Tetra­ethyl­ammonium tris­(thio­cyanato-κN)[tris­(1H-pyrazol-1-yl-κN2)methane]­nickelate(II)

Lyubartseva, G.; Parkin, S.; Mallik, U.P.; Jeon, H.K.

doi:10.1107/S1600536812024774

metal-organic compounds

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ISSN: 2056-9890

Volume 68| Part 7| July 2012| Page m888

https://doi.org/10.1107/S1600536812024774

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Tetraethylammonium tris(thiocyanato-κN)[tris(1H-pyrazol-1-yl-κN²)methane]nickelate(II)

Ganna Lyubartseva,^a ^* Sean Parkin,^b Uma Prasad Mallik ^a and Hee Kyung Jeon ^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 29 May 2012; accepted 30 May 2012; online 13 June 2012)

The title salt, (C₈H₂₀N)[Ni(NCS)₃(C₁₀H₁₀N₆)], consists of a tetraethylammonium cation and an anion comprising an octahedral Ni^II atom surrounded by three N atoms from a tripodal tris(pyrazol-1-yl)methane ligand, and three thiocyanate ligands, each bound at the N-atom end. The ligand Ni—N distances range from 2.097 (2) to 2.127 (2) Å for the tripodal ligand and from 2.045 (2) to 2.075 (2) Å for the thiocyanate ligands. The dihedral angles between the three pyrazole rings are 59.03 (12), 53.09 (10) and 67.90 (10)°.

Related literature

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 literature on tris(pyrazol-1-yl)borate, see: Czernuszewicz et al. (1987 ); Kitajima et al. (1992 ); Lippard & Armstrong (1985 ); Lippard et al. (1990 ). For a related structure, see: Lyubartseva et al. (2011 ).

Experimental

Crystal data

(C₈H₂₀N)[Ni(NCS)₃(C₁₀H₁₀N₆)]
M_r = 577.44
Monoclinic, C 2/c
a = 31.7117 (12) Å
b = 7.4378 (3) Å
c = 24.7885 (9) Å
β = 110.592 (2)°
V = 5473.2 (4) Å³
Z = 8
Cu Kα radiation
μ = 3.41 mm⁻¹
T = 90 K
0.20 × 0.09 × 0.02 mm

Data collection

Bruker X8 Proteum diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2006 ) T_min = 0.562, T_max = 0.935
17387 measured reflections
17387 independent reflections
16112 reflections with I > 2σ(I)
R_int = 0.057

Refinement

R[F² > 2σ(F²)] = 0.054
wR(F²) = 0.186
S = 1.11
17387 reflections
321 parameters
9 restraints
H-atom parameters constrained
Δρ_max = 0.65 e Å⁻³
Δρ_min = −0.51 e Å⁻³

Data collection: APEX2 (Bruker, 2006); cell refinement: APEX2; data reduction: APEX2; 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/S1600536812024774/tk5107sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536812024774/tk5107Isup2.hkl

checkCIF report

Comment top

Tris(pyrazol-1-yl)borate has been used to structurally mimic the three histidine residues in the preparation of a hemerythrin analogue (Lippard & Armstrong, 1985, Lippard et al., 1990, Czernuszewicz et al., 1987), as well as to model methane monooxygenase (Kitajima et al., 1992). Tris(pyrazol-1-yl)methane is isoelectronic with tris(pyrazol-1-yl)borate (Astley et al., 1993). While trying to prepare mononuclear [(tpm)Ni^IIL₃]^-1 , where tpm is tris(pyrazol-1-yl)methane, a symmetrical tridentate neutral nitrogen donor ligand, and L is NCS^-, we obtained [(tpm)₂Ni^II][(tpm)Ni^II(NCS)₃]₂.2CH₃OH as blue monoclinic crystals (Lyubartseva et al., 2011). We hypothesized that by changing the source of nickel and thiocyanate in the reaction, we might be able to synthesize our target compound. Replacement of nickel chloride by commercially available nickel trifluoromethanesulfonate, and tetrabutyl ammonium thiocyanate by tetraethylammonium thiocyanate, the reaction allowed successful isolation of the title complex, tetraethylammonium [tris(1-pyrazolyl)methano tris(thiocyanato) nickelate(II)] as blue monoclinic twinned crystals in moderate yield. Crystallographic analysis of the title complex shows that the structure consists of tetraethylammonium cations and anions consisting of nickel(II) surrounded octahedrally by one tripodal tris(pyrazol-1-yl)methane ligand and three thiocyanate ligands, each bound at the nitrogen end. The tripodal ligand N—Ni distance ranges from 2.097 (2) to 2.127 (2) Å and the distance between N-donor pseudohalide uni-negative anion N—Ni ranges from 2.045 (2) to 2.075 (2) Å, very similar to what we observed before in our previous study (Lyubartseva et al., 2011).

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 literature on tris(pyrazol-1-yl)borate, see: Czernuszewicz et al. (1987); Kitajima et al. (1992); Lippard & Armstrong (1985); Lippard et al. (1990). For a related structure, see: Lyubartseva et al. (2011).

Experimental top

Tris(pyrazolyl)methane ligand was synthesized according to the previously published procedure by Reger et al. (2000). Tetraethylammonium thiocyanate and nickel trifluoromethanesulfonate were commercially available and used as received. Ni(OTf)₂ (179 mg, 0.5 mmol) was dissolved in 35 ml methanol. Tris(pyrazolyl)methane (107 mg, 0.5 mmol) was dissolved in 15 ml methanol. The ligand solution was added drop-wise to the metal containing solution with moderate stirring. Once the addition was complete, tetraethylammonium thiocyanate (0.282 g, 1.5 mmol) was added and stirred for 15 minutes. The clear solution was filtered and methanol was evaporated slowly. Blue crystals were obtained after 1 week (197 mg, 68% yield).

Structure description 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 literature on tris(pyrazol-1-yl)borate, see: Czernuszewicz et al. (1987); Kitajima et al. (1992); Lippard & Armstrong (1985); Lippard et al. (1990). For a related structure, see: Lyubartseva et al. (2011).

Computing details top

Data collection: APEX2 (Bruker, 2006); cell refinement: APEX2 (Bruker, 2006); data reduction: APEX2 (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: SHELXL97 (Sheldrick, 2008) and local procedures.

Figures top

	Fig. 1. View of the title compound with displacement ellipsoids drawn at the 50% probability level.
	Fig. 2. Packing diagram of the title compound as viewed down the b axis. Hydrogen atoms are omitted to enhance clarity.

Tetraethylammonium tris(thiocyanato-κN)[tris(1H-pyrazol-1-yl- κN²)methane]nickelate(II) top

Crystal data top

(C₈H₂₀N)[Ni(NCS)₃(C₁₀H₁₀N₆)]	F(000) = 2416
M_r = 577.44	D_x = 1.402 Mg m⁻³
Monoclinic, C2/c	Cu Kα radiation, λ = 1.54178 Å
Hall symbol: -C 2yc	Cell parameters from 9915 reflections
a = 31.7117 (12) Å	θ = 3.0–68.1°
b = 7.4378 (3) Å	µ = 3.41 mm⁻¹
c = 24.7885 (9) Å	T = 90 K
β = 110.592 (2)°	Plate, blue
V = 5473.2 (4) Å³	0.20 × 0.09 × 0.02 mm
Z = 8

Data collection top

Bruker X8 Proteum diffractometer	17387 independent reflections
Radiation source: fine-focus rotating anode	16112 reflections with I > 2σ(I)
Graded multilayer optics monochromator	R_int = 0.057
Detector resolution: 5.6 pixels mm^-1	θ_max = 68.5°, θ_min = 3.0°
φ and ω scans	h = −38→38
Absorption correction: multi-scan (SADABS; Bruker, 2006)	k = −8→8
T_min = 0.562, T_max = 0.935	l = −29→29
17387 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)] = 0.054	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.186	H-atom parameters constrained
S = 1.11	w = 1/[σ²(F_o²) + (0.1128P)² + 8.5319P] where P = (F_o² + 2F_c²)/3
17387 reflections	(Δ/σ)_max = 0.001
321 parameters	Δρ_max = 0.65 e Å⁻³
9 restraints	Δρ_min = −0.51 e Å⁻³

Crystal data top

(C₈H₂₀N)[Ni(NCS)₃(C₁₀H₁₀N₆)]	V = 5473.2 (4) Å³
M_r = 577.44	Z = 8
Monoclinic, C2/c	Cu Kα radiation
a = 31.7117 (12) Å	µ = 3.41 mm⁻¹
b = 7.4378 (3) Å	T = 90 K
c = 24.7885 (9) Å	0.20 × 0.09 × 0.02 mm
β = 110.592 (2)°

Data collection top

Bruker X8 Proteum diffractometer	17387 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2006)	16112 reflections with I > 2σ(I)
T_min = 0.562, T_max = 0.935	R_int = 0.057
17387 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.054	9 restraints
wR(F²) = 0.186	H-atom parameters constrained
S = 1.11	Δρ_max = 0.65 e Å⁻³
17387 reflections	Δρ_min = −0.51 e Å⁻³
321 parameters

Special details top

Experimental. The crystal is twinned by non-merohedry, in which twin components are related by a 2-fold rotation about the a^* axis. The resulting overlap resulted in a large number of rejections during integration, scaling, merging etc. Despite many attempts using a range of input parameters, the present dataset was the best that we could manage.

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-value wR and goodness of fit S are based on F². Conventional R-values R are based on F, with F set to zero for negative F². The threshold expression of F² > 2σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-values based on F² are statistically about twice as large as those based on F, and R-values based on ALL data will be even larger.

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

	x	y	z	U_iso*/U_eq
Ni1	0.407107 (14)	0.17110 (5)	0.63651 (2)	0.01568 (13)
N1	0.35867 (7)	−0.1867 (3)	0.61187 (10)	0.0153 (5)
N2	0.35110 (7)	−0.0071 (3)	0.61043 (9)	0.0159 (4)
C1	0.32006 (8)	−0.2804 (4)	0.58867 (11)	0.0174 (6)
H1	0.3170	−0.4073	0.5847	0.021*
C2	0.28630 (9)	−0.1564 (4)	0.57207 (12)	0.0214 (6)
H2	0.2550	−0.1794	0.5543	0.026*
C3	0.30707 (9)	0.0117 (4)	0.58641 (11)	0.0191 (6)
H3	0.2916	0.1236	0.5798	0.023*
N3	0.42727 (7)	−0.1922 (3)	0.69244 (10)	0.0169 (5)
N4	0.43242 (7)	−0.0126 (3)	0.70447 (9)	0.0146 (5)
C4	0.44329 (8)	−0.2906 (4)	0.74113 (12)	0.0176 (6)
H4	0.4432	−0.4180	0.7436	0.021*
C5	0.45954 (9)	−0.1741 (4)	0.78610 (13)	0.0219 (7)
H5	0.4728	−0.2031	0.8258	0.026*
C6	0.45241 (9)	−0.0008 (4)	0.76109 (11)	0.0195 (6)
H6	0.4608	0.1085	0.7819	0.023*
N5	0.42885 (7)	−0.1912 (3)	0.59718 (10)	0.0159 (5)
N6	0.43478 (8)	−0.0119 (3)	0.59194 (9)	0.0178 (5)
C7	0.44483 (9)	−0.2883 (4)	0.56257 (12)	0.0212 (6)
H7	0.4441	−0.4155	0.5587	0.025*
C8	0.46233 (10)	−0.1675 (4)	0.53401 (14)	0.0246 (7)
H8	0.4761	−0.1931	0.5065	0.030*
C9	0.45532 (9)	0.0019 (4)	0.55438 (13)	0.0233 (6)
H9	0.4643	0.1125	0.5425	0.028*
C10	0.40484 (8)	−0.2525 (4)	0.63393 (12)	0.0181 (5)
H10	0.4043	−0.3869	0.6336	0.022*
N7	0.37742 (8)	0.3308 (3)	0.68012 (11)	0.0202 (5)
C11	0.35301 (9)	0.4110 (4)	0.69627 (12)	0.0191 (6)
S1	0.31880 (3)	0.52620 (10)	0.71952 (3)	0.02905 (19)
N8	0.37895 (8)	0.3221 (3)	0.56293 (11)	0.0228 (6)
C12	0.35534 (9)	0.3813 (4)	0.52014 (13)	0.0224 (6)
S2	0.32179 (3)	0.46358 (10)	0.45961 (3)	0.0332 (2)
N9	0.46528 (8)	0.3251 (3)	0.65824 (11)	0.0214 (5)
C13	0.49714 (9)	0.3547 (3)	0.64656 (13)	0.0197 (6)
S3	0.54146 (2)	0.39277 (10)	0.63002 (4)	0.0337 (2)
N1C	0.33644 (7)	0.0364 (3)	0.85322 (10)	0.0182 (5)
C1C	0.31210 (10)	−0.0335 (4)	0.89191 (12)	0.0234 (7)
H1C1	0.3128	−0.1665	0.8916	0.028*
H1C2	0.2801	0.0038	0.8754	0.028*
C2C	0.33125 (12)	0.0301 (4)	0.95409 (13)	0.0296 (7)
H2C1	0.3629	−0.0064	0.9711	0.044*
H2C2	0.3141	−0.0238	0.9760	0.044*
H2C3	0.3291	0.1614	0.9553	0.044*
C3C	0.38609 (9)	−0.0102 (4)	0.87637 (12)	0.0232 (6)
H3C1	0.4002	0.0498	0.9141	0.028*
H3C2	0.4003	0.0392	0.8498	0.028*
C4C	0.39633 (11)	−0.2101 (4)	0.88395 (16)	0.0360 (8)
H4C1	0.3836	−0.2598	0.9115	0.054*
H4C2	0.4290	−0.2283	0.8985	0.054*
H4C3	0.3830	−0.2710	0.8467	0.054*
C5C	0.31308 (10)	−0.0509 (4)	0.79491 (13)	0.0223 (6)
H5C1	0.3172	−0.1826	0.7994	0.027*
H5C2	0.2804	−0.0262	0.7830	0.027*
C6C	0.32900 (11)	0.0091 (4)	0.74713 (13)	0.0273 (7)
H6C1	0.3229	0.1377	0.7398	0.041*
H6C2	0.3130	−0.0590	0.7120	0.041*
H6C3	0.3615	−0.0125	0.7585	0.041*
C7C	0.33375 (9)	0.2414 (4)	0.84895 (13)	0.0223 (6)
H7C1	0.3504	0.2926	0.8875	0.027*
H7C2	0.3491	0.2817	0.8226	0.027*
C8C	0.28625 (9)	0.3166 (4)	0.82774 (13)	0.0234 (7)
H8C1	0.2702	0.2754	0.7883	0.035*
H8C2	0.2875	0.4483	0.8284	0.035*
H8C3	0.2703	0.2748	0.8529	0.035*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ni1	0.0155 (2)	0.0125 (3)	0.0192 (3)	−0.00071 (16)	0.0062 (2)	0.00040 (17)
N1	0.0149 (11)	0.0118 (12)	0.0192 (13)	0.0020 (8)	0.0060 (10)	0.0006 (8)
N2	0.0165 (11)	0.0122 (11)	0.0197 (11)	0.0007 (8)	0.0074 (9)	0.0019 (9)
C1	0.0159 (14)	0.0205 (14)	0.0164 (15)	−0.0059 (10)	0.0062 (11)	−0.0019 (11)
C2	0.0128 (14)	0.0307 (17)	0.0206 (16)	−0.0040 (10)	0.0056 (12)	0.0012 (11)
C3	0.0178 (14)	0.0212 (15)	0.0177 (14)	0.0018 (10)	0.0056 (11)	0.0018 (11)
N3	0.0153 (12)	0.0126 (13)	0.0231 (14)	−0.0025 (8)	0.0071 (10)	0.0016 (9)
N4	0.0112 (12)	0.0126 (13)	0.0183 (12)	−0.0028 (8)	0.0030 (9)	−0.0029 (9)
C4	0.0114 (13)	0.0167 (14)	0.0250 (17)	0.0005 (10)	0.0069 (11)	0.0082 (11)
C5	0.0090 (13)	0.0334 (18)	0.0219 (17)	−0.0029 (10)	0.0038 (11)	0.0032 (11)
C6	0.0128 (13)	0.0234 (16)	0.0226 (16)	−0.0012 (10)	0.0066 (11)	−0.0011 (12)
N5	0.0128 (11)	0.0120 (12)	0.0228 (14)	0.0002 (8)	0.0062 (10)	0.0006 (8)
N6	0.0211 (13)	0.0152 (13)	0.0194 (13)	−0.0011 (9)	0.0101 (10)	0.0013 (9)
C7	0.0206 (14)	0.0248 (16)	0.0189 (16)	0.0040 (11)	0.0078 (12)	−0.0004 (11)
C8	0.0270 (16)	0.0271 (18)	0.0283 (19)	0.0036 (11)	0.0202 (14)	−0.0006 (12)
C9	0.0192 (15)	0.0238 (16)	0.0288 (16)	0.0005 (11)	0.0107 (12)	0.0018 (12)
C10	0.0138 (13)	0.0166 (14)	0.0205 (15)	0.0003 (10)	0.0017 (11)	0.0022 (11)
N7	0.0249 (13)	0.0151 (13)	0.0248 (15)	−0.0019 (9)	0.0139 (11)	0.0000 (9)
C11	0.0230 (15)	0.0143 (14)	0.0197 (15)	−0.0039 (11)	0.0072 (11)	0.0030 (11)
S1	0.0347 (4)	0.0252 (4)	0.0350 (4)	0.0087 (3)	0.0220 (4)	0.0034 (3)
N8	0.0226 (13)	0.0137 (14)	0.0290 (16)	0.0033 (9)	0.0051 (11)	0.0009 (10)
C12	0.0261 (15)	0.0141 (14)	0.0282 (17)	0.0021 (11)	0.0112 (13)	−0.0052 (12)
S2	0.0456 (5)	0.0246 (4)	0.0237 (4)	0.0145 (3)	0.0052 (3)	0.0027 (3)
N9	0.0187 (12)	0.0164 (12)	0.0294 (15)	−0.0015 (8)	0.0088 (11)	0.0029 (9)
C13	0.0185 (14)	0.0109 (13)	0.0265 (17)	0.0031 (10)	0.0039 (12)	0.0048 (11)
S3	0.0239 (4)	0.0253 (5)	0.0565 (6)	0.0003 (3)	0.0200 (4)	0.0070 (4)
N1C	0.0157 (12)	0.0221 (14)	0.0189 (12)	0.0017 (9)	0.0085 (10)	0.0018 (10)
C1C	0.0227 (16)	0.0275 (17)	0.0251 (16)	0.0032 (12)	0.0148 (13)	0.0081 (12)
C2C	0.047 (2)	0.0178 (17)	0.0262 (17)	0.0053 (13)	0.0162 (15)	0.0043 (12)
C3C	0.0166 (14)	0.0280 (16)	0.0255 (16)	0.0018 (11)	0.0082 (12)	0.0029 (12)
C4C	0.0287 (18)	0.0391 (19)	0.042 (2)	0.0134 (14)	0.0152 (15)	0.0140 (15)
C5C	0.0219 (16)	0.0215 (16)	0.0253 (17)	−0.0027 (12)	0.0105 (13)	−0.0006 (11)
C6C	0.0346 (18)	0.0257 (17)	0.0245 (16)	−0.0059 (12)	0.0140 (14)	−0.0014 (13)
C7C	0.0286 (15)	0.0128 (15)	0.0268 (16)	−0.0011 (11)	0.0114 (13)	−0.0013 (11)
C8C	0.0218 (15)	0.0216 (17)	0.0287 (18)	0.0039 (11)	0.0114 (13)	0.0034 (12)

Geometric parameters (Å, º) top

Ni1—N7	2.045 (2)	N7—C11	1.155 (4)
Ni1—N8	2.059 (2)	C11—S1	1.638 (3)
Ni1—N9	2.075 (2)	N8—C12	1.149 (4)
Ni1—N4	2.097 (2)	C12—S2	1.623 (3)
Ni1—N2	2.126 (2)	N9—C13	1.166 (4)
Ni1—N6	2.127 (2)	C13—S3	1.621 (3)
N1—C1	1.349 (3)	N1C—C3C	1.514 (3)
N1—N2	1.356 (3)	N1C—C5C	1.519 (4)
N1—C10	1.456 (3)	N1C—C1C	1.519 (3)
N2—C3	1.319 (3)	N1C—C7C	1.529 (4)
C1—C2	1.363 (4)	C1C—C2C	1.520 (4)
C1—H1	0.9500	C1C—H1C1	0.9900
C2—C3	1.400 (4)	C1C—H1C2	0.9900
C2—H2	0.9500	C2C—H2C1	0.9800
C3—H3	0.9500	C2C—H2C2	0.9800
N3—C4	1.349 (3)	C2C—H2C3	0.9800
N3—N4	1.366 (3)	C3C—C4C	1.519 (4)
N3—C10	1.444 (4)	C3C—H3C1	0.9900
N4—C6	1.324 (3)	C3C—H3C2	0.9900
C4—C5	1.362 (4)	C4C—H4C1	0.9800
C4—H4	0.9500	C4C—H4C2	0.9800
C5—C6	1.414 (4)	C4C—H4C3	0.9800
C5—H5	0.9500	C5C—C6C	1.509 (4)
C6—H6	0.9500	C5C—H5C1	0.9900
N5—C7	1.349 (4)	C5C—H5C2	0.9900
N5—N6	1.359 (3)	C6C—H6C1	0.9800
N5—C10	1.451 (3)	C6C—H6C2	0.9800
N6—C9	1.315 (4)	C6C—H6C3	0.9800
C7—C8	1.376 (4)	C7C—C8C	1.517 (4)
C7—H7	0.9500	C7C—H7C1	0.9900
C8—C9	1.404 (4)	C7C—H7C2	0.9900
C8—H8	0.9500	C8C—H8C1	0.9800
C9—H9	0.9500	C8C—H8C2	0.9800
C10—H10	1.0000	C8C—H8C3	0.9800

N7—Ni1—N8	90.83 (9)	N3—C10—H10	108.7
N7—Ni1—N9	94.28 (10)	N5—C10—H10	108.7
N8—Ni1—N9	89.87 (10)	N1—C10—H10	108.7
N7—Ni1—N4	94.08 (9)	C11—N7—Ni1	166.6 (2)
N8—Ni1—N4	172.38 (9)	N7—C11—S1	179.4 (3)
N9—Ni1—N4	95.57 (9)	C12—N8—Ni1	164.9 (2)
N7—Ni1—N2	91.84 (9)	N8—C12—S2	179.6 (3)
N8—Ni1—N2	90.86 (9)	C13—N9—Ni1	144.0 (2)
N9—Ni1—N2	173.83 (9)	N9—C13—S3	179.2 (3)
N4—Ni1—N2	83.16 (8)	C3C—N1C—C5C	110.9 (2)
N7—Ni1—N6	175.50 (9)	C3C—N1C—C1C	112.0 (2)
N8—Ni1—N6	91.07 (9)	C5C—N1C—C1C	105.6 (2)
N9—Ni1—N6	89.81 (9)	C3C—N1C—C7C	106.25 (19)
N4—Ni1—N6	83.63 (8)	C5C—N1C—C7C	111.3 (2)
N2—Ni1—N6	84.05 (9)	C1C—N1C—C7C	110.9 (2)
C1—N1—N2	111.9 (2)	N1C—C1C—C2C	115.0 (3)
C1—N1—C10	128.9 (2)	N1C—C1C—H1C1	108.5
N2—N1—C10	119.13 (19)	C2C—C1C—H1C1	108.5
C3—N2—N1	105.4 (2)	N1C—C1C—H1C2	108.5
C3—N2—Ni1	135.22 (18)	C2C—C1C—H1C2	108.5
N1—N2—Ni1	119.00 (15)	H1C1—C1C—H1C2	107.5
N1—C1—C2	106.1 (2)	C1C—C2C—H2C1	109.5
N1—C1—H1	126.9	C1C—C2C—H2C2	109.5
C2—C1—H1	126.9	H2C1—C2C—H2C2	109.5
C1—C2—C3	106.2 (2)	C1C—C2C—H2C3	109.5
C1—C2—H2	126.9	H2C1—C2C—H2C3	109.5
C3—C2—H2	126.9	H2C2—C2C—H2C3	109.5
N2—C3—C2	110.4 (2)	N1C—C3C—C4C	114.8 (2)
N2—C3—H3	124.8	N1C—C3C—H3C1	108.6
C2—C3—H3	124.8	C4C—C3C—H3C1	108.6
C4—N3—N4	110.9 (2)	N1C—C3C—H3C2	108.6
C4—N3—C10	128.9 (2)	C4C—C3C—H3C2	108.6
N4—N3—C10	120.1 (2)	H3C1—C3C—H3C2	107.5
C6—N4—N3	105.8 (2)	C3C—C4C—H4C1	109.5
C6—N4—Ni1	135.53 (18)	C3C—C4C—H4C2	109.5
N3—N4—Ni1	118.63 (16)	H4C1—C4C—H4C2	109.5
N3—C4—C5	107.6 (2)	C3C—C4C—H4C3	109.5
N3—C4—H4	126.2	H4C1—C4C—H4C3	109.5
C5—C4—H4	126.2	H4C2—C4C—H4C3	109.5
C4—C5—C6	105.4 (3)	C6C—C5C—N1C	115.8 (2)
C4—C5—H5	127.3	C6C—C5C—H5C1	108.3
C6—C5—H5	127.3	N1C—C5C—H5C1	108.3
N4—C6—C5	110.3 (2)	C6C—C5C—H5C2	108.3
N4—C6—H6	124.8	N1C—C5C—H5C2	108.3
C5—C6—H6	124.8	H5C1—C5C—H5C2	107.4
C7—N5—N6	111.7 (2)	C5C—C6C—H6C1	109.5
C7—N5—C10	128.9 (2)	C5C—C6C—H6C2	109.5
N6—N5—C10	119.3 (2)	H6C1—C6C—H6C2	109.5
C9—N6—N5	105.3 (2)	C5C—C6C—H6C3	109.5
C9—N6—Ni1	135.67 (19)	H6C1—C6C—H6C3	109.5
N5—N6—Ni1	118.83 (16)	H6C2—C6C—H6C3	109.5
N5—C7—C8	106.7 (2)	C8C—C7C—N1C	114.6 (2)
N5—C7—H7	126.7	C8C—C7C—H7C1	108.6
C8—C7—H7	126.7	N1C—C7C—H7C1	108.6
C7—C8—C9	104.9 (3)	C8C—C7C—H7C2	108.6
C7—C8—H8	127.5	N1C—C7C—H7C2	108.6
C9—C8—H8	127.5	H7C1—C7C—H7C2	107.6
N6—C9—C8	111.4 (3)	C7C—C8C—H8C1	109.5
N6—C9—H9	124.3	C7C—C8C—H8C2	109.5
C8—C9—H9	124.3	H8C1—C8C—H8C2	109.5
N3—C10—N5	110.5 (2)	C7C—C8C—H8C3	109.5
N3—C10—N1	110.4 (2)	H8C1—C8C—H8C3	109.5
N5—C10—N1	109.8 (2)	H8C2—C8C—H8C3	109.5

C1—N1—N2—C3	0.5 (3)	N9—Ni1—N6—N5	138.72 (19)
C10—N1—N2—C3	177.3 (2)	N4—Ni1—N6—N5	43.10 (17)
C1—N1—N2—Ni1	−173.73 (18)	N2—Ni1—N6—N5	−40.65 (18)
C10—N1—N2—Ni1	3.1 (3)	N6—N5—C7—C8	0.6 (3)
N7—Ni1—N2—C3	49.5 (3)	C10—N5—C7—C8	176.2 (2)
N8—Ni1—N2—C3	−41.3 (3)	N5—C7—C8—C9	0.0 (3)
N4—Ni1—N2—C3	143.4 (3)	N5—N6—C9—C8	1.0 (3)
N6—Ni1—N2—C3	−132.3 (3)	Ni1—N6—C9—C8	−173.5 (2)
N7—Ni1—N2—N1	−138.4 (2)	C7—C8—C9—N6	−0.6 (3)
N8—Ni1—N2—N1	130.8 (2)	C4—N3—C10—N5	−122.9 (3)
N4—Ni1—N2—N1	−44.47 (19)	N4—N3—C10—N5	60.8 (3)
N6—Ni1—N2—N1	39.8 (2)	C4—N3—C10—N1	115.4 (3)
N2—N1—C1—C2	−0.5 (3)	N4—N3—C10—N1	−60.9 (3)
C10—N1—C1—C2	−176.9 (3)	C7—N5—C10—N3	125.4 (3)
N1—C1—C2—C3	0.2 (3)	N6—N5—C10—N3	−59.4 (3)
N1—N2—C3—C2	−0.4 (3)	C7—N5—C10—N1	−112.6 (3)
Ni1—N2—C3—C2	172.5 (2)	N6—N5—C10—N1	62.7 (3)
C1—C2—C3—N2	0.1 (3)	C1—N1—C10—N3	−125.4 (3)
C4—N3—N4—C6	0.9 (3)	N2—N1—C10—N3	58.4 (3)
C10—N3—N4—C6	177.8 (2)	C1—N1—C10—N5	112.5 (3)
C4—N3—N4—Ni1	−176.83 (17)	N2—N1—C10—N5	−63.7 (3)
C10—N3—N4—Ni1	0.1 (3)	N8—Ni1—N7—C11	57.8 (9)
N7—Ni1—N4—C6	−42.9 (3)	N9—Ni1—N7—C11	147.7 (9)
N9—Ni1—N4—C6	51.8 (3)	N4—Ni1—N7—C11	−116.4 (9)
N2—Ni1—N4—C6	−134.3 (3)	N2—Ni1—N7—C11	−33.1 (9)
N6—Ni1—N4—C6	141.0 (3)	N7—Ni1—N8—C12	−85.6 (9)
N7—Ni1—N4—N3	133.94 (18)	N2—Ni1—N8—C12	6.2 (9)
N9—Ni1—N4—N3	−131.34 (18)	N6—Ni1—N8—C12	90.3 (9)
N2—Ni1—N4—N3	42.58 (18)	N7—Ni1—N9—C13	−163.3 (3)
N6—Ni1—N4—N3	−42.16 (17)	N8—Ni1—N9—C13	−72.5 (3)
N4—N3—C4—C5	−0.3 (3)	N4—Ni1—N9—C13	102.2 (3)
C10—N3—C4—C5	−176.9 (2)	N6—Ni1—N9—C13	18.6 (3)
N3—C4—C5—C6	−0.3 (3)	C3C—N1C—C1C—C2C	56.6 (3)
N3—N4—C6—C5	−1.1 (3)	C5C—N1C—C1C—C2C	177.4 (3)
Ni1—N4—C6—C5	176.07 (18)	C7C—N1C—C1C—C2C	−61.9 (3)
C4—C5—C6—N4	0.9 (3)	C5C—N1C—C3C—C4C	−58.8 (3)
C7—N5—N6—C9	−1.0 (3)	C1C—N1C—C3C—C4C	58.8 (3)
C10—N5—N6—C9	−177.0 (2)	C7C—N1C—C3C—C4C	−180.0 (3)
C7—N5—N6—Ni1	174.60 (18)	C3C—N1C—C5C—C6C	−63.1 (3)
C10—N5—N6—Ni1	−1.4 (3)	C1C—N1C—C5C—C6C	175.4 (3)
N8—Ni1—N6—C9	42.5 (3)	C7C—N1C—C5C—C6C	55.0 (3)
N9—Ni1—N6—C9	−47.3 (3)	C3C—N1C—C7C—C8C	−178.6 (2)
N4—Ni1—N6—C9	−143.0 (3)	C5C—N1C—C7C—C8C	60.6 (3)
N2—Ni1—N6—C9	133.3 (3)	C1C—N1C—C7C—C8C	−56.7 (3)
N8—Ni1—N6—N5	−131.41 (19)

Experimental details

Crystal data
Chemical formula	(C₈H₂₀N)[Ni(NCS)₃(C₁₀H₁₀N₆)]
M_r	577.44
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	90
a, b, c (Å)	31.7117 (12), 7.4378 (3), 24.7885 (9)
β (°)	110.592 (2)
V (Å³)	5473.2 (4)
Z	8
Radiation type	Cu Kα
µ (mm⁻¹)	3.41
Crystal size (mm)	0.20 × 0.09 × 0.02

Data collection
Diffractometer	Bruker X8 Proteum
Absorption correction	Multi-scan (SADABS; Bruker, 2006)
T_min, T_max	0.562, 0.935
No. of measured, independent and observed [I > 2σ(I)] reflections	17387, 17387, 16112
R_int	0.057
(sin θ/λ)_max (Å⁻¹)	0.604

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.054, 0.186, 1.11
No. of reflections	17387
No. of parameters	321
No. of restraints	9
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.65, −0.51

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

Acknowledgements

GL gratefully acknowledges Southern Arkansas University for the financial support.

References

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