Pseudo-merohedrally twinned tetra­kis­(1H-imidazole-[kappa]N³)bis­(N-nitro­cyanamidato-[kappa]N)copper(II)

Crystals of the title complex, [Cu(CN₃O₂)₂(C₃H₄N₂)₄], the structure of which has been determined by single-crystal X-ray diffraction at 304 K, appear to be pseudo-merohedrally twinned. Transformation to a monoclinic C-centred cell was necessary in order to derive the twin law. Twin refinement in a triclinic unit cell significantly reduced the R value. The asymmetric unit of the triclinic cell consists of one mol­ecule in a general position and two half entities with the Cu atom on a centre of inversion. The coordination of the Cu atom is quasi-octa­hedral, with four imidazole N-atom donors in the equatorial plane and two cyano N atoms from the N-nitro­cyanamidate anion in axial positions. Owing to symmetry in the centrosymmetric mol­ecules, the trans imidazole ligands are parallel, while those in the non-centrosymmetric mol­ecule make angles of 22.8 (2) and 77.9 (2)°.

S1. Comment

Non-linear pseudohalides, such as dicyanamide, N(CN)₂⁻, tricyanomethananide, C(CN)₃⁻, nitrosodicyananomethanide, ONC(CN)₂⁻ and cyanamidonitrate (can), O₂NN(CN)⁻, exhibit a rich variety of bonding modes for coordination in 3d complexes (Jäger et al., 1997; Hvastijová et al., 1998; Kohout et al., 2000; Potočňák et al., 2001, 2002; Kožíšek et al., 2002; Díaz et al., 2003). A comparison of bond distances for compounds of the type [M(NL)₄(NO₂NCN)₂] [where M = Co, Ni and Cu, and NL is a neutral ligand, such as iz (imidazole), pz (pyrazole) or meiz (1- or 5-methylimidazole)] found in the Cambridge Structural Database (CSD; Version 1.6, 2003 release; Allen, 2002) is shown in Table 3. For Ni and Cu compounds, neutral ligands were found in the equatorial plane and anionic (can) ligands in axial positions. In all previously solved crystal structures, except for CSD refcode OFILEU, the molecules are centrosymmetric.

Cell reduction for the crystal structure of the title compound, (I), revealed that the cell could be transformed to a monoclinic C-centred one, but R_int and R(σ) were significantly better for the triclinic case (0.0301 and 0.0375, respectively) than for a monoclinic lattice (0.0570 and 0.0483). The structure could be solved in the triclinic space group P-1 only, with many difficulties. During refinement, large positional shifts led to unreasonable molecular geometry, and additional peaks appeared in the difference map. This behaviour is typical of merohedral and pseudo-merohedral twins, which are formed when the metric symmetry of the unit cell is higher than that of its contents. Under these conditions, a matrix product (monoclinic to triclinic) × (inversion) × (triclinic to monoclinic) (0 0 1 / 0.5 − 0.5 0 / 0.5 0.5 0) × (−1 0 0 / 0 − 1 0 / 0 0 − 1) × (0 − 1 −1 / 0 − 1 1 / −1 0 0) (matrices written by rows) can be expressed as TWIN 1 0 0 0 0 1 0 1 0 in the SHELXL97 code (Sheldrick, 1997).

An interesting feature of the title compound is the presence of one non-centrosymmetric and two centrosymmetric molecules in the crystal structure (Fig. 1). Although the differences in Cu—N(NL) bond distances are small, it might be supposed that the orientation of the imidazole ligands (and so the interaction of π-electron density with Cu^II d orbitals) could increase the asymmetry on the Cu^II center, the most pronounced distortion being in the axial direction [2.509 (3) and 2.570 (3) Å]. It can be seen that all Cu—N_iz distances that are perpendicular to the cyanamidonitrate/Cu^II/imidazole `plane' are significantly shorter that the Cu—N<sub>iz</sub> distances in the `plane' [Cu1—N7 = 1.998 (3) Å, Cu1—N17 = 2.002 (3) Å, Cu34—N35 = 2.015 (3) Å and Cu51—N57 = 2.005 (3) Å]. The greatest deviations from a regular geometry are in the angles that contain atoms that are more tightly bonded (N7, N17, N35 and N57; see Table 2).

In the CSD for chromofore [CuN₆], 45 crystal structures were found with monodentate nitrogen ligands and with no restrictions for centrosymmetry. However, only five of these stuctures have a non-centrosymmetric molecule [refcodes LAXTEJ (Otieno et al.,1993), LITVEP (Lipkowski et al.,1999), LOYROG (Dalai et al., 2002), MOGMUQ (Fedin et al., 2002) and SOFCEV (Kožíšek et al., 1991)]. No crystal structure containing both centrosymmetric and non-centrosymmetric moieties was found. The greatest difference between the axial distances is in SOFCEV (2.372 and 2.500 Å).

The crystal structure of (I) (see) is stabilized by a three-dimensional network of hydrogen bonds and van der Vaals interactions (Fig. 2 and Table 2). The closest intermolecular contacts [N9—O49= 2.819 (4) Å, N59—O33 = 2.832 (4) Å and N19—O67 = 2.848 (4) Å] do not indicate significant π–π interaction.

S2. Experimental

A solution of Cu(NO₃)₂ (2.0 mmol) in water (3 ml) was mixed with a solution of KNO₂NCN (4.0 mmol) in water (10 ml) and with a solution of imidazole (4.0 mmol) in methanol (10 ml). This system was left to stand for a few days and blue crystals of [Cu(NCNNO₂)₂(iz)₄] were isolated. The mid-IR vibrational spectrum was compared with those of NaNO₂NCN and free imidazole. The comparison revealed that many vibration bands of the cyanoamidonitrate ligand (e.g. 2196 and 2189 cm⁻¹ for NCN asymmetric stretching vibration, 1171 and 1162 cm⁻¹ for NCN symmetric vibration, 1298 and 1284 cm⁻¹ for NO₂ symmetric stretching vibration, 968 and 962 cm⁻¹ for N—N stretching vibration, 551 and 540 cm⁻¹ for C–N torsion, and 511 and 506 cm⁻¹ for NCN bending vibration) are split by only a few wavenumbers. Similar small splittings can also be seen on some imidazole ligand bands. These features may indicate the presence of more than one crystallographically independent molecule in the lattice.

S3. Refinement

H atoms were positioned geometrically and treated as riding atoms (C—H = 0.93 Å and N—H = 0.86 Å), with U_iso(H) set to 1.2U_eq of the parent atom.

Computing details

Data collection: CrysAlis CCD (Oxford Diffraction, 2001); cell refinement: CrysAlis CCD; data reduction: CrysAlis RED (Oxford Diffraction, 2003); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: DIAMOND (Brandenburg, 1998); software used to prepare material for publication: program (reference)?.

Figures

Fig. 1. The atom-numbering scheme of (I). Displacement ellipsoids are shown at the 50% probability level. Fig. 2. Packing diagram of (I), viewed along the a axis. Hydrogen-bond interactions are indicated by dashed lines.

bis(N-nitrocyanamidato-κN)tetrakis(1H-imidazole-κN³)copper(II)

Crystal data

[Cu(CN3O2)2(C3H4N2)4]	Z = 4
Mr = 507.95	F(000) = 1036
Triclinic, P1	Dx = 1.551 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.841 (2) Å	Cell parameters from 1076 reflections
b = 15.249 (3) Å	θ = 2.4–19.0°
c = 15.234 (3) Å	µ = 1.06 mm^−1
α = 104.17 (2)°	T = 304 K
β = 96.65 (2)°	Block, blue
γ = 96.86 (2)°	0.36 × 0.34 × 0.11 mm
V = 2175.6 (8) Å^3

Data collection

Oxford Diffraction Xcalibur CCD diffractometer	8693 independent reflections
Radiation source: fine-focus sealed tube	7962 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.030
ω scans	θmax = 26.4°, θmin = 4.2°
Absorption correction: analytical face-indexed (CrysAlis RED; Oxford Diffraction, 2003)	h = −11→12
Tmin = 0.704, Tmax = 0.893	k = −18→19
14665 measured reflections	l = −19→17

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)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.088	H-atom parameters constrained
S = 1.05	w = 1/[σ^2(Fo^2) + (0.036P)^2 + 2.2497P] where P = (Fo^2 + 2Fc^2)/3
8693 reflections	(Δ/σ)max = 0.001
599 parameters	Δρmax = 0.65 e Å^−3
0 restraints	Δρmin = −0.42 e Å^−3

Special details

Experimental. Mid-IR spectra in the region 4000–400 cm⁻¹ were measured on a Nicolet Nexus 470 F T–IR spectrometer with the resolution 2 cm⁻¹ in KBr pellet.

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
C3	0.8775 (3)	0.3811 (2)	0.3275 (2)	0.0210 (7)
H3A	0.8006	0.3354	0.3103	0.025*
C5	1.0048 (4)	0.5156 (2)	0.3828 (3)	0.0246 (8)
H5A	1.0335	0.5777	0.4099	0.029*
C6	1.0855 (4)	0.4528 (2)	0.3495 (3)	0.0238 (8)
H6A	1.1805	0.4650	0.3500	0.029*
C8	1.1260 (4)	0.2465 (3)	0.0723 (3)	0.0294 (8)
H8A	1.1997	0.2145	0.0785	0.035*
C10	0.9717 (5)	0.3153 (4)	0.0122 (3)	0.0454 (12)
H10A	0.9199	0.3393	−0.0287	0.054*
C11	0.9532 (5)	0.3174 (3)	0.0990 (3)	0.0376 (10)
H11A	0.8850	0.3440	0.1287	0.045*
C13	1.2565 (4)	0.1106 (2)	0.2058 (2)	0.0223 (7)
H13A	1.3319	0.1494	0.2439	0.027*
C15	1.1345 (4)	−0.0055 (3)	0.1028 (3)	0.0255 (8)
H15A	1.1089	−0.0604	0.0576	0.031*
C16	1.0494 (4)	0.0525 (3)	0.1379 (2)	0.0244 (8)
H16A	0.9540	0.0444	0.1209	0.029*
C18	1.1129 (4)	0.2746 (2)	0.4620 (2)	0.0206 (7)
H18A	1.1552	0.3349	0.4727	0.025*
C20	1.0230 (4)	0.1459 (3)	0.4852 (3)	0.0258 (8)
H20A	0.9915	0.1016	0.5137	0.031*
C21	1.0159 (4)	0.1362 (2)	0.3944 (2)	0.0223 (7)
H21A	0.9793	0.0832	0.3487	0.027*
C23	1.4208 (3)	0.3737 (2)	0.3280 (2)	0.0187 (7)
C29	0.7161 (4)	0.1201 (2)	0.1931 (2)	0.0222 (7)
C36	0.4270 (4)	0.1831 (2)	0.4928 (3)	0.0259 (8)
H36A	0.3368	0.1670	0.5023	0.031*
C38	0.6120 (5)	0.2638 (3)	0.4755 (4)	0.0424 (11)
H38A	0.6752	0.3121	0.4704	0.051*
C39	0.6343 (5)	0.1771 (3)	0.4695 (4)	0.0424 (11)
H39A	0.7169	0.1552	0.4595	0.051*
C41	0.2384 (4)	−0.0520 (3)	0.3637 (2)	0.0240 (7)
H41A	0.1889	−0.0186	0.4051	0.029*
C43	0.2860 (4)	−0.1438 (3)	0.2408 (3)	0.0289 (8)
H43A	0.2775	−0.1847	0.1833	0.035*
C44	0.4026 (4)	−0.1112 (3)	0.3019 (3)	0.0274 (8)
H44A	0.4900	−0.1255	0.2927	0.033*
C46	0.7779 (3)	−0.0610 (2)	0.3679 (2)	0.0204 (7)
C53	0.3094 (4)	0.5626 (3)	0.1325 (2)	0.0238 (8)
H53A	0.2326	0.5335	0.0891	0.029*
C55	0.4363 (4)	0.6447 (3)	0.2610 (3)	0.0251 (8)
H55A	0.4638	0.6815	0.3204	0.030*
C56	0.5190 (4)	0.6110 (3)	0.2008 (2)	0.0242 (8)
H56A	0.6152	0.6208	0.2119	0.029*
C58	0.4760 (4)	0.2980 (2)	−0.0169 (3)	0.0267 (8)
H58A	0.4483	0.2827	−0.0799	0.032*
C60	0.5348 (4)	0.2845 (3)	0.1209 (3)	0.0305 (8)
H60A	0.5546	0.2599	0.1703	0.037*
C61	0.5402 (4)	0.3736 (3)	0.1237 (3)	0.0295 (9)
H61A	0.5656	0.4220	0.1761	0.035*
C63	0.8533 (4)	0.5748 (3)	0.1253 (2)	0.0225 (7)
N2	1.0043 (3)	0.36784 (19)	0.31482 (19)	0.0179 (6)
N4	0.8741 (3)	0.4698 (2)	0.3686 (2)	0.0222 (6)
H4A	0.8018	0.4930	0.3832	0.027*
N7	1.0511 (3)	0.2742 (2)	0.1369 (2)	0.0230 (6)
N9	1.0822 (4)	0.2704 (2)	−0.0031 (2)	0.0322 (8)
H9A	1.1175	0.2594	−0.0531	0.039*
N12	1.1276 (3)	0.1264 (2)	0.20360 (19)	0.0187 (6)
N14	1.2650 (3)	0.0315 (2)	0.1461 (2)	0.0235 (6)
H14A	1.3392	0.0083	0.1369	0.028*
N17	1.0716 (3)	0.21757 (19)	0.38050 (19)	0.0174 (6)
N19	1.0854 (3)	0.2333 (2)	0.5272 (2)	0.0232 (6)
H19A	1.1038	0.2575	0.5853	0.028*
N22	1.3201 (3)	0.3220 (2)	0.3043 (2)	0.0249 (6)
N24	1.5450 (3)	0.42621 (19)	0.3500 (2)	0.0192 (6)
N25	1.5360 (3)	0.51067 (19)	0.40017 (19)	0.0172 (6)
N28	0.8172 (3)	0.1717 (2)	0.2232 (2)	0.0266 (7)
N30	0.5914 (3)	0.0705 (2)	0.1641 (2)	0.0289 (7)
N31	0.5969 (3)	−0.0089 (2)	0.1032 (2)	0.0237 (7)
N35	0.5168 (3)	0.12661 (19)	0.4805 (2)	0.0202 (6)
N37	0.4804 (3)	0.2666 (2)	0.4901 (2)	0.0250 (7)
H37A	0.4385	0.3136	0.4965	0.030*
N40	0.3730 (3)	−0.05358 (19)	0.3796 (2)	0.0210 (6)
N42	0.1829 (3)	−0.1045 (2)	0.2806 (2)	0.0239 (6)
H42A	0.0975	−0.1122	0.2564	0.029*
N45	0.7091 (3)	−0.0315 (2)	0.4198 (2)	0.0250 (6)
N47	0.8735 (3)	−0.0889 (2)	0.31643 (19)	0.0229 (6)
N48	0.8156 (3)	−0.1486 (2)	0.2352 (2)	0.0205 (6)
N52	0.4389 (3)	0.5595 (2)	0.11962 (19)	0.0196 (6)
N54	0.3036 (3)	0.6138 (2)	0.2173 (2)	0.0264 (7)
H54A	0.2295	0.6250	0.2399	0.032*
N57	0.5018 (3)	0.38217 (19)	0.03616 (19)	0.0193 (6)
N59	0.4948 (3)	0.2372 (2)	0.0318 (2)	0.0289 (7)
H59A	0.4836	0.1787	0.0105	0.035*
N62	0.7522 (3)	0.5435 (2)	0.0755 (2)	0.0289 (7)
N64	0.9789 (3)	0.6081 (2)	0.1735 (2)	0.0243 (7)
N65	0.9724 (3)	0.6576 (2)	0.25814 (19)	0.0198 (6)
O26	1.4257 (2)	0.53353 (18)	0.42230 (18)	0.0238 (5)
O27	1.6474 (2)	0.56594 (17)	0.42459 (18)	0.0239 (5)
O32	0.7060 (3)	−0.03177 (19)	0.0787 (2)	0.0322 (7)
O33	0.4835 (3)	−0.05920 (18)	0.0716 (2)	0.0292 (6)
O49	0.9007 (3)	−0.17810 (19)	0.18511 (17)	0.0267 (6)
O50	0.6903 (3)	−0.1705 (2)	0.21388 (19)	0.0338 (6)
O66	1.0844 (3)	0.69203 (19)	0.30857 (17)	0.0251 (6)
O67	0.8585 (3)	0.66743 (19)	0.28479 (17)	0.0241 (6)
Cu1	1.06526 (4)	0.24702 (3)	0.25921 (3)	0.01848 (10)
Cu34	0.5000	0.0000	0.5000	0.01926 (13)
Cu51	0.5000	0.5000	0.0000	0.01804 (13)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C3	0.0163 (16)	0.0213 (17)	0.0224 (18)	−0.0008 (13)	0.0047 (13)	0.0010 (14)
C5	0.0248 (18)	0.0166 (17)	0.032 (2)	0.0013 (14)	0.0039 (15)	0.0058 (15)
C6	0.0188 (17)	0.0210 (18)	0.032 (2)	0.0030 (14)	0.0089 (15)	0.0061 (15)
C8	0.032 (2)	0.037 (2)	0.0217 (19)	0.0085 (17)	0.0103 (16)	0.0080 (16)
C10	0.048 (3)	0.068 (3)	0.030 (2)	0.020 (2)	0.005 (2)	0.026 (2)
C11	0.040 (2)	0.054 (3)	0.030 (2)	0.023 (2)	0.0139 (18)	0.021 (2)
C13	0.0225 (17)	0.0171 (17)	0.0265 (18)	0.0022 (14)	0.0053 (14)	0.0038 (14)
C15	0.0240 (18)	0.0214 (18)	0.0272 (19)	0.0011 (14)	0.0036 (15)	0.0005 (15)
C16	0.0194 (17)	0.0258 (19)	0.0239 (18)	0.0021 (14)	0.0016 (14)	0.0000 (15)
C18	0.0230 (17)	0.0202 (17)	0.0155 (16)	0.0042 (14)	0.0008 (13)	−0.0004 (13)
C20	0.0223 (18)	0.029 (2)	0.0286 (19)	0.0023 (15)	0.0042 (15)	0.0133 (16)
C21	0.0230 (17)	0.0196 (17)	0.0237 (18)	−0.0008 (14)	0.0015 (14)	0.0076 (14)
C23	0.0208 (17)	0.0171 (16)	0.0210 (17)	0.0078 (14)	0.0076 (14)	0.0059 (13)
C29	0.0225 (18)	0.0194 (17)	0.0238 (18)	0.0081 (14)	0.0016 (14)	0.0025 (14)
C36	0.0253 (18)	0.0203 (18)	0.035 (2)	0.0061 (14)	0.0044 (16)	0.0107 (16)
C38	0.037 (2)	0.025 (2)	0.073 (3)	0.0057 (18)	0.019 (2)	0.022 (2)
C39	0.035 (2)	0.028 (2)	0.075 (3)	0.0105 (18)	0.029 (2)	0.022 (2)
C41	0.0209 (17)	0.0295 (19)	0.0227 (18)	0.0061 (14)	0.0060 (14)	0.0064 (15)
C43	0.0282 (19)	0.030 (2)	0.0250 (19)	0.0072 (16)	0.0042 (16)	−0.0009 (16)
C44	0.0226 (18)	0.030 (2)	0.0253 (19)	0.0067 (15)	0.0013 (15)	−0.0005 (15)
C46	0.0182 (16)	0.0196 (17)	0.0228 (18)	0.0016 (13)	0.0024 (14)	0.0054 (14)
C53	0.0216 (18)	0.0291 (19)	0.0206 (18)	0.0068 (15)	0.0043 (14)	0.0046 (15)
C55	0.0294 (19)	0.0249 (19)	0.0210 (18)	0.0085 (15)	0.0073 (15)	0.0022 (14)
C56	0.0202 (17)	0.0286 (19)	0.0225 (18)	0.0023 (15)	0.0030 (14)	0.0048 (15)
C58	0.034 (2)	0.0199 (18)	0.0234 (18)	0.0026 (15)	0.0044 (16)	0.0010 (15)
C60	0.043 (2)	0.0243 (19)	0.027 (2)	0.0120 (17)	0.0050 (17)	0.0080 (15)
C61	0.050 (3)	0.0209 (19)	0.0166 (18)	0.0077 (17)	0.0050 (17)	0.0021 (14)
C63	0.0250 (18)	0.0264 (19)	0.0177 (17)	0.0077 (15)	0.0106 (15)	0.0037 (14)
N2	0.0179 (13)	0.0182 (14)	0.0174 (14)	0.0039 (11)	0.0044 (11)	0.0032 (11)
N4	0.0180 (14)	0.0207 (15)	0.0282 (16)	0.0079 (12)	0.0049 (12)	0.0036 (13)
N7	0.0250 (16)	0.0256 (16)	0.0197 (15)	0.0040 (12)	0.0074 (12)	0.0067 (12)
N9	0.045 (2)	0.0373 (19)	0.0146 (15)	0.0048 (16)	0.0104 (14)	0.0056 (14)
N12	0.0162 (13)	0.0216 (15)	0.0171 (14)	0.0032 (11)	0.0016 (11)	0.0034 (12)
N14	0.0207 (15)	0.0214 (15)	0.0287 (17)	0.0067 (12)	0.0085 (13)	0.0034 (13)
N17	0.0139 (13)	0.0180 (14)	0.0199 (14)	0.0016 (11)	0.0026 (11)	0.0050 (11)
N19	0.0267 (16)	0.0325 (17)	0.0121 (14)	0.0102 (13)	0.0033 (12)	0.0062 (12)
N22	0.0240 (14)	0.0206 (15)	0.0271 (16)	0.0013 (12)	0.0052 (12)	0.0010 (12)
N24	0.0181 (14)	0.0151 (14)	0.0215 (15)	0.0026 (11)	0.0024 (11)	−0.0001 (11)
N25	0.0140 (13)	0.0173 (14)	0.0196 (14)	0.0027 (11)	0.0010 (11)	0.0041 (11)
N28	0.0225 (15)	0.0264 (17)	0.0258 (16)	0.0028 (13)	−0.0013 (13)	−0.0002 (13)
N30	0.0198 (15)	0.0223 (16)	0.0384 (19)	0.0053 (13)	0.0072 (14)	−0.0057 (14)
N31	0.0199 (15)	0.0187 (15)	0.0305 (17)	0.0029 (12)	0.0047 (13)	0.0026 (13)
N35	0.0240 (15)	0.0140 (14)	0.0223 (15)	0.0045 (12)	0.0023 (12)	0.0040 (11)
N37	0.0362 (18)	0.0147 (15)	0.0246 (16)	0.0075 (13)	0.0012 (13)	0.0061 (12)
N40	0.0213 (14)	0.0172 (14)	0.0233 (15)	0.0027 (11)	0.0027 (12)	0.0035 (12)
N42	0.0165 (13)	0.0306 (17)	0.0241 (16)	0.0019 (12)	0.0000 (12)	0.0083 (13)
N45	0.0226 (15)	0.0244 (16)	0.0265 (16)	0.0030 (13)	0.0049 (13)	0.0037 (13)
N47	0.0178 (14)	0.0273 (16)	0.0185 (15)	0.0025 (12)	0.0023 (12)	−0.0028 (12)
N48	0.0167 (13)	0.0226 (15)	0.0227 (15)	0.0036 (11)	0.0040 (11)	0.0062 (12)
N52	0.0214 (14)	0.0213 (15)	0.0161 (14)	0.0052 (12)	0.0039 (12)	0.0035 (12)
N54	0.0219 (15)	0.0379 (19)	0.0208 (16)	0.0113 (14)	0.0104 (13)	0.0036 (14)
N57	0.0239 (15)	0.0190 (15)	0.0155 (14)	0.0045 (12)	0.0038 (11)	0.0048 (11)
N59	0.0337 (18)	0.0168 (15)	0.0371 (19)	0.0069 (13)	0.0096 (15)	0.0055 (14)
N62	0.0255 (17)	0.0351 (19)	0.0203 (16)	0.0025 (14)	0.0014 (14)	−0.0017 (14)
N64	0.0193 (15)	0.0327 (17)	0.0157 (15)	0.0044 (13)	0.0012 (12)	−0.0032 (13)
N65	0.0187 (14)	0.0241 (15)	0.0175 (15)	0.0031 (12)	0.0037 (12)	0.0068 (12)
O26	0.0170 (12)	0.0225 (13)	0.0320 (15)	0.0050 (10)	0.0069 (10)	0.0047 (11)
O27	0.0159 (12)	0.0168 (12)	0.0340 (14)	−0.0022 (9)	0.0019 (10)	0.0002 (10)
O32	0.0197 (13)	0.0303 (15)	0.0412 (16)	0.0065 (11)	0.0096 (12)	−0.0043 (13)
O33	0.0193 (14)	0.0186 (14)	0.0401 (17)	−0.0022 (11)	0.0006 (12)	−0.0060 (11)
O49	0.0243 (13)	0.0354 (15)	0.0204 (13)	0.0088 (11)	0.0107 (11)	0.0023 (11)
O50	0.0198 (13)	0.0439 (17)	0.0280 (14)	0.0009 (12)	0.0001 (11)	−0.0051 (12)
O66	0.0172 (12)	0.0328 (15)	0.0215 (13)	0.0015 (11)	0.0024 (10)	0.0011 (11)
O67	0.0177 (12)	0.0353 (15)	0.0202 (13)	0.0071 (11)	0.0079 (10)	0.0050 (11)
Cu1	0.02147 (19)	0.0191 (2)	0.0157 (2)	0.00730 (16)	0.00568 (15)	0.00282 (15)
Cu34	0.0194 (3)	0.0125 (3)	0.0244 (3)	0.0035 (2)	−0.0006 (3)	0.0035 (2)
Cu51	0.0222 (3)	0.0165 (3)	0.0152 (3)	0.0056 (2)	0.0049 (2)	0.0015 (2)

Geometric parameters (Å, º)

C3—N2	1.315 (4)	C55—C56	1.346 (5)
C3—N4	1.351 (4)	C55—N54	1.367 (5)
C3—H3A	0.9300	C55—H55A	0.9300
C5—N4	1.356 (5)	C56—N52	1.385 (5)
C5—C6	1.357 (5)	C56—H56A	0.9300
C5—H5A	0.9300	C58—N57	1.316 (4)
C6—N2	1.384 (4)	C58—N59	1.337 (5)
C6—H6A	0.9300	C58—H58A	0.9300
C8—N7	1.315 (5)	C60—C61	1.344 (5)
C8—N9	1.328 (5)	C60—N59	1.359 (5)
C8—H8A	0.9300	C60—H60A	0.9300
C10—C11	1.348 (6)	C61—N57	1.385 (4)
C10—N9	1.366 (6)	C61—H61A	0.9300
C10—H10A	0.9300	C63—N62	1.152 (5)
C11—N7	1.381 (5)	C63—N62	1.152 (5)
C11—H11A	0.9300	C63—N64	1.335 (5)
C13—N12	1.317 (4)	N2—Cu1	2.022 (3)
C13—N14	1.340 (5)	N4—H4A	0.8600
C13—H13A	0.9300	N7—Cu1	1.998 (3)
C15—C16	1.349 (5)	N9—H9A	0.8600
C15—N14	1.360 (5)	N12—Cu1	2.026 (3)
C15—H15A	0.9300	N14—H14A	0.8600
C16—N12	1.388 (5)	N17—Cu1	2.002 (3)
C16—H16A	0.9300	N19—H19A	0.8600
C18—N17	1.317 (4)	N24—N25	1.346 (4)
C18—N19	1.335 (5)	N25—O26	1.237 (3)
C18—H18A	0.9300	N25—O27	1.258 (4)
C20—C21	1.348 (5)	N30—N31	1.344 (4)
C20—N19	1.364 (5)	N31—O32	1.238 (4)
C20—H20A	0.9300	N31—O33	1.247 (4)
C21—N17	1.370 (4)	N35—Cu34	2.015 (3)
C21—H21A	0.9300	N37—H37A	0.8600
C23—N22	1.151 (4)	N40—Cu34	2.021 (3)
C23—N22	1.151 (4)	N42—H42A	0.8600
C23—N24	1.337 (4)	N47—N48	1.359 (4)
C29—N28	1.161 (5)	N48—O50	1.222 (4)
C29—N28	1.161 (5)	N48—O49	1.247 (4)
C29—N30	1.328 (5)	N52—Cu51	2.020 (3)
C36—N35	1.304 (5)	N54—H54A	0.8600
C36—N37	1.331 (5)	N57—Cu51	2.005 (3)
C36—H36A	0.9300	N59—H59A	0.8600
C38—N37	1.343 (5)	N64—N65	1.339 (4)
C38—C39	1.349 (6)	N65—O66	1.245 (4)
C38—H38A	0.9300	Cu1—N2	2.022 (3)
C39—N35	1.360 (5)	Cu1—N7	1.998 (3)
C39—H39A	0.9300	Cu1—N12	2.026 (3)
C41—N40	1.324 (4)	Cu1—N17	2.002 (3)
C41—N42	1.336 (5)	Cu1—N22	2.570 (3)
C41—H41A	0.9300	Cu1—N28	2.509 (3)
C43—C44	1.350 (5)	Cu34—N35	2.015 (3)
C43—N42	1.366 (5)	Cu34—N40	2.021 (3)
C43—H43A	0.9300	Cu34—N45	2.548 (4)
C44—N40	1.375 (5)	Cu51—N52	2.020 (3)
C44—H44A	0.9300	Cu51—N57	2.005 (3)
C46—N45	1.144 (5)	Cu51—N62	2.549 (3)
C46—N45	1.144 (5)	N22—C23	1.151 (4)
C46—N47	1.335 (4)	N28—C29	1.161 (5)
C53—N52	1.316 (4)	N45—C46	1.144 (5)
C53—N54	1.348 (5)	N62—C63	1.152 (5)
C53—H53A	0.9300
N2—C3—N4	110.9 (3)	C13—N12—Cu1	126.2 (2)
N2—C3—H3A	124.5	C16—N12—Cu1	126.5 (2)
N4—C3—H3A	124.5	C13—N14—C15	107.4 (3)
N4—C5—C6	106.3 (3)	C13—N14—H14A	126.3
N4—C5—H5A	126.9	C15—N14—H14A	126.3
C6—C5—H5A	126.9	C18—N17—C21	106.8 (3)
C5—C6—N2	109.4 (3)	C18—N17—Cu1	127.2 (2)
C5—C6—H6A	125.3	C21—N17—Cu1	125.5 (2)
N2—C6—H6A	125.3	C18—N19—C20	107.9 (3)
N7—C8—N9	111.0 (3)	C18—N19—H19A	126.1
N7—C8—H8A	124.5	C20—N19—H19A	126.1
N9—C8—H8A	124.5	C23—N24—N25	110.8 (3)
C11—C10—N9	105.6 (4)	O26—N25—O27	121.1 (3)
C11—C10—H10A	127.2	O26—N25—N24	122.8 (3)
N9—C10—H10A	127.2	O27—N25—N24	116.1 (3)
C10—C11—N7	109.5 (4)	C29—N30—N31	111.5 (3)
C10—C11—H11A	125.2	O32—N31—O33	121.2 (3)
N7—C11—H11A	125.2	O32—N31—N30	123.2 (3)
N12—C13—N14	111.3 (3)	O33—N31—N30	115.6 (3)
N12—C13—H13A	124.4	C36—N35—C39	105.4 (3)
N14—C13—H13A	124.4	C36—N35—Cu34	127.2 (3)
C16—C15—N14	106.9 (3)	C39—N35—Cu34	126.3 (3)
C16—C15—H15A	126.5	C36—N37—C38	107.2 (3)
N14—C15—H15A	126.5	C36—N37—H37A	126.4
C15—C16—N12	108.9 (3)	C38—N37—H37A	126.4
C15—C16—H16A	125.6	C41—N40—C44	105.3 (3)
N12—C16—H16A	125.6	C41—N40—Cu34	126.7 (2)
N17—C18—N19	110.2 (3)	C44—N40—Cu34	127.3 (2)
N17—C18—H18A	124.9	C41—N42—C43	107.8 (3)
N19—C18—H18A	124.9	C41—N42—H42A	126.1
C21—C20—N19	106.5 (3)	C43—N42—H42A	126.1
C21—C20—H20A	126.7	C46—N47—N48	111.9 (3)
N19—C20—H20A	126.7	O50—N48—O49	123.6 (3)
C20—C21—N17	108.7 (3)	O50—N48—N47	122.0 (3)
C20—C21—H21A	125.7	O49—N48—N47	114.4 (3)
N17—C21—H21A	125.7	C53—N52—C56	105.9 (3)
N22—C23—N24	173.4 (4)	C53—N52—Cu51	125.0 (2)
N22—C23—N24	173.4 (4)	C56—N52—Cu51	128.9 (2)
N28—C29—N30	172.0 (4)	C53—N54—C55	108.0 (3)
N28—C29—N30	172.0 (4)	C53—N54—H54A	126.0
N35—C36—N37	111.6 (3)	C55—N54—H54A	126.0
N35—C36—H36A	124.2	C58—N57—C61	105.4 (3)
N37—C36—H36A	124.2	C58—N57—Cu51	128.4 (2)
N37—C38—C39	106.5 (4)	C61—N57—Cu51	126.0 (2)
N37—C38—H38A	126.8	C58—N59—C60	107.8 (3)
C39—C38—H38A	126.8	C58—N59—H59A	126.1
C38—C39—N35	109.3 (4)	C60—N59—H59A	126.1
C38—C39—H39A	125.3	C63—N64—N65	112.0 (3)
N35—C39—H39A	125.3	O66—N65—O67	122.1 (3)
N40—C41—N42	111.1 (3)	O66—N65—N64	116.9 (3)
N40—C41—H41A	124.5	O67—N65—N64	120.9 (3)
N42—C41—H41A	124.5	N7—Cu1—N17	177.74 (12)
C44—C43—N42	105.9 (3)	N7—Cu1—N2	90.47 (12)
C44—C43—H43A	127.0	N17—Cu1—N2	89.47 (11)
N42—C43—H43A	127.0	N7—Cu1—N12	89.49 (12)
C43—C44—N40	109.9 (3)	N17—Cu1—N12	90.58 (11)
C43—C44—H44A	125.1	N2—Cu1—N12	179.64 (12)
N40—C44—H44A	125.1	N35^i—Cu34—N35	180.0
N45—C46—N47	171.8 (4)	N35^i—Cu34—N40^i	91.91 (11)
N45—C46—N47	171.8 (4)	N35—Cu34—N40^i	88.09 (11)
N52—C53—N54	110.5 (3)	N35^i—Cu34—N40	88.09 (11)
N52—C53—H53A	124.8	N35—Cu34—N40	91.91 (11)
N54—C53—H53A	124.8	N40^i—Cu34—N40	179.999 (1)
C56—C55—N54	106.0 (3)	N57^ii—Cu51—N57	180.00 (16)
C56—C55—H55A	127.0	N57^ii—Cu51—N52	89.23 (11)
N54—C55—H55A	127.0	N57—Cu51—N52	90.77 (11)
C55—C56—N52	109.6 (3)	N57^ii—Cu51—N52^ii	90.77 (11)
C55—C56—H56A	125.2	N57—Cu51—N52^ii	89.23 (11)
N52—C56—H56A	125.2	N52—Cu51—N52^ii	180.00 (9)
N57—C58—N59	111.0 (3)	N2—Cu1—N7	90.5 (1)
N57—C58—H58A	124.5	N2—Cu1—N12	179.6 (1)
N59—C58—H58A	124.5	N2—Cu1—N17	89.5 (1)
C61—C60—N59	106.5 (3)	N7—Cu1—N12	89.5 (1)
C61—C60—H60A	126.7	N7—Cu1—N17	177.7 (1)
N59—C60—H60A	126.7	N12—Cu1—N17	90.6 (1)
C60—C61—N57	109.2 (3)	N2—Cu1—N22	90.3 (1)
C60—C61—H61A	125.4	N2—Cu1—N28	89.7 (1)
N57—C61—H61A	125.4	N7—Cu1—N22	92.9 (1)
N62—C63—N64	172.5 (4)	N7—Cu1—N28	90.2 (1)
N62—C63—N64	172.5 (4)	N12—Cu1—N22	89.3 (1)
C3—N2—C6	105.6 (3)	N12—Cu1—N28	90.7 (1)
C3—N2—Cu1	126.4 (2)	N17—Cu1—N22	89.4 (1)
C6—N2—Cu1	128.0 (2)	N17—Cu1—N28	87.6 (1)
C3—N4—C5	107.9 (3)	N22—Cu1—N28	177.0 (1)
C3—N4—H4A	126.1	N35^i—Cu34—N40	88.1 (1)
C5—N4—H4A	126.1	N35—Cu34—N40	91.9 (1)
C8—N7—C11	105.5 (3)	N35—Cu34—N45	90.6 (1)
C8—N7—Cu1	126.6 (3)	N40—Cu34—N45	90.1 (1)
C11—N7—Cu1	127.6 (3)	N35^i—Cu34—N40^i	91.9 (1)
C8—N9—C10	108.3 (3)	N52—Cu51—N57	90.8 (1)
C8—N9—H9A	125.8	N52—Cu51—N62	90.1 (1)
C10—N9—H9A	125.8	N57—Cu51—N62	87.0 (1)
C13—N12—C16	105.5 (3)	N57^ii—Cu51—N52	89.23 (12)
N4—C5—C6—N2	−0.1 (4)	C46—N47—N48—O50	1.6 (5)
N9—C10—C11—N7	−0.1 (6)	C46—N47—N48—O49	−178.8 (3)
N14—C15—C16—N12	0.1 (4)	N54—C53—N52—C56	0.4 (4)
N19—C20—C21—N17	−0.9 (4)	N54—C53—N52—Cu51	−174.7 (2)
N37—C38—C39—N35	−0.1 (6)	C55—C56—N52—C53	−0.3 (4)
N42—C43—C44—N40	1.1 (4)	C55—C56—N52—Cu51	174.4 (2)
N54—C55—C56—N52	0.2 (4)	N52—C53—N54—C55	−0.3 (4)
N59—C60—C61—N57	0.7 (5)	C56—C55—N54—C53	0.0 (4)
N4—C3—N2—C6	−0.2 (4)	N59—C58—N57—C61	0.4 (4)
N4—C3—N2—Cu1	178.3 (2)	N59—C58—N57—Cu51	176.6 (2)
C5—C6—N2—C3	0.2 (4)	C60—C61—N57—C58	−0.7 (4)
C5—C6—N2—Cu1	−178.3 (2)	C60—C61—N57—Cu51	−177.0 (3)
N2—C3—N4—C5	0.2 (4)	N57—C58—N59—C60	0.0 (4)
C6—C5—N4—C3	0.0 (4)	C61—C60—N59—C58	−0.4 (5)
N9—C8—N7—C11	0.6 (5)	C63—N64—N65—O66	−179.7 (3)
N9—C8—N7—Cu1	174.8 (3)	C63—N64—N65—O67	0.9 (5)
C10—C11—N7—C8	−0.3 (5)	C8—N7—Cu1—N2	149.6 (3)
C10—C11—N7—Cu1	−174.4 (3)	C11—N7—Cu1—N2	−37.5 (4)
N7—C8—N9—C10	−0.7 (5)	C8—N7—Cu1—N12	−30.1 (3)
C11—C10—N9—C8	0.5 (5)	C11—N7—Cu1—N12	142.9 (4)
N14—C13—N12—C16	−0.2 (4)	C18—N17—Cu1—N2	−37.9 (3)
N14—C13—N12—Cu1	−165.9 (2)	C21—N17—Cu1—N2	132.7 (3)
C15—C16—N12—C13	0.1 (4)	C18—N17—Cu1—N12	141.7 (3)
C15—C16—N12—Cu1	165.7 (3)	C21—N17—Cu1—N12	−47.6 (3)
N12—C13—N14—C15	0.3 (4)	C3—N2—Cu1—N7	95.9 (3)
C16—C15—N14—C13	−0.2 (4)	C6—N2—Cu1—N7	−85.9 (3)
N19—C18—N17—C21	−0.3 (4)	C3—N2—Cu1—N17	−81.8 (3)
N19—C18—N17—Cu1	171.8 (2)	C6—N2—Cu1—N17	96.3 (3)
C20—C21—N17—C18	0.8 (4)	C13—N12—Cu1—N7	97.0 (3)
C20—C21—N17—Cu1	−171.5 (2)	C16—N12—Cu1—N7	−65.8 (3)
N17—C18—N19—C20	−0.3 (4)	C13—N12—Cu1—N17	−85.3 (3)
C21—C20—N19—C18	0.7 (4)	C16—N12—Cu1—N17	112.0 (3)
C23—N24—N25—O26	0.7 (4)	C36—N35—Cu34—N40^i	−101.4 (3)
C23—N24—N25—O27	−180.0 (3)	C39—N35—Cu34—N40^i	64.6 (4)
C29—N30—N31—O32	0.6 (5)	C36—N35—Cu34—N40	78.6 (3)
C29—N30—N31—O33	−179.2 (3)	C39—N35—Cu34—N40	−115.4 (4)
N37—C36—N35—C39	0.2 (5)	C41—N40—Cu34—N35^i	99.0 (3)
N37—C36—N35—Cu34	168.5 (2)	C44—N40—Cu34—N35^i	−69.8 (3)
C38—C39—N35—C36	−0.1 (5)	C41—N40—Cu34—N35	−81.0 (3)
C38—C39—N35—Cu34	−168.5 (3)	C44—N40—Cu34—N35	110.2 (3)
N35—C36—N37—C38	−0.2 (5)	C58—N57—Cu51—N52	148.6 (3)
C39—C38—N37—C36	0.1 (5)	C61—N57—Cu51—N52	−35.9 (3)
N42—C41—N40—C44	−0.5 (4)	C58—N57—Cu51—N52^ii	−31.4 (3)
N42—C41—N40—Cu34	−171.3 (2)	C61—N57—Cu51—N52^ii	144.1 (3)
C43—C44—N40—C41	−0.4 (4)	C53—N52—Cu51—N57^ii	87.6 (3)
C43—C44—N40—Cu34	170.3 (3)	C56—N52—Cu51—N57^ii	−86.3 (3)
N40—C41—N42—C43	1.2 (4)	C53—N52—Cu51—N57	−92.4 (3)
C44—C43—N42—C41	−1.4 (4)	C56—N52—Cu51—N57	93.7 (3)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N19—H19A···O67^iii	0.86	2.00	2.848 (4)	171
N59—H59A···O33^iv	0.86	2.03	2.832 (4)	155
N4—H4A···O27^v	0.86	2.06	2.910 (4)	172
N14—H14A···O33^vi	0.86	2.06	2.886 (5)	161
N9—H9A···O49^vii	0.86	2.06	2.819 (4)	146
N54—H54A···O66^v	0.86	2.09	2.918 (4)	163

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