catena-Poly[[{4-bromo-2-[2-(di­methyl­amino)­ethyl­imino­meth­yl]­phenolato}­copper(II)]-μ-thio­cyanato]

The title complex, [Cu(C₁₁H₁₄BrN₂O)(NCS)]_n, is an inter­esting thio­cyanate-bridged polynuclear copper(II) compound, which crystallizes with two independent mol­ecules in the asymmetric unit. Each Cu^II atom is five-coordinate in a square-pyramidal configuration, with one O and two N atoms of one Schiff base ligand and one terminal N atom of a bridging thio­cyanate ligand defining the basal plane, and one terminal S atom of another bridging thio­cyanate ligand occupying the apical position. The {4-bromo-2-[2-(dimethyl­amino)ethyl­imino­meth­yl]phenolato}copper(II) units are linked by the bridging thio­cyanate ligands, forming polymeric chains running along the a axis. There are weak inter­molecular C—H...O and C—H...S hydrogen bonds between the chains in the crystal structure.

S1. Comment

The magnetic properties of extended coordination compounds featuring exchange-coupled magnetic centers have become a fascinating subject in recent years (Dalai et al., 2002; Bhaduri et al., 2003). The prime strategy for designing these molecular materials is to use a suitable bridging ligand that determines the nature of the magnetic interactions (Koner et al., 2003). Owing to the versatile coordination modes of the ambidentate thiocyanate ligand and the wide range of magnetic coupling mediated by thiocyanate bridges, this pseudohalide ligand has become one of the most extensively studied building blocks in the field (Sailaja et al., 2003; Dey et al., 2004). Thiocyanate complexes of various dimensionalities have been obtained (Zurowska et al., 2002; Zhang et al., 2003; You, 2005a). These also include some examples of the so-called alternating one-dimensional magnetic systems, which have two or more different structural bridges and which are of considerable interest in terms of their magnetic behavior (Vicente et al., 1992; Escuer et al., 1994; Ribas et al., 1995; Vicente & Escuer, 1995). A major obstacle to a more comprehensive study of such thiocyanate-based polymeric coordination compounds is the lack of rational synthetic procedures, since with the present state of knowledge it is hardly possible to determine which coordination mode will be adopted by the thiocyanate ligand and whether the sought-after alternating chain structure will finally be formed (Tercero et al., 2002; Ribas et al., 1999; Liu et al., 2003).

Our work is aimed at obtaining multidimensional polymetallic complexes. On the basis of the above considerations, we designed and synthesized a flexible tridentate ligand, 4-bromo-2-[2-(dimethylamino)ethyliminomethyl]phenol (BDMP). The reason we do not use a rigid ligand is that the flexible BDMP ligand can adopt a different coordination mode according to the geometric need of transition metal ions and the coordination environment (Mondal et al., 2001). The second ligand, viz. thiocyanate, is a well known bridging group. It readily bridges different metal ions through the terminal donor atoms, forming polynuclear complexes (Kuang et al., 2001). Copper(II) is a good candidate of octahedral coordination geometry. We report here a new one-dimensional infinite-chain complex, (I), formed by the reaction of the BDMP ligand, ammonium thiocyanate and copper(II) acetate.

Complex (I) is a thiocyanate-bridged polynuclear copper(II) compound. The asymmetric unit contains two independent molecules, A (Fig 1) and B (Fig. 2). Each of the molecules contains two BDMP–Cu^II cations and two bridging thiocyanate anions. The Cu^II atom is in a square-pyramidal coordination configuration and is five-coordinated by the NNO donor set of one Schiff base and by one terminal N atom of a bridging thiocyanate ligand defining the basal plane, and by one terminal N atom of another bridging thiocyanate ligand occupying the apical position. The Schiff base acts as a tridentate ligand and ligates to the metal via the three O and N donor atoms. The thiocyanate anion acts as a bridging ligand and ligates to two different but symmetry-related Cu^II atoms via the terminal N and S atoms. The significant distortion of the square pyramid is revealed by the bond angles between the apical and basal donor atoms (Table 1). The N1—Cu1—N2 and N4—Cu2—N5 bond angles deviate from 90° by 6.10 (14) and 4.65 (14)°, respectively, as a result of the strain created by the five-membered chelate rings Cu1/N1/C8/C9/N2 and Cu2/N4/C20/C21/N5. The apical bonds [Cu1—S1ⁱ and Cu2—S2ⁱⁱ; symmetry codes: (i) x − 1/2, −y, z; (ii) x − 1/2, −y + 1, z] are much longer than the basal bonds, indicating that the Cu—S bond is not very strong. The Cu—O and Cu—N bond lengths are comparable to the corresponding values observed in other Schiff base copper(II) complexes (You & Zhu, 2004; You et al., 2004; Zhang et al., 2001; Elmali et al., 2000), and as expected, the bonds involving amine atoms N2 [2.068 (3) Å] or N5 [2.067 (3) Å] are longer than those involving imine atoms N1 [1.943 (3) Å] or N4 [1.948 (3) Å] (Mondal et al., 2001). The bridging NCS groups are nearly linear and show bent coordination modes with the metal atoms [N3—C12—S1 = 179.9 (5)°, Cu1—N3—C12 = 169.7 (4)°, Cu1ⁱⁱ—S1—C12 = 102.12 (4)°, N6—C24—S2 = 177.7 (4)°, Cu2—N6—C24 = 166.8 (4)° and Cu2^iv—S2—C24 =101.98 (4)°].

The basal least-square planes defined by the four donor atoms of the adjacent two Cu^II centres are not parallel and form dihedral angles of 74.1 (2)° for the Cu1 moiety and 75.0 (2)° for the Cu2 moiety, which can decrease the steric effects among the molecules. The deviation of atom Cu1 from the least-squares plane is 0.180 (2) Å, and the corresponding value for Cu2 is 0.176 (2) Å.

The C7═N1 [1.283 (5) Å] and C19═N4 bond lengths [1.264 (6) Å] conform to the values for double bonds, while the C8—N1 [1.452 (5) Å] and C20—N4 bond lengths [1.487 (6) Å] conform to the values for single bonds (You, 2005b).

In the crystal structure, the {4-bromo-2-[2-(dimethylamino)ethyliminomethyl]phenolato}copper(II) moieties are linked by the bridging thiocyanate ligands, forming polymeric chains running along the a axis; adjacent chains are further linked by weak intermolecular C—H···O and C—H···S hydrogen bonds, forming dimeric chains running along the a axis (Table 2 and Fig. 3).

S2. Experimental

5-Bromosalicylaldehyde (0.1 mmol, 20.1 mg) and N,N-dimethylethane-1,2-diamine (0.1 mmol, 8.8 mg) were dissolved in MeOH (10 ml). The mixture was stirred at room temperature for 10 min to give a yellow solution. To the solution was added an aqueous solution (2 ml) of NH₄NCS (0.1 mmol, 6.5 mg) and an MeOH solution (3 ml) of Cu(CH₃COO)₂·H₂O (0.1 mmol, 19.9 mg), with stirring. The mixture was stirred for another 10 min at room temperature. After the filtrate had been kept in air for 12 d, blue block-shaped crystals were formed.

S3. Refinement

All H atoms were placed in geometrically idealized positions and allowed to ride on their parent atoms with C—H distances of 0.93–0.97 Å, and with U_iso(H) values of 1.2 or 1.5 times U_eq(C). An unassigned maximum residual density was observed 0.81 Å from atom Br1.

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 (Sheldrick, 2000); software used to prepare material for publication: SHELXTL.

Figures

	Fig. 1. The structure of molecule A, showing the atom-numbering scheme and the formation of the polymeric chain. Displacement ellipsoids are drawn at the 50% probability level. H atoms have been omitted for clarity. [Symmetry codes: (i) x − 1/2, −y, z; (iii) x + 1/2, −y, z.]
	Fig. 2. The structure of molecule B, showing the atom-numbering scheme and the formation of the polymeric chain. Displacement ellipsoids are drawn at the 50% probability level. H atoms have been omitted for clarity. [Symmetry codes: (ii) x − 1/2, − y + 1, z; (iv) x + 1/2, 1 − y, z.]
	Fig. 3. The crystal packing of (I), viewed along the b axis. Dashed lines show the weak intermolecular C—H···O and C—H···S hydrogen bonds.

catena-Poly[[{4-bromo-2-[2- (dimethylamino)ethyliminomethyl]phenolato}copper(II)]-µ-thiocyanato]

Crystal data

[Cu(C11H14BrN2O)(NCS)]	F(000) = 1560
Mr = 391.77	Dx = 1.760 Mg m^−3
Orthorhombic, Pca21	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2c -2ac	Cell parameters from 12201 reflections
a = 11.767 (2) Å	θ = 2.4–28.0°
b = 7.4180 (15) Å	µ = 4.32 mm^−1
c = 33.870 (7) Å	T = 298 K
V = 2956.4 (10) Å^3	Block, blue
Z = 8	0.24 × 0.15 × 0.12 mm

Data collection

Bruker SMART CCD area-detector diffractometer	6447 independent reflections
Radiation source: fine-focus sealed tube	5729 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.039
ω scans	θmax = 27.0°, θmin = 1.2°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −15→14
Tmin = 0.424, Tmax = 0.625	k = −9→9
30513 measured reflections	l = −43→43

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.036	H-atom parameters constrained
wR(F^2) = 0.092	w = 1/[σ^2(Fo^2) + (0.0554P)^2 + 0.0383P] where P = (Fo^2 + 2Fc^2)/3
S = 1.06	(Δ/σ)max = 0.001
6447 reflections	Δρmax = 1.09 e Å^−3
347 parameters	Δρmin = −0.65 e Å^−3
1 restraint	Absolute structure: Flack (1983), 3160 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.083 (9)

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
Cu1	0.33425 (3)	0.09184 (6)	0.667215 (13)	0.03169 (11)
Cu2	0.06807 (4)	0.58332 (6)	0.972960 (14)	0.03352 (12)
Br1	0.07567 (5)	−0.48361 (11)	0.820328 (19)	0.0850 (2)
Br2	−0.17916 (4)	−0.04140 (9)	0.826859 (16)	0.06374 (15)
S1	0.70441 (9)	0.11723 (15)	0.61383 (4)	0.0467 (3)
S2	0.43749 (9)	0.62730 (16)	1.02598 (4)	0.0474 (3)
O1	0.3730 (2)	−0.0981 (4)	0.70337 (9)	0.0457 (7)
O2	0.1110 (2)	0.3937 (4)	0.93729 (9)	0.0474 (8)
N1	0.1976 (3)	0.1526 (5)	0.69653 (9)	0.0343 (7)
N2	0.2980 (3)	0.3253 (4)	0.63632 (11)	0.0383 (7)
N3	0.4850 (3)	0.0758 (5)	0.64335 (12)	0.0468 (9)
N4	−0.0690 (3)	0.6343 (5)	0.94268 (10)	0.0362 (8)
N5	0.0290 (3)	0.8161 (4)	1.00366 (11)	0.0398 (8)
N6	0.2195 (3)	0.5719 (5)	0.99760 (12)	0.0470 (9)
C1	0.1920 (3)	−0.1184 (6)	0.73626 (12)	0.0390 (9)
C2	0.3036 (3)	−0.1779 (6)	0.72835 (12)	0.0395 (9)
C3	0.3432 (3)	−0.3259 (7)	0.74964 (16)	0.0504 (11)
H3	0.4174	−0.3650	0.7456	0.060*
C4	0.2769 (4)	−0.4157 (6)	0.77633 (15)	0.0537 (12)
H4	0.3062	−0.5128	0.7904	0.064*
C5	0.1642 (4)	−0.3602 (8)	0.78237 (14)	0.0540 (12)
C6	0.1232 (3)	−0.2129 (7)	0.76302 (13)	0.0467 (10)
H6	0.0491	−0.1747	0.7676	0.056*
C7	0.1461 (3)	0.0470 (6)	0.72063 (12)	0.0409 (10)
H7	0.0734	0.0798	0.7286	0.049*
C8	0.1430 (3)	0.3195 (6)	0.68465 (15)	0.0467 (10)
H8A	0.1677	0.4174	0.7016	0.056*
H8B	0.0612	0.3080	0.6870	0.056*
C9	0.1750 (3)	0.3588 (6)	0.64241 (15)	0.0439 (10)
H9A	0.1312	0.2824	0.6248	0.053*
H9B	0.1575	0.4834	0.6362	0.053*
C10	0.3214 (4)	0.3243 (8)	0.59389 (16)	0.0584 (13)
H10A	0.2739	0.2365	0.5812	0.088*
H10B	0.3998	0.2944	0.5895	0.088*
H10C	0.3059	0.4415	0.5831	0.088*
C11	0.3676 (4)	0.4688 (7)	0.6555 (2)	0.0718 (17)
H11A	0.3483	0.5839	0.6444	0.108*
H11B	0.4468	0.4449	0.6511	0.108*
H11C	0.3526	0.4700	0.6834	0.108*
C12	0.5756 (3)	0.0927 (5)	0.63116 (12)	0.0350 (8)
C13	−0.0689 (3)	0.3627 (7)	0.90387 (12)	0.0403 (10)
C14	0.0439 (3)	0.3088 (6)	0.91264 (11)	0.0387 (9)
C15	0.0872 (4)	0.1556 (8)	0.89327 (14)	0.0501 (12)
H15	0.1622	0.1215	0.8976	0.060*
C16	0.0212 (4)	0.0561 (7)	0.86824 (14)	0.0496 (11)
H16	0.0511	−0.0457	0.8561	0.059*
C17	−0.0912 (4)	0.1068 (7)	0.86090 (12)	0.0457 (11)
C18	−0.1353 (3)	0.2565 (6)	0.87778 (12)	0.0413 (10)
H18	−0.2098	0.2900	0.8722	0.050*
C19	−0.1168 (3)	0.5282 (6)	0.91865 (12)	0.0398 (9)
H19	−0.1890	0.5596	0.9098	0.048*
C20	−0.1267 (4)	0.8041 (6)	0.95454 (15)	0.0482 (11)
H20A	−0.2084	0.7905	0.9522	0.058*
H20B	−0.1029	0.9021	0.9375	0.058*
C21	−0.0952 (3)	0.8449 (6)	0.99657 (16)	0.0481 (11)
H21A	−0.1146	0.9690	1.0026	0.058*
H21B	−0.1385	0.7676	1.0141	0.058*
C22	0.0489 (4)	0.8138 (8)	1.04632 (16)	0.0635 (15)
H22A	0.1288	0.8013	1.0514	0.095*
H22B	0.0089	0.7142	1.0579	0.095*
H22C	0.0221	0.9245	1.0577	0.095*
C23	0.0980 (4)	0.9591 (7)	0.9845 (2)	0.0713 (18)
H23A	0.0916	1.0687	0.9994	0.107*
H23B	0.0708	0.9788	0.9582	0.107*
H23C	0.1761	0.9221	0.9836	0.107*
C24	0.3086 (3)	0.5982 (5)	1.00904 (12)	0.0335 (8)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.0218 (2)	0.0395 (2)	0.0338 (2)	0.00508 (17)	0.00411 (18)	0.0036 (2)
Cu2	0.0211 (2)	0.0453 (3)	0.0342 (2)	0.00549 (17)	−0.00437 (18)	0.0020 (2)
Br1	0.0706 (4)	0.1115 (5)	0.0728 (4)	−0.0320 (4)	0.0057 (3)	0.0429 (4)
Br2	0.0488 (3)	0.0842 (3)	0.0582 (3)	−0.0135 (2)	−0.0110 (2)	−0.0123 (3)
S1	0.0297 (5)	0.0510 (6)	0.0595 (7)	0.0030 (4)	0.0134 (5)	0.0171 (5)
S2	0.0307 (5)	0.0520 (6)	0.0594 (7)	0.0042 (4)	−0.0127 (5)	−0.0214 (6)
O1	0.0284 (14)	0.0650 (19)	0.0436 (16)	0.0085 (13)	0.0038 (12)	0.0225 (15)
O2	0.0256 (15)	0.075 (2)	0.0413 (17)	0.0125 (14)	−0.0063 (12)	−0.0111 (15)
N1	0.0234 (15)	0.0497 (18)	0.0299 (16)	0.0026 (14)	0.0011 (12)	0.0001 (14)
N2	0.0298 (17)	0.0293 (16)	0.056 (2)	−0.0005 (13)	0.0051 (15)	0.0074 (15)
N3	0.0286 (19)	0.061 (2)	0.051 (2)	0.0118 (16)	0.0111 (16)	0.0126 (18)
N4	0.0244 (16)	0.0475 (19)	0.0368 (18)	0.0065 (13)	−0.0014 (13)	0.0116 (15)
N5	0.0283 (16)	0.0308 (17)	0.060 (2)	0.0015 (14)	−0.0064 (15)	0.0006 (15)
N6	0.031 (2)	0.060 (2)	0.050 (2)	0.0102 (16)	−0.0090 (17)	−0.0110 (18)
C1	0.0261 (19)	0.059 (3)	0.032 (2)	−0.0010 (17)	−0.0043 (15)	0.0083 (17)
C2	0.031 (2)	0.055 (3)	0.033 (2)	0.0017 (18)	−0.0004 (16)	0.0062 (18)
C3	0.037 (2)	0.067 (3)	0.047 (2)	0.012 (2)	0.002 (2)	0.014 (2)
C4	0.055 (3)	0.059 (3)	0.047 (3)	−0.003 (2)	−0.007 (2)	0.017 (2)
C5	0.046 (3)	0.073 (3)	0.042 (2)	−0.022 (2)	−0.002 (2)	0.015 (2)
C6	0.029 (2)	0.076 (3)	0.035 (2)	−0.004 (2)	−0.0013 (16)	0.001 (2)
C7	0.0221 (18)	0.067 (3)	0.033 (2)	0.0031 (18)	0.0044 (15)	−0.002 (2)
C8	0.0256 (19)	0.053 (3)	0.062 (3)	0.0123 (18)	0.0042 (19)	−0.002 (2)
C9	0.033 (2)	0.033 (2)	0.066 (3)	0.0086 (16)	0.000 (2)	0.011 (2)
C10	0.054 (3)	0.065 (3)	0.057 (3)	0.008 (2)	0.011 (2)	0.024 (3)
C11	0.044 (3)	0.045 (3)	0.126 (5)	−0.013 (2)	0.004 (3)	−0.013 (3)
C12	0.031 (2)	0.036 (2)	0.038 (2)	0.0070 (15)	0.0022 (17)	0.0067 (16)
C13	0.027 (2)	0.067 (3)	0.0264 (19)	0.0009 (18)	−0.0011 (15)	0.0095 (19)
C14	0.0235 (18)	0.064 (3)	0.0286 (19)	0.0048 (18)	0.0001 (15)	−0.0019 (18)
C15	0.025 (2)	0.077 (3)	0.048 (3)	0.009 (2)	−0.0111 (18)	−0.009 (2)
C16	0.044 (2)	0.068 (3)	0.036 (2)	0.004 (2)	−0.0028 (19)	−0.005 (2)
C17	0.035 (2)	0.073 (3)	0.029 (2)	−0.010 (2)	−0.0017 (17)	0.001 (2)
C18	0.0288 (19)	0.064 (3)	0.032 (2)	−0.0056 (18)	−0.0047 (15)	0.0046 (19)
C19	0.0253 (19)	0.062 (3)	0.032 (2)	0.0029 (19)	−0.0046 (15)	0.011 (2)
C20	0.035 (2)	0.046 (3)	0.064 (3)	0.0100 (19)	−0.0103 (19)	0.009 (2)
C21	0.026 (2)	0.037 (2)	0.082 (3)	0.0045 (17)	−0.007 (2)	−0.006 (2)
C22	0.057 (3)	0.068 (3)	0.066 (3)	0.013 (2)	−0.018 (3)	−0.029 (3)
C23	0.045 (3)	0.048 (3)	0.121 (6)	−0.006 (2)	−0.002 (3)	0.025 (3)
C24	0.032 (2)	0.0323 (19)	0.036 (2)	0.0123 (15)	−0.0050 (16)	−0.0066 (15)

Geometric parameters (Å, º)

Cu1—O1	1.922 (3)	C5—C6	1.363 (7)
Cu1—N1	1.943 (3)	C6—H6	0.9300
Cu1—N3	1.953 (3)	C7—H7	0.9300
Cu1—N2	2.068 (3)	C8—C9	1.508 (7)
Cu1—S1^i	2.8300 (14)	C8—H8A	0.9700
Cu2—O2	1.922 (3)	C8—H8B	0.9700
Cu2—N4	1.948 (3)	C9—H9A	0.9700
Cu2—N6	1.969 (3)	C9—H9B	0.9700
Cu2—N5	2.067 (3)	C10—H10A	0.9600
Cu2—S2^ii	2.8332 (14)	C10—H10B	0.9600
Br1—C5	1.891 (4)	C10—H10C	0.9600
Br2—C17	1.900 (4)	C11—H11A	0.9600
S1—C12	1.635 (4)	C11—H11B	0.9600
S2—C24	1.636 (4)	C11—H11C	0.9600
O1—C2	1.317 (5)	C13—C14	1.417 (5)
O2—C14	1.310 (5)	C13—C18	1.419 (6)
N1—C7	1.283 (5)	C13—C19	1.441 (7)
N1—C8	1.452 (5)	C14—C15	1.407 (7)
N2—C10	1.463 (6)	C15—C16	1.367 (7)
N2—C9	1.483 (5)	C15—H15	0.9300
N2—C11	1.492 (6)	C16—C17	1.397 (6)
N3—C12	1.151 (5)	C16—H16	0.9300
N4—C19	1.264 (6)	C17—C18	1.352 (6)
N4—C20	1.487 (6)	C18—H18	0.9300
N5—C22	1.464 (6)	C19—H19	0.9300
N5—C23	1.484 (6)	C20—C21	1.502 (7)
N5—C21	1.496 (5)	C20—H20A	0.9700
N6—C24	1.135 (5)	C20—H20B	0.9700
C1—C6	1.403 (6)	C21—H21A	0.9700
C1—C2	1.410 (6)	C21—H21B	0.9700
C1—C7	1.442 (6)	C22—H22A	0.9600
C2—C3	1.394 (6)	C22—H22B	0.9600
C3—C4	1.367 (7)	C22—H22C	0.9600
C3—H3	0.9300	C23—H23A	0.9600
C4—C5	1.403 (7)	C23—H23B	0.9600
C4—H4	0.9300	C23—H23C	0.9600
O1—Cu1—N1	92.34 (13)	C9—C8—H8B	110.0
O1—Cu1—N3	90.21 (14)	H8A—C8—H8B	108.4
N1—Cu1—N3	167.79 (16)	N2—C9—C8	110.1 (4)
O1—Cu1—N2	170.22 (15)	N2—C9—H9A	109.6
N1—Cu1—N2	83.90 (14)	C8—C9—H9A	109.6
N3—Cu1—N2	91.65 (13)	N2—C9—H9B	109.6
O1—Cu1—S1^i	97.67 (15)	C8—C9—H9B	109.6
N1—Cu1—S1^i	90.39 (15)	H9A—C9—H9B	108.2
N3—Cu1—S1^i	101.10 (15)	N2—C10—H10A	109.5
N2—Cu1—S1^i	91.40 (15)	N2—C10—H10B	109.5
O2—Cu2—N4	91.63 (13)	H10A—C10—H10B	109.5
O2—Cu2—N6	89.85 (14)	N2—C10—H10C	109.5
N4—Cu2—N6	168.63 (16)	H10A—C10—H10C	109.5
O2—Cu2—N5	170.39 (15)	H10B—C10—H10C	109.5
N4—Cu2—N5	85.35 (14)	N2—C11—H11A	109.5
N6—Cu2—N5	91.36 (14)	N2—C11—H11B	109.5
O2—Cu2—S2^iii	97.89 (15)	H11A—C11—H11B	109.5
N4—Cu2—S2^iii	89.52 (15)	N2—C11—H11C	109.5
N6—Cu2—S2^iii	101.44 (15)	H11A—C11—H11C	109.5
N5—Cu2—S2^iii	91.22 (15)	H11B—C11—H11C	109.5
C2—O1—Cu1	126.3 (3)	N3—C12—S1	179.9 (5)
C14—O2—Cu2	126.4 (3)	C14—C13—C18	119.3 (4)
C7—N1—C8	119.2 (3)	C14—C13—C19	122.3 (4)
C7—N1—Cu1	125.1 (3)	C18—C13—C19	118.3 (4)
C8—N1—Cu1	115.0 (3)	O2—C14—C15	117.8 (3)
C10—N2—C9	108.7 (4)	O2—C14—C13	124.2 (4)
C10—N2—C11	109.2 (4)	C15—C14—C13	118.0 (4)
C9—N2—C11	110.8 (4)	C16—C15—C14	121.3 (4)
C10—N2—Cu1	117.0 (3)	C16—C15—H15	119.4
C9—N2—Cu1	105.7 (2)	C14—C15—H15	119.4
C11—N2—Cu1	105.3 (3)	C15—C16—C17	120.2 (5)
C12—N3—Cu1	169.7 (4)	C15—C16—H16	119.9
C19—N4—C20	119.9 (3)	C17—C16—H16	119.9
C19—N4—Cu2	125.9 (3)	C18—C17—C16	120.6 (4)
C20—N4—Cu2	113.6 (3)	C18—C17—Br2	121.5 (3)
C22—N5—C23	110.6 (4)	C16—C17—Br2	117.9 (4)
C22—N5—C21	108.4 (4)	C17—C18—C13	120.5 (4)
C23—N5—C21	111.2 (4)	C17—C18—H18	119.7
C22—N5—Cu2	116.8 (3)	C13—C18—H18	119.7
C23—N5—Cu2	104.8 (3)	N4—C19—C13	125.4 (4)
C21—N5—Cu2	104.8 (3)	N4—C19—H19	117.3
C24—N6—Cu2	166.8 (4)	C13—C19—H19	117.3
C6—C1—C2	120.3 (4)	N4—C20—C21	108.3 (3)
C6—C1—C7	116.5 (4)	N4—C20—H20A	110.0
C2—C1—C7	123.0 (4)	C21—C20—H20A	110.0
O1—C2—C3	118.6 (4)	N4—C20—H20B	110.0
O1—C2—C1	124.0 (4)	C21—C20—H20B	110.0
C3—C2—C1	117.3 (4)	H20A—C20—H20B	108.4
C4—C3—C2	122.3 (4)	N5—C21—C20	111.4 (4)
C4—C3—H3	118.8	N5—C21—H21A	109.4
C2—C3—H3	118.8	C20—C21—H21A	109.4
C3—C4—C5	119.6 (4)	N5—C21—H21B	109.4
C3—C4—H4	120.2	C20—C21—H21B	109.4
C5—C4—H4	120.2	H21A—C21—H21B	108.0
C6—C5—C4	120.0 (4)	N5—C22—H22A	109.5
C6—C5—Br1	121.3 (4)	N5—C22—H22B	109.5
C4—C5—Br1	118.6 (4)	H22A—C22—H22B	109.5
C5—C6—C1	120.4 (4)	N5—C22—H22C	109.5
C5—C6—H6	119.8	H22A—C22—H22C	109.5
C1—C6—H6	119.8	H22B—C22—H22C	109.5
N1—C7—C1	125.2 (4)	N5—C23—H23A	109.5
N1—C7—H7	117.4	N5—C23—H23B	109.5
C1—C7—H7	117.4	H23A—C23—H23B	109.5
N1—C8—C9	108.5 (3)	N5—C23—H23C	109.5
N1—C8—H8A	110.0	H23A—C23—H23C	109.5
C9—C8—H8A	110.0	H23B—C23—H23C	109.5
N1—C8—H8B	110.0	N6—C24—S2	177.7 (4)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C7—H7···O1^i	0.93	2.51	3.285 (7)	141
C19—H19···O2^iii	0.93	2.55	3.316 (4)	139
C20—H20A···O2^iii	0.97	2.58	3.468 (7)	153

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