Hydrogen-bonding and π-π stacking inter-actions in tris-(1,10-phenanthroline-κN,N')nickel(II) bis-{[1-tert-butyl-imidazole-2(3H)-thione-κS]trichloridonickelate(II)} acetonitrile disolvate.

The asymmetric unit of the title complex, [Ni(C(12)H(8)N(2))(3)][NiCl(3)(C(7)H(12)N(2)S)](2)·2CH(3)CN, consists of one anion, one-half of a cation and one acetonitrile mol-ecule. The Ni(II) atom in the [Ni(phen)(3)](2+) cation (phen is 1,10-phenanthroline) lies on an inversion centre in an octa-hedral environment, whereas in the [NiCl(3)(tm)](-) anion [tm is 1-tert-butyl-imidazole-2(3H)-thione], the geometry is distorted tetra-hedral. In the crystal structure, inter-molecular C-H⋯Cl hydrogen bonds and π-π stacking inter-actions (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-thio-imidazole is disordered between two equally populated positions.

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 ▶).

Experimental

Crystal data

[Ni(C12H8N2)3][Nin class="Chemical">Cl3(C7H12N2S)]2·2C2H3N

M = 1324.04

Monoclinic,

a = 22.8953 (15) Å

b = 15.2934 (10) Å

c = 19.9417 (19) Å

β = 123.543 (3)°

V = 5819.7 (8) Å3

Z = 4

Mo Kα radiation

μ = 1.36 mm−1

T = 298 (2) K

0.24 × 0.20 × 0.18 mm

Data collection

Bruker Kappa APEXII CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T min = 0.737, T max = 0.792

30921 measured reflections

5178 independent reflections

3346 reflections with I > 2σ(I)

R int = 0.076

Refinement

R[F 2 > 2σ(F 2)] = 0.050

wR(F 2) = 0.157

S = 1.07

5178 reflections

370 parameters

3 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 1.24 e Å−3

Δρmin = −0.55 e Å−3

Data collection: APEX2 (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); data reduction: SAINT; 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.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808018060/su2050sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808018060/su2050Isup2.hkl

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

[Ni(C12H8N2)3][NiCl3(C7H12N2S1)]2·2C2H3N	F000 = 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 = 1.7–25.1º
b = 15.2934 (10) Å	µ = 1.36 mm−1
c = 19.9417 (19) Å	T = 298 (2) K
β = 123.543 (3)º	Block, green
V = 5819.7 (8) Å3	0.24 × 0.20 × 0.18 mm
Z = 4

Bruker Kappa APEXII CCD area-detector diffractometer	5178 independent reflections
Radiation source: fine-focus sealed tube	3346 reflections with I > 2σ(I)
Monochromator: graphite	Rint = 0.076
T = 298(2) K	θmax = 25.1º
φ and ω scans	θmin = 1.7º
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 on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.050	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.157	w = 1/[σ2(Fo2) + (0.0987P)2 + 2.7947P] where P = (Fo2 + 2Fc2)/3
S = 1.07	(Δ/σ)max < 0.001
5178 reflections	Δρmax = 1.24 e Å−3
370 parameters	Δρmin = −0.55 e Å−3
3 restraints	Extinction correction: none
Primary atom site location: structure-invariant direct methods

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

	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*

	U11	U22	U33	U12	U13	U23
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)

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—N1i	2.095 (3)	C24—C25	1.337 (13)
Ni1—N2i	2.079 (3)	C8—H8	0.9300
Ni1—N3i	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—C12i	1.436 (7)	C6A—H6A2	0.9600
C13—C13i	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—C25i	1.412 (12)	C26—C27	1.435 (12)
C18—C23i	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—N1i	79.98 (13)	C9—C10—H10	120.00
N1—Ni1—N2i	170.55 (15)	C13i—C13—H13	119.00
N1—Ni1—N3i	90.91 (18)	C11—C13—H13	119.00
N2—Ni1—N3	96.30 (18)	N2—C14—H14	118.00
N1i—Ni1—N2	170.55 (15)	C15—C14—H14	118.00
N2—Ni1—N2i	93.90 (13)	C14—C15—H15	121.00
N2—Ni1—N3i	79.49 (18)	C16—C15—H15	121.00
N1i—Ni1—N3	90.91 (18)	C17—C16—H16	120.00
N2i—Ni1—N3	79.49 (18)	C15—C16—H16	119.00
N3—Ni1—N3i	173.89 (18)	N3—C19—H19	119.00
N1i—Ni1—N2i	93.42 (13)	C20—C19—H19	119.00
N1i—Ni1—N3i	93.77 (18)	C19—C20—H20	120.00
N2i—Ni1—N3i	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)	C17i—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—C12i	117.6 (4)	H5A—C5—H5C	109.00
N1—C12—C11	123.0 (5)	H5B—C5—H5C	109.00
C11—C12—C12i	119.5 (4)	C4—C6—H6A	110.00
C11—C13—C13i	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—C25i	118.7 (6)	C4—C6A—H6A2	110.00
C16—C17—C25i	125.2 (5)	C4—C6A—H6A3	110.00
N2—C18—C23i	117.6 (4)	H6A1—C6A—H6A2	109.00
N2—C18—C17	122.5 (6)	H6A1—C6A—H6A3	109.00
C17—C18—C23i	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—C18i	116.9 (6)	H7A—C7—H7C	110.00
C18i—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
C17i—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)
N1i—Ni1—N1—C8	−178.2 (6)	C2—N5—C1—N4	0.5 (6)
N3i—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)
N1i—Ni1—N1—C12	0.1 (4)	C2—N5—C1—S1	−177.8 (4)
N3i—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)
N2i—Ni1—N2—C14	81.7 (4)	N1—C8—C9—C10	0.5 (11)
N3i—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)
N2i—Ni1—N2—C18	−102.0 (3)	C12—C11—C13—C13i	−2.3 (11)
N3i—Ni1—N2—C18	−6.3 (3)	C10—C11—C12—N1	0.2 (10)
N1—Ni1—N3—C19	9.7 (5)	C13—C11—C12—C12i	0.9 (10)
N2—Ni1—N3—C19	−84.2 (5)	C10—C11—C12—C12i	−179.6 (6)
N1i—Ni1—N3—C19	89.7 (5)	C13—C11—C12—N1	−179.4 (6)
N2i—Ni1—N3—C19	−177.0 (5)	C10—C11—C13—C13i	178.1 (8)
N1—Ni1—N3—C23	−167.3 (3)	N1—C12—C12i—C11i	−180.0 (6)
N2—Ni1—N3—C23	98.9 (3)	C11—C12—C12i—N1i	−180.0 (6)
N1i—Ni1—N3—C23	−87.3 (3)	N1—C12—C12i—N1i	0.3 (8)
N2i—Ni1—N3—C23	6.1 (3)	C11—C12—C12i—C11i	−0.2 (9)
Cl3—Ni2—S1—C1	−81.0 (2)	C11—C13—C13i—C11i	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—C25i	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—C25i—C24i	1.8 (9)
C8—N1—C12—C12i	178.3 (6)	C16—C17—C25i—C24i	−176.8 (7)
Ni1—N1—C12—C11	−180.0 (5)	C16—C17—C18—C23i	177.6 (5)
C12—N1—C8—C9	1.1 (10)	C25i—C17—C18—N2	179.4 (5)
Ni1—N1—C12—C12i	−0.2 (6)	C25i—C17—C18—C23i	−1.1 (8)
C8—N1—C12—C11	−1.5 (9)	C16—C17—C18—N2	−1.9 (8)
Ni1—N2—C18—C23i	5.6 (5)	C17—C18—C23i—C22i	−0.5 (8)
C14—N2—C18—C17	2.0 (7)	N2—C18—C23i—N3i	−0.4 (7)
Ni1—N2—C18—C17	−174.8 (4)	C17—C18—C23i—N3i	−179.9 (5)
Ni1—N2—C14—C15	176.6 (4)	N2—C18—C23i—C22i	179.0 (5)
C14—N2—C18—C23i	−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—C18i	1.5 (8)
Ni1—N3—C23—C18i	−5.0 (6)	C21—C22—C23—N3	0.4 (9)
C19—N3—C23—C18i	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—C18i	−179.0 (6)
C1—N4—C3—C2	−0.1 (7)	C22—C24—C25—C17i	−0.8 (11)
C4—N5—C1—S1	5.2 (8)	N5—C2—C3—N4	0.5 (7)
C1—N5—C4—C5	−62.7 (8)

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···Cl3ii	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···Cl3iii	0.93	2.72	3.557 (7)	151
C25—H25···N6iv	0.93	2.60	3.502 (9)	162

Table 1

Hydrogen-bond geometry (Å, °)

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⋯Cl3i	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⋯Cl3ii	0.93	2.72	3.557 (7)	151
C25—H25⋯N6iii	0.93	2.60	3.502 (9)	162

Symmetry codes: (i) ; (ii) ; (iii) .