catena-Poly[[[bis­(aceto­nitrile-κN)(4,4′-dimeth­oxy-2,2′-bi­pyridine-κ2N,N′)copper(II)]-μ-tri­fluoro­methane­sulfonato-κ2O:O′] tri­fluoro­methane­sulfonate]

Adrian, R.A.; Hernandez, D.R.; Arman, H.D.

doi:10.1107/S2414314620014078

metal-organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 5| Part 10| October 2020| x201407

https://doi.org/10.1107/S2414314620014078

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catena-Poly[[[bis(acetonitrile-κN)(4,4′-dimethoxy-2,2′-bipyridine-κ²N,N′)copper(II)]-μ-trifluoromethanesulfonato-κ²O:O′] trifluoromethanesulfonate]

Rafael A. Adrian,^a ^* Diego R. Hernandez ^a and Hadi D. Arman ^b

^aDepartment of Chemistry and Biochemistry, University of the Incarnate Word, San Antonio, TX 78209, USA, and ^bDepartment of Chemistry, The University of Texas at San Antonio, San Antonio, TX 78249, USA
^*Correspondence e-mail: adrian@uiwtx.edu

Edited by M. Weil, Vienna University of Technology, Austria (Received 22 September 2020; accepted 21 October 2020; online 30 October 2020)

The central copper(II) atom of the title salt, {[Cu(CF₃SO₃)(CH₃CN)₂(C₁₂H₁₂N₂O₂)](CF₃SO₃)}_n or [[Cu(CH₃CN)₂(diOMe-bpy)(CF₃SO₃)](CF₃SO₃)]_n where diOMe-bpy is 4,4′-dimethoxy-2,2′-bipyridine, C₁₂H₁₂N₂O₂, is sixfold coordinated by the N atoms of the chelating bipyridine ligand, the N atoms of two acetonitrile molecules, and two trifluoromethanesulfonate O atoms in a tetragonally distorted octahedral shape. The formation of polymeric chains [Cu(CH₃CN)₂(diOMe-bpy)(CF₃SO₃)]⁺_n leaves voids for the non-coordinating trifluoromethanesulfonate anions that interact with the complex through weak hydrogen bonds. The presence of weakly coordinating ligands like acetonitrile and trifluoromethanesulfonate makes the title compound a convenient starting material for the synthesis of novel metal–organic frameworks.

Keywords: crystal structure; copper(II); coordinating trifluoromethanesulfonate; trifluoromethanesulfonate salt; acetonitrile; 4,4′-dimethoxy-2,2′-bipyridine.

CCDC reference: 2039861

Structure description

4,4′-Dimethoxy-2,2′-bipyridines are continuously being investigated for their photoluminescence features (Ravaro et al., 2018 ), antimicrobial activity (Drzeżdżon et al., 2019 ), good affinity in DNA binding (Anjomshoa et al., 2016 ), and antitumor activity against human cancer cells (Qin et al., 2019 ). As part of our research related to the coordination chemistry of metal ions with bipyridine and terpyridine ligands, in the present report we describe the synthesis and crystal structure of the title copper(II) complex salt, [[Cu(CF₃SO₃)(C₂H₃N)₂(C₁₂H₁₂N₂O₂)](CF₃SO₃)]_n.

As depicted in Fig. 1, the asymmetric unit of the title compound comprises a Cu^II atom, one N,N′-chelating 4,4′-dimethoxy-2,2′-bipyridine ligand, two acetonitrile ligands, and two trifluoromethanesulfonate anions. The central copper(II) atom exhibits a tetragonally distorted octahedral coordination environment defined by the N atoms of the chelating 4,4′-dimethoxy-2,2′-bipyridine ligand and two neutral acetonitrile molecules in the equatorial plane and by two O atoms of symmetry-related trifluoromethanesulfonate anions in axial positions. Although the Cu—N bond lengths with the bipyridine ligand are shorter than the Cu—N bond lengths with the coordinating acetonitrile molecules, their values are comparable with the reported values of other copper(II) complexes with the same chelating ligand (Fettouhi, 2017 ). The acetonitrile ligands are bordering on linearity. All relevant bond lengths and angles involving the Cu^II atom are presented in Table 1. The cations in the title complex are aligned into polymeric chains extending parallel to the a-axis direction and pack into layers parallel to the bc plane, as illustrated in the crystal packing diagram given in Fig. 2. This arrangement leaves voids in which the second type of trifluoromethanesulfonate anions are located. These anions are non-coordinating and interact through hydrogen bonds.

Table 1
Selected geometric parameters (Å, °)

Cu1—O5ⁱ	2.376 (2)	Cu1—N1	1.989 (2)
Cu1—O3	2.333 (2)	Cu1—N3	2.014 (2)
Cu1—N2	1.985 (2)	Cu1—N4	2.012 (2)

N2—Cu1—O5ⁱ	90.71 (8)	N1—Cu1—N3	94.85 (10)
N2—Cu1—O3	94.76 (9)	N1—Cu1—N4	176.62 (9)
N2—Cu1—N1	81.56 (9)	N3—Cu1—O5ⁱ	87.89 (9)
N2—Cu1—N3	175.99 (10)	N3—Cu1—O3	87.27 (9)
N2—Cu1—N4	95.12 (9)	N4—Cu1—O5ⁱ	83.46 (9)
N1—Cu1—O5ⁱ	95.88 (8)	N4—Cu1—O3	86.38 (9)
N1—Cu1—O3	94.53 (9)	N4—Cu1—N3	88.45 (10)
Symmetry code: (i) x+1, y, z.

Figure 1
Asymmetric unit of the title compound with displacement ellipsoids drawn at the 50% probability level; H atoms are omitted for clarity.

Figure 2
Perspective view of the packed structure of the title complex along the crystallographic b axis; H atoms are omitted for clarity.

Graph-set analysis is a method of analyzing hydrogen-bonding patterns in three-dimensional networks. Hydrogen-bonding patterns are classified into one of four pattern designators; rings (R), chains (C), intramolecular hydrogen-bonding patterns described as self (S), finite hydrogen-bonding patterns described as discrete (D). These designators include a superscript with the number of acceptor atoms, subscript with the number of donor atoms, and a number in parentheses indicating the number of atoms in the hydrogen-bonding motif (Grell et al., 1999 ).

There are three types of hydrogen-bonding motifs present in the crystal lattice, with numerical values collated in Table 2. A centrosymmetric hydrogen-bonding ring, R₂¹(7), occurs between the O4 atom on the coordinating trifluoromethanesulfonate anion with two hydrogen atoms on a 4,4′-dimethoxybipyridine molecule on a neighboring asymmetric unit. The non-coordinating trifluoromethanesulfonate anion forms a hydrogen-bonding ring, R₂²(12), through two C—H⋯O interactions with the O6 and O7 atoms. The other oxygen atom, O8, on the non-coordinating trifluoromethanesulfonate anion, has a discrete hydrogen-bonding interaction, D¹₁(3), with a neighboring coordinating acetonitrile molecule.

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C7—H7⋯O4ⁱⁱ	0.95	2.23	3.175 (4)	177
C4—H4⋯O4ⁱⁱ	0.95	2.37	3.315 (3)	175
C9—H9⋯O7	0.95	2.32	3.185 (4)	151
C16—H16A⋯O6	0.98	2.38	3.170 (4)	138
C14—H14A⋯O8ⁱⁱⁱ	0.98	2.35	3.194 (4)	144
Symmetry codes: (ii) ; (iii) .

Synthesis and crystallization

To synthesize the title compound, 4,4′-dimethoxy-2,2′-bipyridine (0.105 g, 0.486 mmol) was suspended in 40 ml of acetonitrile and stirred for 15 min. Solid CuCl₂·2H₂O (0.083 g, 0.49 mmol) was added to the suspension and heated with stirring at 323 K for 1 h. AgOTf (0.250 g, 0.972 mmol) was added to the mixture and stirred without heating for 2 h. After the removal of AgCl by filtration, using a 0.45 µm PTFE syringe filter, the resulting blue solution was used to grow crystals by vapor diffusion with diethyl ether at 278 K.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 3. The highest remaining electron density is located 0.93 Å from atom O3.

Table 3
Experimental details

Crystal data
Chemical formula	[Cu(CF₃SO₃)(C₂H₃N)₂(C₁₂H₁₂N₂O₂)](CF₃O₃S)
M_r	660.02
Crystal system, space group	Triclinic, P $[\overline{1}]$
Temperature (K)	100
a, b, c (Å)	7.1004 (2), 12.0708 (4), 14.8155 (4)
α, β, γ (°)	87.368 (2), 89.436 (2), 76.819 (3)
V (Å³)	1235.04 (6)
Z	2
Radiation type	Mo Kα
μ (mm⁻¹)	1.15
Crystal size (mm)	0.40 × 0.10 × 0.07

Data collection
Diffractometer	XtaLAB AFC12 (RCD3): Kappa single
Absorption correction	Multi-scan (CrysAlis PRO; Rigaku OD, 2019 $[Rigaku OD (2019). CrysAlis PRO. Rigaku Oxford Diffraction, Yarnton, England.]$ )
T_min, T_max	0.884, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	37314, 5666, 5392
R_int	0.040
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.049, 0.125, 1.07
No. of reflections	5666
No. of parameters	356
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	2.01, −0.46
Computer programs: CrysAlis PRO (Rigaku OD, 2019 $[Rigaku OD (2019). CrysAlis PRO. Rigaku Oxford Diffraction, Yarnton, England.]$ ), SHELXT (Sheldrick, 2015a ), SHELXL (Sheldrick, 2015b ) and OLEX2 (Dolomanov et al., 2009 ).

Structural data

CCDC reference: 2039861

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2414314620014078/wm4141sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314620014078/wm4141Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314620014078/wm4141Isup3.mol

3D View. DOI: https://doi.org/10.1107/S2414314620014078/wm4141sup4.tif

Supporting information file. DOI: https://doi.org/10.1107/S2414314620014078/wm4141Isup5.mol

checkCIF report

Computing details top

Data collection: CrysAlis PRO (Rigaku OD, 2019); cell refinement: CrysAlis PRO (Rigaku OD, 2019); data reduction: CrysAlis PRO (Rigaku OD, 2019); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL (Sheldrick, 2015b); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

catena-Poly[[[bis(acetonitrile-κN)(4,4'-dimethoxy-2,2'-bipyridine-κ²N,N')copper(II)]-µ-trifluoromethanesulfonato-κ²O:O'] trifluoromethanesulfonate] top

Crystal data top

[Cu(CF₃SO₃)(C₂H₃N)₂(C₁₂H₁₂N₂O₂)](CF₃O₃S)	Z = 2
M_r = 660.02	F(000) = 666
Triclinic, P1	D_x = 1.775 Mg m⁻³
a = 7.1004 (2) Å	Mo Kα radiation, λ = 0.71073 Å
b = 12.0708 (4) Å	Cell parameters from 13491 reflections
c = 14.8155 (4) Å	θ = 2.7–29.0°
α = 87.368 (2)°	µ = 1.15 mm⁻¹
β = 89.436 (2)°	T = 100 K
γ = 76.819 (3)°	Plate, clear light blue
V = 1235.04 (6) Å³	0.40 × 0.10 × 0.07 mm

Data collection top

XtaLAB AFC12 (RCD3): Kappa single diffractometer	5666 independent reflections
Radiation source: Rotating-anode X-ray tube, Rigaku (Mo) X-ray Source	5392 reflections with I > 2σ(I)
Mirror monochromator	R_int = 0.040
ω scans	θ_max = 27.5°, θ_min = 2.2°
Absorption correction: multi-scan (CrysAlisPro; Rigaku OD, 2019)	h = −9→9
T_min = 0.884, T_max = 1.000	k = −15→15
37314 measured reflections	l = −18→19

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.049	H-atom parameters constrained
wR(F²) = 0.125	w = 1/[σ²(F_o²) + (0.060P)² + 2.9P] where P = (F_o² + 2F_c²)/3
S = 1.07	(Δ/σ)_max = 0.001
5666 reflections	Δρ_max = 2.01 e Å⁻³
356 parameters	Δρ_min = −0.46 e Å⁻³

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

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

	x	y	z	U_iso*/U_eq
Cu1	0.75757 (5)	0.42109 (3)	0.78071 (2)	0.01474 (11)
S1	0.23675 (10)	0.48568 (6)	0.76732 (4)	0.01596 (15)
S2	0.61504 (12)	0.95110 (6)	0.80753 (5)	0.02364 (18)
F3	0.3180 (3)	0.67475 (15)	0.81898 (12)	0.0238 (4)
F2	0.0138 (3)	0.67978 (15)	0.81561 (13)	0.0247 (4)
F1	0.1895 (3)	0.58506 (16)	0.92313 (12)	0.0299 (4)
O5	0.0885 (3)	0.42653 (17)	0.79453 (14)	0.0197 (4)
O3	0.4282 (3)	0.42680 (17)	0.79606 (15)	0.0215 (4)
O4	0.2216 (4)	0.53393 (19)	0.67652 (14)	0.0315 (6)
O2	0.6860 (3)	0.74737 (17)	0.44968 (14)	0.0244 (5)
O1	0.8576 (3)	0.12536 (17)	0.45169 (14)	0.0238 (5)
F5	0.3647 (4)	1.0672 (2)	0.91972 (16)	0.0500 (6)
N2	0.7231 (3)	0.53835 (19)	0.68011 (15)	0.0143 (4)
F6	0.4294 (4)	1.16541 (18)	0.80405 (19)	0.0536 (7)
N1	0.7950 (3)	0.3178 (2)	0.67802 (16)	0.0151 (4)
O6	0.5595 (4)	0.84920 (19)	0.84105 (17)	0.0369 (6)
O7	0.6329 (4)	0.9614 (2)	0.71066 (16)	0.0336 (6)
N3	0.8040 (4)	0.2945 (2)	0.87692 (16)	0.0198 (5)
F4	0.2473 (4)	1.0479 (2)	0.7904 (2)	0.0594 (7)
N4	0.7207 (4)	0.5332 (2)	0.87937 (16)	0.0176 (5)
C6	0.7481 (4)	0.4965 (2)	0.59648 (18)	0.0146 (5)
C5	0.7856 (4)	0.3705 (2)	0.59509 (18)	0.0147 (5)
O8	0.7668 (4)	0.9828 (3)	0.8563 (2)	0.0505 (8)
C7	0.7353 (4)	0.5661 (2)	0.51903 (19)	0.0177 (5)
H7	0.752622	0.534456	0.461161	0.021*
C15	0.7130 (4)	0.5956 (2)	0.93529 (18)	0.0175 (6)
C4	0.8068 (4)	0.3119 (2)	0.51601 (19)	0.0165 (5)
H4	0.801421	0.351339	0.458761	0.020*
C17	0.1866 (4)	0.6126 (2)	0.83457 (19)	0.0181 (5)
C9	0.6697 (4)	0.7277 (2)	0.61315 (19)	0.0172 (5)
H9	0.641922	0.807505	0.620840	0.021*
C8	0.6961 (4)	0.6845 (2)	0.52759 (19)	0.0176 (5)
C13	0.8214 (4)	0.2295 (2)	0.9359 (2)	0.0202 (6)
C10	0.6850 (4)	0.6514 (2)	0.68725 (19)	0.0161 (5)
H10	0.667564	0.680938	0.745858	0.019*
C3	0.8363 (4)	0.1932 (2)	0.52261 (19)	0.0181 (6)
C2	0.8441 (5)	0.1391 (2)	0.6079 (2)	0.0208 (6)
H2	0.863236	0.058601	0.614073	0.025*
C1	0.8236 (4)	0.2034 (2)	0.68297 (19)	0.0184 (6)
H1	0.829999	0.165612	0.740916	0.022*
C16	0.7075 (5)	0.6759 (3)	1.0062 (2)	0.0272 (7)
H16A	0.681353	0.753596	0.979411	0.041*
H16B	0.832382	0.659186	1.037540	0.041*
H16C	0.605032	0.668817	1.049419	0.041*
C14	0.8362 (5)	0.1454 (3)	1.0107 (2)	0.0274 (7)
H14A	0.822734	0.072737	0.987782	0.041*
H14B	0.733475	0.171786	1.054573	0.041*
H14C	0.962531	0.135124	1.040026	0.041*
C11	0.8548 (5)	0.1775 (3)	0.3622 (2)	0.0233 (6)
H11A	0.869985	0.118684	0.317564	0.035*
H11B	0.961202	0.216662	0.356008	0.035*
H11C	0.731362	0.232593	0.352245	0.035*
C18	0.4039 (5)	1.0638 (3)	0.8315 (2)	0.0309 (7)
C12	0.6424 (5)	0.8692 (2)	0.4558 (2)	0.0261 (7)
H12A	0.633264	0.905278	0.394865	0.039*
H12B	0.745317	0.891233	0.489377	0.039*
H12C	0.518965	0.894066	0.487237	0.039*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.02004 (19)	0.01336 (18)	0.01075 (17)	−0.00366 (13)	−0.00062 (12)	−0.00033 (12)
S1	0.0205 (3)	0.0159 (3)	0.0118 (3)	−0.0046 (3)	0.0001 (2)	−0.0019 (2)
S2	0.0348 (4)	0.0170 (3)	0.0196 (4)	−0.0064 (3)	−0.0015 (3)	−0.0030 (3)
F3	0.0251 (9)	0.0198 (9)	0.0292 (10)	−0.0097 (7)	−0.0002 (7)	−0.0047 (7)
F2	0.0228 (9)	0.0184 (8)	0.0310 (10)	−0.0005 (7)	−0.0001 (7)	−0.0025 (7)
F1	0.0532 (13)	0.0235 (9)	0.0120 (8)	−0.0063 (9)	0.0011 (8)	−0.0025 (7)
O5	0.0225 (10)	0.0133 (9)	0.0237 (10)	−0.0048 (8)	−0.0003 (8)	−0.0009 (8)
O3	0.0226 (11)	0.0142 (10)	0.0278 (11)	−0.0039 (8)	0.0009 (9)	−0.0017 (8)
O4	0.0613 (17)	0.0207 (11)	0.0113 (10)	−0.0068 (11)	0.0002 (10)	−0.0001 (8)
O2	0.0413 (13)	0.0137 (10)	0.0174 (10)	−0.0048 (9)	−0.0019 (9)	0.0026 (8)
O1	0.0406 (13)	0.0139 (10)	0.0159 (10)	−0.0035 (9)	−0.0011 (9)	−0.0025 (8)
F5	0.0767 (18)	0.0344 (12)	0.0375 (13)	−0.0086 (12)	0.0220 (12)	−0.0112 (10)
N2	0.0167 (11)	0.0141 (11)	0.0123 (10)	−0.0037 (9)	−0.0011 (8)	−0.0015 (8)
F6	0.0781 (18)	0.0147 (10)	0.0640 (17)	−0.0041 (11)	0.0229 (14)	0.0023 (10)
N1	0.0169 (11)	0.0144 (11)	0.0141 (11)	−0.0037 (9)	−0.0006 (9)	−0.0008 (8)
O6	0.0630 (18)	0.0161 (11)	0.0296 (13)	−0.0063 (11)	0.0090 (12)	0.0034 (9)
O7	0.0578 (17)	0.0232 (12)	0.0214 (12)	−0.0130 (11)	0.0093 (11)	−0.0020 (9)
N3	0.0271 (13)	0.0184 (12)	0.0141 (11)	−0.0054 (10)	−0.0006 (10)	−0.0004 (9)
F4	0.0390 (14)	0.0580 (17)	0.077 (2)	0.0013 (12)	−0.0125 (13)	−0.0180 (14)
N4	0.0198 (12)	0.0176 (11)	0.0149 (11)	−0.0032 (9)	0.0004 (9)	0.0007 (9)
C6	0.0155 (12)	0.0150 (13)	0.0133 (12)	−0.0034 (10)	0.0004 (10)	−0.0015 (10)
C5	0.0144 (12)	0.0153 (13)	0.0146 (12)	−0.0039 (10)	−0.0011 (10)	0.0000 (10)
O8	0.0450 (17)	0.0538 (18)	0.0533 (18)	−0.0083 (14)	−0.0141 (14)	−0.0214 (15)
C7	0.0246 (14)	0.0161 (13)	0.0126 (12)	−0.0042 (11)	−0.0014 (10)	−0.0021 (10)
C15	0.0216 (14)	0.0168 (13)	0.0124 (12)	−0.0017 (11)	0.0003 (10)	0.0035 (10)
C4	0.0197 (13)	0.0137 (12)	0.0152 (13)	−0.0023 (10)	−0.0007 (10)	0.0004 (10)
C17	0.0218 (14)	0.0185 (13)	0.0145 (13)	−0.0050 (11)	0.0014 (10)	−0.0022 (10)
C9	0.0197 (13)	0.0122 (12)	0.0195 (14)	−0.0033 (10)	−0.0015 (11)	−0.0009 (10)
C8	0.0197 (13)	0.0167 (13)	0.0167 (13)	−0.0048 (11)	−0.0012 (10)	0.0010 (10)
C13	0.0248 (15)	0.0170 (13)	0.0189 (14)	−0.0042 (11)	−0.0025 (11)	−0.0036 (11)
C10	0.0173 (13)	0.0158 (13)	0.0152 (13)	−0.0035 (10)	0.0007 (10)	−0.0028 (10)
C3	0.0209 (14)	0.0157 (13)	0.0171 (13)	−0.0028 (11)	−0.0007 (11)	−0.0031 (10)
C2	0.0287 (15)	0.0118 (12)	0.0211 (14)	−0.0033 (11)	0.0001 (12)	−0.0003 (10)
C1	0.0241 (14)	0.0146 (13)	0.0156 (13)	−0.0033 (11)	−0.0006 (11)	0.0031 (10)
C16	0.0411 (19)	0.0219 (15)	0.0171 (14)	−0.0038 (13)	−0.0012 (13)	−0.0038 (12)
C14	0.045 (2)	0.0185 (14)	0.0191 (15)	−0.0086 (13)	−0.0028 (13)	0.0019 (11)
C11	0.0338 (17)	0.0190 (14)	0.0151 (14)	−0.0016 (12)	0.0001 (12)	−0.0023 (11)
C18	0.0414 (19)	0.0191 (15)	0.0317 (18)	−0.0058 (14)	0.0046 (15)	−0.0012 (13)
C12	0.0390 (18)	0.0121 (13)	0.0260 (16)	−0.0042 (12)	−0.0032 (13)	0.0031 (11)

Geometric parameters (Å, º) top

Cu1—O5ⁱ	2.376 (2)	C6—C5	1.484 (4)
Cu1—O3	2.333 (2)	C6—C7	1.382 (4)
Cu1—N2	1.985 (2)	C5—C4	1.386 (4)
Cu1—N1	1.989 (2)	C7—H7	0.9500
Cu1—N3	2.014 (2)	C7—C8	1.403 (4)
Cu1—N4	2.012 (2)	C15—C16	1.456 (4)
S1—O5	1.445 (2)	C4—H4	0.9500
S1—O3	1.442 (2)	C4—C3	1.399 (4)
S1—O4	1.436 (2)	C9—H9	0.9500
S1—C17	1.831 (3)	C9—C8	1.388 (4)
S2—O6	1.441 (2)	C9—C10	1.389 (4)
S2—O7	1.442 (2)	C13—C14	1.456 (4)
S2—O8	1.435 (3)	C10—H10	0.9500
S2—C18	1.824 (4)	C3—C2	1.391 (4)
F3—C17	1.336 (3)	C2—H2	0.9500
F2—C17	1.332 (3)	C2—C1	1.374 (4)
F1—C17	1.338 (3)	C1—H1	0.9500
O2—C8	1.345 (3)	C16—H16A	0.9800
O2—C12	1.439 (3)	C16—H16B	0.9800
O1—C3	1.348 (3)	C16—H16C	0.9800
O1—C11	1.439 (3)	C14—H14A	0.9800
F5—C18	1.335 (4)	C14—H14B	0.9800
N2—C6	1.354 (3)	C14—H14C	0.9800
N2—C10	1.339 (4)	C11—H11A	0.9800
F6—C18	1.325 (4)	C11—H11B	0.9800
N1—C5	1.353 (3)	C11—H11C	0.9800
N1—C1	1.348 (4)	C12—H12A	0.9800
N3—C13	1.136 (4)	C12—H12B	0.9800
F4—C18	1.328 (5)	C12—H12C	0.9800
N4—C15	1.138 (4)

O3—Cu1—O5ⁱ	168.85 (8)	F2—C17—S1	112.0 (2)
N2—Cu1—O5ⁱ	90.71 (8)	F2—C17—F3	107.2 (2)
N2—Cu1—O3	94.76 (9)	F2—C17—F1	107.3 (2)
N2—Cu1—N1	81.56 (9)	F1—C17—S1	111.5 (2)
N2—Cu1—N3	175.99 (10)	C8—C9—H9	120.8
N2—Cu1—N4	95.12 (9)	C8—C9—C10	118.3 (3)
N1—Cu1—O5ⁱ	95.88 (8)	C10—C9—H9	120.8
N1—Cu1—O3	94.53 (9)	O2—C8—C7	115.7 (3)
N1—Cu1—N3	94.85 (10)	O2—C8—C9	125.2 (3)
N1—Cu1—N4	176.62 (9)	C9—C8—C7	119.1 (3)
N3—Cu1—O5ⁱ	87.89 (9)	N3—C13—C14	177.8 (3)
N3—Cu1—O3	87.27 (9)	N2—C10—C9	123.2 (3)
N4—Cu1—O5ⁱ	83.46 (9)	N2—C10—H10	118.4
N4—Cu1—O3	86.38 (9)	C9—C10—H10	118.4
N4—Cu1—N3	88.45 (10)	O1—C3—C4	124.8 (3)
O5—S1—C17	104.08 (13)	O1—C3—C2	116.3 (3)
O3—S1—O5	113.46 (12)	C2—C3—C4	118.8 (3)
O3—S1—C17	103.30 (13)	C3—C2—H2	120.4
O4—S1—O5	115.66 (15)	C1—C2—C3	119.2 (3)
O4—S1—O3	115.70 (15)	C1—C2—H2	120.4
O4—S1—C17	102.27 (13)	N1—C1—C2	122.8 (3)
O6—S2—O7	114.84 (15)	N1—C1—H1	118.6
O6—S2—C18	103.34 (16)	C2—C1—H1	118.6
O7—S2—C18	103.15 (16)	C15—C16—H16A	109.5
O8—S2—O6	115.89 (19)	C15—C16—H16B	109.5
O8—S2—O7	114.17 (19)	C15—C16—H16C	109.5
O8—S2—C18	103.02 (18)	H16A—C16—H16B	109.5
S1—O5—Cu1ⁱⁱ	145.62 (13)	H16A—C16—H16C	109.5
S1—O3—Cu1	144.69 (13)	H16B—C16—H16C	109.5
C8—O2—C12	117.2 (2)	C13—C14—H14A	109.5
C3—O1—C11	118.2 (2)	C13—C14—H14B	109.5
C6—N2—Cu1	114.82 (18)	C13—C14—H14C	109.5
C10—N2—Cu1	126.88 (19)	H14A—C14—H14B	109.5
C10—N2—C6	118.3 (2)	H14A—C14—H14C	109.5
C5—N1—Cu1	115.06 (18)	H14B—C14—H14C	109.5
C1—N1—Cu1	126.97 (19)	O1—C11—H11A	109.5
C1—N1—C5	117.9 (2)	O1—C11—H11B	109.5
C13—N3—Cu1	174.2 (2)	O1—C11—H11C	109.5
C15—N4—Cu1	175.4 (2)	H11A—C11—H11B	109.5
N2—C6—C5	114.5 (2)	H11A—C11—H11C	109.5
N2—C6—C7	122.4 (2)	H11B—C11—H11C	109.5
C7—C6—C5	123.1 (2)	F5—C18—S2	111.6 (2)
N1—C5—C6	114.0 (2)	F6—C18—S2	111.7 (3)
N1—C5—C4	122.8 (2)	F6—C18—F5	107.5 (3)
C4—C5—C6	123.2 (2)	F6—C18—F4	107.8 (3)
C6—C7—H7	120.7	F4—C18—S2	111.2 (2)
C6—C7—C8	118.6 (3)	F4—C18—F5	106.9 (3)
C8—C7—H7	120.7	O2—C12—H12A	109.5
N4—C15—C16	178.7 (3)	O2—C12—H12B	109.5
C5—C4—H4	120.8	O2—C12—H12C	109.5
C5—C4—C3	118.3 (3)	H12A—C12—H12B	109.5
C3—C4—H4	120.8	H12A—C12—H12C	109.5
F3—C17—S1	111.09 (19)	H12B—C12—H12C	109.5
F3—C17—F1	107.6 (2)

Cu1—N2—C6—C5	3.3 (3)	O7—S2—C18—F4	60.7 (3)
Cu1—N2—C6—C7	−178.0 (2)	C6—N2—C10—C9	0.0 (4)
Cu1—N2—C10—C9	177.6 (2)	C6—C5—C4—C3	−178.2 (3)
Cu1—N1—C5—C6	−0.2 (3)	C6—C7—C8—O2	179.9 (3)
Cu1—N1—C5—C4	−179.5 (2)	C6—C7—C8—C9	−0.6 (4)
Cu1—N1—C1—C2	178.6 (2)	C5—N1—C1—C2	0.2 (4)
O5—S1—O3—Cu1	169.10 (19)	C5—C6—C7—C8	179.0 (3)
O5—S1—C17—F3	177.75 (19)	C5—C4—C3—O1	179.4 (3)
O5—S1—C17—F2	−62.4 (2)	C5—C4—C3—C2	−0.3 (4)
O5—S1—C17—F1	57.8 (2)	O8—S2—C18—F5	−61.0 (3)
O3—S1—O5—Cu1ⁱⁱ	−171.80 (19)	O8—S2—C18—F6	59.4 (3)
O3—S1—C17—F3	59.0 (2)	O8—S2—C18—F4	179.7 (3)
O3—S1—C17—F2	178.83 (19)	C7—C6—C5—N1	179.3 (3)
O3—S1—C17—F1	−61.0 (2)	C7—C6—C5—C4	−1.5 (4)
O4—S1—O5—Cu1ⁱⁱ	−34.7 (3)	C4—C3—C2—C1	−0.4 (4)
O4—S1—O3—Cu1	32.0 (3)	C17—S1—O5—Cu1ⁱⁱ	76.6 (2)
O4—S1—C17—F3	−61.5 (2)	C17—S1—O3—Cu1	−78.9 (2)
O4—S1—C17—F2	58.3 (2)	C8—C9—C10—N2	−0.3 (4)
O4—S1—C17—F1	178.5 (2)	C10—N2—C6—C5	−178.8 (2)
O1—C3—C2—C1	179.9 (3)	C10—N2—C6—C7	−0.1 (4)
N2—C6—C5—N1	−2.0 (3)	C10—C9—C8—O2	−180.0 (3)
N2—C6—C5—C4	177.2 (3)	C10—C9—C8—C7	0.6 (4)
N2—C6—C7—C8	0.4 (4)	C3—C2—C1—N1	0.4 (5)
N1—C5—C4—C3	1.0 (4)	C1—N1—C5—C6	178.3 (2)
O6—S2—C18—F5	60.1 (3)	C1—N1—C5—C4	−0.9 (4)
O6—S2—C18—F6	−179.6 (3)	C11—O1—C3—C4	1.6 (4)
O6—S2—C18—F4	−59.2 (3)	C11—O1—C3—C2	−178.7 (3)
O7—S2—C18—F5	180.0 (3)	C12—O2—C8—C7	178.8 (3)
O7—S2—C18—F6	−59.7 (3)	C12—O2—C8—C9	−0.6 (4)

Symmetry codes: (i) x+1, y, z; (ii) x−1, y, z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C7—H7···O4ⁱⁱⁱ	0.95	2.23	3.175 (4)	177
C4—H4···O4ⁱⁱⁱ	0.95	2.37	3.315 (3)	175
C9—H9···O7	0.95	2.32	3.185 (4)	151
C16—H16A···O6	0.98	2.38	3.170 (4)	138
C14—H14A···O8^iv	0.98	2.35	3.194 (4)	144

Symmetry codes: (iii) −x+1, −y+1, −z+1; (iv) x, y−1, z.

Acknowledgements

We are thankful for the support of the Department of Chemistry and Biochemistry at the University of the Incarnate Word and the X-ray Diffraction Laboratory at The University of Texas at San Antonio.

Funding information

Funding for this research was provided by: The Welch Foundation (award No. BN0032).

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