Bis[1-meth­oxy-2,2,2-tris­(pyrazol-1-yl-κN2)ethane]­nickel(II) bis­(tri­fluoro­methane­sulfonate) methanol disolvate

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

doi:10.1107/S1600536813024653

metal-organic compounds

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ISSN: 2056-9890

Volume 69| Part 10| October 2013| Page m537

doi:10.1107/S1600536813024653

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Bis[1-methoxy-2,2,2-tris(pyrazol-1-yl-κN²)ethane]nickel(II) bis(trifluoromethanesulfonate) methanol disolvate

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

^aDepartment of Biochemistry, 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 26 August 2013; accepted 3 September 2013; online 12 September 2013)

In the title salt, [Ni(C₁₂H₁₄N₆O)₂](CF₃SO₃)₂·2CH₃OH, the Ni^II ion is coordinated by six N atoms from two tridentate 1-methoxy-2,2,2-tris(pyrazol-1-yl)ethane ligands in a distorted octahedral geometry. The Ni^II ion is situated on an inversion centre. The Ni—N distances range from 2.0589 (19) to 2.0757 (19) Å, intra-ligand N—Ni—N angles range from 84.50 (8) to 85.15 (8)°, and adjacent inter-ligand N—Ni—N angles range between 94.85 (8) and 95.50 (8)°. In the crystal, O—H⋯O hydrogen bonds between methanol solvent molecules and trifluoromethanesulfonate anions are observed.

Related literature

Pyrazole-based tridentate ligands are drawing attention because of their topology and the nature of the donor atoms, see: Paulo et al. (2004 ); Bigmore et al. (2005 ). For the synthesis of the ligand, see: Maria et al. (2007 ). The compound reported here was prepared as part of our ongoing research effort to study nitrogen donor tridentate scorpionate ligands coordinating to nickel, see: Lyubartseva et al. (2011 , 2012 ); Lyubartseva & Parkin (2009 ).

Experimental

Crystal data

[Ni(C₁₂H₁₄N₆O)₂](CF₃O₃S)₂·2CH₄O
M_r = 937.52
Triclinic, $[P \overline 1]$
a = 9.0025 (2) Å
b = 9.5921 (2) Å
c = 11.9914 (2) Å
α = 105.2683 (8)°
β = 103.4796 (8)°
γ = 102.2596 (8)°
V = 929.15 (3) Å³
Z = 1
Mo Kα radiation
μ = 0.74 mm⁻¹
T = 90 K
0.19 × 0.18 × 0.15 mm

Data collection

Nonius KappaCCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2008a ) T_min = 0.753, T_max = 0.898
22611 measured reflections
4271 independent reflections
3292 reflections with I > 2σ(I)
R_int = 0.040

Refinement

R[F² > 2σ(F²)] = 0.043
wR(F²) = 0.105
S = 1.10
4271 reflections
271 parameters
H-atom parameters constrained
Δρ_max = 0.45 e Å⁻³
Δρ_min = −0.48 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1S—H1S⋯O2A	0.84	1.96	2.782 (3)	168

Data collection: COLLECT (Nonius, 1998 ); cell refinement: SCALEPACK (Otwinowski & Minor, 1997 ); data reduction: DENZO-SMN (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008b ); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2008b); molecular graphics: XP in SHELXTL (Sheldrick, 2008b); software used to prepare material for publication: SHELXL2013.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536813024653/lh5647sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536813024653/lh5647Isup2.hkl

checkCIF report

Comment top

In an attempt to prepare mononuclear [L₂Ni^II]⁺², where L is 1-methoxy-2,2,2-tris(pyrazol-1-yl)ethane, a tridentate neutral nitrogen donor ligand, we isolated the major product [Ni(C₁₂H₁₄N₆₀)₂][CF₃SO₃]₂·2CH₃OH as pink triclinic crystals. In the crystal, the nickel ion is coordinated by six N atoms from the two tridentate tpmOMe ligands (average Ni—N distance = 2.0653 Å) in a distorted octahedral geometry. The Ni atom is situated on an inversion centre. The average N—Ni—N angle between adjacent pyrazole-ring-coordinated N atoms is 84.81° for the six acute angles and 95.19° for the six obtuse angles. Intramolecular O—H···O hydrogen bonds are present between methanol solvent molecules and trifluoromethanesulfonate anions.

Related literature top

Pyrazole-based tridentate ligands are drawing attention because of their topology and the nature of the donor atoms, see: Paulo et al. (2004); Bigmore et al. (2005). For the synthesis of the ligand, see: Maria et al. (2007). The compound reported here was prepared as part of our ongoing research effort to study nitrogen donor tridentate scorpionate ligands coordinated with nickel, see: Lyubartseva et al. (2011, 2012); Lyubartseva & Parkin (2009).

Experimental top

The 1-methoxy-2,2,2-tris(pyrazol-1-yl)ethane ligand was synthesized according to the previously published procedure of Maria et al. (2007). Nickel trifluoromethanesulfonate was used as received. Ni(OTf)₂(358 mg, 1 mmol) was dissolved in 40 ml me thanol. 1-Methoxy-2,2,2-tris(pyrazol-1-yl)ethane (258 mg, 1 mmol) was dissolved in 25 ml me thanol. The ligand solution was added dropwise to metal solution with moderate stirring. Once the addition was complete, the resulting solution was filtered and solvent was slowly evaporated in air. Pink crystals were obtained after 2 weeks (343 mg, 73.2% yield). Elemental analysis, calculated for C₂₈H₃₆N₁₂NiO₁₀F₆S₂: C 35.87, H 3.87, N 17.93; found C 35.69, H 3.64, N 18.02. IR (cm^-1): 3625,3483,3146,2921,1616,1522,1421,1388,1341,1324,1254,1232,1199,1167, 1106,1071,1059, 1028,1011,973,920,855,757,673,653,636,603,573,517.

Computing details top

Data collection: COLLECT (Nonius, 1998); cell refinement: SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO-SMN (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008b); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2008b); molecular graphics: XP in SHELXTL (Sheldrick, 2008b); software used to prepare material for publication: SHELXL2013 (Sheldrick, 2008b).

Figures top

Fig. 1. The title compound with displacement ellipsoids drawn at the 50% probability level. Unlabeled atoms are related by the symmetry operator (-x+1, -y+1, -z+1). Only the symmetry unique anion and solvent molecule are shown.

Bis[1-methoxy-2,2,2-tris(pyrazol-1-yl-κN²)ethane]nickel(II) bis(trifluoromethanesulfonate) methanol disolvate top

Crystal data top

[Ni(C₁₂H₁₄N₆O)₂](CF₃O₃S)₂·2CH₄O	Z = 1
M_r = 937.52	F(000) = 482
Triclinic, P1	D_x = 1.675 Mg m⁻³
a = 9.0025 (2) Å	Mo Kα radiation, λ = 0.71073 Å
b = 9.5921 (2) Å	Cell parameters from 4236 reflections
c = 11.9914 (2) Å	θ = 1.0–27.5°
α = 105.2683 (8)°	µ = 0.74 mm⁻¹
β = 103.4796 (8)°	T = 90 K
γ = 102.2596 (8)°	Block, pink
V = 929.15 (3) Å³	0.19 × 0.18 × 0.15 mm

Data collection top

Nonius KappaCCD diffractometer	4271 independent reflections
Radiation source: fine-focus sealed-tube	3292 reflections with I > 2σ(I)
Detector resolution: 9.1 pixels mm^-1	R_int = 0.040
ϕ and ω scans at fixed χ = 55°	θ_max = 27.5°, θ_min = 1.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 2008a)	h = −11→11
T_min = 0.753, T_max = 0.898	k = −12→12
22611 measured reflections	l = −15→15

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)] = 0.043	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.105	H-atom parameters constrained
S = 1.10	w = 1/[σ²(F_o²) + (0.0411P)² + 1.0985P] where P = (F_o² + 2F_c²)/3
4271 reflections	(Δ/σ)_max < 0.001
271 parameters	Δρ_max = 0.45 e Å⁻³
0 restraints	Δρ_min = −0.48 e Å⁻³

Crystal data top

[Ni(C₁₂H₁₄N₆O)₂](CF₃O₃S)₂·2CH₄O	γ = 102.2596 (8)°
M_r = 937.52	V = 929.15 (3) Å³
Triclinic, P1	Z = 1
a = 9.0025 (2) Å	Mo Kα radiation
b = 9.5921 (2) Å	µ = 0.74 mm⁻¹
c = 11.9914 (2) Å	T = 90 K
α = 105.2683 (8)°	0.19 × 0.18 × 0.15 mm
β = 103.4796 (8)°

Data collection top

Nonius KappaCCD diffractometer	4271 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2008a)	3292 reflections with I > 2σ(I)
T_min = 0.753, T_max = 0.898	R_int = 0.040
22611 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.043	0 restraints
wR(F²) = 0.105	H-atom parameters constrained
S = 1.10	Δρ_max = 0.45 e Å⁻³
4271 reflections	Δρ_min = −0.48 e Å⁻³
271 parameters

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.

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

	x	y	z	U_iso*/U_eq
Ni1	0.5000	0.5000	0.5000	0.01541 (12)
N1	0.5656 (2)	0.7100 (2)	0.63001 (18)	0.0170 (4)
N2	0.7195 (2)	0.7717 (2)	0.70477 (17)	0.0146 (4)
C1	0.4910 (3)	0.8115 (3)	0.6624 (2)	0.0183 (5)
H1	0.3814	0.7993	0.6255	0.022*
C2	0.5939 (3)	0.9387 (3)	0.7576 (2)	0.0215 (5)
H2	0.5688	1.0264	0.7968	0.026*
C3	0.7388 (3)	0.9105 (3)	0.7828 (2)	0.0188 (5)
H3	0.8347	0.9757	0.8433	0.023*
N3	0.6331 (2)	0.4422 (2)	0.63761 (18)	0.0166 (4)
N4	0.7765 (2)	0.5424 (2)	0.71273 (17)	0.0148 (4)
C4	0.6123 (3)	0.3275 (3)	0.6808 (2)	0.0199 (5)
H4	0.5224	0.2401	0.6468	0.024*
C5	0.7402 (3)	0.3530 (3)	0.7828 (2)	0.0211 (5)
H5	0.7536	0.2881	0.8296	0.025*
C6	0.8421 (3)	0.4903 (3)	0.8014 (2)	0.0187 (5)
H6	0.9405	0.5400	0.8646	0.022*
N5	0.7151 (2)	0.5746 (2)	0.47104 (17)	0.0162 (4)
N6	0.8478 (2)	0.6538 (2)	0.56911 (17)	0.0156 (4)
C7	0.7638 (3)	0.5711 (3)	0.3745 (2)	0.0195 (5)
H7	0.6968	0.5233	0.2929	0.023*
C8	0.9267 (3)	0.6469 (3)	0.4085 (2)	0.0210 (5)
H8	0.9895	0.6592	0.3563	0.025*
C9	0.9763 (3)	0.6993 (3)	0.5324 (2)	0.0185 (5)
H9	1.0812	0.7569	0.5835	0.022*
C10	0.8346 (3)	0.6854 (3)	0.6921 (2)	0.0150 (5)
C11	0.9962 (3)	0.7798 (3)	0.7859 (2)	0.0170 (5)
H11A	1.0337	0.8761	0.7712	0.020*
H11B	0.9858	0.8034	0.8688	0.020*
O1	1.10620 (19)	0.69583 (18)	0.77534 (15)	0.0191 (4)
C12	1.2450 (3)	0.7555 (3)	0.8798 (2)	0.0267 (6)
H12A	1.3066	0.8544	0.8824	0.040*
H12B	1.3111	0.6864	0.8752	0.040*
H12C	1.2124	0.7667	0.9534	0.040*
S1A	0.85393 (7)	0.75255 (7)	0.11470 (5)	0.02007 (15)
O1A	0.8467 (3)	0.6007 (2)	0.11115 (19)	0.0381 (5)
O2A	0.8839 (2)	0.8585 (2)	0.23378 (15)	0.0252 (4)
O3A	0.9434 (2)	0.8109 (3)	0.04420 (17)	0.0406 (6)
C1A	0.6486 (3)	0.7358 (3)	0.0358 (2)	0.0261 (6)
F1A	0.60356 (18)	0.64929 (18)	−0.08066 (13)	0.0306 (4)
F2A	0.6306 (3)	0.8709 (2)	0.03702 (18)	0.0555 (6)
F3A	0.5478 (2)	0.6780 (2)	0.08729 (17)	0.0503 (5)
O1S	0.7190 (2)	0.9839 (2)	0.38362 (17)	0.0275 (4)
H1S	0.7699	0.9374	0.3445	0.041*
C1S	0.7689 (3)	0.9892 (3)	0.5057 (3)	0.0286 (6)
H1S1	0.8850	1.0335	0.5393	0.043*
H1S2	0.7396	0.8866	0.5096	0.043*
H1S3	0.7167	1.0512	0.5529	0.043*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ni1	0.0140 (2)	0.0148 (2)	0.0151 (2)	0.00295 (17)	0.00210 (17)	0.00417 (17)
N1	0.0132 (10)	0.0165 (10)	0.0173 (10)	0.0023 (8)	0.0016 (8)	0.0039 (8)
N2	0.0119 (9)	0.0146 (9)	0.0155 (10)	0.0033 (8)	0.0024 (8)	0.0039 (8)
C1	0.0184 (12)	0.0176 (12)	0.0196 (12)	0.0078 (10)	0.0047 (10)	0.0064 (10)
C2	0.0225 (13)	0.0173 (12)	0.0246 (13)	0.0075 (10)	0.0075 (10)	0.0051 (10)
C3	0.0188 (12)	0.0154 (12)	0.0178 (12)	0.0023 (9)	0.0042 (10)	0.0020 (9)
N3	0.0129 (9)	0.0153 (10)	0.0167 (10)	0.0006 (8)	0.0009 (8)	0.0036 (8)
N4	0.0136 (9)	0.0137 (9)	0.0150 (10)	0.0030 (8)	0.0023 (8)	0.0039 (8)
C4	0.0207 (12)	0.0174 (12)	0.0212 (12)	0.0035 (10)	0.0058 (10)	0.0079 (10)
C5	0.0229 (13)	0.0207 (12)	0.0210 (13)	0.0056 (10)	0.0053 (10)	0.0109 (10)
C6	0.0185 (12)	0.0198 (12)	0.0181 (12)	0.0067 (10)	0.0039 (10)	0.0073 (10)
N5	0.0143 (10)	0.0168 (10)	0.0130 (10)	0.0014 (8)	0.0006 (8)	0.0031 (8)
N6	0.0144 (10)	0.0172 (10)	0.0127 (9)	0.0035 (8)	0.0026 (8)	0.0032 (8)
C7	0.0209 (12)	0.0199 (12)	0.0165 (12)	0.0047 (10)	0.0058 (10)	0.0050 (10)
C8	0.0234 (13)	0.0219 (13)	0.0222 (13)	0.0077 (10)	0.0122 (10)	0.0092 (10)
C9	0.0150 (11)	0.0188 (12)	0.0223 (13)	0.0046 (9)	0.0068 (10)	0.0072 (10)
C10	0.0144 (11)	0.0154 (11)	0.0147 (11)	0.0041 (9)	0.0028 (9)	0.0059 (9)
C11	0.0140 (11)	0.0160 (11)	0.0168 (12)	0.0028 (9)	0.0021 (9)	0.0024 (9)
O1	0.0132 (8)	0.0203 (9)	0.0198 (9)	0.0063 (7)	0.0003 (7)	0.0034 (7)
C12	0.0170 (13)	0.0287 (14)	0.0262 (14)	0.0077 (11)	−0.0035 (11)	0.0040 (11)
S1A	0.0172 (3)	0.0233 (3)	0.0172 (3)	0.0048 (2)	0.0039 (2)	0.0049 (2)
O1A	0.0420 (12)	0.0284 (11)	0.0354 (12)	0.0180 (9)	−0.0050 (9)	0.0053 (9)
O2A	0.0288 (10)	0.0268 (10)	0.0166 (9)	0.0059 (8)	0.0059 (8)	0.0043 (7)
O3A	0.0269 (11)	0.0574 (14)	0.0206 (10)	−0.0127 (10)	0.0082 (8)	0.0045 (10)
C1A	0.0256 (14)	0.0271 (14)	0.0246 (14)	0.0103 (11)	0.0070 (11)	0.0053 (11)
F1A	0.0256 (8)	0.0333 (9)	0.0226 (8)	0.0081 (7)	−0.0013 (6)	0.0008 (7)
F2A	0.0671 (14)	0.0359 (10)	0.0487 (12)	0.0332 (10)	−0.0113 (10)	0.0014 (9)
F3A	0.0248 (9)	0.0771 (14)	0.0403 (11)	0.0038 (9)	0.0153 (8)	0.0096 (10)
O1S	0.0268 (10)	0.0322 (11)	0.0262 (10)	0.0138 (8)	0.0083 (8)	0.0096 (8)
C1S	0.0317 (15)	0.0238 (14)	0.0305 (15)	0.0068 (12)	0.0099 (12)	0.0098 (12)

Geometric parameters (Å, º) top

Ni1—N5ⁱ	2.0589 (19)	N6—C10	1.464 (3)
Ni1—N5	2.059 (2)	C7—C8	1.399 (3)
Ni1—N1ⁱ	2.0611 (19)	C7—H7	0.9500
Ni1—N1	2.0611 (19)	C8—C9	1.364 (3)
Ni1—N3ⁱ	2.0757 (19)	C8—H8	0.9500
Ni1—N3	2.0757 (19)	C9—H9	0.9500
N1—C1	1.323 (3)	C10—C11	1.531 (3)
N1—N2	1.366 (3)	C11—O1	1.410 (3)
N2—C3	1.359 (3)	C11—H11A	0.9900
N2—C10	1.468 (3)	C11—H11B	0.9900
C1—C2	1.394 (3)	O1—C12	1.431 (3)
C1—H1	0.9500	C12—H12A	0.9800
C2—C3	1.369 (3)	C12—H12B	0.9800
C2—H2	0.9500	C12—H12C	0.9800
C3—H3	0.9500	S1A—O3A	1.432 (2)
N3—C4	1.331 (3)	S1A—O1A	1.433 (2)
N3—N4	1.369 (3)	S1A—O2A	1.4437 (18)
N4—C6	1.357 (3)	S1A—C1A	1.821 (3)
N4—C10	1.466 (3)	C1A—F3A	1.318 (3)
C4—C5	1.396 (3)	C1A—F2A	1.336 (3)
C4—H4	0.9500	C1A—F1A	1.337 (3)
C5—C6	1.364 (4)	O1S—C1S	1.411 (3)
C5—H5	0.9500	O1S—H1S	0.8400
C6—H6	0.9500	C1S—H1S1	0.9800
N5—C7	1.324 (3)	C1S—H1S2	0.9800
N5—N6	1.370 (3)	C1S—H1S3	0.9800
N6—C9	1.359 (3)

N5ⁱ—Ni1—N5	180.0	C9—N6—C10	129.4 (2)
N5ⁱ—Ni1—N1ⁱ	85.15 (8)	N5—N6—C10	119.86 (18)
N5—Ni1—N1ⁱ	94.85 (8)	N5—C7—C8	111.1 (2)
N5ⁱ—Ni1—N1	94.85 (8)	N5—C7—H7	124.4
N5—Ni1—N1	85.15 (8)	C8—C7—H7	124.4
N1ⁱ—Ni1—N1	180.00 (11)	C9—C8—C7	105.6 (2)
N5ⁱ—Ni1—N3ⁱ	84.78 (8)	C9—C8—H8	127.2
N5—Ni1—N3ⁱ	95.22 (8)	C7—C8—H8	127.2
N1ⁱ—Ni1—N3ⁱ	84.50 (8)	N6—C9—C8	107.2 (2)
N1—Ni1—N3ⁱ	95.50 (8)	N6—C9—H9	126.4
N5ⁱ—Ni1—N3	95.22 (8)	C8—C9—H9	126.4
N5—Ni1—N3	84.78 (8)	N6—C10—N4	109.33 (18)
N1ⁱ—Ni1—N3	95.50 (8)	N6—C10—N2	109.35 (18)
N1—Ni1—N3	84.50 (8)	N4—C10—N2	108.62 (18)
N3ⁱ—Ni1—N3	180.00 (8)	N6—C10—C11	110.37 (19)
C1—N1—N2	105.50 (19)	N4—C10—C11	110.87 (18)
C1—N1—Ni1	134.77 (17)	N2—C10—C11	108.27 (18)
N2—N1—Ni1	119.73 (14)	O1—C11—C10	108.34 (18)
C3—N2—N1	110.70 (19)	O1—C11—H11A	110.0
C3—N2—C10	130.25 (19)	C10—C11—H11A	110.0
N1—N2—C10	119.05 (18)	O1—C11—H11B	110.0
N1—C1—C2	111.3 (2)	C10—C11—H11B	110.0
N1—C1—H1	124.4	H11A—C11—H11B	108.4
C2—C1—H1	124.4	C11—O1—C12	111.62 (18)
C3—C2—C1	105.5 (2)	O1—C12—H12A	109.5
C3—C2—H2	127.2	O1—C12—H12B	109.5
C1—C2—H2	127.2	H12A—C12—H12B	109.5
N2—C3—C2	107.0 (2)	O1—C12—H12C	109.5
N2—C3—H3	126.5	H12A—C12—H12C	109.5
C2—C3—H3	126.5	H12B—C12—H12C	109.5
C4—N3—N4	105.24 (19)	O3A—S1A—O1A	115.91 (14)
C4—N3—Ni1	135.74 (16)	O3A—S1A—O2A	113.55 (12)
N4—N3—Ni1	118.90 (14)	O1A—S1A—O2A	115.10 (12)
C6—N4—N3	110.88 (19)	O3A—S1A—C1A	103.65 (13)
C6—N4—C10	129.58 (19)	O1A—S1A—C1A	102.79 (12)
N3—N4—C10	119.51 (18)	O2A—S1A—C1A	103.55 (12)
N3—C4—C5	110.9 (2)	F3A—C1A—F2A	107.0 (2)
N3—C4—H4	124.6	F3A—C1A—F1A	108.1 (2)
C5—C4—H4	124.6	F2A—C1A—F1A	106.9 (2)
C6—C5—C4	105.9 (2)	F3A—C1A—S1A	111.68 (19)
C6—C5—H5	127.0	F2A—C1A—S1A	111.05 (19)
C4—C5—H5	127.0	F1A—C1A—S1A	111.86 (18)
N4—C6—C5	107.1 (2)	C1S—O1S—H1S	109.5
N4—C6—H6	126.5	O1S—C1S—H1S1	109.5
C5—C6—H6	126.5	O1S—C1S—H1S2	109.5
C7—N5—N6	105.39 (19)	H1S1—C1S—H1S2	109.5
C7—N5—Ni1	135.53 (16)	O1S—C1S—H1S3	109.5
N6—N5—Ni1	119.02 (14)	H1S1—C1S—H1S3	109.5
C9—N6—N5	110.65 (18)	H1S2—C1S—H1S3	109.5

C1—N1—N2—C3	0.1 (3)	N5—N6—C10—N4	59.9 (2)
Ni1—N1—N2—C3	179.31 (15)	C9—N6—C10—N2	117.0 (2)
C1—N1—N2—C10	179.7 (2)	N5—N6—C10—N2	−58.9 (3)
Ni1—N1—N2—C10	−1.1 (3)	C9—N6—C10—C11	−2.0 (3)
N2—N1—C1—C2	−0.2 (3)	N5—N6—C10—C11	−177.94 (18)
Ni1—N1—C1—C2	−179.22 (17)	C6—N4—C10—N6	124.2 (2)
N1—C1—C2—C3	0.2 (3)	N3—N4—C10—N6	−58.1 (3)
N1—N2—C3—C2	0.0 (3)	C6—N4—C10—N2	−116.5 (2)
C10—N2—C3—C2	−179.5 (2)	N3—N4—C10—N2	61.2 (3)
C1—C2—C3—N2	−0.1 (3)	C6—N4—C10—C11	2.3 (3)
C4—N3—N4—C6	−0.4 (3)	N3—N4—C10—C11	−179.97 (19)
Ni1—N3—N4—C6	176.26 (15)	C3—N2—C10—N6	−120.8 (2)
C4—N3—N4—C10	−178.5 (2)	N1—N2—C10—N6	59.7 (3)
Ni1—N3—N4—C10	−1.8 (3)	C3—N2—C10—N4	120.0 (2)
N4—N3—C4—C5	0.1 (3)	N1—N2—C10—N4	−59.5 (2)
Ni1—N3—C4—C5	−175.75 (18)	C3—N2—C10—C11	−0.5 (3)
N3—C4—C5—C6	0.2 (3)	N1—N2—C10—C11	−179.99 (19)
N3—N4—C6—C5	0.6 (3)	N6—C10—C11—O1	−61.4 (2)
C10—N4—C6—C5	178.4 (2)	N4—C10—C11—O1	59.9 (2)
C4—C5—C6—N4	−0.5 (3)	N2—C10—C11—O1	178.97 (18)
C7—N5—N6—C9	0.5 (3)	C10—C11—O1—C12	−163.6 (2)
Ni1—N5—N6—C9	−177.23 (15)	O3A—S1A—C1A—F3A	177.87 (19)
C7—N5—N6—C10	177.1 (2)	O1A—S1A—C1A—F3A	56.8 (2)
Ni1—N5—N6—C10	−0.6 (3)	O2A—S1A—C1A—F3A	−63.4 (2)
N6—N5—C7—C8	0.1 (3)	O3A—S1A—C1A—F2A	−62.8 (2)
Ni1—N5—C7—C8	177.22 (17)	O1A—S1A—C1A—F2A	176.2 (2)
N5—C7—C8—C9	−0.6 (3)	O2A—S1A—C1A—F2A	56.0 (2)
N5—N6—C9—C8	−0.9 (3)	O3A—S1A—C1A—F1A	56.6 (2)
C10—N6—C9—C8	−177.1 (2)	O1A—S1A—C1A—F1A	−64.5 (2)
C7—C8—C9—N6	0.9 (3)	O2A—S1A—C1A—F1A	175.33 (18)
C9—N6—C10—N4	−124.2 (2)

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1S—H1S···O2A	0.84	1.96	2.782 (3)	168

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1S—H1S···O2A	0.84	1.96	2.782 (3)	167.8

Acknowledgements

GL gratefully acknowledges the Southern Arkansas University Faculty Research Grant for financial support.

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