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

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

doi:10.1107/S1600536813024252

metal-organic compounds

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ISSN: 2056-9890

Volume 69| Part 10| October 2013| Pages m532-m533

doi:10.1107/S1600536813024252

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

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 29 August 2013; online 4 September 2013)

In the title salt, [Ni(C₁₂H₁₄N₆O)₂](CF₃SO₃)₂·2H₂O, the Ni^II cation is located on an inversion centre and 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—N distances range from 2.0594 (12) to 2.0664 (12) Å, intra-ligand N—Ni—N angles range from 84.59 (5) to 86.06 (5)°, and adjacent inter-ligand N—Ni—N angles range between 93.94 (5) and 95.41 (5)°. In the crystal, inversion-related pyrazole rings are π–π stacked, with an interplanar spacing of 3.4494 (18) Å, forming chains that propagate parallel to the a-axis direction. Intermolecular O—H⋯O hydrogen bonds are present between water molecules and trifluoromethanesulfonate anions.

Related literature

Pyrazole-based tridentate ligands are drawing more attention because of their topology and nature of donor atoms, see: Paulo et al. (2004 ); Bigmore et al. (2005 ). For the ligand synthesis, 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 to nickel, see: Lyubartseva et al. (2011 , 2012 ); Lyubartseva & Parkin (2009 ).

Experimental

Crystal data

[Ni(C₁₂H₁₄N₆O)₂](CF₃O₃S)₂·2H₂O
M_r = 909.46
Triclinic, $[P \overline 1]$
a = 8.5582 (2) Å
b = 9.6515 (2) Å
c = 12.2347 (2) Å
α = 110.399 (1)°
β = 103.665 (1)°
γ = 97.317 (1)°
V = 895.66 (3) Å³
Z = 1
Mo Kα radiation
μ = 0.76 mm⁻¹
T = 90 K
0.26 × 0.22 × 0.15 mm

Data collection

Nonius KappaCCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2008a ) T_min = 0.760, T_max = 0.862
25573 measured reflections
4095 independent reflections
3708 reflections with I > 2σ(I)
R_int = 0.023

Refinement

R[F² > 2σ(F²)] = 0.029
wR(F²) = 0.072
S = 1.07
4095 reflections
266 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.47 e Å⁻³
Δρ_min = −0.49 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1W—H2W⋯O3A	0.94 (3)	2.06 (3)	2.994 (2)	174 (2)
O1W—H1W⋯O3Aⁱ	0.97 (3)	2.12 (3)	3.0613 (19)	163 (2)
Symmetry code: (i) -x+2, -y+2, -z+1.

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/S1600536813024252/tk5252sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536813024252/tk5252Isup2.hkl

checkCIF report

Comment top

The described structure was studied in continuation of on-going studies (Lyubartseva & Parkin, 2009; Lyubartseva et al., 2011, 2012) owing to interest in pyrazole-based tridentate ligands (Paulo et al., 2004; Bigmore et al., 2005). In an attempt to prepare mononuclear [LNi^II(CN)₃]^-, 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(C₁₂H₁₄N₆0₂)₂][CF₃SO₃]₂·2H₂O as light-pink triclinic crystals. In the crystal, the Ni(II) cation is situated on an inversion centre and is coordinated by six N atoms from the two tridentate tpmOMe ligands, Fig. 1, (average Ni—N distance = 2.062 Å) in a distorted octahedral geometry. The average N—Ni—N angle between adjacent pyrazole-ring coordinated N atoms is 85.13° for the six acute angles and 94.87° for the six obtuse angles. In the crystal, inversion-related (-x, 1 - y, 1 - z) pyrazole rings are π—π stacked, with an interplanar spacing of 3.4494 (18) Å, forming chains that propagate parallel to the a axis. Intramolecular O—H···O hydrogen bonds are present between water and trifluoromethanesulfonate anion, Table 1.

Related literature top

Pyrazole-based tridentate ligands are drawing more attention because of their topology and nature of donor atoms, see: Paulo et al. (2004); Bigmore et al. (2005). For the ligand synthesis, 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

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), 1-methoxy-2,2,2-tris(pyrazol-1-yl)ethane (258 mg, 1 mmol) and NEt₄CN (312 mg, 2 mmol) were suspended in a mixture of methanol (20 ml) and water (10 ml), and stirred for 30 minutes. The resulting solution was filtered and solvent was slowly evaporated in air. Light-pink crystals were obtained after 3 weeks (294 mg, 64.6% yield). Elemental analysis, calculated for C₂₆H₃₂F₆N₁₂NiO₁₀S₂: C 34.34, H 3.55, N 18.48; found C 34.64, H 3.40, N 18.35. IR (cm^-1): 3624, 3487, 3145, 2920, 1615, 1523, 1410, 1388, 1340, 1323, 1257, 1225, 1199, 1164, 1105, 1069, 1059, 1028, 1010, 973, 919, 854, 755, 674, 653, 635, 602, 572, 516.

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. View of the title compound with displacement ellipsoids drawn at the 50% probability level. Unlabelled atoms are related to their labelled counterparts by inversion (1/2 - x, 1.5 - y, 1 - z).

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

Crystal data top

[Ni(C₁₂H₁₄N₆O)₂](CF₃O₃S)₂·2H₂O	Z = 1
M_r = 909.46	F(000) = 466
Triclinic, P1	D_x = 1.686 Mg m⁻³
a = 8.5582 (2) Å	Mo Kα radiation, λ = 0.71073 Å
b = 9.6515 (2) Å	Cell parameters from 25674 reflections
c = 12.2347 (2) Å	θ = 1.0–27.5°
α = 110.399 (1)°	µ = 0.76 mm⁻¹
β = 103.665 (1)°	T = 90 K
γ = 97.317 (1)°	Block, pink
V = 895.66 (3) Å³	0.26 × 0.22 × 0.15 mm

Data collection top

Nonius KappaCCD diffractometer	4095 independent reflections
Radiation source: fine-focus sealed-tube	3708 reflections with I > 2σ(I)
Detector resolution: 9.1 pixels mm^-1	R_int = 0.023
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 = 0.760, T_max = 0.862	k = −12→12
25573 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)] = 0.029	Hydrogen site location: difference Fourier map
wR(F²) = 0.072	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	w = 1/[σ²(F_o²) + (0.0311P)² + 0.6676P] where P = (F_o² + 2F_c²)/3
4095 reflections	(Δ/σ)_max < 0.001
266 parameters	Δρ_max = 0.47 e Å⁻³
0 restraints	Δρ_min = −0.49 e Å⁻³

Crystal data top

[Ni(C₁₂H₁₄N₆O)₂](CF₃O₃S)₂·2H₂O	γ = 97.317 (1)°
M_r = 909.46	V = 895.66 (3) Å³
Triclinic, P1	Z = 1
a = 8.5582 (2) Å	Mo Kα radiation
b = 9.6515 (2) Å	µ = 0.76 mm⁻¹
c = 12.2347 (2) Å	T = 90 K
α = 110.399 (1)°	0.26 × 0.22 × 0.15 mm
β = 103.665 (1)°

Data collection top

Nonius KappaCCD diffractometer	4095 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2008a)	3708 reflections with I > 2σ(I)
T_min = 0.760, T_max = 0.862	R_int = 0.023
25573 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.029	0 restraints
wR(F²) = 0.072	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	Δρ_max = 0.47 e Å⁻³
4095 reflections	Δρ_min = −0.49 e Å⁻³
266 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	0.01222 (8)
N1	0.44622 (15)	0.29426 (14)	0.35443 (11)	0.0145 (3)
N2	0.30215 (15)	0.25366 (14)	0.26196 (11)	0.0130 (2)
C1	0.52676 (19)	0.18620 (17)	0.31824 (14)	0.0173 (3)
H1	0.6315	0.1839	0.3649	0.021*
C2	0.43694 (19)	0.07609 (18)	0.20223 (15)	0.0191 (3)
H2	0.4683	−0.0117	0.1563	0.023*
C3	0.29420 (19)	0.12165 (17)	0.16891 (14)	0.0167 (3)
H3	0.2062	0.0707	0.0948	0.020*
N3	0.39074 (15)	0.58147 (14)	0.37338 (11)	0.0149 (3)
N4	0.24408 (15)	0.49654 (14)	0.28723 (11)	0.0130 (2)
C4	0.4154 (2)	0.71338 (18)	0.36109 (14)	0.0173 (3)
H4	0.5085	0.7955	0.4093	0.021*
C5	0.2853 (2)	0.71481 (18)	0.26739 (15)	0.0192 (3)
H5	0.2738	0.7953	0.2407	0.023*
C6	0.17837 (19)	0.57573 (18)	0.22245 (14)	0.0169 (3)
H6	0.0772	0.5411	0.1581	0.020*
N5	0.26178 (15)	0.43228 (14)	0.50146 (11)	0.0139 (2)
N6	0.14141 (15)	0.35547 (14)	0.39195 (11)	0.0125 (2)
C7	0.19545 (19)	0.41516 (17)	0.58503 (14)	0.0160 (3)
H7	0.2508	0.4571	0.6704	0.019*
C8	0.03292 (19)	0.32692 (18)	0.53068 (14)	0.0170 (3)
H8	−0.0406	0.2992	0.5708	0.020*
C9	0.00275 (18)	0.28935 (17)	0.40787 (14)	0.0154 (3)
H9	−0.0963	0.2285	0.3453	0.018*
C10	0.17782 (18)	0.34450 (16)	0.27853 (13)	0.0127 (3)
C11	0.02317 (18)	0.26347 (17)	0.16833 (13)	0.0147 (3)
H11A	0.0485	0.2605	0.0928	0.018*
H11B	−0.0137	0.1577	0.1596	0.018*
O1	−0.10362 (13)	0.34191 (12)	0.18516 (10)	0.0167 (2)
C12	−0.25257 (19)	0.26218 (19)	0.08624 (15)	0.0204 (3)
H12A	−0.2344	0.2595	0.0095	0.031*
H12B	−0.3413	0.3143	0.1009	0.031*
H12C	−0.2839	0.1581	0.0807	0.031*
S1A	0.86275 (5)	0.86391 (4)	0.17962 (3)	0.01557 (9)
O1A	0.76221 (16)	0.97224 (14)	0.17899 (12)	0.0287 (3)
O2A	0.98159 (15)	0.86458 (15)	0.11398 (11)	0.0272 (3)
O3A	0.92445 (16)	0.85421 (15)	0.29641 (11)	0.0269 (3)
F1A	0.64625 (13)	0.67273 (12)	−0.02656 (9)	0.0292 (2)
F2A	0.79191 (16)	0.56755 (13)	0.07329 (13)	0.0497 (4)
F3A	0.59605 (16)	0.65956 (16)	0.13326 (12)	0.0500 (4)
C1A	0.7161 (2)	0.68201 (19)	0.08608 (16)	0.0220 (3)
O1W	0.76122 (18)	0.99331 (17)	0.48585 (14)	0.0368 (3)
H1W	0.848 (3)	1.032 (3)	0.563 (3)	0.055*
H2W	0.812 (3)	0.944 (3)	0.429 (3)	0.055*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ni1	0.01029 (13)	0.01323 (13)	0.01154 (13)	0.00243 (10)	0.00191 (10)	0.00400 (10)
N1	0.0101 (6)	0.0164 (6)	0.0136 (6)	0.0031 (5)	0.0010 (5)	0.0037 (5)
N2	0.0102 (6)	0.0146 (6)	0.0119 (6)	0.0027 (5)	0.0019 (5)	0.0037 (5)
C1	0.0134 (7)	0.0180 (7)	0.0198 (8)	0.0051 (6)	0.0045 (6)	0.0062 (6)
C2	0.0162 (8)	0.0165 (7)	0.0214 (8)	0.0050 (6)	0.0065 (6)	0.0029 (6)
C3	0.0150 (7)	0.0159 (7)	0.0152 (7)	0.0021 (6)	0.0040 (6)	0.0022 (6)
N3	0.0117 (6)	0.0157 (6)	0.0142 (6)	0.0005 (5)	0.0012 (5)	0.0050 (5)
N4	0.0105 (6)	0.0148 (6)	0.0117 (6)	0.0019 (5)	0.0011 (5)	0.0048 (5)
C4	0.0173 (7)	0.0164 (7)	0.0186 (7)	0.0025 (6)	0.0063 (6)	0.0070 (6)
C5	0.0202 (8)	0.0193 (7)	0.0218 (8)	0.0052 (6)	0.0068 (6)	0.0119 (6)
C6	0.0160 (7)	0.0210 (7)	0.0159 (7)	0.0065 (6)	0.0043 (6)	0.0095 (6)
N5	0.0119 (6)	0.0166 (6)	0.0105 (6)	0.0030 (5)	0.0014 (5)	0.0036 (5)
N6	0.0104 (6)	0.0146 (6)	0.0106 (6)	0.0017 (5)	0.0021 (5)	0.0038 (5)
C7	0.0177 (7)	0.0181 (7)	0.0132 (7)	0.0058 (6)	0.0054 (6)	0.0061 (6)
C8	0.0164 (7)	0.0191 (7)	0.0189 (8)	0.0047 (6)	0.0081 (6)	0.0093 (6)
C9	0.0120 (7)	0.0151 (7)	0.0189 (7)	0.0023 (5)	0.0049 (6)	0.0066 (6)
C10	0.0113 (7)	0.0141 (7)	0.0127 (7)	0.0036 (5)	0.0039 (5)	0.0047 (5)
C11	0.0113 (7)	0.0170 (7)	0.0124 (7)	0.0032 (6)	0.0013 (6)	0.0032 (6)
O1	0.0108 (5)	0.0193 (5)	0.0157 (5)	0.0048 (4)	0.0002 (4)	0.0039 (4)
C12	0.0122 (7)	0.0224 (8)	0.0213 (8)	0.0019 (6)	−0.0030 (6)	0.0082 (7)
S1A	0.01472 (18)	0.01723 (18)	0.01564 (18)	0.00405 (14)	0.00441 (14)	0.00749 (14)
O1A	0.0262 (7)	0.0202 (6)	0.0351 (7)	0.0104 (5)	0.0029 (5)	0.0081 (5)
O2A	0.0200 (6)	0.0363 (7)	0.0205 (6)	−0.0021 (5)	0.0088 (5)	0.0067 (5)
O3A	0.0297 (7)	0.0335 (7)	0.0178 (6)	0.0073 (5)	0.0035 (5)	0.0128 (5)
F1A	0.0236 (5)	0.0295 (5)	0.0251 (5)	−0.0015 (4)	−0.0035 (4)	0.0091 (4)
F2A	0.0461 (8)	0.0180 (5)	0.0645 (9)	0.0101 (5)	−0.0122 (6)	0.0102 (6)
F3A	0.0399 (7)	0.0563 (8)	0.0458 (7)	−0.0180 (6)	0.0195 (6)	0.0166 (6)
C1A	0.0208 (8)	0.0204 (8)	0.0266 (9)	0.0036 (6)	0.0052 (7)	0.0129 (7)
O1W	0.0266 (7)	0.0383 (8)	0.0339 (8)	0.0027 (6)	0.0103 (6)	0.0014 (6)

Geometric parameters (Å, º) top

Ni1—N1	2.0594 (12)	N5—N6	1.3664 (17)
Ni1—N1ⁱ	2.0594 (12)	N6—C9	1.3625 (19)
Ni1—N3ⁱ	2.0602 (13)	N6—C10	1.4643 (18)
Ni1—N3	2.0602 (13)	C7—C8	1.403 (2)
Ni1—N5	2.0664 (12)	C7—H7	0.9500
Ni1—N5ⁱ	2.0664 (12)	C8—C9	1.367 (2)
N1—C1	1.3283 (19)	C8—H8	0.9500
N1—N2	1.3648 (17)	C9—H9	0.9500
N2—C3	1.3617 (19)	C10—C11	1.529 (2)
N2—C10	1.4689 (18)	C11—O1	1.4140 (18)
C1—C2	1.400 (2)	C11—H11A	0.9900
C1—H1	0.9500	C11—H11B	0.9900
C2—C3	1.370 (2)	O1—C12	1.4331 (18)
C2—H2	0.9500	C12—H12A	0.9800
C3—H3	0.9500	C12—H12B	0.9800
N3—C4	1.330 (2)	C12—H12C	0.9800
N3—N4	1.3671 (17)	S1A—O1A	1.4371 (12)
N4—C6	1.3600 (19)	S1A—O2A	1.4378 (12)
N4—C10	1.4618 (18)	S1A—O3A	1.4418 (12)
C4—C5	1.402 (2)	S1A—C1A	1.8237 (17)
C4—H4	0.9500	F1A—C1A	1.333 (2)
C5—C6	1.370 (2)	F2A—C1A	1.332 (2)
C5—H5	0.9500	F3A—C1A	1.322 (2)
C6—H6	0.9500	O1W—H1W	0.97 (3)
N5—C7	1.3278 (19)	O1W—H2W	0.94 (3)

N1—Ni1—N1ⁱ	180.0	C7—N5—Ni1	134.47 (10)
N1—Ni1—N3ⁱ	93.94 (5)	N6—N5—Ni1	118.35 (9)
N1ⁱ—Ni1—N3ⁱ	86.06 (5)	C9—N6—N5	110.86 (12)
N1—Ni1—N3	86.06 (5)	C9—N6—C10	129.46 (12)
N1ⁱ—Ni1—N3	93.94 (5)	N5—N6—C10	119.50 (12)
N3ⁱ—Ni1—N3	180.0	N5—C7—C8	111.13 (14)
N1—Ni1—N5	84.59 (5)	N5—C7—H7	124.4
N1ⁱ—Ni1—N5	95.41 (5)	C8—C7—H7	124.4
N3ⁱ—Ni1—N5	95.27 (5)	C9—C8—C7	105.44 (13)
N3—Ni1—N5	84.73 (5)	C9—C8—H8	127.3
N1—Ni1—N5ⁱ	95.41 (5)	C7—C8—H8	127.3
N1ⁱ—Ni1—N5ⁱ	84.59 (5)	N6—C9—C8	107.16 (13)
N3ⁱ—Ni1—N5ⁱ	84.73 (5)	N6—C9—H9	126.4
N3—Ni1—N5ⁱ	95.27 (5)	C8—C9—H9	126.4
N5—Ni1—N5ⁱ	180.00 (7)	N4—C10—N6	109.51 (11)
C1—N1—N2	105.55 (12)	N4—C10—N2	109.13 (11)
C1—N1—Ni1	135.27 (11)	N6—C10—N2	108.63 (11)
N2—N1—Ni1	118.89 (9)	N4—C10—C11	111.11 (12)
C3—N2—N1	110.80 (12)	N6—C10—C11	110.71 (12)
C3—N2—C10	129.99 (12)	N2—C10—C11	107.69 (11)
N1—N2—C10	118.99 (11)	O1—C11—C10	109.35 (12)
N1—C1—C2	111.08 (14)	O1—C11—H11A	109.8
N1—C1—H1	124.5	C10—C11—H11A	109.8
C2—C1—H1	124.5	O1—C11—H11B	109.8
C3—C2—C1	105.45 (14)	C10—C11—H11B	109.8
C3—C2—H2	127.3	H11A—C11—H11B	108.3
C1—C2—H2	127.3	C11—O1—C12	110.04 (11)
N2—C3—C2	107.11 (13)	O1—C12—H12A	109.5
N2—C3—H3	126.4	O1—C12—H12B	109.5
C2—C3—H3	126.4	H12A—C12—H12B	109.5
C4—N3—N4	105.69 (12)	O1—C12—H12C	109.5
C4—N3—Ni1	135.09 (11)	H12A—C12—H12C	109.5
N4—N3—Ni1	118.51 (9)	H12B—C12—H12C	109.5
C6—N4—N3	110.71 (12)	O1A—S1A—O2A	114.77 (8)
C6—N4—C10	129.53 (13)	O1A—S1A—O3A	114.93 (8)
N3—N4—C10	119.72 (12)	O2A—S1A—O3A	114.87 (8)
N3—C4—C5	110.81 (14)	O1A—S1A—C1A	103.12 (8)
N3—C4—H4	124.6	O2A—S1A—C1A	103.04 (8)
C5—C4—H4	124.6	O3A—S1A—C1A	103.80 (8)
C6—C5—C4	105.58 (14)	F3A—C1A—F2A	108.54 (15)
C6—C5—H5	127.2	F3A—C1A—F1A	107.47 (14)
C4—C5—H5	127.2	F2A—C1A—F1A	106.24 (14)
N4—C6—C5	107.21 (14)	F3A—C1A—S1A	112.04 (12)
N4—C6—H6	126.4	F2A—C1A—S1A	110.88 (12)
C5—C6—H6	126.4	F1A—C1A—S1A	111.42 (11)
C7—N5—N6	105.40 (12)	H1W—O1W—H2W	104 (2)

C1—N1—N2—C3	−0.31 (16)	N3—N4—C10—N6	63.30 (16)
Ni1—N1—N2—C3	174.45 (10)	C6—N4—C10—N2	126.87 (15)
C1—N1—N2—C10	174.92 (12)	N3—N4—C10—N2	−55.48 (16)
Ni1—N1—N2—C10	−10.32 (16)	C6—N4—C10—C11	8.3 (2)
N2—N1—C1—C2	0.58 (17)	N3—N4—C10—C11	−174.09 (12)
Ni1—N1—C1—C2	−172.90 (11)	C9—N6—C10—N4	132.03 (15)
N1—C1—C2—C3	−0.63 (19)	N5—N6—C10—N4	−53.32 (16)
N1—N2—C3—C2	−0.07 (17)	C9—N6—C10—N2	−108.88 (16)
C10—N2—C3—C2	−174.63 (14)	N5—N6—C10—N2	65.78 (16)
C1—C2—C3—N2	0.41 (18)	C9—N6—C10—C11	9.2 (2)
C4—N3—N4—C6	−0.20 (16)	N5—N6—C10—C11	−176.17 (12)
Ni1—N3—N4—C6	171.53 (10)	C3—N2—C10—N4	−120.06 (16)
C4—N3—N4—C10	−178.26 (12)	N1—N2—C10—N4	65.75 (16)
Ni1—N3—N4—C10	−6.53 (16)	C3—N2—C10—N6	120.60 (16)
N4—N3—C4—C5	0.07 (17)	N1—N2—C10—N6	−53.58 (16)
Ni1—N3—C4—C5	−169.62 (11)	C3—N2—C10—C11	0.7 (2)
N3—C4—C5—C6	0.09 (18)	N1—N2—C10—C11	−173.53 (12)
N3—N4—C6—C5	0.26 (17)	N4—C10—C11—O1	−64.66 (15)
C10—N4—C6—C5	178.07 (14)	N6—C10—C11—O1	57.25 (15)
C4—C5—C6—N4	−0.20 (17)	N2—C10—C11—O1	175.87 (11)
C7—N5—N6—C9	−1.01 (16)	C10—C11—O1—C12	−176.45 (12)
Ni1—N5—N6—C9	166.00 (10)	O1A—S1A—C1A—F3A	−60.94 (14)
C7—N5—N6—C10	−176.59 (12)	O2A—S1A—C1A—F3A	179.35 (13)
Ni1—N5—N6—C10	−9.58 (16)	O3A—S1A—C1A—F3A	59.25 (14)
N6—N5—C7—C8	0.35 (17)	O1A—S1A—C1A—F2A	177.62 (13)
Ni1—N5—C7—C8	−163.56 (11)	O2A—S1A—C1A—F2A	57.91 (14)
N5—C7—C8—C9	0.41 (18)	O3A—S1A—C1A—F2A	−62.19 (14)
N5—N6—C9—C8	1.28 (17)	O1A—S1A—C1A—F1A	59.51 (14)
C10—N6—C9—C8	176.30 (14)	O2A—S1A—C1A—F1A	−60.20 (13)
C7—C8—C9—N6	−1.00 (17)	O3A—S1A—C1A—F1A	179.70 (12)
C6—N4—C10—N6	−114.34 (16)

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
O1W—H2W···O3A	0.94 (3)	2.06 (3)	2.994 (2)	174 (2)
O1W—H1W···O3Aⁱⁱ	0.97 (3)	2.12 (3)	3.0613 (19)	163 (2)

Symmetry code: (ii) −x+2, −y+2, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H2W···O3A	0.94 (3)	2.06 (3)	2.994 (2)	174 (2)
O1W—H1W···O3Aⁱ	0.97 (3)	2.12 (3)	3.0613 (19)	163 (2)

Symmetry code: (i) −x+2, −y+2, −z+1.

Acknowledgements

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

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