Hydrogen-bonding and π–π stacking inter­actions in tris­(1,10-phenanthroline-κ²N,N′)nickel(II) bis­{[1-tert-butyl­imidazole-2(3H)-thione-κS]trichloridonickelate(II)} acetonitrile disolvate

The asymmetric unit of the title complex, [Ni(C₁₂H₈N₂)₃][NiCl₃(C₇H₁₂N₂S)]₂·2CH₃CN, consists of one anion, one-half of a cation and one acetonitrile mol­ecule. The Ni^II atom in the [Ni(phen)₃]²⁺ cation (phen is 1,10-phenanthroline) lies on an inversion centre in an octa­hedral environment, whereas in the [NiCl₃(tm)]⁻ anion [tm is 1-tert-butyl­imidazole-2(3H)-thione], the geometry is distorted tetra­hedral. In the crystal structure, inter­molecular C—H...Cl hydrogen bonds and π–π stacking inter­actions (centroid–centroid distance = 3.52 Å) lead to the formation of a three-dimensional framework. One of the methyl groups of the tert-butyl group of N-tert-butyl-2-thio­imidazole is disordered between two equally populated positions.

Key indicators

• Single-crystal X-ray study
• T = 298 K
• Mean [sigma](C-C) = 0.010 Å
• Disorder in main residue
• R factor = 0.051
• wR factor = 0.158
• Data-to-parameter ratio = 14.0

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT242_ALERT_2_B Check Low       Ueq as Compared to Neighbors for         C4

Alert level C
SHFSU01_ALERT_2_C  Test not performed. _refine_ls_shift/su_max and
            _refine_ls_shift/esd_max not present.
            Absolute value of the parameter shift to su ratio given   0.001
PLAT094_ALERT_2_C Ratio of Maximum / Minimum Residual Density ....       2.23
PLAT220_ALERT_2_C Large Non-Solvent    C     Ueq(max)/Ueq(min) ...       2.59 Ratio
PLAT222_ALERT_3_C Large Non-Solvent    H     Ueq(max)/Ueq(min) ...       3.83 Ratio
PLAT245_ALERT_2_C U(iso) H2      Smaller than U(eq) C2      by ...       0.01 AngSq
PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor ....       2.18
PLAT301_ALERT_3_C Main Residue  Disorder .........................       2.00 Perc.
PLAT341_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ...         10
PLAT350_ALERT_3_C Short   C-H Bond (0.96A)   C2     -   H2     ...       0.82 Ang.
PLAT412_ALERT_2_C Short Intra XH3 .. XHn     H7C    ..  H6A2    ..       1.89 Ang.
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?
PLAT164_ALERT_4_C Nr. of Refined C-H H-Atoms in Heavy-At Struct...          2
PLAT244_ALERT_4_C Low   'Solvent' Ueq as Compared to Neighbors for        C26
PLAT720_ALERT_4_C Number of Unusual/Non-Standard Labels ..........          3

Alert level G
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......          3

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

   1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   7 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
   3 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. Comment

2-Thioimidazole (N,N,S donors) and its alkyl derivatives have antithyroid activity and platelet inhibitory effects. (Fatimi et al., 1994; Iradyan et al., 1987). The literature revealed the presence of various nickel(II) complexes with phenanthroline (Suescun et al., 1999; Yu et al. (2003); Fang & Dai, 2006; Chen et al., 2007) but none with N-tert-butyl-2-thioimidazole, except the one reported recently (Senda et al., 2006). The present work reports the first structure of a nickel(II) complex with N-tert-butyl-2-thioimidazole and 1,10 phenanthroline, containing a tetrahedral anion, [Ni(tm)(Cl)₃]^-, and an octahedral cation, [Ni(phen)₃]²⁺.

The title complex (I) is centrosymmetric, ionic in nature and comprises of one complex cation [Ni(phen)₃]²⁺ and two complex anions [Ni(tm)(Cl)₃]^- in the unit cell (Fig. 1). The metal centre in [Ni(phen)₃]²⁺ is in an octahedral environment, the equatorial plane of which is formed by four phen nitrogen atoms, and the axial positions are occupied by another two nitrogen atoms of phen, with Ni1—N bond distances in the range of 2.079 (4)–2.100 (4) Å. The dihedral angles between the meanplanes of the neighboring phen rings are 77.53°, 86.07° and 85.97°. The cis-angles in the octahedron deviate only slightly from 90° and the trans angle in the axial position is almost linear i.e. 170.54 (15)°. The nickel(II) atom in the [Ni(tm)(Cl)₃]^- anion is coordinated by three chlorine atoms and one sulfur atom of tm in a distorted tetrahedral geometry. The Ni—Cl bond distances are in the range of 2.251 (15) to 2.275 (15) Å. In the anion the two short bond distances (Ni2—Cl3 and Ni2—Cl1 of 2.2507 (15) and 2.253 (2) Å, respectively) and two long bond distances (Ni2—S1 and Ni2—Cl2 of 2.3054 (17) and 2.2753 (16) Å, respectively) make the geometry distorted tetrahedral.

Due to the presence of several intermolecular interactions between the three chloride ions bonded to atom Ni2 and the hydrogen atoms present on the phen rings, the complex cation is linked to six complex anions (Fig. 2 and Table 1), whereas the complex anions are linked to four complex cations through C—H···Cl hydrogen bonds (Fig. 3 and Table 1). In the crystal packing of complex (I) two layers are linked by hydrogen bonds in the bc plane. The [Ni(phen)₃]²⁺ cations and the [Ni(tm)(Cl)₃]^- anions interact with each other via hydrogen bonds formed by the terminally coordinated chloride ions of the complex anion (Cl1, Cl2 and Cl3) and the hydrogen atoms present on the phen ligands (Fig. 4). The two complex anions also interact with one another through π–π stacking, with a separation of ca. 3.52 Å, and intermolecular C—H···Cl and C—H···N interactions involving the hydrogen atom of the middle ring of phenanthroline and the nitrogen atom of the acetonitrile molecule present in the lattice (Table 1).

Related literature

For general background, see: Fatimi et al. (1994); Iradyan et al. (1987); Suescun et al. (1999); Yu et al. (2003); Fang & Dai (2006); Chen et al., (2007); Senda et al. (2006). For synthesis details, see: Kister et al. (1979).

S2. Experimental

All the reagents were of commercial grade and were used as received. N-tert-butyl-thioimidazole (tm) was synthesized by a literature method (Kister et al., 1979). To a solution of NiCl₂.6H₂O (1.0 mmol) in 5 ml methanol, a methanolic solution of N-tert-butyl-2-thioimidazole (1.0 mmol) was added and the mixture stirred for 40 minutes. This mixture was then added to the solution obtained by mixing NiCl₂.6H₂O (1.0 mmol) in methanol with a methanolic solution of 1,10-phenanthroline (3.0 mmol). The whole reaction mixture was stirred for a further 30 minutes. The clear solution obtained was filtered and evaporated to dryness. The solid compound obtained was dissolved in acetonitrile and green single crystals, suitable for X-ray analysis, were obtained by slow evaporation at room temperature. Yield 62%. Analysis calculated for C₅₀H₄₈N₁₀S₂Cl₆Ni₃: C 48.30, H 3.86, N 11.27, S 5.15%; found: C 48.24, H 3.78, N 11.21, S 5.12%. Selected IR frequencies (KBr, ν, cm^-1): 725 (s), 849 (s), 1369 (w), 1575 (m), 1623 (w), 3060 (w), 3412 (s).

S3. Refinement

One of the methyl groups of the tert-butyl group of N-tert-butyl-2-thioimidazole is disordered between two equally populated positions (C6 and C6A; H6A and H6A1; H6B and H6B1; H6C and H6C1). C-bound H atoms were placed in geometrically idealized positions, with Csp2—H = 0.93 Å and Csp3—H = 0.96 Å, and treated as riding atoms with U_iso(H) = 1.2Ueq(C). H atoms attached to the O atoms were located in a difference Fourier map and refined as riding in their as found positions, with U_iso(H) = 1.5Ueq(O).

Computing details

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg, 1999); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures

	Fig. 1. The molecular structure of the compound (I), shown with 30% probability displacement ellipsoids [H atoms have been omitted for clarity; Symmetry code: (i) -x, y, 0.5 - z.]
	Fig. 2. A view of the intermolecular C—H···Cl interactions involving the [Ni(phen)3]^+ cation.
	Fig. 3. A view of the intermolecular π–π stacking and C—H···Cl interactions involving the [Ni(tm)(Cl)3]^- anion.
	Fig. 4. A view along the b axis of the crystal packing of complex (I), showing the interaction between two layers.

tris(1,10-phenanthroline-κ²N,N')nickel(II) bis{[1-tert-butylimidazole-2(3H)-thione-κS]trichloridonickelate(II)} acetonitrile disolvate

Crystal data

[Ni(C12H8N2)3][NiCl3(C7H12N2S)]2·2C2H3N	F(000) = 2720
Mr = 1324.04	Dx = 1.511 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 5736 reflections
a = 22.8953 (15) Å	θ = 1.7–25.1°
b = 15.2934 (10) Å	µ = 1.36 mm^−1
c = 19.9417 (19) Å	T = 298 K
β = 123.543 (3)°	Block, green
V = 5819.7 (8) Å^3	0.24 × 0.20 × 0.18 mm
Z = 4

Data collection

Bruker Kappa APEXII CCD area-detector diffractometer	5178 independent reflections
Radiation source: fine-focus sealed tube	3346 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.076
ϕ and ω scans	θmax = 25.1°, θmin = 1.7°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −26→26
Tmin = 0.737, Tmax = 0.792	k = −17→17
30921 measured reflections	l = −22→22

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)] = 0.050	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.157	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	w = 1/[σ^2(Fo^2) + (0.0987P)^2 + 2.7947P] where P = (Fo^2 + 2Fc^2)/3
5178 reflections	(Δ/σ)max < 0.001
370 parameters	Δρmax = 1.24 e Å^−3
3 restraints	Δρmin = −0.55 e Å^−3

Special details

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell esds are taken into account in the estimation of distances, angles and torsion angles

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
Ni1	0.00000	0.00042 (5)	0.25000	0.0324 (3)
N1	0.0571 (2)	0.1054 (2)	0.3259 (2)	0.0353 (12)
N2	0.0560 (2)	−0.0924 (2)	0.3397 (2)	0.0402 (12)
N3	0.0611 (2)	−0.0069 (3)	0.2013 (2)	0.0394 (12)
C8	0.1142 (3)	0.1047 (4)	0.3998 (3)	0.0432 (17)
C9	0.1465 (3)	0.1812 (4)	0.4422 (3)	0.0543 (19)
C10	0.1193 (3)	0.2601 (4)	0.4082 (4)	0.060 (2)
C11	0.0597 (3)	0.2640 (3)	0.3294 (3)	0.048 (2)
C12	0.0304 (2)	0.1842 (3)	0.2905 (3)	0.0359 (17)
C13	0.0280 (3)	0.3432 (4)	0.2882 (4)	0.065 (3)
C14	0.1128 (3)	−0.1368 (3)	0.3578 (3)	0.0534 (19)
C15	0.1476 (4)	−0.1940 (4)	0.4220 (4)	0.069 (2)
C16	0.1245 (4)	−0.2030 (4)	0.4708 (4)	0.071 (2)
C17	0.0649 (3)	−0.1584 (3)	0.4557 (3)	0.0542 (19)
C18	0.0313 (3)	−0.1036 (3)	0.3870 (3)	0.0424 (17)
C19	0.1208 (3)	0.0335 (4)	0.2245 (3)	0.0503 (17)
C20	0.1528 (3)	0.0259 (4)	0.1814 (4)	0.066 (3)
C21	0.1223 (4)	−0.0231 (5)	0.1145 (4)	0.068 (3)
C22	0.0604 (3)	−0.0683 (4)	0.0887 (4)	0.058 (2)
C23	0.0315 (3)	−0.0582 (3)	0.1348 (3)	0.0410 (17)
C24	0.0231 (4)	−0.1241 (5)	0.0183 (4)	0.072 (3)
C25	−0.0359 (4)	−0.1657 (4)	−0.0022 (4)	0.071 (3)
Ni2	0.29979 (3)	0.96924 (4)	0.47969 (4)	0.0434 (2)
Cl1	0.25801 (8)	0.97552 (11)	0.55872 (9)	0.0625 (6)
Cl2	0.27465 (7)	0.88260 (10)	0.37416 (8)	0.0583 (5)
Cl3	0.27772 (7)	1.10207 (9)	0.42193 (8)	0.0528 (5)
S1	0.41282 (7)	0.93790 (9)	0.58439 (8)	0.0452 (4)
N4	0.4404 (2)	0.8996 (3)	0.4710 (3)	0.0408 (16)
N5	0.5332 (2)	0.8910 (3)	0.5920 (2)	0.0381 (12)
C1	0.4636 (3)	0.9081 (3)	0.5493 (3)	0.0359 (17)
C2	0.5514 (3)	0.8728 (4)	0.5376 (3)	0.0479 (19)
C3	0.4945 (3)	0.8778 (4)	0.4641 (3)	0.0481 (17)
C4	0.5832 (3)	0.8870 (4)	0.6823 (3)	0.0452 (17)
C5	0.5869 (4)	0.9750 (4)	0.7181 (4)	0.089 (3)
C6	0.6584 (6)	0.8705 (16)	0.7056 (9)	0.093 (6)	0.75 (3)
C7	0.5581 (4)	0.8178 (5)	0.7141 (4)	0.077 (3)
C6A	0.643 (2)	0.830 (4)	0.695 (3)	0.093 (6)	0.25 (3)
N6	0.3858 (4)	0.7541 (4)	0.3045 (4)	0.091 (3)
C26	0.3366 (4)	0.7841 (4)	0.2533 (4)	0.066 (3)
C27	0.2734 (4)	0.8224 (5)	0.1875 (5)	0.093 (3)
H8	0.13350	0.05120	0.42420	0.0520*
H9	0.18670	0.17810	0.49400	0.0650*
H10	0.14000	0.31130	0.43680	0.0720*
H13	0.04640	0.39620	0.31450	0.0780*
H14	0.13000	−0.12900	0.32550	0.0640*
H15	0.18620	−0.22550	0.43130	0.0830*
H16	0.14870	−0.23950	0.51540	0.0860*
H19	0.14210	0.06790	0.27070	0.0600*
H20	0.19480	0.05460	0.19920	0.0790*
H21	0.14270	−0.02700	0.08520	0.0810*
H24	0.04090	−0.13130	−0.01350	0.0870*
H25	−0.05840	−0.20020	−0.04830	0.0850*
H2	0.593 (3)	0.867 (3)	0.555 (3)	0.036 (14)*
H3	0.486 (3)	0.868 (4)	0.409 (4)	0.061 (16)*
H5A	0.59570	1.01920	0.69050	0.1340*
H5B	0.62410	0.97510	0.77410	0.1340*
H4	0.397 (3)	0.897 (3)	0.435 (3)	0.039 (15)*
H6A	0.67440	0.92000	0.69040	0.1380*	0.75 (3)
H6B	0.65930	0.81930	0.67830	0.1380*	0.75 (3)
H6C	0.68860	0.86190	0.76270	0.1380*	0.75 (3)
H7A	0.50960	0.82750	0.69350	0.1160*
H7B	0.58520	0.82040	0.77180	0.1160*
H7C	0.56360	0.76130	0.69730	0.1160*
H5C	0.54330	0.98700	0.71250	0.1340*
H6A1	0.66990	0.86260	0.67940	0.1380*	0.25 (3)
H6A2	0.62430	0.77870	0.66220	0.1380*	0.25 (3)
H6A3	0.67260	0.81410	0.75030	0.1380*	0.25 (3)
H27A	0.24970	0.85310	0.20790	0.1400*
H27B	0.24340	0.77720	0.15140	0.1400*
H27C	0.28470	0.86250	0.15930	0.1400*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ni1	0.0334 (5)	0.0360 (5)	0.0257 (5)	0.0000	0.0151 (4)	0.0000
N1	0.035 (2)	0.042 (2)	0.028 (2)	0.0003 (18)	0.0168 (19)	−0.0034 (18)
N2	0.042 (2)	0.035 (2)	0.034 (2)	−0.0035 (19)	0.015 (2)	0.0018 (17)
N3	0.039 (2)	0.042 (2)	0.036 (2)	−0.0011 (19)	0.020 (2)	−0.0032 (18)
C8	0.035 (3)	0.060 (3)	0.030 (3)	−0.001 (2)	0.015 (2)	−0.005 (2)
C9	0.046 (3)	0.081 (4)	0.034 (3)	−0.016 (3)	0.021 (3)	−0.019 (3)
C10	0.077 (4)	0.062 (4)	0.055 (4)	−0.023 (3)	0.045 (4)	−0.029 (3)
C11	0.062 (4)	0.046 (3)	0.051 (4)	−0.010 (3)	0.041 (3)	−0.014 (3)
C12	0.043 (3)	0.040 (3)	0.035 (3)	−0.003 (2)	0.028 (2)	−0.004 (2)
C13	0.092 (5)	0.039 (3)	0.087 (5)	−0.016 (3)	0.064 (4)	−0.015 (3)
C14	0.042 (3)	0.043 (3)	0.057 (4)	0.007 (3)	0.016 (3)	−0.001 (3)
C15	0.062 (4)	0.050 (4)	0.063 (4)	0.008 (3)	0.014 (4)	0.007 (3)
C16	0.069 (4)	0.043 (3)	0.046 (4)	0.000 (3)	−0.003 (3)	0.014 (3)
C17	0.063 (4)	0.039 (3)	0.034 (3)	−0.014 (3)	0.010 (3)	0.005 (2)
C18	0.047 (3)	0.033 (3)	0.035 (3)	−0.009 (2)	0.015 (3)	−0.001 (2)
C19	0.044 (3)	0.057 (3)	0.051 (3)	−0.001 (3)	0.027 (3)	−0.002 (3)
C20	0.053 (4)	0.085 (5)	0.078 (5)	0.008 (3)	0.047 (4)	0.015 (4)
C21	0.074 (5)	0.091 (5)	0.064 (5)	0.021 (4)	0.054 (4)	0.018 (4)
C22	0.077 (4)	0.059 (3)	0.051 (4)	0.034 (3)	0.043 (3)	0.016 (3)
C23	0.049 (3)	0.040 (3)	0.034 (3)	0.014 (2)	0.023 (3)	0.005 (2)
C24	0.105 (6)	0.078 (4)	0.051 (4)	0.027 (4)	0.054 (4)	0.000 (3)
C25	0.104 (6)	0.059 (4)	0.041 (4)	0.022 (4)	0.035 (4)	−0.005 (3)
Ni2	0.0394 (4)	0.0561 (4)	0.0325 (4)	0.0045 (3)	0.0185 (3)	−0.0031 (3)
Cl1	0.0540 (9)	0.0980 (12)	0.0409 (8)	0.0098 (8)	0.0297 (7)	0.0020 (7)
Cl2	0.0496 (8)	0.0748 (10)	0.0400 (8)	0.0050 (7)	0.0181 (7)	−0.0152 (7)
Cl3	0.0476 (8)	0.0590 (8)	0.0495 (9)	−0.0008 (6)	0.0254 (7)	0.0015 (6)
S1	0.0413 (7)	0.0626 (8)	0.0318 (7)	0.0068 (6)	0.0203 (6)	−0.0018 (6)
N4	0.042 (3)	0.053 (3)	0.026 (2)	0.000 (2)	0.018 (2)	−0.0013 (19)
N5	0.039 (2)	0.051 (2)	0.026 (2)	0.0010 (19)	0.019 (2)	0.0021 (18)
C1	0.041 (3)	0.040 (3)	0.027 (3)	−0.001 (2)	0.019 (2)	0.002 (2)
C2	0.039 (3)	0.067 (4)	0.043 (3)	−0.004 (3)	0.026 (3)	−0.003 (3)
C3	0.051 (3)	0.061 (3)	0.040 (3)	−0.003 (3)	0.030 (3)	0.000 (3)
C4	0.040 (3)	0.065 (3)	0.029 (3)	0.004 (3)	0.018 (2)	0.006 (2)
C5	0.096 (6)	0.076 (5)	0.040 (4)	−0.009 (4)	0.003 (4)	−0.008 (3)
C6	0.036 (6)	0.183 (16)	0.043 (6)	0.002 (7)	0.012 (6)	0.004 (9)
C7	0.080 (5)	0.091 (5)	0.050 (4)	−0.001 (4)	0.029 (4)	0.023 (3)
C6A	0.036 (6)	0.183 (16)	0.043 (6)	0.002 (7)	0.012 (6)	0.004 (9)
N6	0.103 (5)	0.105 (5)	0.062 (4)	0.008 (4)	0.043 (4)	0.005 (4)
C26	0.088 (5)	0.066 (4)	0.054 (4)	−0.010 (4)	0.045 (4)	−0.002 (3)
C27	0.099 (6)	0.080 (5)	0.073 (5)	0.004 (4)	0.030 (5)	0.006 (4)

Geometric parameters (Å, º)

Ni1—N1	2.095 (3)	C21—C22	1.395 (12)
Ni1—N2	2.079 (3)	C22—C24	1.450 (10)
Ni1—N3	2.101 (5)	C22—C23	1.407 (10)
Ni1—N1^i	2.095 (3)	C24—C25	1.337 (13)
Ni1—N2^i	2.079 (3)	C8—H8	0.9300
Ni1—N3^i	2.101 (5)	C9—H9	0.9300
Ni2—Cl2	2.2753 (16)	C10—H10	0.9300
Ni2—Cl3	2.2507 (15)	C13—H13	0.9300
Ni2—S1	2.3054 (17)	C14—H14	0.9300
Ni2—Cl1	2.253 (2)	C15—H15	0.9300
S1—C1	1.717 (7)	C16—H16	0.9300
N1—C8	1.324 (7)	C19—H19	0.9300
N1—C12	1.359 (6)	C20—H20	0.9300
N2—C18	1.352 (8)	C21—H21	0.9300
N2—C14	1.328 (8)	C24—H24	0.9300
N3—C23	1.357 (6)	C25—H25	0.9300
N3—C19	1.329 (9)	C2—C3	1.320 (8)
N4—C1	1.349 (7)	C4—C5	1.504 (9)
N4—C3	1.361 (9)	C4—C6A	1.52 (6)
N5—C1	1.354 (8)	C4—C6	1.536 (19)
N5—C2	1.388 (8)	C4—C7	1.502 (11)
N5—C4	1.510 (6)	C2—H2	0.82 (7)
N4—H4	0.85 (6)	C3—H3	1.02 (7)
N6—C26	1.118 (11)	C5—H5A	0.9600
C8—C9	1.393 (8)	C5—H5B	0.9600
C9—C10	1.355 (9)	C5—H5C	0.9600
C10—C11	1.402 (9)	C6—H6A	0.9600
C11—C12	1.402 (7)	C6—H6B	0.9600
C11—C13	1.418 (8)	C6—H6C	0.9600
C12—C12^i	1.436 (7)	C6A—H6A2	0.9600
C13—C13^i	1.344 (10)	C6A—H6A3	0.9500
C14—C15	1.383 (8)	C6A—H6A1	0.9700
C15—C16	1.347 (13)	C7—H7B	0.9600
C16—C17	1.401 (12)	C7—H7C	0.9600
C17—C18	1.417 (7)	C7—H7A	0.9600
C17—C25^i	1.412 (12)	C26—C27	1.435 (12)
C18—C23^i	1.431 (10)	C27—H27A	0.9600
C19—C20	1.409 (10)	C27—H27B	0.9600
C20—C21	1.341 (10)	C27—H27C	0.9600
N1—Ni1—N2	93.42 (13)	C8—C9—H9	120.00
N1—Ni1—N3	93.77 (18)	C11—C10—H10	120.00
N1—Ni1—N1^i	79.98 (13)	C9—C10—H10	120.00
N1—Ni1—N2^i	170.55 (15)	C13^i—C13—H13	119.00
N1—Ni1—N3^i	90.91 (18)	C11—C13—H13	119.00
N2—Ni1—N3	96.30 (18)	N2—C14—H14	118.00
N1^i—Ni1—N2	170.55 (15)	C15—C14—H14	118.00
N2—Ni1—N2^i	93.90 (13)	C14—C15—H15	121.00
N2—Ni1—N3^i	79.49 (18)	C16—C15—H15	121.00
N1^i—Ni1—N3	90.91 (18)	C17—C16—H16	120.00
N2^i—Ni1—N3	79.49 (18)	C15—C16—H16	119.00
N3—Ni1—N3^i	173.89 (18)	N3—C19—H19	119.00
N1^i—Ni1—N2^i	93.42 (13)	C20—C19—H19	119.00
N1^i—Ni1—N3^i	93.77 (18)	C19—C20—H20	120.00
N2^i—Ni1—N3^i	96.30 (18)	C21—C20—H20	120.00
Cl1—Ni2—Cl2	133.14 (7)	C20—C21—H21	120.00
Cl1—Ni2—Cl3	104.92 (7)	C22—C21—H21	120.00
Cl1—Ni2—S1	94.21 (6)	C25—C24—H24	119.00
Cl2—Ni2—Cl3	100.47 (6)	C22—C24—H24	119.00
Cl2—Ni2—S1	107.47 (6)	C24—C25—H25	119.00
Cl3—Ni2—S1	118.25 (6)	C17^i—C25—H25	119.00
Ni2—S1—C1	111.11 (19)	N4—C1—N5	106.5 (6)
Ni1—N1—C8	129.5 (3)	S1—C1—N5	128.4 (4)
Ni1—N1—C12	112.5 (3)	S1—C1—N4	125.1 (5)
C8—N1—C12	118.0 (4)	N5—C2—C3	108.5 (6)
C14—N2—C18	118.0 (4)	N4—C3—C2	107.3 (6)
Ni1—N2—C18	112.9 (4)	N5—C4—C6	110.6 (7)
Ni1—N2—C14	128.9 (4)	N5—C4—C5	109.7 (5)
Ni1—N3—C19	129.3 (4)	C5—C4—C6	104.1 (10)
C19—N3—C23	118.1 (5)	C5—C4—C7	111.4 (6)
Ni1—N3—C23	112.5 (4)	C5—C4—C6A	129 (2)
C1—N4—C3	110.0 (5)	C6—C4—C7	112.5 (10)
C2—N5—C4	124.5 (5)	C6A—C4—C7	93 (2)
C1—N5—C2	107.7 (4)	N5—C4—C7	108.5 (5)
C1—N5—C4	127.7 (5)	N5—C4—C6A	104.0 (19)
C1—N4—H4	121 (5)	N5—C2—H2	118 (4)
C3—N4—H4	128 (5)	C3—C2—H2	133 (4)
N1—C8—C9	122.4 (5)	N4—C3—H3	120 (4)
C8—C9—C10	120.1 (5)	C2—C3—H3	132 (4)
C9—C10—C11	119.5 (5)	C4—C5—H5A	109.00
C10—C11—C12	117.1 (5)	C4—C5—H5B	110.00
C12—C11—C13	119.2 (5)	C4—C5—H5C	110.00
C10—C11—C13	123.7 (5)	H5A—C5—H5B	109.00
N1—C12—C12^i	117.6 (4)	H5A—C5—H5C	109.00
N1—C12—C11	123.0 (5)	H5B—C5—H5C	109.00
C11—C12—C12^i	119.5 (4)	C4—C6—H6A	110.00
C11—C13—C13^i	121.3 (6)	C4—C6—H6B	110.00
N2—C14—C15	123.5 (7)	C4—C6—H6C	109.00
C14—C15—C16	118.6 (8)	H6A—C6—H6B	109.00
C15—C16—C17	121.3 (6)	H6A—C6—H6C	109.00
C16—C17—C18	116.1 (6)	H6B—C6—H6C	109.00
C18—C17—C25^i	118.7 (6)	C4—C6A—H6A2	110.00
C16—C17—C25^i	125.2 (5)	C4—C6A—H6A3	110.00
N2—C18—C23^i	117.6 (4)	H6A1—C6A—H6A2	109.00
N2—C18—C17	122.5 (6)	H6A1—C6A—H6A3	109.00
C17—C18—C23^i	119.9 (6)	H6A2—C6A—H6A3	110.00
N3—C19—C20	122.1 (5)	C4—C6A—H6A1	109.00
C19—C20—C21	119.5 (7)	H7B—C7—H7C	109.00
C20—C21—C22	120.5 (8)	C4—C7—H7A	109.00
C21—C22—C23	117.0 (6)	C4—C7—H7B	109.00
C21—C22—C24	125.7 (8)	C4—C7—H7C	109.00
C23—C22—C24	117.3 (7)	H7A—C7—H7B	110.00
N3—C23—C18^i	116.9 (6)	H7A—C7—H7C	110.00
C18^i—C23—C22	120.3 (5)	N6—C26—C27	179.9 (12)
N3—C23—C22	122.8 (6)	C26—C27—H27A	109.00
C22—C24—C25	122.1 (8)	C26—C27—H27B	110.00
C17^i—C25—C24	121.6 (6)	C26—C27—H27C	110.00
N1—C8—H8	119.00	H27A—C27—H27B	109.00
C9—C8—H8	119.00	H27A—C27—H27C	110.00
C10—C9—H9	120.00	H27B—C27—H27C	109.00
N2—Ni1—N1—C8	8.6 (6)	C1—N5—C2—C3	−0.6 (7)
N3—Ni1—N1—C8	−87.9 (6)	C4—N5—C2—C3	176.5 (5)
N1^i—Ni1—N1—C8	−178.2 (6)	C2—N5—C1—N4	0.5 (6)
N3^i—Ni1—N1—C8	88.2 (6)	C2—N5—C4—C7	−117.4 (7)
N2—Ni1—N1—C12	−173.1 (4)	C1—N5—C4—C7	59.2 (8)
N3—Ni1—N1—C12	90.3 (4)	C4—N5—C1—N4	−176.5 (5)
N1^i—Ni1—N1—C12	0.1 (4)	C2—N5—C1—S1	−177.8 (4)
N3^i—Ni1—N1—C12	−93.6 (4)	C2—N5—C4—C5	120.8 (7)
N1—Ni1—N2—C14	−92.3 (4)	C1—N5—C4—C6	−176.9 (11)
N3—Ni1—N2—C14	1.9 (4)	C2—N5—C4—C6	6.5 (12)
N2^i—Ni1—N2—C14	81.7 (4)	N1—C8—C9—C10	0.5 (11)
N3^i—Ni1—N2—C14	177.4 (4)	C8—C9—C10—C11	−1.8 (11)
N1—Ni1—N2—C18	84.0 (3)	C9—C10—C11—C12	1.4 (11)
N3—Ni1—N2—C18	178.2 (3)	C9—C10—C11—C13	−179.0 (7)
N2^i—Ni1—N2—C18	−102.0 (3)	C12—C11—C13—C13^i	−2.3 (11)
N3^i—Ni1—N2—C18	−6.3 (3)	C10—C11—C12—N1	0.2 (10)
N1—Ni1—N3—C19	9.7 (5)	C13—C11—C12—C12^i	0.9 (10)
N2—Ni1—N3—C19	−84.2 (5)	C10—C11—C12—C12^i	−179.6 (6)
N1^i—Ni1—N3—C19	89.7 (5)	C13—C11—C12—N1	−179.4 (6)
N2^i—Ni1—N3—C19	−177.0 (5)	C10—C11—C13—C13^i	178.1 (8)
N1—Ni1—N3—C23	−167.3 (3)	N1—C12—C12^i—C11^i	−180.0 (6)
N2—Ni1—N3—C23	98.9 (3)	C11—C12—C12^i—N1^i	−180.0 (6)
N1^i—Ni1—N3—C23	−87.3 (3)	N1—C12—C12^i—N1^i	0.3 (8)
N2^i—Ni1—N3—C23	6.1 (3)	C11—C12—C12^i—C11^i	−0.2 (9)
Cl3—Ni2—S1—C1	−81.0 (2)	C11—C13—C13^i—C11^i	3.1 (12)
Cl1—Ni2—S1—C1	169.56 (19)	N2—C14—C15—C16	−2.6 (9)
Cl2—Ni2—S1—C1	31.7 (2)	C14—C15—C16—C17	2.5 (10)
Ni2—S1—C1—N4	−3.1 (5)	C15—C16—C17—C25^i	178.2 (6)
Ni2—S1—C1—N5	175.0 (4)	C15—C16—C17—C18	−0.4 (9)
Ni1—N1—C8—C9	179.3 (5)	C18—C17—C25^i—C24^i	1.8 (9)
C8—N1—C12—C12^i	178.3 (6)	C16—C17—C25^i—C24^i	−176.8 (7)
Ni1—N1—C12—C11	−180.0 (5)	C16—C17—C18—C23^i	177.6 (5)
C12—N1—C8—C9	1.1 (10)	C25^i—C17—C18—N2	179.4 (5)
Ni1—N1—C12—C12^i	−0.2 (6)	C25^i—C17—C18—C23^i	−1.1 (8)
C8—N1—C12—C11	−1.5 (9)	C16—C17—C18—N2	−1.9 (8)
Ni1—N2—C18—C23^i	5.6 (5)	C17—C18—C23^i—C22^i	−0.5 (8)
C14—N2—C18—C17	2.0 (7)	N2—C18—C23^i—N3^i	−0.4 (7)
Ni1—N2—C18—C17	−174.8 (4)	C17—C18—C23^i—N3^i	−179.9 (5)
Ni1—N2—C14—C15	176.6 (4)	N2—C18—C23^i—C22^i	179.0 (5)
C14—N2—C18—C23^i	−177.6 (4)	N3—C19—C20—C21	0.4 (10)
C18—N2—C14—C15	0.4 (7)	C19—C20—C21—C22	−1.8 (10)
Ni1—N3—C19—C20	−175.5 (4)	C20—C21—C22—C24	−179.1 (7)
C23—N3—C19—C20	1.3 (8)	C20—C21—C22—C23	1.4 (10)
C19—N3—C23—C22	−1.7 (8)	C24—C22—C23—C18^i	1.5 (8)
Ni1—N3—C23—C18^i	−5.0 (6)	C21—C22—C23—N3	0.4 (9)
C19—N3—C23—C18^i	177.6 (5)	C24—C22—C23—N3	−179.2 (5)
Ni1—N3—C23—C22	175.6 (4)	C23—C22—C24—C25	−0.9 (10)
C3—N4—C1—N5	−0.3 (6)	C21—C22—C24—C25	179.6 (7)
C3—N4—C1—S1	178.2 (4)	C21—C22—C23—C18^i	−179.0 (6)
C1—N4—C3—C2	−0.1 (7)	C22—C24—C25—C17^i	−0.8 (11)
C4—N5—C1—S1	5.2 (8)	N5—C2—C3—N4	0.5 (7)
C1—N5—C4—C5	−62.7 (8)

Symmetry code: (i) −x, y, −z+1/2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N4—H4···Cl2	0.85 (6)	2.37 (7)	3.178 (6)	160 (6)
C2—H2···Cl3^ii	0.82 (7)	2.77 (7)	3.552 (8)	160 (4)
C5—H5C···S1	0.96	2.75	3.402 (9)	126
C7—H7A···S1	0.96	2.68	3.409 (8)	133
C10—H10···Cl3^iii	0.93	2.72	3.557 (7)	151
C25—H25···N6^iv	0.93	2.60	3.502 (9)	162

Symmetry codes: (ii) −x+1, −y+2, −z+1; (iii) −x+1/2, −y+3/2, −z+1; (iv) x−1/2, −y+1/2, z−1/2.