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.

The title dinuclear copper(II) complex [Cu2(C18H16Br2N2O4S2)2] was prepared by direct synthesis of a dianionic Schiff base derived from 5-bromo-salicyl-aldehyde and cyste-amine. The discrete mol-ecules lie across inversion centers and crystallize with two di-methyl-formamide (DMF) mol-ecules of crystallization. The unique CuII ion is four-coordinated by two tetra-dentate Schiff base ligands in a distorted square-planar N2O2 environment. In the crystal, short inter-molecular S⋯Br contacts, weak C-H⋯O hydrogen bonds and intra- and inter-molecular π-π stacking inter-actions between rings of the ligand link the components into a two-dimensional network parallel to (010).

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 CuII complex whose structure is very similar to that of the already published compound (CSD refcode FEDCIB; Dhar et al., 2005 ▸).

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 CuII ion bonded to four donor sites of the ligand. Each CuII ion in the complex has a distorted square-planar CuN2O2 environment. The ligand fragments coordinated to CuII 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 CuII ion is comparable to that found in the aforementioned CuII 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 CuII 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 ▸).

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.

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) .

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.

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 ▸)

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%.

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
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[F 2 > 2σ(F 2)], wR(F 2), S	0.059, 0.135, 0.97
No. of reflections	6224
No. of parameters	309
H-atom treatment	H-atom parameters constrained
Δρmax, Δρmin (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 ▸).

Crystal structure: contains datablock(s) I. DOI: 10.1107/S2056989017015584/lh5856sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989017015584/lh5856Isup2.hkl

CCDC reference: 1582118

Additional supporting information: crystallographic information; 3D view; checkCIF report

[Cu2(C18H16Br2N2O4S2)2]·2C3H7NO	Z = 1
Mr = 1369.81	F(000) = 682
Triclinic, P1	Dx = 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

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

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(Fo2) + (0.032P)2] where P = (Fo2 + 2Fc2)/3
S = 0.97	(Δ/σ)max = 0.006
6224 reflections	Δρmax = 0.68 e Å−3
309 parameters	Δρmin = −0.77 e Å−3

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.

	x	y	z	Uiso*/Ueq
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*

	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)

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

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