(2)[Pd(C(6)N(4)S(2))(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 = 975.80

Triclinic,

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[F 2 > 2σ(F 2)] = 0.093

wR(F 2) = 0.222

S = 0.98

4835 reflections

272 parameters

H-atom parameters constrained

Δρmax = 0.39 e Å−3

Δρmin = −0.41 e Å−3

Data collection: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1988 ▶); 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.

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536811053402/hy2494sup1.cif

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

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

(C16H36N)2[Pd(C6N4S2)2]	Z = 1
Mr = 975.80	F(000) = 516
Triclinic, P1	Dx = 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

Rigaku AFC-7R diffractometer	Rint = 0.087
Radiation source: rotating anode	θmax = 27.5°, θmin = 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 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(Fo2) + (0.0782P)2] where P = (Fo2 + 2Fc2)/3
4835 reflections	(Δ/σ)max < 0.001
272 parameters	Δρmax = 0.39 e Å−3
0 restraints	Δρmin = −0.41 e Å−3

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.

	x	y	z	Uiso*/Ueq
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*

	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)

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)