1-(4-Cyano­benz­yl)-4-methyl­pyridinium bis­(benzene-1,2-dithiol­ato)nickelate(III)

The asymmetric unit of the title compound, (C₁₄H₁₃N₂)[Ni(C₆H₄S₂)₂], contains two cations, one anion and two half-anions. One of the half-anions has Ni on a twofold rotation axis, while the other has Ni on a centre of symmetry. In the anions, the Ni ions are surrounded by four S atoms in a distorted square-planar geometry. In the crystal structure, the anions exhibit two different packing modes by stacking in face-to-face and side-by-side fashions.

Key indicators

• Single-crystal X-ray study
• T = 294 K
• Mean [sigma](C-C) = 0.010 Å
• R factor = 0.060
• wR factor = 0.078
• Data-to-parameter ratio = 14.2

checkCIF/PLATON results

No syntax errors found



Alert level C
RINTA01_ALERT_3_C  The value of Rint is greater than 0.10
            Rint given   0.113
PLAT020_ALERT_3_C The value of Rint is greater than 0.10 .........       0.11
PLAT026_ALERT_3_C Ratio Observed / Unique Reflections too Low ....         40 Perc.
PLAT029_ALERT_3_C _diffrn_measured_fraction_theta_full Low .......       0.97
PLAT220_ALERT_2_C Large Non-Solvent    N     Ueq(max)/Ueq(min) ...       3.07 Ratio
PLAT220_ALERT_2_C Large Non-Solvent    N     Ueq(max)/Ueq(min) ...       2.89 Ratio
PLAT230_ALERT_2_C Hirshfeld Test Diff for    C47    -   C48     ..       5.05 su
PLAT230_ALERT_2_C Hirshfeld Test Diff for    C47    -   C50_b   ..       5.05 su
PLAT230_ALERT_2_C Hirshfeld Test Diff for    C50    -   C47_b   ..       5.05 su
PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for        C22
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        C16
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        C19
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        C25
PLAT341_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ...         10
PLAT371_ALERT_2_C Long   C(sp2)-C(sp1) Bond  C1     -   C2     ...       1.45 Ang.
PLAT371_ALERT_2_C Long   C(sp2)-C(sp1) Bond  C15    -   C16    ...       1.42 Ang.

Alert level G
REFLT03_ALERT_1_G ALERT: Expected hkl max differ from CIF values
           From the CIF: _diffrn_reflns_theta_max           25.00
           From the CIF: _reflns_number_total               8530
           From the CIF: _diffrn_reflns_limit_ max hkl   47.    7.   36.
           From the CIF: _diffrn_reflns_limit_ min hkl  -50.   -8.  -36.
           TEST1: Expected hkl limits for theta max
           Calculated maximum hkl   50.    8.   38.
           Calculated minimum hkl  -50.   -8.  -38.
PLAT794_ALERT_5_G Check Predicted Bond Valency for Ni1         (3)       3.05
PLAT794_ALERT_5_G Check Predicted Bond Valency for Ni2         (3)       3.05
PLAT794_ALERT_5_G Check Predicted Bond Valency for Ni3         (3)       3.01

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
  16 ALERT level C = Check and explain
   4 ALERT level G = General alerts; check

   1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
  11 ALERT type 2 Indicator that the structure model may be wrong or deficient
   5 ALERT type 3 Indicator that the structure quality may be low
   0 ALERT type 4 Improvement, methodology, query or suggestion
   3 ALERT type 5 Informative message, check

---

S1. Comment

Since their discovery in 1963, square planar bis(benzene-1,2-dithiolato)metal complexes have received considerable attention due to their interesting and often unusual electronic structures. It has been established that the square planar complexes [M(L)₂]^2-, [M(L)₂]^-, and [M(L)₂]⁰ (where M = Ni, Pt) form a three membered electron-transfer series, where the neutral species and the dianionic forms are diamagnetic (S = 0), whereas the monoanions are paramagnetic (S = 1/2) (de Caro et al., 2004; Ray et al., 2005). In our previous research using benzylpyridinium derivatives ([RBzPy]⁺) as the counter-cation of TCNQ^- (where TCNQ = 7,7,8,8-tetracyanoquinodimethanide), a series of ion-pair compounds with segregated columnar stacks of cations and anions has been prepared (Liu, 2007; Liu et al., 2005; Wang et al., 2006). The quasi one-dimensional magnetic nature of these compounds was attributed to intermolecular-orbital interactions within the anionic columns. As an extension of our work on this series of complexes, we herein report the crystal structure of the title compound, (I).

The asymmetric unit of (I), contains two (C₁₄H₁₃N₂)⁺ cations, one and two halves centrosymmetric [Ni(C₆H₄S₂)₂] anions. In the anions, the Ni ions are surrounded by four S atoms in a distorted square-planar geometry. The dihedral angle between (Ni1/S5/S6/C41/C46) and (Ni1/S5A/S6A/C41A/C46A) planes is 18.98 (2)° [symmetry code (A): -x, y, 1/2 - z]. It is peculiar and interesting. The Ni—S bond lengths and S—Ni—S bond angles (Table 1) are in agreement with the corresponding values in analogous complexes (Sellmann et al., 1991; Xie et al., 2002). The cations have Λ-shaped conformations with the dihedral angles of A/B = 65.03 (3), A/C = 46.37 (4), B/C = 86.96 (4) ° and D/E = 60.62 (3), D/F = 59.72 (3), E/F = 83.56 (4) ° between A (C5/C8/N1), B (C2—C7), C (N1/C9—C13) and D (C19/C22/N2), E (C16—C21), F (N2/C23—C28) planes.

In the crystal structure, the packing of the two anions is different (Fig. 2). The Ni1, Ni3-containing anions stack in a face-to-face fashion with an alternating arrangement of anions and cations, such that the pyridine ring of the cation lies above the benzene ring of the anion. The shortest distance between the adjacent Ni^III ions is 7.245 (2) Å. The Ni2-containing anions stack in a side by side fashion with C—H···S interactions (Table 2).

Related literature

For general backgroud, see: de Caro et al. (2004); Ray et al. (2005); Liu (2007); Liu et al. (2005); Wang et al. (2006). For related literature, see: Sellmann et al. (1991); Xie et al. (2002).

S2. Experimental

Benzene-1,2-dithiol (142 mg, 1.0 mmol) was added to a solution of sodium metal (46 mg, 2.0 mmol) in absolute ethanol (25 ml), under nitrogen atmosphere at room temperature, and then a solution of NiCl₂.6H₂O (120 mg, 0.5 mmol) in ethanol (25 ml) was added, resulting in a mixture turning a muddy red–brown color. Following this, [NCBzPyCH₃]Br (289 mg, 1.0 mmol) was added and the mixture allowed to stand with stirring for 1 h, and then stirred for an additional 24 h in air. The color of the mixture gradually turned green, indicating oxidation from a dianionic species to the more stable monoanionic form. The precipitate was washed with absolute ethanol and diethyl ether and then dried. The crude product was recrystallized twice from dichloromethane to give the title compound (yield; 241 mg, 69%, m.p. 483–485 K).

S3. Refinement

H atoms were positioned geometrically, with C—H = 0.93, 0.97 and 0.96 Å for aromatic, methylene and methyl H atoms, respectively, and constrained to ride on their parent atoms, with U_iso(H) = xUeq(C), where x = 1.5 for methyl H, and x = 1.2 for all other H atoms.

Computing details

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Bruker, 2000); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Figures

	Fig. 1. The molecular structure of the title molecule, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. The symmetry codes A in Ni1 and Ni3 anions are (-x, y, 1/2 - z) and (1/2 - x, 1/2 - y, 1 - z), respectively.
	Fig. 2. A packing diagram of (I). The C—H···S interactions are shown as dashed lines.

1-(4-Cyanobenzyl)-4-methylpyridinium bis(benzene-1,2-dithiolato)nickelate(III)

Crystal data

(C14H13N2)[Ni(C6H4S2)2]	F(000) = 4528
Mr = 548.40	Dx = 1.459 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 1320 reflections
a = 42.344 (3) Å	θ = 2.9–16.5°
b = 7.2455 (6) Å	µ = 1.13 mm^−1
c = 32.768 (2) Å	T = 294 K
β = 96.480 (5)°	Prism, dark green
V = 9988.9 (13) Å^3	0.20 × 0.12 × 0.10 mm
Z = 16

Data collection

Bruker SMART APEX CCD area-detector diffractometer	8530 independent reflections
Radiation source: sealed tube	3392 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.113
φ and ω scans	θmax = 25.0°, θmin = 1.5°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −50→47
Tmin = 0.806, Tmax = 0.896	k = −8→7
27982 measured reflections	l = −36→36

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.060	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.078	H-atom parameters constrained
S = 0.89	w = 1/[σ^2(Fo^2)] where P = (Fo^2 + 2Fc^2)/3
8530 reflections	(Δ/σ)max = 0.001
599 parameters	Δρmax = 0.34 e Å^−3
0 restraints	Δρmin = −0.27 e Å^−3

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
Ni1	0.0000	0.56508 (13)	0.2500	0.0602 (3)
Ni2	0.125597 (16)	0.62664 (10)	0.12628 (2)	0.0551 (2)
Ni3	0.2500	0.2500	0.5000	0.0615 (3)
S1	0.11139 (3)	0.88755 (19)	0.09943 (4)	0.0620 (4)
S2	0.09055 (4)	0.48396 (19)	0.08584 (5)	0.0667 (5)
S3	0.16124 (4)	0.7690 (2)	0.16585 (5)	0.0700 (5)
S4	0.13900 (3)	0.3664 (2)	0.15386 (4)	0.0641 (4)
S5	0.04314 (4)	0.5815 (2)	0.22143 (4)	0.0647 (5)
S6	0.02601 (4)	0.5293 (2)	0.30913 (4)	0.0737 (5)
S7	0.22258 (4)	0.1943 (2)	0.44230 (4)	0.0718 (5)
S8	0.29206 (4)	0.19526 (19)	0.47107 (5)	0.0646 (5)
N1	0.31857 (14)	0.6691 (6)	0.45220 (15)	0.0574 (13)
N2	0.06481 (13)	1.1024 (6)	0.20015 (15)	0.0563 (13)
N3	0.17638 (18)	0.9953 (13)	0.3108 (2)	0.177 (4)
N4	−0.06790 (18)	0.6563 (12)	0.0635 (2)	0.162 (3)
C1	0.1980 (2)	0.9276 (13)	0.3264 (2)	0.118 (3)
C2	0.2261 (2)	0.8448 (13)	0.3481 (2)	0.082 (2)
C3	0.22698 (19)	0.6628 (13)	0.3573 (2)	0.098 (3)
H3	0.2091	0.5914	0.3494	0.118*
C4	0.2529 (2)	0.5804 (10)	0.3775 (2)	0.087 (2)
H4	0.2526	0.4552	0.3837	0.105*
C5	0.27987 (16)	0.6851 (10)	0.38877 (17)	0.0586 (17)
C6	0.27969 (15)	0.8707 (9)	0.37946 (17)	0.0627 (17)
H6	0.2976	0.9424	0.3871	0.075*
C7	0.25306 (19)	0.9490 (9)	0.35900 (19)	0.072 (2)
H7	0.2531	1.0738	0.3524	0.087*
C8	0.30959 (14)	0.5990 (7)	0.40965 (16)	0.0659 (17)
H8A	0.3066	0.4664	0.4107	0.079*
H8B	0.3269	0.6229	0.3934	0.079*
C9	0.29658 (14)	0.6769 (7)	0.4786 (2)	0.0640 (18)
H9	0.2755	0.6482	0.4698	0.077*
C10	0.30535 (18)	0.7270 (7)	0.5183 (2)	0.071 (2)
H10	0.2899	0.7319	0.5363	0.085*
C11	0.3359 (2)	0.7703 (8)	0.5326 (3)	0.074 (2)
C12	0.35750 (19)	0.7611 (8)	0.5045 (3)	0.084 (2)
H12	0.3787	0.7897	0.5127	0.101*
C13	0.34874 (17)	0.7113 (8)	0.4649 (2)	0.073 (2)
H13	0.3639	0.7065	0.4465	0.088*
C14	0.34560 (16)	0.8237 (8)	0.57622 (19)	0.102 (2)
H14A	0.3680	0.8039	0.5828	0.152*
H14B	0.3342	0.7499	0.5940	0.152*
H14C	0.3408	0.9517	0.5800	0.152*
C15	−0.0476 (2)	0.7422 (13)	0.0787 (3)	0.124 (3)
C16	−0.0223 (2)	0.8514 (12)	0.09821 (19)	0.076 (2)
C17	0.00624 (19)	0.7662 (8)	0.11170 (19)	0.0665 (19)
H17	0.0088	0.6403	0.1077	0.080*
C18	0.03053 (14)	0.8689 (9)	0.13096 (16)	0.0612 (17)
H18	0.0498	0.8122	0.1400	0.073*
C19	0.02699 (17)	1.0549 (9)	0.13723 (16)	0.0556 (17)
C20	−0.0010 (2)	1.1392 (9)	0.1235 (2)	0.081 (2)
H20	−0.0036	1.2654	0.1272	0.097*
C21	−0.02549 (17)	1.0359 (12)	0.1041 (2)	0.088 (2)
H21	−0.0446	1.0933	0.0948	0.106*
C22	0.05457 (14)	1.1652 (8)	0.15794 (17)	0.0750 (19)
H22A	0.0723	1.1558	0.1418	0.090*
H22B	0.0485	1.2941	0.1586	0.090*
C23	0.04440 (14)	1.1099 (7)	0.2284 (2)	0.0643 (17)
H23	0.0237	1.1489	0.2208	0.077*
C24	0.05327 (16)	1.0622 (7)	0.2678 (2)	0.0666 (19)
H24	0.0386	1.0658	0.2869	0.080*
C25	0.08412 (19)	1.0082 (7)	0.2799 (2)	0.0576 (18)
C26	0.09546 (15)	0.9591 (7)	0.32383 (18)	0.092 (2)
H26A	0.1087	0.8512	0.3244	0.137*
H26B	0.0775	0.9347	0.3384	0.137*
H26C	0.1075	1.0600	0.3366	0.137*
C27	0.10478 (18)	0.9985 (7)	0.2500 (3)	0.076 (2)
H27	0.1256	0.9598	0.2568	0.091*
C28	0.09443 (17)	1.0457 (8)	0.2108 (2)	0.0685 (19)
H28	0.1084	1.0383	0.1908	0.082*
C29	0.08084 (13)	0.8376 (9)	0.06148 (16)	0.0535 (15)
C30	0.06495 (15)	0.9756 (8)	0.0381 (2)	0.0685 (19)
H30	0.0707	1.0985	0.0426	0.082*
C31	0.04077 (15)	0.9301 (10)	0.00835 (19)	0.074 (2)
H31	0.0302	1.0234	−0.0072	0.089*
C32	0.03178 (15)	0.7498 (10)	0.0011 (2)	0.082 (2)
H32	0.0154	0.7214	−0.0193	0.099*
C33	0.04738 (15)	0.6106 (9)	0.02449 (19)	0.0724 (18)
H33	0.0415	0.4881	0.0197	0.087*
C34	0.07160 (13)	0.6535 (8)	0.05490 (16)	0.0526 (15)
C35	0.18004 (13)	0.5986 (9)	0.19720 (17)	0.0573 (16)
C36	0.16966 (13)	0.4172 (9)	0.19115 (16)	0.0563 (16)
C37	0.18521 (16)	0.2797 (8)	0.2164 (2)	0.074 (2)
H37	0.1786	0.1577	0.2130	0.089*
C38	0.20967 (17)	0.3218 (10)	0.2457 (2)	0.085 (2)
H38	0.2196	0.2293	0.2621	0.102*
C39	0.21959 (16)	0.5034 (11)	0.2507 (2)	0.086 (2)
H39	0.2363	0.5324	0.2705	0.103*
C40	0.20502 (15)	0.6400 (9)	0.2270 (2)	0.0742 (18)
H40	0.2119	0.7614	0.2307	0.089*
C41	0.07300 (17)	0.5359 (6)	0.2607 (2)	0.0542 (17)
C42	0.1047 (2)	0.5224 (7)	0.2529 (2)	0.070 (2)
H42	0.1099	0.5408	0.2263	0.084*
C43	0.12827 (17)	0.4822 (8)	0.2840 (3)	0.085 (2)
H43	0.1493	0.4726	0.2786	0.102*
C44	0.12051 (17)	0.4560 (7)	0.3236 (2)	0.079 (2)
H44	0.1363	0.4280	0.3448	0.095*
C45	0.0897 (2)	0.4715 (7)	0.3313 (2)	0.073 (2)
H45	0.0847	0.4551	0.3580	0.088*
C46	0.06564 (16)	0.5109 (7)	0.3005 (2)	0.0590 (18)
C47	0.18323 (15)	0.2118 (7)	0.4527 (2)	0.0563 (17)
C48	0.15871 (19)	0.1752 (7)	0.42208 (19)	0.0690 (19)
H48	0.1633	0.1424	0.3959	0.083*
C49	0.12791 (17)	0.1871 (8)	0.4301 (2)	0.0752 (19)
H49	0.1115	0.1633	0.4094	0.090*
C50	0.32329 (17)	0.2401 (6)	0.50796 (18)	0.0539 (18)
C51	0.35497 (18)	0.2307 (7)	0.5006 (2)	0.064 (2)
H51	0.3598	0.2000	0.4745	0.077*
C52	0.37907 (16)	0.2653 (7)	0.5308 (2)	0.078 (2)
H52	0.4001	0.2571	0.5253	0.094*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ni1	0.0747 (9)	0.0539 (7)	0.0541 (7)	0.000	0.0170 (6)	0.000
Ni2	0.0557 (5)	0.0523 (5)	0.0574 (5)	−0.0065 (4)	0.0069 (4)	−0.0029 (4)
Ni3	0.0682 (9)	0.0607 (7)	0.0576 (8)	−0.0042 (6)	0.0156 (6)	0.0002 (5)
S1	0.0613 (11)	0.0554 (10)	0.0674 (11)	−0.0082 (9)	−0.0007 (9)	−0.0025 (8)
S2	0.0686 (13)	0.0552 (10)	0.0733 (12)	−0.0089 (8)	−0.0053 (10)	−0.0027 (8)
S3	0.0744 (13)	0.0597 (11)	0.0725 (12)	−0.0112 (9)	−0.0062 (10)	−0.0029 (9)
S4	0.0635 (12)	0.0553 (10)	0.0717 (11)	−0.0046 (8)	0.0000 (9)	−0.0001 (8)
S5	0.0771 (13)	0.0637 (11)	0.0550 (10)	−0.0004 (9)	0.0154 (9)	0.0043 (8)
S6	0.0834 (14)	0.0861 (13)	0.0541 (11)	0.0030 (9)	0.0185 (10)	0.0024 (8)
S7	0.0742 (13)	0.0874 (13)	0.0560 (11)	−0.0049 (9)	0.0170 (10)	−0.0041 (8)
S8	0.0729 (13)	0.0640 (11)	0.0586 (11)	0.0006 (9)	0.0149 (9)	−0.0025 (8)
N1	0.065 (4)	0.049 (3)	0.062 (4)	0.009 (3)	0.023 (4)	0.008 (2)
N2	0.064 (4)	0.049 (3)	0.056 (4)	−0.007 (3)	0.009 (3)	−0.004 (3)
N3	0.097 (7)	0.267 (10)	0.159 (7)	0.039 (6)	−0.030 (5)	0.070 (6)
N4	0.128 (7)	0.229 (9)	0.125 (6)	−0.074 (6)	−0.003 (5)	−0.019 (6)
C1	0.090 (8)	0.183 (9)	0.079 (6)	0.028 (7)	−0.001 (6)	0.031 (6)
C2	0.072 (7)	0.118 (7)	0.057 (5)	0.003 (6)	0.016 (5)	0.013 (5)
C3	0.082 (7)	0.134 (8)	0.075 (6)	−0.035 (6)	−0.013 (5)	0.002 (5)
C4	0.097 (7)	0.085 (6)	0.080 (6)	−0.027 (6)	0.008 (5)	0.004 (4)
C5	0.061 (5)	0.068 (5)	0.050 (4)	0.006 (4)	0.017 (4)	0.003 (4)
C6	0.067 (5)	0.057 (5)	0.065 (4)	0.004 (4)	0.007 (4)	−0.006 (4)
C7	0.072 (6)	0.080 (5)	0.066 (5)	0.024 (5)	0.012 (4)	0.006 (4)
C8	0.092 (5)	0.061 (4)	0.046 (4)	0.012 (4)	0.013 (4)	−0.003 (3)
C9	0.058 (5)	0.084 (5)	0.052 (5)	0.004 (3)	0.012 (4)	0.010 (4)
C10	0.087 (6)	0.075 (5)	0.053 (5)	0.002 (4)	0.019 (5)	0.008 (4)
C11	0.082 (7)	0.049 (4)	0.087 (7)	0.009 (4)	−0.001 (6)	0.005 (4)
C12	0.075 (7)	0.078 (5)	0.093 (7)	0.002 (4)	−0.011 (6)	−0.012 (4)
C13	0.053 (5)	0.069 (5)	0.100 (7)	0.005 (4)	0.021 (5)	0.003 (4)
C14	0.156 (8)	0.077 (5)	0.065 (5)	−0.002 (5)	−0.016 (5)	−0.011 (4)
C15	0.120 (10)	0.169 (10)	0.082 (7)	−0.052 (7)	0.011 (6)	−0.018 (6)
C16	0.082 (7)	0.100 (7)	0.046 (4)	−0.014 (6)	0.002 (4)	−0.005 (4)
C17	0.078 (6)	0.066 (5)	0.058 (5)	−0.005 (5)	0.018 (4)	0.009 (4)
C18	0.055 (5)	0.071 (5)	0.056 (4)	−0.010 (4)	0.003 (3)	0.009 (4)
C19	0.070 (6)	0.057 (5)	0.039 (4)	−0.007 (4)	0.004 (4)	0.001 (3)
C20	0.089 (6)	0.070 (5)	0.080 (5)	0.025 (5)	−0.004 (5)	−0.006 (4)
C21	0.052 (6)	0.126 (8)	0.083 (6)	0.025 (5)	−0.006 (4)	−0.002 (5)
C22	0.104 (6)	0.072 (5)	0.049 (4)	−0.014 (4)	0.009 (4)	0.008 (3)
C23	0.069 (5)	0.065 (4)	0.060 (5)	0.005 (4)	0.012 (4)	0.001 (4)
C24	0.071 (6)	0.062 (4)	0.068 (5)	0.007 (4)	0.012 (4)	−0.009 (4)
C25	0.081 (6)	0.043 (4)	0.045 (5)	−0.009 (4)	−0.011 (5)	−0.004 (3)
C26	0.127 (7)	0.069 (5)	0.073 (5)	−0.006 (4)	−0.017 (5)	0.011 (4)
C27	0.067 (6)	0.081 (5)	0.076 (6)	−0.005 (4)	−0.005 (5)	0.004 (4)
C28	0.065 (6)	0.067 (5)	0.075 (6)	−0.002 (4)	0.015 (5)	−0.006 (4)
C29	0.042 (4)	0.070 (5)	0.049 (4)	−0.004 (4)	0.005 (3)	0.000 (3)
C30	0.061 (5)	0.076 (5)	0.068 (5)	0.007 (4)	0.007 (4)	0.008 (4)
C31	0.057 (5)	0.098 (6)	0.065 (5)	0.011 (4)	−0.005 (4)	0.003 (4)
C32	0.058 (5)	0.098 (6)	0.088 (6)	−0.006 (5)	−0.004 (4)	−0.020 (5)
C33	0.059 (5)	0.076 (5)	0.081 (5)	−0.002 (4)	0.002 (4)	−0.007 (4)
C34	0.042 (4)	0.064 (4)	0.050 (4)	−0.010 (3)	−0.003 (3)	−0.009 (3)
C35	0.037 (4)	0.075 (5)	0.061 (4)	−0.001 (4)	0.009 (3)	−0.003 (4)
C36	0.049 (4)	0.062 (4)	0.058 (4)	0.003 (4)	0.009 (3)	0.004 (4)
C37	0.074 (6)	0.075 (5)	0.071 (5)	0.012 (4)	0.003 (4)	0.005 (4)
C38	0.074 (6)	0.099 (6)	0.080 (6)	0.014 (5)	−0.005 (4)	0.016 (5)
C39	0.057 (5)	0.117 (7)	0.080 (6)	0.005 (5)	−0.007 (4)	0.004 (5)
C40	0.058 (5)	0.085 (5)	0.077 (5)	−0.004 (4)	−0.005 (4)	−0.009 (4)
C41	0.065 (6)	0.040 (4)	0.058 (5)	0.001 (3)	0.008 (4)	−0.004 (3)
C42	0.085 (7)	0.062 (5)	0.066 (6)	0.008 (4)	0.019 (5)	0.002 (3)
C43	0.084 (7)	0.083 (5)	0.091 (6)	−0.001 (4)	0.021 (6)	−0.005 (4)
C44	0.076 (6)	0.074 (5)	0.085 (6)	0.013 (4)	−0.001 (5)	−0.004 (4)
C45	0.099 (7)	0.059 (4)	0.062 (5)	0.009 (4)	0.011 (5)	0.004 (3)
C46	0.068 (6)	0.049 (4)	0.062 (5)	0.001 (3)	0.014 (4)	−0.001 (3)
C47	0.051 (5)	0.049 (4)	0.068 (5)	−0.004 (3)	0.001 (4)	0.011 (3)
C48	0.083 (6)	0.065 (5)	0.063 (5)	0.000 (4)	0.026 (5)	0.012 (3)
C49	0.081 (6)	0.081 (5)	0.061 (5)	−0.005 (4)	−0.004 (4)	0.010 (4)
C50	0.078 (6)	0.046 (4)	0.039 (5)	0.002 (3)	0.013 (4)	0.006 (3)
C51	0.069 (6)	0.075 (5)	0.054 (5)	0.005 (4)	0.024 (5)	0.003 (3)
C52	0.065 (6)	0.082 (5)	0.086 (6)	−0.010 (4)	0.000 (5)	0.012 (4)

Geometric parameters (Å, º)

Ni1—S6	2.1337 (16)	C19—C20	1.365 (7)
Ni1—S6^i	2.1338 (16)	C19—C22	1.511 (7)
Ni1—S5	2.1477 (14)	C20—C21	1.374 (8)
Ni1—S5^i	2.1478 (14)	C20—H20	0.9300
Ni2—S4	2.1400 (16)	C21—H21	0.9300
Ni2—S3	2.1405 (17)	C22—H22A	0.9700
Ni2—S2	2.1408 (17)	C22—H22B	0.9700
Ni2—S1	2.1424 (16)	C23—C24	1.348 (7)
Ni3—S7	2.1424 (15)	C23—H23	0.9300
Ni3—S7^ii	2.1424 (15)	C24—C25	1.378 (7)
Ni3—S8^ii	2.1470 (14)	C24—H24	0.9300
Ni3—S8	2.1470 (14)	C25—C27	1.387 (8)
S1—C29	1.728 (6)	C25—C26	1.508 (7)
S2—C34	1.731 (6)	C26—H26A	0.9600
S3—C35	1.741 (6)	C26—H26B	0.9600
S4—C36	1.719 (6)	C26—H26C	0.9600
S5—C41	1.732 (6)	C27—C28	1.354 (8)
S6—C46	1.738 (6)	C27—H27	0.9300
S7—C47	1.742 (6)	C28—H28	0.9300
S8—C50	1.719 (6)	C29—C30	1.387 (7)
N1—C13	1.333 (6)	C29—C34	1.400 (6)
N1—C9	1.342 (6)	C30—C31	1.371 (7)
N1—C8	1.492 (6)	C30—H30	0.9300
N2—C28	1.328 (6)	C31—C32	1.374 (7)
N2—C23	1.338 (6)	C31—H31	0.9300
N2—C22	1.474 (6)	C32—C33	1.388 (7)
N3—C1	1.109 (8)	C32—H32	0.9300
N4—C15	1.129 (8)	C33—C34	1.383 (7)
C1—C2	1.449 (9)	C33—H33	0.9300
C2—C3	1.352 (9)	C35—C40	1.388 (7)
C2—C7	1.381 (8)	C35—C36	1.393 (7)
C3—C4	1.356 (8)	C36—C37	1.410 (7)
C3—H3	0.9300	C37—C38	1.364 (7)
C4—C5	1.385 (8)	C37—H37	0.9300
C4—H4	0.9300	C38—C39	1.386 (7)
C5—C6	1.379 (7)	C38—H38	0.9300
C5—C8	1.499 (7)	C39—C40	1.363 (7)
C6—C7	1.369 (7)	C39—H39	0.9300
C6—H6	0.9300	C40—H40	0.9300
C7—H7	0.9300	C41—C46	1.386 (7)
C8—H8A	0.9700	C41—C42	1.400 (8)
C8—H8B	0.9700	C42—C43	1.375 (8)
C9—C10	1.361 (7)	C42—H42	0.9300
C9—H9	0.9300	C43—C44	1.387 (7)
C10—C11	1.363 (8)	C43—H43	0.9300
C10—H10	0.9300	C44—C45	1.360 (7)
C11—C12	1.370 (9)	C44—H44	0.9300
C11—C14	1.494 (8)	C45—C46	1.381 (8)
C12—C13	1.357 (8)	C45—H45	0.9300
C12—H12	0.9300	C47—C48	1.385 (7)
C13—H13	0.9300	C47—C50^ii	1.394 (7)
C14—H14A	0.9600	C48—C49	1.362 (7)
C14—H14B	0.9600	C48—H48	0.9300
C14—H14C	0.9600	C49—C52^ii	1.389 (7)
C15—C16	1.426 (9)	C49—H49	0.9300
C16—C21	1.359 (8)	C50—C51	1.391 (7)
C16—C17	1.384 (8)	C50—C47^ii	1.394 (7)
C17—C18	1.365 (7)	C51—C52	1.362 (8)
C17—H17	0.9300	C51—H51	0.9300
C18—C19	1.374 (7)	C52—C49^ii	1.389 (7)
C18—H18	0.9300	C52—H52	0.9300
S6—Ni1—S6^i	166.03 (9)	N2—C22—H22A	109.0
S6—Ni1—S5	91.45 (6)	C19—C22—H22A	109.0
S6^i—Ni1—S5	89.32 (6)	N2—C22—H22B	109.0
S6—Ni1—S5^i	89.33 (6)	C19—C22—H22B	109.0
S6^i—Ni1—S5^i	91.45 (6)	H22A—C22—H22B	107.8
S5—Ni1—S5^i	173.64 (10)	N2—C23—C24	121.4 (6)
S4—Ni2—S3	91.93 (7)	N2—C23—H23	119.3
S4—Ni2—S2	88.17 (6)	C24—C23—H23	119.3
S3—Ni2—S2	178.93 (8)	C23—C24—C25	120.0 (6)
S4—Ni2—S1	178.82 (6)	C23—C24—H24	120.0
S3—Ni2—S1	88.26 (6)	C25—C24—H24	120.0
S2—Ni2—S1	91.66 (6)	C24—C25—C27	117.7 (7)
S7—Ni3—S7^ii	179.998 (1)	C24—C25—C26	122.0 (7)
S7—Ni3—S8^ii	91.76 (6)	C27—C25—C26	120.3 (7)
S7^ii—Ni3—S8^ii	88.25 (6)	C25—C26—H26A	109.5
S7—Ni3—S8	88.25 (6)	C25—C26—H26B	109.5
S7^ii—Ni3—S8	91.75 (6)	H26A—C26—H26B	109.5
S8^ii—Ni3—S8	179.998 (1)	C25—C26—H26C	109.5
C29—S1—Ni2	105.3 (2)	H26A—C26—H26C	109.5
C34—S2—Ni2	105.2 (2)	H26B—C26—H26C	109.5
C35—S3—Ni2	105.1 (2)	C28—C27—C25	119.7 (7)
C36—S4—Ni2	104.7 (2)	C28—C27—H27	120.2
C41—S5—Ni1	104.5 (2)	C25—C27—H27	120.2
C46—S6—Ni1	105.7 (3)	N2—C28—C27	121.4 (6)
C47—S7—Ni3	104.4 (3)	N2—C28—H28	119.3
C50—S8—Ni3	105.4 (2)	C27—C28—H28	119.3
C13—N1—C9	120.0 (6)	C30—C29—C34	119.5 (6)
C13—N1—C8	120.2 (5)	C30—C29—S1	121.6 (5)
C9—N1—C8	119.6 (6)	C34—C29—S1	118.9 (5)
C28—N2—C23	119.7 (6)	C31—C30—C29	119.8 (6)
C28—N2—C22	120.7 (6)	C31—C30—H30	120.1
C23—N2—C22	119.5 (6)	C29—C30—H30	120.1
N3—C1—C2	177.6 (12)	C30—C31—C32	121.4 (6)
C3—C2—C7	118.4 (8)	C30—C31—H31	119.3
C3—C2—C1	120.9 (9)	C32—C31—H31	119.3
C7—C2—C1	120.7 (9)	C31—C32—C33	119.4 (7)
C2—C3—C4	122.5 (8)	C31—C32—H32	120.3
C2—C3—H3	118.7	C33—C32—H32	120.3
C4—C3—H3	118.7	C34—C33—C32	120.1 (7)
C3—C4—C5	119.1 (7)	C34—C33—H33	119.9
C3—C4—H4	120.4	C32—C33—H33	119.9
C5—C4—H4	120.4	C33—C34—C29	119.8 (6)
C6—C5—C4	119.4 (6)	C33—C34—S2	121.3 (5)
C6—C5—C8	119.3 (6)	C29—C34—S2	118.9 (5)
C4—C5—C8	121.2 (7)	C40—C35—C36	120.5 (6)
C7—C6—C5	119.8 (6)	C40—C35—S3	121.5 (5)
C7—C6—H6	120.1	C36—C35—S3	118.0 (5)
C5—C6—H6	120.1	C35—C36—C37	117.6 (6)
C6—C7—C2	120.7 (7)	C35—C36—S4	120.3 (5)
C6—C7—H7	119.6	C37—C36—S4	122.1 (5)
C2—C7—H7	119.6	C38—C37—C36	121.5 (6)
N1—C8—C5	113.4 (5)	C38—C37—H37	119.3
N1—C8—H8A	108.9	C36—C37—H37	119.3
C5—C8—H8A	108.9	C37—C38—C39	119.5 (7)
N1—C8—H8B	108.9	C37—C38—H38	120.3
C5—C8—H8B	108.9	C39—C38—H38	120.3
H8A—C8—H8B	107.7	C40—C39—C38	120.6 (7)
N1—C9—C10	119.5 (6)	C40—C39—H39	119.7
N1—C9—H9	120.2	C38—C39—H39	119.7
C10—C9—H9	120.2	C39—C40—C35	120.3 (7)
C9—C10—C11	122.4 (7)	C39—C40—H40	119.8
C9—C10—H10	118.8	C35—C40—H40	119.8
C11—C10—H10	118.8	C46—C41—C42	119.1 (7)
C10—C11—C12	116.0 (8)	C46—C41—S5	120.1 (6)
C10—C11—C14	122.4 (8)	C42—C41—S5	120.8 (6)
C12—C11—C14	121.6 (8)	C43—C42—C41	120.6 (7)
C13—C12—C11	121.6 (8)	C43—C42—H42	119.7
C13—C12—H12	119.2	C41—C42—H42	119.7
C11—C12—H12	119.2	C42—C43—C44	119.7 (7)
N1—C13—C12	120.5 (7)	C42—C43—H43	120.2
N1—C13—H13	119.7	C44—C43—H43	120.2
C12—C13—H13	119.7	C45—C44—C43	119.7 (7)
C11—C14—H14A	109.5	C45—C44—H44	120.2
C11—C14—H14B	109.5	C43—C44—H44	120.2
H14A—C14—H14B	109.5	C44—C45—C46	121.7 (7)
C11—C14—H14C	109.5	C44—C45—H45	119.2
H14A—C14—H14C	109.5	C46—C45—H45	119.2
H14B—C14—H14C	109.5	C45—C46—C41	119.3 (7)
N4—C15—C16	179.3 (11)	C45—C46—S6	122.9 (6)
C21—C16—C17	119.4 (7)	C41—C46—S6	117.8 (6)
C21—C16—C15	121.8 (9)	C48—C47—C50^ii	120.4 (6)
C17—C16—C15	118.8 (9)	C48—C47—S7	120.0 (6)
C18—C17—C16	119.3 (7)	C50^ii—C47—S7	119.5 (6)
C18—C17—H17	120.3	C49—C48—C47	120.3 (6)
C16—C17—H17	120.3	C49—C48—H48	119.9
C17—C18—C19	121.0 (6)	C47—C48—H48	119.9
C17—C18—H18	119.5	C48—C49—C52^ii	120.1 (6)
C19—C18—H18	119.5	C48—C49—H49	119.9
C20—C19—C18	119.7 (6)	C52^ii—C49—H49	119.9
C20—C19—C22	120.7 (7)	C51—C50—C47^ii	117.9 (6)
C18—C19—C22	119.6 (6)	C51—C50—S8	123.3 (5)
C19—C20—C21	119.4 (7)	C47^ii—C50—S8	118.8 (6)
C19—C20—H20	120.3	C52—C51—C50	121.5 (7)
C21—C20—H20	120.3	C52—C51—H51	119.2
C16—C21—C20	121.3 (7)	C50—C51—H51	119.2
C16—C21—H21	119.4	C51—C52—C49^ii	119.7 (7)
C20—C21—H21	119.4	C51—C52—H52	120.2
N2—C22—C19	112.9 (5)	C49^ii—C52—H52	120.2
S3—Ni2—S1—C29	178.71 (17)	C24—C25—C27—C28	1.5 (8)
S2—Ni2—S1—C29	−0.22 (17)	C26—C25—C27—C28	−179.0 (5)
S4—Ni2—S2—C34	179.64 (18)	C23—N2—C28—C27	−1.4 (8)
S1—Ni2—S2—C34	0.82 (19)	C22—N2—C28—C27	175.8 (5)
S4—Ni2—S3—C35	−0.44 (18)	C25—C27—C28—N2	0.4 (9)
S1—Ni2—S3—C35	178.39 (18)	Ni2—S1—C29—C30	178.1 (4)
S3—Ni2—S4—C36	0.29 (18)	Ni2—S1—C29—C34	−0.6 (4)
S2—Ni2—S4—C36	179.22 (18)	C34—C29—C30—C31	−1.1 (8)
S6—Ni1—S5—C41	5.32 (18)	S1—C29—C30—C31	−179.8 (4)
S6^i—Ni1—S5—C41	−160.73 (17)	C29—C30—C31—C32	0.1 (9)
S6^i—Ni1—S6—C46	87.36 (18)	C30—C31—C32—C33	0.3 (10)
S5—Ni1—S6—C46	−5.65 (19)	C31—C32—C33—C34	0.4 (9)
S5^i—Ni1—S6—C46	−179.34 (19)	C32—C33—C34—C29	−1.4 (8)
S8^ii—Ni3—S7—C47	−3.25 (18)	C32—C33—C34—S2	177.6 (4)
S8—Ni3—S7—C47	176.75 (18)	C30—C29—C34—C33	1.8 (8)
S7—Ni3—S8—C50	176.17 (17)	S1—C29—C34—C33	−179.5 (4)
S7^ii—Ni3—S8—C50	−3.83 (17)	C30—C29—C34—S2	−177.3 (4)
C7—C2—C3—C4	1.5 (10)	S1—C29—C34—S2	1.4 (6)
C1—C2—C3—C4	179.9 (6)	Ni2—S2—C34—C33	179.5 (4)
C2—C3—C4—C5	−1.0 (11)	Ni2—S2—C34—C29	−1.5 (4)
C3—C4—C5—C6	0.4 (9)	Ni2—S3—C35—C40	179.4 (4)
C3—C4—C5—C8	−177.5 (6)	Ni2—S3—C35—C36	0.6 (4)
C4—C5—C6—C7	−0.4 (8)	C40—C35—C36—C37	0.5 (8)
C8—C5—C6—C7	177.5 (5)	S3—C35—C36—C37	179.4 (4)
C5—C6—C7—C2	1.0 (9)	C40—C35—C36—S4	−179.3 (4)
C3—C2—C7—C6	−1.5 (9)	S3—C35—C36—S4	−0.4 (6)
C1—C2—C7—C6	−179.9 (6)	Ni2—S4—C36—C35	0.0 (4)
C13—N1—C8—C5	−136.2 (6)	Ni2—S4—C36—C37	−179.8 (4)
C9—N1—C8—C5	48.6 (7)	C35—C36—C37—C38	−0.3 (8)
C6—C5—C8—N1	66.0 (6)	S4—C36—C37—C38	179.5 (5)
C4—C5—C8—N1	−116.1 (6)	C36—C37—C38—C39	−0.2 (10)
C13—N1—C9—C10	−0.4 (8)	C37—C38—C39—C40	0.4 (11)
C8—N1—C9—C10	174.9 (5)	C38—C39—C40—C35	−0.2 (10)
N1—C9—C10—C11	0.0 (9)	C36—C35—C40—C39	−0.3 (9)
C9—C10—C11—C12	0.2 (9)	S3—C35—C40—C39	−179.2 (5)
C9—C10—C11—C14	−179.4 (5)	Ni1—S5—C41—C46	−3.9 (4)
C10—C11—C12—C13	−0.2 (9)	Ni1—S5—C41—C42	175.7 (4)
C14—C11—C12—C13	179.5 (6)	C46—C41—C42—C43	1.0 (8)
C9—N1—C13—C12	0.4 (8)	S5—C41—C42—C43	−178.6 (4)
C8—N1—C13—C12	−174.8 (5)	C41—C42—C43—C44	−0.4 (9)
C11—C12—C13—N1	−0.2 (10)	C42—C43—C44—C45	−0.4 (9)
C21—C16—C17—C18	0.6 (9)	C43—C44—C45—C46	0.7 (9)
C15—C16—C17—C18	−179.1 (6)	C44—C45—C46—C41	−0.2 (8)
C16—C17—C18—C19	0.2 (8)	C44—C45—C46—S6	179.3 (4)
C17—C18—C19—C20	−1.0 (8)	C42—C41—C46—C45	−0.7 (8)
C17—C18—C19—C22	−178.8 (5)	S5—C41—C46—C45	178.9 (4)
C18—C19—C20—C21	0.9 (9)	C42—C41—C46—S6	179.8 (4)
C22—C19—C20—C21	178.8 (5)	S5—C41—C46—S6	−0.6 (6)
C17—C16—C21—C20	−0.7 (10)	Ni1—S6—C46—C45	−174.7 (4)
C15—C16—C21—C20	179.1 (6)	Ni1—S6—C46—C41	4.8 (4)
C19—C20—C21—C16	−0.1 (10)	Ni3—S7—C47—C48	−177.0 (4)
C28—N2—C22—C19	121.6 (6)	Ni3—S7—C47—C50^ii	1.9 (4)
C23—N2—C22—C19	−61.2 (7)	C50^ii—C47—C48—C49	0.5 (8)
C20—C19—C22—N2	120.5 (6)	S7—C47—C48—C49	179.4 (4)
C18—C19—C22—N2	−61.7 (7)	C47—C48—C49—C52^ii	−0.5 (9)
C28—N2—C23—C24	0.4 (8)	Ni3—S8—C50—C51	−176.4 (4)
C22—N2—C23—C24	−176.8 (5)	Ni3—S8—C50—C47^ii	3.7 (4)
N2—C23—C24—C25	1.5 (9)	C47^ii—C50—C51—C52	0.6 (8)
C23—C24—C25—C27	−2.4 (8)	S8—C50—C51—C52	−179.3 (4)
C23—C24—C25—C26	178.1 (5)	C50—C51—C52—C49^ii	−0.6 (9)

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