Crystal structure of bis(μ2-4-bromo-2-[({2-[({2-[(5-bromo-2-oxidobenzylidene)amino]ethyl}sulfanyl)sulfonyl]ethyl}imino)methyl]phenolato)dicopper(II) dimethylformamide disolvate

Rusanova, J.A.; Bederak, D.

doi:10.1107/S2056989017015584

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ISSN: 2056-9890

Volume 73| Part 11| November 2017| Pages 1797-1800

https://doi.org/10.1107/S2056989017015584

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Crystal structure of bis(μ₂-4-bromo-2-[({2-[({2-[(5-bromo-2-oxidobenzylidene)amino]ethyl}sulfanyl)sulfonyl]ethyl}imino)methyl]phenolato)dicopper(II) dimethylformamide disolvate

Julia A. Rusanova ^a ^* and Dmytro Bederak ^a

^aDepartment of Chemistry, Taras Shevchenko National University of Kyiv, 64/13, Volodymyrska Street, Kyiv, 01601, Ukraine
^*Correspondence e-mail: rusanova.j@gmail.com

Edited by A. J. Lough, University of Toronto, Canada (Received 20 September 2017; accepted 25 October 2017; online 31 October 2017)

The title dinuclear copper(II) complex [Cu₂(C₁₈H₁₆Br₂N₂O₄S₂)₂] was prepared by direct synthesis of a dianionic Schiff base derived from 5-bromosalicylaldehyde and cysteamine. The discrete molecules lie across inversion centers and crystallize with two dimethylformamide (DMF) molecules of crystallization. The unique Cu^II ion is four-coordinated by two tetradentate Schiff base ligands in a distorted square-planar N₂O₂ environment. In the crystal, short intermolecular S⋯Br contacts, weak C—H⋯O hydrogen bonds and intra- and intermolecular π–π stacking interactions between rings of the ligand link the components into a two-dimensional network parallel to (010).

Keywords: crystal structure; dinuclear copper(II) complex; Schiff base; 5-bromosalicylaldehyde; cysteamine (2-aminoethanthiol).

CCDC reference: 1582118

1. Chemical context

Schiff bases and their metal complexes have been studied extensively over the past few decades and represent one of the most widely used organic compounds due to their synthetic flexibility and wide range of applications (Mitra et al.,1997 ; Bera et al.,1998 ; Prabhakaran et al., 2004 ). Spontaneous self-assembly of Schiff base ligands appears to be an extremely powerful tool for the construction of novel polynuclear compounds. Such complexes having sulfur-containing ligands are of considerable interest because of their diverse coordination modes and bridging ability. The formation and cleavage of disulfide bonds are known to be important for the biological activity of several sulfur-containing peptides and proteins (Gilbert et al.,1999 ; Jacob et al., 2003 ). It has been shown earlier that copper(II) complexes containing ligands having thioalkyl moieties are efficient DNA-cleaving agents on treatment with either a reducing agent or on photo-irradiation (Dhar et al., 2005 ). In these studies, we continued our investigations in the field of direct synthesis – an efficient method to obtain novel mixed-valence (Kovbasyuk et al., 1997 ) and heterometallic complexes with polynuclear (Vassilyeva et al., 1997 ; Kovbasyuk et al., 1998 ; Semenaka et al., 2010 ) and polymeric [Nesterova (Pryma) et al., 2004 , Nesterova et al., 2005 , 2008 ] structures. The conditions of direct synthesis influence the spontaneous self-assembly process enabling preparation of coordination compounds with commonly simple ligands e.g. aminoalcohols (Vassilyeva et al., 1997; Kovbasyuk et al.,1998; Semenaka et al., 2010), ethylenediamine or related compounds [Kokozay & Sienkiewicz, 1995 ; Nesterova (Pryma) et al., 2004, Nesterova et al., 2005, 2008]. The title compound was isolated in an attempt to prepare a heterometallic Cu/Mn complex with a Schiff base ligand, a product of condensation between 5-bromsalicylaldehyde and cysteamine, formed in situ in a methanol/dimethylformamide (DMF) mixture starting from zero-valent Cu and MnCl₂. We were unable to obtain the heterometallic complex, nevertheless we suppose that in this system MnCl₂ catalysed conversion of disulfides to thiosulfonates. Synthesis from the same starting materials with the same conditions without MnCl₂ leads to a Cu^II complex whose structure is very similar to that of the already published compound (CSD refcode FEDCIB; Dhar et al., 2005).

2. Structural commentary

The title compound is a discrete dinuclear complex that lies across an inversion center (Fig. 1). The formula unit also contains two DMF molecules of crystallization. The Schiff base acts as a tetradentate bridging ligand with each Cu^II ion bonded to four donor sites of the ligand. Each Cu^II ion in the complex has a distorted square-planar CuN₂O₂ environment. The ligand fragments coordinated to Cu^II ions are twisted, as defined by the dihedral angle of 22.6 (2)° between the mean planes of atoms O1/N1/C1/C7 and O2/N2/C8/C14. The thiosulfonate moiety is not involved in a metal–ligand interaction. The coordination geometry around the Cu^II ion is comparable to that found in the aforementioned Cu^II complex with a very similar ligand that results from the condensation between salicylaldehyde and cysteamine hydrochloride (CSD refcode FEDCIB; Dhar et al., 2005). The separation between the two symmetry-related Cu^II ions in the title complex is 4.6533 (15) Å. In general, all bonding parameters and the dimensions of the angles in the title complex are in good agreement with those encountered in related complexes (Dhar et al., 2005; Zhang et al., 2010 ). A fairly short intramolecular C—H⋯O hydrogen bond is observed (Table 1).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C14—H14⋯O5	0.95	2.32	3.257 (7)	167
C18—H18A⋯O5ⁱ	0.99	2.39	3.201 (7)	138
Symmetry code: (i) -x, -y+2, -z+1.

Figure 1
The molecular structure of the title compound with ellipsoids drawn at the 50% probability level. Cu1A and unlabelled atoms are generated by the symmetry code (−x + 1, −y + 2, −z + 1). For the sake of clarity, the DMF solvent molecules are not shown.

3. Supramolecular features

In the crystal, weak C—H⋯O hydrogen bonds (Table 1) connect the solvent DMF molecules to the complex molecules. In addition, short S⋯Br(x, y, −1 + x) contacts [3.4551 (18) Å] connect the complex molecules into chains along [001] (Fig. 2). Furthermore, π–π stacking interactions with a centroid–centroid distance of 3.513 (4) Å for Cg1⋯Cg3(−x, −y + 2, −z + 1) connect the chains into a two-dimensional network parallel to (010) (Fig. 3). There is an intramolecular π–π stacking interaction between the symmetry-related parts of the complex with a centroid–centroid distance of 3.774 (3) Å for Cg1⋯Cg2(−x + 1, −y + 2, −z + 1). Cg1, Cg2 and Cg3 are the centroids of the Cu1/O2/C8/C9/C14/N2, C1–C6 and C8–C13 rings, respectively.

Figure 2
The crystal packing of the title compound viewed along the c axis. Short S⋯Br contacts and weak C–H⋯O hydrogen bonds are shown as dashed lines. Only selected H atoms are shown.

Figure 3
The crystal packing of the title compound viewed along the b axis. Short S⋯Br contacts and weak C–H⋯O hydrogen bonds are shown as dashed lines. Only selected H atoms are shown.

4. Database survey

A search of the Cambridge Structural Database (Version 5.38; last update November 2016; Groom et al., 2016 ) for related complexes with an aminoethanethiol group gave 165 hits, including two closely related structures {bis[(μ²-sulfato)(6-salicylideneamino-3,4-dithiahexylammonium)copper(II)] and bis[μ²-N,N′-(3,4-dithiahexane-1,6-diyl)bis(salicylideneiminato)-N,N′,O,O′]dicopper(II)} with a disulfide moiety (Dhar et al., 2004 , 2005) and similar weak intermolecular π–π stacking interactions (Dhar et al., 2005). The value of the the S⋯Br contact in the title compound is in good agreement with those in related complexes (CSD refcodes WEMCAT and QELVIN; Salivon et al., 2006 , 2007 ; CSD refcode PODDAO; Xia et al., 2008 )

5. Synthesis and crystallization

A solution of KOH (0.12 g, 2 mmol) in minimum amount of methanol was added to a solution of aminoethanethiol hydrochloride (0.23g, 2 mmol) in methanol (5 ml) and stirred in an ice bath for 10 min. The white precipitate of solid KCl was removed by filtration and 5-bromosalicylaldehyde (0.402 g, 2 mmol) in dimethylformamide (10 ml) were added to the filtrate and stirred magnetically for 40 min. Copper powder (0.064 g, 1 mmol) and MnCl₂·4H₂O (0.198 g, 1 mmol) were added to the yellow solution of the Schiff base formed in situ, and the resulting deep green–brown solution was stirred magnetically and heated in air at 323–333 K for 2 h, resulting in a deep-brown precipitate. Crystals suitable for crystallographic study were grown from a saturated solution in DMF after successive addition of CH₂Cl₂. The crystals were filtered off, washed with dry i-PrOH and finally dried at room temperature (yield: 18%). The IR spectrum of the title compound (as KBr pellets) is consistent with the structural data. It shows all the characteristic functional group peaks in the range 4000–400 cm⁻¹: ν(CH) due to aromatic =C—H stretching at 3000–3100 cm⁻¹, the aromatic ring vibrations in the 1600–1400 cm⁻¹ region, weak S—S absorptions at 500–540 cm⁻¹ as well as absorbance at 1630 cm⁻¹ assigned to the azomethine ν(C=N) group and ν(SO) at 1330cm⁻¹. Analysis calculated for C₄₂H₄₆Br₄Cu₂N₆O₁₀S₄: C 36.83, H 3.38, N 6.14, S 9.36%; found: C 37.1, H 3.4, N 6.0, S 9.4%.

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. All hydrogen atoms were placed in calculated positions and refined in a riding-model approximation.: C—H = 0.95–0.99 Å with U_iso(H) = 1.5U_eq(C-methyl) and = 1.2U_eq(C) for other H atoms.

Table 2
Experimental details

Crystal data
Chemical formula	[Cu₂(C₁₈H₁₆Br₂N₂O₄S₂)₂]·2C₃H₇NO
M_r	1369.81
Crystal system, space group	Triclinic, P $[\overline{1}]$
Temperature (K)	173
a, b, c (Å)	10.9140 (4), 12.1104 (5), 12.2394 (5)
α, β, γ (°)	95.620 (2), 116.098 (2), 114.545 (2)
V (Å³)	1241.05 (9)
Z	1
Radiation type	Mo Kα
μ (mm⁻¹)	4.31
Crystal size (mm)	0.25 × 0.12 × 0.04

Data collection
Diffractometer	Bruker SMART APEXII
Absorption correction	Multi-scan (SADABS; Bruker, 2008 )
T_min, T_max	0.68, 0.85
No. of measured, independent and observed [I > 2σ(I)] reflections	16963, 6224, 3363
R_int	0.094
(sin θ/λ)_max (Å⁻¹)	0.671

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.059, 0.135, 0.97
No. of reflections	6224
No. of parameters	309
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.68, −0.77
Computer programs: SMART and SAINT (Bruker, 2008), SHELXT (Sheldrick, 2015a ), SHELXL2016/4 (Sheldrick, 2015b ), SHELXTL (Sheldrick, 2008 ) and publCIF (Westrip, 2010 ).

Supporting information

CCDC reference: 1582118

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989017015584/lh5856sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989017015584/lh5856Isup2.hkl

checkCIF report

Computing details top

Data collection: SMART (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2016/4 (Sheldrick, 2015b); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: publCIF (Westrip, 2010).

Bis(µ₂-4-bromo-2-[({2-[({2-[(5-bromo-2-oxidobenzylidene)amino]ethyl}sulfanyl)sulfonyl]ethyl}imino)methyl]phenolato)dicopper(II) dimethylformamide disolvate top

Crystal data top

[Cu₂(C₁₈H₁₆Br₂N₂O₄S₂)₂]·2C₃H₇NO	Z = 1
M_r = 1369.81	F(000) = 682
Triclinic, P1	D_x = 1.833 Mg m⁻³
a = 10.9140 (4) Å	Mo Kα radiation, λ = 0.71073 Å
b = 12.1104 (5) Å	Cell parameters from 1470 reflections
c = 12.2394 (5) Å	θ = 2.3–20.6°
α = 95.620 (2)°	µ = 4.31 mm⁻¹
β = 116.098 (2)°	T = 173 K
γ = 114.545 (2)°	Plate, brown
V = 1241.05 (9) Å³	0.25 × 0.12 × 0.04 mm

Data collection top

Bruker SMART APEXII diffractometer	6224 independent reflections
Radiation source: sealed tube	3363 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.094
φ and ω scans	θ_max = 28.5°, θ_min = 2.0°
Absorption correction: multi-scan (SADABS; Bruker, 2008)	h = −14→14
T_min = 0.68, T_max = 0.85	k = −16→16
16963 measured reflections	l = −16→15

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.059	H-atom parameters constrained
wR(F²) = 0.135	w = 1/[σ²(F_o²) + (0.032P)²] where P = (F_o² + 2F_c²)/3
S = 0.97	(Δ/σ)_max = 0.006
6224 reflections	Δρ_max = 0.68 e Å⁻³
309 parameters	Δρ_min = −0.77 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
BR1	0.45806 (7)	0.76624 (6)	−0.04584 (6)	0.03464 (19)
BR2	0.14178 (8)	1.24956 (7)	0.90146 (7)	0.0395 (2)
CU1	0.25760 (8)	0.99181 (7)	0.40372 (7)	0.02356 (19)
S1	0.30738 (18)	0.61966 (14)	0.56704 (15)	0.0279 (4)
S2	0.51135 (18)	0.64464 (15)	0.72196 (16)	0.0301 (4)
O1	0.3216 (5)	0.8784 (4)	0.3645 (4)	0.0286 (10)
O2	0.2484 (5)	1.1322 (4)	0.4727 (4)	0.0298 (10)
O3	0.2979 (5)	0.5785 (4)	0.4494 (4)	0.0412 (12)
O4	0.1851 (5)	0.5389 (4)	0.5884 (4)	0.0423 (12)
O5	0.0481 (6)	0.7837 (5)	0.7614 (5)	0.0486 (13)
N1	0.2568 (5)	1.0581 (4)	0.2600 (4)	0.0231 (11)
N2	0.1960 (5)	0.8973 (4)	0.5109 (4)	0.0206 (11)
N3	0.0268 (6)	0.6113 (5)	0.8280 (5)	0.0268 (12)
C1	0.3470 (6)	0.8562 (5)	0.2717 (5)	0.0241 (14)
C2	0.3903 (6)	0.7617 (5)	0.2610 (5)	0.0250 (14)
H2	0.398268	0.715302	0.319666	0.030*
C3	0.4202 (7)	0.7372 (6)	0.1676 (6)	0.0291 (15)
H3	0.449161	0.673889	0.162259	0.035*
C4	0.4097 (7)	0.8017 (6)	0.0809 (5)	0.0270 (15)
C5	0.3633 (6)	0.8916 (5)	0.0840 (5)	0.0255 (14)
H5	0.352938	0.934001	0.021899	0.031*
C6	0.3312 (6)	0.9203 (5)	0.1798 (5)	0.0203 (13)
C7	0.2823 (6)	1.0132 (5)	0.1779 (6)	0.0278 (14)
H7	0.267112	1.045352	0.108075	0.033*
C8	0.2247 (7)	1.1539 (6)	0.5672 (6)	0.0255 (14)
C9	0.1854 (6)	1.0633 (5)	0.6268 (5)	0.0216 (13)
C10	0.1596 (6)	1.0929 (5)	0.7270 (5)	0.0227 (13)
H10	0.130767	1.031398	0.766808	0.027*
C11	0.1767 (7)	1.2110 (6)	0.7658 (6)	0.0279 (15)
C12	0.2151 (7)	1.3013 (5)	0.7078 (6)	0.0277 (14)
H12	0.225837	1.382493	0.736110	0.033*
C13	0.2379 (7)	1.2733 (6)	0.6090 (6)	0.0298 (15)
H13	0.262727	1.335049	0.568479	0.036*
C14	0.1674 (6)	0.9392 (5)	0.5925 (5)	0.0200 (13)
H14	0.130912	0.882246	0.633566	0.024*
C15	0.1701 (6)	0.7651 (5)	0.4940 (5)	0.0220 (13)
H15A	0.135156	0.722038	0.404124	0.026*
H15B	0.086443	0.713221	0.510496	0.026*
C16	0.3263 (7)	0.7752 (5)	0.5895 (5)	0.0261 (14)
H16A	0.357001	0.813545	0.679209	0.031*
H16B	0.411204	0.832782	0.576874	0.031*
C17	0.6560 (7)	0.7086 (5)	0.6740 (6)	0.0287 (15)
H17A	0.700749	0.652070	0.675639	0.034*
H17B	0.601620	0.707533	0.584097	0.034*
C18	0.2096 (7)	1.1545 (6)	0.2377 (6)	0.0297 (15)
H18A	0.120633	1.133532	0.251267	0.036*
H18B	0.170671	1.149670	0.146472	0.036*
C21	0.0446 (7)	0.5001 (5)	0.8217 (6)	0.0374 (17)
H21A	−0.055679	0.423200	0.796506	0.056*
H21B	0.128827	0.513038	0.906755	0.056*
H21C	0.072770	0.488293	0.757429	0.056*
C23	0.0558 (7)	0.6851 (6)	0.7593 (6)	0.0289 (15)
H23	0.085171	0.659635	0.703306	0.035*
C24	−0.0258 (7)	0.6383 (6)	0.9115 (6)	0.0345 (16)
H24A	0.043606	0.642601	0.998719	0.052*
H24B	−0.135278	0.569401	0.877022	0.052*
H24C	−0.021486	0.721154	0.915536	0.052*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
BR1	0.0377 (4)	0.0455 (4)	0.0301 (4)	0.0223 (3)	0.0243 (3)	0.0116 (3)
BR2	0.0575 (5)	0.0446 (4)	0.0420 (4)	0.0336 (4)	0.0378 (4)	0.0178 (3)
CU1	0.0301 (4)	0.0239 (4)	0.0229 (4)	0.0149 (3)	0.0173 (3)	0.0104 (3)
S1	0.0320 (9)	0.0245 (8)	0.0316 (9)	0.0159 (7)	0.0186 (8)	0.0102 (7)
S2	0.0337 (9)	0.0331 (9)	0.0356 (9)	0.0204 (8)	0.0225 (8)	0.0212 (8)
O1	0.046 (3)	0.032 (2)	0.027 (2)	0.025 (2)	0.027 (2)	0.018 (2)
O2	0.043 (3)	0.026 (2)	0.033 (2)	0.020 (2)	0.027 (2)	0.014 (2)
O3	0.048 (3)	0.043 (3)	0.041 (3)	0.030 (2)	0.024 (2)	0.013 (2)
O4	0.039 (3)	0.032 (3)	0.063 (3)	0.019 (2)	0.029 (3)	0.023 (2)
O5	0.071 (3)	0.058 (3)	0.075 (4)	0.052 (3)	0.058 (3)	0.053 (3)
N1	0.029 (3)	0.022 (3)	0.023 (3)	0.012 (2)	0.018 (2)	0.007 (2)
N2	0.023 (3)	0.022 (3)	0.020 (2)	0.013 (2)	0.011 (2)	0.012 (2)
N3	0.032 (3)	0.025 (3)	0.029 (3)	0.015 (2)	0.019 (2)	0.011 (2)
C1	0.024 (3)	0.026 (3)	0.022 (3)	0.011 (3)	0.014 (3)	0.005 (3)
C2	0.034 (3)	0.025 (3)	0.022 (3)	0.020 (3)	0.015 (3)	0.012 (3)
C3	0.030 (3)	0.034 (4)	0.026 (3)	0.019 (3)	0.015 (3)	0.007 (3)
C4	0.025 (3)	0.039 (4)	0.020 (3)	0.012 (3)	0.019 (3)	0.006 (3)
C5	0.026 (3)	0.026 (3)	0.023 (3)	0.010 (3)	0.015 (3)	0.008 (3)
C6	0.021 (3)	0.023 (3)	0.018 (3)	0.011 (3)	0.012 (3)	0.008 (3)
C7	0.027 (3)	0.027 (3)	0.029 (3)	0.010 (3)	0.017 (3)	0.014 (3)
C8	0.025 (3)	0.027 (3)	0.028 (3)	0.012 (3)	0.018 (3)	0.009 (3)
C9	0.023 (3)	0.019 (3)	0.025 (3)	0.011 (3)	0.014 (3)	0.008 (3)
C10	0.024 (3)	0.023 (3)	0.023 (3)	0.011 (3)	0.015 (3)	0.011 (3)
C11	0.033 (3)	0.034 (4)	0.024 (3)	0.019 (3)	0.018 (3)	0.007 (3)
C12	0.036 (4)	0.018 (3)	0.032 (4)	0.015 (3)	0.019 (3)	0.008 (3)
C13	0.035 (4)	0.025 (3)	0.029 (3)	0.015 (3)	0.017 (3)	0.007 (3)
C14	0.019 (3)	0.024 (3)	0.023 (3)	0.010 (3)	0.015 (3)	0.012 (3)
C15	0.023 (3)	0.014 (3)	0.030 (3)	0.010 (3)	0.015 (3)	0.008 (3)
C16	0.030 (3)	0.023 (3)	0.025 (3)	0.015 (3)	0.014 (3)	0.010 (3)
C17	0.032 (3)	0.024 (3)	0.037 (4)	0.016 (3)	0.021 (3)	0.012 (3)
C18	0.034 (4)	0.036 (4)	0.033 (4)	0.023 (3)	0.022 (3)	0.019 (3)
C21	0.046 (4)	0.020 (3)	0.043 (4)	0.014 (3)	0.024 (4)	0.010 (3)
C23	0.033 (4)	0.039 (4)	0.033 (4)	0.023 (3)	0.025 (3)	0.019 (3)
C24	0.040 (4)	0.046 (4)	0.034 (4)	0.028 (3)	0.026 (3)	0.012 (3)

Geometric parameters (Å, º) top

BR1—C4	1.910 (5)	C7—H7	0.9500
BR2—C11	1.916 (6)	C8—C9	1.400 (8)
CU1—O2	1.883 (4)	C8—C13	1.411 (7)
CU1—O1	1.888 (4)	C9—C10	1.419 (7)
CU1—N2	1.979 (5)	C9—C14	1.424 (7)
CU1—N1	2.002 (5)	C10—C11	1.369 (8)
S1—O3	1.421 (4)	C10—H10	0.9500
S1—O4	1.442 (4)	C11—C12	1.381 (8)
S1—C16	1.786 (6)	C12—C13	1.376 (8)
S1—S2	2.063 (2)	C12—H12	0.9500
S2—C17	1.823 (6)	C13—H13	0.9500
O1—C1	1.311 (6)	C14—H14	0.9500
O2—C8	1.317 (6)	C15—C16	1.528 (7)
O5—C23	1.229 (7)	C15—H15A	0.9900
N1—C7	1.284 (7)	C15—H15B	0.9900
N1—C18	1.463 (7)	C16—H16A	0.9900
N2—C14	1.288 (6)	C16—H16B	0.9900
N2—C15	1.481 (6)	C17—C18ⁱ	1.517 (7)
N3—C23	1.324 (7)	C17—H17A	0.9900
N3—C21	1.438 (7)	C17—H17B	0.9900
N3—C24	1.445 (7)	C18—C17ⁱ	1.517 (7)
C1—C2	1.423 (8)	C18—H18A	0.9900
C1—C6	1.418 (8)	C18—H18B	0.9900
C2—C3	1.358 (7)	C21—H21A	0.9800
C2—H2	0.9500	C21—H21B	0.9800
C3—C4	1.371 (9)	C21—H21C	0.9800
C3—H3	0.9500	C23—H23	0.9500
C4—C5	1.382 (8)	C24—H24A	0.9800
C5—C6	1.415 (7)	C24—H24B	0.9800
C5—H5	0.9500	C24—H24C	0.9800
C6—C7	1.429 (8)

O2—CU1—O1	165.71 (17)	C9—C10—H10	120.3
O2—CU1—N2	92.47 (18)	C10—C11—C12	121.6 (5)
O1—CU1—N2	90.01 (18)	C10—C11—BR2	118.8 (5)
O2—CU1—N1	88.89 (18)	C12—C11—BR2	119.6 (4)
O1—CU1—N1	92.47 (17)	C13—C12—C11	119.8 (6)
N2—CU1—N1	164.48 (18)	C13—C12—H12	120.1
O3—S1—O4	120.1 (3)	C11—C12—H12	120.1
O3—S1—C16	108.6 (3)	C12—C13—C8	120.8 (6)
O4—S1—C16	108.1 (3)	C12—C13—H13	119.6
O3—S1—S2	110.1 (2)	C8—C13—H13	119.6
O4—S1—S2	103.0 (2)	N2—C14—C9	125.9 (5)
C16—S1—S2	106.0 (2)	N2—C14—H14	117.0
C17—S2—S1	103.1 (2)	C9—C14—H14	117.0
C1—O1—CU1	129.9 (4)	N2—C15—C16	108.4 (4)
C8—O2—CU1	129.4 (4)	N2—C15—H15A	110.0
C7—N1—C18	116.9 (5)	C16—C15—H15A	110.0
C7—N1—CU1	123.8 (4)	N2—C15—H15B	110.0
C18—N1—CU1	119.0 (4)	C16—C15—H15B	110.0
C14—N2—C15	115.4 (5)	H15A—C15—H15B	108.4
C14—N2—CU1	124.8 (4)	C15—C16—S1	110.9 (4)
C15—N2—CU1	119.7 (3)	C15—C16—H16A	109.5
C23—N3—C21	121.5 (5)	S1—C16—H16A	109.5
C23—N3—C24	121.4 (5)	C15—C16—H16B	109.5
C21—N3—C24	117.1 (5)	S1—C16—H16B	109.5
O1—C1—C2	118.7 (6)	H16A—C16—H16B	108.1
O1—C1—C6	123.2 (5)	C18ⁱ—C17—S2	112.3 (4)
C2—C1—C6	118.1 (5)	C18ⁱ—C17—H17A	109.1
C3—C2—C1	120.5 (6)	S2—C17—H17A	109.1
C3—C2—H2	119.7	C18ⁱ—C17—H17B	109.1
C1—C2—H2	119.7	S2—C17—H17B	109.1
C2—C3—C4	121.6 (6)	H17A—C17—H17B	107.9
C2—C3—H3	119.2	N1—C18—C17ⁱ	113.1 (5)
C4—C3—H3	119.2	N1—C18—H18A	109.0
C3—C4—C5	120.5 (5)	C17ⁱ—C18—H18A	109.0
C3—C4—BR1	119.8 (5)	N1—C18—H18B	109.0
C5—C4—BR1	119.8 (5)	C17ⁱ—C18—H18B	109.0
C4—C5—C6	119.8 (6)	H18A—C18—H18B	107.8
C4—C5—H5	120.1	N3—C21—H21A	109.5
C6—C5—H5	120.1	N3—C21—H21B	109.5
C5—C6—C1	119.4 (5)	H21A—C21—H21B	109.5
C5—C6—C7	117.5 (5)	N3—C21—H21C	109.5
C1—C6—C7	123.1 (5)	H21A—C21—H21C	109.5
N1—C7—C6	127.2 (6)	H21B—C21—H21C	109.5
N1—C7—H7	116.4	O5—C23—N3	125.9 (6)
C6—C7—H7	116.4	O5—C23—H23	117.0
O2—C8—C9	122.9 (5)	N3—C23—H23	117.0
O2—C8—C13	118.3 (6)	N3—C24—H24A	109.5
C9—C8—C13	118.7 (5)	N3—C24—H24B	109.5
C8—C9—C10	119.7 (5)	H24A—C24—H24B	109.5
C8—C9—C14	124.0 (5)	N3—C24—H24C	109.5
C10—C9—C14	116.3 (5)	H24A—C24—H24C	109.5
C11—C10—C9	119.4 (6)	H24B—C24—H24C	109.5
C11—C10—H10	120.3

Symmetry code: (i) −x+1, −y+2, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C14—H14···O5	0.95	2.32	3.257 (7)	167
C18—H18A···O5ⁱⁱ	0.99	2.39	3.201 (7)	138

Symmetry code: (ii) −x, −y+2, −z+1.

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