(Dimethyl­formamide-κO){4,4′,6,6′-tetra­bromo-2,2′-[o-phenyl­enebis(nitrilo­methyl­idyne)]diphenolato-κ⁴O,N,N′,O′}copper(II) dimethyl­formamide solvate

In the title compound, [Cu(C₂₀H₁₀Br₄N₂O₂)(C₃H₇NO)]·C₃H₇NO, the Cu^II ion is coordinated by two N atoms and two O atoms from a tetra­dentate Schiff base ligand and the O atom of one dimethyl­formamide ligand in an almost square-pyramidal geometry. The uncoordinated dimethyl­formamide solvent mol­ecule is disordered over two sets of positions with occupancies of 0.741 (4) and 0.259 (4). The crystal packing is stabilized by C—H...O inter­actions.

Key indicators

• Single-crystal X-ray study
• T = 93 K
• Mean [sigma](C-C) = 0.005 Å
• Disorder in solvent or counterion
• R factor = 0.035
• wR factor = 0.063
• Data-to-parameter ratio = 16.1

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT220_ALERT_2_B Large Non-Solvent    C     Ueq(max)/Ueq(min) ...       3.83 Ratio
PLAT230_ALERT_2_B Hirshfeld Test Diff for    O3     --  C21     ..       8.28 su

Alert level C
PLAT029_ALERT_3_C _diffrn_measured_fraction_theta_full Low .......       0.96
PLAT222_ALERT_3_C Large Non-Solvent    H     Ueq(max)/Ueq(min) ...       3.35 Ratio
PLAT311_ALERT_2_C Isolated Disordered Oxygen Atom (No H's ?) .....       <O4'
PLAT431_ALERT_2_C Short Inter HL..A Contact  Br2    ..  Br3     ..       3.56 Ang.
PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd.  #          2
              C3 H7 N O

Alert level G
ABSTM02_ALERT_3_G  When printed, the submitted absorption T values will be
            replaced by the scaled T values. Since the ratio of scaled T's
            is identical to the ratio of reported T values, the scaling
            does not imply a change to the absorption corrections used in
            the study.
            Ratio of Tmax expected/reported      0.681
            Tmax scaled      0.204 Tmin scaled      0.204
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......          8
PLAT062_ALERT_4_G Rescale T(min) & T(max) by .....................       0.68
PLAT302_ALERT_4_G Note Anion/Solvent Disorder ....................      50.00 Perc.

   0 ALERT level A = In general: serious problem
   2 ALERT level B = Potentially serious problem
   5 ALERT level C = Check and explain
   4 ALERT level G = General alerts; check

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

---

S1. Comment

The crystal structure and some properties of 1,2-N,N'-disalicylidenephenylaminato-nickel(II) was previously reported by Bei et al. (2003). We report here the synthesis and crystal structure of the title complex, [Cu(C₁₄H₈N₂O₃Br₂)(C₃H₇NO)](C₃H₇NO).

The contents of the asymmetric unit are shown in Fig.1. The Cu^II ion is coordinated by two N atoms and two O atoms from one 4,4',6,6'-tetrabromo-2,2'-[1,2-phenylenebis(nitrilomethylidyne)]diphenolate dianion and one O atom of N,N-dimethylformamide ligand in a square-pyramidal geometry (Table 1). The crystal packing is stabilized by C—H···O interactions (Table 2).

Related literature

For the preparation of 3,5-dibromosalicylaldehyde, see: Elzbieta et al. (1964). For a related structure, see: Bei et al. (2003).

S2. Experimental

The title complex was synthesized in two stages. In the first stage, 3,5- dibromosalicylaldehyde was prepared according to Elzbieta et al. (1964). Two mole equivalents of 3,5-dibromosalicylaldehyde in ethanol (50 ml) was slowly added to 1,2-phenylenediamine (6 g) in ethanol (100 ml) with continuous stirring. The Schiff base molecule, viz. 4,4',6,6'-tetrabromo-2,2'-[1,2-phenylenebis(nitrilomethylidyne)] diphenol, precipitated immediately. In the second stage, the ligand (1 mmol), Cu(OAc)₂ (1 mmol) and DMF (25 ml) were refluxed for 1 h. The hot solution was filtered and allowed to stand at room temperature undisturbed for about three weeks, resulting in dark green crystals.

S3. Refinement

The uncoordinated N,N-dimethylformamide solvent molecule is disordered over two positions with occupancies of 0.741 (4) and 0.259 (4). The N—C(sp³), N—C(sp²) and C—O distances in both disorder components were restrained to 1.460 (3), 1.340 (3) and 1.220 (3) Å, respectively. H atoms were positioned geometrically and refined using a riding model, with C—H = 0.95 or 0.98 Å and U_iso(H) = 1.2U_eq(C).

Computing details

Data collection: RAPID-AUTO (Rigaku, 2004); cell refinement: RAPID-AUTO (Rigaku, 2004); data reduction: RAPID-AUTO (Rigaku, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures

Fig. 1. A view of the title complex, showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level. H atoms have been omitted for the sake of clarity. Both disorder components of the uncoordinated solvent molecule are shown.

(Dimethylformamide-κO){4,4',6,6'-tetrabromo-2,2'-[o- phenylenebis(nitrilomethylidyne)]diphenolato- κ⁴O,N,N',O'}copper(II) dimethylformamide solvate

Crystal data

[Cu(C20H10Br4N2O2)(C3H7NO)]·C3H7NO	Z = 2
Mr = 839.67	F(000) = 818
Triclinic, P1	Dx = 1.941 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.3742 (10) Å	Cell parameters from 4531 reflections
b = 11.9542 (19) Å	θ = 3.1–27.5°
c = 17.212 (2) Å	µ = 6.36 mm^−1
α = 94.207 (9)°	T = 93 K
β = 100.310 (6)°	Block, dark green
γ = 104.117 (5)°	0.25 × 0.25 × 0.25 mm
V = 1436.8 (3) Å^3

Data collection

Rigaku SPIDER diffractometer	6330 independent reflections
Radiation source: Rotating Anode	5305 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.027
ω scans	θmax = 27.5°, θmin = 3.1°
Absorption correction: multi-scan (RAPID-AUTO; Rigaku, 2004)	h = −8→9
Tmin = 0.299, Tmax = 0.299	k = −15→15
11906 measured reflections	l = −22→22

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)] = 0.035	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.063	H-atom parameters constrained
S = 1.02	w = 1/[σ^2(Fo^2) + (0.0247P)^2] where P = (Fo^2 + 2Fc^2)/3
6330 reflections	(Δ/σ)max = 0.002
392 parameters	Δρmax = 0.75 e Å^−3
8 restraints	Δρmin = −0.52 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	0.39299 (5)	0.60816 (3)	0.67052 (2)	0.01305 (9)
Br1	0.12215 (5)	0.88993 (3)	0.535887 (19)	0.01998 (8)
Br2	−0.00681 (5)	0.60574 (3)	0.244696 (18)	0.02312 (9)
Br3	0.74637 (5)	0.75127 (3)	1.105720 (18)	0.02390 (9)
Br4	0.49378 (5)	0.96915 (3)	0.842406 (19)	0.02212 (9)
O1	0.2620 (3)	0.69347 (17)	0.60103 (11)	0.0141 (5)
O2	0.4409 (3)	0.73265 (18)	0.75456 (11)	0.0152 (5)
N1	0.3449 (3)	0.4761 (2)	0.58884 (14)	0.0124 (5)
N2	0.4835 (4)	0.5038 (2)	0.74155 (14)	0.0142 (6)
C1	0.2062 (4)	0.6699 (3)	0.52455 (17)	0.0129 (6)
C2	0.1319 (4)	0.7497 (3)	0.48000 (17)	0.0137 (6)
C3	0.0698 (4)	0.7320 (3)	0.39909 (17)	0.0150 (7)
H3	0.0224	0.7885	0.3718	0.018*
C4	0.0777 (4)	0.6295 (3)	0.35772 (17)	0.0161 (7)
C5	0.1450 (4)	0.5472 (3)	0.39550 (17)	0.0157 (7)
H5	0.1484	0.4777	0.3660	0.019*
C6	0.2099 (4)	0.5664 (3)	0.47917 (17)	0.0125 (6)
C7	0.2743 (4)	0.4742 (3)	0.51432 (18)	0.0142 (6)
H7	0.2642	0.4061	0.4799	0.017*
C8	0.3973 (4)	0.3788 (3)	0.61884 (18)	0.0134 (6)
C9	0.3827 (4)	0.2740 (3)	0.57325 (19)	0.0172 (7)
H9	0.3361	0.2643	0.5174	0.021*
C10	0.4360 (4)	0.1849 (3)	0.60964 (19)	0.0191 (7)
H10	0.4272	0.1139	0.5788	0.023*
C11	0.5026 (5)	0.1987 (3)	0.69131 (19)	0.0217 (7)
H11	0.5367	0.1361	0.7159	0.026*
C12	0.5201 (4)	0.3013 (3)	0.73727 (19)	0.0184 (7)
H12	0.5667	0.3097	0.7931	0.022*
C13	0.4690 (4)	0.3924 (3)	0.70124 (18)	0.0139 (6)
C14	0.5440 (4)	0.5275 (3)	0.81769 (17)	0.0149 (7)
H14	0.5803	0.4682	0.8457	0.018*
C15	0.5606 (4)	0.6358 (3)	0.86300 (17)	0.0147 (7)
C16	0.6296 (4)	0.6425 (3)	0.94604 (17)	0.0168 (7)
H16	0.6600	0.5771	0.9680	0.020*
C17	0.6526 (4)	0.7431 (3)	0.99485 (17)	0.0172 (7)
C18	0.6111 (4)	0.8407 (3)	0.96363 (18)	0.0174 (7)
H18	0.6280	0.9104	0.9976	0.021*
C19	0.5458 (4)	0.8344 (3)	0.88351 (18)	0.0156 (7)
C20	0.5124 (4)	0.7327 (3)	0.82895 (17)	0.0142 (7)
O3	0.7162 (3)	0.69177 (19)	0.64181 (13)	0.0218 (5)
N3	0.8292 (4)	0.8852 (2)	0.68559 (16)	0.0251 (7)
C21	0.8417 (5)	0.7771 (3)	0.6803 (2)	0.0272 (8)
H21	0.9556	0.7628	0.7081	0.033*
C22	0.6627 (5)	0.9150 (3)	0.6398 (2)	0.0278 (8)
H22A	0.5753	0.8447	0.6082	0.033*
H22B	0.7052	0.9719	0.6043	0.033*
H22C	0.5967	0.9483	0.6765	0.033*
C23	0.9791 (6)	0.9809 (3)	0.7305 (3)	0.0478 (12)
H23A	1.0806	0.9512	0.7597	0.057*
H23B	0.9273	1.0233	0.7682	0.057*
H23C	1.0315	1.0333	0.6941	0.057*
O4	1.225 (3)	0.6119 (8)	1.0649 (3)	0.0317 (16)	0.741 (4)
C24	1.1892 (7)	0.7023 (4)	1.0473 (2)	0.0281 (12)	0.741 (4)
H24	1.2090	0.7632	1.0891	0.034*	0.741 (4)
N4	1.1242 (16)	0.7216 (4)	0.9731 (2)	0.0216 (12)	0.741 (4)
C25	1.0952 (8)	0.8347 (4)	0.9571 (4)	0.0382 (14)	0.741 (4)
H25A	1.1095	0.8828	1.0075	0.046*	0.741 (4)
H25B	0.9665	0.8243	0.9254	0.046*	0.741 (4)
H25C	1.1900	0.8729	0.9276	0.046*	0.741 (4)
C26	1.0890 (7)	0.6327 (4)	0.9057 (3)	0.0340 (13)	0.741 (4)
H26A	1.1286	0.5649	0.9240	0.041*	0.741 (4)
H26B	1.1622	0.6637	0.8663	0.041*	0.741 (4)
H26C	0.9525	0.6095	0.8815	0.041*	0.741 (4)
O4'	1.229 (8)	0.603 (3)	1.0485 (10)	0.0317 (16)	0.26
C24'	1.1591 (17)	0.6115 (9)	0.9800 (7)	0.018 (3)	0.259 (4)
H24'	1.1272	0.5434	0.9429	0.022*	0.259 (4)
N4'	1.123 (5)	0.7071 (13)	0.9520 (7)	0.0216 (12)	0.26
C25'	1.0462 (17)	0.7099 (12)	0.8680 (6)	0.022 (3)	0.259 (4)
H25D	1.1422	0.7618	0.8453	0.026*	0.259 (4)
H25E	0.9312	0.7383	0.8630	0.026*	0.259 (4)
H25F	1.0138	0.6314	0.8395	0.026*	0.259 (4)
C26'	1.1704 (18)	0.8156 (10)	1.0052 (7)	0.019 (3)	0.259 (4)
H26D	1.0541	0.8407	1.0070	0.023*	0.259 (4)
H26E	1.2613	0.8756	0.9854	0.023*	0.259 (4)
H26F	1.2280	0.8034	1.0587	0.023*	0.259 (4)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.0175 (2)	0.01176 (19)	0.01046 (18)	0.00541 (16)	0.00143 (15)	0.00295 (15)
Br1	0.02559 (19)	0.01350 (16)	0.02113 (17)	0.00819 (14)	0.00104 (14)	0.00254 (13)
Br2	0.02115 (18)	0.0359 (2)	0.01140 (16)	0.00857 (15)	−0.00079 (13)	0.00359 (14)
Br3	0.02659 (19)	0.0333 (2)	0.01011 (16)	0.00644 (15)	0.00017 (14)	0.00550 (14)
Br4	0.0337 (2)	0.01807 (17)	0.01618 (16)	0.01086 (15)	0.00296 (14)	0.00318 (13)
O1	0.0191 (12)	0.0135 (11)	0.0094 (10)	0.0063 (9)	−0.0006 (9)	0.0018 (9)
O2	0.0226 (12)	0.0148 (11)	0.0090 (10)	0.0081 (10)	0.0009 (9)	0.0018 (9)
N1	0.0110 (13)	0.0112 (13)	0.0143 (13)	0.0025 (10)	0.0010 (11)	0.0016 (11)
N2	0.0157 (14)	0.0127 (13)	0.0164 (13)	0.0049 (11)	0.0060 (11)	0.0050 (11)
C1	0.0115 (15)	0.0142 (16)	0.0120 (15)	0.0013 (12)	0.0015 (12)	0.0045 (13)
C2	0.0134 (16)	0.0121 (15)	0.0160 (16)	0.0029 (12)	0.0038 (13)	0.0035 (13)
C3	0.0103 (15)	0.0182 (17)	0.0167 (16)	0.0031 (13)	0.0013 (13)	0.0080 (13)
C4	0.0119 (16)	0.0222 (18)	0.0114 (15)	0.0017 (13)	−0.0014 (13)	0.0032 (14)
C5	0.0166 (17)	0.0175 (17)	0.0127 (15)	0.0043 (13)	0.0039 (13)	−0.0017 (13)
C6	0.0146 (16)	0.0131 (16)	0.0118 (15)	0.0057 (13)	0.0043 (13)	0.0027 (13)
C7	0.0143 (16)	0.0127 (16)	0.0160 (16)	0.0014 (13)	0.0070 (13)	0.0017 (13)
C8	0.0093 (15)	0.0114 (15)	0.0209 (16)	0.0021 (12)	0.0058 (13)	0.0060 (13)
C9	0.0149 (16)	0.0156 (16)	0.0202 (17)	0.0039 (13)	0.0013 (14)	0.0027 (14)
C10	0.0188 (17)	0.0125 (16)	0.0267 (18)	0.0047 (14)	0.0064 (15)	0.0015 (14)
C11	0.0241 (19)	0.0177 (17)	0.0294 (19)	0.0095 (14)	0.0117 (15)	0.0127 (15)
C12	0.0197 (17)	0.0226 (18)	0.0181 (17)	0.0098 (14)	0.0088 (14)	0.0086 (14)
C13	0.0145 (16)	0.0113 (15)	0.0179 (16)	0.0041 (12)	0.0064 (13)	0.0031 (13)
C14	0.0146 (16)	0.0183 (17)	0.0144 (15)	0.0055 (13)	0.0049 (13)	0.0094 (13)
C15	0.0122 (16)	0.0202 (17)	0.0120 (15)	0.0049 (13)	0.0017 (13)	0.0029 (13)
C16	0.0147 (16)	0.0237 (18)	0.0150 (16)	0.0085 (14)	0.0028 (13)	0.0101 (14)
C17	0.0158 (17)	0.0257 (18)	0.0085 (15)	0.0039 (14)	0.0001 (13)	0.0027 (14)
C18	0.0152 (17)	0.0217 (18)	0.0151 (16)	0.0047 (14)	0.0036 (13)	0.0003 (14)
C19	0.0168 (17)	0.0161 (16)	0.0159 (16)	0.0066 (13)	0.0042 (13)	0.0049 (13)
C20	0.0113 (16)	0.0193 (17)	0.0127 (15)	0.0041 (13)	0.0034 (12)	0.0037 (13)
O3	0.0247 (13)	0.0146 (12)	0.0243 (13)	0.0014 (10)	0.0073 (11)	−0.0015 (10)
N3	0.0296 (17)	0.0163 (15)	0.0258 (16)	0.0010 (13)	0.0043 (13)	−0.0002 (13)
C21	0.030 (2)	0.029 (2)	0.0271 (19)	0.0131 (17)	0.0084 (17)	0.0096 (17)
C22	0.036 (2)	0.0224 (19)	0.0259 (19)	0.0092 (17)	0.0055 (17)	0.0013 (16)
C23	0.047 (3)	0.023 (2)	0.057 (3)	−0.0038 (19)	−0.012 (2)	−0.001 (2)
O4	0.0336 (19)	0.031 (2)	0.029 (3)	0.0112 (18)	−0.003 (4)	0.011 (2)
C24	0.021 (3)	0.032 (3)	0.027 (3)	0.004 (2)	−0.002 (2)	0.006 (2)
N4	0.0193 (16)	0.021 (2)	0.024 (3)	0.005 (2)	0.001 (4)	0.007 (2)
C25	0.030 (3)	0.035 (3)	0.056 (4)	0.012 (3)	0.014 (3)	0.023 (3)
C26	0.024 (3)	0.049 (4)	0.032 (3)	0.010 (3)	0.008 (2)	0.012 (3)
O4'	0.0336 (19)	0.031 (2)	0.029 (3)	0.0112 (18)	−0.003 (4)	0.011 (2)
C24'	0.013 (6)	0.013 (6)	0.028 (7)	−0.004 (5)	0.007 (6)	0.011 (6)
N4'	0.0193 (16)	0.021 (2)	0.024 (3)	0.005 (2)	0.001 (4)	0.007 (2)
C25'	0.014 (7)	0.037 (8)	0.014 (6)	0.006 (6)	−0.003 (5)	0.016 (6)
C26'	0.013 (7)	0.021 (8)	0.024 (7)	0.005 (6)	0.004 (6)	−0.002 (6)

Geometric parameters (Å, º)

Cu1—O1	1.910 (2)	C16—C17	1.372 (4)
Cu1—O2	1.9174 (19)	C16—H16	0.95
Cu1—N1	1.954 (2)	C17—C18	1.397 (4)
Cu1—N2	1.958 (2)	C18—C19	1.367 (4)
Cu1—O3	2.501 (2)	C18—H18	0.95
Br1—C2	1.894 (3)	C19—C20	1.423 (4)
Br2—C4	1.911 (3)	O3—C21	1.247 (4)
Br3—C17	1.897 (3)	N3—C21	1.316 (4)
Br4—C19	1.901 (3)	N3—C23	1.441 (4)
O1—C1	1.295 (3)	N3—C22	1.471 (4)
O2—C20	1.294 (3)	C21—H21	0.95
N1—C7	1.291 (4)	C22—H22A	0.98
N1—C8	1.416 (4)	C22—H22B	0.98
N2—C14	1.293 (4)	C22—H22C	0.98
N2—C13	1.426 (4)	C23—H23A	0.98
C1—C2	1.418 (4)	C23—H23B	0.98
C1—C6	1.423 (4)	C23—H23C	0.98
C2—C3	1.369 (4)	O4—C24	1.218 (3)
C3—C4	1.390 (4)	C24—N4	1.340 (3)
C3—H3	0.95	C24—H24	0.95
C4—C5	1.361 (4)	N4—C26	1.456 (3)
C5—C6	1.416 (4)	N4—C25	1.457 (3)
C5—H5	0.95	C25—H25A	0.98
C6—C7	1.434 (4)	C25—H25B	0.98
C7—H7	0.95	C25—H25C	0.98
C8—C9	1.399 (4)	C26—H26A	0.98
C8—C13	1.405 (4)	C26—H26B	0.98
C9—C10	1.377 (4)	C26—H26C	0.98
C9—H9	0.95	O4'—C24'	1.220 (3)
C10—C11	1.387 (4)	C24'—N4'	1.340 (3)
C10—H10	0.95	C24'—H24'	0.95
C11—C12	1.375 (4)	N4'—C25'	1.460 (3)
C11—H11	0.95	N4'—C26'	1.460 (3)
C12—C13	1.389 (4)	C25'—H25D	0.98
C12—H12	0.95	C25'—H25E	0.98
C14—C15	1.428 (4)	C25'—H25F	0.98
C14—H14	0.95	C26'—H26D	0.98
C15—C16	1.418 (4)	C26'—H26E	0.98
C15—C20	1.427 (4)	C26'—H26F	0.98
O1—Cu1—O2	89.11 (8)	C16—C15—C14	115.6 (3)
O1—Cu1—N1	93.40 (9)	C20—C15—C14	123.6 (3)
O2—Cu1—N1	177.19 (10)	C17—C16—C15	120.3 (3)
O1—Cu1—N2	170.18 (10)	C17—C16—H16	119.9
O2—Cu1—N2	93.64 (9)	C15—C16—H16	119.9
N1—Cu1—N2	83.67 (10)	C16—C17—C18	120.7 (3)
O1—Cu1—O3	96.00 (9)	C16—C17—Br3	119.8 (2)
O2—Cu1—O3	89.70 (8)	C18—C17—Br3	119.4 (2)
N1—Cu1—O3	91.29 (9)	C19—C18—C17	119.0 (3)
N2—Cu1—O3	93.44 (9)	C19—C18—H18	120.5
C1—O1—Cu1	126.73 (19)	C17—C18—H18	120.5
C20—O2—Cu1	126.9 (2)	C18—C19—C20	124.0 (3)
C7—N1—C8	121.5 (3)	C18—C19—Br4	118.1 (2)
C7—N1—Cu1	125.3 (2)	C20—C19—Br4	117.9 (2)
C8—N1—Cu1	113.22 (19)	O2—C20—C19	119.9 (3)
C14—N2—C13	121.4 (3)	O2—C20—C15	124.9 (3)
C14—N2—Cu1	125.7 (2)	C19—C20—C15	115.2 (3)
C13—N2—Cu1	112.92 (19)	C21—O3—Cu1	126.8 (2)
O1—C1—C2	119.9 (3)	C21—N3—C23	123.2 (3)
O1—C1—C6	125.0 (3)	C21—N3—C22	120.3 (3)
C2—C1—C6	115.1 (3)	C23—N3—C22	116.3 (3)
C3—C2—C1	123.8 (3)	O3—C21—N3	125.4 (3)
C3—C2—Br1	118.3 (2)	O3—C21—H21	117.3
C1—C2—Br1	117.8 (2)	N3—C21—H21	117.3
C2—C3—C4	118.6 (3)	N3—C22—H22A	109.5
C2—C3—H3	120.7	N3—C22—H22B	109.5
C4—C3—H3	120.7	H22A—C22—H22B	109.5
C5—C4—C3	121.8 (3)	N3—C22—H22C	109.5
C5—C4—Br2	119.8 (2)	H22A—C22—H22C	109.5
C3—C4—Br2	118.5 (2)	H22B—C22—H22C	109.5
C4—C5—C6	119.3 (3)	N3—C23—H23A	109.5
C4—C5—H5	120.3	N3—C23—H23B	109.5
C6—C5—H5	120.3	H23A—C23—H23B	109.5
C5—C6—C1	121.4 (3)	N3—C23—H23C	109.5
C5—C6—C7	115.7 (3)	H23A—C23—H23C	109.5
C1—C6—C7	123.0 (3)	H23B—C23—H23C	109.5
N1—C7—C6	125.4 (3)	O4—C24—N4	124.5 (4)
N1—C7—H7	117.3	O4—C24—H24	117.8
C6—C7—H7	117.3	N4—C24—H24	117.8
C9—C8—C13	119.4 (3)	C24—N4—C26	121.2 (4)
C9—C8—N1	125.2 (3)	C24—N4—C25	120.7 (4)
C13—C8—N1	115.3 (3)	C26—N4—C25	118.0 (4)
C10—C9—C8	119.8 (3)	O4'—C24'—N4'	126.4 (14)
C10—C9—H9	120.1	O4'—C24'—H24'	116.8
C8—C9—H9	120.1	N4'—C24'—H24'	116.8
C9—C10—C11	120.1 (3)	C24'—N4'—C25'	122.5 (11)
C9—C10—H10	119.9	C24'—N4'—C26'	119.9 (11)
C11—C10—H10	119.9	C25'—N4'—C26'	117.5 (10)
C12—C11—C10	121.2 (3)	N4'—C25'—H25D	109.5
C12—C11—H11	119.4	N4'—C25'—H25E	109.5
C10—C11—H11	119.4	H25D—C25'—H25E	109.5
C11—C12—C13	119.3 (3)	N4'—C25'—H25F	109.5
C11—C12—H12	120.3	H25D—C25'—H25F	109.5
C13—C12—H12	120.3	H25E—C25'—H25F	109.5
C12—C13—C8	120.1 (3)	N4'—C26'—H26D	109.5
C12—C13—N2	125.0 (3)	N4'—C26'—H26E	109.5
C8—C13—N2	114.8 (3)	H26D—C26'—H26E	109.5
N2—C14—C15	125.1 (3)	N4'—C26'—H26F	109.5
N2—C14—H14	117.4	H26D—C26'—H26F	109.5
C15—C14—H14	117.4	H26E—C26'—H26F	109.5
C16—C15—C20	120.8 (3)
O2—Cu1—O1—C1	169.2 (2)	C8—C9—C10—C11	0.5 (5)
N1—Cu1—O1—C1	−12.0 (2)	C9—C10—C11—C12	−1.2 (5)
O3—Cu1—O1—C1	79.6 (2)	C10—C11—C12—C13	0.4 (5)
O1—Cu1—O2—C20	171.6 (2)	C11—C12—C13—C8	1.0 (5)
N2—Cu1—O2—C20	1.1 (3)	C11—C12—C13—N2	−178.7 (3)
O3—Cu1—O2—C20	−92.4 (2)	C9—C8—C13—C12	−1.6 (5)
O1—Cu1—N1—C7	9.3 (3)	N1—C8—C13—C12	178.3 (3)
N2—Cu1—N1—C7	179.9 (3)	C9—C8—C13—N2	178.1 (3)
O3—Cu1—N1—C7	−86.8 (3)	N1—C8—C13—N2	−1.9 (4)
O1—Cu1—N1—C8	−171.3 (2)	C14—N2—C13—C12	−1.5 (5)
N2—Cu1—N1—C8	−0.7 (2)	Cu1—N2—C13—C12	−179.0 (3)
O3—Cu1—N1—C8	92.6 (2)	C14—N2—C13—C8	178.7 (3)
O2—Cu1—N2—C14	1.5 (3)	Cu1—N2—C13—C8	1.3 (3)
N1—Cu1—N2—C14	−177.6 (3)	C13—N2—C14—C15	−179.1 (3)
O3—Cu1—N2—C14	91.5 (3)	Cu1—N2—C14—C15	−2.0 (4)
O2—Cu1—N2—C13	178.8 (2)	N2—C14—C15—C16	179.7 (3)
N1—Cu1—N2—C13	−0.3 (2)	N2—C14—C15—C20	−0.4 (5)
O3—Cu1—N2—C13	−91.2 (2)	C20—C15—C16—C17	−0.6 (5)
Cu1—O1—C1—C2	−172.1 (2)	C14—C15—C16—C17	179.3 (3)
Cu1—O1—C1—C6	8.9 (4)	C15—C16—C17—C18	−0.9 (5)
O1—C1—C2—C3	179.9 (3)	C15—C16—C17—Br3	−179.6 (2)
C6—C1—C2—C3	−1.0 (5)	C16—C17—C18—C19	0.4 (5)
O1—C1—C2—Br1	1.0 (4)	Br3—C17—C18—C19	179.2 (2)
C6—C1—C2—Br1	−179.9 (2)	C17—C18—C19—C20	1.5 (5)
C1—C2—C3—C4	0.7 (5)	C17—C18—C19—Br4	−179.2 (2)
Br1—C2—C3—C4	179.6 (2)	Cu1—O2—C20—C19	177.6 (2)
C2—C3—C4—C5	0.0 (5)	Cu1—O2—C20—C15	−3.4 (4)
C2—C3—C4—Br2	−179.4 (2)	C18—C19—C20—O2	176.3 (3)
C3—C4—C5—C6	−0.3 (5)	Br4—C19—C20—O2	−3.0 (4)
Br2—C4—C5—C6	179.1 (2)	C18—C19—C20—C15	−2.8 (5)
C4—C5—C6—C1	0.0 (5)	Br4—C19—C20—C15	177.9 (2)
C4—C5—C6—C7	178.6 (3)	C16—C15—C20—O2	−176.8 (3)
O1—C1—C6—C5	179.7 (3)	C14—C15—C20—O2	3.3 (5)
C2—C1—C6—C5	0.6 (4)	C16—C15—C20—C19	2.3 (4)
O1—C1—C6—C7	1.1 (5)	C14—C15—C20—C19	−177.6 (3)
C2—C1—C6—C7	−177.9 (3)	O1—Cu1—O3—C21	94.1 (3)
C8—N1—C7—C6	177.3 (3)	O2—Cu1—O3—C21	5.0 (3)
Cu1—N1—C7—C6	−3.4 (4)	N1—Cu1—O3—C21	−172.4 (3)
C5—C6—C7—N1	177.4 (3)	N2—Cu1—O3—C21	−88.6 (3)
C1—C6—C7—N1	−4.0 (5)	Cu1—O3—C21—N3	−66.7 (4)
C7—N1—C8—C9	1.1 (5)	C23—N3—C21—O3	−179.6 (4)
Cu1—N1—C8—C9	−178.4 (2)	C22—N3—C21—O3	−4.2 (5)
C7—N1—C8—C13	−178.9 (3)	O4—C24—N4—C26	0.4 (17)
Cu1—N1—C8—C13	1.6 (3)	O4—C24—N4—C25	−176.8 (12)
C13—C8—C9—C10	0.9 (5)	O4'—C24'—N4'—C25'	177 (4)
N1—C8—C9—C10	−179.1 (3)	O4'—C24'—N4'—C26'	1 (6)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C5—H5···O3^i	0.95	2.47	3.319 (4)	148
C7—H7···O3^i	0.95	2.37	3.243 (4)	153
C14—H14···O4^ii	0.95	2.33	3.226 (14)	156
C22—H22A···O1	0.98	2.54	3.378 (4)	143

Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+2, −y+1, −z+2.