Bis[tris­(1H-pyrazol-1-yl-κN2)methane]­nickel(II) bis­{[tris­(1H-pyrazol-1-yl-κN2)methane]­tris­(thio­cyanato-κN)nickelate(II)} methanol disolvate

Lyubartseva, G.; Parkin, S.; Mallik, U.P.

doi:10.1107/S1600536811045144

metal-organic compounds

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ISSN: 2056-9890

Volume 67| Part 12| December 2011| Pages m1656-m1657

https://doi.org/10.1107/S1600536811045144

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Bis[tris(1H-pyrazol-1-yl-κN²)methane]nickel(II) bis{[tris(1H-pyrazol-1-yl-κN²)methane]tris(thiocyanato-κN)nickelate(II)} methanol disolvate

Ganna Lyubartseva,^a ^* Sean Parkin ^b and Uma Prasad Mallik ^a

^aDepartment of Chemistry and Physics, Southern Arkansas University, Magnolia, AR 71753, USA, and ^bDepartment of Chemistry, University of Kentucky, Lexington, KY 40506, USA
^*Correspondence e-mail: gannalyubartseva@saumag.edu

(Received 20 October 2011; accepted 27 October 2011; online 5 November 2011)

Attempts to prepare the mononuclear [(tpm)Ni^IIL₃]⁻¹ [tpm = tris(1H-pyrazol-1-yl)methane and L = thiocyanate] anion yielded the methanol-solvated salt, [(tpm)₂Ni^II][(tpm)Ni^II(NCS)₃]₂·2CH₃OH or [Ni(C₁₀H₁₀N₆)₂][Ni(NCS)₃(C₁₀H₁₀N₆)]₂·2CH₃OH. The asymmetric unit consists of half a centrosymmetric bis[tris(1H-pyrazol-1-yl)methane]nickel(II) cation and an octahedral nickelate(II) anion bound to one tpm and three L ligands, and a methanol solvent molecule. 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 interactions between the methanol and the disordered thiocyanate 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_r = 1445.65
Monoclinic, C 2/c
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[F² > 2σ(F²)] = 0.049
wR(F²) = 0.128
S = 1.11
5605 reflections
418 parameters
6 restraints
H-atom parameters constrained
Δρ_max = 1.34 e Å⁻³
Δρ_min = −0.44 e Å⁻³

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) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ .

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.

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536811045144/ng5255sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536811045144/ng5255Isup2.hkl

checkCIF report

Comment top

Tripodal ligands with three pyrazolyl groups are increasingly being used in small-molecule modeling of the active sites of metallo-enzymes in which the metal is coordinated to two or three imidazole groups from histidine (Kitajima et al. 1992, Trofimenko et al. 1992, Looney et al. 1992, Looney & Parkin 1994). One of the goals of this research is to explore the chemistry of the neutral ligand tris(pyrazol-1-yl)methane compared to the more extensively studied isoelectronic but anionic ligand tris(pyrazol-1-yl)borate. In attempts to prepare mononuclear [(tpm)Ni^IIL₃]^-1 , where tpm is tris(pyrazol-1-yl)methane, a symmetrical tripodal neutral nitrogen donor ligand, and L is NCS^-, a uninegative N-donor pseudohalide anion, we obtained [(tpm)₂Ni^II][(tpm)Ni^II(NCS)₃]₂.2CH₃OH as blue monoclinic crystals in 57% isolated yield. The structure consists of centrosymmetric [bis[tris(1-pyrazolyl)methane-κ³]-nickel(II) cations, with Ni^II—N distances ranging from 2.077 (2) to 2.082 (2) Å. The intraligand N—Ni—N angles in the cation range from 85.81 (10) to 95.27 (10)°, which introduces a slight trigonal distortion from perfect octahedral geometry. The anion consists of nickellate (II) atom surrounded octahedrally by one tripodal tris(pyrazol-1-yl)methane ligand and three isothiocyanate ligands. The tpm ligand N—Ni distances range from 2.080 (3) to 2.119 (3) Å, and the isothiocyanate N—Ni distances range from 2.046 (3) to 2.070 (3) Å.

Related literature top

For the ligand synthesis, see: Reger et al. (2000). For structural, spectroscopic and angular overlap studies of tris(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 top

The tris(pyrazolyl)methane ligand was synthesized according to the previously published procedure by Reger et al. (2000). Tetrabutylammonium thiocyanate was purchased from Aldrich and used as received. NiCl₂.6H₂0 (475 mg, 2 mmol) was dissolved in 15 ml methanol. Tris(pyrazolyl) methane (428 mg, 2 mmol) was dissolved in 15 ml methanol. The ligand solution was added dropwise to metal solution and with moderate stirring. Once the addition was complete, tetrabutylammonium thiocyanate (1.81 g, 6 mmol) was added. The solution was filtered and methanol was evaporated slowly. Blue crystals were obtained after 3 days (549 mg, 57% yield). Elemental analysis, calculated for Ni₃C₄₈H₄₈N₃₀S₆O₂ : C 39.88, H 3.35, N 29.07; found C 39.21, H 2.99, N 29.27%. IR (cm^-1): 3361, 3133, 2977, 2071, 1516, 1440, 1400, 1284, 1247, 1220, 1088, 1050, 980, 905, 858, 788, 766, 660, 608, 475.

Structure description top

Computing details top

Data collection: APEX2 (Bruker, 2006); cell refinement: SAINT (Bruker, 2006); data reduction: SAINT (Bruker, 2006); 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: SHELX97 (Sheldrick, 2008) and local procedures.

Figures top

	Fig. 1. View of the title compound with displacement ellipsoids drawn at the 50% probability level. The minor isothiocynate disorder component is shown with open bonds. Unlabelled atoms are related to their labelled counterparts by inversion (0.5 - x, 1.5 - y, 1 - z).
	Fig. 2. Packing diagram of the title compound as viewed down the b axis. The hydrogen atoms are omitted to enhance clarity.

Bis[tris(1H-pyrazol-1-yl-κN²)methane]nickel(II) bis{[tris(1H-pyrazol-1-yl-κN²)methane]tris(thiocyanato- κN)nickelate(II)} methanol disolvate top

Crystal data top

[Ni(C₁₀H₁₀N₆)₂][Ni(NCS)₃(C₁₀H₁₀N₆)]₂·2CH₄O	F(000) = 2968
M_r = 1445.65	D_x = 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

Data collection top

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

Refinement top

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(F_o²) + (0.0515P)² + 28.6001P] where P = (F_o² + 2F_c²)/3
5605 reflections	(Δ/σ)_max = 0.001
418 parameters	Δρ_max = 1.34 e Å⁻³
6 restraints	Δρ_min = −0.44 e Å⁻³

Crystal data top

[Ni(C₁₀H₁₀N₆)₂][Ni(NCS)₃(C₁₀H₁₀N₆)]₂·2CH₄O	V = 6171.3 (3) Å³
M_r = 1445.65	Z = 4
Monoclinic, C2/c	Cu Kα radiation
a = 33.4463 (8) Å	µ = 3.52 mm⁻¹
b = 7.3287 (2) Å	T = 90 K
c = 27.2689 (7) Å	0.20 × 0.06 × 0.02 mm
β = 112.590 (1)°

Data collection top

Bruker X8 Proteum diffractometer	5605 independent reflections
Absorption correction: multi-scan (SADABS in APEX2; Bruker, 2006)	4932 reflections with I > 2σ(I)
T_min = 0.740, T_max = 0.933	R_int = 0.061
41685 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.049	6 restraints
wR(F²) = 0.128	H-atom parameters constrained
S = 1.11	w = 1/[σ²(F_o²) + (0.0515P)² + 28.6001P] where P = (F_o² + 2F_c²)/3
5605 reflections	Δρ_max = 1.34 e Å⁻³
418 parameters	Δρ_min = −0.44 e Å⁻³

Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	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*

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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)

Symmetry code: (i) −x+1/2, −y+3/2, −z+1.

Hydrogen-bond geometry (Å, º) top

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

Symmetry code: (ii) x−1/2, −y+1/2, z−1/2.

Experimental details

Crystal data
Chemical formula	[Ni(C₁₀H₁₀N₆)₂][Ni(NCS)₃(C₁₀H₁₀N₆)]₂·2CH₄O
M_r	1445.65
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	90
a, b, c (Å)	33.4463 (8), 7.3287 (2), 27.2689 (7)
β (°)	112.590 (1)
V (Å³)	6171.3 (3)
Z	4
Radiation type	Cu Kα
µ (mm⁻¹)	3.52
Crystal size (mm)	0.20 × 0.06 × 0.02

Data collection
Diffractometer	Bruker X8 Proteum
Absorption correction	Multi-scan (SADABS in APEX2; Bruker, 2006)
T_min, T_max	0.740, 0.933
No. of measured, independent and observed [I > 2σ(I)] reflections	41685, 5605, 4932
R_int	0.061
(sin θ/λ)_max (Å⁻¹)	0.601

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.049, 0.128, 1.11
No. of reflections	5605
No. of parameters	418
No. of restraints	6
H-atom treatment	H-atom parameters constrained
	w = 1/[σ²(F_o²) + (0.0515P)² + 28.6001P] where P = (F_o² + 2F_c²)/3
Δρ_max, Δρ_min (e Å⁻³)	1.34, −0.44

Computer programs: APEX2 (Bruker, 2006), SAINT (Bruker, 2006), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), XP in SHELXTL (Sheldrick, 2008), SHELX97 (Sheldrick, 2008) and local procedures.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1S—H1S···S3ⁱ	0.84	2.43	3.267 (4)	175.2
O1S—H1S···S3'ⁱ	0.84	2.88	3.459 (6)	128.2
C23—H23···O1S	1.00	2.15	3.118 (4)	161.5

Symmetry code: (i) x−1/2, −y+1/2, z−1/2.

Acknowledgements

GL gratefully acknowledges Southern Arkansas University for the financial support.

References

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