(4-Bromo-2-formyl­phenolato)­perchlorato­(1,10-phenanthroline)­copper(II)

In the title copper(II) compound, [Cu(C₇H₄BrO₂)(ClO₄)(C₁₂H₈N₂)], the Cu atom is five-coordinated in a distorted square-pyramidal geometry by the N- and O-donors of 4-bromo-2-formyl­phenolate, 1,10-phenanthroline and perchlorate. Pairs of complexes are linked together by Cu...O(phenolate) and [pi]-[pi] stacking inter­actions between 4-bromo-2-formyl­phenolate and 1,10-phenanthroline. Along the crystallographic a axis, the dimers are linked by hydrogen bonds between a perchlorate O atom and a 4-bromo-2-formyl­phenolate H atom, and by further [pi]-[pi] stacking inter­actions. Hydrogen bonding between the Br atom and a 1,10-phenanthroline H atom takes place between the stacks of dimers.

S1. Comment

Studies of complexes containing salicylaldehyde and its derivatives have been reported by Janzen et al. (2004) and other groups. The five-coordinated Cu^II complexes have been extensively investigated and the relationship between their structures and reactivities is of major importance. In the light of conflicting opinions on how best to estimate the geometry of five-coordinated Cu^II complexes, Addison et al. (1984) introduced a very useful parameter, τ, which provides a measure of the degree of SP (square-pyramidal) versus TBP (trigonal–bipyramidal) geometry adopted by five-coordinate Cu^II complexes.

We report here the synthesis and structure of the title complex, (I). This is the first reported crystal structure of a complex involving Cu²⁺, 1,10-phenanthroline, 4-bromo-2-formylphenolate and ClO₄⁻. Elemental analysis data for this compound are in good agreement with the experimental crystal pattern. The larger of the basal angles, O2—Cu1—N2, is 176.33 (17)° and the remaining angle, O1—Cu1—N1, is 170.43 (17)°. According to Addison's rule, we calculated the parameter τ to be 0.098. Thus, we can conclude that the complex in this paper will show a square-pyramidal coordination geometry.

In complex (I), the Cu^II ion is coordinated by phenolate atom O1, carbonyl atom O2, 1,10-phenanthroline atoms N1 and N2, and atom O3 of the ClO₄⁻ anion. Atom O3 lies in the axial position, and the equatorial positions are occupied by the other four donor atoms. The bond distances for Cu1—N1 and Cu1—N2 of 2.007 (4) and 1.999 (4) Å, respectively, are nearly as long as those found for the similar auxiliary ligand 1,10-phenanthroline (Youngme et al. 2005). The bond lengths for Cu1—O1 and Cu1—O2 are 1.898 (4) and 1.995 (4) Å, respectively, which are in the range of those reported for similar copper(II) complexes [1.953 (2) and 1.952 (2) Å; Yang et al., 2004]. The Cu1—O3 bond distance of 2.423 (11) Å is in the range observed in analogous compounds [2.381 (4) and 2.559 (4) Å; Plieger et al., 2004]. The larger angles around Cu are near 180° (see above), so the ligands form a satisfactory N₂O₂ square, with atom O3 inhabiting the axial position. In this way, a distorted square pyramid is formed (Fig. 1).

It is interesting that there are weak Cu···O interactions, π–π stacking interactions and intermolecular hydrogen bonds in this complex. There are no intramolecular hydrogen bonds in the structure of (I). The CH groups participate in a hydrogen bond with an O atom of the ClO₄⁻ anion, forming a C—H···O hydrogen bond, with the C—H···O angle being 161.6°. The Br atom and an H atom of the 1,10-phenanthroline ligand form a weaker hydrogen bond, with the C—H···Br angle being 135.8°. Adjacent dimers are then linked by face-to-face π–π stacking interactions between 4-bromo-2-formylphenolate and 1,10-phenanthroline ligands, the shortest centroid–centriod contact being 3.628 Å, which is in the range of average values in π–π stacking interactions (Janiak, 2000). In addition, the Cu···O(phenolate) distance in (I) is 2.820 Å, which is in the range of values in the previous literature [Lower limit?–3.076 (4) Å; Yang et al., 2004]. Dimers based on above-mentioned Cu···O weak interaction and π–π stacking interaction are linked along the crystallographic a axis by hydrogen bonding (Fig. 2).

The solid-state IR spectrum of (I) in the region 450–4000 cm⁻¹ is in agreement with the X-ray diffraction data with respect to the mode of coordination. The absorption bands in the spectrum of (I) were red-shifted by 10–20 cm⁻¹ relative to the bands in the spectrum of the free ligand. The two shortest absorption bands in the UV–vis spectrum of the free ligand, at about 230 nm, characterized by high molecular absorption coeffcients, can be attributed to the π–π* transition of the ligands. The longest wavelength band, at about 650 nm, can be characterized by a d–d transition of the metal ion. This case is very similar to those observed for the structurally well characterized square-bipyramidal geometry (Lever, 1984).

S2. Experimental

For the preparation of the title compound, triethylamine (0.1 mmol) was added to a solution of 5-bromosalicylaldimine (0.0220 g, 0.1 mmol) in methanol (10 ml). After stirring the mixture for 10 min, 1,10-phenanthroline (0.0198 g, 0.1 mmol) was added. To the resulting solution, a methanolic solution (5 ml) of Cu(ClO₄)₂·6H₂O (0.0370 g, 0.1 mmol) was added with stirring at room temperature. The solution was then heated and stirred for 2 h. After about 10 d, green block crystals of (I) suitable for X-ray analysis appeared. These were collected by filtration, washed with H₂O and dried over silica gel (yield 58%). Analysis, calculated for C₁₉H₁₂BrClCuN₂O₆: C 42.01, H 2.23, N 5.16%; found: C 42.96, H 2.16, N 5.82%.

S3. Refinement

H atoms were included in calculated positions and refined as riding on their parent atoms, with C—H distances in the range 0.93–0.98 Å, and with U_iso(H) = 1.2U_eq(C,N). The perchlorate ion is disordered. The occupancies of atoms O3, O4, O5 and O6 are 0.42 (1) and those of atoms O3', O4', O5' and O6' are 0.58 (1).

Computing details

Data collection: SMART (Bruker, 1998); cell refinement: SMART; data reduction: SAINT (Bruker, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1998); software used to prepare material for publication: SHELXTL.

Figures

	Fig. 1. The independent components of the title complex, showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level and H atoms are drawn as small spheres of arbitrary radii.
	Fig. 2. The dimer units of the title complex, along the a axis, showing the Cu···O weak interaction, π–π stacking interaction, and C—H···O and C—H···Br hydrogen bonds. For the sake of clarity, H atoms have been omitted.

(4-Bromo-2-formylphenolato)perchlorato(1,10-phenanthroline)copper(II)

Crystal data

[Cu(C7H4BrO2)(ClO4)(C12H8N2)]	Z = 2
Mr = 543.21	F(000) = 538
Triclinic, P1	Dx = 1.861 Mg m^−3
a = 7.7560 (15) Å	Mo Kα radiation, λ = 0.71073 Å
b = 10.336 (2) Å	Cell parameters from 1965 reflections
c = 12.873 (3) Å	θ = 2.7–26.1°
α = 83.802 (3)°	µ = 3.37 mm^−1
β = 75.795 (3)°	T = 294 K
γ = 76.010 (3)°	Block, green
V = 969.5 (3) Å^3	0.22 × 0.18 × 0.12 mm

Data collection

Bruker SMART CCD area-detector diffractometer	3353 independent reflections
Radiation source: fine-focus sealed tube	2427 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.019
ϕ and ω scans	θmax = 25.0°, θmin = 1.6°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −9→8
Tmin = 0.763, Tmax = missing	k = −10→12
4860 measured reflections	l = −15→13

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.049	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.138	H-atom parameters constrained
S = 1.02	w = 1/[σ^2(Fo^2) + (0.0786P)^2 + 0.9337P] where P = (Fo^2 + 2Fc^2)/3
3353 reflections	(Δ/σ)max = 0.002
308 parameters	Δρmax = 1.31 e Å^−3
68 restraints	Δρmin = −0.53 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.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
Cu1	0.06431 (9)	0.56851 (6)	0.60366 (5)	0.0394 (2)
Br1	0.32031 (11)	0.97317 (8)	0.11163 (6)	0.0758 (3)
O1	0.1859 (5)	0.5492 (4)	0.4571 (3)	0.0478 (10)
O2	−0.0713 (5)	0.7494 (4)	0.5756 (3)	0.0442 (9)
N1	−0.0730 (6)	0.5590 (5)	0.7572 (4)	0.0424 (11)
N2	0.1948 (6)	0.3846 (4)	0.6423 (4)	0.0429 (11)
C1	0.2141 (7)	0.6467 (5)	0.3877 (4)	0.0386 (12)
C2	0.3525 (8)	0.6171 (6)	0.2927 (4)	0.0450 (13)
H2	0.4248	0.5312	0.2842	0.054*
C3	0.3792 (8)	0.7136 (7)	0.2146 (5)	0.0511 (15)
H3	0.4690	0.6928	0.1523	0.061*
C4	0.2741 (7)	0.8440 (6)	0.2257 (4)	0.0447 (13)
C5	0.1413 (7)	0.8787 (6)	0.3155 (5)	0.0436 (13)
H5	0.0714	0.9655	0.3220	0.052*
C6	0.1118 (7)	0.7790 (5)	0.3994 (4)	0.0377 (12)
C7	−0.0300 (7)	0.8188 (5)	0.4924 (4)	0.0413 (12)
H7	−0.0984	0.9060	0.4901	0.050*
C8	−0.2066 (8)	0.6495 (7)	0.8089 (5)	0.0553 (16)
H8	−0.2447	0.7312	0.7740	0.066*
C9	−0.2931 (10)	0.6248 (9)	0.9161 (6)	0.076 (2)
H9	−0.3882	0.6896	0.9518	0.092*
C10	−0.2368 (11)	0.5050 (9)	0.9677 (6)	0.077 (2)
H10	−0.2915	0.4888	1.0392	0.092*
C11	−0.0949 (9)	0.4054 (7)	0.9121 (5)	0.0588 (17)
C12	−0.0322 (12)	0.2743 (9)	0.9572 (6)	0.074 (2)
H12	−0.0854	0.2507	1.0274	0.089*
C13	0.1036 (12)	0.1848 (8)	0.8982 (6)	0.073 (2)
H13	0.1436	0.1007	0.9290	0.088*
C14	0.1868 (9)	0.2167 (6)	0.7895 (5)	0.0539 (16)
C15	0.3255 (10)	0.1294 (6)	0.7209 (6)	0.0642 (19)
H15	0.3692	0.0427	0.7459	0.077*
C16	0.3960 (9)	0.1704 (6)	0.6187 (6)	0.0607 (18)
H16	0.4884	0.1124	0.5742	0.073*
C17	0.3288 (8)	0.3005 (6)	0.5809 (5)	0.0514 (15)
H17	0.3789	0.3287	0.5114	0.062*
C18	0.1271 (8)	0.3438 (6)	0.7450 (5)	0.0451 (13)
C19	−0.0167 (8)	0.4388 (6)	0.8065 (4)	0.0465 (14)
Cl1	0.2990 (2)	0.76688 (18)	0.70234 (16)	0.0691 (5)
O3	0.2947 (19)	0.6829 (12)	0.6188 (9)	0.070 (4)	0.423 (12)
O4	0.1408 (15)	0.8575 (13)	0.7357 (12)	0.102 (6)	0.423 (12)
O5	0.4650 (14)	0.8130 (14)	0.6673 (11)	0.084 (5)	0.423 (12)
O6	0.331 (2)	0.6660 (14)	0.7934 (9)	0.149 (8)	0.423 (12)
O3'	0.3012 (15)	0.6437 (7)	0.6652 (10)	0.083 (4)	0.577 (12)
O4'	0.1370 (14)	0.8166 (12)	0.7807 (8)	0.119 (5)	0.577 (12)
O5'	0.4588 (14)	0.7759 (12)	0.7275 (12)	0.127 (5)	0.577 (12)
O6'	0.2738 (15)	0.8692 (8)	0.6082 (7)	0.106 (4)	0.577 (12)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.0431 (4)	0.0416 (4)	0.0301 (4)	−0.0109 (3)	−0.0030 (3)	0.0035 (3)
Br1	0.0839 (5)	0.0861 (6)	0.0548 (5)	−0.0333 (4)	−0.0124 (4)	0.0327 (4)
O1	0.059 (2)	0.040 (2)	0.036 (2)	−0.0109 (18)	0.0016 (18)	0.0006 (16)
O2	0.045 (2)	0.046 (2)	0.036 (2)	−0.0079 (18)	−0.0018 (17)	−0.0023 (17)
N1	0.042 (3)	0.053 (3)	0.033 (2)	−0.015 (2)	−0.006 (2)	0.000 (2)
N2	0.041 (3)	0.043 (3)	0.047 (3)	−0.013 (2)	−0.012 (2)	0.001 (2)
C1	0.041 (3)	0.043 (3)	0.034 (3)	−0.015 (2)	−0.009 (2)	0.002 (2)
C2	0.044 (3)	0.052 (3)	0.039 (3)	−0.012 (3)	−0.006 (2)	−0.005 (2)
C3	0.052 (3)	0.074 (4)	0.030 (3)	−0.029 (3)	−0.001 (3)	0.001 (3)
C4	0.044 (3)	0.060 (4)	0.033 (3)	−0.021 (3)	−0.010 (3)	0.010 (2)
C5	0.043 (3)	0.046 (3)	0.045 (3)	−0.017 (3)	−0.014 (3)	0.008 (2)
C6	0.039 (3)	0.052 (3)	0.025 (3)	−0.019 (2)	−0.007 (2)	0.004 (2)
C7	0.042 (3)	0.037 (3)	0.042 (3)	−0.003 (2)	−0.010 (2)	−0.002 (2)
C8	0.050 (4)	0.077 (4)	0.038 (3)	−0.020 (3)	−0.005 (3)	−0.001 (3)
C9	0.060 (4)	0.113 (7)	0.050 (4)	−0.021 (4)	0.005 (3)	−0.013 (4)
C10	0.079 (5)	0.121 (7)	0.034 (4)	−0.042 (5)	−0.006 (4)	0.001 (4)
C11	0.073 (4)	0.080 (5)	0.037 (3)	−0.040 (4)	−0.020 (3)	0.008 (3)
C12	0.097 (6)	0.098 (6)	0.046 (4)	−0.052 (5)	−0.035 (4)	0.027 (4)
C13	0.110 (6)	0.067 (5)	0.068 (5)	−0.046 (5)	−0.058 (5)	0.037 (4)
C14	0.068 (4)	0.048 (3)	0.062 (4)	−0.024 (3)	−0.036 (3)	0.007 (3)
C15	0.082 (5)	0.046 (4)	0.085 (5)	−0.020 (4)	−0.057 (4)	0.009 (3)
C16	0.063 (4)	0.045 (3)	0.080 (5)	0.000 (3)	−0.034 (4)	−0.012 (3)
C17	0.048 (3)	0.048 (3)	0.061 (4)	−0.010 (3)	−0.017 (3)	−0.004 (3)
C18	0.052 (3)	0.051 (3)	0.043 (3)	−0.027 (3)	−0.022 (3)	0.009 (3)
C19	0.049 (3)	0.064 (4)	0.036 (3)	−0.030 (3)	−0.017 (3)	0.008 (3)
Cl1	0.0562 (10)	0.0699 (11)	0.0835 (13)	−0.0170 (8)	−0.0099 (9)	−0.0219 (9)
O3	0.066 (7)	0.088 (8)	0.066 (7)	−0.028 (6)	−0.022 (6)	−0.006 (6)
O4	0.093 (9)	0.088 (9)	0.110 (10)	0.008 (7)	−0.022 (7)	−0.002 (8)
O5	0.080 (8)	0.095 (8)	0.088 (8)	−0.037 (6)	−0.017 (6)	−0.017 (7)
O6	0.155 (11)	0.148 (11)	0.109 (10)	0.006 (8)	−0.016 (8)	0.023 (8)
O3'	0.072 (6)	0.055 (5)	0.134 (9)	−0.007 (4)	−0.054 (6)	−0.005 (5)
O4'	0.130 (8)	0.102 (8)	0.090 (8)	0.004 (6)	0.009 (6)	0.006 (6)
O5'	0.112 (8)	0.127 (9)	0.173 (10)	−0.027 (6)	−0.092 (7)	−0.002 (7)
O6'	0.133 (8)	0.088 (6)	0.092 (7)	−0.029 (6)	−0.017 (6)	0.008 (5)

Geometric parameters (Å, º)

Cu1—O1	1.898 (4)	C9—H9	0.9300
Cu1—O2	1.955 (4)	C10—C11	1.417 (10)
Cu1—N2	1.999 (4)	C10—H10	0.9300
Cu1—N1	2.007 (4)	C11—C19	1.388 (8)
Cu1—O3	2.423 (11)	C11—C12	1.435 (10)
Br1—C4	1.902 (5)	C12—C13	1.353 (11)
O1—C1	1.295 (6)	C12—H12	0.9300
O2—C7	1.242 (6)	C13—C14	1.430 (10)
N1—C8	1.311 (7)	C13—H13	0.9300
N1—C19	1.357 (7)	C14—C18	1.393 (8)
N2—C17	1.329 (7)	C14—C15	1.410 (10)
N2—C18	1.360 (7)	C15—C16	1.359 (10)
C1—C6	1.408 (7)	C15—H15	0.9300
C1—C2	1.421 (8)	C16—C17	1.401 (9)
C2—C3	1.353 (8)	C16—H16	0.9300
C2—H2	0.9300	C17—H17	0.9300
C3—C4	1.398 (8)	C18—C19	1.428 (8)
C3—H3	0.9300	Cl1—O4	1.357 (7)
C4—C5	1.361 (8)	Cl1—O5'	1.382 (7)
C5—C6	1.427 (7)	Cl1—O3'	1.403 (6)
C5—H5	0.9300	Cl1—O4'	1.427 (7)
C6—C7	1.433 (7)	Cl1—O5	1.433 (8)
C7—H7	0.9300	Cl1—O3	1.464 (7)
C8—C9	1.405 (9)	Cl1—O6	1.509 (8)
C8—H8	0.9300	Cl1—O6'	1.538 (7)
C9—C10	1.367 (11)
O1—Cu1—O2	92.72 (16)	C13—C12—H12	119.8
O1—Cu1—N2	90.96 (18)	C11—C12—H12	119.8
O2—Cu1—N2	176.33 (17)	C12—C13—C14	121.4 (6)
O1—Cu1—N1	170.43 (17)	C18—C14—C15	115.9 (6)
O2—Cu1—N1	93.61 (17)	C18—C14—C13	118.6 (7)
N2—Cu1—N1	82.74 (19)	C15—C14—C13	125.6 (6)
O1—Cu1—O3	87.0 (3)	C16—C15—C14	120.7 (6)
O2—Cu1—O3	83.3 (4)	C16—C15—H15	119.6
N2—Cu1—O3	96.9 (4)	C14—C15—H15	119.6
N1—Cu1—O3	100.8 (3)	C15—C16—C17	119.6 (6)
C1—O1—Cu1	125.2 (3)	C15—C16—H16	120.2
C7—O2—Cu1	124.0 (3)	C17—C16—H16	120.2
C8—N1—C19	120.3 (5)	N2—C17—C16	121.4 (6)
C8—N1—Cu1	128.2 (4)	N2—C17—H17	119.3
C19—N1—Cu1	111.4 (4)	C16—C17—H17	119.3
C17—N2—C18	118.7 (5)	C12—C13—H13	119.3
C17—N2—Cu1	128.8 (4)	C14—C13—H13	119.3
C18—N2—Cu1	112.4 (4)	N2—C18—C14	123.7 (6)
O1—C1—C6	123.8 (5)	N2—C18—C19	115.9 (5)
O1—C1—C2	117.9 (5)	C14—C18—C19	120.4 (6)
C6—C1—C2	118.3 (5)	N1—C19—C11	122.7 (6)
C3—C2—C1	120.2 (6)	N1—C19—C18	117.5 (5)
C3—C2—H2	119.9	C11—C19—C18	119.9 (6)
C1—C2—H2	119.9	O4—Cl1—O5'	121.2 (10)
C2—C3—C4	121.2 (5)	O4—Cl1—O3'	121.7 (9)
C2—C3—H3	119.4	O5'—Cl1—O3'	115.3 (6)
C4—C3—H3	119.4	O4—Cl1—O4'	28.0 (7)
C2—C3—C4	121.2 (5)	O5'—Cl1—O4'	114.6 (7)
C5—C4—C3	121.3 (5)	O3'—Cl1—O4'	113.0 (6)
C5—C4—Br1	120.3 (4)	O4—Cl1—O5	118.5 (7)
C3—C4—Br1	118.4 (4)	O5'—Cl1—O5	33.9 (7)
C4—C5—C6	118.5 (5)	O3'—Cl1—O5	116.0 (8)
C4—C5—H5	120.7	O4'—Cl1—O5	130.5 (8)
C6—C5—H5	120.7	O4—Cl1—O3	114.2 (7)
C1—C6—C5	120.5 (5)	O5'—Cl1—O3	123.0 (9)
C1—C6—C7	122.5 (5)	O3'—Cl1—O3	27.7 (6)
C5—C6—C7	117.0 (5)	O4'—Cl1—O3	120.5 (9)
O2—C7—C6	126.9 (5)	O5—Cl1—O3	106.5 (6)
O2—C7—H7	116.5	O4—Cl1—O6	109.1 (7)
C6—C7—H7	116.5	O5'—Cl1—O6	72.2 (8)
N1—C8—C9	121.0 (7)	O3'—Cl1—O6	74.7 (7)
N1—C8—H8	119.5	O4'—Cl1—O6	81.1 (7)
C9—C8—H8	119.5	O5—Cl1—O6	104.6 (7)
C10—C9—C8	119.6 (7)	O3—Cl1—O6	102.3 (6)
C10—C9—H9	120.2	O4—Cl1—O6'	72.6 (7)
C8—C9—H9	120.2	O5'—Cl1—O6'	105.9 (6)
C9—C10—C11	119.9 (7)	O3'—Cl1—O6'	105.5 (5)
C9—C10—H10	120.0	O4'—Cl1—O6'	100.6 (5)
C11—C10—H10	120.0	O5—Cl1—O6'	73.4 (7)
C19—C11—C10	116.5 (6)	O3—Cl1—O6'	77.8 (6)
C19—C11—C12	119.3 (7)	O6—Cl1—O6'	177.9 (7)
C10—C11—C12	124.2 (7)	Cl1—O3—Cu1	130.6 (8)
C13—C12—C11	120.4 (7)
O2—Cu1—O1—C1	24.6 (4)	C8—C9—C10—C11	−1.6 (11)
N2—Cu1—O1—C1	−155.4 (4)	C9—C10—C11—C19	1.8 (10)
N1—Cu1—O1—C1	156.0 (9)	C9—C10—C11—C12	−176.7 (7)
O3—Cu1—O1—C1	−58.5 (5)	C19—C11—C12—C13	1.1 (10)
O1—Cu1—O2—C7	−16.6 (4)	C10—C11—C12—C13	179.6 (7)
N2—Cu1—O2—C7	164 (2)	C11—C12—C13—C14	−0.9 (10)
N1—Cu1—O2—C7	170.6 (4)	C12—C13—C14—C18	0.9 (9)
O3—Cu1—O2—C7	70.1 (5)	C12—C13—C14—C15	−178.3 (6)
O1—Cu1—N1—C8	−130.0 (10)	C18—C14—C15—C16	1.1 (8)
O2—Cu1—N1—C8	1.3 (5)	C13—C14—C15—C16	−179.6 (6)
N2—Cu1—N1—C8	−179.1 (5)	C14—C15—C16—C17	−0.6 (9)
O3—Cu1—N1—C8	85.2 (6)	C18—N2—C17—C16	2.3 (8)
O1—Cu1—N1—C19	47.2 (12)	Cu1—N2—C17—C16	−175.0 (4)
O2—Cu1—N1—C19	178.5 (4)	C15—C16—C17—N2	−1.1 (9)
N2—Cu1—N1—C19	−1.9 (3)	C17—N2—C18—C14	−1.8 (8)
O3—Cu1—N1—C19	−97.6 (5)	Cu1—N2—C18—C14	176.0 (4)
O1—Cu1—N2—C17	6.9 (5)	C17—N2—C18—C19	−179.9 (5)
O2—Cu1—N2—C17	−174 (2)	Cu1—N2—C18—C19	−2.2 (6)
N1—Cu1—N2—C17	179.7 (5)	C15—C14—C18—N2	0.1 (8)
O3—Cu1—N2—C17	−80.2 (5)	C13—C14—C18—N2	−179.2 (5)
O1—Cu1—N2—C18	−170.5 (4)	C15—C14—C18—C19	178.1 (5)
O2—Cu1—N2—C18	9 (3)	C13—C14—C18—C19	−1.2 (8)
N1—Cu1—N2—C18	2.2 (3)	C8—N1—C19—C11	−0.2 (8)
O3—Cu1—N2—C18	102.3 (4)	Cu1—N1—C19—C11	−177.7 (4)
Cu1—O1—C1—C6	−21.3 (7)	C8—N1—C19—C18	178.8 (5)
Cu1—O1—C1—C2	160.8 (4)	Cu1—N1—C19—C18	1.3 (6)
O1—C1—C2—C3	175.7 (5)	C10—C11—C19—N1	−1.0 (8)
C6—C1—C2—C3	−2.3 (8)	C12—C11—C19—N1	177.7 (5)
C1—C2—C3—C4	0.8 (8)	C10—C11—C19—C18	−179.9 (5)
C2—C3—C4—C5	0.0 (9)	C12—C11—C19—C18	−1.3 (8)
C2—C3—C4—Br1	−179.8 (4)	N2—C18—C19—N1	0.6 (7)
C3—C4—C5—C6	0.5 (8)	C14—C18—C19—N1	−177.6 (5)
Br1—C4—C5—C6	−179.6 (4)	N2—C18—C19—C11	179.6 (5)
O1—C1—C6—C5	−174.9 (5)	C14—C18—C19—C11	1.4 (8)
C2—C1—C6—C5	2.9 (7)	O4—Cl1—O3—Cu1	−44.7 (14)
O1—C1—C6—C7	2.4 (8)	O5'—Cl1—O3—Cu1	149.7 (9)
C2—C1—C6—C7	−179.8 (5)	O3'—Cl1—O3—Cu1	67.9 (17)
C4—C5—C6—C1	−2.1 (8)	O4'—Cl1—O3—Cu1	−13.8 (14)
C4—C5—C6—C7	−179.5 (5)	O5—Cl1—O3—Cu1	−177.4 (10)
Cu1—O2—C7—C6	5.0 (8)	O6—Cl1—O3—Cu1	73.1 (12)
C1—C6—C7—O2	6.2 (9)	O6'—Cl1—O3—Cu1	−109.1 (11)
C5—C6—C7—O2	−176.4 (5)	O1—Cu1—O3—Cl1	164.7 (10)
C19—N1—C8—C9	0.6 (9)	O2—Cu1—O3—Cl1	71.6 (10)
Cu1—N1—C8—C9	177.6 (5)	N2—Cu1—O3—Cl1	−104.7 (10)
N1—C8—C9—C10	0.3 (11)	N1—Cu1—O3—Cl1	−20.8 (11)