Aqua­bis­[3,6-bis­(pyridin-2-yl)pyridazine-κ2N1,N6]copper(II) bis­(tri­fluoro­methane­sulfonate)

Showrilu, K.; Rajarajan, K.; Martin Britto Dhas, S.A.; Athimoolam, S.

doi:10.1107/S2414314617011427

metal-organic compounds

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ISSN: 2414-3146

Volume 2| Part 8| August 2017| x171142

https://doi.org/10.1107/S2414314617011427

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Aquabis[3,6-bis(pyridin-2-yl)pyridazine-κ²N¹,N⁶]copper(II) bis(trifluoromethanesulfonate)

K. Showrilu,^a K. Rajarajan,^b S. A. Martin Britto Dhas ^c and S. Athimoolam ^d ^*

^aResearch and Development Centre, Bharathiar University, Coimbatore 641 046, India, ^bDepartment of Physics, Rajeswari Vedachalam Government Arts College, Chengalpattu 603 001, India, ^cDepartment of Physics, Abraham Panampara Research Centre, Sacred Heart College, Tirupattur Vellore 635 601, India, and ^dDepartment of Physics, University College of Engineering Nagercoil, Anna University, Nagercoil 629 004, India
^*Correspondence e-mail: athi81s@yahoo.co.in

Edited by M. Bolte, Goethe-Universität Frankfurt, Germany (Received 20 July 2017; accepted 2 August 2017; online 15 August 2017)

The title salt, [Cu(C₁₄H₁₀N₄)₂(H₂O)](CF₃SO₃)₂, contains a Cu²⁺ cation coordinated by two bidentate 3,6-bis(pyridin-2-yl)pyridazine ligands and one water molecule. The charge is balanced by two disordered trifluoromethanesulfonate anions. The asymmetric unit contains half of a cation (point group symmetry 2) and one anion. The coordinating water molecule is engaged in intermolecular O—H⋯O hydrogen bonds, which connect the cation to the anion. C—H⋯X (X = N, O, F) interactions stabilize the crystal structure.

Keywords: crystal structure; copper complex; metalorganic; 3,6-bis(pyridin-2-yl)pyridazine; hydrogen bond; disorder.

CCDC reference: 880897

Structure description

The coordination chemistry of aromatic diazine and related ligands has gained immense popularity (Xu & Thompson, 2004 ). 3,6-Bis(pyridin-2-yl)pyridazine is a potential candidate for forming a grid-type architecture because of the multiple binding sites, which can permit coordination of one or two metal atoms depending on the cis–cis or trans–trans configuration it can adopt (Yuste et al., 2007 ; Schottel et al., 2006 ). Understanding the properties and structures of smaller building units with a similar ligand structure will help us to understand the chemistry of larger arrays and synergistic effects in supramolecular frameworks containing the secondary building units (SBU). A large number of transition-metal complexes with a grid-type architecture in two-dimensional arrays, interconnected by the above ligand are known (Constable et al., 2008 ; Alam et al., 2005 ; Grove et al., 2001 ). Furthermore, copper complexes with these ligands can accommodate different oxidation states as bipyridine is an ambivalent ligand (Desbouis et al., 2012 ). Since the redox potentials of several copper complexes are appropriate for carrying out catalytic redox functions, they are important in technological and biological applications (Farver & Pecht, 1989 ).

The title compound crystallizes in a monoclinic C-centered lattice with four molecules per unit cell. The asymmetric unit contains half of a cation and one anion (Fig. 1). In the anion, except for one of the O atoms (O1) and one of the F atoms (F1), all the atoms are disordered over two positions with major and minor site occupancies of 0.82 and 0.18, respectively. The copper atom is coordinated by nitrogen atoms of the pyridazine and pyridine rings. Hence, the metal coordination, with four Cu—N bonds and one Cu—O(water) bond, adopts a pyramidal geometry with the N atoms forming the base and the O atom at the top of the pyramid. The Cu—N distances are 1.984 (3) and 2.013 (3) Å, while the Cu—O1W distance amounts to 2.128 (6) Å. The ligands are inclined at an angle of 49.58 (2)° to each other.

Figure 1
The atom-numbering scheme and 50% probability displacement ellipsoids of the copper complex cation and the anion. The trifluoromethanesulfonate anion shows disorder over two positions with 0.82 and 0.18 site occupancies.

The coordinating water molecule is engaged in intermolecular O—H⋯O hydrogen bonds, which connects the cation with two anions. Further, the crystal structure is stabilized by C—H⋯X (X = N, O, F) intermolecular interactions (Fig. 2, Table 1).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C1—H1⋯N3ⁱ	0.93	2.63	3.104 (5)	112
C2—H2⋯O3ⁱⁱ	0.93	2.55	3.376 (6)	149
C11—H11⋯F1ⁱⁱⁱ	0.93	2.55	3.334 (7)	142
C12—H12⋯O2^iv	0.93	2.59	3.443 (8)	152
O1W—H1W⋯O2ⁱ	0.83 (1)	1.91 (3)	2.710 (6)	161 (7)
C1—H1⋯N3ⁱ	0.93	2.63	3.104 (5)	112
C2—H2⋯O3ⁱⁱ	0.93	2.55	3.376 (6)	149
C11—H11⋯F1ⁱⁱⁱ	0.93	2.55	3.334 (7)	142
C12—H12⋯O2^iv	0.93	2.59	3.443 (8)	152
O1W—H1W⋯O2ⁱ	0.83 (1)	1.91 (3)	2.710 (6)	161 (7)
Symmetry codes: (i) $[-x+2, y, -z+{\script{3\over 2}}]$ ; (ii) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (iii) -x+2, -y, -z+2; (iv) $[x, -y, z+{\script{1\over 2}}]$ .

Figure 2
Packing diagram of the title compound viewed down the b axis. Hydrogen bonds are shown as dashed lines. The minor component of the disordered trifluoromethanesulfonate anion has been omitted for clarity.

Synthesis and crystallization

Two moles of 3,6-bis(pyridin-2-yl)pyridazine (bppz) and one mole of Cu(CF₃SO₃)₂ were dissolved in dry benzene (10 ml) separately and stirred for 2 h at 323 K. The bppz solution was then added dropwise to the Cu(CF₃SO₃)₂ solution and stirred well. The colour of the solution slowly turned to a light blue and a precipitate of the same colour was formed. It was filtered off and washed with benzene. Good quality needle-shaped crystals were obtained from methanol by the solvent evaporation method.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2.

Table 2
Experimental details

Crystal data
Chemical formula	[Cu(C₁₄H₁₀N₄)₂H₂O](CF₃O₃S)₂
M_r	848.21
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	293
a, b, c (Å)	20.7092 (13), 8.7911 (8), 21.1274 (14)
β (°)	116.292 (9)
V (Å³)	3448.5 (5)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.85
Crystal size (mm)	0.22 × 0.14 × 0.12

Data collection
Diffractometer	Bruker SMART APEX CCD area-detector
No. of measured, independent and observed [I > 2σ(I)] reflections	3562, 3038, 1662
R_int	0.036
(sin θ/λ)_max (Å⁻¹)	0.594

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.043, 0.136, 1.03
No. of reflections	3038
No. of parameters	273
No. of restraints	1
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.41, −0.28
Computer programs: SMART and SAINT (Bruker, 2001 ), SHELX2014 (Sheldrick, 2015a ), SHELXL2014 (Sheldrick, 2015b ), PLATON (Spek, 2009 ).

Structural data

CCDC reference: 880897

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2414314617011427/bt4057sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314617011427/bt4057Isup2.hkl

checkCIF report

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXT2014 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXL2014 (Sheldrick, 2015b).

Aquabis[3,6-bis(pyridin-2-yl)pyridazine-κ²N¹,N⁶]copper(II) bis(trifluoromethanesulfonate) top

Crystal data top

[Cu(C₁₄H₁₀N₄)₂H₂O](CF₃O₃S)₂	F(000) = 1716
M_r = 848.21	D_x = 1.634 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 20.7092 (13) Å	Cell parameters from 2463 reflections
b = 8.7911 (8) Å	θ = 2.4–24.5°
c = 21.1274 (14) Å	µ = 0.85 mm⁻¹
β = 116.292 (9)°	T = 293 K
V = 3448.5 (5) Å³	Needle, light blue
Z = 4	0.22 × 0.14 × 0.12 mm

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	R_int = 0.036
Radiation source: fine-focus sealed tube	θ_max = 25.0°, θ_min = 2.2°
ω scans	h = 0→24
3562 measured reflections	k = −1→10
3038 independent reflections	l = −25→22
1662 reflections with I > 2σ(I)

Refinement top

Refinement on F²	1 restraint
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.043	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.136	w = 1/[σ²(F_o²) + (0.0652P)² + 1.9713P] where P = (F_o² + 2F_c²)/3
S = 1.03	(Δ/σ)_max < 0.001
3038 reflections	Δρ_max = 0.41 e Å⁻³
273 parameters	Δρ_min = −0.28 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.

Refinement. All the H atoms, except water hydrogen atoms, were constrained and refined in the riding atom approximation with C—H = 0.93 Å and U_iso(H) = 1.2 U_eq(parent carbon atom). The water hydrogen atoms were located from difference Fourier map and refined isotropically with the O—H distance restrained to 0.84 (1) Å. All the atoms in the anion, except O1 and F1, are disordered over two positions with major and minor site occupancies of 0.82 and 0.18, respectively. The minor occupied atoms were isotropically refined.

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
C1	0.8715 (2)	0.0852 (5)	0.6131 (2)	0.0585 (12)
H1	0.9039	0.1137	0.5957	0.070*
C2	0.7985 (3)	0.0927 (5)	0.5689 (2)	0.0644 (13)
H2	0.7820	0.1242	0.5223	0.077*
C3	0.7508 (3)	0.0527 (6)	0.5951 (3)	0.0699 (14)
H3	0.7015	0.0564	0.5662	0.084*
C4	0.7765 (2)	0.0071 (5)	0.6644 (2)	0.0622 (13)
H4	0.7449	−0.0179	0.6832	0.075*
C5	0.8502 (2)	−0.0009 (5)	0.7056 (2)	0.0509 (11)
C6	0.8834 (2)	−0.0565 (5)	0.7791 (2)	0.0482 (10)
C7	0.8475 (2)	−0.1223 (5)	0.8134 (2)	0.0614 (12)
H7	0.7977	−0.1334	0.7909	0.074*
C8	0.8861 (2)	−0.1704 (6)	0.8804 (2)	0.0627 (12)
H8	0.8632	−0.2133	0.9054	0.075*
C9	0.9612 (2)	−0.1545 (5)	0.9117 (2)	0.0492 (10)
C10	1.0075 (2)	−0.2088 (5)	0.9842 (2)	0.0539 (11)
C11	1.0151 (3)	−0.3321 (8)	1.0818 (3)	0.0950 (19)
H11	0.9925	−0.3833	1.1049	0.114*
C12	1.0885 (3)	−0.3126 (7)	1.1172 (3)	0.0819 (16)
H12	1.1146	−0.3505	1.1627	0.098*
C13	1.1217 (3)	−0.2369 (6)	1.0843 (3)	0.0729 (14)
H13	1.1712	−0.2208	1.1068	0.088*
C14	1.0811 (2)	−0.1837 (6)	1.0166 (2)	0.0653 (13)
H14	1.1029	−0.1315	0.9929	0.078*
N1	0.89698 (18)	0.0381 (4)	0.68029 (17)	0.0502 (8)
N2	0.9741 (2)	−0.2823 (6)	1.0161 (2)	0.0796 (13)
N3	0.99497 (17)	−0.0912 (4)	0.87806 (16)	0.0492 (9)
N4	0.95559 (17)	−0.0410 (4)	0.81159 (16)	0.0492 (8)
Cu1	1.0000	0.03557 (9)	0.7500	0.0529 (3)
O1W	1.0000	0.2776 (6)	0.7500	0.0893 (16)
C15	1.1403 (6)	0.6066 (12)	0.8757 (5)	0.092 (3)	0.82
S1	1.18594 (9)	0.50258 (19)	0.83360 (9)	0.0587 (4)	0.82
O2	1.1340 (4)	0.3927 (7)	0.7914 (3)	0.0942 (18)	0.82
O3	1.2477 (2)	0.4436 (6)	0.8942 (2)	0.0850 (13)	0.82
F2	1.1834 (4)	0.7126 (7)	0.9176 (3)	0.124 (2)	0.82
F3	1.0797 (3)	0.6670 (7)	0.8270 (4)	0.153 (2)	0.82
O1	1.2036 (2)	0.6180 (4)	0.79347 (19)	0.0887 (11)
F1	1.1262 (2)	0.5086 (5)	0.9157 (2)	0.1269 (15)
C15'	1.169 (2)	0.560 (5)	0.877 (2)	0.075 (12)*	0.18
S1'	1.1532 (6)	0.5444 (11)	0.7986 (5)	0.072 (2)*	0.18
O2'	1.0868 (19)	0.578 (4)	0.7664 (17)	0.155 (11)*	0.18
O3'	1.169 (2)	0.381 (6)	0.799 (2)	0.139 (17)*	0.18
F2'	1.1434 (16)	0.715 (4)	0.8872 (16)	0.107 (9)*	0.18
F3'	1.237 (2)	0.560 (4)	0.9289 (19)	0.183 (11)*	0.18
H1W	0.964 (2)	0.332 (6)	0.741 (4)	0.13 (3)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.055 (3)	0.063 (3)	0.052 (3)	0.009 (2)	0.019 (2)	0.004 (2)
C2	0.059 (3)	0.063 (3)	0.054 (3)	0.014 (2)	0.009 (2)	0.002 (2)
C3	0.048 (3)	0.073 (3)	0.069 (3)	0.011 (3)	0.008 (2)	−0.006 (3)
C4	0.044 (2)	0.074 (4)	0.062 (3)	−0.001 (2)	0.017 (2)	−0.007 (2)
C5	0.045 (2)	0.053 (3)	0.049 (2)	0.002 (2)	0.016 (2)	−0.0096 (19)
C6	0.041 (2)	0.055 (3)	0.049 (2)	0.000 (2)	0.0199 (19)	−0.009 (2)
C7	0.041 (2)	0.085 (4)	0.057 (3)	−0.008 (2)	0.021 (2)	−0.011 (2)
C8	0.052 (3)	0.080 (3)	0.059 (3)	−0.015 (3)	0.027 (2)	−0.006 (3)
C9	0.045 (2)	0.058 (3)	0.047 (2)	−0.002 (2)	0.023 (2)	−0.006 (2)
C10	0.052 (3)	0.061 (3)	0.051 (3)	−0.002 (2)	0.025 (2)	−0.001 (2)
C11	0.087 (4)	0.134 (6)	0.077 (4)	0.002 (4)	0.048 (3)	0.032 (4)
C12	0.082 (4)	0.101 (4)	0.059 (3)	0.010 (3)	0.027 (3)	0.016 (3)
C13	0.060 (3)	0.083 (4)	0.069 (3)	−0.003 (3)	0.022 (3)	0.010 (3)
C14	0.056 (3)	0.079 (3)	0.058 (3)	−0.009 (3)	0.023 (2)	0.007 (3)
N1	0.0452 (19)	0.054 (2)	0.0465 (19)	0.0034 (17)	0.0153 (17)	−0.0025 (18)
N2	0.066 (3)	0.110 (4)	0.069 (3)	−0.008 (3)	0.036 (2)	0.020 (2)
N3	0.0422 (19)	0.062 (2)	0.0424 (19)	−0.0037 (17)	0.0178 (17)	−0.0025 (17)
N4	0.0427 (19)	0.060 (2)	0.0421 (18)	−0.0029 (18)	0.0161 (16)	−0.0047 (17)
Cu1	0.0402 (4)	0.0692 (6)	0.0453 (4)	0.000	0.0154 (3)	0.000
O1W	0.060 (4)	0.056 (3)	0.132 (5)	0.000	0.025 (4)	0.000
C15	0.106 (8)	0.063 (6)	0.138 (8)	−0.008 (6)	0.082 (7)	−0.012 (5)
S1	0.0556 (9)	0.0612 (10)	0.0614 (9)	−0.0086 (8)	0.0277 (9)	−0.0031 (8)
O2	0.089 (4)	0.094 (4)	0.095 (4)	−0.035 (4)	0.036 (4)	−0.039 (3)
O3	0.061 (3)	0.098 (3)	0.091 (3)	0.023 (3)	0.029 (2)	0.039 (3)
F2	0.163 (6)	0.098 (4)	0.121 (4)	−0.050 (4)	0.072 (4)	−0.059 (3)
F3	0.085 (3)	0.141 (5)	0.214 (6)	0.045 (3)	0.049 (4)	−0.005 (4)
O1	0.089 (3)	0.096 (3)	0.090 (3)	−0.010 (2)	0.047 (2)	0.024 (2)
F1	0.153 (4)	0.133 (3)	0.138 (3)	−0.039 (3)	0.104 (3)	−0.010 (2)

Geometric parameters (Å, º) top

C1—N1	1.343 (5)	C12—H12	0.9300
C1—C2	1.381 (6)	C13—C14	1.381 (6)
C1—H1	0.9300	C13—H13	0.9300
C2—C3	1.375 (6)	C14—H14	0.9300
C2—H2	0.9300	N1—Cu1	1.984 (3)
C3—C4	1.377 (7)	N3—N4	1.348 (4)
C3—H3	0.9300	N4—Cu1	2.013 (3)
C4—C5	1.384 (6)	Cu1—N1ⁱ	1.984 (3)
C4—H4	0.9300	Cu1—N4ⁱ	2.013 (3)
C5—N1	1.342 (5)	Cu1—O1W	2.128 (6)
C5—C6	1.475 (6)	O1W—H1W	0.834 (10)
C6—N4	1.347 (5)	C15—F2	1.323 (10)
C6—C7	1.376 (6)	C15—F1	1.327 (9)
C7—C8	1.349 (6)	C15—F3	1.330 (12)
C7—H7	0.9300	C15—S1	1.808 (10)
C8—C9	1.402 (6)	S1—O2	1.426 (6)
C8—H8	0.9300	S1—O3	1.447 (4)
C9—N3	1.321 (5)	S1—O1	1.469 (4)
C9—C10	1.480 (6)	O1—S1'	1.273 (9)
C10—N2	1.327 (5)	F1—C15'	1.52 (4)
C10—C14	1.385 (6)	C15'—F3'	1.34 (4)
C11—N2	1.340 (6)	C15'—F2'	1.51 (5)
C11—C12	1.375 (7)	C15'—S1'	1.54 (4)
C11—H11	0.9300	S1'—O2'	1.27 (3)
C12—C13	1.351 (7)	S1'—O3'	1.47 (5)

N1—C1—C2	121.9 (4)	C5—N1—Cu1	115.5 (3)
N1—C1—H1	119.0	C1—N1—Cu1	125.3 (3)
C2—C1—H1	119.0	C10—N2—C11	116.8 (4)
C3—C2—C1	118.8 (4)	C9—N3—N4	118.6 (3)
C3—C2—H2	120.6	C6—N4—N3	121.4 (3)
C1—C2—H2	120.6	C6—N4—Cu1	115.2 (3)
C2—C3—C4	119.7 (4)	N3—N4—Cu1	123.0 (2)
C2—C3—H3	120.2	N1ⁱ—Cu1—N1	178.7 (2)
C4—C3—H3	120.2	N1ⁱ—Cu1—N4ⁱ	80.48 (13)
C3—C4—C5	118.8 (4)	N1—Cu1—N4ⁱ	99.95 (13)
C3—C4—H4	120.6	N1ⁱ—Cu1—N4	99.94 (13)
C5—C4—H4	120.6	N1—Cu1—N4	80.48 (13)
N1—C5—C4	121.8 (4)	N4ⁱ—Cu1—N4	140.9 (2)
N1—C5—C6	114.9 (4)	N1ⁱ—Cu1—O1W	89.37 (10)
C4—C5—C6	123.3 (4)	N1—Cu1—O1W	89.37 (11)
N4—C6—C7	120.7 (4)	N4ⁱ—Cu1—O1W	109.53 (10)
N4—C6—C5	113.5 (3)	N4—Cu1—O1W	109.53 (10)
C7—C6—C5	125.8 (4)	Cu1—O1W—H1W	125 (5)
C8—C7—C6	118.6 (4)	F2—C15—F1	107.7 (8)
C8—C7—H7	120.7	F2—C15—F3	111.3 (10)
C6—C7—H7	120.7	F1—C15—F3	110.8 (8)
C7—C8—C9	118.7 (4)	F2—C15—S1	109.9 (7)
C7—C8—H8	120.6	F1—C15—S1	107.2 (7)
C9—C8—H8	120.6	F3—C15—S1	109.9 (7)
N3—C9—C8	122.0 (4)	O2—S1—O3	115.9 (4)
N3—C9—C10	116.0 (3)	O2—S1—O1	114.8 (3)
C8—C9—C10	122.0 (4)	O3—S1—O1	114.2 (2)
N2—C10—C14	122.3 (4)	O2—S1—C15	103.7 (4)
N2—C10—C9	116.0 (4)	O3—S1—C15	101.3 (4)
C14—C10—C9	121.7 (4)	O1—S1—C15	104.6 (4)
N2—C11—C12	124.4 (5)	F3'—C15'—F2'	101 (3)
N2—C11—H11	117.8	F3'—C15'—F1	102 (3)
C12—C11—H11	117.8	F2'—C15'—F1	82 (3)
C13—C12—C11	118.2 (5)	F3'—C15'—S1'	122 (3)
C13—C12—H12	120.9	F2'—C15'—S1'	108 (3)
C11—C12—H12	120.9	F1—C15'—S1'	131 (3)
C12—C13—C14	119.0 (5)	O2'—S1'—O1	124.7 (18)
C12—C13—H13	120.5	O2'—S1'—O3'	115 (2)
C14—C13—H13	120.5	O1—S1'—O3'	107.6 (16)
C13—C14—C10	119.3 (4)	O2'—S1'—C15'	103 (2)
C13—C14—H14	120.3	O1—S1'—C15'	104.6 (17)
C10—C14—H14	120.3	O3'—S1'—C15'	99 (2)
C5—N1—C1	119.0 (4)

N1—C1—C2—C3	1.0 (7)	C5—C6—N4—N3	−177.4 (3)
C1—C2—C3—C4	0.3 (7)	C7—C6—N4—Cu1	173.3 (3)
C2—C3—C4—C5	−1.6 (7)	C5—C6—N4—Cu1	−5.2 (4)
C3—C4—C5—N1	1.7 (7)	C9—N3—N4—C6	−1.1 (6)
C3—C4—C5—C6	−176.4 (4)	C9—N3—N4—Cu1	−172.8 (3)
N1—C5—C6—N4	7.8 (5)	F2—C15—S1—O2	179.3 (8)
C4—C5—C6—N4	−173.9 (4)	F1—C15—S1—O2	62.5 (8)
N1—C5—C6—C7	−170.5 (4)	F3—C15—S1—O2	−58.0 (7)
C4—C5—C6—C7	7.7 (7)	F2—C15—S1—O3	58.8 (9)
N4—C6—C7—C8	0.3 (7)	F1—C15—S1—O3	−57.9 (7)
C5—C6—C7—C8	178.5 (4)	F3—C15—S1—O3	−178.4 (6)
C6—C7—C8—C9	−1.4 (7)	F2—C15—S1—O1	−60.1 (9)
C7—C8—C9—N3	1.4 (7)	F1—C15—S1—O1	−176.9 (6)
C7—C8—C9—C10	−178.1 (4)	F3—C15—S1—O1	62.6 (7)
N3—C9—C10—N2	−175.2 (4)	O2—S1—O1—S1'	44.7 (8)
C8—C9—C10—N2	4.3 (6)	O3—S1—O1—S1'	−178.1 (8)
N3—C9—C10—C14	4.9 (6)	C15—S1—O1—S1'	−68.2 (8)
C8—C9—C10—C14	−175.6 (4)	F2—C15—F1—C15'	−95 (4)
N2—C11—C12—C13	0.7 (10)	F3—C15—F1—C15'	143 (4)
C11—C12—C13—C14	−0.6 (8)	S1—C15—F1—C15'	23 (4)
C12—C13—C14—C10	0.2 (8)	C15—F1—C15'—F3'	124 (6)
N2—C10—C14—C13	0.2 (7)	C15—F1—C15'—F2'	25 (3)
C9—C10—C14—C13	−180.0 (4)	C15—F1—C15'—S1'	−83 (4)
C4—C5—N1—C1	−0.4 (6)	S1—O1—S1'—O2'	166 (3)
C6—C5—N1—C1	177.9 (4)	S1—O1—S1'—O3'	−54.9 (19)
C4—C5—N1—Cu1	174.9 (3)	S1—O1—S1'—C15'	49.2 (18)
C6—C5—N1—Cu1	−6.8 (5)	F3'—C15'—S1'—O2'	−168 (4)
C2—C1—N1—C5	−1.0 (6)	F2'—C15'—S1'—O2'	−52 (3)
C2—C1—N1—Cu1	−175.8 (3)	F1—C15'—S1'—O2'	44 (4)
C14—C10—N2—C11	−0.1 (8)	F3'—C15'—S1'—O1	−37 (4)
C9—C10—N2—C11	−179.9 (5)	F2'—C15'—S1'—O1	79 (3)
C12—C11—N2—C10	−0.4 (9)	F1—C15'—S1'—O1	175 (3)
C8—C9—N3—N4	−0.1 (6)	F3'—C15'—S1'—O3'	74 (4)
C10—C9—N3—N4	179.4 (4)	F2'—C15'—S1'—O3'	−170 (3)
C7—C6—N4—N3	1.1 (6)	F1—C15'—S1'—O3'	−74 (4)

Symmetry code: (i) −x+2, y, −z+3/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1···N3ⁱ	0.93	2.63	3.104 (5)	112
C2—H2···O3ⁱⁱ	0.93	2.55	3.376 (6)	149
C11—H11···F1ⁱⁱⁱ	0.93	2.55	3.334 (7)	142
C12—H12···O2^iv	0.93	2.59	3.443 (8)	152
O1W—H1W···O2ⁱ	0.83 (1)	1.91 (3)	2.710 (6)	161 (7)
C1—H1···N3ⁱ	0.93	2.63	3.104 (5)	112
C2—H2···O3ⁱⁱ	0.93	2.55	3.376 (6)	149
C11—H11···F1ⁱⁱⁱ	0.93	2.55	3.334 (7)	142
C12—H12···O2^iv	0.93	2.59	3.443 (8)	152
O1W—H1W···O2ⁱ	0.83 (1)	1.91 (3)	2.710 (6)	161 (7)

Symmetry codes: (i) −x+2, y, −z+3/2; (ii) x−1/2, −y+1/2, z−1/2; (iii) −x+2, −y, −z+2; (iv) x, −y, z+1/2.

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