Bis[2,4-di-bromo-6-(N-{4-[(E)-1-(benzyl-oxy-imino)-eth-yl]phen-yl}carboximido-yl)phenolato]copper(II).

In the title complex, [Cu(C22H17Br2N2O2)2], the Cu(II) ion is four-coordinated in a trans-CuN2O2 square-planar geometry by two phenolate O and two imino N atoms from two deprotonated N,O-bidentate ligands. In the crystal, the packing of the mol-ecules is controlled by C-H⋯π and π-π inter-actions [centroid-centroid distances = 3.568 (3), 3.678 (2), 3.717 (3) and 3.799 (2) Å] and weak Br⋯Br halogen bonds [3.508 (4) Å], linking the mol-ecules into an infinite three-dimensional supra-molecular network.

Related literature

For background to oxime-based salen-type tetra­dentate ligands, see: Akine et al. (2001 ▶); Dong & Ding (2007 ▶); Dong et al. (2012 ▶); Bertolasi et al. (1982 ▶); Tarafder et al. (2002 ▶). For the synthesis and related crystal structures, see: Zhao & Ng (2010 ▶); Zhao et al. (2012 ▶); Dong et al. (2010 ▶).

Experimental

Crystal data

[Cu(C22H17Br2N2O2)2]

M = 1065.93

Monoclinic,

a = 27.4484 (7) Å

b = 13.3116 (3) Å

c = 22.3609 (5) Å

β = 91.165 (2)°

V = 8168.6 (3) Å3

Z = 8

Mo Kα radiation

μ = 4.50 mm−1

T = 293 K

0.30 × 0.21 × 0.10 mm

Data collection

Bruker SMART 1000 CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T min = 0.346, T max = 0.662

27775 measured reflections

7199 independent reflections

4682 reflections with I > 2σ(I)

R int = 0.063

Refinement

R[F 2 > 2σ(F 2)] = 0.041

wR(F 2) = 0.078

S = 1.01

7199 reflections

514 parameters

H-atom parameters constrained

Δρmax = 0.38 e Å−3

Δρmin = −0.36 e Å−3

Data collection: SMART (Bruker, 2001 ▶); cell refinement: SAINT (Bruker, 2001 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Click here for additional data file.

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536813009847/zl2543sup1.cif

Click here for additional data file.

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813009847/zl2543Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

[Cu(C22H17Br2N2O2)2]	F(000) = 4216
Mr = 1065.93	Dx = 1.733 Mg m−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 5329 reflections
a = 27.4484 (7) Å	θ = 2.5–28.4°
b = 13.3116 (3) Å	µ = 4.50 mm−1
c = 22.3609 (5) Å	T = 293 K
β = 91.165 (2)°	Block-like, brown
V = 8168.6 (3) Å3	0.30 × 0.21 × 0.10 mm
Z = 8

Bruker SMART 1000 CCD area-detector diffractometer	7199 independent reflections
Radiation source: fine-focus sealed tube	4682 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.063
phi and ω scans	θmax = 25.0°, θmin = 2.5°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −32→32
Tmin = 0.346, Tmax = 0.662	k = −15→15
27775 measured reflections	l = −26→26

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.078	H-atom parameters constrained
S = 1.01	w = 1/[σ2(Fo2) + (0.0217P)2 + 4.428P] where P = (Fo2 + 2Fc2)/3
7199 reflections	(Δ/σ)max = 0.001
514 parameters	Δρmax = 0.38 e Å−3
0 restraints	Δρmin = −0.36 e Å−3

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.

	x	y	z	Uiso*/Ueq
Cu1	0.393085 (19)	0.80478 (4)	0.56844 (2)	0.03676 (15)
Br1	0.313417 (19)	1.00341 (3)	0.41540 (2)	0.05451 (16)
Br2	0.202079 (18)	0.66785 (3)	0.34341 (2)	0.04794 (14)
Br3	0.51425 (2)	0.59414 (4)	0.66431 (3)	0.07055 (19)
Br4	0.61488 (2)	0.93975 (4)	0.74609 (3)	0.0720 (2)
N1	0.40018 (14)	0.3244 (3)	0.75569 (17)	0.0462 (10)
N2	0.36392 (12)	0.6673 (2)	0.56013 (14)	0.0334 (9)
N3	0.34560 (16)	1.3351 (3)	0.44525 (19)	0.0558 (12)
N4	0.41632 (12)	0.9450 (2)	0.58442 (15)	0.0369 (9)
O1	0.41180 (12)	0.2328 (2)	0.78465 (14)	0.0582 (9)
O2	0.35153 (10)	0.85865 (18)	0.50786 (12)	0.0377 (7)
O3	0.32379 (14)	1.4261 (2)	0.42526 (16)	0.0681 (11)
O4	0.44441 (10)	0.74996 (19)	0.61628 (12)	0.0427 (8)
C1	0.4484 (2)	0.2458 (4)	0.6779 (2)	0.0712 (17)
H1A	0.4798	0.2719	0.6680	0.107*
H1B	0.4326	0.2197	0.6425	0.107*
H1C	0.4523	0.1929	0.7068	0.107*
C2	0.41821 (17)	0.3274 (3)	0.7033 (2)	0.0403 (11)
C3	0.40625 (15)	0.4177 (3)	0.66696 (19)	0.0356 (11)
C4	0.38720 (17)	0.5041 (3)	0.69259 (19)	0.0466 (12)
H4	0.3828	0.5063	0.7337	0.056*
C5	0.37466 (17)	0.5867 (3)	0.6582 (2)	0.0457 (12)
H5	0.3629	0.6444	0.6765	0.055*
C6	0.37943 (15)	0.5841 (3)	0.59716 (19)	0.0352 (11)
C7	0.39876 (15)	0.4995 (3)	0.57136 (19)	0.0406 (11)
H7	0.4030	0.4976	0.5302	0.049*
C8	0.41192 (16)	0.4171 (3)	0.60602 (19)	0.0390 (11)
H8	0.4248	0.3605	0.5877	0.047*
C9	0.33200 (15)	0.6446 (3)	0.51906 (17)	0.0354 (11)
H9	0.3225	0.5776	0.5175	0.042*
C10	0.30944 (15)	0.7097 (3)	0.47563 (17)	0.0312 (10)
C11	0.32100 (15)	0.8134 (3)	0.47231 (18)	0.0331 (10)
C12	0.29653 (15)	0.8671 (3)	0.42596 (18)	0.0325 (10)
C13	0.26243 (15)	0.8249 (3)	0.38851 (18)	0.0363 (11)
H13	0.2468	0.8636	0.3593	0.044*
C14	0.25130 (15)	0.7241 (3)	0.39428 (18)	0.0360 (11)
C15	0.27448 (15)	0.6672 (3)	0.43670 (18)	0.0372 (11)
H15	0.2670	0.5992	0.4399	0.045*
C16	0.38905 (19)	0.2287 (4)	0.8420 (2)	0.0617 (15)
H16A	0.3783	0.1605	0.8494	0.074*
H16B	0.3605	0.2717	0.8413	0.074*
C17	0.42285 (17)	0.2612 (4)	0.8916 (2)	0.0478 (13)
C18	0.44426 (19)	0.1915 (4)	0.9290 (2)	0.0588 (14)
H18	0.4375	0.1237	0.9235	0.071*
C19	0.4758 (2)	0.2208 (5)	0.9748 (2)	0.0738 (17)
H19	0.4898	0.1729	1.0000	0.089*
C20	0.4861 (2)	0.3197 (6)	0.9829 (3)	0.0772 (18)
H20	0.5074	0.3395	1.0135	0.093*
C21	0.4656 (2)	0.3894 (5)	0.9463 (3)	0.0780 (18)
H21	0.4727	0.4571	0.9519	0.094*
C22	0.4340 (2)	0.3602 (4)	0.9009 (2)	0.0674 (16)
H22	0.4199	0.4087	0.8761	0.081*
C23	0.28957 (18)	1.3574 (3)	0.5297 (2)	0.0584 (14)
H23A	0.3038	1.3891	0.5644	0.088*
H23B	0.2659	1.3089	0.5419	0.088*
H23C	0.2740	1.4073	0.5049	0.088*
C24	0.32845 (18)	1.3061 (3)	0.4953 (2)	0.0445 (12)
C25	0.35100 (17)	1.2114 (3)	0.5185 (2)	0.0408 (12)
C26	0.33122 (18)	1.1602 (3)	0.5662 (2)	0.0509 (13)
H26	0.3039	1.1860	0.5848	0.061*
C27	0.35166 (17)	1.0705 (3)	0.5865 (2)	0.0494 (13)
H27	0.3378	1.0361	0.6181	0.059*
C28	0.39222 (16)	1.0333 (3)	0.5599 (2)	0.0364 (11)
C29	0.41171 (17)	1.0817 (3)	0.5122 (2)	0.0496 (13)
H29	0.4387	1.0548	0.4935	0.060*
C30	0.39136 (18)	1.1708 (3)	0.4915 (2)	0.0502 (13)
H30	0.4050	1.2036	0.4592	0.060*
C31	0.45492 (16)	0.9665 (3)	0.61517 (19)	0.0432 (12)
H31	0.4622	1.0344	0.6191	0.052*
C32	0.48802 (16)	0.8982 (3)	0.64407 (19)	0.0412 (12)
C33	0.48142 (17)	0.7931 (3)	0.64184 (18)	0.0398 (11)
C34	0.51902 (17)	0.7353 (3)	0.66960 (19)	0.0432 (12)
C35	0.55761 (17)	0.7769 (3)	0.70001 (19)	0.0468 (13)
H35	0.5808	0.7359	0.7186	0.056*
C36	0.56205 (17)	0.8805 (3)	0.7030 (2)	0.0482 (13)
C37	0.52853 (17)	0.9402 (3)	0.6752 (2)	0.0504 (13)
H37	0.5323	1.0096	0.6765	0.060*
C38	0.3297 (2)	1.4292 (4)	0.3611 (2)	0.0734 (17)
H38A	0.3619	1.4047	0.3515	0.088*
H38B	0.3271	1.4982	0.3474	0.088*
C39	0.2922 (2)	1.3669 (4)	0.3295 (2)	0.0670 (16)
C40	0.2531 (3)	1.4106 (5)	0.2979 (3)	0.094 (2)
H40	0.2512	1.4800	0.2937	0.112*
C41	0.2170 (3)	1.3490 (7)	0.2726 (3)	0.099 (2)
H41	0.1913	1.3782	0.2512	0.119*
C42	0.2187 (3)	1.2477 (7)	0.2784 (3)	0.100 (2)
H42	0.1936	1.2082	0.2625	0.120*
C43	0.2571 (3)	1.2046 (5)	0.3074 (2)	0.088 (2)
H43	0.2589	1.1350	0.3104	0.106*
C44	0.2934 (2)	1.2630 (4)	0.3324 (2)	0.0703 (17)
H44	0.3196	1.2319	0.3518	0.084*

	U11	U22	U33	U12	U13	U23
Cu1	0.0360 (3)	0.0314 (3)	0.0423 (3)	0.0009 (2)	−0.0114 (3)	0.0010 (2)
Br1	0.0655 (4)	0.0335 (2)	0.0637 (3)	−0.0007 (2)	−0.0166 (3)	0.0084 (2)
Br2	0.0466 (3)	0.0513 (3)	0.0453 (3)	−0.0020 (2)	−0.0140 (2)	−0.0079 (2)
Br3	0.0702 (4)	0.0431 (3)	0.0970 (4)	0.0108 (3)	−0.0295 (4)	0.0048 (3)
Br4	0.0546 (4)	0.0807 (4)	0.0791 (4)	−0.0073 (3)	−0.0361 (3)	−0.0002 (3)
N1	0.048 (3)	0.042 (2)	0.049 (3)	0.0007 (19)	−0.001 (2)	0.015 (2)
N2	0.036 (2)	0.0293 (18)	0.035 (2)	0.0047 (17)	−0.0067 (19)	0.0026 (16)
N3	0.069 (3)	0.037 (2)	0.061 (3)	0.010 (2)	−0.012 (3)	0.007 (2)
N4	0.034 (2)	0.0289 (19)	0.047 (2)	0.0040 (17)	−0.013 (2)	−0.0001 (17)
O1	0.067 (2)	0.055 (2)	0.053 (2)	0.0056 (18)	0.0068 (19)	0.0220 (17)
O2	0.0375 (18)	0.0325 (15)	0.0427 (18)	−0.0023 (14)	−0.0125 (16)	0.0009 (14)
O3	0.095 (3)	0.043 (2)	0.065 (2)	0.018 (2)	−0.006 (2)	0.0105 (18)
O4	0.044 (2)	0.0315 (16)	0.0516 (19)	0.0005 (14)	−0.0208 (17)	0.0043 (14)
C1	0.085 (4)	0.065 (4)	0.063 (4)	0.029 (3)	0.012 (3)	0.016 (3)
C2	0.040 (3)	0.039 (3)	0.042 (3)	0.005 (2)	−0.003 (2)	0.008 (2)
C3	0.035 (3)	0.035 (2)	0.037 (3)	0.000 (2)	0.001 (2)	0.002 (2)
C4	0.061 (3)	0.048 (3)	0.031 (3)	0.006 (3)	0.002 (2)	0.005 (2)
C5	0.057 (3)	0.038 (3)	0.042 (3)	0.008 (2)	0.000 (3)	−0.002 (2)
C6	0.035 (3)	0.031 (2)	0.039 (3)	0.002 (2)	−0.010 (2)	0.003 (2)
C7	0.046 (3)	0.045 (3)	0.031 (3)	0.002 (2)	0.001 (2)	0.003 (2)
C8	0.042 (3)	0.035 (2)	0.039 (3)	0.004 (2)	0.001 (2)	0.001 (2)
C9	0.037 (3)	0.033 (2)	0.036 (3)	−0.002 (2)	−0.003 (2)	−0.003 (2)
C10	0.029 (3)	0.034 (2)	0.030 (2)	0.002 (2)	0.000 (2)	0.001 (2)
C11	0.031 (3)	0.034 (2)	0.034 (3)	0.004 (2)	0.001 (2)	−0.002 (2)
C12	0.030 (3)	0.033 (2)	0.034 (2)	0.004 (2)	0.001 (2)	0.002 (2)
C13	0.038 (3)	0.040 (3)	0.031 (2)	0.007 (2)	−0.002 (2)	0.002 (2)
C14	0.034 (3)	0.043 (3)	0.031 (2)	0.001 (2)	−0.005 (2)	−0.007 (2)
C15	0.039 (3)	0.034 (2)	0.038 (3)	−0.004 (2)	−0.001 (2)	0.001 (2)
C16	0.055 (4)	0.073 (4)	0.057 (3)	−0.007 (3)	0.007 (3)	0.028 (3)
C17	0.039 (3)	0.058 (3)	0.047 (3)	0.000 (3)	0.012 (3)	0.012 (3)
C18	0.060 (4)	0.062 (3)	0.055 (3)	0.009 (3)	0.012 (3)	0.013 (3)
C19	0.065 (4)	0.100 (5)	0.058 (4)	0.014 (4)	0.007 (3)	0.020 (4)
C20	0.060 (4)	0.115 (6)	0.057 (4)	−0.015 (4)	0.009 (3)	−0.001 (4)
C21	0.082 (5)	0.077 (4)	0.076 (4)	−0.013 (4)	0.020 (4)	−0.006 (4)
C22	0.065 (4)	0.067 (4)	0.070 (4)	0.004 (3)	0.011 (3)	0.017 (3)
C23	0.055 (3)	0.042 (3)	0.078 (4)	0.006 (3)	−0.006 (3)	0.007 (3)
C24	0.045 (3)	0.033 (3)	0.055 (3)	0.001 (2)	−0.009 (3)	−0.002 (2)
C25	0.040 (3)	0.030 (2)	0.051 (3)	−0.003 (2)	−0.010 (3)	0.001 (2)
C26	0.047 (3)	0.047 (3)	0.058 (3)	0.015 (3)	0.001 (3)	0.007 (3)
C27	0.050 (3)	0.043 (3)	0.056 (3)	0.009 (3)	0.004 (3)	0.009 (2)
C28	0.033 (3)	0.029 (2)	0.048 (3)	−0.003 (2)	−0.010 (2)	0.000 (2)
C29	0.040 (3)	0.044 (3)	0.065 (3)	0.008 (2)	0.004 (3)	0.006 (3)
C30	0.051 (3)	0.043 (3)	0.057 (3)	0.002 (3)	0.003 (3)	0.012 (2)
C31	0.043 (3)	0.034 (2)	0.052 (3)	0.002 (2)	−0.008 (3)	−0.002 (2)
C32	0.040 (3)	0.036 (3)	0.047 (3)	0.002 (2)	−0.013 (2)	0.003 (2)
C33	0.039 (3)	0.044 (3)	0.036 (3)	0.005 (2)	−0.004 (2)	0.000 (2)
C34	0.044 (3)	0.042 (3)	0.043 (3)	0.006 (2)	−0.007 (3)	0.002 (2)
C35	0.041 (3)	0.054 (3)	0.045 (3)	0.007 (3)	−0.010 (3)	0.006 (2)
C36	0.040 (3)	0.056 (3)	0.049 (3)	0.000 (2)	−0.018 (3)	0.001 (2)
C37	0.049 (3)	0.043 (3)	0.058 (3)	−0.003 (2)	−0.016 (3)	−0.004 (2)
C38	0.098 (5)	0.059 (4)	0.063 (4)	0.017 (3)	0.012 (4)	0.020 (3)
C39	0.077 (5)	0.078 (4)	0.046 (3)	0.030 (4)	0.003 (3)	0.007 (3)
C40	0.111 (6)	0.103 (5)	0.067 (4)	0.053 (5)	0.002 (4)	−0.005 (4)
C41	0.085 (6)	0.144 (7)	0.069 (5)	0.057 (5)	−0.013 (4)	−0.006 (5)
C42	0.079 (5)	0.150 (7)	0.071 (5)	0.015 (5)	−0.003 (4)	−0.008 (5)
C43	0.096 (5)	0.108 (5)	0.061 (4)	0.003 (5)	−0.012 (4)	0.003 (4)
C44	0.073 (4)	0.081 (4)	0.056 (4)	0.010 (4)	−0.011 (3)	0.003 (3)

Cu1—O2	1.894 (2)	C17—C18	1.373 (6)
Cu1—O4	1.897 (3)	C18—C19	1.382 (7)
Cu1—N4	2.002 (3)	C18—H18	0.9300
Cu1—N2	2.005 (3)	C19—C20	1.358 (7)
Br1—C12	1.888 (4)	C19—H19	0.9300
Br2—C14	1.902 (4)	C20—C21	1.352 (7)
Br3—C34	1.887 (4)	C20—H20	0.9300
Br4—C36	1.896 (4)	C21—C22	1.377 (7)
N1—C2	1.282 (5)	C21—H21	0.9300
N1—O1	1.413 (4)	C22—H22	0.9300
N2—C9	1.292 (4)	C23—C24	1.494 (6)
N2—C6	1.442 (5)	C23—H23A	0.9600
N3—C24	1.283 (6)	C23—H23B	0.9600
N3—O3	1.420 (4)	C23—H23C	0.9600
N4—C31	1.284 (5)	C24—C25	1.492 (6)
N4—C28	1.451 (5)	C25—C30	1.383 (6)
O1—C16	1.438 (5)	C25—C26	1.385 (6)
O2—C11	1.292 (4)	C26—C27	1.392 (5)
O3—C38	1.447 (6)	C26—H26	0.9300
O4—C33	1.290 (5)	C27—C28	1.366 (6)
C1—C2	1.487 (6)	C27—H27	0.9300
C1—H1A	0.9600	C28—C29	1.364 (6)
C1—H1B	0.9600	C29—C30	1.387 (6)
C1—H1C	0.9600	C29—H29	0.9300
C2—C3	1.483 (5)	C30—H30	0.9300
C3—C8	1.375 (5)	C31—C32	1.430 (5)
C3—C4	1.393 (5)	C31—H31	0.9300
C4—C5	1.381 (5)	C32—C33	1.411 (5)
C4—H4	0.9300	C32—C37	1.415 (5)
C5—C6	1.375 (6)	C33—C34	1.420 (5)
C5—H5	0.9300	C34—C35	1.364 (6)
C6—C7	1.377 (5)	C35—C36	1.386 (6)
C7—C8	1.387 (5)	C35—H35	0.9300
C7—H7	0.9300	C36—C37	1.357 (6)
C8—H8	0.9300	C37—H37	0.9300
C9—C10	1.433 (5)	C38—C39	1.490 (7)
C9—H9	0.9300	C38—H38A	0.9700
C10—C15	1.402 (5)	C38—H38B	0.9700
C10—C11	1.419 (5)	C39—C44	1.385 (7)
C11—C12	1.417 (5)	C39—C40	1.398 (7)
C12—C13	1.365 (5)	C40—C41	1.396 (9)
C13—C14	1.382 (5)	C40—H40	0.9300
C13—H13	0.9300	C41—C42	1.355 (9)
C14—C15	1.362 (5)	C41—H41	0.9300
C15—H15	0.9300	C42—C43	1.354 (8)
C16—C17	1.496 (6)	C42—H42	0.9300
C16—H16A	0.9700	C43—C44	1.375 (7)
C16—H16B	0.9700	C43—H43	0.9300
C17—C22	1.368 (6)	C44—H44	0.9300
O2—Cu1—O4	168.03 (13)	C21—C20—C19	120.0 (6)
O2—Cu1—N4	87.69 (12)	C21—C20—H20	120.0
O4—Cu1—N4	91.59 (12)	C19—C20—H20	120.0
O2—Cu1—N2	92.63 (12)	C20—C21—C22	120.0 (6)
O4—Cu1—N2	89.52 (12)	C20—C21—H21	120.0
N4—Cu1—N2	173.08 (15)	C22—C21—H21	120.0
C2—N1—O1	111.0 (4)	C17—C22—C21	121.3 (5)
C9—N2—C6	114.6 (3)	C17—C22—H22	119.3
C9—N2—Cu1	122.9 (3)	C21—C22—H22	119.3
C6—N2—Cu1	122.4 (2)	C24—C23—H23A	109.5
C24—N3—O3	111.8 (4)	C24—C23—H23B	109.5
C31—N4—C28	112.7 (3)	H23A—C23—H23B	109.5
C31—N4—Cu1	124.0 (3)	C24—C23—H23C	109.5
C28—N4—Cu1	123.2 (2)	H23A—C23—H23C	109.5
N1—O1—C16	110.1 (3)	H23B—C23—H23C	109.5
C11—O2—Cu1	129.6 (2)	N3—C24—C25	113.6 (5)
N3—O3—C38	106.3 (4)	N3—C24—C23	126.2 (4)
C33—O4—Cu1	130.3 (3)	C25—C24—C23	120.2 (4)
C2—C1—H1A	109.5	C30—C25—C26	118.3 (4)
C2—C1—H1B	109.5	C30—C25—C24	120.6 (4)
H1A—C1—H1B	109.5	C26—C25—C24	121.1 (5)
C2—C1—H1C	109.5	C25—C26—C27	120.8 (5)
H1A—C1—H1C	109.5	C25—C26—H26	119.6
H1B—C1—H1C	109.5	C27—C26—H26	119.6
N1—C2—C3	116.2 (4)	C28—C27—C26	119.7 (5)
N1—C2—C1	123.7 (4)	C28—C27—H27	120.2
C3—C2—C1	120.1 (4)	C26—C27—H27	120.2
C8—C3—C4	117.6 (4)	C29—C28—C27	120.4 (4)
C8—C3—C2	120.7 (4)	C29—C28—N4	119.6 (4)
C4—C3—C2	121.6 (4)	C27—C28—N4	119.9 (4)
C5—C4—C3	121.4 (4)	C28—C29—C30	120.2 (5)
C5—C4—H4	119.3	C28—C29—H29	119.9
C3—C4—H4	119.3	C30—C29—H29	119.9
C6—C5—C4	120.3 (4)	C25—C30—C29	120.6 (5)
C6—C5—H5	119.8	C25—C30—H30	119.7
C4—C5—H5	119.8	C29—C30—H30	119.7
C5—C6—C7	118.8 (4)	N4—C31—C32	127.6 (4)
C5—C6—N2	121.2 (4)	N4—C31—H31	116.2
C7—C6—N2	120.0 (4)	C32—C31—H31	116.2
C6—C7—C8	120.7 (4)	C33—C32—C37	120.5 (4)
C6—C7—H7	119.6	C33—C32—C31	122.3 (4)
C8—C7—H7	119.6	C37—C32—C31	117.2 (4)
C3—C8—C7	121.1 (4)	O4—C33—C32	123.8 (4)
C3—C8—H8	119.5	O4—C33—C34	120.7 (4)
C7—C8—H8	119.5	C32—C33—C34	115.5 (4)
N2—C9—C10	128.1 (4)	C35—C34—C33	123.2 (4)
N2—C9—H9	115.9	C35—C34—Br3	119.2 (3)
C10—C9—H9	115.9	C33—C34—Br3	117.6 (3)
C15—C10—C11	120.8 (4)	C34—C35—C36	119.6 (4)
C15—C10—C9	117.2 (4)	C34—C35—H35	120.2
C11—C10—C9	122.0 (4)	C36—C35—H35	120.2
O2—C11—C12	120.4 (4)	C37—C36—C35	120.1 (4)
O2—C11—C10	124.3 (3)	C37—C36—Br4	119.6 (3)
C12—C11—C10	115.2 (4)	C35—C36—Br4	120.3 (3)
C13—C12—C11	123.3 (4)	C36—C37—C32	120.9 (4)
C13—C12—Br1	119.1 (3)	C36—C37—H37	119.6
C11—C12—Br1	117.5 (3)	C32—C37—H37	119.6
C12—C13—C14	119.5 (4)	O3—C38—C39	111.4 (5)
C12—C13—H13	120.2	O3—C38—H38A	109.4
C14—C13—H13	120.2	C39—C38—H38A	109.4
C15—C14—C13	120.3 (4)	O3—C38—H38B	109.4
C15—C14—Br2	120.9 (3)	C39—C38—H38B	109.4
C13—C14—Br2	118.8 (3)	H38A—C38—H38B	108.0
C14—C15—C10	120.8 (4)	C44—C39—C40	117.2 (6)
C14—C15—H15	119.6	C44—C39—C38	121.2 (5)
C10—C15—H15	119.6	C40—C39—C38	121.6 (6)
O1—C16—C17	112.1 (4)	C41—C40—C39	119.4 (6)
O1—C16—H16A	109.2	C41—C40—H40	120.3
C17—C16—H16A	109.2	C39—C40—H40	120.3
O1—C16—H16B	109.2	C42—C41—C40	121.5 (6)
C17—C16—H16B	109.2	C42—C41—H41	119.2
H16A—C16—H16B	107.9	C40—C41—H41	119.2
C22—C17—C18	117.8 (5)	C43—C42—C41	119.4 (7)
C22—C17—C16	121.7 (5)	C43—C42—H42	120.3
C18—C17—C16	120.6 (5)	C41—C42—H42	120.3
C17—C18—C19	121.0 (5)	C42—C43—C44	120.4 (7)
C17—C18—H18	119.5	C42—C43—H43	119.8
C19—C18—H18	119.5	C44—C43—H43	119.8
C20—C19—C18	119.9 (5)	C43—C44—C39	122.0 (6)
C20—C19—H19	120.1	C43—C44—H44	119.0
C18—C19—H19	120.1	C39—C44—H44	119.0
O2—Cu1—N2—C9	5.8 (3)	C22—C17—C18—C19	0.4 (8)
O4—Cu1—N2—C9	−162.4 (3)	C16—C17—C18—C19	179.6 (5)
O2—Cu1—N2—C6	−178.4 (3)	C17—C18—C19—C20	−0.5 (8)
O4—Cu1—N2—C6	13.3 (3)	C18—C19—C20—C21	0.3 (9)
O2—Cu1—N4—C31	−165.0 (4)	C19—C20—C21—C22	0.1 (9)
O4—Cu1—N4—C31	3.0 (4)	C18—C17—C22—C21	0.0 (8)
O2—Cu1—N4—C28	12.1 (3)	C16—C17—C22—C21	−179.3 (5)
O4—Cu1—N4—C28	−179.9 (4)	C20—C21—C22—C17	−0.2 (9)
C2—N1—O1—C16	−176.9 (4)	O3—N3—C24—C25	−179.0 (3)
O4—Cu1—O2—C11	93.3 (6)	O3—N3—C24—C23	1.3 (6)
N4—Cu1—O2—C11	−179.9 (4)	N3—C24—C25—C30	9.1 (6)
N2—Cu1—O2—C11	−6.9 (4)	C23—C24—C25—C30	−171.1 (4)
C24—N3—O3—C38	−156.9 (4)	N3—C24—C25—C26	−168.6 (4)
O2—Cu1—O4—C33	79.9 (7)	C23—C24—C25—C26	11.1 (6)
N4—Cu1—O4—C33	−6.5 (4)	C30—C25—C26—C27	0.5 (7)
N2—Cu1—O4—C33	−179.7 (4)	C24—C25—C26—C27	178.2 (4)
O1—N1—C2—C3	176.8 (3)	C25—C26—C27—C28	1.1 (7)
O1—N1—C2—C1	−1.5 (6)	C26—C27—C28—C29	−2.3 (6)
N1—C2—C3—C8	−162.1 (4)	C26—C27—C28—N4	174.3 (4)
C1—C2—C3—C8	16.3 (7)	C31—N4—C28—C29	74.8 (5)
N1—C2—C3—C4	15.4 (7)	Cu1—N4—C28—C29	−102.5 (4)
C1—C2—C3—C4	−166.3 (4)	C31—N4—C28—C27	−101.9 (5)
C8—C3—C4—C5	−0.4 (7)	Cu1—N4—C28—C27	80.7 (5)
C2—C3—C4—C5	−177.9 (4)	C27—C28—C29—C30	2.0 (7)
C3—C4—C5—C6	2.0 (7)	N4—C28—C29—C30	−174.6 (4)
C4—C5—C6—C7	−2.7 (7)	C26—C25—C30—C29	−0.8 (7)
C4—C5—C6—N2	176.4 (4)	C24—C25—C30—C29	−178.5 (4)
C9—N2—C6—C5	−122.6 (4)	C28—C29—C30—C25	−0.5 (7)
Cu1—N2—C6—C5	61.4 (5)	C28—N4—C31—C32	−178.1 (4)
C9—N2—C6—C7	56.4 (5)	Cu1—N4—C31—C32	−0.8 (7)
Cu1—N2—C6—C7	−119.6 (4)	N4—C31—C32—C33	−0.1 (8)
C5—C6—C7—C8	1.8 (7)	N4—C31—C32—C37	179.5 (5)
N2—C6—C7—C8	−177.2 (4)	Cu1—O4—C33—C32	7.5 (7)
C4—C3—C8—C7	−0.5 (7)	Cu1—O4—C33—C34	−172.0 (3)
C2—C3—C8—C7	177.1 (4)	C37—C32—C33—O4	177.3 (4)
C6—C7—C8—C3	−0.3 (7)	C31—C32—C33—O4	−3.2 (7)
C6—N2—C9—C10	179.8 (4)	C37—C32—C33—C34	−3.3 (7)
Cu1—N2—C9—C10	−4.2 (6)	C31—C32—C33—C34	176.2 (4)
N2—C9—C10—C15	−178.1 (4)	O4—C33—C34—C35	−176.4 (4)
N2—C9—C10—C11	0.9 (7)	C32—C33—C34—C35	4.2 (7)
Cu1—O2—C11—C12	−174.0 (3)	O4—C33—C34—Br3	2.9 (6)
Cu1—O2—C11—C10	5.7 (6)	C32—C33—C34—Br3	−176.5 (3)
C15—C10—C11—O2	177.6 (4)	C33—C34—C35—C36	−2.1 (7)
C9—C10—C11—O2	−1.3 (7)	Br3—C34—C35—C36	178.6 (4)
C15—C10—C11—C12	−2.7 (6)	C34—C35—C36—C37	−0.9 (8)
C9—C10—C11—C12	178.4 (4)	C34—C35—C36—Br4	179.0 (4)
O2—C11—C12—C13	−177.2 (4)	C35—C36—C37—C32	1.7 (8)
C10—C11—C12—C13	3.0 (6)	Br4—C36—C37—C32	−178.3 (4)
O2—C11—C12—Br1	4.0 (5)	C33—C32—C37—C36	0.5 (7)
C10—C11—C12—Br1	−175.8 (3)	C31—C32—C37—C36	−179.0 (5)
C11—C12—C13—C14	−1.5 (7)	N3—O3—C38—C39	80.7 (5)
Br1—C12—C13—C14	177.3 (3)	O3—C38—C39—C44	−71.0 (7)
C12—C13—C14—C15	−0.6 (7)	O3—C38—C39—C40	106.2 (6)
C12—C13—C14—Br2	177.9 (3)	C44—C39—C40—C41	1.8 (9)
C13—C14—C15—C10	0.8 (7)	C38—C39—C40—C41	−175.5 (6)
Br2—C14—C15—C10	−177.6 (3)	C39—C40—C41—C42	0.6 (10)
C11—C10—C15—C14	0.9 (6)	C40—C41—C42—C43	−2.5 (11)
C9—C10—C15—C14	179.8 (4)	C41—C42—C43—C44	2.0 (10)
N1—O1—C16—C17	−96.1 (4)	C42—C43—C44—C39	0.5 (10)
O1—C16—C17—C22	75.4 (6)	C40—C39—C44—C43	−2.4 (9)
O1—C16—C17—C18	−103.8 (5)	C38—C39—C44—C43	174.9 (5)

D—H···A	D—H	H···A	D···A	D—H···A
C19—H19···Cg1i	0.93	2.82	3.575 (5)	118
C16—H16B···Cg2i	0.97	2.96	3.511 (5)	117

Table 1

Hydrogen-bond geometry (Å, °)

Cg1 and Cg2 are the centroids of the Cu/O4/C33–C31/N4 and C10–C15 rings, respectively.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C19—H19⋯Cg1i	0.93	2.82	3.575 (5)	118
C16—H16B⋯Cg2i	0.97	2.96	3.511 (5)	117

Symmetry code: (i) .