Bis[μ-N,N′-(pyridine-2,6-di­yl)bis­(tri­methyl­silyl­amido)-1κ2N1,N2;2:3κ2N6:N6]bis­(tetra­hydro­furan)-2:3κ2O-1-nickel(II)-2,3-lithium(I)

Boltin, A.M.; Guillet, G.L.

doi:10.1107/S2414314618000585

metal-organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 3| Part 1| January 2018| x180058

https://doi.org/10.1107/S2414314618000585

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Bis[μ-N,N′-(pyridine-2,6-diyl)bis(trimethylsilylamido)-1κ²N¹,N²;2:3κ²N⁶:N⁶]bis(tetrahydrofuran)-2:3κ²O-1-nickel(II)-2,3-lithium(I)

Alan M. Boltin ^a and Gary L. Guillet ^a ^*

^aDepartment of Chemistry and Biochemistry, Georgia Southern University, Savannah, GA 31419, USA
^*Correspondence e-mail: gary.guillet@armstrong.edu

Edited by S. Bernès, Benemérita Universidad Autónoma de Puebla, México (Received 13 December 2017; accepted 9 January 2018; online 12 January 2018)

The title complex, [Li₂Ni(C₁₁H₂₁N₃Si₂)₂(C₄H₈O)₂], is a trimetallic complex of two Li^I cations and a Ni^II cation bridged by two N,N′-(pyridine-2,6-diyl)bis(trimethylsilylamide) ligands that crystallizes in the Fdd2 space group. The molecule has C₂ rotational symmetry, with the Ni^II cation located on the twofold axis. The coordination sphere of the Ni^II cation is composed of two amido N and two pyridyl N-atom donors in a distorted square-planar geometry. The Li^I cations are coordinated by two amido N-atom donors and a tetrahydrofuran molecule with a long interaction with a pyridyl N-atom donor. The coordinating tetrahydrofuran ligand and a trimethylsilyl group are disordered. Intra- or intermolecular hydrogen bonding, as well as π–π stacking, are not observed between the molecules, likely indicating that weak electrostatic interactions are the dominant feature leading to the crystal structure.

Keywords: crystal structure; lithium complex; nickel(II) complex; heteromultimetallic; 2,6-bis(trimethylsilylamino)pyridine.

CCDC reference: 1815878

Structure description

The title complex (Fig. 1) represents a unique mixed trimetallic complex of Li^I and Ni^II. There are a number of multimetallic complexes supported by 2,6-bis(trialkylsilylamido)pyridines (see: Glatz & Kempe, 2008a ,b ,c ; Huang et al., 2012 ), but to the best of the authors' knowledge this is the first with Ni^II and the first with an alkali metal and a transition metal cation. Although there are multiple metals in close proximity, there is no indication of a metal-to-metal interaction with an Li1⋯Ni1 distance of 3.20 (2) Å.

Figure 1
Structure of the title complex. H atoms and the minor disorder components of the disordered SiMe₃ group and THF molecule were omitted for clarity. Displacement ellipsoids are drawn at the 30% probability level. [Symmetry code: (i) $[{3\over 2}]$ − x, $[{1\over 2}]$ − y, z].

The Ni1 dication is in a special position on a twofold rotation axis. The coordination geometry about Ni1 is best described as distorted square planar. Ni1 is coordinated by pyridyl atoms N1 and N1ⁱ with bond distances of 1.952 (6) Å and to the amido atoms N2 and N2ⁱ with bond distances of 1.911 (6) Å [symmetry code: (i) $[{3\over 2}]$ − x, $[{1\over 2}]$ − y, z]. The extent of distortion from planarity about Ni1 can be described by the distance of N1ⁱ or N2ⁱ from the plane defined by Ni1, N1, C1, and N2. For N1ⁱ this distance is 0.38 (1) Å and for N2ⁱ it is 0.52 (1) Å. The angle N1—Ni1—N2 is 69.6 (3)°, a typical value for a bidentate 2-silylamidopyridine. The angles N1—Ni—N1ⁱ and N2—Ni—N2ⁱ are 115.3 (4)° and 109.0 (4)°, respectively.

The coordination about Li1 is best described as distorted tetrahedral with one bond significantly longer than the other three. Li1 has typical bond lengths to amido atoms N3 and N3ⁱ, N3—Li1 = 2.085 (17) Å and N3ⁱ—Li1 = 2.031 (18) Å, and ethereal O1—Li1 = 1.854 (19) Å. On the other hand, the bond length to the pyridyl atom N1, N1—Li1 = 2.473 (17) Å, is significantly longer. Li1 is lifted only slightly out of the trigonal plane O1, N3, and N3ⁱ by 0.12 (2) Å towards N1. The three bond angles in the trigonal plane about Li1 sum to 358.9°. The behaviour of Li1 could be described as a trigonal plane that is capped by N1. It is hoped that the title complex could be a useful synthon for heterometallic transition metal complexes.

Synthesis and crystallization

For this synthesis, bis-2,6-(trimethylsilylamino)pyridine (H₂L) is lithiated with n-butyllithium in tetrahydrofuran (THF) prior to reaction with transition metals. The lithiated starting material (Li₄L₂·4THF, 0.151 g, 0.184 mmol) was dissolved in 5 ml of THF and NiCl₂ (0.048 g, 0.368 mmol) was added directly to the reaction mixture. The reaction proceeded overnight and in that time the solution turned from pale yellow to black with concomitant LiCl precipitation. The solvent was removed under vacuum, the residue taken up in 5 ml of diethyl ether, and then filtered through celite. The resulting solution was allowed to evaporate slowly until crystal formation began, at which point the reaction was cooled to −30°C to induce further crystallization. The title complex was isolated as dark-purple block-shaped crystals.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1. One SiMe₃ group is disordered over two positions, Si2/C9/C10/C11 and Si2A/C9A/C10A/C11A, with site occupancies converging to 0.70 (7) and 0.30 (7). The solvated THF molecule is disordered over two positions, C12/C13/C14/C15 and C12A/C13A/C14A/C15A, with site occupancies converging to 0.70 (1) and 0.30 (1). The thermal displacement parameters for O1/C12/C13/C14/C15/C12A/C13A/C14A/C15A were constrained.

Table 1
Experimental details

Crystal data
Chemical formula	[Li₂Ni(C₁₁H₂₁N₃Si₂)₂(C₄H₈O)₂]
M_r	719.77
Crystal system, space group	Orthorhombic, Fdd2
Temperature (K)	170
a, b, c (Å)	21.023 (7), 28.508 (9), 13.566 (4)
V (Å³)	8129 (4)
Z	8
Radiation type	Mo Kα
μ (mm⁻¹)	0.63
Crystal size (mm)	0.4 × 0.29 × 0.18

Data collection
Diffractometer	Rigaku XtaLAB mini
Absorption correction	Multi-scan (REQAB; Rigaku, 1998 )
T_min, T_max	0.733, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	17664, 3717, 3041
R_int	0.075
(sin θ/λ)_max (Å⁻¹)	0.602

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.060, 0.156, 1.05
No. of reflections	3717
No. of parameters	239
No. of restraints	207
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.42, −0.34
Absolute structure	Flack x determined using 1094 quotients [(I⁺)-(I^-)]/[(I⁺)+(I^-)] (Parsons et al., 2013 )
Absolute structure parameter	0.022 (14)
Computer programs: CrystalClear (Rigaku, 2009 ), SHELXT2014 (Sheldrick, 2015a ), SHELXL2014 (Sheldrick, 2015b ) and OLEX2 (Dolomanov et al., 2009 ).

Structural data

CCDC reference: 1815878

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2414314618000585/bh4033sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314618000585/bh4033Isup2.hkl

checkCIF report

Computing details top

Data collection: CrystalClear (Rigaku, 2009); cell refinement: CrystalClear (Rigaku, 2009); data reduction: CrystalClear (Rigaku, 2009); program(s) used to solve structure: SHELXT2014 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

Bis[µ-N,N'-(pyridine-2,6-diyl)bis(trimethylsilylamido)-1κ²N¹,N²;2:3κ²N⁶:N⁶]bis(tetrahydrofuran)-2:3κ²O-1-nickel(II)-2,3-lithium(I) top

Crystal data top

[Li₂Ni(C₁₁H₂₁N₃Si₂)₂(C₄H₈O)₂]	D_x = 1.176 Mg m⁻³
M_r = 719.77	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Fdd2	Cell parameters from 3922 reflections
a = 21.023 (7) Å	θ = 1.9–25.4°
b = 28.508 (9) Å	µ = 0.63 mm⁻¹
c = 13.566 (4) Å	T = 170 K
V = 8129 (4) Å³	Block, clear dark violet
Z = 8	0.4 × 0.29 × 0.18 mm
F(000) = 3088

Data collection top

Rigaku XtaLAB mini diffractometer	3717 independent reflections
Radiation source: Sealed Tube	3041 reflections with I > 2σ(I)
Graphite Monochromator monochromator	R_int = 0.075
Detector resolution: 13.6612 pixels mm^-1	θ_max = 25.4°, θ_min = 2.4°
profile data from ω–scans	h = −25→25
Absorption correction: multi-scan (REQAB; Rigaku, 1998)	k = −34→34
T_min = 0.733, T_max = 1.000	l = −16→16
17664 measured reflections

Refinement top

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)] = 0.060	H-atom parameters constrained
wR(F²) = 0.156	w = 1/[σ²(F_o²) + (0.0788P)² + 9.9425P] where P = (F_o² + 2F_c²)/3
S = 1.05	(Δ/σ)_max = 0.001
3717 reflections	Δρ_max = 0.42 e Å⁻³
239 parameters	Δρ_min = −0.34 e Å⁻³
207 restraints	Absolute structure: Flack x determined using 1094 quotients [(I⁺)-(I^-)]/[(I⁺)+(I^-)] (Parsons et al., 2013)
Primary atom site location: dual	Absolute structure parameter: 0.022 (14)

Special details top

Refinement. H atoms bonded to C atoms were included at calculated positions using a riding model, with aromatic, methylene, and methyl C—H bond lengths of 0.93, 0.97 and 0.96 Å, respectively, and U_iso(H) set to 1.2U_equiv(C).

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
Ni1	0.7500	0.2500	0.42790 (10)	0.0421 (3)
Si1	0.67645 (12)	0.30931 (11)	0.24185 (18)	0.0736 (8)
O1	0.7103 (5)	0.3553 (3)	0.6360 (8)	0.131 (3)
N1	0.6730 (3)	0.2608 (2)	0.5049 (5)	0.0469 (14)
N2	0.6842 (3)	0.2750 (2)	0.3461 (5)	0.0545 (16)
N3	0.6770 (3)	0.2341 (3)	0.6654 (5)	0.0603 (17)
C1	0.6418 (3)	0.2746 (3)	0.4207 (6)	0.0508 (16)
C2	0.5769 (4)	0.2841 (4)	0.4233 (7)	0.074 (2)
H2	0.5557	0.2952	0.3679	0.089*
C3	0.5451 (4)	0.2765 (4)	0.5106 (7)	0.077 (3)
H3	0.5019	0.2833	0.5141	0.092*
C4	0.5749 (4)	0.2593 (3)	0.5915 (6)	0.067 (2)
H4	0.5518	0.2532	0.6486	0.080*
C5	0.6415 (3)	0.2504 (3)	0.5892 (6)	0.0485 (17)
C6	0.7539 (5)	0.3125 (5)	0.1748 (9)	0.109 (4)
H6A	0.7753	0.3412	0.1916	0.163*
H6B	0.7463	0.3116	0.1050	0.163*
H6C	0.7800	0.2863	0.1933	0.163*
C7	0.6143 (6)	0.2860 (5)	0.1556 (8)	0.114 (4)
H7A	0.6173	0.2525	0.1527	0.170*
H7B	0.6209	0.2989	0.0910	0.170*
H7C	0.5729	0.2948	0.1790	0.170*
C8	0.6535 (7)	0.3702 (4)	0.2800 (10)	0.115 (4)
H8A	0.6129	0.3694	0.3124	0.173*
H8B	0.6508	0.3899	0.2228	0.173*
H8C	0.6849	0.3825	0.3244	0.173*
Li1	0.7346 (7)	0.2929 (6)	0.6448 (12)	0.069 (4)
Si2	0.6452 (16)	0.2234 (19)	0.778 (3)	0.068 (6)	0.30 (7)
C9	0.603 (2)	0.271 (2)	0.847 (3)	0.074 (10)	0.30 (7)
H9A	0.6318	0.2860	0.8922	0.112*	0.30 (7)
H9B	0.5678	0.2582	0.8832	0.112*	0.30 (7)
H9C	0.5872	0.2943	0.8013	0.112*	0.30 (7)
C10	0.7127 (19)	0.201 (3)	0.856 (3)	0.075 (11)	0.30 (7)
H10A	0.7241	0.1702	0.8346	0.112*	0.30 (7)
H10B	0.6999	0.2005	0.9235	0.112*	0.30 (7)
H10C	0.7487	0.2217	0.8484	0.112*	0.30 (7)
C11	0.587 (2)	0.174 (2)	0.760 (4)	0.075 (11)	0.30 (7)
H11A	0.5500	0.1857	0.7273	0.113*	0.30 (7)
H11B	0.5755	0.1615	0.8232	0.113*	0.30 (7)
H11C	0.6066	0.1500	0.7210	0.113*	0.30 (7)
C12	0.6601 (11)	0.3780 (7)	0.6872 (16)	0.131 (3)	0.701 (12)
H12A	0.6760	0.4017	0.7322	0.157*	0.701 (12)
H12B	0.6339	0.3558	0.7231	0.157*	0.701 (12)
C13	0.6251 (10)	0.3992 (6)	0.6035 (17)	0.131 (3)	0.701 (12)
H13A	0.5978	0.4246	0.6250	0.157*	0.701 (12)
H13B	0.5999	0.3761	0.5685	0.157*	0.701 (12)
C14	0.6842 (10)	0.4183 (6)	0.5366 (18)	0.131 (3)	0.701 (12)
H14A	0.6707	0.4234	0.4691	0.157*	0.701 (12)
H14B	0.7006	0.4475	0.5629	0.157*	0.701 (12)
C15	0.7315 (10)	0.3823 (6)	0.5413 (19)	0.131 (3)	0.701 (12)
H15A	0.7738	0.3954	0.5485	0.157*	0.701 (12)
H15B	0.7303	0.3623	0.4834	0.157*	0.701 (12)
Si2A	0.6446 (6)	0.2070 (8)	0.7699 (10)	0.062 (3)	0.70 (7)
C9A	0.6048 (10)	0.2500 (13)	0.8547 (15)	0.084 (6)	0.70 (7)
H9AA	0.6348	0.2736	0.8741	0.126*	0.70 (7)
H9AB	0.5895	0.2339	0.9121	0.126*	0.70 (7)
H9AC	0.5697	0.2645	0.8212	0.126*	0.70 (7)
C10A	0.7124 (10)	0.1789 (14)	0.837 (2)	0.092 (7)	0.70 (7)
H10D	0.7197	0.1481	0.8113	0.138*	0.70 (7)
H10E	0.7022	0.1767	0.9061	0.138*	0.70 (7)
H10F	0.7500	0.1976	0.8291	0.138*	0.70 (7)
C11A	0.5866 (11)	0.1586 (10)	0.739 (2)	0.091 (6)	0.70 (7)
H11D	0.5653	0.1658	0.6785	0.136*	0.70 (7)
H11E	0.5558	0.1559	0.7912	0.136*	0.70 (7)
H11F	0.6091	0.1295	0.7326	0.136*	0.70 (7)
C12A	0.638 (2)	0.3589 (11)	0.672 (5)	0.131 (3)	0.299 (12)
H12C	0.6085	0.3493	0.6204	0.157*	0.299 (12)
H12D	0.6303	0.3409	0.7309	0.157*	0.299 (12)
C13A	0.635 (2)	0.4091 (11)	0.690 (4)	0.131 (3)	0.299 (12)
H13C	0.6445	0.4165	0.7580	0.157*	0.299 (12)
H13D	0.5942	0.4221	0.6720	0.157*	0.299 (12)
C14A	0.6915 (19)	0.4276 (11)	0.616 (4)	0.131 (3)	0.299 (12)
H14C	0.6755	0.4305	0.5491	0.157*	0.299 (12)
H14D	0.7071	0.4580	0.6372	0.157*	0.299 (12)
C15A	0.7421 (18)	0.3929 (14)	0.620 (5)	0.131 (3)	0.299 (12)
H15C	0.7654	0.3912	0.5587	0.157*	0.299 (12)
H15D	0.7715	0.3993	0.6738	0.157*	0.299 (12)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ni1	0.0426 (6)	0.0483 (6)	0.0355 (6)	−0.0009 (6)	0.000	0.000
Si1	0.0678 (15)	0.107 (2)	0.0465 (13)	0.0204 (14)	0.0037 (11)	0.0264 (13)
O1	0.165 (7)	0.080 (4)	0.148 (7)	0.008 (4)	0.003 (6)	−0.025 (4)
N1	0.041 (3)	0.060 (3)	0.040 (3)	−0.002 (3)	−0.004 (3)	0.010 (3)
N2	0.048 (4)	0.076 (5)	0.039 (3)	0.007 (3)	0.000 (3)	0.012 (3)
N3	0.047 (3)	0.090 (4)	0.043 (4)	−0.006 (3)	−0.001 (3)	0.021 (3)
C1	0.046 (4)	0.060 (4)	0.047 (4)	0.004 (3)	−0.005 (4)	0.007 (4)
C2	0.056 (5)	0.112 (7)	0.054 (5)	0.017 (4)	−0.003 (5)	0.016 (5)
C3	0.045 (4)	0.122 (8)	0.063 (6)	0.017 (5)	0.005 (4)	0.018 (6)
C4	0.050 (5)	0.104 (7)	0.047 (4)	−0.004 (4)	0.005 (4)	0.013 (5)
C5	0.037 (4)	0.063 (4)	0.045 (4)	−0.004 (3)	−0.001 (3)	0.009 (4)
C6	0.097 (7)	0.151 (11)	0.078 (7)	0.026 (6)	0.024 (6)	0.052 (8)
C7	0.106 (8)	0.171 (11)	0.064 (7)	0.023 (7)	−0.022 (6)	0.021 (7)
C8	0.144 (10)	0.101 (7)	0.100 (8)	0.050 (7)	0.024 (7)	0.047 (6)
Li1	0.062 (8)	0.083 (10)	0.062 (9)	−0.015 (7)	0.003 (7)	−0.008 (8)
Si2	0.059 (6)	0.092 (17)	0.054 (8)	−0.026 (10)	−0.008 (5)	0.025 (10)
C9	0.076 (17)	0.10 (2)	0.047 (16)	−0.026 (15)	0.012 (13)	0.027 (15)
C10	0.066 (12)	0.12 (3)	0.036 (16)	−0.022 (15)	0.008 (10)	0.045 (17)
C11	0.065 (15)	0.10 (2)	0.06 (2)	−0.030 (14)	0.010 (13)	0.026 (16)
C12	0.165 (7)	0.080 (4)	0.148 (7)	0.008 (4)	0.003 (6)	−0.025 (4)
C13	0.165 (7)	0.080 (4)	0.148 (7)	0.008 (4)	0.003 (6)	−0.025 (4)
C14	0.165 (7)	0.080 (4)	0.148 (7)	0.008 (4)	0.003 (6)	−0.025 (4)
C15	0.165 (7)	0.080 (4)	0.148 (7)	0.008 (4)	0.003 (6)	−0.025 (4)
Si2A	0.051 (3)	0.089 (7)	0.046 (3)	−0.015 (4)	0.001 (2)	0.026 (4)
C9A	0.078 (10)	0.116 (14)	0.056 (8)	−0.010 (9)	0.025 (7)	0.024 (9)
C10A	0.065 (8)	0.128 (17)	0.084 (14)	−0.007 (9)	0.002 (7)	0.044 (12)
C11A	0.087 (10)	0.103 (12)	0.082 (14)	−0.036 (9)	−0.005 (10)	0.033 (10)
C12A	0.165 (7)	0.080 (4)	0.148 (7)	0.008 (4)	0.003 (6)	−0.025 (4)
C13A	0.165 (7)	0.080 (4)	0.148 (7)	0.008 (4)	0.003 (6)	−0.025 (4)
C14A	0.165 (7)	0.080 (4)	0.148 (7)	0.008 (4)	0.003 (6)	−0.025 (4)
C15A	0.165 (7)	0.080 (4)	0.148 (7)	0.008 (4)	0.003 (6)	−0.025 (4)

Geometric parameters (Å, º) top

Ni1—N1ⁱ	1.952 (6)	Si2—C11	1.88 (2)
Ni1—N1	1.952 (6)	C9—H9A	0.9600
Ni1—N2	1.911 (6)	C9—H9B	0.9600
Ni1—N2ⁱ	1.911 (6)	C9—H9C	0.9600
Ni1—C1ⁱ	2.382 (7)	C10—H10A	0.9600
Ni1—C1	2.382 (7)	C10—H10B	0.9600
Ni1—Li1ⁱ	3.202 (16)	C10—H10C	0.9600
Ni1—Li1	3.202 (16)	C11—H11A	0.9600
Si1—N2	1.727 (7)	C11—H11B	0.9600
Si1—C6	1.868 (10)	C11—H11C	0.9600
Si1—C7	1.875 (11)	C12—H12A	0.9700
Si1—C8	1.875 (12)	C12—H12B	0.9700
O1—Li1	1.854 (19)	C12—C13	1.48 (2)
O1—C12	1.42 (2)	C13—H13A	0.9700
O1—C15	1.56 (2)	C13—H13B	0.9700
O1—C12A	1.60 (4)	C13—C14	1.63 (3)
O1—C15A	1.28 (4)	C14—H14A	0.9700
N1—C1	1.374 (10)	C14—H14B	0.9700
N1—C5	1.353 (10)	C14—C15	1.43 (2)
N1—Li1	2.473 (17)	C15—H15A	0.9700
N2—C1	1.349 (10)	C15—H15B	0.9700
N3—C5	1.356 (10)	Si2A—Li1ⁱ	3.05 (2)
N3—Li1ⁱ	2.031 (18)	Si2A—C9A	1.880 (15)
N3—Li1	2.085 (17)	Si2A—C10A	1.872 (13)
N3—Si2	1.70 (3)	Si2A—C11A	1.887 (14)
N3—Si2A	1.753 (14)	C9A—H9AA	0.9600
C1—C2	1.391 (10)	C9A—H9AB	0.9600
C2—H2	0.9300	C9A—H9AC	0.9600
C2—C3	1.378 (13)	C10A—H10D	0.9600
C3—H3	0.9300	C10A—H10E	0.9600
C3—C4	1.355 (12)	C10A—H10F	0.9600
C4—H4	0.9300	C11A—H11D	0.9600
C4—C5	1.424 (11)	C11A—H11E	0.9600
C6—H6A	0.9600	C11A—H11F	0.9600
C6—H6B	0.9600	C12A—H12C	0.9700
C6—H6C	0.9600	C12A—H12D	0.9700
C7—H7A	0.9600	C12A—C13A	1.45 (3)
C7—H7B	0.9600	C13A—H13C	0.9700
C7—H7C	0.9600	C13A—H13D	0.9700
C8—H8A	0.9600	C13A—C14A	1.64 (3)
C8—H8B	0.9600	C14A—H14C	0.9700
C8—H8C	0.9600	C14A—H14D	0.9700
Li1—N3ⁱ	2.031 (17)	C14A—C15A	1.46 (3)
Si2—Li1ⁱ	3.14 (4)	C15A—H15C	0.9700
Si2—C9	1.88 (2)	C15A—H15D	0.9700
Si2—C10	1.88 (2)

N1—Ni1—N1ⁱ	115.3 (4)	C9—Si2—Li1ⁱ	140.8 (16)
N1—Ni1—C1ⁱ	149.4 (3)	C10—Si2—Li1ⁱ	70.4 (15)
N1ⁱ—Ni1—C1ⁱ	35.2 (3)	C10—Si2—C9	108.9 (18)
N1ⁱ—Ni1—C1	149.4 (3)	C11—Si2—Li1ⁱ	109.7 (18)
N1—Ni1—C1	35.2 (3)	C11—Si2—C9	107.5 (17)
N1—Ni1—Li1	50.5 (3)	C11—Si2—C10	108.1 (18)
N1ⁱ—Ni1—Li1ⁱ	50.5 (3)	Si2—C9—H9A	109.5
N1—Ni1—Li1ⁱ	69.7 (3)	Si2—C9—H9B	109.5
N1ⁱ—Ni1—Li1	69.7 (3)	Si2—C9—H9C	109.5
N2ⁱ—Ni1—N1	166.0 (3)	H9A—C9—H9B	109.5
N2ⁱ—Ni1—N1ⁱ	69.6 (3)	H9A—C9—H9C	109.5
N2—Ni1—N1ⁱ	166.0 (3)	H9B—C9—H9C	109.5
N2—Ni1—N1	69.6 (3)	Si2—C10—H10A	109.5
N2ⁱ—Ni1—N2	109.0 (4)	Si2—C10—H10B	109.5
N2—Ni1—C1	34.5 (3)	Si2—C10—H10C	109.5
N2—Ni1—C1ⁱ	141.0 (3)	H10A—C10—H10B	109.5
N2ⁱ—Ni1—C1	141.0 (3)	H10A—C10—H10C	109.5
N2ⁱ—Ni1—C1ⁱ	34.5 (3)	H10B—C10—H10C	109.5
N2ⁱ—Ni1—Li1	138.5 (3)	Si2—C11—H11A	109.5
N2—Ni1—Li1ⁱ	138.5 (3)	Si2—C11—H11B	109.5
N2ⁱ—Ni1—Li1ⁱ	108.5 (4)	Si2—C11—H11C	109.5
N2—Ni1—Li1	108.5 (4)	H11A—C11—H11B	109.5
C1—Ni1—C1ⁱ	175.3 (4)	H11A—C11—H11C	109.5
C1—Ni1—Li1ⁱ	104.3 (3)	H11B—C11—H11C	109.5
C1ⁱ—Ni1—Li1	104.3 (3)	O1—C12—H12A	111.7
C1ⁱ—Ni1—Li1ⁱ	80.2 (3)	O1—C12—H12B	111.7
C1—Ni1—Li1	80.2 (3)	O1—C12—C13	100.4 (16)
Li1ⁱ—Ni1—Li1	46.5 (6)	H12A—C12—H12B	109.5
N2—Si1—C6	110.1 (4)	C13—C12—H12A	111.7
N2—Si1—C7	112.1 (5)	C13—C12—H12B	111.7
N2—Si1—C8	108.8 (5)	C12—C13—H13A	111.6
C6—Si1—C7	108.7 (6)	C12—C13—H13B	111.6
C6—Si1—C8	108.3 (6)	C12—C13—C14	100.6 (15)
C7—Si1—C8	108.7 (6)	H13A—C13—H13B	109.4
C12—O1—Li1	127.6 (12)	C14—C13—H13A	111.6
C12—O1—C15	112.8 (13)	C14—C13—H13B	111.6
C15—O1—Li1	116.7 (10)	C13—C14—H14A	110.7
C12A—O1—Li1	107.8 (14)	C13—C14—H14B	110.7
C15A—O1—Li1	132.1 (18)	H14A—C14—H14B	108.8
C15A—O1—C12A	119 (2)	C15—C14—C13	105.4 (15)
Ni1—N1—Li1	92.0 (4)	C15—C14—H14A	110.7
C1—N1—Ni1	89.7 (5)	C15—C14—H14B	110.7
C1—N1—Li1	141.5 (6)	O1—C15—H15A	111.5
C5—N1—Ni1	145.4 (5)	O1—C15—H15B	111.5
C5—N1—C1	122.2 (6)	C14—C15—O1	101.1 (15)
C5—N1—Li1	71.8 (5)	C14—C15—H15A	111.5
Si1—N2—Ni1	139.1 (4)	C14—C15—H15B	111.5
C1—N2—Ni1	92.2 (4)	H15A—C15—H15B	109.4
C1—N2—Si1	123.8 (5)	N3—Si2A—Li1ⁱ	39.4 (5)
C5—N3—Li1ⁱ	121.9 (7)	N3—Si2A—C9A	112.3 (8)
C5—N3—Li1	86.7 (6)	N3—Si2A—C10A	106.7 (10)
C5—N3—Si2	122.2 (14)	N3—Si2A—C11A	113.3 (10)
C5—N3—Si2A	123.7 (7)	C9A—Si2A—Li1ⁱ	135.2 (7)
Li1ⁱ—N3—Li1	75.8 (8)	C9A—Si2A—C11A	108.9 (9)
Si2—N3—Li1	119.6 (18)	C10A—Si2A—Li1ⁱ	68.9 (9)
Si2—N3—Li1ⁱ	114.6 (15)	C10A—Si2A—C9A	108.6 (10)
Si2A—N3—Li1	133.5 (9)	C10A—Si2A—C11A	106.7 (10)
Si2A—N3—Li1ⁱ	107.4 (7)	C11A—Si2A—Li1ⁱ	114.6 (9)
N1—C1—C2	120.1 (8)	Si2A—C9A—H9AA	109.5
N2—C1—N1	108.1 (6)	Si2A—C9A—H9AB	109.5
N2—C1—C2	131.7 (8)	Si2A—C9A—H9AC	109.5
C1—C2—H2	121.1	H9AA—C9A—H9AB	109.5
C3—C2—C1	117.8 (8)	H9AA—C9A—H9AC	109.5
C3—C2—H2	121.1	H9AB—C9A—H9AC	109.5
C2—C3—H3	119.0	Si2A—C10A—H10D	109.5
C4—C3—C2	122.0 (8)	Si2A—C10A—H10E	109.5
C4—C3—H3	119.0	Si2A—C10A—H10F	109.5
C3—C4—H4	120.0	H10D—C10A—H10E	109.5
C3—C4—C5	120.0 (8)	H10D—C10A—H10F	109.5
C5—C4—H4	120.0	H10E—C10A—H10F	109.5
N1—C5—N3	116.8 (6)	Si2A—C11A—H11D	109.5
N1—C5—C4	117.4 (7)	Si2A—C11A—H11E	109.5
N3—C5—C4	125.7 (7)	Si2A—C11A—H11F	109.5
Si1—C6—H6A	109.5	H11D—C11A—H11E	109.5
Si1—C6—H6B	109.5	H11D—C11A—H11F	109.5
Si1—C6—H6C	109.5	H11E—C11A—H11F	109.5
H6A—C6—H6B	109.5	O1—C12A—H12C	112.0
H6A—C6—H6C	109.5	O1—C12A—H12D	112.0
H6B—C6—H6C	109.5	H12C—C12A—H12D	109.7
Si1—C7—H7A	109.5	C13A—C12A—O1	99 (2)
Si1—C7—H7B	109.5	C13A—C12A—H12C	112.0
Si1—C7—H7C	109.5	C13A—C12A—H12D	112.0
H7A—C7—H7B	109.5	C12A—C13A—H13C	111.6
H7A—C7—H7C	109.5	C12A—C13A—H13D	111.6
H7B—C7—H7C	109.5	C12A—C13A—C14A	101 (2)
Si1—C8—H8A	109.5	H13C—C13A—H13D	109.4
Si1—C8—H8B	109.5	C14A—C13A—H13C	111.6
Si1—C8—H8C	109.5	C14A—C13A—H13D	111.6
H8A—C8—H8B	109.5	C13A—C14A—H14C	110.4
H8A—C8—H8C	109.5	C13A—C14A—H14D	110.4
H8B—C8—H8C	109.5	H14C—C14A—H14D	108.6
O1—Li1—N3	128.2 (9)	C15A—C14A—C13A	106 (2)
O1—Li1—N3ⁱ	128.6 (9)	C15A—C14A—H14C	110.4
O1—Li1—C5	103.7 (8)	C15A—C14A—H14D	110.4
N3ⁱ—Li1—N3	102.1 (8)	O1—C15A—C14A	101 (2)
N3—Li1—C5	34.0 (3)	O1—C15A—H15C	111.5
N3ⁱ—Li1—C5	126.4 (8)	O1—C15A—H15D	111.5
N3—Si2—Li1ⁱ	36.0 (10)	C14A—C15A—H15C	111.5
N3—Si2—C9	120 (2)	C14A—C15A—H15D	111.5
N3—Si2—C10	106 (2)	H15C—C15A—H15D	109.3
N3—Si2—C11	106 (2)

Symmetry code: (i) −x+3/2, −y+1/2, z.

Funding information

The authors would like to thank Armstrong State University for funding.

References

Dolomanov, O. V., Bourhis, L. J., Gildea, R. J., Howard, J. A. K. & Puschmann, H. (2009). J. Appl. Cryst. 42, 339–341. Web of Science CrossRef CAS IUCr Journals Google Scholar
Glatz, G. & Kempe, R. (2008a). Z. Kristallogr. New Cryst. Struct. 223, 307–308. CAS Google Scholar
Glatz, G. & Kempe, R. (2008b). Z. Kristallogr. New Cryst. Struct. 223, 313–315. CAS Google Scholar
Glatz, G. & Kempe, R. (2008c). Z. Kristallogr. New Cryst. Struct. 223, 309–310. CAS Google Scholar
Huang, Y.-L., Lu, D.-Y., Yu, H.-C., Yu, J. K., Hsu, C.-W., Kuo, T.-S., Lee, G.-H., Wang, Y. & Tsai, Y.-C. (2012). Angew. Chem. Int. Ed. 51, 7781–7785. Web of Science CSD CrossRef CAS Google Scholar
Parsons, S., Flack, H. D. & Wagner, T. (2013). Acta Cryst. B69, 249–259. Web of Science CrossRef CAS IUCr Journals Google Scholar
Rigaku (1998). REQAB. Rigaku Corporation, Tokyo, Japan. Google Scholar
Rigaku (2009). CrystalClear. Rigaku Corporation, Tokyo, Japan. Google Scholar
Sheldrick, G. M. (2015a). Acta Cryst. A71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2015b). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar

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