Crystal structure of bis­(μ₂-tetra­bromo­phthalato-κ²O¹:O²)bis[aqua(N,N,N′,N′-tetra­methyl­ethane-1,2-di­amine-κ²N,N′)copper(II)]

In the title complex, [Cu₂(C₈Br₄O₄)₂(C₆H₁₆N₂)₂(H₂O)₂], the Cu^II cation is chelated by a tetra­methyl­ethane-1,2-di­amine ligand and coordinated by a water mol­ecule as well as bridged by two tetra­bromo­phthalate anions in a distorted O₃N₂ trigonal–bipyramidal geometry. The two symmetry-related tetra­bromo­phthalate anions bridge the two Cu^II cations, forming a centrosymmetric dinuclear complex in which the Cu...Cu separation is 5.054 (2) Å. Intra­molecular classic O—H...O hydrogen bonds and weak C—H...O hydrogen bonds occur in the dinuclear mol­ecule. In the crystal, the mol­ecules are linked by weak C—H...Br and C—H...O inter­actions into supra­molecular chains propagating along the b-axis direction.

Key indicators

• Single-crystal X-ray study
• T = 100 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.016
• wR factor = 0.039
• Data-to-parameter ratio = 15.3

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT431_ALERT_2_C Short Inter HL..A  Contact Br4    ..  O2      ..       3.15 Ang.
PLAT761_ALERT_1_C CIF Contains no X-H Bonds ......................     Please Check
PLAT762_ALERT_1_C CIF Contains no X-Y-H or H-Y-H Angles ..........     Please Check
PLAT913_ALERT_3_C Missing # of Very Strong Reflections in FCF ....          1 Note

Alert level G
PLAT002_ALERT_2_G Number of Distance or Angle Restraints on AtSite          3 Note
PLAT232_ALERT_2_G Hirshfeld Test Diff (M-X)  Cu1    --  O5      ..        6.4 su
PLAT794_ALERT_5_G Tentative Bond Valency for Cu1     (II)    .....       2.04 Note
PLAT860_ALERT_3_G Number of Least-Squares Restraints .............          2 Note
PLAT910_ALERT_3_G Missing # of FCF Reflection(s) Below Th(Min) ...          1 Report

   0 ALERT level A = Most likely a serious problem - resolve or explain
   0 ALERT level B = A potentially serious problem, consider carefully
   4 ALERT level C = Check. Ensure it is not caused by an omission or oversight
   5 ALERT level G = General information/check it is not something unexpected

   2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   3 ALERT type 2 Indicator that the structure model may be wrong or deficient
   3 ALERT type 3 Indicator that the structure quality may be low
   0 ALERT type 4 Improvement, methodology, query or suggestion
   1 ALERT type 5 Informative message, check

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S1. Introduction

The self-assembly of metal complexes with benzene-multi­carboxyl­ate ligands remains an active area in coordination chemistry especially with copper due to the very wide structural diversity and inter­esting properties in magnetism, host-guest systems, porous material (Ene et al., 2009; Dorazco-González et al., 2013; Liang et al., 2004). Dinuclear copper(II) compounds have been used in magnetism, as biomimetic active sites in bioinorganic chemistry and in the design and synthesis of metallic networks (Lu et al., 2004). Herein we present a dinuclear copper complex synthesised by self-assembly between copper perchlorate, a aliphatic di­amine (tmen) and a bulky benzendi­carboxyl­ate (tetra­bromo­phthalate). The tittle compound represents the first example of copper complex with tetra­bromo­phthalate.

S2. Experimental

Compound. Cu(ClO₄)₂.6H₂O (0.1 mmol, 0.037 g) was added directly to a solution of tmen (0.1 mmol) in metanol-water solution 1:1 (8 mL). Then the dianion of tetra­bromo­phthalic acid (0.1 mmol, 0.055 g) in methanol-water solution 1:1 again (12 mL) was slowly added with stirring at room temperature, and a slight warming at 50 °C for 3 minutes.

S2.1. Synthesis and crystallization

Blue deep suitable crystals for diffraction X-ray were grown directly from solution by slow evaporation during 5 days. IR(KBr pellet), 3012 (w), 2971 (w), 2947 (w), 1741 (s), 1606 (m), 1396 (m), 1504 (w), 1459 (w), 1371 (s), 1315 (m), 1213 (m), 1096 (w), 1018 (w), 951 (w), 867 (w), 805 (w), 765 (w), 733 (w), 558 (w), 525 (w).

S2.2. Refinement

Water H atoms were placed in a difference Fourier map and positional parameters were refined, U_iso(H) = 1.2U_eq(O). Other H atoms were placed in calculated positions with C—H = 0.98–0.99 Å and refined in riding mode, U_iso(H) = 1.2U_eq(C) for methyl­ene H atoms and 1.5U_eq(C) for methyl H atoms.

S3. Results and discussion

The reaction between the aqua-complex [Cu(tmen)(H₂O)_x](ClO₄)₂ and potassium salt of tetra­bromo­phthalate in mixture ethanol gives the title compound in good yield (>94 %) as blue suitable crystals for X ray diffraction. The single-crystal X-ray analysis reveals that the compound is a neutral dinuclear centro-symmetric copper (II) complex which crystallizes in monoclinic crystal system, space group P21/n (Figure 1). The asymmetric unit contains a five-coordinate copper atom [Cu(N₂O₃)] with two sites occupied by di­amine and three sites by oxygen atoms from two carboxyl­ate groups and one molecule of water. The Addison tau-parameter has been used to describe the distortion around coordination geometry, τ = (difference between two largest angles/60 for five-coordinated metal centers allows the distinction between trigonal-bipyramidal (ideally τ = 1) and square-pyramidal (ideally τ = 0). In this context, the coordination geometry of complex is distorted trigonal-bypiramide, τ = 0.68. The distance Cu ··· Cu is 5.054 (2) Å and a macrocycle is formed by 14 atoms containing two TBr-phthalate-bridge ligands. The combination of copper(II) with multi-carb­oxy­lic acids has formed one of the largest subgroups in metal-organic compounds and despite this there are few examples of coordination complex with 1,2,3,4,-tetra­halogenated benzenes among these only with tetra­chloro­phthalate have been reported (Hong & You, 2004; Yang et al., 2002). The present compound represents the first example with tetra­bromo­phthalate.

Related literature

For the crystal structures of related copper(II) complexes with tetramethylethylene and carboxylate ligands; see: Ene et al. (2009); Dorazco-González et al. (2013); Liang et al. (2004). For the synthesis of one-dimensional coordination polymers, see: Hong & You (2004); Colacio et al. (2009); Rodpun et al. (2015); Yang et al. (2002). For their magnetic properties, see: Ene et al. (2009); Kozlevčar et al. (2004). For supramolecular polymorphism, see: Dorazco-González et al. (2013); Stibrany et al. (2009); Aakeröy et al. (2003); Valdés-Martínez et al. (1993); Julve et al. (1984). For molecular recognition and sensing; see: Dorazco-González & Yatsimirsky (2010); Mendy et al. (2010).

Structure description

The self-assembly of metal complexes with benzene-multi­carboxyl­ate ligands remains an active area in coordination chemistry especially with copper due to the very wide structural diversity and inter­esting properties in magnetism, host-guest systems, porous material (Ene et al., 2009; Dorazco-González et al., 2013; Liang et al., 2004). Dinuclear copper(II) compounds have been used in magnetism, as biomimetic active sites in bioinorganic chemistry and in the design and synthesis of metallic networks (Lu et al., 2004). Herein we present a dinuclear copper complex synthesised by self-assembly between copper perchlorate, a aliphatic di­amine (tmen) and a bulky benzendi­carboxyl­ate (tetra­bromo­phthalate). The tittle compound represents the first example of copper complex with tetra­bromo­phthalate.

Compound. Cu(ClO₄)₂.6H₂O (0.1 mmol, 0.037 g) was added directly to a solution of tmen (0.1 mmol) in metanol-water solution 1:1 (8 mL). Then the dianion of tetra­bromo­phthalic acid (0.1 mmol, 0.055 g) in methanol-water solution 1:1 again (12 mL) was slowly added with stirring at room temperature, and a slight warming at 50 °C for 3 minutes.

The reaction between the aqua-complex [Cu(tmen)(H₂O)_x](ClO₄)₂ and potassium salt of tetra­bromo­phthalate in mixture ethanol gives the title compound in good yield (>94 %) as blue suitable crystals for X ray diffraction. The single-crystal X-ray analysis reveals that the compound is a neutral dinuclear centro-symmetric copper (II) complex which crystallizes in monoclinic crystal system, space group P21/n (Figure 1). The asymmetric unit contains a five-coordinate copper atom [Cu(N₂O₃)] with two sites occupied by di­amine and three sites by oxygen atoms from two carboxyl­ate groups and one molecule of water. The Addison tau-parameter has been used to describe the distortion around coordination geometry, τ = (difference between two largest angles/60 for five-coordinated metal centers allows the distinction between trigonal-bipyramidal (ideally τ = 1) and square-pyramidal (ideally τ = 0). In this context, the coordination geometry of complex is distorted trigonal-bypiramide, τ = 0.68. The distance Cu ··· Cu is 5.054 (2) Å and a macrocycle is formed by 14 atoms containing two TBr-phthalate-bridge ligands. The combination of copper(II) with multi-carb­oxy­lic acids has formed one of the largest subgroups in metal-organic compounds and despite this there are few examples of coordination complex with 1,2,3,4,-tetra­halogenated benzenes among these only with tetra­chloro­phthalate have been reported (Hong & You, 2004; Yang et al., 2002). The present compound represents the first example with tetra­bromo­phthalate.

For the crystal structures of related copper(II) complexes with tetramethylethylene and carboxylate ligands; see: Ene et al. (2009); Dorazco-González et al. (2013); Liang et al. (2004). For the synthesis of one-dimensional coordination polymers, see: Hong & You (2004); Colacio et al. (2009); Rodpun et al. (2015); Yang et al. (2002). For their magnetic properties, see: Ene et al. (2009); Kozlevčar et al. (2004). For supramolecular polymorphism, see: Dorazco-González et al. (2013); Stibrany et al. (2009); Aakeröy et al. (2003); Valdés-Martínez et al. (1993); Julve et al. (1984). For molecular recognition and sensing; see: Dorazco-González & Yatsimirsky (2010); Mendy et al. (2010).

Synthesis and crystallization

Blue deep suitable crystals for diffraction X-ray were grown directly from solution by slow evaporation during 5 days. IR(KBr pellet), 3012 (w), 2971 (w), 2947 (w), 1741 (s), 1606 (m), 1396 (m), 1504 (w), 1459 (w), 1371 (s), 1315 (m), 1213 (m), 1096 (w), 1018 (w), 951 (w), 867 (w), 805 (w), 765 (w), 733 (w), 558 (w), 525 (w).

Refinement details

Water H atoms were placed in a difference Fourier map and positional parameters were refined, U_iso(H) = 1.2U_eq(O). Other H atoms were placed in calculated positions with C—H = 0.98–0.99 Å and refined in riding mode, U_iso(H) = 1.2U_eq(C) for methyl­ene H atoms and 1.5U_eq(C) for methyl H atoms.

Computing details

Data collection: APEX2 (Bruker, 2012); cell refinement: SAINT (Bruker, 2012); data reduction: SAINT (Bruker, 2012); program(s) used to solve structure: SHELXS97 (Sheldrick 2008); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures

	Fig. 1. The structure with displacement ellipsoids drawn at the 30% probability level and H atoms shown as small spheres of arbitrary radii.
	Fig. 2. View of interactions in the crystal.

Bis(µ₂-tetrabromophthalato-κ²O¹:O²)bis[aqua(N,N,N',N'-tetramethylethane-1,2-diamine-κ²N,N')copper(II)]

Crystal data

[Cu2(C8Br4O4)2(C6H16N2)2(H2O)2]	F(000) = 1300
Mr = 1354.97	Dx = 2.207 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 9.0961 (2) Å	Cell parameters from 9880 reflections
b = 9.2281 (2) Å	θ = 2.4–25.7°
c = 24.4026 (7) Å	µ = 8.94 mm^−1
β = 95.4910 (6)°	T = 100 K
V = 2038.95 (9) Å^3	Prism, blue
Z = 2	0.25 × 0.15 × 0.08 mm

Data collection

Bruker APEXII CCD diffractometer	3739 independent reflections
Radiation source: Incoatec ImuS	3547 reflections with I > 2σ(I)
Mirrors monochromator	Rint = 0.019
ω scans	θmax = 25.4°, θmin = 2.3°
Absorption correction: multi-scan (SADABS; Bruker, 2012)	h = −10→10
Tmin = 0.442, Tmax = 0.745	k = −11→11
17394 measured reflections	l = −29→29

Refinement

Refinement on F^2	2 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.016	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.039	w = 1/[σ^2(Fo^2) + (0.0162P)^2 + 2.4857P] where P = (Fo^2 + 2Fc^2)/3
S = 1.07	(Δ/σ)max = 0.002
3739 reflections	Δρmax = 0.80 e Å^−3
245 parameters	Δρmin = −0.41 e Å^−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
Br1	0.34950 (2)	0.30336 (3)	0.71377 (2)	0.01607 (6)
Br2	0.62992 (3)	0.47283 (3)	0.78249 (2)	0.02118 (6)
Br3	0.95418 (3)	0.47738 (3)	0.73268 (2)	0.01934 (6)
Br4	1.00627 (2)	0.27574 (3)	0.62483 (2)	0.01671 (6)
Cu1	0.32727 (3)	−0.12890 (3)	0.55897 (2)	0.01122 (6)
O1	0.45257 (16)	0.02014 (16)	0.59851 (6)	0.0143 (3)
O2	0.32220 (16)	0.22748 (16)	0.58559 (6)	0.0135 (3)
O3	0.65378 (16)	0.19336 (16)	0.52428 (6)	0.0132 (3)
O4	0.79787 (17)	0.02815 (16)	0.57131 (6)	0.0144 (3)
O5	0.17319 (17)	0.01324 (17)	0.53376 (6)	0.0133 (3)
H5A	0.205 (3)	0.091 (2)	0.5454 (10)	0.016*
H5B	0.179 (3)	0.014 (3)	0.5006 (7)	0.016*
N1	0.4780 (2)	−0.2831 (2)	0.58485 (7)	0.0153 (4)
N2	0.1667 (2)	−0.2787 (2)	0.57861 (8)	0.0180 (4)
C1	0.5567 (2)	0.2309 (2)	0.63834 (8)	0.0102 (4)
C2	0.5382 (2)	0.3046 (2)	0.68693 (8)	0.0108 (4)
C3	0.6563 (2)	0.3755 (2)	0.71631 (8)	0.0119 (4)
C4	0.7951 (2)	0.3723 (2)	0.69622 (8)	0.0123 (4)
C5	0.8155 (2)	0.2926 (2)	0.64905 (8)	0.0114 (4)
C6	0.6979 (2)	0.2221 (2)	0.62005 (8)	0.0101 (4)
C7	0.4303 (2)	0.1547 (2)	0.60456 (8)	0.0104 (4)
C8	0.7190 (2)	0.1388 (2)	0.56745 (8)	0.0112 (4)
C9	0.3941 (3)	−0.4200 (2)	0.57551 (10)	0.0206 (5)
H9A	0.4525	−0.5017	0.5925	0.025*
H9B	0.3757	−0.4388	0.5355	0.025*
C10	0.2483 (3)	−0.4091 (3)	0.60056 (11)	0.0267 (6)
H10A	0.1885	−0.4970	0.5915	0.032*
H10B	0.2665	−0.4022	0.6411	0.032*
C11	0.6075 (3)	−0.2849 (3)	0.55284 (11)	0.0221 (5)
H11A	0.5747	−0.2979	0.5137	0.033*
H11B	0.6728	−0.3651	0.5655	0.033*
H11C	0.6611	−0.1931	0.5581	0.033*
C12	0.5316 (3)	−0.2652 (3)	0.64386 (10)	0.0295 (6)
H12A	0.5925	−0.1776	0.6485	0.044*
H12B	0.5908	−0.3497	0.6564	0.044*
H12C	0.4470	−0.2564	0.6657	0.044*
C13	0.0750 (3)	−0.2171 (3)	0.61946 (10)	0.0270 (6)
H13A	0.0211	−0.1327	0.6036	0.040*
H13B	0.1384	−0.1874	0.6523	0.040*
H13C	0.0045	−0.2903	0.6297	0.040*
C14	0.0693 (3)	−0.3163 (3)	0.52836 (10)	0.0244 (5)
H14A	0.0251	−0.2277	0.5119	0.037*
H14B	−0.0091	−0.3815	0.5381	0.037*
H14C	0.1275	−0.3644	0.5019	0.037*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Br1	0.01284 (11)	0.02352 (12)	0.01199 (11)	0.00231 (9)	0.00185 (8)	−0.00263 (9)
Br2	0.02459 (13)	0.02531 (13)	0.01399 (11)	−0.00390 (10)	0.00359 (9)	−0.01160 (9)
Br3	0.02013 (12)	0.02323 (13)	0.01411 (11)	−0.01075 (9)	−0.00115 (8)	−0.00597 (9)
Br4	0.01220 (11)	0.02355 (13)	0.01461 (11)	−0.00571 (9)	0.00253 (8)	−0.00292 (9)
Cu1	0.01308 (13)	0.00842 (13)	0.01167 (13)	−0.00056 (10)	−0.00133 (10)	−0.00121 (10)
O1	0.0144 (8)	0.0097 (8)	0.0178 (8)	−0.0008 (6)	−0.0039 (6)	−0.0018 (6)
O2	0.0123 (8)	0.0125 (8)	0.0151 (8)	0.0011 (6)	−0.0019 (6)	−0.0023 (6)
O3	0.0172 (8)	0.0142 (8)	0.0080 (7)	0.0012 (6)	0.0002 (6)	−0.0017 (6)
O4	0.0168 (8)	0.0129 (8)	0.0130 (7)	0.0032 (6)	−0.0005 (6)	−0.0012 (6)
O5	0.0160 (8)	0.0127 (8)	0.0109 (7)	−0.0013 (6)	−0.0006 (6)	−0.0043 (6)
N1	0.0210 (10)	0.0108 (9)	0.0136 (9)	−0.0004 (8)	−0.0011 (7)	0.0003 (7)
N2	0.0196 (10)	0.0167 (10)	0.0185 (10)	−0.0029 (8)	0.0052 (8)	0.0036 (8)
C1	0.0138 (10)	0.0060 (10)	0.0103 (10)	0.0006 (8)	−0.0015 (8)	0.0030 (8)
C2	0.0125 (10)	0.0084 (10)	0.0116 (10)	0.0017 (8)	0.0023 (8)	0.0020 (8)
C3	0.0190 (11)	0.0095 (10)	0.0070 (10)	0.0005 (9)	0.0003 (8)	−0.0012 (8)
C4	0.0160 (11)	0.0100 (10)	0.0100 (10)	−0.0037 (9)	−0.0040 (8)	0.0007 (8)
C5	0.0131 (10)	0.0115 (10)	0.0100 (10)	−0.0017 (8)	0.0032 (8)	0.0027 (8)
C6	0.0148 (11)	0.0084 (10)	0.0069 (10)	0.0001 (8)	−0.0003 (8)	0.0031 (8)
C7	0.0122 (10)	0.0117 (11)	0.0074 (9)	−0.0017 (8)	0.0022 (8)	−0.0004 (8)
C8	0.0104 (10)	0.0117 (11)	0.0116 (10)	−0.0047 (9)	0.0025 (8)	−0.0009 (8)
C9	0.0255 (13)	0.0097 (11)	0.0260 (13)	−0.0008 (10)	0.0003 (10)	0.0021 (9)
C10	0.0288 (14)	0.0165 (12)	0.0357 (15)	−0.0019 (11)	0.0077 (11)	0.0117 (11)
C11	0.0169 (12)	0.0180 (12)	0.0311 (14)	0.0039 (10)	0.0009 (10)	0.0069 (10)
C12	0.0426 (16)	0.0238 (14)	0.0194 (13)	0.0077 (12)	−0.0113 (11)	0.0013 (10)
C13	0.0276 (14)	0.0328 (15)	0.0228 (13)	0.0022 (12)	0.0140 (11)	0.0060 (11)
C14	0.0196 (12)	0.0228 (13)	0.0307 (14)	−0.0104 (10)	0.0010 (10)	−0.0042 (11)

Geometric parameters (Å, º)

Br1—C2	1.895 (2)	N1—C9	1.482 (3)
Br2—C3	1.883 (2)	N1—C12	1.485 (3)
Br3—C4	1.892 (2)	N2—C13	1.473 (3)
Br4—C5	1.893 (2)	N2—C14	1.484 (3)
Cu1—O5	1.9744 (16)	N2—C10	1.487 (3)
Cu1—O1	1.9776 (15)	C1—C2	1.391 (3)
Cu1—N1	2.0340 (19)	C1—C6	1.402 (3)
Cu1—N2	2.0995 (19)	C1—C7	1.521 (3)
Cu1—O3^i	2.1396 (14)	C2—C3	1.396 (3)
O1—C7	1.269 (3)	C3—C4	1.398 (3)
O2—C7	1.243 (3)	C4—C5	1.393 (3)
O3—C8	1.263 (3)	C5—C6	1.387 (3)
O3—Cu1^i	2.1396 (14)	C6—C8	1.524 (3)
O4—C8	1.246 (3)	C9—C10	1.516 (3)
N1—C11	1.475 (3)
O5—Cu1—O1	92.80 (6)	C2—C1—C7	122.73 (19)
O5—Cu1—N1	177.14 (7)	C6—C1—C7	117.98 (18)
O1—Cu1—N1	89.71 (7)	C1—C2—C3	121.13 (19)
O5—Cu1—N2	91.13 (7)	C1—C2—Br1	118.64 (16)
O1—Cu1—N2	136.68 (7)	C3—C2—Br1	120.21 (16)
N1—Cu1—N2	86.10 (8)	C2—C3—C4	119.12 (19)
O5—Cu1—O3^i	90.46 (6)	C2—C3—Br2	120.61 (16)
O1—Cu1—O3^i	124.17 (6)	C4—C3—Br2	120.27 (15)
N1—Cu1—O3^i	89.26 (7)	C5—C4—C3	119.80 (19)
N2—Cu1—O3^i	98.90 (7)	C5—C4—Br3	120.18 (16)
C7—O1—Cu1	130.25 (14)	C3—C4—Br3	120.02 (15)
C8—O3—Cu1^i	127.37 (14)	C6—C5—C4	120.80 (19)
C11—N1—C9	109.53 (18)	C6—C5—Br4	119.17 (16)
C11—N1—C12	108.07 (19)	C4—C5—Br4	120.01 (16)
C9—N1—C12	111.12 (19)	C5—C6—C1	119.73 (19)
C11—N1—Cu1	113.14 (14)	C5—C6—C8	120.89 (19)
C9—N1—Cu1	103.09 (14)	C1—C6—C8	119.35 (18)
C12—N1—Cu1	111.86 (15)	O2—C7—O1	127.93 (19)
C13—N2—C14	108.52 (19)	O2—C7—C1	118.85 (18)
C13—N2—C10	111.32 (19)	O1—C7—C1	113.20 (18)
C14—N2—C10	110.3 (2)	O4—C8—O3	127.65 (19)
C13—N2—Cu1	110.61 (15)	O4—C8—C6	117.88 (18)
C14—N2—Cu1	109.81 (14)	O3—C8—C6	114.47 (18)
C10—N2—Cu1	106.31 (14)	N1—C9—C10	109.8 (2)
C2—C1—C6	119.26 (19)	N2—C10—C9	109.52 (19)
C6—C1—C2—C3	3.0 (3)	C2—C1—C6—C8	178.75 (18)
C7—C1—C2—C3	−178.78 (19)	C7—C1—C6—C8	0.5 (3)
C6—C1—C2—Br1	−175.50 (15)	Cu1—O1—C7—O2	−1.5 (3)
C7—C1—C2—Br1	2.7 (3)	Cu1—O1—C7—C1	−179.92 (13)
C1—C2—C3—C4	0.2 (3)	C2—C1—C7—O2	60.4 (3)
Br1—C2—C3—C4	178.71 (15)	C6—C1—C7—O2	−121.4 (2)
C1—C2—C3—Br2	−179.24 (15)	C2—C1—C7—O1	−121.0 (2)
Br1—C2—C3—Br2	−0.7 (2)	C6—C1—C7—O1	57.2 (2)
C2—C3—C4—C5	−3.3 (3)	Cu1^i—O3—C8—O4	−6.9 (3)
Br2—C3—C4—C5	176.09 (16)	Cu1^i—O3—C8—C6	172.16 (13)
C2—C3—C4—Br3	176.10 (15)	C5—C6—C8—O4	66.3 (3)
Br2—C3—C4—Br3	−4.5 (2)	C1—C6—C8—O4	−115.6 (2)
C3—C4—C5—C6	3.3 (3)	C5—C6—C8—O3	−112.8 (2)
Br3—C4—C5—C6	−176.16 (16)	C1—C6—C8—O3	65.3 (3)
C3—C4—C5—Br4	−175.18 (16)	C11—N1—C9—C10	−170.79 (19)
Br3—C4—C5—Br4	5.4 (2)	C12—N1—C9—C10	69.9 (2)
C4—C5—C6—C1	0.0 (3)	Cu1—N1—C9—C10	−50.1 (2)
Br4—C5—C6—C1	178.46 (15)	C13—N2—C10—C9	−148.7 (2)
C4—C5—C6—C8	178.09 (19)	C14—N2—C10—C9	90.8 (2)
Br4—C5—C6—C8	−3.4 (3)	Cu1—N2—C10—C9	−28.2 (2)
C2—C1—C6—C5	−3.1 (3)	N1—C9—C10—N2	54.4 (3)
C7—C1—C6—C5	178.62 (18)

Symmetry code: (i) −x+1, −y, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O5—H5A···O2	0.81 (2)	1.87 (2)	2.649 (2)	161 (2)
O5—H5B···O4^i	0.82 (2)	1.83 (2)	2.630 (2)	167 (3)
C10—H10A···Br4^ii	0.99	2.84	3.729 (3)	150
C11—H11C···O4	0.98	2.40	3.376 (3)	179
C13—H13A···O4^iii	0.98	2.58	3.506 (3)	158

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