A mixed-valence chair-like tetra­nuclear copper(I,II) cluster with three linking modes of the 3,5-bis­(2-pyri­dyl)-1,2,4-triazole ligand

In the tetra­nuclear copper complex tetra­kis­[μ-3,5-bis­(2-pyrid­yl)-1,2,4-triazolido]bis­[3,5-bis­(2-pyrid­yl)-1,2,4-triazolido]dicopper(I)dicopper(II) dihydrate, [Cu^I₂Cu^II₂(C₁₂H₈N₅)₆]·2H₂O, the asymmetric unit is composed of one Cu^I center, one Cu^II center, three anionic 3,5-bis­(2-pyrid­yl)-1,2,4-triazole (2-BPT) ligands and one solvent water mol­ecule. The Cu^I and Cu^II centers exhibit [Cu^IN₄] tetra­hedral and [Cu^IIN₆] octa­hedral coordination environments, respectively. The three independent 2-BPT ligands adopt different chelating modes, which link the copper centers to generate a chair-like tetra­nuclear metallomacrocycle with metal–metal distances of about 4.4 × 6.2 Å disposed about a crystallographic inversion center. Furthermore, strong π–π stacking inter­actions and O—H...N hydrogen-bonding systems link the tetra­copper clusters into a two-dimensional supra­molecular network.

S1. Comment

In the past decade, pyridyl- and/or carboxylate-containing organic ligands have been mostly utilized in the synthesis of functional metal–organic coordination compounds (Kitagawa et al., 2004; Ye et al., 2005). Among these ligands, dipyridyl-type building blocks have been identified as excellent connectors to construct polynuclear clusters or one- to three-dimensional frameworks upon metalation. More recently, work on the modification of dipyridyl via the introduction of different spacers between two terminal pyridyl groups has produced several unexpected metal–organic architectures. In this regard, a series of angular dipyridyl derivatives, namely 2,5-bis(2/3/4-pyridyl)-1,3,4-oxadiazole or 4-R-3,5-bis(2/3/4-pyridyl)-1,2,4-triazole (R = H, NH₂, phenyl, pyridyl etc.) have been intensively investigated (Dong et al., 2005, and references therein; Du et al., 2008, and references therein). Because of the specific geometry of such diazole- or triazole-containing ligands and the coordination preferences of transition metals, many new types of coordination complexes with unprecedented topologies and potential applications have been prepared. As part of our ongoing research project dealing with the coordination chemistry of polyazaheteroaromatic ligands, we have synthesized a series of d¹⁰ transition metal (Cu^I, Ag^I, Zn^II and Cd^II) triazolates utilizing dialkyl–substituted 1,2,4-triazole ligands (Zhai et al., 2007, and references therein). This has encouraged us to continue this project and expand from dialkyl–substituted ligands to dipyridyl–substituted ligands. By controlling the reaction temperatures, the self-assembly of AgNO₃ and 4-amino-3,5-bis(3-pyridyl)-1,2,4-triazole under hydrothermal conditions has produced three novel high-dimensional coordination polymers (Zhai et al., 2009). We report here the structure of the title complex, (I), in which a mixed-valence chair-like tetranuclear cluster is observed along with three independent 3,5-bis(2-pyridyl)-1,2,4-triazole (2-BPT) ligands; this may be regarded as the first example that exhibits three different chelating modes of 2-BPT in the same structure.

Compound (I) was separated from the hydrothermal reaction of CuCN and 2-BPT ligands as pure brown block-like crystals. The absence of characteristic bands at about 2100 cm^-1 for the cyanide groups indicates that the CN^- ions are absent from the structure of (I). The structural analysis shows that (I) possesses a centrosymmetrical, tetranuclear metallomacrocycle structure. As shown in Fig. 1, one Cu^I center, one Cu^II center, three anionic 2-BPT ligands and one solvent water molecule occupy the asymmetric unit of (I). The Cu^I ion is in a distorted [Cu^IN₄] tetrahedral environment with Cu—N distances and N—Cu—N angles spanning the ranges 1.957 (4)–2.179 (4) Å and 80.14 (15)–140.54 (17)°, respectively. The Cu^II center is six-coordinated by three pyridyl N atoms and three triazole N atoms to form an octahedral environment [Cu—N = 2.103 (4)–2.225 (4) Å, N—Cu—N (trans) = 163.13 (14)–169.46 (15)° and N—Cu—N (cis) = 75.99 (14)– 100.13 (15)°]. The three 2-BPT ligands adopt distinct linking modes: cisoid–cisoid tetradentate, cisoid–transoid tetradentate and transoid bidentate. The cisoid–cisoid and cisoid–transoid 2-BPT ligands both act as µ₂-bridges to connect two copper centers, and the transoid bidentate 2-BPT serves as a terminal ligand to finish the Cu^II octahedron. Because the two bidentate chelating sites are both fused to a five-membered ring, the central triazole ring and two 2-pyridyl groups are basically coplanar in the two tetradentate ligands. However, the dihedral angle between two pyridyl groups in the terminal bidentate 2-BPT ligand is about 50°, which is comparable to waht is found in other structurally characterized complexes with similar chelating behavior (Dong et al., 2005; Du et al., 2008).

Compared with the commonly expected grid-like tetranuclear architectures, this chair-like structure of (I) displays several unique features. The four metal centers in (I) define a quadrangle [Cu1···Cu2 = 4.4197 (11) Å, Cu1···Cu2ⁱ = 6.1869 (9) Å and Cu2···Cu1···Cu2ⁱ = 74.638 (13)°; symmetry code: (i) -x + 1, -y + 1, -z + 1; Fig. 2]. The two inversely-related cisoid–transoid ligands are engaged in a strong intramolecular face-to-face π–π interaction (ca 3.6 Å), which may effectively stabilize the chair-like metallomacrocycle. It is noted that such face-to-face separations should be close to the intermetallic distances in the regular grid-like structures, but can be shortened when the square distorts into a rhomb. Furthermore, intermolecular aromatic π–π stacking interactions between 2-pyridyl rings from terminal 2-BPT ligands are observed with a center-to-center distance of about 3.8 Å, which link adjacent tetranuclear clusters into a one-dimensional chain. On the other hand, the chair-like clusters are also connected through O—H···N [O1···N3 = 2.9201 (1) Å and O1···N10 = 3.089 (8) Å] hydrogen-bonding systems to give the other one-dimensional chain. Ultimately, two kinds of chains interweave with each other to form a two-dimensional supramolecular network as depicted in Fig. 3.

To the best of our knowledge, although the squares, grids and circular helicates have been extensively studied, such a chair-like metallomacrocycle has been rarely described previously. Zhang et al. have created two similar chair-like tetranuclear compounds {[Cu^I₄(2-BPT)₄], (II) (Zhang et al., 2005a), and [Cu^I₂Cu^II₂(2-BPT)₄(2-pa)₂].2H₂O, (III) (2-Hpa is pyridine-2-carboxylic acid; Zhang et al., 2005b)} with the same ligands generated via in situ oxidative cycloaddition of 2-cyanopyridine and ammonia under solvothermal conditions. Just like the title compound, (II) crystallizes in the space group P2₁/c, but four tetrahedral copper(I) centers form a quasi-rectangle with a Cu2···Cu1···Cu2ⁱ angle of 90.7°. If the pyridine-2-carboxylic acid ligands take the place of the two terminal 2-BPT ligands in (I), compound (III) will be generated. However, this difference leads (III) to crystallize in the P1 space group. As pointed out by Zhang et al. (2005a), the unique structure of 2-BPT usually gives a five-membered ring upon metalation, but a six-membered ring is commonly observed for a grid and a long and flexible ring is required for a helicate. Thus, no grid or other hypothetical circular helicate compounds have been synthesized with 2-BPT ligands to date.

Upon excitation of solid samples of (I) at λ = 278 nm, intense bands in the emission spectra are observed at 380 nm. To understand more thoroughly the nature of the emission band, we also investigated the luminescence of the organic ligand. The rigid 2-BPT exhibits an emission with a maximum at λ = 420 nm upon excitation at λ = 357 nm. In our opinion, the emission of complex (I) is neither metal-to-ligand charge transfer nor ligand-to-metal charge transfer in nature, and may be assigned to intraligand fluorescence emission. Compared with the organic ligands, the enhancement and marked blueshifts are probably due to the unique coordination of the organic ligands to the copper center, increasing the ligand conformational rigidity, thereby reducing the nonradiative decay of the intraligand (π–π*) excited state (Ding et al., 2006).

Related literature

For related literature, see: Ding et al. (2006); Dong et al. (2005); Du et al. (2008); Kitagawa et al. (2004); Ye et al. (2005); Zhai et al. (2007, 2009).

S2. Experimental

A mixture of CuCN (0.09 g, 1.0 mmol), K₄Fe(CN)₆.3H₂O (0.42 g, 1.0 mmol) and 3,5-bis(2-pyridyl)-1,2,4-triazole (2-BPT; 0.33 g, 1.5 mmol) in water (10 ml) was introduced into a Parr Teflon-lined stainless steel vessel (25 ml). The vessel was sealed and heated at 453 K for 5 d under autogenous pressure. After the reaction mixture had been cooled to room temperature over a period of 72 h, brown block-like crystals of (I) were produced (yield 68%, based on Cu). Analysis calculated for C₇₂H₅₂Cu₄N₃₀O₂: C 53.26, H 3.23, N 25.88%; found: C 53.35, H 3.18, N 25.63%. IR (KBr, cm^-1): 3418 (m), 3062 (w), 1600 (s), 1566 (m), 1516 (w), 1493 (s), 1461 (s), 1436 (m), 1412 (s), 1276 (w), 1255 (w), 1188 (w), 1168 (w), 1091 (w), 1047 (w), 1011 (w), 797 (s), 748(s), 724 (m), 634 (w), 563 (w), 464 (w).

S3. Refinement

H atoms were positioned geometrically and included in the refinement using a riding model [C—H = 0.93 Å and O—H = 0.85 Å, and U_iso(H) = 1.2U_eq(parent atom)]. The directions of the O—H vectors were aligned with peaks initially located from difference maps. The maximum residual electrondensity is located 0.70 Å from atom Cu2 and the minimum density lies 0.42 Å from atom Cu1.

Computing details

Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1994); data reduction: SAINT (Siemens, 1994); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and publCIF (Westrip, 2010).

Figures

	Fig. 1. The asymmetric unit in (I), shown with 30% probability displacement ellipsoids. All H atoms have been omitted for clarity. [Symmetry code: (i) -x + 1, -y + 1, -z = 1.]
	Fig. 2. The chair-like tetranuclear metallomacrocycle structure of (I).
	Fig. 3. The two-dimensional supramolecular network of (I) generated by π–π interactions (green broken lines in the electronic versoin of the journal) and hydrogen bonds (red broken lines in the electronic version). All H atoms have been omitted for clarity.

tetrakis[µ-3,5-bis(2-pyridyl)-1,2,4-triazolido]bis[3,5-bis(2-pyridyl)- 1,2,4-triazolido]dicopper(I)dicopper(II) dihydrate

Crystal data

[Cu4(C12H8N5)6]·2H2O	F(000) = 1652
Mr = 1623.60	Dx = 1.551 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 6045 reflections
a = 10.5696 (10) Å	θ = 2.2–26.8°
b = 27.589 (2) Å	µ = 1.28 mm^−1
c = 12.6090 (14) Å	T = 298 K
β = 109.039 (2)°	Block, brown
V = 3475.7 (6) Å^3	0.23 × 0.20 × 0.04 mm
Z = 2

Data collection

Bruker SMART CCD diffractometer	6122 independent reflections
Radiation source: sealed tube	4601 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.029
Detector resolution: 14.6306 pixels mm^-1	θmax = 25.0°, θmin = 1.5°
CCD_Profile_fitting scans	h = −12→11
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	k = −32→32
Tmin = 0.757, Tmax = 0.948	l = −11→15
17303 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)] = 0.054	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.170	H-atom parameters constrained
S = 1.07	w = 1/[σ^2(Fo^2) + (0.081P)^2 + 8.7617P] where P = (Fo^2 + 2Fc^2)/3
6122 reflections	(Δ/σ)max = 0.001
487 parameters	Δρmax = 0.65 e Å^−3
0 restraints	Δρmin = −1.16 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
Cu1	0.37902 (6)	0.58314 (2)	0.19970 (5)	0.0375 (2)
Cu2	0.50421 (7)	0.61595 (2)	0.56237 (6)	0.0444 (2)
C1	0.6728 (5)	0.65882 (17)	0.4575 (4)	0.0294 (10)
C2	0.6292 (4)	0.63789 (17)	0.2914 (4)	0.0293 (10)
C3	0.6283 (5)	0.62927 (17)	0.1764 (4)	0.0301 (10)
C4	0.7295 (5)	0.6450 (2)	0.1366 (4)	0.0415 (12)
H4	0.8020	0.6625	0.1825	0.050*
C5	0.7199 (5)	0.6341 (2)	0.0274 (4)	0.0433 (13)
H5	0.7859	0.6444	−0.0015	0.052*
C6	0.6126 (6)	0.6082 (2)	−0.0379 (4)	0.0439 (13)
H6	0.6048	0.6004	−0.1115	0.053*
C7	0.5159 (5)	0.59375 (18)	0.0072 (4)	0.0346 (11)
H7	0.4436	0.5759	−0.0377	0.042*
C8	0.7301 (5)	0.67954 (17)	0.5699 (4)	0.0304 (10)
C9	0.8324 (5)	0.71324 (19)	0.5977 (4)	0.0382 (12)
H9	0.8689	0.7242	0.5442	0.046*
C10	0.8795 (5)	0.7303 (2)	0.7067 (4)	0.0461 (13)
H10	0.9486	0.7529	0.7277	0.055*
C11	0.8230 (6)	0.7136 (2)	0.7831 (5)	0.0549 (16)
H11	0.8544	0.7239	0.8574	0.066*
C12	0.7193 (7)	0.6813 (2)	0.7477 (5)	0.0567 (16)
H12	0.6795	0.6709	0.7996	0.068*
C13	0.1954 (5)	0.68421 (17)	0.1757 (4)	0.0341 (11)
C14	0.1285 (4)	0.62822 (18)	0.0573 (4)	0.0316 (10)
C15	0.1235 (5)	0.58149 (18)	0.0018 (4)	0.0328 (11)
C16	0.0156 (5)	0.5672 (2)	−0.0909 (4)	0.0445 (13)
H16	−0.0576	0.5875	−0.1211	0.053*
C17	0.0212 (6)	0.5224 (2)	−0.1361 (5)	0.0567 (17)
H17	−0.0499	0.5117	−0.1969	0.068*
C18	0.1308 (7)	0.4932 (2)	−0.0922 (5)	0.0536 (15)
H18	0.1356	0.4629	−0.1231	0.064*
C19	0.2339 (6)	0.50995 (19)	−0.0010 (5)	0.0472 (14)
H19	0.3089	0.4904	0.0286	0.057*
C20	0.2745 (5)	0.71548 (17)	0.2686 (4)	0.0379 (12)
C21	0.4065 (6)	0.72670 (19)	0.2863 (5)	0.0485 (14)
H21	0.4516	0.7138	0.2405	0.058*
C22	0.4715 (7)	0.7579 (2)	0.3747 (6)	0.069 (2)
H22	0.5614	0.7655	0.3899	0.082*
C23	0.4019 (9)	0.7769 (2)	0.4381 (6)	0.070 (2)
H23	0.4427	0.7981	0.4965	0.084*
C24	0.2703 (8)	0.7642 (2)	0.4145 (5)	0.0584 (17)
H24	0.2230	0.7778	0.4577	0.070*
C25	0.5772 (4)	0.44836 (17)	0.2976 (4)	0.0293 (10)
C26	0.4231 (4)	0.48975 (17)	0.3216 (4)	0.0280 (10)
C27	0.3169 (4)	0.51056 (17)	0.3583 (4)	0.0307 (10)
C28	0.2685 (5)	0.4878 (2)	0.4351 (5)	0.0433 (13)
H28	0.3008	0.4577	0.4648	0.052*
C29	0.1704 (6)	0.5114 (2)	0.4665 (5)	0.0526 (15)
H29	0.1360	0.4973	0.5183	0.063*
C30	0.1250 (6)	0.5550 (2)	0.4212 (5)	0.0540 (15)
H30	0.0584	0.5709	0.4410	0.065*
C31	0.1782 (5)	0.5760 (2)	0.3451 (5)	0.0442 (13)
H31	0.1468	0.6062	0.3153	0.053*
C32	0.6701 (5)	0.40807 (17)	0.3115 (4)	0.0320 (10)
C33	0.7696 (5)	0.4061 (2)	0.2629 (5)	0.0440 (13)
H33	0.7815	0.4314	0.2183	0.053*
C34	0.8510 (6)	0.3656 (2)	0.2819 (5)	0.0551 (16)
H34	0.9189	0.3634	0.2502	0.066*
C35	0.8318 (6)	0.3289 (2)	0.3473 (5)	0.0508 (14)
H35	0.8859	0.3015	0.3609	0.061*
C36	0.7304 (6)	0.33337 (19)	0.3927 (5)	0.0455 (13)
H36	0.7173	0.3083	0.4372	0.055*
N1	0.5326 (4)	0.61899 (13)	0.3245 (3)	0.0267 (8)
N2	0.5609 (4)	0.63229 (14)	0.4337 (3)	0.0281 (8)
N3	0.7200 (4)	0.66360 (15)	0.3709 (3)	0.0327 (9)
N4	0.5211 (4)	0.60410 (13)	0.1124 (3)	0.0286 (8)
N5	0.6716 (4)	0.66388 (16)	0.6436 (3)	0.0405 (10)
N6	0.0309 (4)	0.66061 (17)	0.0326 (4)	0.0456 (11)
N7	0.0741 (4)	0.69702 (16)	0.1099 (4)	0.0455 (11)
N8	0.2368 (4)	0.64114 (13)	0.1459 (3)	0.0292 (8)
N9	0.2308 (4)	0.55295 (14)	0.0465 (3)	0.0344 (9)
N10	0.2063 (5)	0.73370 (16)	0.3336 (4)	0.0459 (11)
N11	0.4676 (4)	0.51426 (14)	0.2484 (3)	0.0299 (8)
N12	0.5687 (4)	0.48716 (14)	0.2324 (3)	0.0304 (9)
N13	0.4875 (4)	0.44809 (14)	0.3547 (3)	0.0295 (8)
N14	0.2739 (4)	0.55421 (15)	0.3130 (3)	0.0327 (9)
N15	0.6502 (4)	0.37172 (14)	0.3761 (3)	0.0361 (9)
O1	1.0018 (6)	0.6638 (2)	0.3795 (6)	0.113 (2)
H1A	0.9212	0.6714	0.3713	0.135*
H1B	1.0407	0.6881	0.3625	0.135*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.0359 (4)	0.0363 (4)	0.0404 (4)	−0.0025 (3)	0.0125 (3)	−0.0001 (3)
Cu2	0.0537 (4)	0.0464 (4)	0.0422 (4)	−0.0129 (3)	0.0279 (3)	0.0050 (3)
C1	0.032 (2)	0.034 (2)	0.022 (2)	−0.004 (2)	0.0095 (19)	−0.0005 (19)
C2	0.029 (2)	0.036 (3)	0.023 (2)	−0.006 (2)	0.0095 (19)	−0.001 (2)
C3	0.031 (2)	0.034 (2)	0.026 (2)	−0.002 (2)	0.011 (2)	0.000 (2)
C4	0.037 (3)	0.055 (3)	0.034 (3)	−0.013 (2)	0.013 (2)	−0.001 (2)
C5	0.044 (3)	0.058 (3)	0.036 (3)	−0.004 (3)	0.024 (2)	0.002 (3)
C6	0.058 (3)	0.047 (3)	0.031 (3)	−0.005 (3)	0.021 (3)	−0.006 (2)
C7	0.041 (3)	0.036 (3)	0.026 (3)	−0.005 (2)	0.009 (2)	−0.005 (2)
C8	0.033 (2)	0.034 (2)	0.024 (2)	−0.001 (2)	0.0088 (19)	0.002 (2)
C9	0.035 (3)	0.047 (3)	0.034 (3)	−0.009 (2)	0.013 (2)	0.000 (2)
C10	0.041 (3)	0.054 (3)	0.039 (3)	−0.014 (3)	0.007 (2)	−0.011 (3)
C11	0.071 (4)	0.061 (4)	0.031 (3)	−0.019 (3)	0.014 (3)	−0.012 (3)
C12	0.079 (4)	0.066 (4)	0.031 (3)	−0.025 (3)	0.026 (3)	−0.006 (3)
C13	0.039 (3)	0.030 (2)	0.037 (3)	0.003 (2)	0.017 (2)	0.002 (2)
C14	0.025 (2)	0.039 (3)	0.030 (3)	−0.001 (2)	0.009 (2)	0.003 (2)
C15	0.031 (3)	0.040 (3)	0.030 (3)	−0.010 (2)	0.014 (2)	−0.001 (2)
C16	0.036 (3)	0.059 (4)	0.038 (3)	−0.010 (3)	0.011 (2)	−0.002 (3)
C17	0.057 (4)	0.070 (4)	0.041 (3)	−0.030 (3)	0.013 (3)	−0.014 (3)
C18	0.070 (4)	0.043 (3)	0.049 (4)	−0.018 (3)	0.022 (3)	−0.014 (3)
C19	0.056 (3)	0.034 (3)	0.054 (4)	−0.009 (3)	0.021 (3)	−0.005 (3)
C20	0.047 (3)	0.027 (2)	0.038 (3)	0.008 (2)	0.011 (2)	0.004 (2)
C21	0.047 (3)	0.035 (3)	0.063 (4)	0.006 (2)	0.016 (3)	−0.001 (3)
C22	0.060 (4)	0.043 (3)	0.086 (5)	−0.014 (3)	0.000 (4)	0.003 (4)
C23	0.106 (6)	0.043 (4)	0.053 (4)	−0.011 (4)	0.013 (4)	−0.013 (3)
C24	0.092 (5)	0.042 (3)	0.042 (3)	0.001 (3)	0.023 (3)	−0.005 (3)
C25	0.028 (2)	0.036 (3)	0.026 (2)	−0.004 (2)	0.0125 (19)	−0.001 (2)
C26	0.027 (2)	0.034 (3)	0.025 (2)	−0.0068 (19)	0.0099 (19)	0.0003 (19)
C27	0.026 (2)	0.038 (3)	0.029 (2)	−0.007 (2)	0.0112 (19)	−0.005 (2)
C28	0.040 (3)	0.047 (3)	0.048 (3)	−0.004 (2)	0.022 (2)	0.003 (3)
C29	0.049 (3)	0.068 (4)	0.053 (4)	−0.010 (3)	0.033 (3)	0.000 (3)
C30	0.045 (3)	0.064 (4)	0.067 (4)	−0.005 (3)	0.037 (3)	−0.017 (3)
C31	0.037 (3)	0.043 (3)	0.058 (4)	−0.004 (2)	0.023 (3)	−0.010 (3)
C32	0.033 (2)	0.034 (3)	0.029 (2)	−0.003 (2)	0.010 (2)	0.001 (2)
C33	0.042 (3)	0.048 (3)	0.052 (3)	0.007 (2)	0.028 (3)	0.012 (3)
C34	0.051 (3)	0.058 (4)	0.068 (4)	0.010 (3)	0.036 (3)	0.006 (3)
C35	0.050 (3)	0.044 (3)	0.060 (4)	0.011 (3)	0.021 (3)	0.002 (3)
C36	0.057 (3)	0.033 (3)	0.050 (3)	0.001 (2)	0.021 (3)	0.009 (2)
N1	0.0274 (19)	0.030 (2)	0.0224 (19)	−0.0058 (16)	0.0074 (15)	−0.0018 (16)
N2	0.032 (2)	0.031 (2)	0.0224 (19)	−0.0030 (17)	0.0108 (16)	0.0004 (16)
N3	0.030 (2)	0.044 (2)	0.027 (2)	−0.0108 (18)	0.0123 (17)	−0.0033 (18)
N4	0.030 (2)	0.030 (2)	0.025 (2)	−0.0025 (16)	0.0086 (16)	−0.0012 (16)
N5	0.052 (3)	0.046 (2)	0.026 (2)	−0.015 (2)	0.0163 (19)	−0.0026 (19)
N6	0.034 (2)	0.053 (3)	0.045 (3)	0.008 (2)	0.006 (2)	−0.002 (2)
N7	0.039 (3)	0.047 (3)	0.047 (3)	0.013 (2)	0.010 (2)	−0.002 (2)
N8	0.030 (2)	0.0254 (19)	0.032 (2)	0.0022 (16)	0.0098 (17)	0.0042 (16)
N9	0.033 (2)	0.032 (2)	0.038 (2)	−0.0080 (18)	0.0112 (18)	−0.0034 (18)
N10	0.062 (3)	0.038 (2)	0.040 (3)	0.005 (2)	0.019 (2)	−0.001 (2)
N11	0.030 (2)	0.033 (2)	0.030 (2)	0.0013 (17)	0.0130 (17)	0.0032 (17)
N12	0.032 (2)	0.033 (2)	0.030 (2)	−0.0006 (17)	0.0153 (17)	0.0041 (17)
N13	0.028 (2)	0.033 (2)	0.030 (2)	−0.0036 (17)	0.0122 (16)	0.0022 (17)
N14	0.029 (2)	0.036 (2)	0.036 (2)	−0.0023 (17)	0.0146 (17)	−0.0064 (18)
N15	0.043 (2)	0.032 (2)	0.037 (2)	−0.0010 (18)	0.0192 (19)	0.0039 (18)
O1	0.079 (4)	0.111 (5)	0.148 (6)	0.014 (4)	0.037 (4)	0.026 (4)

Geometric parameters (Å, º)

Cu1—N1	2.103 (4)	C18—C19	1.381 (8)
Cu1—N11	2.119 (4)	C18—H18	0.9300
Cu1—N8	2.149 (4)	C19—N9	1.334 (7)
Cu1—N4	2.209 (4)	C19—H19	0.9300
Cu1—N9	2.215 (4)	C20—N10	1.352 (7)
Cu1—N14	2.225 (4)	C20—C21	1.375 (8)
Cu2—N2	1.957 (4)	C21—C22	1.398 (9)
Cu2—N13^i	2.040 (4)	C21—H21	0.9300
Cu2—N15^i	2.051 (4)	C22—C23	1.356 (11)
Cu2—N5	2.179 (4)	C22—H22	0.9300
C1—N2	1.339 (6)	C23—C24	1.369 (10)
C1—N3	1.347 (6)	C23—H23	0.9300
C1—C8	1.463 (6)	C24—N10	1.326 (8)
C2—N1	1.328 (6)	C24—H24	0.9300
C2—N3	1.342 (6)	C25—N12	1.334 (6)
C2—C3	1.467 (6)	C25—N13	1.366 (6)
C3—N4	1.349 (6)	C25—C32	1.456 (7)
C3—C4	1.391 (7)	C26—N13	1.332 (6)
C4—C5	1.381 (7)	C26—N11	1.346 (6)
C4—H4	0.9300	C26—C27	1.463 (6)
C5—C6	1.366 (8)	C27—N14	1.347 (6)
C5—H5	0.9300	C27—C28	1.385 (7)
C6—C7	1.381 (7)	C28—C29	1.387 (8)
C6—H6	0.9300	C28—H28	0.9300
C7—N4	1.341 (6)	C29—C30	1.352 (9)
C7—H7	0.9300	C29—H29	0.9300
C8—N5	1.345 (6)	C30—C31	1.387 (8)
C8—C9	1.382 (7)	C30—H30	0.9300
C9—C10	1.382 (7)	C31—N14	1.347 (6)
C9—H9	0.9300	C31—H31	0.9300
C10—C11	1.369 (8)	C32—N15	1.351 (6)
C10—H10	0.9300	C32—C33	1.380 (7)
C11—C12	1.370 (8)	C33—C34	1.383 (8)
C11—H11	0.9300	C33—H33	0.9300
C12—N5	1.333 (7)	C34—C35	1.361 (8)
C12—H12	0.9300	C34—H34	0.9300
C13—N7	1.328 (6)	C35—C36	1.375 (8)
C13—N8	1.361 (6)	C35—H35	0.9300
C13—C20	1.475 (7)	C36—N15	1.329 (7)
C14—N6	1.323 (6)	C36—H36	0.9300
C14—N8	1.360 (6)	N1—N2	1.361 (5)
C14—C15	1.460 (7)	N6—N7	1.370 (6)
C15—N9	1.344 (6)	N11—N12	1.372 (5)
C15—C16	1.397 (7)	N13—Cu2^i	2.040 (4)
C16—C17	1.371 (9)	N15—Cu2^i	2.051 (4)
C16—H16	0.9300	O1—H1A	0.8497
C17—C18	1.370 (9)	O1—H1B	0.8500
C17—H17	0.9300
N1—Cu1—N4	76.41 (14)	C22—C21—H21	120.8
N1—Cu1—N8	100.13 (15)	C23—C22—C21	119.2 (7)
N1—Cu1—N9	169.46 (15)	C23—C22—H22	120.4
N1—Cu1—N11	92.56 (15)	C21—C22—H22	120.4
N1—Cu1—N14	96.53 (14)	C22—C23—C24	118.8 (6)
N4—Cu1—N9	93.81 (14)	C22—C23—H23	120.6
N4—Cu1—N14	167.72 (14)	C24—C23—H23	120.6
N8—Cu1—N4	99.63 (14)	N10—C24—C23	123.8 (6)
N8—Cu1—N9	77.39 (15)	N10—C24—H24	118.1
N8—Cu1—N14	91.44 (14)	C23—C24—H24	118.1
N9—Cu1—N14	93.78 (14)	N12—C25—N13	114.2 (4)
N11—Cu1—N4	94.10 (14)	N12—C25—C32	126.5 (4)
N11—Cu1—N9	92.04 (15)	N13—C25—C32	119.3 (4)
N11—Cu1—N8	163.13 (14)	N13—C26—N11	113.1 (4)
N11—Cu1—N14	75.99 (14)	N13—C26—C27	127.3 (4)
N2—Cu2—N5	80.14 (15)	N11—C26—C27	119.7 (4)
N2—Cu2—N13^i	130.59 (16)	N14—C27—C28	123.4 (4)
N2—Cu2—N15^i	140.54 (17)	N14—C27—C26	113.9 (4)
N13^i—Cu2—N5	113.08 (16)	C28—C27—C26	122.7 (5)
N13^i—Cu2—N15^i	81.75 (15)	C27—C28—C29	118.0 (5)
N15^i—Cu2—N5	110.23 (17)	C27—C28—H28	121.0
N2—C1—N3	113.9 (4)	C29—C28—H28	121.0
N2—C1—C8	119.1 (4)	C30—C29—C28	119.4 (5)
N3—C1—C8	127.0 (4)	C30—C29—H29	120.3
N1—C2—N3	114.1 (4)	C28—C29—H29	120.3
N1—C2—C3	119.3 (4)	C29—C30—C31	119.8 (5)
N3—C2—C3	126.6 (4)	C29—C30—H30	120.1
N4—C3—C4	122.7 (4)	C31—C30—H30	120.1
N4—C3—C2	114.0 (4)	N14—C31—C30	122.3 (5)
C4—C3—C2	123.3 (4)	N14—C31—H31	118.9
C5—C4—C3	118.5 (5)	C30—C31—H31	118.9
C5—C4—H4	120.8	N15—C32—C33	122.0 (5)
C3—C4—H4	120.8	N15—C32—C25	114.1 (4)
C6—C5—C4	119.4 (5)	C33—C32—C25	123.9 (4)
C6—C5—H5	120.3	C32—C33—C34	118.4 (5)
C4—C5—H5	120.3	C32—C33—H33	120.8
C5—C6—C7	118.9 (5)	C34—C33—H33	120.8
C5—C6—H6	120.5	C35—C34—C33	119.9 (5)
C7—C6—H6	120.5	C35—C34—H34	120.1
N4—C7—C6	123.3 (5)	C33—C34—H34	120.1
N4—C7—H7	118.3	C34—C35—C36	118.5 (5)
C6—C7—H7	118.3	C34—C35—H35	120.8
N5—C8—C9	122.6 (4)	C36—C35—H35	120.8
N5—C8—C1	113.9 (4)	N15—C36—C35	123.3 (5)
C9—C8—C1	123.5 (4)	N15—C36—H36	118.3
C8—C9—C10	118.7 (5)	C35—C36—H36	118.3
C8—C9—H9	120.6	C2—N1—N2	105.9 (3)
C10—C9—H9	120.6	C2—N1—Cu1	115.8 (3)
C11—C10—C9	119.1 (5)	N2—N1—Cu1	138.1 (3)
C11—C10—H10	120.4	C1—N2—N1	105.1 (3)
C9—C10—H10	120.4	C1—N2—Cu2	115.3 (3)
C10—C11—C12	118.4 (5)	N1—N2—Cu2	138.7 (3)
C10—C11—H11	120.8	C2—N3—C1	100.9 (4)
C12—C11—H11	120.8	C7—N4—C3	117.1 (4)
N5—C12—C11	124.1 (5)	C7—N4—Cu1	128.5 (3)
N5—C12—H12	117.9	C3—N4—Cu1	114.3 (3)
C11—C12—H12	117.9	C12—N5—C8	117.0 (4)
N7—C13—N8	113.0 (4)	C12—N5—Cu2	132.1 (4)
N7—C13—C20	121.5 (4)	C8—N5—Cu2	110.8 (3)
N8—C13—C20	125.5 (4)	C14—N6—N7	105.9 (4)
N6—C14—N8	113.5 (4)	C13—N7—N6	106.2 (4)
N6—C14—C15	125.4 (4)	C14—N8—C13	101.3 (4)
N8—C14—C15	121.0 (4)	C14—N8—Cu1	112.3 (3)
N9—C15—C16	122.2 (5)	C13—N8—Cu1	144.9 (3)
N9—C15—C14	115.0 (4)	C19—N9—C15	118.3 (4)
C16—C15—C14	122.8 (5)	C19—N9—Cu1	127.7 (4)
C17—C16—C15	117.9 (6)	C15—N9—Cu1	113.9 (3)
C17—C16—H16	121.1	C24—N10—C20	117.6 (5)
C15—C16—H16	121.1	C26—N11—N12	106.9 (4)
C18—C17—C16	120.5 (5)	C26—N11—Cu1	115.4 (3)
C18—C17—H17	119.7	N12—N11—Cu1	137.5 (3)
C16—C17—H17	119.7	C25—N12—N11	104.2 (3)
C17—C18—C19	118.2 (6)	C26—N13—C25	101.6 (4)
C17—C18—H18	120.9	C26—N13—Cu2^i	147.2 (3)
C19—C18—H18	120.9	C25—N13—Cu2^i	110.7 (3)
N9—C19—C18	122.9 (6)	C27—N14—C31	117.1 (4)
N9—C19—H19	118.6	C27—N14—Cu1	115.0 (3)
C18—C19—H19	118.6	C31—N14—Cu1	127.8 (4)
N10—C20—C21	122.1 (5)	C36—N15—C32	117.9 (4)
N10—C20—C13	115.0 (5)	C36—N15—Cu2^i	128.2 (3)
C21—C20—C13	122.8 (5)	C32—N15—Cu2^i	113.9 (3)
C20—C21—C22	118.5 (6)	H1A—O1—H1B	108.9
C20—C21—H21	120.8
N1—C2—C3—N4	3.4 (6)	C11—C12—N5—C8	−0.3 (9)
N3—C2—C3—N4	−176.8 (5)	C11—C12—N5—Cu2	−176.4 (5)
N1—C2—C3—C4	−175.9 (5)	C9—C8—N5—C12	−1.9 (8)
N3—C2—C3—C4	3.9 (8)	C1—C8—N5—C12	179.9 (5)
N4—C3—C4—C5	−0.4 (8)	C9—C8—N5—Cu2	175.0 (4)
C2—C3—C4—C5	178.8 (5)	C1—C8—N5—Cu2	−3.2 (5)
C3—C4—C5—C6	−0.3 (8)	N2—Cu2—N5—C12	175.2 (6)
C4—C5—C6—C7	0.3 (8)	N13^i—Cu2—N5—C12	−54.8 (6)
C5—C6—C7—N4	0.4 (8)	N15^i—Cu2—N5—C12	34.7 (6)
N2—C1—C8—N5	8.5 (6)	N2—Cu2—N5—C8	−1.1 (3)
N3—C1—C8—N5	−172.1 (5)	N13^i—Cu2—N5—C8	128.9 (3)
N2—C1—C8—C9	−169.8 (5)	N15^i—Cu2—N5—C8	−141.6 (3)
N3—C1—C8—C9	9.6 (8)	N8—C14—N6—N7	−1.3 (6)
N5—C8—C9—C10	2.2 (8)	C15—C14—N6—N7	175.7 (4)
C1—C8—C9—C10	−179.7 (5)	N8—C13—N7—N6	0.6 (6)
C8—C9—C10—C11	−0.4 (9)	C20—C13—N7—N6	179.1 (4)
C9—C10—C11—C12	−1.6 (10)	C14—N6—N7—C13	0.4 (6)
C10—C11—C12—N5	2.0 (11)	N6—C14—N8—C13	1.5 (5)
N6—C14—C15—N9	−175.3 (5)	C15—C14—N8—C13	−175.6 (4)
N8—C14—C15—N9	1.4 (6)	N6—C14—N8—Cu1	170.9 (3)
N6—C14—C15—C16	4.7 (8)	C15—C14—N8—Cu1	−6.2 (5)
N8—C14—C15—C16	−178.5 (4)	N7—C13—N8—C14	−1.3 (5)
N9—C15—C16—C17	0.4 (7)	C20—C13—N8—C14	−179.7 (5)
C14—C15—C16—C17	−179.7 (5)	N7—C13—N8—Cu1	−164.0 (4)
C15—C16—C17—C18	−1.2 (8)	C20—C13—N8—Cu1	17.5 (9)
C16—C17—C18—C19	0.8 (9)	N1—Cu1—N8—C14	175.5 (3)
C17—C18—C19—N9	0.6 (9)	N11—Cu1—N8—C14	−46.3 (7)
N7—C13—C20—N10	45.9 (7)	N4—Cu1—N8—C14	97.7 (3)
N8—C13—C20—N10	−135.8 (5)	N9—Cu1—N8—C14	6.0 (3)
N7—C13—C20—C21	−132.1 (6)	N14—Cu1—N8—C14	−87.6 (3)
N8—C13—C20—C21	46.2 (7)	N1—Cu1—N8—C13	−22.8 (6)
N10—C20—C21—C22	0.2 (8)	N11—Cu1—N8—C13	115.4 (6)
C13—C20—C21—C22	178.0 (5)	N4—Cu1—N8—C13	−100.5 (5)
C20—C21—C22—C23	−1.6 (9)	N9—Cu1—N8—C13	167.7 (6)
C21—C22—C23—C24	1.1 (10)	N14—Cu1—N8—C13	74.1 (6)
C22—C23—C24—N10	0.9 (10)	C18—C19—N9—C15	−1.4 (8)
N13—C26—C27—N14	177.7 (4)	C18—C19—N9—Cu1	175.0 (4)
N11—C26—C27—N14	−0.3 (6)	C16—C15—N9—C19	0.9 (7)
N13—C26—C27—C28	−0.5 (8)	C14—C15—N9—C19	−179.1 (4)
N11—C26—C27—C28	−178.5 (4)	C16—C15—N9—Cu1	−176.0 (4)
N14—C27—C28—C29	0.2 (8)	C14—C15—N9—Cu1	4.0 (5)
C26—C27—C28—C29	178.2 (5)	N1—Cu1—N9—C19	100.5 (9)
C27—C28—C29—C30	0.4 (9)	N11—Cu1—N9—C19	−15.3 (4)
C28—C29—C30—C31	−0.9 (9)	N8—Cu1—N9—C19	177.9 (4)
C29—C30—C31—N14	0.7 (9)	N4—Cu1—N9—C19	78.9 (4)
N12—C25—C32—N15	−175.2 (4)	N14—Cu1—N9—C19	−91.4 (4)
N13—C25—C32—N15	4.6 (6)	N1—Cu1—N9—C15	−83.0 (9)
N12—C25—C32—C33	4.1 (8)	N11—Cu1—N9—C15	161.2 (3)
N13—C25—C32—C33	−176.1 (5)	N8—Cu1—N9—C15	−5.5 (3)
N15—C32—C33—C34	−0.4 (8)	N4—Cu1—N9—C15	−104.5 (3)
C25—C32—C33—C34	−179.5 (5)	N14—Cu1—N9—C15	85.1 (3)
C32—C33—C34—C35	0.1 (9)	C23—C24—N10—C20	−2.3 (9)
C33—C34—C35—C36	0.1 (9)	C21—C20—N10—C24	1.7 (8)
C34—C35—C36—N15	−0.1 (9)	C13—C20—N10—C24	−176.3 (5)
N3—C2—N1—N2	−0.8 (5)	N13—C26—N11—N12	−0.3 (5)
C3—C2—N1—N2	179.1 (4)	C27—C26—N11—N12	178.0 (4)
N3—C2—N1—Cu1	175.2 (3)	N13—C26—N11—Cu1	−176.1 (3)
C3—C2—N1—Cu1	−5.0 (6)	C27—C26—N11—Cu1	2.2 (5)
N11—Cu1—N1—C2	97.1 (3)	N1—Cu1—N11—C26	93.9 (3)
N8—Cu1—N1—C2	−94.0 (3)	N8—Cu1—N11—C26	−45.0 (7)
N4—Cu1—N1—C2	3.5 (3)	N4—Cu1—N11—C26	170.5 (3)
N9—Cu1—N1—C2	−18.7 (10)	N9—Cu1—N11—C26	−95.6 (3)
N14—Cu1—N1—C2	173.3 (3)	N14—Cu1—N11—C26	−2.2 (3)
N11—Cu1—N1—N2	−88.7 (4)	N1—Cu1—N11—N12	−80.2 (4)
N8—Cu1—N1—N2	80.2 (4)	N8—Cu1—N11—N12	140.9 (5)
N4—Cu1—N1—N2	177.7 (5)	N4—Cu1—N11—N12	−3.6 (4)
N9—Cu1—N1—N2	155.6 (7)	N9—Cu1—N11—N12	90.3 (4)
N14—Cu1—N1—N2	−12.5 (4)	N14—Cu1—N11—N12	−176.3 (5)
N3—C1—N2—N1	−0.2 (5)	N13—C25—N12—N11	0.4 (5)
C8—C1—N2—N1	179.2 (4)	C32—C25—N12—N11	−179.8 (4)
N3—C1—N2—Cu2	170.9 (3)	C26—N11—N12—C25	−0.1 (5)
C8—C1—N2—Cu2	−9.6 (6)	Cu1—N11—N12—C25	174.4 (4)
C2—N1—N2—C1	0.6 (5)	N11—C26—N13—C25	0.5 (5)
Cu1—N1—N2—C1	−174.0 (4)	C27—C26—N13—C25	−177.6 (4)
C2—N1—N2—Cu2	−167.3 (4)	N11—C26—N13—Cu2^i	−169.8 (4)
Cu1—N1—N2—Cu2	18.1 (7)	C27—C26—N13—Cu2^i	12.0 (9)
N13^i—Cu2—N2—C1	−106.4 (3)	N12—C25—N13—C26	−0.6 (5)
N15^i—Cu2—N2—C1	115.6 (4)	C32—C25—N13—C26	179.6 (4)
N5—Cu2—N2—C1	5.7 (3)	N12—C25—N13—Cu2^i	173.8 (3)
N13^i—Cu2—N2—N1	60.7 (5)	C32—C25—N13—Cu2^i	−6.0 (5)
N15^i—Cu2—N2—N1	−77.3 (5)	C28—C27—N14—C31	−0.3 (7)
N5—Cu2—N2—N1	172.7 (5)	C26—C27—N14—C31	−178.5 (4)
N1—C2—N3—C1	0.6 (5)	C28—C27—N14—Cu1	176.6 (4)
C3—C2—N3—C1	−179.2 (5)	C26—C27—N14—Cu1	−1.6 (5)
N2—C1—N3—C2	−0.2 (5)	C30—C31—N14—C27	−0.1 (7)
C8—C1—N3—C2	−179.6 (5)	C30—C31—N14—Cu1	−176.6 (4)
C6—C7—N4—C3	−1.1 (7)	N1—Cu1—N14—C27	−89.0 (3)
C6—C7—N4—Cu1	−178.8 (4)	N11—Cu1—N14—C27	2.0 (3)
C4—C3—N4—C7	1.1 (7)	N8—Cu1—N14—C27	170.7 (3)
C2—C3—N4—C7	−178.1 (4)	N4—Cu1—N14—C27	−34.8 (8)
C4—C3—N4—Cu1	179.1 (4)	N9—Cu1—N14—C27	93.2 (3)
C2—C3—N4—Cu1	−0.2 (5)	N1—Cu1—N14—C31	87.6 (4)
N1—Cu1—N4—C7	176.0 (4)	N11—Cu1—N14—C31	178.6 (4)
N11—Cu1—N4—C7	84.3 (4)	N8—Cu1—N14—C31	−12.8 (4)
N8—Cu1—N4—C7	−85.8 (4)	N4—Cu1—N14—C31	141.7 (6)
N9—Cu1—N4—C7	−8.0 (4)	N9—Cu1—N14—C31	−90.2 (4)
N14—Cu1—N4—C7	120.1 (7)	C35—C36—N15—C32	−0.2 (8)
N1—Cu1—N4—C3	−1.7 (3)	C35—C36—N15—Cu2^i	−179.8 (4)
N11—Cu1—N4—C3	−93.4 (3)	C33—C32—N15—C36	0.4 (7)
N8—Cu1—N4—C3	96.5 (3)	C25—C32—N15—C36	179.7 (4)
N9—Cu1—N4—C3	174.3 (3)	C33—C32—N15—Cu2^i	−179.9 (4)
N14—Cu1—N4—C3	−57.6 (8)	C25—C32—N15—Cu2^i	−0.7 (5)

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···N3	0.85	2.14	2.945 (7)	159
O1—H1B···N10^ii	0.85	2.28	3.089 (8)	159

Symmetry code: (ii) x+1, y, z.