[Bis(quinolin-2-ylcarbon­yl)amido-κ³N,N′,N′′]bromido­(N,N-di­methyl­formamide-κO)copper(II)

In the mononuclear title complex, [CuBr(C₂₀H₁₂N₃O₂)(C₃H₇NO)], synthesized from the quinoline-derived reduced Schiff base 4-(quinolin-2-ylmeth­yl)amino­phenol, the coordination geometry around Cu²⁺ is distorted square-pyramidal, comprising a bromide anion at the apex [Cu—Br = 2.4671 (5) Å]. The base of the pyramid is built up from one di­methyl­formamide O-atom donor [Cu—O = 2.078 (2) Å] and three N-atom donors from the monoanionic, tridentate bis­(quinolin-2-ylcarbon­yl)di­imide ligand [Cu—N_di­imide = 1.941 (3) Å, and Cu—N_quinol­yl = 2.060 (3) and 2.049 (3) Å]. An intra­molecular C—H...O occurs. In the crystal, weak methyl and aromatic C—H...Br and formyl C—H...O_carbon­yl hydrogen-bonding inter­actions generate an overall layered structure lying parallel to (001).

Key indicators

• Single-crystal X-ray study
• T = 100 K
• Mean [sigma](C-C) = 0.005 Å
• R factor = 0.034
• wR factor = 0.081
• Data-to-parameter ratio = 12.5

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT906_ALERT_3_C Large K value in the Analysis of Variance ......      2.431 Check

Alert level G
PLAT005_ALERT_5_G No _iucr_refine_instructions_details  in the CIF     Please Do !
PLAT164_ALERT_4_G Nr. of Refined C-H H-Atoms in Heavy-Atom Struct.          3 Note
PLAT380_ALERT_4_G Incorrectly? Oriented X(sp2)-Methyl Moiety .....        C24 Check
PLAT794_ALERT_5_G Tentative Bond Valency for Cu1     (II)    .....       2.09 Note
PLAT909_ALERT_3_G Percentage of Observed Data at Theta(Max) still          72 %
PLAT910_ALERT_3_G Missing # of FCF Reflections Below Th(Min) .....          1 Why ?

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

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   0 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
   2 ALERT type 4 Improvement, methodology, query or suggestion
   2 ALERT type 5 Informative message, check

---

S1. Comment

The new ligand bis(2-quinolylcarbonyl)diimide monoanion (BQCD), formed from the quinoliny derived reduced Schiff base 4-(quinolin-2-ylmethyl)aminophenol (R-QMAP), is an important compound widely used in biological applications such as an HIV-1 protease inhibitor and in coordination chemistry (Castro et al., 1990; Castro et al., 1991; Lebon et al., 1998; Castro et al., 1999; Calatayud et al., 2000; Vangdal et al., 2002; Carlucci et al., 2011). In the synthesis of a compound from the reaction of CuBr with BQCD in ethanol with subsequent recrystallization from dimethylformamide generated the title Cu^II complex [Cu(C₂₀H₁₂N₃O₂)(C₃H₇NO)Br] which contains the monoanionic bis(2-quinolylcarbonyl) diimide ligand (BQCD), one bromido anion and an O-bonded dimethylformamide solvent molecule. The ligand, a bis(2-quinolylcarbonyl)diimide monoanion (BQCD) was formed from a reduced Schiff base 4-(quinolin-2-ylmethyl)aminophenol (ⁱR-QMAP), by the breaking of the aminophenol and subsequent oxidation of the –CH₂– group to a carbonyl group in the presence of dioxygen and copper(I) bromide. This oxidation of the –CH₂– group to a carbonyl group in the presence of dioxygen and metal salts has previously been reported (Sahu et al., 2010).

In the title mononuclear complex (Fig. 1), the Cu^II center is penta-coordinated with a distorted square pyramidal coordination geometry comprising an axial Br anion [Cu—Br = 2.4671 (5) Å] and in the meridional site, a dimethylformamide oxygen atom donor [Cu—O = 2.078 (2) Å] and three N-atom donors from the monoanionic bis(2-quinolylcarbonyl)diimide (BQCD) ligand, viz. two quinolyl nitrogens [Cu—N = 2.060 (3) and 2.049 (3) Å] and one diimide nitrogen [Cu—N = 1.941 (3) Å]. The observed Cu—N bond lengths and bond angles in the title compound are considered normal for this type of Cu^II complex, e.g. Cu—N(quinolyl) = 2.035 (5) Å] and [Cu—N(diimide) = 1.966 (5) Å] (Sahu et al., 2010).

In the crystal, a weak intermolecular methyl C23—H···Br1ⁱ interaction (Table 1) generates a chain structure extending along the c axial direction (Fig. 2), and is further extended into a two-dimensional sheet structure lying parallel to (001) through aromatic C15—H···Brⁱⁱ and formyl C22—H···O3ⁱⁱⁱ hydrogen bonds (Fig. 3). Also present in the structure is an intramolecular aromatic C20—H···O1_formyl hydrogen bond.

Related literature

For applications of the title complex and related structures, see: Castro et al. (1990), 1991, 1999); Vangdal et al. (2002); Sahu et al. (2010); Carlucci et al. (2011); Calatayud et al. (2000); Lebon et al. (1998).

S2. Experimental

A mixture of reduced Schiff base 4-(quinolin-2-ylmethyl)aminophenol (ⁱR-QMAP) (0.10 g, 0.40 mmol), copper(I) bromide (0.060 g, 0.40 mmol), ethanol (5 mL) were stirred vigorously for 30 min, the precipitate was filtered off and dissolved in dimethylformamide and kept for crystallization. Crystals suitable for X-ray analysis were obtained within a week by slow evaporation of the DMF solvent.

S3. Refinement

The H-atoms of the methyl group involved in the chain formation (C23) were located in a difference-Fourier and were fully refined. All other H-atoms were positioned geometrically and refined using a riding model with C—H = 0.93–0.96 Å and U_iso(H) = 1.2U_eq(aromatic C) or 1.5U_eq(methyl C).

Computing details

Data collection: SMART (Bruker, 2003); cell refinement: SAINT (Bruker, 2003); data reduction: SAINT (Bruker, 2003); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenberg & Putz, 2006); software used to prepare material for publication: DIAMOND (Brandenberg & Putz, 2006).

Figures

	Fig. 1. The molecular conformation and atom-numbering scheme for the title complex with non-H atoms drawn as 30% probability displacement ellipsoids.
	Fig. 2. The one-dimensional chain structure in the title complex extending along c, with weak C—H···Br hydrogen bonds shown as dashed lines.
	Fig. 3. The two-dimensional structure viewed along the c-axial direction.

[Bis(quinolin-2-ylcarbonyl)amido-κ³N,N',N'']bromido(N,N-dimethylformamide-κO)copper(II)

Crystal data

[CuBr(C20H12N3O2)(C3H7NO)]	F(000) = 1092
Mr = 542.87	Dx = 1.692 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 7192 reflections
a = 9.2137 (6) Å	θ = 2.2–28.3°
b = 23.5220 (16) Å	µ = 2.93 mm^−1
c = 10.4842 (7) Å	T = 100 K
β = 110.284 (1)°	Needle, red
V = 2131.3 (2) Å^3	0.26 × 0.20 × 0.14 mm
Z = 4

Data collection

Bruker SMART APEX CCD diffractometer	3753 independent reflections
Radiation source: fine-focus sealed tube	3223 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.033
ω and ϕ scans	θmax = 25.0°, θmin = 2.2°
Absorption correction: multi-scan (SADABS; Sheldrick, 2004)	h = −10→10
Tmin = 0.592, Tmax = 0.681	k = −27→27
13799 measured reflections	l = −12→10

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)] = 0.034	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.081	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ^2(Fo^2) + (0.0432P)^2 + 2.2471P] where P = (Fo^2 + 2Fc^2)/3
3753 reflections	(Δ/σ)max = 0.001
301 parameters	Δρmax = 0.81 e Å^−3
0 restraints	Δρmin = −0.45 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
C1	1.2311 (4)	0.17727 (13)	0.9003 (3)	0.0186 (7)
C2	1.2627 (4)	0.11829 (14)	0.9138 (3)	0.0225 (8)
H2	1.1818	0.0922	0.8872	0.027*
C3	1.4112 (4)	0.09975 (15)	0.9655 (3)	0.0276 (8)
H3	1.4309	0.0609	0.9747	0.033*
C4	1.5355 (4)	0.13798 (16)	1.0051 (4)	0.0305 (9)
H4	1.6365	0.1244	1.0397	0.037*
C5	1.5086 (4)	0.19471 (16)	0.9931 (4)	0.0294 (9)
H5	1.5916	0.2199	1.0191	0.035*
C6	1.3571 (4)	0.21600 (14)	0.9420 (3)	0.0245 (8)
C7	1.3227 (5)	0.27458 (15)	0.9297 (4)	0.0298 (9)
H7	1.4024	0.3011	0.9549	0.036*
C8	1.1742 (4)	0.29206 (14)	0.8811 (4)	0.0277 (8)
H8	1.1511	0.3307	0.8747	0.033*
C9	1.0551 (4)	0.25196 (13)	0.8405 (3)	0.0219 (8)
C10	0.8890 (4)	0.27133 (14)	0.7873 (3)	0.0238 (8)
N4	0.7906 (3)	0.22593 (11)	0.7571 (3)	0.0210 (6)
C12	0.6353 (4)	0.23086 (14)	0.7065 (3)	0.0249 (8)
C13	0.5577 (4)	0.17340 (14)	0.6804 (3)	0.0207 (7)
C14	0.3975 (4)	0.17069 (15)	0.6286 (3)	0.0255 (8)
H14	0.3388	0.2038	0.6070	0.031*
C15	0.3275 (4)	0.11898 (16)	0.6097 (3)	0.0292 (8)
H15	0.2202	0.1164	0.5748	0.035*
C16	0.4180 (4)	0.06968 (15)	0.6433 (3)	0.0235 (8)
C17	0.3511 (4)	0.01469 (16)	0.6265 (4)	0.0307 (9)
H17	0.2441	0.0106	0.5903	0.037*
C18	0.4423 (4)	−0.03185 (15)	0.6630 (4)	0.0304 (9)
H18	0.3975	−0.0678	0.6510	0.036*
C19	0.6035 (4)	−0.02662 (14)	0.7185 (3)	0.0269 (8)
H19	0.6643	−0.0590	0.7454	0.032*
C20	0.6726 (4)	0.02559 (14)	0.7337 (3)	0.0219 (7)
H20	0.7799	0.0285	0.7688	0.026*
C21	0.5808 (4)	0.07501 (14)	0.6959 (3)	0.0195 (7)
C22	0.9923 (4)	0.10622 (13)	1.0635 (3)	0.0191 (7)
H22	1.0592	0.1372	1.0867	0.023*
C23	1.0494 (6)	0.09139 (18)	1.3042 (4)	0.0348 (10)
C24	0.8692 (5)	0.02789 (15)	1.1333 (4)	0.0341 (9)
H24A	0.8694	0.0116	1.2173	0.051*
H24B	0.9036	0.0000	1.0833	0.051*
H24C	0.7663	0.0399	1.0806	0.051*
N1	1.0803 (3)	0.19603 (11)	0.8492 (3)	0.0183 (6)
N2	0.6487 (3)	0.12808 (11)	0.7128 (3)	0.0180 (6)
N3	0.9720 (3)	0.07624 (11)	1.1617 (3)	0.0219 (6)
O1	0.9264 (3)	0.09523 (9)	0.9413 (2)	0.0223 (5)
O2	0.8575 (3)	0.32184 (9)	0.7751 (3)	0.0337 (6)
O3	0.5551 (3)	0.27363 (10)	0.6817 (3)	0.0399 (7)
Cu1	0.87800 (5)	0.150012 (15)	0.77633 (4)	0.01711 (12)
Br1	0.93628 (4)	0.090477 (13)	0.60641 (3)	0.01868 (11)
H23A	0.972 (5)	0.1009 (16)	1.346 (4)	0.033 (11)*
H23B	1.114 (5)	0.0610 (18)	1.354 (4)	0.038 (11)*
H23C	1.111 (4)	0.1234 (17)	1.315 (4)	0.030 (11)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0256 (18)	0.0192 (17)	0.0137 (16)	−0.0035 (14)	0.0102 (14)	−0.0026 (13)
C2	0.032 (2)	0.0153 (17)	0.0189 (17)	−0.0025 (14)	0.0067 (15)	0.0008 (13)
C3	0.033 (2)	0.0251 (19)	0.0238 (18)	0.0015 (16)	0.0085 (16)	0.0017 (15)
C4	0.028 (2)	0.034 (2)	0.0267 (19)	−0.0001 (17)	0.0058 (16)	0.0017 (16)
C5	0.030 (2)	0.034 (2)	0.0247 (19)	−0.0120 (17)	0.0100 (16)	−0.0072 (16)
C6	0.036 (2)	0.0228 (18)	0.0163 (17)	−0.0076 (16)	0.0110 (16)	−0.0064 (14)
C7	0.040 (2)	0.0210 (19)	0.030 (2)	−0.0163 (17)	0.0143 (18)	−0.0087 (15)
C8	0.045 (2)	0.0115 (16)	0.031 (2)	−0.0079 (16)	0.0188 (18)	−0.0034 (14)
C9	0.038 (2)	0.0120 (16)	0.0193 (17)	−0.0020 (14)	0.0138 (16)	−0.0019 (13)
C10	0.042 (2)	0.0134 (17)	0.0223 (18)	0.0008 (15)	0.0191 (17)	−0.0008 (13)
N4	0.0318 (17)	0.0102 (13)	0.0229 (15)	0.0016 (12)	0.0120 (13)	0.0002 (11)
C12	0.033 (2)	0.0202 (18)	0.0254 (19)	0.0062 (16)	0.0154 (16)	0.0062 (14)
C13	0.0279 (19)	0.0181 (17)	0.0183 (16)	0.0049 (15)	0.0107 (15)	0.0050 (13)
C14	0.0264 (19)	0.0274 (19)	0.0229 (18)	0.0069 (16)	0.0090 (15)	0.0060 (15)
C15	0.0232 (19)	0.041 (2)	0.0225 (18)	−0.0011 (17)	0.0068 (16)	0.0034 (16)
C16	0.0286 (19)	0.0279 (19)	0.0141 (16)	−0.0057 (15)	0.0073 (15)	−0.0014 (14)
C17	0.029 (2)	0.037 (2)	0.0237 (18)	−0.0135 (17)	0.0067 (16)	−0.0029 (16)
C18	0.040 (2)	0.0223 (19)	0.0288 (19)	−0.0165 (17)	0.0123 (18)	−0.0041 (15)
C19	0.040 (2)	0.0159 (17)	0.0259 (18)	−0.0040 (15)	0.0120 (17)	−0.0017 (14)
C20	0.0268 (18)	0.0182 (17)	0.0219 (17)	−0.0022 (14)	0.0100 (15)	−0.0020 (13)
C21	0.0280 (19)	0.0188 (17)	0.0133 (16)	−0.0031 (14)	0.0093 (14)	−0.0027 (13)
C22	0.0299 (19)	0.0083 (15)	0.0213 (18)	0.0001 (14)	0.0115 (15)	−0.0014 (13)
C23	0.061 (3)	0.028 (2)	0.0172 (18)	0.000 (2)	0.015 (2)	−0.0017 (16)
C24	0.039 (2)	0.026 (2)	0.036 (2)	−0.0036 (17)	0.0112 (18)	0.0131 (17)
N1	0.0292 (16)	0.0115 (14)	0.0165 (13)	−0.0043 (11)	0.0107 (12)	−0.0022 (10)
N2	0.0246 (15)	0.0150 (14)	0.0163 (14)	−0.0011 (11)	0.0095 (12)	0.0005 (11)
N3	0.0347 (17)	0.0133 (14)	0.0193 (14)	−0.0003 (12)	0.0114 (13)	0.0018 (11)
O1	0.0359 (14)	0.0137 (11)	0.0151 (12)	−0.0038 (10)	0.0061 (11)	0.0021 (9)
O2	0.0499 (17)	0.0094 (13)	0.0490 (17)	0.0040 (11)	0.0262 (14)	0.0010 (11)
O3	0.0388 (16)	0.0192 (14)	0.0627 (19)	0.0107 (12)	0.0188 (14)	0.0121 (13)
Cu1	0.0243 (2)	0.0083 (2)	0.0190 (2)	−0.00018 (15)	0.00791 (17)	0.00038 (15)
Br1	0.02579 (19)	0.01385 (17)	0.01721 (17)	0.00011 (13)	0.00847 (14)	−0.00126 (12)

Geometric parameters (Å, º)

Br1—Cu1	2.4671 (5)	C13—C14	1.386 (5)
Cu1—O1	2.078 (2)	C14—C15	1.359 (5)
Cu1—N1	2.060 (3)	C15—C16	1.400 (5)
Cu1—N2	2.049 (3)	C16—C17	1.417 (5)
Cu1—N4	1.941 (3)	C16—C21	1.413 (5)
O1—C22	1.240 (4)	C17—C18	1.352 (5)
O2—C10	1.219 (4)	C18—C19	1.400 (5)
O3—C12	1.222 (4)	C19—C20	1.367 (5)
N1—C1	1.377 (5)	C20—C21	1.411 (5)
N1—C9	1.334 (4)	C2—H2	0.9300
N2—C13	1.326 (4)	C3—H3	0.9300
N2—C21	1.380 (4)	C4—H4	0.9300
N3—C22	1.314 (4)	C5—H5	0.9300
N3—C23	1.459 (5)	C7—H7	0.9300
N3—C24	1.444 (5)	C8—H8	0.9300
N4—C10	1.365 (4)	C14—H14	0.9300
N4—C12	1.348 (5)	C15—H15	0.9300
C1—C2	1.415 (5)	C17—H17	0.9300
C1—C6	1.420 (5)	C18—H18	0.9300
C2—C3	1.357 (5)	C19—H19	0.9300
C3—C4	1.401 (5)	C20—H20	0.9300
C4—C5	1.355 (5)	C22—H22	0.9300
C5—C6	1.403 (5)	C23—H23A	0.98 (5)
C6—C7	1.410 (5)	C23—H23B	0.96 (4)
C7—C8	1.348 (6)	C23—H23C	0.93 (4)
C8—C9	1.397 (5)	C24—H24A	0.9600
C9—C10	1.506 (5)	C24—H24B	0.9600
C12—C13	1.509 (5)	C24—H24C	0.9600
Br1—Cu1—O1	102.21 (6)	C15—C16—C17	122.0 (3)
Br1—Cu1—N1	99.83 (8)	C15—C16—C21	118.9 (3)
Br1—Cu1—N2	94.61 (8)	C17—C16—C21	119.1 (3)
Br1—Cu1—N4	129.33 (9)	C16—C17—C18	120.2 (4)
O1—Cu1—N1	96.41 (11)	C17—C18—C19	120.8 (3)
O1—Cu1—N2	90.80 (11)	C18—C19—C20	120.8 (3)
O1—Cu1—N4	128.23 (11)	C19—C20—C21	119.9 (3)
N1—Cu1—N2	162.09 (11)	N2—C21—C16	120.2 (3)
N1—Cu1—N4	81.05 (12)	N2—C21—C20	120.6 (3)
N2—Cu1—N4	81.60 (11)	C16—C21—C20	119.2 (3)
Cu1—O1—C22	128.2 (2)	O1—C22—N3	123.1 (3)
Cu1—N1—C1	129.6 (2)	C1—C2—H2	120.00
Cu1—N1—C9	112.3 (2)	C3—C2—H2	120.00
C1—N1—C9	118.1 (3)	C2—C3—H3	119.00
Cu1—N2—C13	111.7 (2)	C4—C3—H3	119.00
Cu1—N2—C21	129.8 (2)	C3—C4—H4	120.00
C13—N2—C21	118.4 (3)	C5—C4—H4	120.00
C22—N3—C23	121.3 (3)	C4—C5—H5	120.00
C22—N3—C24	121.5 (3)	C6—C5—H5	120.00
C23—N3—C24	117.2 (3)	C6—C7—H7	120.00
Cu1—N4—C10	118.5 (2)	C8—C7—H7	120.00
Cu1—N4—C12	117.8 (2)	C7—C8—H8	120.00
C10—N4—C12	123.6 (3)	C9—C8—H8	120.00
N1—C1—C2	119.9 (3)	C13—C14—H14	120.00
N1—C1—C6	121.4 (3)	C15—C14—H14	120.00
C2—C1—C6	118.7 (3)	C14—C15—H15	120.00
C1—C2—C3	119.9 (3)	C16—C15—H15	120.00
C2—C3—C4	121.3 (3)	C16—C17—H17	120.00
C3—C4—C5	120.0 (4)	C18—C17—H17	120.00
C4—C5—C6	120.9 (4)	C17—C18—H18	120.00
C1—C6—C5	119.2 (3)	C19—C18—H18	120.00
C1—C6—C7	117.7 (3)	C18—C19—H19	120.00
C5—C6—C7	123.1 (4)	C20—C19—H19	120.00
C6—C7—C8	120.0 (4)	C19—C20—H20	120.00
C7—C8—C9	119.8 (3)	C21—C20—H20	120.00
N1—C9—C8	123.1 (3)	O1—C22—H22	118.00
N1—C9—C10	117.0 (3)	N3—C22—H22	118.00
C8—C9—C10	119.9 (3)	N3—C23—H23A	110 (2)
O2—C10—N4	128.6 (3)	N3—C23—H23B	111 (2)
O2—C10—C9	120.5 (3)	N3—C23—H23C	113 (2)
N4—C10—C9	110.9 (3)	H23A—C23—H23B	110 (3)
O3—C12—N4	129.5 (3)	H23A—C23—H23C	106 (3)
O3—C12—C13	119.0 (3)	H23B—C23—H23C	108 (4)
N4—C12—C13	111.5 (3)	N3—C24—H24A	109.00
N2—C13—C12	117.1 (3)	N3—C24—H24B	110.00
N2—C13—C14	123.8 (3)	N3—C24—H24C	109.00
C12—C13—C14	119.0 (3)	H24A—C24—H24B	109.00
C13—C14—C15	119.0 (3)	H24A—C24—H24C	109.00
C14—C15—C16	119.6 (3)	H24B—C24—H24C	110.00
C6—C1—C2—C3	−0.1 (5)	C12—C13—C14—C15	−177.7 (3)
N1—C1—C2—C3	−179.3 (3)	N2—C13—C14—C15	0.4 (5)
C2—C1—C6—C5	1.0 (5)	C12—C13—N2—C21	177.2 (3)
C2—C1—C6—C7	−179.1 (3)	C12—C13—N2—Cu1	−5.0 (4)
N1—C1—C6—C5	−179.8 (3)	C14—C13—N2—C21	−0.9 (5)
N1—C1—C6—C7	0.1 (5)	C14—C13—N2—Cu1	177.0 (3)
C2—C1—N1—C9	178.7 (3)	C13—C14—C15—C16	0.1 (5)
C2—C1—N1—Cu1	−2.9 (5)	C14—C15—C16—C17	179.6 (3)
C6—C1—N1—C9	−0.4 (5)	C14—C15—C16—C21	−0.1 (5)
C6—C1—N1—Cu1	177.9 (2)	C15—C16—C17—C18	−178.5 (3)
C1—C2—C3—C4	−0.6 (5)	C21—C16—C17—C18	1.2 (5)
C2—C3—C4—C5	0.4 (6)	C15—C16—C21—C20	178.0 (3)
C3—C4—C5—C6	0.5 (6)	C15—C16—C21—N2	−0.4 (5)
C4—C5—C6—C1	−1.3 (5)	C17—C16—C21—C20	−1.6 (5)
C4—C5—C6—C7	178.9 (4)	C17—C16—C21—N2	179.9 (3)
C1—C6—C7—C8	0.8 (5)	C16—C17—C18—C19	0.5 (6)
C5—C6—C7—C8	−179.3 (4)	C17—C18—C19—C20	−1.8 (6)
C6—C7—C8—C9	−1.3 (6)	C18—C19—C20—C21	1.4 (5)
C7—C8—C9—C10	179.5 (3)	C19—C20—C21—C16	0.4 (5)
C7—C8—C9—N1	1.0 (6)	C19—C20—C21—N2	178.8 (3)
C8—C9—C10—N4	−178.3 (3)	C16—C21—N2—C13	0.9 (5)
C8—C9—C10—O2	2.4 (5)	C16—C21—N2—Cu1	−176.5 (2)
N1—C9—C10—N4	0.4 (4)	C20—C21—N2—C13	−177.5 (3)
N1—C9—C10—O2	−179.0 (3)	C20—C21—N2—Cu1	5.1 (5)
C8—C9—N1—C1	−0.1 (5)	O1—C22—N3—C23	−178.7 (3)
C8—C9—N1—Cu1	−178.7 (3)	O1—C22—N3—C24	−0.4 (5)
C10—C9—N1—C1	−178.6 (3)	N3—C22—O1—Cu1	155.7 (2)
C10—C9—N1—Cu1	2.7 (4)	C1—N1—Cu1—N4	178.0 (3)
C9—C10—N4—C12	−179.4 (3)	C1—N1—Cu1—N2	163.4 (3)
C9—C10—N4—Cu1	−3.6 (4)	C1—N1—Cu1—O1	50.2 (3)
O2—C10—N4—C12	−0.0 (6)	C1—N1—Cu1—Br1	−53.4 (3)
O2—C10—N4—Cu1	175.7 (3)	C9—N1—Cu1—N4	−3.6 (2)
C10—N4—C12—C13	178.7 (3)	C9—N1—Cu1—N2	−18.2 (5)
C10—N4—C12—O3	−1.9 (6)	C9—N1—Cu1—O1	−131.4 (2)
Cu1—N4—C12—C13	3.0 (4)	C9—N1—Cu1—Br1	125.0 (2)
Cu1—N4—C12—O3	−177.6 (3)	C13—N2—Cu1—N4	5.1 (2)
C10—N4—Cu1—N1	4.1 (2)	C13—N2—Cu1—N1	19.6 (5)
C10—N4—Cu1—N2	179.6 (3)	C13—N2—Cu1—O1	133.6 (2)
C10—N4—Cu1—O1	95.2 (3)	C13—N2—Cu1—Br1	−124.1 (2)
C10—N4—Cu1—Br1	−91.4 (2)	C21—N2—Cu1—N4	−177.4 (3)
C12—N4—Cu1—N1	−180.0 (3)	C21—N2—Cu1—N1	−162.8 (3)
C12—N4—Cu1—N2	−4.5 (2)	C21—N2—Cu1—O1	−48.8 (3)
C12—N4—Cu1—O1	−88.8 (3)	C21—N2—Cu1—Br1	53.5 (3)
C12—N4—Cu1—Br1	84.6 (3)	C22—O1—Cu1—N4	−45.9 (3)
N4—C12—C13—C14	179.8 (3)	C22—O1—Cu1—N1	37.8 (3)
N4—C12—C13—N2	1.6 (4)	C22—O1—Cu1—N2	−125.8 (3)
O3—C12—C13—C14	0.3 (5)	C22—O1—Cu1—Br1	139.3 (3)
O3—C12—C13—N2	−177.9 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C23—H23A···Br1^i	0.98 (5)	2.87 (4)	3.663 (5)	138 (3)
C15—H15···Br1^ii	0.93	2.82	3.655 (4)	151
C20—H20···O1	0.93	2.42	3.059 (4)	126
C22—H22···O3^iii	0.93	2.33	3.060 (4)	135

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