Two different one-dimensional structural motifs in [catena-{Cu(tacn)}₂Pd(CN)₄]Br₂·[catena-Cu(tacn)Pd(CN)₄]₂·H₂O (tacn is 1,4,7-triaza­cyclo­nonane)

The title compound, catena-poly[[bis[(triazacyclononane-κ³N,N′,N′′)copper(II)]-di-μ-cyanido-κ⁴N:C-palladate(II)-di-μ-cyanido-κ⁴C:N] dibromide bis[[(triazacyclononane-κ³N,N′,N′′)copper(II)]-μ-cyan­ido-κ²N:C-[dicyanidopalladate(II)]-μ-cyan­ido-κ²C:N] monohydrate], {[Cu₂Pd(CN)₄(C₆H₁₅N₃)₂]Br₂·[Cu₂Pd₂(CN)₈(C₆H₁₅N₃)₂]·H₂O}_n, (I), was isolated from an aqueous solution containing tacn·3HBr (tacn is 1,4,7-triaza­cyclo­nonane), Cu²⁺ and tetra­cyanidopalladate(2−) anions. The crystal structure of (I) is essentially ionic and built up of 2,2-electroneutral chains, viz. [Cu(tacn)(NC)–Pd(CN)₂–(CN)–], positively charged 2,4-ribbons exhibiting the composition {[Cu(tacn)(NC)₂–Pd(CN)₂–Cu(tacn)]²ⁿ⁺}_n, bromide anions and one disordered water mol­ecule of crystallization. The O atom of the water mol­ecule occupies two unique crystallographic positions, one on a centre of symmetry, which is half occupied, and the other in a general position with one-quarter occupancy. One of the tacn ligands also exhibits disorder. The formation of two different types of one-dimensional structural motif within the same structure is a unique feature of this compound.

S1. Comment

Cyano complexes exhibit great structural variability due to the bridging ability of the cyano ligand. This structural variability allied with the presence of paramagnetic central atoms makes cyanocomplexes popular among chemists and physicists as materials exhibiting various interesting magnetic properties (Lescouezec et al., 2005; Ohba & Okawa, 2000; Garde et al., 2008; Bernhardt et al., 2005; Klokishner et al., 2007; Herrera et al., 2008).

In construction of low-dimensional cyano complexes, the so-called `brick and mortar' method can be applied (Willet et al., 1993), in which a metallic central atom coordinated by suitable blocking ligand(s) acts as the `brick' and the cyanide complex anion is used as the `mortar'. Previously, following these ideas we have prepared, structurally characterized and studied the magnetic properties of several low-dimensional cyanide complexes in which various bidentate ligands were used (Hanko et al., 2007; Kuchár et al., 2004, 2003). These complexes are also interesting as models for studies of the role of hydrogen bonds in mediating magnetic exchange interactions.

As a continuation of our effort to prepare one-dimensional cyano complexes, we have decided to use a cyclic triaza ligand, 1,4,7-triazacyclononane (tacn). This tridentate ligand, connected to a Cu^II central atom, affords mainly five-coordination (Han et al., 2004; Wang et al., 2004), thus leaving two coordination sites free for the polymerization process during crystallization. As a result of our synthetic procedure using tacn.3HBr, prepared according to the literature (White et al., 1979), we have isolated the title compound, (I).

The crystal structure of (I) is essentially ionic (Figs. 1–3). It is built up of positively charged 2,4-ribbons exhibiting composition [Cu(tacn)(NC)₂—Pd(CN)₂—Cu(tacn)]_n²ⁿ⁺ and running along the (100) direction, bromide anions, electroneutral 2,2-CT chains [Cu(tacn)(NC)—Pd(CN)₂—(CN)–] running along the (001) direction and one water molecule of crystallization. An alternative view of the structure is that it is formed of the abovementioned chains, with ribbons running perpendicularly between the chains, and with bromide anions and water molecules of crystallization placed in the free space between the chains and ribbons.

This type of 2,4-ribbon incorporating cyanide ligands and Cu^II central atoms has not been described previously, but a similar ribbon structural motif was found in [Mn₆(tptz)₆(MeOH)₄(DMF)₂W₄(CN)₃₂]₈.2H₂O.2.3MeOH [tptz is 2,4,6-tris(2-pyridyl)-1,3,5-triazine and DMF is N,N-dimethylformamide; Zhao et al., 2007). On the other hand, chains built up of cyano complex anions and Cu^II ions are not uncommon; as examples, Cu(en)₂Ni(CN)₄ or Cu(dmen)₂Pd(CN)₄ can be mentioned (en and dmen are ??; Seitz et al., 2001; Kuchár et al., 2004). The presence of both one-dimensional structural motifs within the same structure is, however, a unique feature of this structure.

Both the ribbon and the chain parts of the structure contain five-coordinated Cu^II ions. As expected, three coordination sites are occupied by the blocking tacn ligand, with Cu—N bonds within the range 1.917 (11)–2.216 (4) Å and with intrachelate N—Cu—N angles of 83.38 (17), 83.47 (18) and 83.7 (2)° (Table 1). The remaining two coordination sites around the Cu^II central ions are occupied by N atoms from bridging cyanide ligands with Cu—N distances in the range 1.976 (4)–1.998 (4) Å. As calculated following the suggestion of Addison et al. (1984), the τ parameters of atoms Cu1 (chain) and Cu2 are 0.98 and 1/3, respectively, indicating that the polyhedron around atom Cu1 is close to ideal trigonal bipyramidal while that around atom Cu2 is closer to square pyramidal. The geometric parameters within the tacn ligands are as expected (Schwindinger et al., 1980).

There are three crystallographically independent Pd^II ions in the structure. Each of them occupies a special position (centre of symmetry). All Pd^II ions exhibit square-planar coordination by four cyano ligands with a mean Pd—C bond length of 2.004 (3) Å; this value is close to that of 1.994 (1) found in [Cu(tn)Pd(CN)₄] (tn is 1,3-diaminopropane; Legendre et al., 2008). All of the cyanide ligands within the ribbon exhibit bridging character, while amongst those in the [Pd(CN)₄]^2- anion within the chain, two are terminal and two link Cu and Pd ions. The C≡N bonds are from the range 1.126 (7)–1.151 (7) Å, which are normal values (Legendre et al., 2008). The Cu—N≡C angles formed by bridging cyanide ligands exhibit values in the range 167.1 (4)—177.6 (5)°. The presence of both bridging and terminal cyanide ligands in the structure was also detected by IR spectroscopy; in the spectrum there are absorption bands at 2183 and 2145 cm^-1, which were attributed to the stretching vibrations of the bridging (higher wavenumbers) and terminal cyanide ligands. The absorption band at higher wavenumbers exhibits greater intensity, in line with the larger number of bridging cyanide ligands in the structure.

There is one non-coordinated bromide anion that occupies a general position, which hydrogen bonds to NH groups of the tacn ligands (Table 2). Two unique crystallographic positions are occupied by the O atom of the water molecule, one on a centre of symmetry, which is half occupied, and the other in a general position, 1.432 (2) Å away, with one-quarter occupancy. The water molecule, N atoms from the tacn ligands and terminal n atoms from the cyanide groups are involved in N—H···O and N—H···N(≡C) hydrogen bonds, respectively (Table 2 and Fig. 3).

N—H···N(≡C) hydrogen bonds connect the electroneutral chains to one another as well as to the chains of negatively charged ribbons, with N···N distances in the range 2.942 (6)–3.282 (11) Å. The water molecule interacts via an N—H···O hydrogen-bond interaction with H atoms from the electroneutral chain. At the same time, the O1B···Br1 (2.992 Å) and O1A···Br1 distances (3.249 and 3.384 Å), respectively, suggest the presence of further hydrogen-bonding interactions. The bromide anions form further weak hydrogen-bonding interactions of the N—H···Br type, with H···Br distances in the range 2.35–2.66 Å.

Related literature

For related literature, see: Addison et al. (1984); Bernhardt et al. (2005); Garde et al. (2008); Han et al. (2004); Hanko et al. (2007); Herrera et al. (2008); Klokishner et al. (2007); Kuchár et al. (2003, 2004); Legendre et al. (2008); Lescouezec et al. (2005); Ohba & Okawa (2000); Schwindinger et al. (1980); Seitz et al. (2001); Wang et al. (2004); White et al. (1979); Willet et al. (1993); Zhao et al. (2007).

S2. Experimental

A solution formed by mixing a 0.1 M warm solution of CuSO₄ (10 ml, 1 mmol) and tacn.3HBr in 10 ml of methanol and 10 ml of water (0.22 ml, 2 mmol) was mixed with a 0.1 M warm solution of K₂[Pd(CN)₄] (10 ml, 1 mmol). The resulting precipitate was dissolved by addition of a concentrated aqueous solution of ammonia (25%). Finally, the solution was filtered and left to crystallize at ambient temperature (291 K). The first single crystals appeared as blue prisms after one day. Analysis found (M_r 1580.28): C 26.95, H 4.05, N 21.05%; calculated: C 27.36, H 3.95, N 21.27. FT–IR (cm^-1, KBr): ν(OH): 3507 (s), 3437 (s); ν(NH): 3302 (s); ν(CH): 2959 (m), 2924 (m); ν(CN): 2183 (vs), 2145 (vs); δ(OH₂): 1651 (m); δ(CH₂) [δ or \v?]: 1485 (m), 1454 (m); ν(C—N): 1153 (w); ν(C—C): 1099 (m).

S3. Refinement

All H-atom positions were calculated using the appropriate riding model with U_iso values of 1.2 times U_eq of the parent atoms, and with C—H distances of 0.99 and N—H distances of 0.93 Å. H atoms that belong to the water molecule were not modelled. During the solving of the structure, in the Fourier difference map several peaks appeared that could be assigned to the N and C atoms of the tacn ligand. By careful assignment of the observed maxima in the electron map to the N and C atoms two different orientations could be modelled. The site occupation factors were freely refined, giving a major occupancy of 50.6 (10)%.

Computing details

Data collection: X-AREA (Stoe & Cie, 2003); cell refinement: X-AREA (Stoe & Cie, 2003); data reduction: X-AREA (Stoe & Cie, 2003); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Crystal Impact, 2002); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures

	Fig. 1. The chain (a) and 2,4-ribbon (b) in the title compound, along with atom numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. A perspective view of the crystal structure of (I), displaying the chains and ribbons as well as the bromide anions and water molecules of crystallization. H atoms have been omitted for clarity.
	Fig. 3. The hydrogen-bond system in (I), connecting neighbouring chains (a) as well as the chains and ribbons (b). [Symmetry codes: (v) -x + 1, -y + 1, -z + 2; (vi) -x + 1, -y + 1, -z + 1; (vii) x - 1, y - 1, z. [Only one figure was supplied; please check. Code vii not used in existing figure.]

catena-poly[[bis[(triazacyclononane-κ³N,N',N'')copper(II)]- di-µ-cyanido-κ⁴N:C-palladate(II)-di-µ-cyanido-κ⁴C:N] dibromide bis[[(triazacyclononane-κ³N,N',N'')copper(II)]-µ-cyanido-κ²N:C- [dicyanidopalladate(II)]-µ-cyanido-κ²C:N] monohydrate]

Crystal data

[Cu2Pd(CN)4(C6H15N3)2]Br2·[Cu2Pd2(CN)8(C6H15N3)2]·H2O	Z = 1
Mr = 1580.28	F(000) = 778
Triclinic, P1	Dx = 1.943 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.3214 (8) Å	Cell parameters from 39615 reflections
b = 12.9466 (14) Å	θ = 1.9–30.7°
c = 14.5178 (16) Å	µ = 4.05 mm^−1
α = 83.699 (9)°	T = 193 K
β = 84.378 (9)°	Column, blue
γ = 82.878 (9)°	0.40 × 0.12 × 0.10 mm
V = 1352.3 (3) Å^3

Data collection

Stoe IPDS-II diffractometer	5903 independent reflections
Radiation source: fine-focus sealed tube	4826 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.062
Detector resolution: 150 pixels mm^-1	θmax = 27.0°, θmin = 2.0°
ω–scans	h = −9→7
Absorption correction: multi-scan (WinGX; Farrugia, 1999)	k = −16→16
Tmin = 0.410, Tmax = 0.667	l = −18→18
22649 measured reflections

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)] = 0.044	H-atom parameters constrained
wR(F^2) = 0.115	w = 1/[σ^2(Fo^2) + (0.0643P)^2 + 2.2827P] where P = (Fo^2 + 2Fc^2)/3
S = 1.03	(Δ/σ)max < 0.001
5903 reflections	Δρmax = 1.18 e Å^−3
394 parameters	Δρmin = −1.36 e Å^−3
0 restraints	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0047 (6)

Special details

Experimental. For CHNS analysis: CHNS Elemental Analyzer Flash EA 1112; Thermo Finnigan

For FT–IR: Nicolet Avatar 330 FT–IR, in KBr

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. H-atoms of water molecules of crystallization not included 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)
Pd1	0.0000	0.5000	0.5000	0.02885 (14)
Pd2	0.0000	0.5000	1.0000	0.02774 (14)
Pd3	0.0000	0.0000	0.5000	0.03002 (14)
Br1	−1.05503 (10)	−0.07867 (5)	0.81959 (5)	0.05234 (19)
Cu1	0.35590 (9)	0.28367 (4)	0.75330 (4)	0.02838 (15)
Cu2	−0.48752 (9)	−0.21174 (4)	0.67676 (4)	0.03105 (16)
N1	0.1897 (6)	0.3507 (3)	0.6570 (3)	0.0313 (9)
N2	0.3545 (7)	0.6193 (4)	0.4729 (3)	0.0399 (10)
N3	0.3444 (8)	0.5838 (4)	1.0675 (4)	0.0469 (12)
N4	0.2267 (7)	0.3702 (3)	0.8491 (3)	0.0365 (10)
N5	−0.2899 (7)	−0.1428 (4)	0.5994 (3)	0.0367 (10)
N6	0.3216 (7)	−0.1416 (3)	0.5962 (3)	0.0364 (10)
N7	0.2894 (7)	0.1245 (3)	0.8068 (3)	0.0384 (10)
H7	0.1625	0.1214	0.8146	0.046*
N8	0.5775 (7)	0.2447 (4)	0.8283 (3)	0.0414 (11)
H8	0.5822	0.2962	0.8676	0.050*
N9	0.5187 (6)	0.2066 (3)	0.6550 (3)	0.0322 (9)
H9	0.5204	0.2495	0.5993	0.039*
C1	0.1184 (7)	0.4021 (4)	0.6001 (3)	0.0301 (10)
C2	0.2244 (8)	0.5763 (4)	0.4831 (4)	0.0341 (11)
C3	0.2222 (8)	0.5525 (4)	1.0409 (4)	0.0340 (11)
C4	0.1489 (7)	0.4169 (4)	0.9044 (3)	0.0319 (10)
C5	−0.1823 (8)	−0.0933 (4)	0.5632 (4)	0.0344 (11)
C6	0.2058 (8)	−0.0918 (4)	0.5601 (4)	0.0323 (11)
C7	0.3713 (10)	0.1111 (4)	0.8968 (4)	0.0498 (16)
H7A	0.3746	0.0370	0.9229	0.060*
H7B	0.2936	0.1545	0.9410	0.060*
C8	0.5658 (10)	0.1426 (5)	0.8851 (4)	0.0517 (17)
H8A	0.6076	0.1470	0.9472	0.062*
H8B	0.6500	0.0879	0.8549	0.062*
C9	0.7401 (8)	0.2440 (5)	0.7592 (5)	0.0453 (14)
H9A	0.8525	0.2132	0.7895	0.054*
H9B	0.7575	0.3166	0.7336	0.054*
C10	0.7111 (8)	0.1803 (4)	0.6812 (4)	0.0370 (11)
H10A	0.7991	0.1960	0.6267	0.044*
H10B	0.7336	0.1047	0.7019	0.044*
C11	0.4227 (8)	0.1152 (4)	0.6444 (3)	0.0352 (11)
H11A	0.5010	0.0691	0.6026	0.042*
H11B	0.3057	0.1392	0.6156	0.042*
C12	0.3811 (9)	0.0538 (4)	0.7381 (4)	0.0401 (12)
H12A	0.2999	0.0001	0.7308	0.048*
H12B	0.4977	0.0176	0.7610	0.048*
N10A	−0.4042 (17)	−0.3695 (7)	0.6499 (7)	0.029 (2)	0.494 (10)
H10C	−0.3897	−0.3761	0.5863	0.035*	0.494 (10)
N10B	−0.5063 (17)	−0.3778 (6)	0.6657 (6)	0.027 (2)	0.506 (10)
H10D	−0.4980	−0.3921	0.6039	0.033*	0.506 (10)
N11A	−0.6968 (14)	−0.2722 (8)	0.7589 (8)	0.036 (2)	0.494 (10)
H11C	−0.8056	−0.2271	0.7556	0.043*	0.494 (10)
N11B	−0.6590 (13)	−0.2332 (7)	0.7934 (6)	0.028 (2)	0.506 (10)
H11D	−0.7586	−0.1812	0.7905	0.033*	0.506 (10)
N12A	−0.3481 (16)	−0.2365 (10)	0.7837 (7)	0.030 (2)	0.494 (10)
H12C	−0.2684	−0.1856	0.7823	0.036*	0.494 (10)
N12B	−0.2904 (16)	−0.2799 (11)	0.7717 (7)	0.025 (2)	0.506 (10)
H12D	−0.1974	−0.2365	0.7690	0.030*	0.506 (10)
C13A	−0.488 (2)	−0.2301 (17)	0.8680 (14)	0.031 (4)	0.494 (10)
H13A	−0.4279	−0.2588	0.9250	0.037*	0.494 (10)
H13B	−0.5366	−0.1562	0.8745	0.037*	0.494 (10)
C13B	−0.3753 (17)	−0.2915 (8)	0.8677 (7)	0.033 (2)	0.506 (10)
H13C	−0.2917	−0.2713	0.9106	0.040*	0.506 (10)
H13D	−0.3957	−0.3654	0.8858	0.040*	0.506 (10)
C14A	−0.6427 (18)	−0.2907 (8)	0.8569 (8)	0.040 (3)	0.494 (10)
H14A	−0.7502	−0.2694	0.9003	0.048*	0.494 (10)
H14B	−0.6044	−0.3662	0.8724	0.048*	0.494 (10)
C15A	−0.5421 (16)	−0.4335 (10)	0.6969 (8)	0.036 (3)*	0.494 (10)
H15A	−0.5543	−0.4908	0.6588	0.043*	0.494 (10)
H15B	−0.4997	−0.4655	0.7574	0.043*	0.494 (10)
C14B	−0.561 (2)	−0.2215 (17)	0.8750 (15)	0.029 (3)	0.506 (10)
H14C	−0.6350	−0.2429	0.9331	0.035*	0.506 (10)
H14D	−0.5393	−0.1476	0.8758	0.035*	0.506 (10)
C15B	−0.7330 (15)	−0.3385 (7)	0.8004 (7)	0.031 (2)	0.506 (10)
H15C	−0.6648	−0.3887	0.8449	0.038*	0.506 (10)
H15D	−0.8652	−0.3310	0.8236	0.038*	0.506 (10)
C16	−0.7121 (9)	−0.3767 (4)	0.7120 (4)	0.0434 (13)
H16A	−0.7949	−0.4202	0.7529	0.052*	0.494 (10)
H16B	−0.7673	−0.3579	0.6520	0.052*	0.494 (10)
H16C	−0.7968	−0.3328	0.6706	0.052*	0.506 (10)
H16D	−0.7475	−0.4486	0.7195	0.052*	0.506 (10)
C17A	−0.224 (2)	−0.3828 (11)	0.6899 (12)	0.036 (3)	0.494 (10)
H17A	−0.1336	−0.3458	0.6472	0.044*	0.494 (10)
H17B	−0.1763	−0.4579	0.6975	0.044*	0.494 (10)
C17B	−0.3657 (15)	−0.4449 (7)	0.7178 (7)	0.034 (2)	0.506 (10)
H17C	−0.3151	−0.5048	0.6826	0.041*	0.506 (10)
H17D	−0.4234	−0.4728	0.7785	0.041*	0.506 (10)
C18A	−0.2443 (19)	−0.3391 (15)	0.7836 (9)	0.038 (3)	0.494 (10)
H18A	−0.3065	−0.3880	0.8301	0.045*	0.494 (10)
H18B	−0.1197	−0.3352	0.8033	0.045*	0.494 (10)
C18B	−0.2086 (19)	−0.3823 (10)	0.7338 (12)	0.034 (3)	0.506 (10)
H18C	−0.1276	−0.4234	0.7786	0.041*	0.506 (10)
H18D	−0.1331	−0.3677	0.6745	0.041*	0.506 (10)
O1A	−0.0494 (19)	0.1069 (11)	0.9660 (11)	0.0353 (19)	0.25
O1B	0.0000	0.0000	1.0000	0.0353 (19)	0.50

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Pd1	0.0304 (3)	0.0251 (2)	0.0303 (3)	0.0029 (2)	−0.0037 (2)	−0.00509 (18)
Pd2	0.0301 (3)	0.0228 (2)	0.0299 (3)	0.00031 (19)	0.0000 (2)	−0.00717 (18)
Pd3	0.0304 (3)	0.0279 (2)	0.0317 (3)	−0.0078 (2)	0.0052 (2)	−0.00439 (19)
Br1	0.0460 (4)	0.0434 (3)	0.0697 (4)	0.0030 (3)	−0.0053 (3)	−0.0240 (3)
Cu1	0.0304 (3)	0.0244 (3)	0.0296 (3)	0.0039 (2)	−0.0024 (2)	−0.0077 (2)
Cu2	0.0345 (4)	0.0260 (3)	0.0323 (3)	−0.0074 (2)	0.0066 (3)	−0.0052 (2)
N1	0.032 (2)	0.032 (2)	0.028 (2)	0.0039 (17)	0.0007 (17)	−0.0070 (17)
N2	0.043 (3)	0.037 (2)	0.039 (2)	−0.004 (2)	−0.001 (2)	−0.0018 (18)
N3	0.044 (3)	0.055 (3)	0.046 (3)	−0.011 (2)	−0.003 (2)	−0.019 (2)
N4	0.042 (3)	0.028 (2)	0.038 (2)	0.0013 (19)	−0.005 (2)	−0.0075 (17)
N5	0.036 (2)	0.041 (2)	0.033 (2)	−0.011 (2)	−0.0009 (19)	0.0000 (18)
N6	0.035 (3)	0.032 (2)	0.041 (2)	−0.0062 (19)	0.008 (2)	−0.0033 (18)
N7	0.046 (3)	0.029 (2)	0.037 (2)	0.0029 (19)	0.009 (2)	−0.0030 (17)
N8	0.044 (3)	0.038 (2)	0.044 (3)	0.012 (2)	−0.016 (2)	−0.019 (2)
N9	0.030 (2)	0.030 (2)	0.033 (2)	0.0050 (17)	0.0034 (17)	−0.0040 (16)
C1	0.033 (3)	0.025 (2)	0.031 (2)	−0.0003 (19)	0.000 (2)	−0.0057 (18)
C2	0.040 (3)	0.029 (2)	0.032 (2)	0.002 (2)	0.000 (2)	−0.0037 (19)
C3	0.034 (3)	0.033 (2)	0.034 (2)	0.001 (2)	0.003 (2)	−0.010 (2)
C4	0.030 (3)	0.030 (2)	0.034 (2)	0.004 (2)	0.001 (2)	−0.0043 (19)
C5	0.038 (3)	0.033 (2)	0.033 (2)	−0.008 (2)	0.002 (2)	−0.0054 (19)
C6	0.032 (3)	0.030 (2)	0.036 (3)	−0.012 (2)	0.005 (2)	−0.008 (2)
C7	0.073 (5)	0.034 (3)	0.034 (3)	0.012 (3)	0.010 (3)	0.002 (2)
C8	0.067 (4)	0.052 (3)	0.032 (3)	0.023 (3)	−0.012 (3)	−0.013 (2)
C9	0.029 (3)	0.047 (3)	0.061 (4)	0.007 (2)	−0.012 (3)	−0.015 (3)
C10	0.031 (3)	0.036 (3)	0.041 (3)	0.007 (2)	0.000 (2)	−0.008 (2)
C11	0.043 (3)	0.031 (2)	0.031 (2)	0.001 (2)	0.002 (2)	−0.0116 (19)
C12	0.053 (4)	0.026 (2)	0.039 (3)	0.001 (2)	0.001 (3)	−0.007 (2)
N10A	0.025 (5)	0.026 (4)	0.036 (5)	0.003 (4)	−0.002 (4)	−0.010 (3)
N10B	0.029 (5)	0.023 (4)	0.029 (4)	−0.005 (4)	0.005 (4)	−0.001 (3)
N11A	0.030 (5)	0.033 (5)	0.043 (6)	0.001 (4)	0.007 (4)	−0.004 (5)
N11B	0.033 (5)	0.019 (4)	0.030 (4)	−0.003 (3)	0.004 (4)	0.000 (3)
N12A	0.030 (6)	0.021 (5)	0.040 (6)	−0.004 (4)	−0.005 (4)	−0.002 (4)
N12B	0.024 (5)	0.018 (6)	0.033 (5)	−0.002 (4)	−0.007 (4)	0.003 (5)
C13A	0.037 (10)	0.036 (8)	0.019 (5)	−0.002 (10)	0.007 (8)	−0.006 (4)
C13B	0.043 (6)	0.031 (5)	0.026 (5)	−0.006 (5)	−0.005 (4)	−0.003 (4)
C14A	0.047 (7)	0.033 (5)	0.035 (6)	0.001 (5)	0.013 (5)	−0.002 (4)
C14B	0.029 (8)	0.028 (6)	0.029 (7)	−0.003 (8)	0.000 (7)	−0.005 (5)
C15B	0.041 (6)	0.021 (4)	0.031 (5)	−0.012 (4)	0.011 (4)	−0.002 (4)
C16	0.049 (4)	0.038 (3)	0.045 (3)	−0.021 (3)	−0.006 (3)	0.007 (2)
C17A	0.035 (7)	0.030 (6)	0.042 (8)	0.002 (5)	0.001 (7)	−0.003 (6)
C17B	0.038 (6)	0.022 (4)	0.041 (5)	0.004 (4)	0.002 (4)	−0.006 (4)
C18A	0.027 (6)	0.040 (8)	0.044 (8)	−0.001 (6)	−0.002 (5)	0.003 (7)
C18B	0.033 (6)	0.028 (6)	0.038 (7)	0.010 (4)	0.001 (7)	−0.005 (7)
O1A	0.017 (4)	0.036 (4)	0.047 (5)	0.001 (3)	−0.001 (3)	0.016 (4)
O1B	0.017 (4)	0.036 (4)	0.047 (5)	0.001 (3)	−0.001 (3)	0.016 (4)

Geometric parameters (Å, º)

Pd1—C2^i	2.002 (6)	C11—H11A	0.9900
Pd1—C1	2.010 (5)	C11—H11B	0.9900
Pd1—C2	2.002 (6)	C12—H12A	0.9900
Pd1—C1^i	2.010 (5)	C12—H12B	0.9900
Pd2—C3^ii	2.003 (6)	N10A—C15A	1.457 (16)
Pd2—C3	2.003 (6)	N10A—C17A	1.479 (19)
Pd2—C4^ii	2.003 (5)	N10A—H10C	0.9300
Pd2—C4	2.003 (5)	N10B—C17B	1.475 (14)
Pd3—C5^iii	2.000 (5)	N10B—C16	1.588 (13)
Pd3—C5	2.000 (5)	N10B—H10D	0.9300
Pd3—C6^iii	2.007 (6)	N11A—C14A	1.500 (16)
Pd3—C6	2.007 (6)	N11A—C16	1.600 (13)
Cu1—N1	1.998 (4)	N11A—H11C	0.9300
Cu1—N4	1.976 (4)	N11B—C14B	1.48 (2)
Cu1—N7	2.216 (4)	N11B—C15B	1.518 (12)
Cu1—N8	2.024 (5)	N11B—H11D	0.9300
Cu1—N9	2.033 (4)	N12A—C18A	1.446 (19)
Cu2—N5	1.983 (5)	N12A—C13A	1.52 (2)
N6—Cu2^iv	1.980 (5)	N12A—H12C	0.9300
Cu2—N10A	2.125 (8)	N12B—C13B	1.470 (14)
Cu2—N11A	2.029 (10)	N12B—C18B	1.522 (18)
Cu2—N12A	1.917 (11)	N12B—H12D	0.9300
Cu2—N10B	2.195 (8)	C13A—C14A	1.48 (2)
Cu2—N6^v	1.980 (5)	C13A—H13A	0.9900
Cu2—N11B	2.022 (8)	C13A—H13B	0.9900
Cu2—N12B	2.137 (11)	C13B—C14B	1.537 (18)
N1—C1	1.130 (7)	C13B—H13C	0.9900
N2—C2	1.151 (7)	C13B—H13D	0.9900
N3—C3	1.143 (8)	C14A—H14A	0.9900
N4—C4	1.126 (7)	C14A—H14B	0.9900
N5—C5	1.130 (7)	C15A—C16	1.376 (13)
N6—C6	1.134 (7)	C15A—H15A	0.9900
N7—C7	1.475 (8)	C15A—H15B	0.9900
N7—C12	1.483 (6)	C14B—H14C	0.9900
N7—H7	0.9300	C14B—H14D	0.9900
N8—C9	1.479 (8)	C15B—C16	1.413 (11)
N8—C8	1.486 (8)	C15B—H15C	0.9900
N8—H8	0.9300	C15B—H15D	0.9900
N9—C11	1.479 (7)	C16—H16A	0.9900
N9—C10	1.484 (7)	C16—H16B	0.9900
N9—H9	0.9300	C16—H16C	0.9900
C7—C8	1.519 (11)	C16—H16D	0.9901
C7—H7A	0.9900	C17A—C18A	1.517 (19)
C7—H7B	0.9900	C17A—H17A	0.9900
C8—H8A	0.9900	C17A—H17B	0.9900
C8—H8B	0.9900	C17B—C18B	1.536 (19)
C9—C10	1.518 (8)	C17B—H17C	0.9900
C9—H9A	0.9900	C17B—H17D	0.9900
C9—H9B	0.9900	C18A—H18A	0.9900
C10—H10A	0.9900	C18A—H18B	0.9900
C10—H10B	0.9900	C18B—H18C	0.9900
C11—C12	1.522 (7)	C18B—H18D	0.9900
C2^i—Pd1—C2	180.000 (1)	N7—C12—H12A	109.5
C2^i—Pd1—C1^i	89.0 (2)	C11—C12—H12A	109.5
C2—Pd1—C1^i	91.0 (2)	N7—C12—H12B	109.5
C2^i—Pd1—C1	91.0 (2)	C11—C12—H12B	109.5
C2—Pd1—C1	89.0 (2)	H12A—C12—H12B	108.1
C1^i—Pd1—C1	180.0 (2)	C15A—N10A—C17A	116.0 (10)
C3^ii—Pd2—C3	180.000 (1)	C15A—N10A—Cu2	108.2 (7)
C3^ii—Pd2—C4^ii	93.4 (2)	C17A—N10A—Cu2	98.1 (8)
C3—Pd2—C4^ii	86.6 (2)	C15A—N10A—H10C	111.3
C3^ii—Pd2—C4	86.6 (2)	C17A—N10A—H10C	111.3
C3—Pd2—C4	93.4 (2)	C17B—N10B—C16	115.2 (7)
C4^ii—Pd2—C4	180.000 (1)	C17B—N10B—Cu2	110.9 (7)
C5^iii—Pd3—C5	180.0 (2)	C16—N10B—Cu2	95.3 (5)
C5^iii—Pd3—C6^iii	90.2 (2)	C17B—N10B—H10D	111.5
C5—Pd3—C6^iii	89.8 (2)	C16—N10B—H10D	111.5
C5^iii—Pd3—C6	89.8 (2)	Cu2—N10B—H10D	111.5
C5—Pd3—C6	90.2 (2)	C14A—N11A—C16	114.3 (8)
C6^iii—Pd3—C6	180.0 (3)	C14A—N11A—Cu2	108.5 (8)
N1—Cu1—N4	92.42 (18)	C16—N11A—Cu2	101.7 (5)
N4—Cu1—N8	91.79 (19)	C14B—N11B—C15B	112.0 (11)
N1—Cu1—N8	162.4 (2)	C14B—N11B—Cu2	109.1 (9)
N4—Cu1—N9	172.0 (2)	C15B—N11B—Cu2	111.0 (7)
N1—Cu1—N9	90.27 (17)	C14B—N11B—H11D	108.2
N8—Cu1—N9	83.47 (18)	C15B—N11B—H11D	108.2
N4—Cu1—N7	102.54 (18)	Cu2—N11B—H11D	108.2
N1—Cu1—N7	111.97 (19)	C18A—N12A—C13A	111.3 (12)
N7—Cu1—N8	83.7 (2)	C18A—N12A—Cu2	108.8 (8)
N7—Cu1—N9	83.38 (17)	C13A—N12A—Cu2	106.3 (10)
N12A—Cu2—N6^v	157.1 (4)	C13B—N12B—C18B	114.5 (11)
N5—Cu2—N12A	93.0 (3)	C13B—N12B—Cu2	111.5 (8)
N6^v—Cu2—N5	91.86 (19)	C18B—N12B—Cu2	104.7 (8)
N6^v—Cu2—N11B	96.5 (3)	C13B—N12B—H12D	108.6
N5—Cu2—N11B	153.1 (3)	C18B—N12B—H12D	108.6
N11A—Cu2—N12A	86.9 (5)	Cu2—N12B—H12D	108.6
N6^v—Cu2—N11A	86.7 (3)	C14A—C13A—N12A	109.7 (14)
N5—Cu2—N11A	176.0 (3)	C14A—C13A—H13A	109.7
N10A—Cu2—N12A	88.5 (5)	N12A—C13A—H13A	109.7
N6^v—Cu2—N10A	112.7 (3)	C14A—C13A—H13B	109.7
N5—Cu2—N10A	99.7 (4)	N12A—C13A—H13B	109.7
N10A—Cu2—N11A	84.4 (4)	H13A—C13A—H13B	108.2
N6^v—Cu2—N12B	175.6 (4)	N12B—C13B—C14B	109.6 (11)
N5—Cu2—N12B	89.5 (3)	N12B—C13B—H13C	109.8
N11B—Cu2—N12B	80.4 (4)	C14B—C13B—H13C	109.8
N6^v—Cu2—N10B	102.2 (3)	N12B—C13B—H13D	109.8
N5—Cu2—N10B	118.8 (3)	C14B—C13B—H13D	109.8
N10B—Cu2—N11B	84.3 (4)	H13C—C13B—H13D	108.2
N10B—Cu2—N12B	80.7 (4)	C13A—C14A—N11A	110.4 (11)
C1—N1—Cu1	167.1 (4)	C13A—C14A—H14A	109.6
C4—N4—Cu1	177.6 (5)	N11A—C14A—H14A	109.6
C5—N5—Cu2	170.7 (4)	C13A—C14A—H14B	109.6
C6—N6—Cu2^iv	169.8 (4)	N11A—C14A—H14B	109.6
C7—N7—C12	114.5 (5)	H14A—C14A—H14B	108.1
C7—N7—Cu1	100.8 (4)	C16—C15A—N10A	112.3 (9)
C12—N7—Cu1	106.2 (3)	C16—C15A—H15A	109.1
C7—N7—H7	111.6	N10A—C15A—H15A	109.1
C12—N7—H7	111.6	C16—C15A—H15B	109.1
Cu1—N7—H7	111.6	N10A—C15A—H15B	109.1
C9—N8—C8	113.1 (5)	H15A—C15A—H15B	107.9
C9—N8—Cu1	105.3 (3)	N11B—C14B—C13B	107.7 (13)
C8—N8—Cu1	111.1 (4)	N11B—C14B—H14C	110.2
C9—N8—H8	109.1	C13B—C14B—H14C	110.2
C8—N8—H8	109.1	N11B—C14B—H14D	110.2
Cu1—N8—H8	109.1	C13B—C14B—H14D	110.2
C11—N9—C10	114.6 (4)	H14C—C14B—H14D	108.5
C11—N9—Cu1	104.6 (3)	C16—C15B—N11B	109.7 (7)
C10—N9—Cu1	111.6 (3)	C16—C15B—H15C	109.7
C11—N9—H9	108.6	N11B—C15B—H15C	109.7
C10—N9—H9	108.6	C16—C15B—H15D	109.7
Cu1—N9—H9	108.6	N11B—C15B—H15D	109.7
N1—C1—Pd1	176.8 (5)	H15C—C15B—H15D	108.2
N2—C2—Pd1	179.2 (5)	C15B—C16—N10B	112.2 (7)
N3—C3—Pd2	177.0 (5)	C15A—C16—N11A	111.7 (7)
N4—C4—Pd2	177.4 (5)	C15A—C16—H16A	109.3
N5—C5—Pd3	177.4 (5)	N11A—C16—H16A	109.3
N6—C6—Pd3	177.9 (5)	C15A—C16—H16B	109.3
N7—C7—C8	110.8 (5)	N11A—C16—H16B	109.3
N7—C7—H7A	109.5	H16A—C16—H16B	107.9
C8—C7—H7A	109.5	C15B—C16—H16C	109.5
N7—C7—H7B	109.5	N10B—C16—H16C	109.3
C8—C7—H7B	109.5	C15B—C16—H16D	108.3
H7A—C7—H7B	108.1	N10B—C16—H16D	109.4
N8—C8—C7	112.5 (5)	H16C—C16—H16D	108.1
N8—C8—H8A	109.1	N10A—C17A—C18A	110.0 (11)
C7—C8—H8A	109.1	N10A—C17A—H17A	109.7
N8—C8—H8B	109.1	C18A—C17A—H17A	109.7
C7—C8—H8B	109.1	N10A—C17A—H17B	109.7
H8A—C8—H8B	107.8	C18A—C17A—H17B	109.7
N8—C9—C10	109.5 (5)	H17A—C17A—H17B	108.2
N8—C9—H9A	109.8	N10B—C17B—C18B	110.4 (9)
C10—C9—H9A	109.8	N10B—C17B—H17C	109.6
N8—C9—H9B	109.8	C18B—C17B—H17C	109.6
C10—C9—H9B	109.8	N10B—C17B—H17D	109.6
H9A—C9—H9B	108.2	C18B—C17B—H17D	109.6
N9—C10—C9	109.1 (4)	H17C—C17B—H17D	108.1
N9—C10—H10A	109.9	N12A—C18A—C17A	113.8 (11)
C9—C10—H10A	109.9	N12A—C18A—H18A	108.8
N9—C10—H10B	109.9	C17A—C18A—H18A	108.8
C9—C10—H10B	109.9	N12A—C18A—H18B	108.8
H10A—C10—H10B	108.3	C17A—C18A—H18B	108.8
N9—C11—C12	111.0 (4)	H18A—C18A—H18B	107.7
N9—C11—H11A	109.4	N12B—C18B—C17B	109.3 (10)
C12—C11—H11A	109.4	N12B—C18B—H18C	109.8
N9—C11—H11B	109.4	C17B—C18B—H18C	109.8
C12—C11—H11B	109.4	N12B—C18B—H18D	109.8
H11A—C11—H11B	108.0	C17B—C18B—H18D	109.8
N7—C12—C11	110.6 (4)	H18C—C18B—H18D	108.3
N4—Cu1—N1—C1	85.7 (18)	N6^v—Cu2—N11B—C14B	−144.6 (10)
N8—Cu1—N1—C1	−18 (2)	N5—Cu2—N11B—C14B	−37.2 (12)
N9—Cu1—N1—C1	−86.8 (18)	N11A—Cu2—N11B—C14B	149.1 (14)
N7—Cu1—N1—C1	−169.8 (17)	N10A—Cu2—N11B—C14B	100.8 (10)
N4—Cu1—N7—C7	−60.6 (4)	N12B—Cu2—N11B—C14B	32.2 (10)
N1—Cu1—N7—C7	−158.5 (3)	N10B—Cu2—N11B—C14B	113.7 (10)
N8—Cu1—N7—C7	29.8 (4)	N12A—Cu2—N11B—C15B	−107.7 (8)
N9—Cu1—N7—C7	113.9 (4)	N6^v—Cu2—N11B—C15B	91.4 (7)
N4—Cu1—N7—C12	179.7 (4)	N5—Cu2—N11B—C15B	−161.2 (6)
N1—Cu1—N7—C12	81.9 (4)	N11A—Cu2—N11B—C15B	25.1 (9)
N8—Cu1—N7—C12	−89.8 (4)	N10A—Cu2—N11B—C15B	−23.2 (7)
N9—Cu1—N7—C12	−5.7 (4)	N12B—Cu2—N11B—C15B	−91.8 (7)
N4—Cu1—N8—C9	−141.6 (4)	N10B—Cu2—N11B—C15B	−10.3 (7)
N1—Cu1—N8—C9	−37.9 (7)	N6^v—Cu2—N12A—C18A	165.7 (7)
N9—Cu1—N8—C9	31.9 (3)	N5—Cu2—N12A—C18A	−92.3 (8)
N7—Cu1—N8—C9	115.9 (4)	N11B—Cu2—N12A—C18A	109.0 (8)
N4—Cu1—N8—C8	95.6 (4)	N11A—Cu2—N12A—C18A	91.7 (8)
N1—Cu1—N8—C8	−160.6 (5)	N10A—Cu2—N12A—C18A	7.3 (8)
N9—Cu1—N8—C8	−90.9 (4)	N12B—Cu2—N12A—C18A	−12.8 (10)
N7—Cu1—N8—C8	−6.9 (4)	N10B—Cu2—N12A—C18A	26.9 (8)
N1—Cu1—N9—C11	−81.3 (3)	N6^v—Cu2—N12A—C13A	45.8 (15)
N8—Cu1—N9—C11	115.2 (3)	N5—Cu2—N12A—C13A	147.7 (11)
N7—Cu1—N9—C11	30.8 (3)	N11B—Cu2—N12A—C13A	−10.9 (10)
N1—Cu1—N9—C10	154.3 (4)	N11A—Cu2—N12A—C13A	−28.2 (11)
N8—Cu1—N9—C10	−9.3 (4)	N10A—Cu2—N12A—C13A	−112.7 (11)
N7—Cu1—N9—C10	−93.6 (4)	N12B—Cu2—N12A—C13A	−132.8 (19)
C12—N7—C7—C8	66.0 (6)	N10B—Cu2—N12A—C13A	−93.1 (11)
Cu1—N7—C7—C8	−47.4 (5)	N12A—Cu2—N12B—C13B	46.5 (14)
C9—N8—C8—C7	−136.3 (5)	N5—Cu2—N12B—C13B	147.4 (8)
Cu1—N8—C8—C7	−18.1 (5)	N11B—Cu2—N12B—C13B	−7.6 (8)
N7—C7—C8—N8	47.1 (6)	N11A—Cu2—N12B—C13B	−28.7 (8)
C8—N8—C9—C10	72.2 (6)	N10A—Cu2—N12B—C13B	−112.2 (8)
Cu1—N8—C9—C10	−49.3 (5)	N10B—Cu2—N12B—C13B	−93.4 (8)
C11—N9—C10—C9	−134.1 (5)	N12A—Cu2—N12B—C18B	170.9 (17)
Cu1—N9—C10—C9	−15.4 (6)	N5—Cu2—N12B—C18B	−88.3 (7)
N8—C9—C10—N9	43.0 (6)	N11B—Cu2—N12B—C18B	116.8 (8)
C10—N9—C11—C12	69.8 (6)	N11A—Cu2—N12B—C18B	95.6 (8)
Cu1—N9—C11—C12	−52.7 (5)	N10A—Cu2—N12B—C18B	12.1 (7)
C7—N7—C12—C11	−131.0 (5)	N10B—Cu2—N12B—C18B	31.0 (7)
Cu1—N7—C12—C11	−20.7 (6)	C18A—N12A—C13A—C14A	−72.4 (16)
N9—C11—C12—N7	50.2 (7)	Cu2—N12A—C13A—C14A	45.8 (16)
N12A—Cu2—N10A—C15A	90.9 (7)	C18B—N12B—C13B—C14B	−136.2 (12)
N6^v—Cu2—N10A—C15A	−80.2 (7)	Cu2—N12B—C13B—C14B	−17.5 (12)
N5—Cu2—N10A—C15A	−176.3 (7)	N12A—C13A—C14A—N11A	−41.7 (17)
N11B—Cu2—N10A—C15A	21.5 (8)	C16—N11A—C14A—C13A	130.5 (11)
N11A—Cu2—N10A—C15A	3.9 (7)	Cu2—N11A—C14A—C13A	17.8 (12)
N12B—Cu2—N10A—C15A	97.5 (7)	C17A—N10A—C15A—C16	133.2 (10)
N10B—Cu2—N10A—C15A	−17.5 (9)	Cu2—N10A—C15A—C16	24.2 (10)
N12A—Cu2—N10A—C17A	−29.9 (8)	C15B—N11B—C14B—C13B	72.7 (14)
N6^v—Cu2—N10A—C17A	159.0 (7)	Cu2—N11B—C14B—C13B	−50.7 (14)
N5—Cu2—N10A—C17A	62.9 (8)	N12B—C13B—C14B—N11B	43.8 (16)
N11B—Cu2—N10A—C17A	−99.3 (8)	C14B—N11B—C15B—C16	−141.3 (10)
N11A—Cu2—N10A—C17A	−116.9 (9)	Cu2—N11B—C15B—C16	−19.0 (10)
N12B—Cu2—N10A—C17A	−23.3 (8)	N10A—C15A—C16—C15B	−92.5 (9)
N10B—Cu2—N10A—C17A	−138.4 (15)	N10A—C15A—C16—N10B	6.0 (8)
N12A—Cu2—N10B—C17B	−18.2 (8)	N10A—C15A—C16—N11A	−49.7 (11)
N6^v—Cu2—N10B—C17B	177.0 (7)	N11B—C15B—C16—C15A	88.2 (10)
N5—Cu2—N10B—C17B	78.0 (7)	N11B—C15B—C16—N10B	52.6 (10)
N11B—Cu2—N10B—C17B	−87.5 (7)	N11B—C15B—C16—N11A	−10.8 (7)
N11A—Cu2—N10B—C17B	−102.4 (8)	C17B—N10B—C16—C15A	−33.6 (10)
N10A—Cu2—N10B—C17B	54.0 (12)	Cu2—N10B—C16—C15A	−149.7 (12)
N12B—Cu2—N10B—C17B	−6.3 (7)	C17B—N10B—C16—C15B	61.4 (9)
N12A—Cu2—N10B—C16	101.4 (5)	Cu2—N10B—C16—C15B	−54.7 (7)
N6^v—Cu2—N10B—C16	−63.5 (5)	C17B—N10B—C16—N11A	96.3 (8)
N5—Cu2—N10B—C16	−162.5 (4)	Cu2—N10B—C16—N11A	−19.8 (5)
N11B—Cu2—N10B—C16	32.0 (5)	C14A—N11A—C16—C15A	−68.0 (11)
N11A—Cu2—N10B—C16	17.1 (5)	Cu2—N11A—C16—C15A	48.6 (8)
N10A—Cu2—N10B—C16	173.5 (13)	C14A—N11A—C16—C15B	29.4 (10)
N12B—Cu2—N10B—C16	113.2 (5)	Cu2—N11A—C16—C15B	146.0 (11)
N12A—Cu2—N11A—C14A	6.6 (7)	C14A—N11A—C16—N10B	−94.7 (9)
N6^v—Cu2—N11A—C14A	−151.5 (7)	Cu2—N11A—C16—N10B	21.9 (6)
N11B—Cu2—N11A—C14A	−37.1 (9)	C15A—N10A—C17A—C18A	−69.2 (13)
N10A—Cu2—N11A—C14A	95.4 (7)	Cu2—N10A—C17A—C18A	45.6 (12)
N12B—Cu2—N11A—C14A	24.5 (8)	C16—N10B—C17B—C18B	−127.2 (10)
N10B—Cu2—N11A—C14A	103.5 (7)	Cu2—N10B—C17B—C18B	−20.4 (11)
N12A—Cu2—N11A—C16	−114.2 (6)	C13A—N12A—C18A—C17A	134.9 (13)
N6^v—Cu2—N11A—C16	87.7 (5)	Cu2—N12A—C18A—C17A	18.2 (13)
N11B—Cu2—N11A—C16	−158.0 (13)	N10A—C17A—C18A—N12A	−47.0 (15)
N10A—Cu2—N11A—C16	−25.4 (5)	C13B—N12B—C18B—C17B	70.6 (14)
N12B—Cu2—N11A—C16	−96.3 (6)	Cu2—N12B—C18B—C17B	−51.9 (12)
N10B—Cu2—N11A—C16	−17.3 (5)	N10B—C17B—C18B—N12B	48.8 (14)
N12A—Cu2—N11B—C14B	16.3 (10)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N7—H7···O1A	0.93	2.57	3.233 (15)	129
N8—H8···N3^vi	0.93	2.05	2.960 (6)	165
N9—H9···N2^vii	0.93	2.15	2.942 (6)	142
N10A—H10C···N2^viii	0.93	2.62	3.282 (11)	129
N10B—H10D···N2^viii	0.93	2.26	3.076 (10)	146
N11A—H11C···Br1	0.93	2.66	3.513 (10)	153
N11B—H11D···Br1	0.93	2.42	3.327 (9)	163
N12A—H12C···Br1^iv	0.93	2.35	3.254 (10)	165
N12B—H12D···Br1^iv	0.93	2.61	3.461 (10)	153

Symmetry codes: (iv) x+1, y, z; (vi) −x+1, −y+1, −z+2; (vii) −x+1, −y+1, −z+1; (viii) x−1, y−1, z.