Synthesis, structural characterization and thermal properties of a new copper(II) one-dimensional coordination polymer based on bridging N,N′-bis­(2-hy­droxy­benzyl­idene)-2,2-di­methyl­propane-1,3-di­amine and dicyanamide ligands

The design and synthesis of polymeric coordination compounds of 3d transition metals are of great inter­est in the search for functional materials. The coordination chemistry of the copper(II) ion is of inter­est currently due to potential applications in the areas of mol­ecular biology and magnetochemistry. A novel coordination polymer of Cu^II with bridging N,N′-bis­(2-hy­­droxy­phen­yl)-2,2-di­methyl­propane-1,3-di­amine (H₂L-DM) and dicyanamide (dca) ligands, catena-poly[[[μ₂-2,2-di­methyl-N,N′-bis­(2-oxido­benzyl­idene)­pro­pane-1,3-di­amine-1:2κ⁶O,N,N′,O′:O,O′]­dicopper(II)]-di-μ-dicyanamido-1:2′κ²N¹:N⁵;2:1′κ²N¹:N⁵], [Cu₂(C₁₉H₂₀N₂O₂)(C₂N₃)₂]_n, has been synthesized and characterized by CHN elemental analysis, IR spectroscopy, thermal analysis and X-ray single-crystal diffraction analysis. Structural studies show that the Cu^II centres in the dimeric asymmetric unit adopt distorted square-pyramidal geometries, as confirmed by the Addison parameter (τ) values. The chelating characteristics of the L-DM²⁻ ligand results in the formation of a Cu^II dimer with a double phenolate bridge in the asymmetric unit. In the crystal, the dimeric units are further linked to adjacent dimeric units through μ_1,5-dca bridges to produce one-dimensional polymeric chains.

S1. Introduction

The design and synthesis of polymeric coordination compounds of 3d transition metals have witnessed a great inter­est in search of functional materials find wide applications such as model compounds for the investigation of the role of polymetallic active sites in biological systems and new magnetic molecular materials (Sadhukhan et al., 2011; Bhar et al., 2011; Talukder et al., 2011). The complexes derived from N,N'-bis­(2-hy­droxy­phenyl)­propane-1,3-di­amine (H₂L) and its derivatives have been used widely in the construction of dinuclear or trinuclear complexes due to their facile preparation and varied chemical properties (Carbonaro et al., 1999; Heinicke et al., 2005; Drew et al., 1985). On the other hand, the coordination chemistry of the copper(II) ion is of considerable inter­est currently, particularly due to potential applications in the areas of molecular biology and magnetochemistry (Talukder et al., 2011; Li et al., 2014; Hopa et al., 2015). Bridging ligands such as N₃^-, NCS^-, NCO^- and N(CN)₂^- play a key role in the preparation of polynuclear coordination compounds. The larger pseudohalide ligand dicyanamide (dca) has three potential nitro­gen-donor sites and coordinates to metal ions in various modes (see Scheme 1); this is particularly inter­esting and allows the preparation of compounds with various kinds of architectures, viz. mononuclear and polynuclear, as well as one-, two- and three-dimensional networks (Batten & Murray, 2003). As part of our outgoing study of the design of homo- and heteropolynuclear transition metal complexes using O,N,N',O'- and N,N',N''-type ligands with various pseudohalide coligands, we report here the synthesis and crystal structure of a new polymeric complex incorporating the salicyaldimine-type molecule N,N'-bis­(2-hy­droxy­phenyl)-2,2-di­methyl­propane-1,3-di­amine (H₂L-DM) and using dca as coligand. The dca ligand leads to the formation of the one-dimensional polymeric complex, [Cu₂(L-DM)(dca)₂]_n, (1).

Recently, the structural characterization of the dinuclear Cu–Cu(dca)₂ (Biswas & Ghosh, 2012), heterodinuclear Cu–Cd(dca)₂ (Shi et al., 2009), hexanuclear Cu₃–Cu₃(dca)₂ (Talukder et al., 2011), dinuclear Cu–Cu(dca)₂ (Sadhukhan et al., 2011), trinuclear Cu–Ni–Cu(dca)₂ (Biswas et al., 2013), polymeric Cu–Co–Cu(dca)₂ (Mondal et al., 2014), Cu–Zn–Cu(dca)₂ (Shi et al., 2009; Das et al., 2014), Cu₄(dca)₄ (Wang et al., 2014), Cu–Cu(dca)₂ (Mondal et al., 2014), Cu₄(dca)₂ (Zhang et al., 2013), polymeric Cu–Cu(dca)₂ (Mal et al., 2011) Schiff base complexes have been reported. To the best of our knowledge, the structural characterization of the one-dimensional polymeric zigzag chain complex Cu–Cu(dca)₂ of H₂L-DM with dca is described here for the first time.

S2. Experimental

All reagents and solvents were purchased from commercial sources and were used without further purification. The elementel analyses of C, H and N were performed with a LECO CHNS-932 analyzer. The IR spectra were recorded using IR grade KBr disks on a PerkinElmer 1600 series FT–IR spectrophotometer in the range 4000–250 cm^-1. The thermogravimetry/differential thermal analysis (TG/DTA) measurements were run on a PerkinElmer Diamond instrument. In this study, the TG curves were obtained with the flow rate of carrier gas at 100 ml min^-1 and a heating rate of 20K min^-1 in nitro­gen (3 bar; 1 bar = 10 ⁵ Pa) with the sample contained in a ceramic pan in the range 303–1473 K.

S2.1. Synthesis and crystallization

S2.1.1. Preparation of N,N'-bis­(2-hy­droxy­phenyl)-2,2-di­methyl­propane-1,3-di­amine (H\~2\~L-DM)

H₂L-DM was synthesized (see Scheme 2) by refluxing with stirring for 2 h a 2:1 molar ratio of salicyl­aldehyde and 2,2-di­methyl­propane-1,3-di­amine in EtOH using the known general condensation method of Atakol et al. (2003).

S2.1.2. Preparation of [Cu\~2\~(L-DM)(dca)\~2\~]\~n\~, (1).

To a hot methano­lic solution (20 ml) of H₂L-DM (0.310 g, 1 mmol), a solution of Cu(NO₃)₂.3H₂O (0.483, 2 mmol) in hot MeOH was added slowly in a glass beaker. To this boiling solution, an aqueous solution of sodium dicyanamide (0.178, 2 mmol) was added dropwise with constant stirring. The final solution was then filtered to eliminate impurities and the supernatant liquid was kept in air for slow evaporation. After a week, black block-like crystals of (1) suitable for X-ray measurements separated out (yield 75%) (see Scheme 3). Analysis calculated for C₂₃H₂₀Cu₂N₈O₂): C 48.7, H 3.5, N 19.7%; found: C 49.0, H 3.6, N 19.9%.

S2.2. Crystal data collection and refinement

Crystal data, data collection and structure refinement details are summarized in Table 1. H atoms attached to C atoms were placed at calculated positions, with C—H = 0.95 Å , and refined using a riding model, with U_iso(H) values set at 1.5U_eq of their respective parent atoms.

S3. Results and discussion

The IR spectrum of [Cu₂(L-DM)(dca)₂]_n, (1), has been analysed in comparison with that of free H₂L-DM and dca in order to study the binding mode of the ligands to the Cu^II metal centres in the complex. The IR spectrum of free H₂L-DM shows a strong and sharp band due to the azomethine ν(C═N) group at 1628 cm^-1. In the spectrum of the complex, this band has been shifted towards higher region around 1661 cm^-1 indicating the participation of the azomethine group in the complex formation (Kiranmai et al., 2010). Free H₂L-DM shows a medium intensity band at 1279 cm^-1 due to the phenolate ν(C—O) group which is shifted to a higher region at around 1358 cm^-1 in the spectrum of the complex, indicating that the deprotonated ligand (L-DM) is coordinated to the Cu^II centre. These bands prove that the shifts are due to coordination of H₂L-DM to the Cu^II ion by through azomethine N and phenolate O atoms (Mapari et al., 2011; Canpolat & Kaya, 2005). The dca ion has been observed to coordinate to metal cations in a variety of modes (see Scheme 1), which can be terminal or bridging. If the dca group is terminally bonded, the bands at 2286, 2232 and 2173 cm^-1 bands, which are attributed to the characteristic ν_sym+ν_asym(C≡N), ν_asym(C≡N) and ν_sym(C≡ N) vibration bands, respectively, of free dca shift towards lower frequencies, whereas the spectra of the bridging ions are shifted to higher frequencies. The strong absorbtion peaks at 2303, 2242 and 2194 cm^-1 for (1) might be characteristic vibrations of the C≡N bonds of bridging dca anions. Furthermore, in µ_1,5-dca-bridged copper(II) complexes, the ν_sym(C—N) and ν_asym(C—N) vibration bands are usually observed in the ranges 1400–1300 and 950–900 cm^-1 (Talukder et al., 2011; Batten & Murray, 2003). These bands appear at 1359 and 927 cm^-1, respectively, in complex (1). [Can IR spectra or a full list of IR data be provided?]

The dimeric asymmetric unit of (1) (Fig. 1a) can be formulated as [Cu₂(L-DM)(dca)₂] and contains two Cu^II atoms, a Schiff base L-DM^2- ligand connecting pairs of Cu^II centres through a double phenolate bridge and two independent dca anions. The molecular propagation constructing the one-dimensional polymeric architecture of (1) is shown in Fig. 1(b). The geometry of the each Cu^II centre is very close to square pyramidal, with τ = 0.016 and 0.040 [τ = (α-β)/60], where α and β are the two largest angles around the central atom (τ =0 and 1 for the perfect square pyramidal and trigonal bipyramidal geometries, respectively; Addison et al., 1984). The square-pyramidal equatorial plane of the Cu1 centre is formed by the imine N atoms (N1 and N2) and the two phenolate O atoms (O1 and O2) of the tetra­dentate Schiff base L-DM^2- ligand (Table 2). Dca atom N8 coordinates in the axial position (Fig. 2). The equatorial plane of the Cu2 atom is created by two coordinated L-DM^2- phenolate O atoms (O1 and O2) and two dca N atoms (N3 and N4). Dca atom N5 occupies the axial position. The Cu^II ions deviate from the square plane by 0.168 and 0.336 Å, respectively. The –NCNCN– bridge adopts a V-type conformation, in which the C—N—C angles of 123.4 (2) and 120.25 (19)° indicate that dca atoms N7 and N6 are sp²-hybridized. These results are close to the values found in similar salen-type compounds [salen is bis­(salicyl­idene)ethyl­enedi­amine] (Yardan et al., 2015; Bermejo et al., 2007; Kurtaran et al., 2003; Wang et al., 2000).

The formation of a one-dimensional zigzag polymeric chain may be viewed as follows (Fig. 3). The phenolate O atoms of the Cu(L-DM) unit coordinate to the Cu^II atom of a Cu(dca)₂ unit to form a dinuclear unit, as shown in Fig. 1(a). Each unit is connected to adjacent units via one double and two single µ_1,5-bridging dca anions, resulting in a one-dimensional zigzag-like chain with a Cu···Cu distance between adjacent units of 8.099(?) Å.

For investigation of thermal properties of (1), thermogravimetric (TG) analysis and differential thermal analysis (DTA) were carried out from ambient temperature up to ≈ 1473 K under a static nitro­gen atmosphere and the heating rates were suitably controlled at 10 K min^-1. The TG/DTG/DTA curves (DTG is the rate of weight change) (Fig. 4) show that complex (1) is thermally stable up to σim 402 K and decomposes in four successive steps with the DTG maximum at 426, 589, 773 and 1353 K. The endothermic peaks DTA curve at 531, 691 and 797 K are attributed to decomposition of (1). An exo effect is observed around 1354 K and may correspond to decomposition of the ligands accompanied by formation of metalic oxide and carbon residue as an end product.

In summary, we have described the synthesis of a new dicyanamide-bridged one-dimensional polymeric complex of copper with an N₂O₂-donor Schiff base ligand. In the asymetric unit, penta­coordinated Cu^II ions are bridged by phenolate O atoms from the Schiff base ligand and are further inter­linked into a one-dimensional zigzag chain by one double and two single dca ions in µ_1,5-modes. Furthermore, this coordination polymer is thermally stable below 403 K. We are currently investigating the chemistry of dca with other transition metal ions in combination with different neutral O,N,N',O'-type Schiff base ligands.

Structure description

The design and synthesis of polymeric coordination compounds of 3d transition metals have witnessed a great inter­est in search of functional materials find wide applications such as model compounds for the investigation of the role of polymetallic active sites in biological systems and new magnetic molecular materials (Sadhukhan et al., 2011; Bhar et al., 2011; Talukder et al., 2011). The complexes derived from N,N'-bis­(2-hy­droxy­phenyl)­propane-1,3-di­amine (H₂L) and its derivatives have been used widely in the construction of dinuclear or trinuclear complexes due to their facile preparation and varied chemical properties (Carbonaro et al., 1999; Heinicke et al., 2005; Drew et al., 1985). On the other hand, the coordination chemistry of the copper(II) ion is of considerable inter­est currently, particularly due to potential applications in the areas of molecular biology and magnetochemistry (Talukder et al., 2011; Li et al., 2014; Hopa et al., 2015). Bridging ligands such as N₃^-, NCS^-, NCO^- and N(CN)₂^- play a key role in the preparation of polynuclear coordination compounds. The larger pseudohalide ligand dicyanamide (dca) has three potential nitro­gen-donor sites and coordinates to metal ions in various modes (see Scheme 1); this is particularly inter­esting and allows the preparation of compounds with various kinds of architectures, viz. mononuclear and polynuclear, as well as one-, two- and three-dimensional networks (Batten & Murray, 2003). As part of our outgoing study of the design of homo- and heteropolynuclear transition metal complexes using O,N,N',O'- and N,N',N''-type ligands with various pseudohalide coligands, we report here the synthesis and crystal structure of a new polymeric complex incorporating the salicyaldimine-type molecule N,N'-bis­(2-hy­droxy­phenyl)-2,2-di­methyl­propane-1,3-di­amine (H₂L-DM) and using dca as coligand. The dca ligand leads to the formation of the one-dimensional polymeric complex, [Cu₂(L-DM)(dca)₂]_n, (1).

Recently, the structural characterization of the dinuclear Cu–Cu(dca)₂ (Biswas & Ghosh, 2012), heterodinuclear Cu–Cd(dca)₂ (Shi et al., 2009), hexanuclear Cu₃–Cu₃(dca)₂ (Talukder et al., 2011), dinuclear Cu–Cu(dca)₂ (Sadhukhan et al., 2011), trinuclear Cu–Ni–Cu(dca)₂ (Biswas et al., 2013), polymeric Cu–Co–Cu(dca)₂ (Mondal et al., 2014), Cu–Zn–Cu(dca)₂ (Shi et al., 2009; Das et al., 2014), Cu₄(dca)₄ (Wang et al., 2014), Cu–Cu(dca)₂ (Mondal et al., 2014), Cu₄(dca)₂ (Zhang et al., 2013), polymeric Cu–Cu(dca)₂ (Mal et al., 2011) Schiff base complexes have been reported. To the best of our knowledge, the structural characterization of the one-dimensional polymeric zigzag chain complex Cu–Cu(dca)₂ of H₂L-DM with dca is described here for the first time.

All reagents and solvents were purchased from commercial sources and were used without further purification. The elementel analyses of C, H and N were performed with a LECO CHNS-932 analyzer. The IR spectra were recorded using IR grade KBr disks on a PerkinElmer 1600 series FT–IR spectrophotometer in the range 4000–250 cm^-1. The thermogravimetry/differential thermal analysis (TG/DTA) measurements were run on a PerkinElmer Diamond instrument. In this study, the TG curves were obtained with the flow rate of carrier gas at 100 ml min^-1 and a heating rate of 20K min^-1 in nitro­gen (3 bar; 1 bar = 10 ⁵ Pa) with the sample contained in a ceramic pan in the range 303–1473 K.

H₂L-DM was synthesized (see Scheme 2) by refluxing with stirring for 2 h a 2:1 molar ratio of salicyl­aldehyde and 2,2-di­methyl­propane-1,3-di­amine in EtOH using the known general condensation method of Atakol et al. (2003).

To a hot methano­lic solution (20 ml) of H₂L-DM (0.310 g, 1 mmol), a solution of Cu(NO₃)₂.3H₂O (0.483, 2 mmol) in hot MeOH was added slowly in a glass beaker. To this boiling solution, an aqueous solution of sodium dicyanamide (0.178, 2 mmol) was added dropwise with constant stirring. The final solution was then filtered to eliminate impurities and the supernatant liquid was kept in air for slow evaporation. After a week, black block-like crystals of (1) suitable for X-ray measurements separated out (yield 75%) (see Scheme 3). Analysis calculated for C₂₃H₂₀Cu₂N₈O₂): C 48.7, H 3.5, N 19.7%; found: C 49.0, H 3.6, N 19.9%.

The IR spectrum of [Cu₂(L-DM)(dca)₂]_n, (1), has been analysed in comparison with that of free H₂L-DM and dca in order to study the binding mode of the ligands to the Cu^II metal centres in the complex. The IR spectrum of free H₂L-DM shows a strong and sharp band due to the azomethine ν(C═N) group at 1628 cm^-1. In the spectrum of the complex, this band has been shifted towards higher region around 1661 cm^-1 indicating the participation of the azomethine group in the complex formation (Kiranmai et al., 2010). Free H₂L-DM shows a medium intensity band at 1279 cm^-1 due to the phenolate ν(C—O) group which is shifted to a higher region at around 1358 cm^-1 in the spectrum of the complex, indicating that the deprotonated ligand (L-DM) is coordinated to the Cu^II centre. These bands prove that the shifts are due to coordination of H₂L-DM to the Cu^II ion by through azomethine N and phenolate O atoms (Mapari et al., 2011; Canpolat & Kaya, 2005). The dca ion has been observed to coordinate to metal cations in a variety of modes (see Scheme 1), which can be terminal or bridging. If the dca group is terminally bonded, the bands at 2286, 2232 and 2173 cm^-1 bands, which are attributed to the characteristic ν_sym+ν_asym(C≡N), ν_asym(C≡N) and ν_sym(C≡ N) vibration bands, respectively, of free dca shift towards lower frequencies, whereas the spectra of the bridging ions are shifted to higher frequencies. The strong absorbtion peaks at 2303, 2242 and 2194 cm^-1 for (1) might be characteristic vibrations of the C≡N bonds of bridging dca anions. Furthermore, in µ_1,5-dca-bridged copper(II) complexes, the ν_sym(C—N) and ν_asym(C—N) vibration bands are usually observed in the ranges 1400–1300 and 950–900 cm^-1 (Talukder et al., 2011; Batten & Murray, 2003). These bands appear at 1359 and 927 cm^-1, respectively, in complex (1). [Can IR spectra or a full list of IR data be provided?]

The dimeric asymmetric unit of (1) (Fig. 1a) can be formulated as [Cu₂(L-DM)(dca)₂] and contains two Cu^II atoms, a Schiff base L-DM^2- ligand connecting pairs of Cu^II centres through a double phenolate bridge and two independent dca anions. The molecular propagation constructing the one-dimensional polymeric architecture of (1) is shown in Fig. 1(b). The geometry of the each Cu^II centre is very close to square pyramidal, with τ = 0.016 and 0.040 [τ = (α-β)/60], where α and β are the two largest angles around the central atom (τ =0 and 1 for the perfect square pyramidal and trigonal bipyramidal geometries, respectively; Addison et al., 1984). The square-pyramidal equatorial plane of the Cu1 centre is formed by the imine N atoms (N1 and N2) and the two phenolate O atoms (O1 and O2) of the tetra­dentate Schiff base L-DM^2- ligand (Table 2). Dca atom N8 coordinates in the axial position (Fig. 2). The equatorial plane of the Cu2 atom is created by two coordinated L-DM^2- phenolate O atoms (O1 and O2) and two dca N atoms (N3 and N4). Dca atom N5 occupies the axial position. The Cu^II ions deviate from the square plane by 0.168 and 0.336 Å, respectively. The –NCNCN– bridge adopts a V-type conformation, in which the C—N—C angles of 123.4 (2) and 120.25 (19)° indicate that dca atoms N7 and N6 are sp²-hybridized. These results are close to the values found in similar salen-type compounds [salen is bis­(salicyl­idene)ethyl­enedi­amine] (Yardan et al., 2015; Bermejo et al., 2007; Kurtaran et al., 2003; Wang et al., 2000).

The formation of a one-dimensional zigzag polymeric chain may be viewed as follows (Fig. 3). The phenolate O atoms of the Cu(L-DM) unit coordinate to the Cu^II atom of a Cu(dca)₂ unit to form a dinuclear unit, as shown in Fig. 1(a). Each unit is connected to adjacent units via one double and two single µ_1,5-bridging dca anions, resulting in a one-dimensional zigzag-like chain with a Cu···Cu distance between adjacent units of 8.099(?) Å.

For investigation of thermal properties of (1), thermogravimetric (TG) analysis and differential thermal analysis (DTA) were carried out from ambient temperature up to ≈ 1473 K under a static nitro­gen atmosphere and the heating rates were suitably controlled at 10 K min^-1. The TG/DTG/DTA curves (DTG is the rate of weight change) (Fig. 4) show that complex (1) is thermally stable up to σim 402 K and decomposes in four successive steps with the DTG maximum at 426, 589, 773 and 1353 K. The endothermic peaks DTA curve at 531, 691 and 797 K are attributed to decomposition of (1). An exo effect is observed around 1354 K and may correspond to decomposition of the ligands accompanied by formation of metalic oxide and carbon residue as an end product.

In summary, we have described the synthesis of a new dicyanamide-bridged one-dimensional polymeric complex of copper with an N₂O₂-donor Schiff base ligand. In the asymetric unit, penta­coordinated Cu^II ions are bridged by phenolate O atoms from the Schiff base ligand and are further inter­linked into a one-dimensional zigzag chain by one double and two single dca ions in µ_1,5-modes. Furthermore, this coordination polymer is thermally stable below 403 K. We are currently investigating the chemistry of dca with other transition metal ions in combination with different neutral O,N,N',O'-type Schiff base ligands.

Refinement details

Crystal data, data collection and structure refinement details are summarized in Table 1. H atoms attached to C atoms were placed at calculated positions, with C—H = 0.95 Å , and refined using a riding model, with U_iso(H) values set at 1.5U_eq of their respective parent atoms.

Computing details

Data collection: APEX2 (Bruker, 2012); cell refinement: APEX2 (Bruker, 2012); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008) and Mercury (Macrae et al., 2006); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures

	Fig. 1. (a) The molecular structure of complex (1), shown with 50% probability displacement ellipsoids. (b) The molecular propagation of the complex.
	Fig. 2. The coordination sphere of two Cu^II atoms in the copper(II) dimer of (1), showing the main bond lengths (in Å).
	Fig. 3. The polymeric zigzag chain of (1).
	Fig. 4. The DTA/TG/DTG curves of (1).

catena-Poly[[[µ₂-N,N'-bis(2-oxidobenzylidene)-2,2-dimethylpropane-1,3-diamine-1:2κ⁶O,N,N',O':O,O']dicopper]-di-µ-dicyanamido-1:2'κ²N¹:N⁵;2:1'κ²N¹:N⁵]

Crystal data

[Cu2(C19H20N2O2)(C2N3)2]	Z = 2
Mr = 567.55	F(000) = 576
Triclinic, P1	Dx = 1.636 Mg m^−3
a = 10.1140 (3) Å	Mo Kα radiation, λ = 0.71073 Å
b = 10.1578 (4) Å	Cell parameters from 96 reflections
c = 11.9844 (4) Å	θ = 4.4–28.3°
α = 72.725 (2)°	µ = 1.89 mm^−1
β = 87.397 (2)°	T = 150 K
γ = 78.487 (2)°	Block, black
V = 1151.91 (7) Å^3	0.43 × 0.14 × 0.12 mm

Data collection

Bruker APEXII QUAZAR three-circle diffractometer	5252 independent reflections
Radiation source: microfocus sealed tube, ImuS	4672 reflections with I > 2σ(I)
Multilayer QUAZAR mirrors monochromator	Rint = 0.046
Detector resolution: 8.3333 pixels mm^-1	θmax = 27.5°, θmin = 1.8°
φ and ω scans	h = −13→13
Absorption correction: multi-scan (SADABS; Bruker, 2008)	k = −13→13
Tmin = 0.59, Tmax = 0.81	l = −15→15
19441 measured reflections

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)] = 0.027	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.072	H-atom parameters constrained
S = 1.05	w = 1/[σ^2(Fo^2) + (0.0221P)^2 + 0.9123P] where P = (Fo^2 + 2Fc^2)/3
5252 reflections	(Δ/σ)max = 0.001
318 parameters	Δρmax = 0.47 e Å^−3
0 restraints	Δρmin = −0.39 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	0.33153 (18)	1.04563 (19)	0.62662 (17)	0.0184 (4)
C2	0.3425 (2)	1.1488 (2)	0.67968 (19)	0.0237 (4)
H2	0.3385	1.128	0.7623	0.028*
C3	0.3591 (2)	1.2811 (2)	0.6121 (2)	0.0262 (4)
H3	0.365	1.3505	0.6492	0.031*
C4	0.3672 (2)	1.3142 (2)	0.4913 (2)	0.0277 (4)
H4	0.3793	1.405	0.4459	0.033*
C5	0.3574 (2)	1.2130 (2)	0.43809 (19)	0.0236 (4)
H5	0.3652	1.2342	0.3556	0.028*
C6	0.33609 (18)	1.07938 (19)	0.50344 (17)	0.0191 (4)
C7	0.32068 (19)	0.9813 (2)	0.44049 (17)	0.0205 (4)
H7	0.3452	1.0045	0.3606	0.025*
C8	0.26715 (19)	0.7820 (2)	0.40353 (17)	0.0207 (4)
H8A	0.3239	0.6873	0.4348	0.025*
H8B	0.3021	0.8269	0.326	0.025*
C9	0.1210 (2)	0.7676 (2)	0.38959 (17)	0.0205 (4)
C10	0.0274 (2)	0.9116 (2)	0.35510 (19)	0.0266 (4)
H10A	−0.0625	0.9015	0.3358	0.04*
H10B	0.0636	0.9739	0.2869	0.04*
H10C	0.021	0.952	0.4204	0.04*
C11	0.1199 (2)	0.6995 (2)	0.29090 (19)	0.0292 (5)
H11A	0.1849	0.6102	0.3096	0.044*
H11B	0.1446	0.7627	0.2173	0.044*
H11C	0.0294	0.6822	0.2829	0.044*
C12	0.0739 (2)	0.6677 (2)	0.49949 (18)	0.0241 (4)
H12A	−0.0185	0.6576	0.4846	0.029*
H12B	0.1332	0.574	0.5132	0.029*
C13	−0.0182 (2)	0.6714 (2)	0.68230 (18)	0.0214 (4)
H13	−0.0829	0.6303	0.6565	0.026*
C14	−0.03521 (19)	0.6819 (2)	0.79997 (18)	0.0206 (4)
C15	0.05453 (19)	0.73163 (19)	0.85758 (17)	0.0186 (4)
C16	0.0258 (2)	0.7360 (2)	0.97190 (18)	0.0235 (4)
H16	0.0824	0.7736	1.0104	0.028*
C17	−0.0839 (2)	0.6862 (2)	1.02945 (19)	0.0265 (4)
H17	−0.1007	0.6884	1.1076	0.032*
C18	−0.1702 (2)	0.6330 (2)	0.9747 (2)	0.0280 (5)
H18	−0.2448	0.5979	1.0152	0.034*
C19	−0.1457 (2)	0.6321 (2)	0.86122 (19)	0.0254 (4)
H19	−0.2051	0.597	0.8232	0.031*
C20	0.5917 (2)	0.9165 (2)	0.87860 (18)	0.0237 (4)
C21	0.2691 (2)	0.9999 (2)	1.02887 (19)	0.0233 (4)
C22	0.3917 (2)	0.5891 (2)	1.09173 (19)	0.0255 (4)
C23	0.5319 (2)	0.4571 (2)	1.24614 (18)	0.0220 (4)
Cu1	0.21463 (2)	0.79864 (2)	0.64198 (2)	0.01685 (7)
Cu2	0.32406 (2)	0.82273 (2)	0.86030 (2)	0.01858 (7)
N1	0.27706 (16)	0.86616 (16)	0.48235 (14)	0.0187 (3)
N2	0.07269 (16)	0.71012 (16)	0.60758 (14)	0.0193 (3)
N3	0.50636 (18)	0.8601 (2)	0.86892 (16)	0.0277 (4)
N4	0.35727 (18)	0.65888 (19)	0.99954 (16)	0.0286 (4)
N5	0.22712 (19)	0.97801 (19)	0.94960 (17)	0.0295 (4)
N6	0.68947 (19)	0.9831 (2)	0.87531 (16)	0.0305 (4)
N7	0.41222 (19)	0.5090 (2)	1.19859 (17)	0.0395 (5)
N8	0.62869 (18)	0.40418 (19)	1.30103 (16)	0.0279 (4)
O1	0.31523 (14)	0.91775 (14)	0.69091 (12)	0.0204 (3)
O2	0.16362 (13)	0.77484 (14)	0.80379 (12)	0.0204 (3)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0128 (9)	0.0181 (9)	0.0234 (10)	−0.0031 (7)	−0.0035 (7)	−0.0042 (7)
C2	0.0244 (10)	0.0229 (10)	0.0253 (11)	−0.0062 (8)	−0.0034 (8)	−0.0076 (8)
C3	0.0260 (11)	0.0208 (10)	0.0345 (12)	−0.0060 (8)	−0.0008 (9)	−0.0108 (9)
C4	0.0280 (11)	0.0171 (9)	0.0352 (12)	−0.0051 (8)	−0.0002 (9)	−0.0030 (8)
C5	0.0212 (10)	0.0220 (10)	0.0238 (10)	−0.0034 (8)	−0.0011 (8)	−0.0015 (8)
C6	0.0146 (9)	0.0192 (9)	0.0223 (10)	−0.0021 (7)	−0.0035 (7)	−0.0045 (8)
C7	0.0175 (9)	0.0224 (9)	0.0187 (10)	−0.0007 (7)	−0.0030 (7)	−0.0035 (8)
C8	0.0205 (10)	0.0209 (9)	0.0213 (10)	0.0003 (7)	−0.0025 (7)	−0.0094 (8)
C9	0.0214 (10)	0.0215 (9)	0.0201 (10)	−0.0019 (7)	−0.0061 (7)	−0.0092 (8)
C10	0.0241 (11)	0.0269 (10)	0.0260 (11)	0.0042 (8)	−0.0086 (8)	−0.0081 (9)
C11	0.0311 (12)	0.0363 (12)	0.0263 (11)	−0.0075 (9)	−0.0030 (9)	−0.0172 (9)
C12	0.0269 (11)	0.0244 (10)	0.0256 (11)	−0.0071 (8)	−0.0043 (8)	−0.0121 (8)
C13	0.0194 (9)	0.0199 (9)	0.0260 (10)	−0.0047 (7)	−0.0061 (7)	−0.0067 (8)
C14	0.0185 (9)	0.0179 (9)	0.0241 (10)	−0.0013 (7)	−0.0046 (7)	−0.0049 (8)
C15	0.0167 (9)	0.0153 (8)	0.0211 (10)	−0.0007 (7)	−0.0045 (7)	−0.0019 (7)
C16	0.0241 (10)	0.0231 (10)	0.0232 (10)	−0.0028 (8)	−0.0047 (8)	−0.0071 (8)
C17	0.0255 (11)	0.0282 (10)	0.0225 (11)	−0.0010 (8)	−0.0002 (8)	−0.0054 (8)
C18	0.0216 (10)	0.0286 (11)	0.0324 (12)	−0.0074 (8)	0.0040 (8)	−0.0060 (9)
C19	0.0220 (10)	0.0250 (10)	0.0304 (12)	−0.0071 (8)	−0.0033 (8)	−0.0076 (9)
C20	0.0224 (10)	0.0268 (10)	0.0196 (10)	−0.0017 (8)	−0.0032 (8)	−0.0050 (8)
C21	0.0204 (10)	0.0206 (9)	0.0292 (11)	−0.0058 (8)	0.0027 (8)	−0.0072 (8)
C22	0.0174 (10)	0.0285 (10)	0.0287 (11)	−0.0040 (8)	−0.0038 (8)	−0.0050 (9)
C23	0.0246 (10)	0.0180 (9)	0.0221 (10)	−0.0033 (8)	−0.0001 (8)	−0.0044 (8)
Cu1	0.01737 (12)	0.01686 (12)	0.01658 (13)	−0.00418 (9)	−0.00482 (8)	−0.00404 (9)
Cu2	0.01828 (13)	0.01919 (12)	0.01802 (13)	−0.00386 (9)	−0.00657 (9)	−0.00394 (9)
N1	0.0180 (8)	0.0201 (8)	0.0180 (8)	−0.0022 (6)	−0.0053 (6)	−0.0058 (6)
N2	0.0197 (8)	0.0185 (8)	0.0200 (8)	−0.0032 (6)	−0.0056 (6)	−0.0058 (6)
N3	0.0230 (9)	0.0345 (10)	0.0253 (10)	−0.0074 (8)	−0.0075 (7)	−0.0059 (8)
N4	0.0254 (9)	0.0302 (9)	0.0252 (10)	−0.0055 (7)	−0.0089 (7)	0.0010 (8)
N5	0.0296 (10)	0.0311 (10)	0.0334 (11)	−0.0077 (8)	−0.0002 (8)	−0.0166 (8)
N6	0.0337 (10)	0.0389 (11)	0.0228 (10)	−0.0179 (8)	−0.0006 (8)	−0.0074 (8)
N7	0.0213 (9)	0.0537 (13)	0.0270 (10)	−0.0037 (9)	−0.0048 (8)	0.0115 (9)
N8	0.0253 (9)	0.0244 (9)	0.0286 (10)	0.0021 (7)	−0.0070 (7)	−0.0030 (7)
O1	0.0256 (7)	0.0193 (6)	0.0168 (7)	−0.0085 (5)	−0.0060 (5)	−0.0024 (5)
O2	0.0202 (7)	0.0246 (7)	0.0177 (7)	−0.0077 (5)	−0.0035 (5)	−0.0055 (5)

Geometric parameters (Å, º)

C1—O1	1.337 (2)	C14—C19	1.405 (3)
C1—C2	1.401 (3)	C14—C15	1.415 (3)
C1—C6	1.414 (3)	C15—O2	1.337 (2)
C2—C3	1.387 (3)	C15—C16	1.399 (3)
C2—H2	0.95	C16—C17	1.382 (3)
C3—C4	1.388 (3)	C16—H16	0.95
C3—H3	0.95	C17—C18	1.391 (3)
C4—C5	1.382 (3)	C17—H17	0.95
C4—H4	0.95	C18—C19	1.374 (3)
C5—C6	1.404 (3)	C18—H18	0.95
C5—H5	0.95	C19—H19	0.95
C6—C7	1.451 (3)	C20—N3	1.154 (3)
C7—N1	1.285 (3)	C20—N6	1.298 (3)
C7—H7	0.95	C21—N5	1.154 (3)
C8—N1	1.469 (2)	C21—N6^i	1.309 (3)
C8—C9	1.536 (3)	C22—N4	1.147 (3)
C8—H8A	0.99	C22—N7	1.297 (3)
C8—H8B	0.99	C23—N8	1.148 (3)
C9—C10	1.527 (3)	C23—N7	1.303 (3)
C9—C12	1.528 (3)	Cu1—O2	1.9404 (14)
C9—C11	1.538 (3)	Cu1—O1	1.9518 (13)
C10—H10A	0.98	Cu1—N1	1.9527 (17)
C10—H10B	0.98	Cu1—N2	1.9567 (16)
C10—H10C	0.98	Cu1—N8^ii	2.2763 (17)
C11—H11A	0.98	Cu1—Cu2	2.9802 (3)
C11—H11B	0.98	Cu2—N4	1.9611 (18)
C11—H11C	0.98	Cu2—N3	1.9684 (18)
C12—N2	1.481 (2)	Cu2—O1	1.9695 (13)
C12—H12A	0.99	Cu2—O2	1.9847 (13)
C12—H12B	0.99	Cu2—N5	2.2101 (18)
C13—N2	1.289 (3)	N6—C21^i	1.309 (3)
C13—C14	1.446 (3)	N8—Cu1^ii	2.2763 (17)
C13—H13	0.95
O1—C1—C2	120.80 (18)	C15—C16—H16	119.6
O1—C1—C6	120.27 (17)	C16—C17—C18	121.0 (2)
C2—C1—C6	118.93 (17)	C16—C17—H17	119.5
C3—C2—C1	120.28 (19)	C18—C17—H17	119.5
C3—C2—H2	119.9	C19—C18—C17	118.9 (2)
C1—C2—H2	119.9	C19—C18—H18	120.6
C2—C3—C4	121.23 (19)	C17—C18—H18	120.6
C2—C3—H3	119.4	C18—C19—C14	121.68 (19)
C4—C3—H3	119.4	C18—C19—H19	119.2
C5—C4—C3	118.97 (19)	C14—C19—H19	119.2
C5—C4—H4	120.5	N3—C20—N6	172.7 (2)
C3—C4—H4	120.5	N5—C21—N6^i	174.9 (2)
C4—C5—C6	121.3 (2)	N4—C22—N7	171.6 (2)
C4—C5—H5	119.3	N8—C23—N7	171.1 (2)
C6—C5—H5	119.3	O2—Cu1—N8^ii	89.63 (6)
C5—C6—C1	119.18 (18)	N1—Cu1—N8^ii	97.37 (7)
C5—C6—C7	117.92 (18)	O2—Cu1—O1	76.62 (6)
C1—C6—C7	122.90 (17)	O1—Cu1—N1	89.96 (6)
N1—C7—C6	126.33 (18)	O2—Cu1—N1	165.58 (6)
N1—C7—H7	116.8	O2—Cu1—N2	94.30 (6)
C6—C7—H7	116.8	N1—Cu1—N2	97.59 (7)
N1—C8—C9	111.71 (15)	O1—Cu1—N8^ii	97.18 (6)
N1—C8—H8A	109.3	N2—Cu1—N8^ii	95.18 (7)
C9—C8—H8A	109.3	O1—Cu1—N2	164.57 (6)
N1—C8—H8B	109.3	C20—N6—C21^i	120.25 (19)
C9—C8—H8B	109.3	N4—Cu2—O1	154.49 (7)
H8A—C8—H8B	107.9	N3—Cu2—O2	161.47 (7)
C10—C9—C12	112.07 (17)	N4—Cu2—N3	92.21 (8)
C10—C9—C8	110.74 (16)	N3—Cu2—O1	90.43 (7)
C12—C9—C8	111.35 (16)	N4—Cu2—O2	95.88 (7)
C10—C9—C11	108.96 (17)	O1—Cu2—O2	75.21 (6)
C12—C9—C11	106.62 (16)	N3—Cu2—N5	94.46 (7)
C8—C9—C11	106.85 (16)	O2—Cu2—N5	101.00 (6)
C9—C10—H10A	109.5	N4—Cu2—N5	97.19 (8)
C9—C10—H10B	109.5	O1—Cu2—N5	107.90 (7)
H10A—C10—H10B	109.5	C22—N7—C23	123.4 (2)
C9—C10—H10C	109.5	O2—Cu1—Cu2	41.16 (4)
H10A—C10—H10C	109.5	O1—Cu1—Cu2	40.76 (4)
H10B—C10—H10C	109.5	N1—Cu1—Cu2	128.01 (5)
C9—C11—H11A	109.5	N2—Cu1—Cu2	134.35 (5)
C9—C11—H11B	109.5	N8^ii—Cu1—Cu2	78.69 (5)
H11A—C11—H11B	109.5	N4—Cu2—Cu1	120.10 (6)
C9—C11—H11C	109.5	N3—Cu2—Cu1	121.95 (5)
H11A—C11—H11C	109.5	O1—Cu2—Cu1	40.32 (4)
H11B—C11—H11C	109.5	O2—Cu2—Cu1	40.05 (4)
N2—C12—C9	115.84 (16)	N5—Cu2—Cu1	123.57 (5)
N2—C12—H12A	108.3	C7—N1—C8	118.03 (17)
C9—C12—H12A	108.3	C7—N1—Cu1	124.71 (14)
N2—C12—H12B	108.3	C8—N1—Cu1	117.20 (13)
C9—C12—H12B	108.3	C13—N2—C12	115.83 (16)
H12A—C12—H12B	107.4	C13—N2—Cu1	122.36 (14)
N2—C13—C14	128.89 (18)	C12—N2—Cu1	121.38 (13)
N2—C13—H13	115.6	C20—N3—Cu2	160.46 (18)
C14—C13—H13	115.6	C22—N4—Cu2	160.73 (18)
C19—C14—C15	119.05 (19)	C21—N5—Cu2	127.01 (16)
C19—C14—C13	116.32 (18)	C23—N8—Cu1^ii	143.52 (17)
C15—C14—C13	124.55 (18)	C1—O1—Cu1	125.34 (12)
O2—C15—C16	120.64 (17)	C1—O1—Cu2	132.99 (12)
O2—C15—C14	120.85 (17)	Cu1—O1—Cu2	98.93 (6)
C16—C15—C14	118.50 (18)	C15—O2—Cu1	128.45 (12)
C17—C16—C15	120.80 (19)	C15—O2—Cu2	132.68 (12)
C17—C16—H16	119.6	Cu1—O2—Cu2	98.79 (6)
O1—C1—C2—C3	−179.87 (18)	N1—Cu1—N2—C13	−166.47 (15)
C6—C1—C2—C3	−0.8 (3)	N8^ii—Cu1—N2—C13	95.36 (16)
C1—C2—C3—C4	−0.9 (3)	Cu2—Cu1—N2—C13	16.12 (19)
C2—C3—C4—C5	0.5 (3)	O2—Cu1—N2—C12	−166.87 (14)
C3—C4—C5—C6	1.6 (3)	O1—Cu1—N2—C12	140.0 (2)
C4—C5—C6—C1	−3.3 (3)	N1—Cu1—N2—C12	21.32 (15)
C4—C5—C6—C7	177.18 (19)	N8^ii—Cu1—N2—C12	−76.85 (15)
O1—C1—C6—C5	−178.09 (17)	Cu2—Cu1—N2—C12	−156.09 (11)
C2—C1—C6—C5	2.8 (3)	N6—C20—N3—Cu2	−105.9 (17)
O1—C1—C6—C7	1.4 (3)	N4—Cu2—N3—C20	−116.9 (5)
C2—C1—C6—C7	−177.68 (18)	O1—Cu2—N3—C20	88.5 (5)
C5—C6—C7—N1	−166.61 (19)	O2—Cu2—N3—C20	127.1 (5)
C1—C6—C7—N1	13.9 (3)	N5—Cu2—N3—C20	−19.5 (5)
N1—C8—C9—C10	52.3 (2)	Cu1—Cu2—N3—C20	115.1 (5)
N1—C8—C9—C12	−73.1 (2)	N7—C22—N4—Cu2	119.6 (16)
N1—C8—C9—C11	170.85 (16)	N3—Cu2—N4—C22	44.4 (6)
C10—C9—C12—N2	−63.3 (2)	O1—Cu2—N4—C22	140.1 (5)
C8—C9—C12—N2	61.3 (2)	O2—Cu2—N4—C22	−152.3 (5)
C11—C9—C12—N2	177.54 (16)	N5—Cu2—N4—C22	−50.3 (6)
N2—C13—C14—C19	179.18 (19)	Cu1—Cu2—N4—C22	173.8 (5)
N2—C13—C14—C15	−4.1 (3)	N6^i—C21—N5—Cu2	−94 (3)
C19—C14—C15—O2	177.46 (17)	N4—Cu2—N5—C21	52.6 (2)
C13—C14—C15—O2	0.8 (3)	N3—Cu2—N5—C21	−40.2 (2)
C19—C14—C15—C16	−3.2 (3)	O1—Cu2—N5—C21	−132.1 (2)
C13—C14—C15—C16	−179.88 (18)	O2—Cu2—N5—C21	150.0 (2)
O2—C15—C16—C17	−177.42 (18)	Cu1—Cu2—N5—C21	−173.75 (18)
C14—C15—C16—C17	3.2 (3)	N3—C20—N6—C21^i	180.100
C15—C16—C17—C18	−1.2 (3)	N4—C22—N7—C23	174.4 (16)
C16—C17—C18—C19	−0.8 (3)	N8—C23—N7—C22	177.1 (14)
C17—C18—C19—C14	0.8 (3)	N7—C23—N8—Cu1^ii	89.3 (15)
C15—C14—C19—C18	1.2 (3)	C2—C1—O1—Cu1	148.05 (15)
C13—C14—C19—C18	178.18 (19)	C6—C1—O1—Cu1	−31.0 (2)
O2—Cu1—Cu2—N4	59.63 (9)	C2—C1—O1—Cu2	−9.0 (3)
O1—Cu1—Cu2—N4	−158.30 (9)	C6—C1—O1—Cu2	171.88 (13)
N1—Cu1—Cu2—N4	−133.57 (9)	O2—Cu1—O1—C1	−138.67 (15)
N2—Cu1—Cu2—N4	43.18 (9)	N1—Cu1—O1—C1	36.01 (15)
N8^ii—Cu1—Cu2—N4	−43.00 (8)	N2—Cu1—O1—C1	−83.6 (3)
O2—Cu1—Cu2—N3	174.10 (9)	N8^ii—Cu1—O1—C1	133.44 (15)
O1—Cu1—Cu2—N3	−43.83 (9)	Cu2—Cu1—O1—C1	−163.24 (18)
N1—Cu1—Cu2—N3	−19.10 (9)	O2—Cu1—O1—Cu2	24.57 (6)
N2—Cu1—Cu2—N3	157.64 (9)	N1—Cu1—O1—Cu2	−160.75 (7)
N8^ii—Cu1—Cu2—N3	71.46 (8)	N2—Cu1—O1—Cu2	79.7 (2)
O2—Cu1—Cu2—O1	−142.07 (9)	N8^ii—Cu1—O1—Cu2	−63.33 (7)
N1—Cu1—Cu2—O1	24.73 (9)	N4—Cu2—O1—C1	−150.80 (17)
N2—Cu1—Cu2—O1	−158.52 (9)	N3—Cu2—O1—C1	−54.75 (17)
N8^ii—Cu1—Cu2—O1	115.30 (8)	O2—Cu2—O1—C1	137.09 (17)
O1—Cu1—Cu2—O2	142.07 (9)	N5—Cu2—O1—C1	40.07 (18)
N1—Cu1—Cu2—O2	166.80 (8)	Cu1—Cu2—O1—C1	161.2 (2)
N2—Cu1—Cu2—O2	−16.45 (9)	N4—Cu2—O1—Cu1	47.96 (17)
N8^ii—Cu1—Cu2—O2	−102.63 (8)	N3—Cu2—O1—Cu1	144.01 (7)
O2—Cu1—Cu2—N5	−64.31 (9)	O2—Cu2—O1—Cu1	−24.15 (6)
O1—Cu1—Cu2—N5	77.76 (9)	N5—Cu2—O1—Cu1	−121.17 (7)
N1—Cu1—Cu2—N5	102.49 (8)	C16—C15—O2—Cu1	−172.59 (13)
N2—Cu1—Cu2—N5	−80.77 (9)	C14—C15—O2—Cu1	6.7 (2)
N8^ii—Cu1—Cu2—N5	−166.95 (8)	C16—C15—O2—Cu2	11.4 (3)
C6—C7—N1—C8	179.18 (17)	C14—C15—O2—Cu2	−169.25 (13)
C6—C7—N1—Cu1	2.2 (3)	O1—Cu1—O2—C15	158.63 (15)
C9—C8—N1—C7	−118.02 (19)	N1—Cu1—O2—C15	136.8 (2)
C9—C8—N1—Cu1	59.19 (18)	N2—Cu1—O2—C15	−8.73 (16)
O2—Cu1—N1—C7	0.2 (4)	N8^ii—Cu1—O2—C15	−103.90 (15)
O1—Cu1—N1—C7	−21.03 (16)	Cu2—Cu1—O2—C15	−177.01 (18)
N2—Cu1—N1—C7	145.47 (16)	O1—Cu1—O2—Cu2	−24.36 (6)
N8^ii—Cu1—N1—C7	−118.26 (16)	N1—Cu1—O2—Cu2	−46.2 (3)
Cu2—Cu1—N1—C7	−36.88 (18)	N2—Cu1—O2—Cu2	168.28 (6)
O2—Cu1—N1—C8	−176.8 (2)	N8^ii—Cu1—O2—Cu2	73.11 (7)
O1—Cu1—N1—C8	161.97 (13)	N4—Cu2—O2—C15	45.44 (17)
N2—Cu1—N1—C8	−31.53 (14)	N3—Cu2—O2—C15	160.9 (2)
N8^ii—Cu1—N1—C8	64.74 (13)	O1—Cu2—O2—C15	−158.90 (17)
Cu2—Cu1—N1—C8	146.12 (11)	N5—Cu2—O2—C15	−53.09 (17)
C14—C13—N2—C12	172.06 (19)	Cu1—Cu2—O2—C15	176.81 (19)
C14—C13—N2—Cu1	−0.6 (3)	N4—Cu2—O2—Cu1	−131.38 (7)
C9—C12—N2—C13	149.04 (18)	N3—Cu2—O2—Cu1	−15.9 (2)
C9—C12—N2—Cu1	−38.3 (2)	O1—Cu2—O2—Cu1	24.29 (6)
O2—Cu1—N2—C13	5.35 (16)	N5—Cu2—O2—Cu1	130.10 (7)
O1—Cu1—N2—C13	−47.8 (3)

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