Bis[tris-(1H-pyrazol-1-yl-κN)methane]-nickel(II) bis-{[tris-(1H-pyrazol-1-yl-κN)methane]-tris-(thio-cyanato-κN)nickelate(II)} methanol disolvate.

Attempts to prepare the mononuclear [(tpm)Ni(II)L(3)](-1) [tpm = tris-(1H-pyrazol-1-yl)methane and L = thio-cyanate] anion yielded the methanol-solvated salt, [(tpm)(2)Ni(II)][(tpm)Ni(II)(NCS)(3)](2)·2CH(3)OH or [Ni(C(10)H(10)N(6))(2)][Ni(NCS)(3)(C(10)H(10)N(6))](2)·2CH(3)OH. The asymmetric unit consists of half a centrosymmetric bis-[tris-(1H-pyrazol-1-yl)methane]-nickel(II) cation and an octa-hedral nickelate(II) anion bound to one tpm and three L ligands, and a methanol solvent mol-ecule. One of the L ligands is disordered over two positions with occupancy factors of 0.650 (3) and 0.350 (3). There are O-H⋯S inter-actions between the methanol and the disordered thio-cyanate anion, and a weak C-H⋯O hydrogen bond between the cation and the methanol O atom.

Related literature

For the ligand synthesis, see: Reger et al. (2000 ▶). For structural, spectroscopic and angular overlap studies of tris­(1H-pyrazol-1-yl)methane complexes, see: Astley et al. (1993 ▶). For background information on the modelling of metallo-enzyme sites by small mol­ecules, see: Kitajima et al. (1992 ▶); Trofimenko et al. (1992 ▶); Looney et al. (1992 ▶); Looney & Parkin (1994 ▶). A previous attempt to make similar building blocks with nickel(II) and a cyanide ligand is given in Lyubartseva & Parkin (2009 ▶).

Experimental

Crystal data

[Ni(C10H10N6)2][Ni(NCS)3(C10H10N6)]2·2CH4O

M = 1445.65

Monoclinic,

a = 33.4463 (8) Å

b = 7.3287 (2) Å

c = 27.2689 (7) Å

β = 112.590 (1)°

V = 6171.3 (3) Å3

Z = 4

Cu Kα radiation

μ = 3.52 mm−1

T = 90 K

0.20 × 0.06 × 0.02 mm

Data collection

Bruker X8 Proteum diffractometer

Absorption correction: multi-scan (SADABS in APEX2; Bruker, 2006 ▶) T min = 0.740, T max = 0.933

41685 measured reflections

5605 independent reflections

4932 reflections with I > 2σ(I)

R int = 0.061

Refinement

R[F 2 > 2σ(F 2)] = 0.049

wR(F 2) = 0.128

S = 1.11

5605 reflections

418 parameters

6 restraints

H-atom parameters constrained

Δρmax = 1.34 e Å−3

Δρmin = −0.44 e Å−3

Data collection: APEX2 (Bruker, 2006 ▶); cell refinement: SAINT (Bruker, 2006 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: XP in SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXL97 and local procedures.

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536811045144/ng5255sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811045144/ng5255Isup2.hkl

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

[Ni(C10H10N6)2][Ni(NCS)3(C10H10N6)]2·2CH4O	F(000) = 2968
Mr = 1445.65	Dx = 1.556 Mg m−3
Monoclinic, C2/c	Cu Kα radiation, λ = 1.54178 Å
Hall symbol: -C 2yc	Cell parameters from 9957 reflections
a = 33.4463 (8) Å	θ = 2.9–67.8°
b = 7.3287 (2) Å	µ = 3.52 mm−1
c = 27.2689 (7) Å	T = 90 K
β = 112.590 (1)°	Rod, blue
V = 6171.3 (3) Å3	0.20 × 0.06 × 0.02 mm
Z = 4

Bruker X8 Proteum diffractometer	5605 independent reflections
Radiation source: fine-focus rotating anode	4932 reflections with I > 2σ(I)
graded multilayer optics	Rint = 0.061
Detector resolution: 5.6 pixels mm-1	θmax = 68.0°, θmin = 2.9°
φ and ω scans	h = −39→39
Absorption correction: multi-scan (SADABS in APEX2; Bruker, 2006)	k = −8→8
Tmin = 0.740, Tmax = 0.933	l = −32→32
41685 measured reflections

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)] = 0.049	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.128	H-atom parameters constrained
S = 1.11	w = 1/[σ2(Fo2) + (0.0515P)2 + 28.6001P] where P = (Fo2 + 2Fc2)/3
5605 reflections	(Δ/σ)max = 0.001
418 parameters	Δρmax = 1.34 e Å−3
6 restraints	Δρmin = −0.44 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. The crystals were covered in a blue powder, which was likely caused by partial drying of the crystal. Some of this blue stuff was easy to remove, but some was stuck to the crystal surface and could not be removed without damaging the crystal.In the final difference map there are small residual peaks clustered around the disordered thiocyanate group. This could perhaps be due to partial occupancy/disordered solvent, but all attempts to model it as such did not improve the refinement enough to warrant retention of the extra details.

	x	y	z	Uiso*/Ueq	Occ. (<1)
Ni1	0.388647 (18)	0.19922 (7)	0.82166 (2)	0.02134 (16)
C1	0.38951 (11)	−0.2289 (4)	0.82452 (14)	0.0230 (7)
H1	0.3895	−0.3653	0.8251	0.028*
N1	0.33737 (9)	0.0180 (4)	0.80613 (11)	0.0212 (6)
N2	0.34542 (9)	−0.1642 (4)	0.80957 (11)	0.0196 (6)
C2	0.29596 (11)	0.0339 (5)	0.79732 (13)	0.0221 (7)
H2	0.2810	0.1467	0.7933	0.027*
C3	0.27681 (11)	−0.1379 (5)	0.79473 (13)	0.0236 (7)
H3	0.2474	−0.1630	0.7885	0.028*
C4	0.30942 (11)	−0.2617 (5)	0.80312 (13)	0.0214 (7)
H4	0.3072	−0.3908	0.8042	0.026*
N3	0.41898 (9)	0.0209 (4)	0.88658 (12)	0.0234 (6)
N4	0.41572 (9)	−0.1623 (4)	0.87707 (11)	0.0220 (6)
C5	0.44066 (11)	0.0375 (5)	0.93835 (14)	0.0253 (7)
H5	0.4477	0.1506	0.9567	0.030*
C6	0.45189 (12)	−0.1344 (5)	0.96261 (15)	0.0322 (8)
H6	0.4677	−0.1592	0.9992	0.039*
C7	0.43519 (11)	−0.2583 (5)	0.92251 (15)	0.0290 (8)
H7	0.4369	−0.3874	0.9258	0.035*
N5	0.41142 (9)	0.0136 (4)	0.77985 (12)	0.0241 (6)
N6	0.40755 (9)	−0.1675 (4)	0.78705 (12)	0.0226 (6)
C8	0.43166 (12)	0.0246 (5)	0.74650 (15)	0.0286 (8)
H8	0.4389	0.1359	0.7340	0.034*
C9	0.44093 (12)	−0.1481 (5)	0.73221 (15)	0.0322 (8)
H9	0.4551	−0.1762	0.7089	0.039*
C10	0.42528 (11)	−0.2688 (5)	0.75883 (15)	0.0286 (8)
H10	0.4266	−0.3982	0.7578	0.034*
N7	0.36703 (10)	0.3584 (4)	0.86862 (12)	0.0280 (7)
C11	0.36862 (11)	0.3894 (4)	0.91106 (15)	0.0253 (8)
S1	0.37247 (3)	0.43823 (13)	0.97092 (4)	0.0346 (2)
N8	0.35651 (10)	0.3522 (4)	0.75539 (12)	0.0276 (6)
C12	0.33809 (11)	0.4581 (5)	0.72297 (13)	0.0221 (7)
S2	0.31218 (3)	0.61217 (12)	0.67928 (3)	0.0267 (2)
N9	0.44458 (11)	0.3525 (4)	0.84076 (15)	0.0371 (8)	0.650 (3)
C13	0.4780 (2)	0.3745 (8)	0.8323 (3)	0.0346 (11)	0.650 (3)
S3	0.52288 (6)	0.4092 (2)	0.82170 (10)	0.0554 (6)	0.650 (3)
N9'	0.44458 (11)	0.3525 (4)	0.84076 (15)	0.0371 (8)	0.350 (3)
C13'	0.4749 (4)	0.3881 (14)	0.8716 (5)	0.0346 (11)	0.350 (3)
S3'	0.52609 (11)	0.4382 (5)	0.91591 (17)	0.0639 (14)	0.350 (3)
Ni2	0.2500	0.7500	0.5000	0.01688 (18)
N10	0.30477 (8)	0.5976 (4)	0.54331 (10)	0.0187 (6)
N11	0.34180 (9)	0.6897 (4)	0.57058 (10)	0.0190 (6)
C14	0.31541 (11)	0.4229 (4)	0.55193 (13)	0.0219 (7)
H14	0.2959	0.3242	0.5379	0.026*
C15	0.35916 (11)	0.4038 (5)	0.58445 (14)	0.0246 (7)
H15	0.3746	0.2931	0.5964	0.030*
C16	0.37506 (11)	0.5770 (4)	0.59556 (13)	0.0220 (7)
H16	0.4040	0.6112	0.6168	0.026*
N12	0.26851 (9)	0.9206 (4)	0.56604 (11)	0.0207 (6)
N13	0.31151 (9)	0.9582 (3)	0.59102 (11)	0.0187 (6)
C17	0.31975 (12)	1.0505 (5)	0.63671 (14)	0.0256 (7)
H17	0.3473	1.0900	0.6611	0.031*
C18	0.28065 (13)	1.0760 (5)	0.64097 (15)	0.0331 (9)
H18	0.2755	1.1379	0.6686	0.040*
C19	0.24998 (12)	0.9929 (5)	0.59665 (14)	0.0262 (7)
H19	0.2198	0.9885	0.5893	0.031*
N14	0.20875 (8)	0.5902 (4)	0.52268 (11)	0.0195 (6)
N15	0.16941 (9)	0.5474 (4)	0.48424 (11)	0.0188 (6)
C20	0.20858 (11)	0.5150 (4)	0.56683 (13)	0.0220 (7)
H20	0.2319	0.5215	0.6004	0.026*
C21	0.16970 (12)	0.4255 (5)	0.55738 (14)	0.0262 (7)
H21	0.1618	0.3611	0.5826	0.031*
C22	0.14512 (11)	0.4486 (4)	0.50472 (13)	0.0217 (7)
H22	0.1166	0.4044	0.4860	0.026*
C23	0.15845 (11)	0.6126 (4)	0.43080 (13)	0.0188 (6)
H23	0.1287	0.5681	0.4084	0.023*
O1S	0.06346 (9)	0.4684 (4)	0.38493 (13)	0.0447 (7)
H1S	0.0533	0.3683	0.3705	0.067*
C1S	0.03005 (16)	0.5722 (8)	0.3923 (2)	0.0562 (13)
H1S1	0.0428	0.6501	0.4237	0.084*
H1S2	0.0090	0.4892	0.3974	0.084*
H1S3	0.0155	0.6484	0.3610	0.084*

	U11	U22	U33	U12	U13	U23
Ni1	0.0240 (3)	0.0130 (3)	0.0281 (3)	−0.0013 (2)	0.0112 (2)	0.0001 (2)
C1	0.0249 (17)	0.0149 (16)	0.0311 (18)	−0.0032 (13)	0.0129 (14)	−0.0018 (13)
N1	0.0254 (15)	0.0134 (13)	0.0269 (14)	0.0003 (11)	0.0123 (12)	0.0014 (11)
N2	0.0199 (14)	0.0145 (13)	0.0261 (14)	−0.0017 (10)	0.0107 (11)	−0.0015 (11)
C2	0.0239 (17)	0.0188 (16)	0.0255 (17)	0.0024 (13)	0.0114 (14)	0.0016 (13)
C3	0.0216 (17)	0.0243 (17)	0.0278 (17)	−0.0021 (14)	0.0126 (14)	0.0007 (14)
C4	0.0239 (17)	0.0174 (16)	0.0258 (16)	−0.0037 (13)	0.0128 (14)	−0.0021 (13)
N3	0.0241 (15)	0.0135 (13)	0.0336 (16)	−0.0005 (11)	0.0121 (12)	−0.0009 (11)
N4	0.0217 (14)	0.0152 (13)	0.0290 (15)	−0.0009 (11)	0.0093 (12)	−0.0010 (11)
C5	0.0193 (17)	0.0281 (18)	0.0273 (18)	−0.0020 (14)	0.0075 (14)	−0.0043 (14)
C6	0.0223 (18)	0.037 (2)	0.0326 (19)	−0.0025 (15)	0.0053 (15)	0.0040 (16)
C7	0.0219 (17)	0.0202 (17)	0.041 (2)	−0.0002 (14)	0.0079 (15)	0.0092 (15)
N5	0.0266 (15)	0.0175 (14)	0.0324 (16)	−0.0019 (11)	0.0158 (13)	0.0000 (12)
N6	0.0241 (15)	0.0153 (13)	0.0343 (16)	−0.0006 (11)	0.0176 (12)	−0.0031 (11)
C8	0.0275 (19)	0.0284 (19)	0.0330 (19)	−0.0053 (15)	0.0151 (15)	0.0003 (15)
C9	0.0298 (19)	0.036 (2)	0.037 (2)	−0.0051 (16)	0.0198 (16)	−0.0094 (17)
C10	0.0249 (18)	0.0234 (18)	0.040 (2)	−0.0006 (14)	0.0153 (16)	−0.0080 (15)
N7	0.0352 (17)	0.0172 (14)	0.0327 (17)	0.0006 (12)	0.0141 (13)	−0.0011 (12)
C11	0.0242 (18)	0.0132 (16)	0.041 (2)	−0.0018 (13)	0.0157 (15)	−0.0005 (14)
S1	0.0471 (6)	0.0277 (5)	0.0401 (5)	−0.0074 (4)	0.0290 (5)	−0.0065 (4)
N8	0.0303 (16)	0.0204 (15)	0.0350 (17)	−0.0018 (12)	0.0157 (13)	0.0014 (13)
C12	0.0238 (17)	0.0198 (17)	0.0264 (17)	−0.0048 (14)	0.0138 (14)	−0.0030 (14)
S2	0.0291 (5)	0.0257 (4)	0.0254 (4)	−0.0008 (3)	0.0104 (3)	0.0054 (3)
N9	0.0317 (18)	0.0188 (16)	0.057 (2)	−0.0024 (13)	0.0135 (16)	0.0059 (14)
C13	0.040 (3)	0.019 (2)	0.042 (3)	−0.003 (2)	0.013 (2)	0.002 (2)
S3	0.0371 (10)	0.0350 (10)	0.0990 (16)	−0.0052 (7)	0.0315 (10)	0.0063 (9)
N9'	0.0317 (18)	0.0188 (16)	0.057 (2)	−0.0024 (13)	0.0135 (16)	0.0059 (14)
C13'	0.040 (3)	0.019 (2)	0.042 (3)	−0.003 (2)	0.013 (2)	0.002 (2)
S3'	0.0323 (18)	0.056 (2)	0.077 (3)	−0.0159 (15)	−0.0082 (16)	0.0269 (19)
Ni2	0.0191 (4)	0.0123 (4)	0.0213 (4)	0.0001 (3)	0.0100 (3)	0.0002 (3)
N10	0.0208 (14)	0.0133 (13)	0.0237 (14)	−0.0007 (10)	0.0105 (11)	−0.0002 (10)
N11	0.0226 (14)	0.0145 (13)	0.0213 (13)	−0.0015 (11)	0.0099 (11)	0.0003 (10)
C14	0.0272 (18)	0.0106 (15)	0.0311 (18)	0.0003 (13)	0.0147 (14)	0.0007 (13)
C15	0.0263 (18)	0.0159 (16)	0.0324 (18)	0.0057 (13)	0.0121 (15)	0.0019 (13)
C16	0.0200 (17)	0.0206 (17)	0.0256 (17)	0.0019 (13)	0.0089 (13)	0.0049 (13)
N12	0.0208 (14)	0.0164 (13)	0.0268 (15)	−0.0007 (11)	0.0112 (12)	−0.0019 (11)
N13	0.0212 (14)	0.0128 (13)	0.0237 (14)	0.0002 (10)	0.0105 (11)	−0.0009 (10)
C17	0.0332 (19)	0.0195 (17)	0.0246 (17)	−0.0043 (14)	0.0117 (15)	−0.0058 (13)
C18	0.044 (2)	0.0280 (19)	0.035 (2)	−0.0018 (16)	0.0233 (18)	−0.0105 (16)
C19	0.0296 (19)	0.0216 (17)	0.0336 (19)	0.0016 (14)	0.0190 (15)	−0.0036 (14)
N14	0.0184 (14)	0.0172 (13)	0.0223 (14)	0.0001 (11)	0.0071 (11)	0.0009 (11)
N15	0.0202 (14)	0.0151 (13)	0.0227 (14)	−0.0019 (10)	0.0101 (11)	0.0007 (10)
C20	0.0254 (18)	0.0208 (17)	0.0228 (16)	0.0017 (13)	0.0125 (14)	0.0017 (13)
C21	0.0312 (19)	0.0238 (18)	0.0287 (18)	−0.0015 (14)	0.0171 (15)	0.0044 (14)
C22	0.0242 (17)	0.0164 (16)	0.0278 (17)	−0.0034 (13)	0.0134 (14)	0.0024 (13)
C23	0.0230 (16)	0.0135 (15)	0.0219 (16)	0.0000 (12)	0.0109 (13)	0.0009 (12)
O1S	0.0299 (15)	0.0500 (19)	0.0543 (19)	−0.0059 (13)	0.0164 (13)	−0.0060 (15)
C1S	0.049 (3)	0.067 (3)	0.061 (3)	0.001 (2)	0.031 (2)	0.005 (3)

Ni1—N8	2.046 (3)	Ni2—N14i	2.077 (3)
Ni1—N7	2.058 (3)	Ni2—N14	2.077 (3)
Ni1—N9	2.070 (3)	Ni2—N12i	2.081 (3)
Ni1—N1	2.080 (3)	Ni2—N12	2.081 (3)
Ni1—N5	2.097 (3)	Ni2—N10i	2.082 (3)
Ni1—N3	2.119 (3)	Ni2—N10	2.082 (3)
C1—N6	1.444 (4)	N10—C14	1.325 (4)
C1—N4	1.447 (4)	N10—N11	1.355 (4)
C1—N2	1.450 (4)	N11—C16	1.342 (4)
C1—H1	1.0000	N11—C23i	1.449 (4)
N1—C2	1.317 (4)	C14—C15	1.396 (5)
N1—N2	1.358 (4)	C14—H14	0.9500
N2—C4	1.352 (4)	C15—C16	1.365 (5)
C2—C3	1.402 (5)	C15—H15	0.9500
C2—H2	0.9500	C16—H16	0.9500
C3—C4	1.369 (5)	N12—C19	1.327 (4)
C3—H3	0.9500	N12—N13	1.362 (4)
C4—H4	0.9500	N13—C17	1.349 (4)
N3—C5	1.322 (5)	N13—C23i	1.447 (4)
N3—N4	1.364 (4)	C17—C18	1.369 (5)
N4—C7	1.355 (5)	C17—H17	0.9500
C5—C6	1.405 (5)	C18—C19	1.390 (5)
C5—H5	0.9500	C18—H18	0.9500
C6—C7	1.365 (6)	C19—H19	0.9500
C6—H6	0.9500	N14—C20	1.326 (4)
C7—H7	0.9500	N14—N15	1.367 (4)
N5—C8	1.328 (5)	N15—C22	1.358 (4)
N5—N6	1.355 (4)	N15—C23	1.441 (4)
N6—C10	1.359 (4)	C20—C21	1.389 (5)
C8—C9	1.394 (5)	C20—H20	0.9500
C8—H8	0.9500	C21—C22	1.364 (5)
C9—C10	1.369 (5)	C21—H21	0.9500
C9—H9	0.9500	C22—H22	0.9500
C10—H10	0.9500	C23—N13i	1.447 (4)
N7—C11	1.160 (5)	C23—N11i	1.449 (4)
C11—S1	1.627 (4)	C23—H23	1.0000
N8—C12	1.160 (5)	O1S—C1S	1.429 (6)
C12—S2	1.629 (4)	O1S—H1S	0.8400
N9—C13	1.237 (7)	C1S—H1S1	0.9800
C13—S3	1.652 (7)	C1S—H1S2	0.9800
C13'—S3'	1.713 (12)	C1S—H1S3	0.9800
N8—Ni1—N7	92.74 (12)	N14i—Ni2—N12i	95.27 (10)
N8—Ni1—N9	92.42 (13)	N14—Ni2—N12i	84.73 (10)
N7—Ni1—N9	92.02 (14)	N14i—Ni2—N12	84.73 (10)
N8—Ni1—N1	93.31 (12)	N14—Ni2—N12	95.27 (10)
N7—Ni1—N1	91.68 (12)	N12i—Ni2—N12	179.996 (1)
N9—Ni1—N1	173.02 (12)	N14i—Ni2—N10i	93.96 (10)
N8—Ni1—N5	93.02 (12)	N14—Ni2—N10i	86.04 (10)
N7—Ni1—N5	173.64 (12)	N12i—Ni2—N10i	85.81 (10)
N9—Ni1—N5	90.41 (13)	N12—Ni2—N10i	94.19 (10)
N1—Ni1—N5	85.31 (11)	N14i—Ni2—N10	86.04 (10)
N8—Ni1—N3	175.06 (12)	N14—Ni2—N10	93.96 (10)
N7—Ni1—N3	89.98 (12)	N12i—Ni2—N10	94.19 (10)
N9—Ni1—N3	91.61 (12)	N12—Ni2—N10	85.81 (10)
N1—Ni1—N3	82.48 (11)	N10i—Ni2—N10	180.00 (15)
N5—Ni1—N3	84.08 (11)	C14—N10—N11	104.9 (3)
N6—C1—N4	109.7 (3)	C14—N10—Ni2	137.4 (2)
N6—C1—N2	110.8 (3)	N11—N10—Ni2	117.63 (19)
N4—C1—N2	109.4 (3)	C16—N11—N10	112.2 (3)
N6—C1—H1	109.0	C16—N11—C23i	128.6 (3)
N4—C1—H1	109.0	N10—N11—C23i	119.3 (3)
N2—C1—H1	109.0	N10—C14—C15	110.7 (3)
C2—N1—N2	105.4 (3)	N10—C14—H14	124.6
C2—N1—Ni1	135.1 (2)	C15—C14—H14	124.6
N2—N1—Ni1	119.2 (2)	C16—C15—C14	105.8 (3)
C4—N2—N1	111.6 (3)	C16—C15—H15	127.1
C4—N2—C1	128.5 (3)	C14—C15—H15	127.1
N1—N2—C1	119.6 (3)	N11—C16—C15	106.4 (3)
N1—C2—C3	111.0 (3)	N11—C16—H16	126.8
N1—C2—H2	124.5	C15—C16—H16	126.8
C3—C2—H2	124.5	C19—N12—N13	105.2 (3)
C4—C3—C2	105.5 (3)	C19—N12—Ni2	136.8 (2)
C4—C3—H3	127.2	N13—N12—Ni2	117.43 (19)
C2—C3—H3	127.2	C17—N13—N12	111.4 (3)
N2—C4—C3	106.5 (3)	C17—N13—C23i	129.2 (3)
N2—C4—H4	126.8	N12—N13—C23i	119.2 (3)
C3—C4—H4	126.8	N13—C17—C18	106.5 (3)
C5—N3—N4	105.3 (3)	N13—C17—H17	126.8
C5—N3—Ni1	136.5 (2)	C18—C17—H17	126.8
N4—N3—Ni1	118.1 (2)	C17—C18—C19	106.0 (3)
C7—N4—N3	111.3 (3)	C17—C18—H18	127.0
C7—N4—C1	128.7 (3)	C19—C18—H18	127.0
N3—N4—C1	119.6 (3)	N12—C19—C18	110.8 (3)
N3—C5—C6	111.0 (3)	N12—C19—H19	124.6
N3—C5—H5	124.5	C18—C19—H19	124.6
C6—C5—H5	124.5	C20—N14—N15	105.2 (3)
C7—C6—C5	105.4 (3)	C20—N14—Ni2	137.7 (2)
C7—C6—H6	127.3	N15—N14—Ni2	117.06 (19)
C5—C6—H6	127.3	C22—N15—N14	111.0 (3)
N4—C7—C6	107.0 (3)	C22—N15—C23	129.3 (3)
N4—C7—H7	126.5	N14—N15—C23	119.7 (3)
C6—C7—H7	126.5	N14—C20—C21	111.0 (3)
C8—N5—N6	105.1 (3)	N14—C20—H20	124.5
C8—N5—Ni1	136.0 (2)	C21—C20—H20	124.5
N6—N5—Ni1	118.8 (2)	C22—C21—C20	106.2 (3)
N5—N6—C10	111.5 (3)	C22—C21—H21	126.9
N5—N6—C1	119.8 (3)	C20—C21—H21	126.9
C10—N6—C1	128.5 (3)	N15—C22—C21	106.6 (3)
N5—C8—C9	111.2 (3)	N15—C22—H22	126.7
N5—C8—H8	124.4	C21—C22—H22	126.7
C9—C8—H8	124.4	N15—C23—N13i	110.5 (3)
C10—C9—C8	105.5 (3)	N15—C23—N11i	110.8 (3)
C10—C9—H9	127.2	N13i—C23—N11i	110.3 (3)
C8—C9—H9	127.2	N15—C23—H23	108.4
N6—C10—C9	106.6 (3)	N13i—C23—H23	108.4
N6—C10—H10	126.7	N11i—C23—H23	108.4
C9—C10—H10	126.7	C1S—O1S—H1S	109.5
C11—N7—Ni1	147.0 (3)	O1S—C1S—H1S1	109.5
N7—C11—S1	177.7 (3)	O1S—C1S—H1S2	109.5
C12—N8—Ni1	170.1 (3)	H1S1—C1S—H1S2	109.5
N8—C12—S2	177.7 (3)	O1S—C1S—H1S3	109.5
C13—N9—Ni1	144.9 (4)	H1S1—C1S—H1S3	109.5
N9—C13—S3	178.5 (5)	H1S2—C1S—H1S3	109.5
N14i—Ni2—N14	180.00 (10)
N8—Ni1—N1—C2	−54.5 (3)	N8—Ni1—N7—C11	−174.3 (5)
N7—Ni1—N1—C2	38.3 (3)	N9—Ni1—N7—C11	−81.8 (5)
N5—Ni1—N1—C2	−147.3 (3)	N1—Ni1—N7—C11	92.3 (5)
N3—Ni1—N1—C2	128.1 (3)	N3—Ni1—N7—C11	9.8 (5)
N8—Ni1—N1—N2	133.0 (2)	N8—Ni1—N9—C13	−83.5 (6)
N7—Ni1—N1—N2	−134.1 (2)	N7—Ni1—N9—C13	−176.4 (6)
N5—Ni1—N1—N2	40.2 (2)	N5—Ni1—N9—C13	9.5 (6)
N3—Ni1—N1—N2	−44.4 (2)	N3—Ni1—N9—C13	93.6 (6)
C2—N1—N2—C4	−0.2 (4)	N14i—Ni2—N10—C14	−135.9 (3)
Ni1—N1—N2—C4	174.3 (2)	N14—Ni2—N10—C14	44.1 (3)
C2—N1—N2—C1	−173.8 (3)	N12i—Ni2—N10—C14	−40.9 (3)
Ni1—N1—N2—C1	0.7 (4)	N12—Ni2—N10—C14	139.1 (3)
N6—C1—N2—C4	127.4 (3)	N14i—Ni2—N10—N11	41.9 (2)
N4—C1—N2—C4	−111.5 (4)	N14—Ni2—N10—N11	−138.1 (2)
N6—C1—N2—N1	−60.1 (4)	N12i—Ni2—N10—N11	136.9 (2)
N4—C1—N2—N1	61.0 (4)	N12—Ni2—N10—N11	−43.1 (2)
N2—N1—C2—C3	−0.3 (4)	C14—N10—N11—C16	0.3 (3)
Ni1—N1—C2—C3	−173.5 (2)	Ni2—N10—N11—C16	−178.1 (2)
N1—C2—C3—C4	0.6 (4)	C14—N10—N11—C23i	179.5 (3)
N1—N2—C4—C3	0.5 (4)	Ni2—N10—N11—C23i	1.0 (3)
C1—N2—C4—C3	173.5 (3)	N11—N10—C14—C15	−0.2 (4)
C2—C3—C4—N2	−0.7 (4)	Ni2—N10—C14—C15	177.8 (2)
N7—Ni1—N3—C5	−38.7 (3)	N10—C14—C15—C16	0.0 (4)
N9—Ni1—N3—C5	53.3 (4)	N10—N11—C16—C15	−0.3 (4)
N1—Ni1—N3—C5	−130.4 (3)	C23i—N11—C16—C15	−179.4 (3)
N5—Ni1—N3—C5	143.5 (3)	C14—C15—C16—N11	0.1 (4)
N7—Ni1—N3—N4	137.9 (2)	N14i—Ni2—N12—C19	144.3 (4)
N9—Ni1—N3—N4	−130.0 (2)	N14—Ni2—N12—C19	−35.7 (4)
N1—Ni1—N3—N4	46.2 (2)	N10i—Ni2—N12—C19	50.7 (4)
N5—Ni1—N3—N4	−39.8 (2)	N10—Ni2—N12—C19	−129.3 (4)
C5—N3—N4—C7	0.0 (4)	N14i—Ni2—N12—N13	−45.7 (2)
Ni1—N3—N4—C7	−177.6 (2)	N14—Ni2—N12—N13	134.3 (2)
C5—N3—N4—C1	173.4 (3)	N10i—Ni2—N12—N13	−139.3 (2)
Ni1—N3—N4—C1	−4.3 (4)	N10—Ni2—N12—N13	40.7 (2)
N6—C1—N4—C7	−124.3 (4)	C19—N12—N13—C17	0.7 (4)
N2—C1—N4—C7	114.0 (4)	Ni2—N12—N13—C17	−172.2 (2)
N6—C1—N4—N3	63.7 (4)	C19—N12—N13—C23i	176.2 (3)
N2—C1—N4—N3	−58.1 (4)	Ni2—N12—N13—C23i	3.3 (3)
N4—N3—C5—C6	0.5 (4)	N12—N13—C17—C18	−1.0 (4)
Ni1—N3—C5—C6	177.4 (3)	C23i—N13—C17—C18	−176.0 (3)
N3—C5—C6—C7	−0.8 (4)	N13—C17—C18—C19	0.9 (4)
N3—N4—C7—C6	−0.5 (4)	N13—N12—C19—C18	−0.1 (4)
C1—N4—C7—C6	−173.1 (3)	Ni2—N12—C19—C18	170.7 (3)
C5—C6—C7—N4	0.8 (4)	C17—C18—C19—N12	−0.5 (4)
N8—Ni1—N5—C8	50.3 (4)	N12i—Ni2—N14—C20	138.3 (3)
N9—Ni1—N5—C8	−42.1 (4)	N12—Ni2—N14—C20	−41.7 (3)
N1—Ni1—N5—C8	143.4 (4)	N10i—Ni2—N14—C20	−135.6 (3)
N3—Ni1—N5—C8	−133.7 (4)	N10—Ni2—N14—C20	44.4 (3)
N8—Ni1—N5—N6	−132.6 (3)	N12i—Ni2—N14—N15	−43.9 (2)
N9—Ni1—N5—N6	135.0 (3)	N12—Ni2—N14—N15	136.1 (2)
N1—Ni1—N5—N6	−39.5 (2)	N10i—Ni2—N14—N15	42.2 (2)
N3—Ni1—N5—N6	43.4 (2)	N10—Ni2—N14—N15	−137.8 (2)
C8—N5—N6—C10	0.3 (4)	C20—N14—N15—C22	0.7 (3)
Ni1—N5—N6—C10	−177.6 (2)	Ni2—N14—N15—C22	−177.7 (2)
C8—N5—N6—C1	175.6 (3)	C20—N14—N15—C23	178.6 (3)
Ni1—N5—N6—C1	−2.3 (4)	Ni2—N14—N15—C23	0.2 (3)
N4—C1—N6—N5	−59.9 (4)	N15—N14—C20—C21	−0.3 (4)
N2—C1—N6—N5	60.9 (4)	Ni2—N14—C20—C21	177.6 (3)
N4—C1—N6—C10	114.5 (4)	N14—C20—C21—C22	−0.2 (4)
N2—C1—N6—C10	−124.6 (4)	N14—N15—C22—C21	−0.8 (4)
N6—N5—C8—C9	−0.1 (4)	C23—N15—C22—C21	−178.5 (3)
Ni1—N5—C8—C9	177.3 (3)	C20—C21—C22—N15	0.6 (4)
N5—C8—C9—C10	−0.1 (4)	C22—N15—C23—N13i	−121.3 (3)
N5—N6—C10—C9	−0.4 (4)	N14—N15—C23—N13i	61.3 (4)
C1—N6—C10—C9	−175.1 (3)	C22—N15—C23—N11i	116.3 (4)
C8—C9—C10—N6	0.3 (4)	N14—N15—C23—N11i	−61.2 (4)

D—H···A	D—H	H···A	D···A	D—H···A
O1S—H1S···S3ii	0.84	2.43	3.267 (4)	175.
O1S—H1S···S3'ii	0.84	2.88	3.459 (6)	128.
C23—H23···O1S	1.00	2.15	3.118 (4)	162.

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1S—H1S⋯S3i	0.84	2.43	3.267 (4)	175
O1S—H1S⋯S3′i	0.84	2.88	3.459 (6)	128
C23—H23⋯O1S	1.00	2.15	3.118 (4)	162

Symmetry code: (i) .