N-Ethylpyridinium bis(2-thioxo-1,3-dithiole-4,5-dithiolato)nickelate

The title compound, (C₇H₁₀N)[Ni(C₃S₅)₂] or (Etpy)[Ni(dmit)₂] (where Etpy is the N-ethyl­pyridinium cation, C₇H₁₀N⁺, and dmit is the 2-thio­xo-1,3-di­thiole-4,5-di­thiol­ate dianion, C₃S₅²⁻), crystallizes in the P space group with two mol­ecules in the asymmetric unit. The [Ni(dmit)₂]⁻ monoanion has a planar D_2h conformation, with the central Ni atom and the four coordinated S atoms forming an NiS₄ square plane. The six-membered ring of the Etpy cation also shows good planarity, as expected. There are two main types of disorder in the two Etpy cations. Several short intermolecular interactions are present, such as S...S, Ni...S and Ni...Ni, which help to form the enhanced three-dimensional structure of the crystal.

S1. Comment

Metal-dmit coordination anions, [M(dmit)₂]^x- (0 ≤ x ≤ 1), as the conducting component in the Z[M(dmit)₂]_n type of molecular conductors and superconductors, have attracted intense research interest over the past 20 years (Lindqvist et al., 1979; Valade et al., 1985; Bousseau et al., 1986; Kobayashi et al., 1987; Cornelissen et al., 1991; Miyazaki et al., 1992; Tajima et al., 1993; Veldhuizen et al., 1995; Fun et al., 1996; Xu et al., 2001). Various crystals, and consequently various conductivities, can be obtained by using different monocations in the 1:2 salts of Z[Ni(dmit)₂]₂, which has formed the most dominant group in the Z[M(dmit)₂]_n family. From the synthesis point of view, conductive 1:2 Z[Ni(dmit)₂]₂ salts are prepared from the non-conductive precursor of 1:1 Z[Ni(dmit)₂] salts. To date, most cations have been tetraalkyl ammonium, and less attention has been paid to planar cations. The synthesis of [guanidinium][Ni(dmit)₂]₂ (Veldhuizen et al., 1995) has aroused our interest in such small planar cations, such as N-ethylpyridinine, because small planar cations may reduce the spacing between the conductive anions and enhance the overlap between molecular orbitals. Thus, we synthesized the title 1:1 complex, (I), as a precursor of the 1:2 complex [Etpy][Ni(dmit)₂]₂, which we failed to obtain, and report its structure in this paper. Surprisingly, even the 1:1 title complex shows considerable conductivity. \sch

The unit cell of (I) contains two crystallographically independent [Ni(dmit)₂]⁻ anions and two Etpy cations, as depicted in Figs. 1 and 2. Statistically speaking, there are no significant differences in the bond lengths and angles between the two [Ni(dmit)₂]⁻ anions, except that the planarity of [Ni2(dmit)₂]⁻ is more perfect than that of [Ni1(dmit)₂]⁻. Both of the [Ni(dmit)₂]⁻ anions have a D_{2 h} symmetrical conformation and exhibit perfect planarity, with maximum deviations from the least-squares plane of 0.078 (1) Å for atom S10 in [Ni1(dmit)₂]⁻ and 0.055 (1) Å for atom S18 in [Ni2(dmit)₂]⁻. The NiS₄ core adopts a slightly distorted square-planar conformation. The Ni—S bond lengths range from 2.1535 (13) to 2.1751 (13) Å, with the average length being 2.1604 (13) Å, and S—Ni—S angles range from 86.65 (5) to 93.09 (5)°. The Etpy ring is also planar, as expected. There are two types of disorder in the two Etpy cations. One type affects all four C atoms (C22, C23, C24 and C25) in one Etpy ring, with occupancies of 0.55 (2) and 0.45 (2), and the other affects atom C14 in the ethyl group of another Etpy cation, with occupancies of 0.648 (19) and 0.352 (19).

There are many S···S, Ni···S and Ni···Ni interactions between neighbouring molecules of (I) (Figs. 2 and 3). Table 2 lists all the intermolecular S···S contacts shorter than 3.60 Å (the sum of the van der Waals radii), Ni···S contacts shorter than 4.10 Å and Ni···Ni contacts shorter than 4.60 Å. The shortest intermolecular S···S contact is 3.383 (2) Å, between atoms S17 and S17^? [symmetry code?], which is shorter than the shortest value reported in the literature (Cornelissen et al., 1991).

Referring to Figs. 2 and 3 and Table 2, the anions of (I) form weak dimers via Ni···S and Ni···Ni interactions. The angle between the planes of two independent anions is 2.99 (4)°, showing the basic parallel arrangement of the two anions; the two long axes of the two planar anions are also parallel. In fact, all planar [Ni(dmit)₂]⁻ anions are parallel to each other. The anions form a kind of zigzag chain via five pairs of strong intermolecular S···S interactions between neighbouring [Ni(dmit)₂]⁻ anions. Thus, (I) shows the typical characteristic of one-dimensional structure required for conductivity.

Additionally, the structure of (I) exhibits a slight two- or three-dimensional feature, due to Ni···Ni dimer interactions, terminal S···S interactions and anionic-cationic coulombic interactions. The Etpy cations are located between the anionic zigzag chains. This kind of crystal, with strong intermolecular interactions, may have a high conductivity. In fact, the measured conductivity (by the two-probe contact method) of the crystal of (I) is 5 × 10⁻⁷ S cm⁻¹ at room temperature, which is quite high among the Z[M(dmit)₂] type of 1:1 complexes.

Table 2 Intermolecular S···S, Ni···S and Ni···Ni contacts (Å) shorter than the van der Waals radii

S2. Experimental

Ethyl iodide (15 ml) was mixed with pyridine (24 ml) and then kept at 339–341 K for several hours. The resulting solution was washed with a large excess of petroleum ether until white N-ethylpyridine iodide precipitated. Dmit(COPh)₂ (0.816 g, 2 mmol) was treated with an excess of sodium methylate (0.5M) in MeOH (20 ml) under nitrogen at room temperature with stirring. To the resulting red solution, NiCl₂·6H₂O (0.237 g, 1 mmol) in MeOH (20 ml) and N-ethylpyridine iodide (0.550 g, 2.4 mmol) in MeOH (20 ml) were added. The resulting precipitate was washed with MeOH (yield 0.555 g). This precipitate was then dissolved in acetone and oxidated by I₂/NaI. Thick black platelets of (I), one of which was used for the present structure determination, could be obtained from the filtrate by slow evaporation (m.p. 470 K). The crystal could be further purified by recrystallization from acetone in air.

S3. Refinement

After checking their presence in the difference map, all H atoms were geometrically fixed and allowed to ride on their attached atoms, with C—H distances in the range 0.93–0.97 Å and U_iso(H) = 1.2U_eq(C).

Computing details

Data collection: XSCANS (Siemens, 1996); cell refinement: XSCANS; data reduction: XSCANS; program(s) used to solve structure: SHELXTL (Bruker, 1997); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL.

Figures

	Fig. 1. A view of the two independent cations and anions of (I), with the atomic numbering scheme. Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii.
	Fig. 2. The crystal packing of (I), viewed along the a axis.
	Fig. 3. The packing of the [Ni(dmit)2]^− anion of (I).

N-ethylpyridinium bis(2-thioxo-1,3-dithiole-4,5-dithiolato)nickelate(II)

Crystal data

[C7H10N][Ni(C3S5)2]	Z = 4
Mr = 559.61	F(000) = 1132
Triclinic, P1	Dx = 1.792 Mg m^−3
Hall symbol: -P1	Melting point: 470 K
a = 8.7825 (8) Å	Mo Kα radiation, λ = 0.71073 Å
b = 16.209 (2) Å	Cell parameters from 36 reflections
c = 16.7077 (16) Å	θ = 5.3–12.4°
α = 112.555 (9)°	µ = 1.94 mm^−1
β = 104.477 (7)°	T = 293 K
γ = 95.876 (10)°	Prism, black
V = 2073.8 (4) Å^3	0.24 × 0.22 × 0.20 mm

Data collection

Bruker P4 diffractometer	4722 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.024
Graphite monochromator	θmax = 25.0°, θmin = 2.4°
θ/2θ scans	h = −1→10
Absorption correction: ψ scan (XSCANS; Siemens, 1996)	k = −17→17
Tmin = 0.566, Tmax = 0.678	l = −19→19
8565 measured reflections	3 standard reflections every 97 reflections
7056 independent reflections	intensity decay: 2%

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.043	H-atom parameters constrained
wR(F^2) = 0.118	w = 1/[σ^2(Fo^2) + (0.0509P)^2 + 2.0853P] where P = (Fo^2 + 2Fc^2)/3
S = 0.95	(Δ/σ)max = 0.001
7056 reflections	Δρmax = 0.55 e Å^−3
449 parameters	Δρmin = −0.40 e Å^−3
11 restraints	Extinction correction: SHELXTL (Bruker, 1997), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.00173 (19)

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
Ni1	0.44569 (7)	0.11278 (4)	0.07908 (4)	0.04380 (17)
Ni2	0.13204 (6)	0.47959 (4)	0.41612 (4)	0.04227 (17)
S1	0.0926 (2)	−0.29906 (10)	0.08577 (12)	0.0791 (5)
S2	0.07027 (15)	−0.15109 (9)	0.02304 (10)	0.0627 (4)
S3	0.36857 (17)	−0.14206 (9)	0.15004 (9)	0.0620 (4)
S4	0.20784 (14)	0.02452 (8)	0.01498 (9)	0.0557 (3)
S5	0.53062 (15)	0.03354 (9)	0.15274 (9)	0.0600 (3)
S6	0.35915 (14)	0.19539 (9)	0.00852 (9)	0.0561 (3)
S7	0.68467 (14)	0.19928 (8)	0.14317 (9)	0.0527 (3)
S8	0.52845 (15)	0.37205 (9)	0.01430 (9)	0.0595 (3)
S9	0.82505 (15)	0.37524 (8)	0.13826 (9)	0.0575 (3)
S10	0.8120 (2)	0.52678 (10)	0.08163 (11)	0.0790 (5)
S11	−0.24903 (19)	0.08352 (9)	0.43960 (11)	0.0733 (4)
S12	−0.25584 (16)	0.22509 (9)	0.36852 (9)	0.0616 (4)
S13	0.04297 (16)	0.22650 (9)	0.48967 (10)	0.0617 (4)
S14	−0.10791 (14)	0.39424 (8)	0.35476 (9)	0.0561 (3)
S15	0.21771 (14)	0.39629 (9)	0.48552 (9)	0.0574 (3)
S16	0.04955 (14)	0.55996 (8)	0.34293 (9)	0.0554 (3)
S17	0.37140 (14)	0.56555 (8)	0.47898 (9)	0.0558 (3)
S18	0.22611 (16)	0.72704 (9)	0.33556 (9)	0.0580 (3)
S19	0.51998 (15)	0.73448 (8)	0.46417 (10)	0.0599 (4)
S20	0.51421 (19)	0.87549 (10)	0.39244 (12)	0.0795 (5)
N1	−0.0079 (8)	−0.0472 (4)	0.2979 (5)	0.0947 (18)
N2	0.3953 (8)	0.4319 (4)	0.2320 (4)	0.0866 (16)
C1	0.1732 (6)	−0.2023 (3)	0.0862 (3)	0.0558 (12)
C2	0.2270 (5)	−0.0579 (3)	0.0549 (3)	0.0462 (11)
C3	0.3659 (6)	−0.0542 (3)	0.1142 (3)	0.0459 (11)
C4	0.5273 (5)	0.2813 (3)	0.0461 (3)	0.0461 (11)
C5	0.6674 (5)	0.2830 (3)	0.1043 (3)	0.0447 (10)
C6	0.7257 (6)	0.4291 (3)	0.0773 (3)	0.0548 (12)
C7	−0.1587 (6)	0.1736 (3)	0.4329 (3)	0.0528 (12)
C8	−0.0940 (5)	0.3126 (3)	0.3959 (3)	0.0466 (11)
C9	0.0480 (6)	0.3140 (3)	0.4526 (3)	0.0495 (11)
C10	0.2187 (5)	0.6429 (3)	0.3755 (3)	0.0431 (10)
C11	0.3578 (5)	0.6454 (3)	0.4355 (3)	0.0437 (10)
C12	0.4229 (6)	0.7837 (3)	0.3974 (3)	0.0535 (12)
C13	−0.1734 (9)	−0.2026 (5)	0.2393 (5)	0.125 (3)
H13A	−0.2762	−0.2298	0.2388	0.188*
H13B	−0.1016	−0.2434	0.2399	0.188*
H13C	−0.1868	−0.1916	0.1857	0.188*
C14	−0.1051 (16)	−0.1150 (8)	0.3215 (9)	0.103 (5)*	0.648 (19)
H14A	−0.0351	−0.1250	0.3703	0.123*	0.648 (19)
H14B	−0.1912	−0.0898	0.3420	0.123*	0.648 (19)
C14'	−0.1809 (16)	−0.1029 (7)	0.2715 (16)	0.088 (8)*	0.352 (19)
H14C	−0.2198	−0.0838	0.3239	0.105*	0.352 (19)
H14D	−0.2536	−0.0933	0.2233	0.105*	0.352 (19)
C15	−0.0526 (10)	−0.0070 (6)	0.2429 (6)	0.123 (3)
H15A	−0.1607	−0.0204	0.2089	0.147*
C16	0.0503 (15)	0.0508 (7)	0.2352 (5)	0.126 (3)
H16A	0.0149	0.0792	0.1973	0.151*
C17	0.2059 (12)	0.0694 (5)	0.2815 (7)	0.108 (3)
H17A	0.2804	0.1089	0.2743	0.129*
C18	0.2539 (9)	0.0313 (5)	0.3377 (6)	0.111 (3)
H18A	0.3620	0.0450	0.3718	0.133*
C19	0.1461 (12)	−0.0270 (6)	0.3453 (5)	0.108 (2)
H19A	0.1801	−0.0539	0.3848	0.130*
C20	0.2410 (12)	0.2967 (7)	0.2333 (7)	0.191 (5)
H20A	0.2451	0.2481	0.2526	0.286*
H20B	0.1984	0.2712	0.1680	0.286*
H20C	0.1727	0.3341	0.2596	0.286*
C21	0.4016 (11)	0.3520 (6)	0.2632 (6)	0.145 (4)
H21A	0.4711	0.3143	0.2371	0.175*
H21B	0.4456	0.3772	0.3292	0.175*
C22	0.2846 (18)	0.4593 (13)	0.1830 (11)	0.080 (5)*	0.45 (2)
H22B	0.1797	0.4244	0.1589	0.096*	0.45 (2)
C23	0.311 (2)	0.5339 (13)	0.1650 (11)	0.071 (5)*	0.45 (2)
H23B	0.2301	0.5479	0.1277	0.085*	0.45 (2)
C24	0.471 (2)	0.5890 (10)	0.2071 (11)	0.069 (5)*	0.45 (2)
H24B	0.4951	0.6417	0.1984	0.083*	0.45 (2)
C25	0.580 (3)	0.5684 (10)	0.2552 (14)	0.088 (6)*	0.45 (2)
H25B	0.6856	0.6031	0.2809	0.106*	0.45 (2)
C22'	0.2626 (15)	0.4234 (14)	0.1729 (9)	0.097 (5)*	0.55 (2)
H22A	0.1755	0.3738	0.1480	0.117*	0.55 (2)
C23'	0.2649 (15)	0.4928 (11)	0.1520 (8)	0.079 (4)*	0.55 (2)
H23A	0.1683	0.4921	0.1127	0.094*	0.55 (2)
C24'	0.386 (2)	0.5662 (8)	0.1785 (9)	0.073 (4)*	0.55 (2)
H24A	0.3774	0.6132	0.1599	0.087*	0.55 (2)
C25'	0.524 (2)	0.5617 (11)	0.2366 (12)	0.112 (7)*	0.55 (2)
H25A	0.6148	0.6080	0.2567	0.134*	0.55 (2)
C26	0.5384 (9)	0.4946 (5)	0.2676 (4)	0.099 (2)
H26A	0.6200	0.4836	0.3073	0.119*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ni1	0.0387 (3)	0.0409 (3)	0.0527 (4)	0.0023 (3)	0.0127 (3)	0.0235 (3)
Ni2	0.0398 (3)	0.0372 (3)	0.0524 (3)	0.0023 (2)	0.0125 (3)	0.0245 (3)
S1	0.0956 (11)	0.0564 (9)	0.1104 (12)	0.0103 (8)	0.0477 (10)	0.0533 (9)
S2	0.0469 (7)	0.0519 (7)	0.0944 (10)	−0.0006 (6)	0.0152 (7)	0.0435 (7)
S3	0.0696 (9)	0.0562 (8)	0.0710 (9)	0.0145 (7)	0.0173 (7)	0.0408 (7)
S4	0.0415 (7)	0.0531 (7)	0.0761 (8)	0.0000 (6)	0.0061 (6)	0.0416 (7)
S5	0.0459 (7)	0.0543 (7)	0.0750 (9)	0.0002 (6)	0.0005 (6)	0.0368 (7)
S6	0.0416 (6)	0.0601 (8)	0.0684 (8)	−0.0018 (6)	0.0060 (6)	0.0393 (7)
S7	0.0415 (6)	0.0478 (7)	0.0682 (8)	−0.0006 (5)	0.0061 (6)	0.0336 (6)
S8	0.0559 (8)	0.0602 (8)	0.0740 (9)	0.0090 (6)	0.0160 (7)	0.0440 (7)
S9	0.0492 (7)	0.0531 (7)	0.0682 (8)	−0.0063 (6)	0.0082 (6)	0.0345 (6)
S10	0.0857 (11)	0.0584 (9)	0.1032 (12)	−0.0014 (8)	0.0260 (9)	0.0516 (9)
S11	0.0860 (10)	0.0492 (8)	0.0923 (10)	−0.0058 (7)	0.0388 (9)	0.0365 (7)
S12	0.0565 (8)	0.0569 (8)	0.0669 (8)	−0.0121 (6)	0.0112 (7)	0.0328 (7)
S13	0.0591 (8)	0.0549 (8)	0.0869 (9)	0.0059 (6)	0.0226 (7)	0.0483 (7)
S14	0.0435 (7)	0.0556 (7)	0.0697 (8)	−0.0041 (6)	0.0043 (6)	0.0392 (7)
S15	0.0421 (7)	0.0565 (7)	0.0791 (9)	−0.0034 (6)	0.0069 (6)	0.0456 (7)
S16	0.0462 (7)	0.0486 (7)	0.0691 (8)	−0.0012 (6)	0.0037 (6)	0.0345 (6)
S17	0.0429 (7)	0.0497 (7)	0.0784 (9)	−0.0025 (5)	0.0034 (6)	0.0437 (7)
S18	0.0630 (8)	0.0525 (7)	0.0708 (8)	0.0100 (6)	0.0168 (7)	0.0420 (7)
S19	0.0473 (7)	0.0511 (7)	0.0896 (9)	0.0001 (6)	0.0136 (7)	0.0459 (7)
S20	0.0774 (10)	0.0688 (9)	0.1244 (13)	0.0097 (8)	0.0400 (9)	0.0704 (10)
N1	0.098 (5)	0.068 (3)	0.131 (5)	0.021 (3)	0.068 (4)	0.036 (4)
N2	0.119 (5)	0.095 (4)	0.072 (3)	0.053 (4)	0.051 (4)	0.041 (3)
C1	0.065 (3)	0.046 (3)	0.068 (3)	0.015 (2)	0.030 (3)	0.029 (2)
C2	0.042 (3)	0.040 (2)	0.065 (3)	0.005 (2)	0.021 (2)	0.030 (2)
C3	0.052 (3)	0.036 (2)	0.059 (3)	0.010 (2)	0.022 (2)	0.026 (2)
C4	0.047 (3)	0.049 (3)	0.050 (3)	0.009 (2)	0.019 (2)	0.028 (2)
C5	0.040 (2)	0.041 (2)	0.053 (3)	0.001 (2)	0.017 (2)	0.021 (2)
C6	0.060 (3)	0.047 (3)	0.058 (3)	0.004 (2)	0.017 (2)	0.025 (2)
C7	0.059 (3)	0.042 (3)	0.058 (3)	0.000 (2)	0.028 (2)	0.019 (2)
C8	0.045 (3)	0.042 (2)	0.052 (3)	−0.002 (2)	0.017 (2)	0.022 (2)
C9	0.053 (3)	0.045 (3)	0.062 (3)	0.009 (2)	0.024 (2)	0.031 (2)
C10	0.049 (3)	0.035 (2)	0.051 (3)	0.007 (2)	0.017 (2)	0.025 (2)
C11	0.041 (2)	0.034 (2)	0.057 (3)	0.0004 (19)	0.014 (2)	0.024 (2)
C12	0.057 (3)	0.050 (3)	0.071 (3)	0.014 (2)	0.030 (3)	0.037 (2)
C13	0.095 (5)	0.109 (6)	0.156 (8)	0.010 (5)	0.032 (5)	0.049 (6)
C15	0.079 (5)	0.108 (7)	0.138 (8)	0.018 (5)	−0.012 (5)	0.037 (6)
C16	0.171 (10)	0.135 (8)	0.075 (5)	0.044 (8)	0.016 (6)	0.062 (5)
C17	0.130 (7)	0.079 (5)	0.142 (8)	0.029 (5)	0.079 (6)	0.052 (5)
C18	0.069 (5)	0.080 (5)	0.139 (7)	0.016 (4)	−0.007 (4)	0.026 (5)
C19	0.132 (7)	0.101 (6)	0.094 (5)	0.038 (6)	0.013 (5)	0.055 (5)
C20	0.185 (11)	0.175 (11)	0.155 (9)	0.018 (9)	0.095 (9)	−0.008 (8)
C21	0.143 (9)	0.176 (10)	0.097 (6)	0.075 (8)	0.041 (6)	0.025 (6)
C26	0.079 (5)	0.134 (7)	0.062 (4)	0.046 (5)	0.004 (4)	0.023 (4)

Geometric parameters (Å, º)

Ni1—S7	2.1540 (13)	C4—C5	1.354 (6)
Ni1—S4	2.1567 (13)	C8—C9	1.356 (6)
Ni1—S5	2.1612 (13)	C10—C11	1.358 (6)
Ni1—S6	2.1751 (13)	C13—C14	1.476 (12)
Ni2—S17	2.1535 (13)	C13—C14'	1.509 (9)
Ni2—S14	2.1542 (13)	C13—H13A	0.9600
Ni2—S16	2.1657 (13)	C13—H13B	0.9600
Ni2—S15	2.1693 (13)	C13—H13C	0.9600
S1—C1	1.650 (5)	C14—H14A	0.9700
S2—C1	1.722 (5)	C14—H14B	0.9700
S2—C2	1.746 (4)	C14'—H14C	0.9700
S3—C1	1.726 (5)	C14'—H14D	0.9700
S3—C3	1.744 (4)	C15—C16	1.299 (11)
S4—C2	1.712 (4)	C15—H15A	0.9300
S5—C3	1.715 (4)	C16—C17	1.329 (11)
S6—C4	1.719 (4)	C16—H16A	0.9300
S7—C5	1.719 (4)	C17—C18	1.320 (10)
S8—C6	1.726 (5)	C17—H17A	0.9300
S8—C4	1.746 (4)	C18—C19	1.331 (10)
S9—C6	1.719 (5)	C18—H18A	0.9300
S9—C5	1.735 (4)	C19—H19A	0.9300
S10—C6	1.651 (5)	C20—C21	1.445 (8)
S11—C7	1.646 (4)	C20—H20A	0.9600
S12—C7	1.719 (5)	C20—H20B	0.9600
S12—C8	1.734 (4)	C20—H20C	0.9600
S13—C7	1.731 (5)	C21—H21A	0.9700
S13—C9	1.754 (4)	C21—H21B	0.9700
S14—C8	1.712 (4)	C22—C23	1.365 (10)
S15—C9	1.709 (5)	C22—H22B	0.9300
S16—C10	1.713 (4)	C23—C24	1.43 (2)
S17—C11	1.711 (4)	C23—H23B	0.9300
S18—C12	1.718 (5)	C24—C25	1.25 (2)
S18—C10	1.736 (4)	C24—H24B	0.9300
S19—C12	1.719 (5)	C25—C26	1.322 (9)
S19—C11	1.746 (4)	C25—H25B	0.9300
S20—C12	1.658 (4)	C22'—C23'	1.30 (2)
N1—C15	1.325 (10)	C22'—H22A	0.9300
N1—C19	1.319 (9)	C23'—C24'	1.359 (9)
N1—C14	1.549 (12)	C23'—H23A	0.9300
N1—C14'	1.548 (9)	C24'—C25'	1.377 (10)
N2—C22'	1.281 (9)	C24'—H24A	0.9300
N2—C22	1.336 (9)	C25'—C26	1.375 (9)
N2—C26	1.367 (8)	C25'—H25A	0.9300
N2—C21	1.571 (7)	C26—H26A	0.9300
C2—C3	1.344 (6)
S1···S10^i	3.520 (3)	S15···S17^iv	3.4566 (19)
S2···S4^ii	3.439 (2)	S15···S19^iv	3.450 (2)
S4···S4^ii	3.5209 (19)	S17···S17^iv	3.383 (2)
S7···S12^iii	3.5195 (19)	Ni1···S5^v	3.7586 (15)
S7···S14^iii	3.582 (2)	Ni2···S14^vi	3.6565 (15)
S9···S14^iii	3.4014 (19)	Ni1···Ni1^v	3.9778 (10)
S9···S16^iii	3.4802 (19)	Ni2···Ni2^vi	3.9768 (9)
S11···S20^i	3.467 (2)
S7—Ni1—S4	179.17 (5)	C14'—C13—H13A	101.7
S7—Ni1—S5	86.65 (5)	C14—C13—H13B	109.5
S4—Ni1—S5	92.63 (5)	H13A—C13—H13B	109.5
S7—Ni1—S6	93.09 (5)	C14—C13—H13C	109.5
S4—Ni1—S6	87.63 (5)	H13A—C13—H13C	109.5
S5—Ni1—S6	178.32 (6)	H13B—C13—H13C	109.5
S17—Ni2—S14	179.33 (6)	C13—C14—N1	108.9 (8)
S17—Ni2—S16	92.55 (5)	C13—C14—H14A	109.9
S14—Ni2—S16	87.66 (5)	N1—C14—H14A	109.9
S17—Ni2—S15	87.32 (5)	C13—C14—H14B	109.9
S14—Ni2—S15	92.50 (5)	N1—C14—H14B	109.9
S16—Ni2—S15	177.97 (6)	H14A—C14—H14B	108.3
C1—S2—C2	97.6 (2)	C13—C14'—N1	107.2 (8)
C1—S3—C3	97.0 (2)	C13—C14'—H14C	110.3
C2—S4—Ni1	102.44 (15)	N1—C14'—H14C	110.3
C3—S5—Ni1	102.34 (16)	C13—C14'—H14D	110.3
C4—S6—Ni1	101.85 (16)	N1—C14'—H14D	110.3
C5—S7—Ni1	102.34 (15)	H14C—C14'—H14D	108.5
C6—S8—C4	97.2 (2)	C16—C15—N1	121.9 (8)
C6—S9—C5	97.7 (2)	C16—C15—H15A	119.1
C7—S12—C8	97.7 (2)	N1—C15—H15A	119.1
C7—S13—C9	97.5 (2)	C15—C16—C17	120.1 (8)
C8—S14—Ni2	103.14 (16)	C15—C16—H16A	120.0
C9—S15—Ni2	102.16 (16)	C17—C16—H16A	120.0
C10—S16—Ni2	102.78 (15)	C18—C17—C16	119.4 (8)
C11—S17—Ni2	102.68 (15)	C18—C17—H17A	120.3
C12—S18—C10	97.6 (2)	C16—C17—H17A	120.3
C12—S19—C11	97.3 (2)	C17—C18—C19	119.5 (7)
C15—N1—C19	117.8 (7)	C17—C18—H18A	120.3
C15—N1—C14	132.1 (9)	C19—C18—H18A	120.3
C19—N1—C14	110.1 (9)	N1—C19—C18	121.3 (7)
C15—N1—C14'	93.4 (10)	N1—C19—H19A	119.4
C19—N1—C14'	148.7 (11)	C18—C19—H19A	119.4
C22'—N2—C26	131.1 (11)	C21—C20—H20A	109.5
C22—N2—C26	108.9 (10)	C21—C20—H20B	109.5
C22'—N2—C21	115.1 (11)	H20A—C20—H20B	109.5
C22—N2—C21	137.4 (11)	C21—C20—H20C	109.5
C26—N2—C21	113.6 (7)	H20A—C20—H20C	109.5
S1—C1—S2	123.3 (3)	H20B—C20—H20C	109.5
S1—C1—S3	123.4 (3)	C20—C21—N2	109.6 (8)
S2—C1—S3	113.2 (3)	C20—C21—H21A	109.7
C3—C2—S4	121.4 (3)	N2—C21—H21A	109.7
C3—C2—S2	115.5 (3)	C20—C21—H21B	109.7
S4—C2—S2	123.1 (3)	N2—C21—H21B	109.7
C2—C3—S5	121.1 (3)	H21A—C21—H21B	108.2
C2—C3—S3	116.7 (3)	N2—C22—C23	126.1 (14)
S5—C3—S3	122.2 (3)	N2—C22—H22B	117.0
C5—C4—S6	121.3 (3)	C23—C22—H22B	117.0
C5—C4—S8	115.8 (3)	C22—C23—C24	115.6 (14)
S6—C4—S8	122.9 (3)	C22—C23—H23B	122.2
C4—C5—S7	121.4 (3)	C24—C23—H23B	122.2
C4—C5—S9	116.0 (3)	C25—C24—C23	121.7 (13)
S7—C5—S9	122.5 (3)	C25—C24—H24B	119.1
S10—C6—S9	122.5 (3)	C23—C24—H24B	119.1
S10—C6—S8	124.3 (3)	C26—C25—C24	116.5 (17)
S9—C6—S8	113.2 (3)	C26—C25—H25B	121.8
S11—C7—S12	123.2 (3)	C24—C25—H25B	121.8
S11—C7—S13	123.8 (3)	N2—C22'—C23'	111.6 (13)
S12—C7—S13	113.0 (2)	N2—C22'—H22A	124.2
C9—C8—S14	120.3 (3)	C23'—C22'—H22A	124.2
C9—C8—S12	116.7 (3)	C24'—C23'—C22'	130.2 (12)
S14—C8—S12	123.0 (3)	C24'—C23'—H23A	114.9
C8—C9—S15	121.9 (3)	C22'—C23'—H23A	114.9
C8—C9—S13	115.0 (3)	C23'—C24'—C25'	110.9 (12)
S15—C9—S13	123.1 (3)	C23'—C24'—H24A	124.6
C11—C10—S16	120.4 (3)	C25'—C24'—H24A	124.6
C11—C10—S18	115.9 (3)	C24'—C25'—C26	125.7 (14)
S16—C10—S18	123.7 (3)	C24'—C25'—H25A	117.1
C10—C11—S17	121.5 (3)	C26—C25'—H25A	117.1
C10—C11—S19	115.7 (3)	C25—C26—N2	130.9 (13)
S17—C11—S19	122.8 (3)	C25'—C26—N2	110.1 (10)
S20—C12—S19	122.4 (3)	C25—C26—H26A	114.5
S20—C12—S18	124.1 (3)	C25'—C26—H26A	135.3
S19—C12—S18	113.5 (2)	N2—C26—H26A	114.5
C14—C13—H13A	109.5

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