catena-Poly[{μ(3)-4,4',6,6'-tetra-bromo-2,2'-[butane-1,4-diylbis(nitrilo-methan-ylyl-idene)]diphenolato}{μ(2)-4,4',6,6'-tetra-bromo-2,2'-[butane-1,4-diylbis(nitrilo-methanylyl-idene)]dipheno-lato}dicopper(II)].

The asymmetric unit of the title coordination polymer consists of a dinuclear neutral complex mol-ecule of formula [Cu(2)(C(18)H(14)Br(4)N(2)O(2))(2)](n). One of the Cu(II) ions is coordinated in a distorted square-planar geometry, whereas the other is coordinated in a distorted square-pyramidal geometry, the long apical Cu-O bond [2.885 (4) Å] of the square-pyramidal coordination being provided by a symmetry-related O atom creating a one-dimensional polymer along [010]. π-π stacking inter-actions [centroid-centroid distance = 3.783 (4) Å] and short inter-chain Br⋯Br inter-actions [3.6142 (12)-3.6797 (12) Å] are observed.

Related literature

For standard bond lengths, see: Allen et al. (1987 ▶). For van der Waals radii, see: Bondi (1964 ▶). For background to coordination polymers, see: Kido & Okamoto (2002 ▶); Li et al. (2006 ▶). For background to bis-bidentate Schiff base complexes, see: Hannon et al. (1999 ▶); Lavalette et al. (2003 ▶). For the synthesis and structural variations of Schiff base complexes, see: Granovski et al. (1993 ▶); Elmali et al. (2000 ▶). For related structures, see: Kargar & Kia (2011 ▶).

Experimental

Crystal data

[Cu2(C18H14Br4N2O2)2]

M = 1345.98

Orthorhombic,

a = 27.4100 (11) Å

b = 7.9055 (4) Å

c = 18.8291 (7) Å

V = 4080.1 (3) Å3

Z = 4

Mo Kα radiation

μ = 8.92 mm−1

T = 291 K

0.36 × 0.18 × 0.16 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2001 ▶) T min = 0.142, T max = 0.329

33878 measured reflections

8854 independent reflections

5887 reflections with I > 2σ(I)

R int = 0.071

Refinement

R[F 2 > 2σ(F 2)] = 0.042

wR(F 2) = 0.068

S = 1.00

8854 reflections

487 parameters

1 restraint

H-atom parameters constrained

Δρmax = 0.55 e Å−3

Δρmin = −0.45 e Å−3

Absolute structure: Flack (1983 ▶), 4178 Friedel pairs

Flack parameter: 0.069 (8)

Data collection: APEX2 (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); 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 and PLATON (Spek, 2009 ▶).

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812029285/rz2776sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812029285/rz2776Isup2.hkl

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

[Cu2(C18H14Br4N2O2)2]	F(000) = 2564
Mr = 1345.98	Dx = 2.191 Mg m−3
Orthorhombic, Pca21	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2c -2ac	Cell parameters from 2567 reflections
a = 27.4100 (11) Å	θ = 2.5–27.7°
b = 7.9055 (4) Å	µ = 8.92 mm−1
c = 18.8291 (7) Å	T = 291 K
V = 4080.1 (3) Å3	Needle, dark-brown
Z = 4	0.36 × 0.18 × 0.16 mm

Bruker SMART APEXII CCD area-detector diffractometer	8854 independent reflections
Radiation source: fine-focus sealed tube	5887 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.071
φ and ω scans	θmax = 27.2°, θmin = 1.5°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −35→35
Tmin = 0.142, Tmax = 0.329	k = −10→7
33878 measured reflections	l = −24→24

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.042	H-atom parameters constrained
wR(F2) = 0.068	w = 1/[σ2(Fo2) + (0.0125P)2] where P = (Fo2 + 2Fc2)/3
S = 1.00	(Δ/σ)max = 0.001
8854 reflections	Δρmax = 0.55 e Å−3
487 parameters	Δρmin = −0.45 e Å−3
1 restraint	Absolute structure: Flack (1983), 4178 Friedel pairs
Primary atom site location: structure-invariant direct methods	Flack parameter: 0.069 (8)

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.

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 > 2sigma(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	0.33709 (3)	0.59065 (10)	0.49527 (4)	0.03293 (19)
Cu2	0.37343 (2)	1.17409 (10)	0.50858 (4)	0.03289 (19)
Br1	0.17168 (3)	0.56192 (11)	0.40823 (4)	0.0593 (2)
Br2	0.10462 (3)	0.83048 (10)	0.66708 (4)	0.0541 (2)
Br3	0.62640 (3)	0.96666 (13)	0.39602 (5)	0.0732 (3)
Br4	0.44790 (3)	1.16280 (11)	0.27446 (4)	0.0561 (2)
Br5	0.30469 (3)	1.27351 (11)	0.74365 (4)	0.0578 (2)
Br6	0.11632 (3)	1.30310 (11)	0.62177 (5)	0.0632 (2)
Br7	0.56876 (3)	0.57140 (14)	0.29593 (4)	0.0761 (3)
Br8	0.50186 (2)	0.48746 (10)	0.57844 (4)	0.05028 (19)
O1	0.26874 (14)	0.5837 (6)	0.4829 (2)	0.0381 (11)
O2	0.41492 (15)	1.1542 (6)	0.4276 (2)	0.0405 (12)
O3	0.33343 (14)	1.2315 (5)	0.5877 (2)	0.0404 (11)
O4	0.40368 (14)	0.5235 (5)	0.5055 (2)	0.0402 (11)
N1	0.32999 (17)	0.6362 (6)	0.5991 (2)	0.0308 (13)
N2	0.42674 (17)	1.1050 (6)	0.5741 (2)	0.0310 (12)
N3	0.31486 (19)	1.1816 (7)	0.4438 (3)	0.0368 (14)
N4	0.34345 (17)	0.6214 (6)	0.3909 (2)	0.0306 (12)
C1	0.2344 (2)	0.6384 (8)	0.5247 (3)	0.0339 (16)
C2	0.1857 (2)	0.6452 (8)	0.5005 (3)	0.0377 (16)
C3	0.1483 (2)	0.7013 (8)	0.5410 (3)	0.0390 (17)
H3	0.1167	0.7031	0.5230	0.047*
C4	0.1575 (2)	0.7563 (8)	0.6100 (3)	0.0356 (16)
C5	0.2036 (2)	0.7512 (8)	0.6359 (3)	0.0398 (17)
H5	0.2093	0.7868	0.6822	0.048*
C6	0.24245 (19)	0.6945 (8)	0.5954 (3)	0.0300 (15)
C7	0.2895 (2)	0.6784 (8)	0.6279 (3)	0.0354 (16)
H7	0.2908	0.7015	0.6763	0.042*
C8	0.3727 (2)	0.6193 (8)	0.6465 (3)	0.0338 (16)
H8A	0.3904	0.5168	0.6346	0.041*
H8B	0.3616	0.6094	0.6952	0.041*
C9	0.4068 (2)	0.7694 (8)	0.6403 (3)	0.0349 (17)
H9A	0.4358	0.7475	0.6684	0.042*
H9B	0.4169	0.7810	0.5912	0.042*
C10	0.3844 (2)	0.9332 (8)	0.6645 (3)	0.0367 (16)
H10A	0.3777	0.9263	0.7149	0.044*
H10B	0.3536	0.9495	0.6400	0.044*
C11	0.4172 (2)	1.0860 (9)	0.6505 (3)	0.0391 (17)
H11A	0.4016	1.1874	0.6684	0.047*
H11B	0.4479	1.0717	0.6755	0.047*
C12	0.4703 (2)	1.0696 (8)	0.5534 (3)	0.0372 (17)
H12	0.4922	1.0414	0.5892	0.045*
C13	0.4896 (2)	1.0676 (8)	0.4826 (3)	0.0334 (16)
C14	0.5388 (2)	1.0243 (9)	0.4740 (3)	0.0440 (18)
H14	0.5574	0.9950	0.5135	0.053*
C15	0.5599 (2)	1.0248 (9)	0.4078 (4)	0.0479 (19)
C16	0.5327 (2)	1.0691 (9)	0.3491 (3)	0.0452 (19)
H16	0.5470	1.0714	0.3043	0.054*
C17	0.4846 (2)	1.1095 (8)	0.3570 (3)	0.0354 (17)
C18	0.4607 (2)	1.1130 (8)	0.4237 (3)	0.0334 (16)
C19	0.2864 (2)	1.2337 (8)	0.5952 (3)	0.0315 (15)
C20	0.2645 (2)	1.2575 (8)	0.6626 (3)	0.0388 (17)
C21	0.2150 (2)	1.2745 (8)	0.6710 (4)	0.0444 (18)
H21	0.2021	1.2931	0.7160	0.053*
C22	0.1841 (2)	1.2639 (9)	0.6129 (4)	0.0408 (18)
C23	0.2034 (2)	1.2353 (8)	0.5477 (4)	0.0389 (17)
H23	0.1826	1.2261	0.5088	0.047*
C24	0.2540 (2)	1.2192 (8)	0.5373 (3)	0.0331 (16)
C25	0.2710 (2)	1.2002 (9)	0.4655 (3)	0.0407 (18)
H25	0.2471	1.2017	0.4304	0.049*
C26	0.3207 (2)	1.1622 (8)	0.3660 (3)	0.0369 (17)
H26A	0.3478	1.2310	0.3499	0.044*
H26B	0.2914	1.2019	0.3423	0.044*
C27	0.3299 (2)	0.9758 (9)	0.3458 (3)	0.0408 (18)
H27A	0.3369	0.9704	0.2954	0.049*
H27B	0.3588	0.9373	0.3708	0.049*
C28	0.2886 (2)	0.8547 (9)	0.3619 (4)	0.0417 (18)
H28A	0.2796	0.8666	0.4114	0.050*
H28B	0.2605	0.8859	0.3334	0.050*
C29	0.3009 (2)	0.6721 (8)	0.3476 (3)	0.0370 (17)
H29	0.2841	0.6019	0.3163	0.044*
C30	0.3837 (2)	0.6062 (8)	0.3574 (3)	0.0363 (17)
H30	0.3821	0.6166	0.3083	0.044*
C31	0.4315 (2)	0.5745 (8)	0.3870 (3)	0.0362 (16)
C32	0.4705 (2)	0.5838 (8)	0.3391 (3)	0.0404 (17)
H32	0.4647	0.6030	0.2911	0.048*
C33	0.5173 (2)	0.5642 (10)	0.3635 (4)	0.049 (2)
C34	0.5266 (2)	0.5366 (8)	0.4343 (4)	0.0432 (18)
H34	0.5586	0.5253	0.4501	0.052*
C35	0.4886 (2)	0.5256 (8)	0.4817 (3)	0.0365 (17)
C36	0.4388 (2)	0.5406 (8)	0.4602 (3)	0.0361 (17)

	U11	U22	U33	U12	U13	U23
Cu1	0.0269 (4)	0.0410 (5)	0.0308 (4)	0.0002 (4)	0.0004 (3)	−0.0006 (4)
Cu2	0.0310 (4)	0.0391 (5)	0.0286 (4)	0.0032 (4)	−0.0009 (3)	−0.0020 (4)
Br1	0.0431 (4)	0.0917 (7)	0.0429 (4)	0.0022 (4)	−0.0096 (3)	−0.0238 (4)
Br2	0.0415 (4)	0.0759 (6)	0.0448 (4)	0.0152 (4)	0.0078 (3)	−0.0095 (4)
Br3	0.0422 (5)	0.1092 (8)	0.0683 (5)	0.0223 (5)	0.0063 (4)	−0.0097 (5)
Br4	0.0487 (4)	0.0878 (7)	0.0318 (4)	−0.0031 (4)	−0.0042 (3)	−0.0035 (4)
Br5	0.0506 (5)	0.0907 (7)	0.0321 (4)	−0.0025 (4)	0.0023 (3)	−0.0020 (4)
Br6	0.0347 (4)	0.0777 (7)	0.0770 (5)	0.0032 (4)	0.0163 (4)	0.0150 (5)
Br7	0.0415 (5)	0.1278 (9)	0.0589 (5)	0.0105 (5)	0.0207 (4)	0.0162 (5)
Br8	0.0361 (4)	0.0671 (6)	0.0476 (4)	0.0007 (4)	−0.0064 (3)	0.0057 (4)
O1	0.025 (2)	0.057 (3)	0.033 (2)	−0.001 (2)	0.0020 (18)	−0.012 (2)
O2	0.036 (3)	0.058 (4)	0.028 (2)	0.005 (2)	0.0009 (19)	0.001 (2)
O3	0.030 (3)	0.056 (3)	0.035 (2)	0.005 (2)	−0.002 (2)	−0.008 (2)
O4	0.027 (2)	0.058 (3)	0.035 (3)	0.002 (2)	0.005 (2)	0.007 (2)
N1	0.029 (3)	0.027 (4)	0.036 (3)	−0.008 (2)	−0.001 (2)	0.001 (2)
N2	0.033 (3)	0.032 (3)	0.028 (3)	−0.008 (3)	0.002 (2)	−0.002 (2)
N3	0.037 (3)	0.046 (4)	0.027 (3)	0.003 (3)	0.001 (2)	−0.001 (3)
N4	0.026 (3)	0.036 (4)	0.030 (3)	−0.006 (2)	−0.003 (2)	−0.002 (2)
C1	0.035 (4)	0.031 (5)	0.036 (4)	−0.007 (3)	0.001 (3)	0.004 (3)
C2	0.033 (4)	0.047 (5)	0.033 (4)	−0.003 (3)	−0.001 (3)	−0.005 (3)
C3	0.029 (4)	0.045 (5)	0.044 (4)	−0.002 (3)	−0.004 (3)	0.000 (3)
C4	0.034 (4)	0.047 (5)	0.027 (4)	0.008 (3)	0.005 (3)	0.004 (3)
C5	0.040 (4)	0.058 (5)	0.022 (3)	0.001 (3)	0.005 (3)	−0.001 (3)
C6	0.023 (3)	0.038 (4)	0.029 (3)	−0.005 (3)	0.002 (3)	0.001 (3)
C7	0.037 (4)	0.041 (5)	0.028 (3)	−0.003 (3)	−0.004 (3)	0.000 (3)
C8	0.032 (4)	0.032 (5)	0.038 (4)	−0.001 (3)	−0.010 (3)	0.004 (3)
C9	0.025 (3)	0.040 (5)	0.040 (4)	−0.003 (3)	0.000 (3)	0.000 (3)
C10	0.039 (4)	0.041 (5)	0.030 (3)	−0.003 (3)	−0.001 (3)	0.003 (3)
C11	0.040 (4)	0.054 (5)	0.024 (3)	−0.001 (4)	−0.001 (3)	−0.006 (3)
C12	0.042 (4)	0.040 (5)	0.030 (4)	−0.004 (3)	−0.003 (3)	0.002 (3)
C13	0.033 (4)	0.032 (5)	0.035 (4)	−0.005 (3)	0.004 (3)	0.003 (3)
C14	0.039 (4)	0.051 (5)	0.042 (4)	0.006 (4)	−0.010 (3)	−0.003 (3)
C15	0.042 (4)	0.063 (6)	0.039 (4)	0.007 (4)	0.008 (4)	−0.005 (4)
C16	0.035 (4)	0.068 (6)	0.033 (4)	0.000 (4)	0.011 (3)	−0.014 (4)
C17	0.034 (4)	0.041 (5)	0.032 (3)	−0.001 (3)	−0.001 (3)	−0.006 (3)
C18	0.032 (4)	0.033 (5)	0.035 (4)	−0.003 (3)	0.003 (3)	−0.008 (3)
C19	0.036 (4)	0.026 (4)	0.032 (4)	−0.002 (3)	0.001 (3)	0.002 (3)
C20	0.041 (4)	0.045 (5)	0.031 (3)	−0.006 (3)	0.008 (3)	−0.002 (3)
C21	0.052 (5)	0.037 (5)	0.044 (4)	−0.002 (3)	0.017 (4)	−0.003 (4)
C22	0.027 (4)	0.039 (5)	0.056 (5)	0.003 (3)	0.014 (3)	0.004 (4)
C23	0.034 (4)	0.039 (5)	0.044 (4)	0.000 (3)	−0.005 (3)	0.006 (3)
C24	0.040 (4)	0.032 (5)	0.027 (3)	0.004 (3)	0.001 (3)	0.004 (3)
C25	0.033 (4)	0.056 (5)	0.033 (4)	0.001 (4)	−0.008 (3)	−0.004 (3)
C26	0.033 (4)	0.052 (5)	0.026 (3)	0.004 (3)	−0.006 (3)	0.001 (3)
C27	0.041 (4)	0.049 (5)	0.032 (4)	−0.003 (4)	0.001 (3)	−0.007 (3)
C28	0.033 (4)	0.049 (5)	0.043 (4)	0.004 (3)	0.005 (3)	0.009 (4)
C29	0.037 (4)	0.039 (5)	0.035 (4)	0.001 (3)	−0.015 (3)	−0.011 (3)
C30	0.039 (4)	0.044 (5)	0.026 (3)	0.005 (3)	0.005 (3)	0.004 (3)
C31	0.032 (4)	0.038 (5)	0.038 (4)	0.003 (3)	0.006 (3)	0.002 (3)
C32	0.031 (4)	0.055 (5)	0.035 (4)	0.007 (3)	0.007 (3)	0.009 (4)
C33	0.030 (4)	0.065 (6)	0.050 (4)	0.009 (4)	0.019 (3)	0.006 (4)
C34	0.032 (4)	0.039 (5)	0.059 (5)	0.002 (3)	0.004 (3)	0.008 (4)
C35	0.030 (4)	0.031 (5)	0.049 (4)	0.011 (3)	0.002 (3)	−0.001 (3)
C36	0.026 (4)	0.035 (5)	0.047 (4)	0.003 (3)	0.009 (3)	0.000 (3)

Cu1—O1	1.889 (4)	C10—H10A	0.9700
Cu1—O4	1.911 (4)	C10—H10B	0.9700
Cu1—N4	1.989 (5)	C11—H11A	0.9700
Cu1—N1	1.997 (5)	C11—H11B	0.9700
Cu2—O3	1.905 (4)	C12—C13	1.435 (8)
Cu2—O2	1.909 (4)	C12—H12	0.9300
Cu2—N2	1.989 (5)	C13—C14	1.402 (8)
Cu2—N3	2.016 (5)	C13—C18	1.409 (8)
Br1—C2	1.897 (6)	C14—C15	1.373 (8)
Br2—C4	1.899 (6)	C14—H14	0.9300
Br3—C15	1.892 (6)	C15—C16	1.380 (9)
Br4—C17	1.899 (6)	C16—C17	1.363 (8)
Br5—C20	1.887 (6)	C16—H16	0.9300
Br6—C22	1.890 (6)	C17—C18	1.417 (8)
Br7—C33	1.901 (6)	C19—C24	1.411 (8)
Br8—C35	1.882 (6)	C19—C20	1.416 (8)
O1—C1	1.301 (7)	C20—C21	1.374 (8)
O2—C18	1.299 (7)	C21—C22	1.387 (9)
O3—C19	1.297 (7)	C21—H21	0.9300
O4—C36	1.293 (7)	C22—C23	1.356 (8)
N1—C7	1.279 (7)	C23—C24	1.406 (8)
N1—C8	1.479 (6)	C23—H23	0.9300
N2—C12	1.286 (7)	C24—C25	1.437 (8)
N2—C11	1.469 (7)	C25—H25	0.9300
N3—C25	1.279 (7)	C26—C27	1.543 (9)
N3—C26	1.482 (7)	C26—H26A	0.9700
N4—C30	1.277 (7)	C26—H26B	0.9700
N4—C29	1.479 (7)	C27—C28	1.513 (8)
C1—C2	1.411 (8)	C27—H27A	0.9700
C1—C6	1.421 (8)	C27—H27B	0.9700
C2—C3	1.352 (8)	C28—C29	1.506 (9)
C3—C4	1.393 (8)	C28—H28A	0.9700
C3—H3	0.9300	C28—H28B	0.9700
C4—C5	1.355 (8)	C29—H29	0.9300
C5—C6	1.383 (7)	C30—C31	1.444 (8)
C5—H5	0.9300	C30—H30	0.9300
C6—C7	1.434 (7)	C31—C32	1.401 (8)
C7—H7	0.9300	C31—C36	1.418 (9)
C8—C9	1.514 (8)	C32—C33	1.372 (8)
C8—H8A	0.9700	C32—H32	0.9300
C8—H8B	0.9700	C33—C34	1.374 (9)
C9—C10	1.503 (8)	C34—C35	1.374 (8)
C9—H9A	0.9700	C34—H34	0.9300
C9—H9B	0.9700	C35—C36	1.429 (8)
C10—C11	1.528 (8)
O1—Cu1—O4	162.17 (19)	C15—C14—C13	120.6 (6)
O1—Cu1—N4	88.22 (18)	C15—C14—H14	119.7
O4—Cu1—N4	92.86 (18)	C13—C14—H14	119.7
O1—Cu1—N1	91.66 (18)	C14—C15—C16	120.0 (6)
O4—Cu1—N1	92.55 (18)	C14—C15—Br3	120.8 (5)
N4—Cu1—N1	162.58 (19)	C16—C15—Br3	119.3 (5)
O3—Cu2—O2	170.95 (19)	C17—C16—C15	119.7 (6)
O3—Cu2—N2	90.16 (19)	C17—C16—H16	120.2
O2—Cu2—N2	92.04 (18)	C15—C16—H16	120.2
O3—Cu2—N3	90.44 (19)	C16—C17—C18	123.3 (6)
O2—Cu2—N3	89.63 (19)	C16—C17—Br4	118.4 (5)
N2—Cu2—N3	165.5 (2)	C18—C17—Br4	118.3 (5)
C1—O1—Cu1	129.4 (4)	O2—C18—C13	124.2 (5)
C18—O2—Cu2	129.9 (4)	O2—C18—C17	120.2 (5)
C19—O3—Cu2	131.3 (4)	C13—C18—C17	115.6 (6)
C36—O4—Cu1	128.0 (4)	O3—C19—C24	122.8 (5)
C7—N1—C8	117.0 (5)	O3—C19—C20	121.3 (5)
C7—N1—Cu1	123.2 (4)	C24—C19—C20	115.9 (5)
C8—N1—Cu1	119.9 (4)	C21—C20—C19	122.4 (6)
C12—N2—C11	116.1 (5)	C21—C20—Br5	118.5 (5)
C12—N2—Cu2	123.6 (4)	C19—C20—Br5	119.1 (4)
C11—N2—Cu2	120.3 (4)	C20—C21—C22	120.4 (6)
C25—N3—C26	115.3 (5)	C20—C21—H21	119.8
C25—N3—Cu2	124.0 (4)	C22—C21—H21	119.8
C26—N3—Cu2	120.6 (4)	C23—C22—C21	119.1 (6)
C30—N4—C29	115.9 (5)	C23—C22—Br6	119.4 (5)
C30—N4—Cu1	123.5 (4)	C21—C22—Br6	121.4 (5)
C29—N4—Cu1	120.6 (4)	C22—C23—C24	121.8 (6)
O1—C1—C2	120.2 (5)	C22—C23—H23	119.1
O1—C1—C6	123.8 (5)	C24—C23—H23	119.1
C2—C1—C6	116.0 (5)	C23—C24—C19	120.4 (6)
C3—C2—C1	123.2 (6)	C23—C24—C25	117.4 (6)
C3—C2—Br1	118.5 (5)	C19—C24—C25	122.0 (6)
C1—C2—Br1	118.2 (5)	N3—C25—C24	128.1 (6)
C2—C3—C4	119.4 (6)	N3—C25—H25	115.9
C2—C3—H3	120.3	C24—C25—H25	115.9
C4—C3—H3	120.3	N3—C26—C27	111.1 (5)
C5—C4—C3	119.8 (6)	N3—C26—H26A	109.4
C5—C4—Br2	121.2 (4)	C27—C26—H26A	109.4
C3—C4—Br2	119.0 (5)	N3—C26—H26B	109.4
C4—C5—C6	121.9 (5)	C27—C26—H26B	109.4
C4—C5—H5	119.1	H26A—C26—H26B	108.0
C6—C5—H5	119.1	C28—C27—C26	115.6 (5)
C5—C6—C1	119.8 (5)	C28—C27—H27A	108.4
C5—C6—C7	119.0 (5)	C26—C27—H27A	108.4
C1—C6—C7	120.9 (5)	C28—C27—H27B	108.4
N1—C7—C6	128.5 (5)	C26—C27—H27B	108.4
N1—C7—H7	115.8	H27A—C27—H27B	107.4
C6—C7—H7	115.8	C29—C28—C27	113.8 (5)
N1—C8—C9	111.8 (5)	C29—C28—H28A	108.8
N1—C8—H8A	109.3	C27—C28—H28A	108.8
C9—C8—H8A	109.3	C29—C28—H28B	108.8
N1—C8—H8B	109.3	C27—C28—H28B	108.8
C9—C8—H8B	109.3	H28A—C28—H28B	107.7
H8A—C8—H8B	107.9	N4—C29—C28	109.7 (5)
C10—C9—C8	113.6 (5)	N4—C29—H29	125.1
C10—C9—H9A	108.8	C28—C29—H29	125.1
C8—C9—H9A	108.8	N4—C30—C31	127.5 (6)
C10—C9—H9B	108.8	N4—C30—H30	116.2
C8—C9—H9B	108.8	C31—C30—H30	116.2
H9A—C9—H9B	107.7	C32—C31—C36	121.9 (6)
C9—C10—C11	112.9 (5)	C32—C31—C30	115.7 (6)
C9—C10—H10A	109.0	C36—C31—C30	122.4 (5)
C11—C10—H10A	109.0	C33—C32—C31	119.4 (6)
C9—C10—H10B	109.0	C33—C32—H32	120.3
C11—C10—H10B	109.0	C31—C32—H32	120.3
H10A—C10—H10B	107.8	C32—C33—C34	121.1 (6)
N2—C11—C10	110.7 (5)	C32—C33—Br7	117.8 (5)
N2—C11—H11A	109.5	C34—C33—Br7	121.1 (5)
C10—C11—H11A	109.5	C33—C34—C35	120.0 (6)
N2—C11—H11B	109.5	C33—C34—H34	120.0
C10—C11—H11B	109.5	C35—C34—H34	120.0
H11A—C11—H11B	108.1	C34—C35—C36	122.3 (6)
N2—C12—C13	128.8 (6)	C34—C35—Br8	119.6 (5)
N2—C12—H12	115.6	C36—C35—Br8	118.1 (5)
C13—C12—H12	115.6	O4—C36—C31	123.7 (6)
C14—C13—C18	120.8 (6)	O4—C36—C35	121.0 (6)
C14—C13—C12	117.7 (6)	C31—C36—C35	115.2 (5)
C18—C13—C12	121.4 (6)
O4—Cu1—O1—C1	120.3 (6)	C12—C13—C14—C15	−178.1 (6)
N4—Cu1—O1—C1	−145.9 (5)	C13—C14—C15—C16	0.3 (11)
N1—Cu1—O1—C1	16.7 (5)	C13—C14—C15—Br3	179.9 (5)
N2—Cu2—O2—C18	−1.2 (5)	C14—C15—C16—C17	−1.1 (11)
N3—Cu2—O2—C18	−166.7 (5)	Br3—C15—C16—C17	179.3 (5)
N2—Cu2—O3—C19	−152.3 (5)	C15—C16—C17—C18	1.7 (11)
N3—Cu2—O3—C19	13.2 (5)	C15—C16—C17—Br4	−178.1 (5)
O1—Cu1—O4—C36	108.0 (7)	Cu2—O2—C18—C13	2.1 (9)
N4—Cu1—O4—C36	14.9 (5)	Cu2—O2—C18—C17	−178.7 (4)
N1—Cu1—O4—C36	−148.6 (5)	C14—C13—C18—O2	179.9 (6)
O1—Cu1—N1—C7	−12.7 (5)	C12—C13—C18—O2	−2.2 (10)
O4—Cu1—N1—C7	−175.4 (5)	C14—C13—C18—C17	0.6 (9)
N4—Cu1—N1—C7	76.6 (8)	C12—C13—C18—C17	178.5 (6)
O1—Cu1—N1—C8	166.4 (4)	C16—C17—C18—O2	179.3 (6)
O4—Cu1—N1—C8	3.8 (4)	Br4—C17—C18—O2	−0.9 (8)
N4—Cu1—N1—C8	−104.2 (7)	C16—C17—C18—C13	−1.4 (10)
O3—Cu2—N2—C12	−170.4 (5)	Br4—C17—C18—C13	178.3 (5)
O2—Cu2—N2—C12	0.8 (5)	Cu2—O3—C19—C24	−11.7 (9)
N3—Cu2—N2—C12	97.2 (9)	Cu2—O3—C19—C20	170.7 (5)
O3—Cu2—N2—C11	11.8 (4)	O3—C19—C20—C21	174.4 (6)
O2—Cu2—N2—C11	−177.0 (4)	C24—C19—C20—C21	−3.4 (9)
N3—Cu2—N2—C11	−80.6 (9)	O3—C19—C20—Br5	−3.6 (8)
O3—Cu2—N3—C25	−7.0 (6)	C24—C19—C20—Br5	178.7 (5)
O2—Cu2—N3—C25	−177.9 (5)	C19—C20—C21—C22	1.9 (10)
N2—Cu2—N3—C25	85.3 (10)	Br5—C20—C21—C22	179.9 (5)
O3—Cu2—N3—C26	174.2 (5)	C20—C21—C22—C23	0.5 (10)
O2—Cu2—N3—C26	3.2 (5)	C20—C21—C22—Br6	−175.3 (5)
N2—Cu2—N3—C26	−93.5 (9)	C21—C22—C23—C24	−1.2 (10)
O1—Cu1—N4—C30	−166.8 (5)	Br6—C22—C23—C24	174.7 (5)
O4—Cu1—N4—C30	−4.6 (5)	C22—C23—C24—C19	−0.4 (10)
N1—Cu1—N4—C30	103.3 (8)	C22—C23—C24—C25	−176.0 (6)
O1—Cu1—N4—C29	16.1 (4)	O3—C19—C24—C23	−175.1 (6)
O4—Cu1—N4—C29	178.2 (4)	C20—C19—C24—C23	2.6 (9)
N1—Cu1—N4—C29	−73.8 (8)	O3—C19—C24—C25	0.2 (10)
Cu1—O1—C1—C2	169.9 (4)	C20—C19—C24—C25	177.9 (6)
Cu1—O1—C1—C6	−9.9 (9)	C26—N3—C25—C24	178.9 (6)
O1—C1—C2—C3	−179.7 (6)	Cu2—N3—C25—C24	0.0 (10)
C6—C1—C2—C3	0.1 (10)	C23—C24—C25—N3	−179.1 (7)
O1—C1—C2—Br1	3.2 (8)	C19—C24—C25—N3	5.5 (11)
C6—C1—C2—Br1	−177.0 (4)	C25—N3—C26—C27	−103.0 (6)
C1—C2—C3—C4	0.3 (10)	Cu2—N3—C26—C27	76.0 (6)
Br1—C2—C3—C4	177.3 (5)	N3—C26—C27—C28	64.1 (7)
C2—C3—C4—C5	−0.7 (10)	C26—C27—C28—C29	−174.7 (5)
C2—C3—C4—Br2	−178.7 (5)	C30—N4—C29—C28	−105.3 (6)
C3—C4—C5—C6	0.8 (10)	Cu1—N4—C29—C28	72.0 (6)
Br2—C4—C5—C6	178.8 (5)	C27—C28—C29—N4	58.9 (7)
C4—C5—C6—C1	−0.5 (10)	C29—N4—C30—C31	173.5 (6)
C4—C5—C6—C7	−174.6 (6)	Cu1—N4—C30—C31	−3.7 (9)
O1—C1—C6—C5	179.8 (6)	N4—C30—C31—C32	−172.6 (6)
C2—C1—C6—C5	0.0 (9)	N4—C30—C31—C36	5.8 (11)
O1—C1—C6—C7	−6.2 (9)	C36—C31—C32—C33	−1.8 (10)
C2—C1—C6—C7	174.0 (6)	C30—C31—C32—C33	176.6 (6)
C8—N1—C7—C6	−176.3 (6)	C31—C32—C33—C34	−0.4 (11)
Cu1—N1—C7—C6	2.9 (9)	C31—C32—C33—Br7	178.2 (5)
C5—C6—C7—N1	−176.5 (6)	C32—C33—C34—C35	1.0 (11)
C1—C6—C7—N1	9.5 (10)	Br7—C33—C34—C35	−177.6 (5)
C7—N1—C8—C9	−103.6 (6)	C33—C34—C35—C36	0.5 (10)
Cu1—N1—C8—C9	77.2 (6)	C33—C34—C35—Br8	179.9 (6)
N1—C8—C9—C10	64.5 (7)	Cu1—O4—C36—C31	−16.8 (9)
C8—C9—C10—C11	−173.8 (5)	Cu1—O4—C36—C35	163.3 (5)
C12—N2—C11—C10	−108.8 (6)	C32—C31—C36—O4	−176.7 (6)
Cu2—N2—C11—C10	69.2 (6)	C30—C31—C36—O4	5.0 (10)
C9—C10—C11—N2	61.0 (7)	C32—C31—C36—C35	3.1 (9)
C11—N2—C12—C13	176.4 (6)	C30—C31—C36—C35	−175.2 (6)
Cu2—N2—C12—C13	−1.4 (10)	C34—C35—C36—O4	177.4 (6)
N2—C12—C13—C14	180.0 (6)	Br8—C35—C36—O4	−2.0 (8)
N2—C12—C13—C18	2.0 (11)	C34—C35—C36—C31	−2.5 (10)
C18—C13—C14—C15	−0.1 (10)	Br8—C35—C36—C31	178.1 (5)

D—H···A	D—H	H···A	D···A	D—H···A
C10—H10B···O3	0.97	2.50	3.099 (7)	120
C27—H27B···O2	0.97	2.54	3.129 (7)	119

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C10—H10B⋯O3	0.97	2.50	3.099 (7)	120
C27—H27B⋯O2	0.97	2.54	3.129 (7)	119