Crystal structure of poly[N,N-diethyl-2-hy-droxy-ethan-1-aminium [μ3-cyanido-κ(3) C:C:N-di-μ-cyanido-κ(4) C:N-dicuprate(I)]].

In the title compound, {(C6H16NO)[Cu2(CN)3]} n , the cyanide groups link the Cu(I) atoms into an open three-dimensional anionic network, with the mol-ecular formula Cu2(CN)3 (-). One Cu(I) atom is tetra-hedrally bound to four CN groups, and the other Cu(I) atom is bonded to three CN groups in an approximate trigonal-planar coordination. The tetra-hedrally coordinated Cu(I) atoms are linked into centrosymmetric dimers by the C atoms of two end-on bridging CN groups which bring the Cu(I) atoms into close contact at 2.5171 (7) Å. Two of the cyanide groups bonded to the Cu(I) atoms with trigonal-planar surrounding link the dimeric units into columns along the a axis, and the third links the columns together to form the network. The N,N-di-ethyl-ethano-lamine mol-ecules used in the synthesis have become protonated at the N atoms and are situated in cavities in the network, providing charge neutrality, with no covalent inter-actions between the cations and the anionic network.

Chemical context

This structure determination was undertaken as part of our ongoing study of mixed-valn class="Chemical">ence copper cyanide complexes, with the goal of directed synthesis of new polymeric structures. The intention is to build amine-coordinated CuII atoms into CuI cyanide-bridged networks by having two or more CN groups coordinating to the CuII atoms as well as the amine N atoms. This has proved somewhat elusive, however. For example, in the classic mixed-valence complex Cu3(CN)4en2·H2O where en is ethyl­enedi­amine (Williams et al., 1972 ▸), there is a three-dimensional CuI 2(CN)4 2− network, with coordinated CuII cations situated in cavities with no covalent links to the network. One case where a CN-linked network incorporates both CuI and CuII is that of Cu3(CN)4oen2, where oen is ethano­lamine (Corfield et al., 1991 ▸; Jin et al., 2006 ▸). Here, there are two CN groups coordinating in a trans configuration to CuII atoms (the resulting coordination polyhedron is distorted octa­hedral), with incorporation of CuII into the two-dimensional network. This led us to attempt a similar synthesis involving the substituted ligand dieth­yl(2-hy­droxy­eth­yl)amine, or N,N-di­ethyl­ethano­lamine, et2oen. Instead of the expected blue or black mixed-valence crystals, pale-yellow crystals of the title compound, (et2oenH)[Cu2(CN)3], were formed, in which the amine base has been protonated and does not coordinate to any Cu atom.

Structural commentary

The title compound crystallizes as a three-dimensional anionic network, [n class="Chemical">Cu2(CN)3]−, with the cationic protonated base occupying cavities in the network. Fig. 1 ▸ shows the structures for the asymmetric unit of the network and for the cation. The crystal structure may be considered to be built up from centrosymmetric Cu2(CN)6 dimers linked together by Cu(CN)3 units that are in rough trigonal–planar coordination (Fig. 2 ▸). The dimeric units are held together by two μ3-CN groups bonded to the dimer Cu2 atoms via the cyanide C atoms. There is a short Cu2⋯Cu2 distance of 2.5171 (7) Å, similar to the distance in copper metal, 2.56 Å. While there is undoubtedly some form of inter­action between the Cu2 atoms, the stereochemistry about the metal is easier to understand if the Cu⋯Cu contacts are not considered. Then the CuI atoms in the dimers are seen as bonded tetra­hedrally to four cyanide groups, two pointing away from the dimer center, and the other two bridging the two CuI atoms. Cu—C distances to the C atom of the bridging CN group are unequal, at 2.022 (3) and 2.221 (3) Å. Angles at the CuI atoms vary from 103.87 (11) to 118.03 (12) °; angles at the trigonally coordinated Cu1 atom vary from 110.73 (11) to 124.64 (11) °, and the Cu1 atom is 0.088 (2) Å from the trigonal plane through its bonded atoms, N1, C2, and N3. Selected inter­atomic distances are given in Table 1 ▸.

Figure 1

The asymmetric unit of the anionic network and of the guest cation for the title compound. Ellipsoids are drawn at the 40% probability level. Arbitrary temperature factors are used to show the H atoms, except for H13, which was refined.

Figure 2

Schematic representation of the centrosymmetric Cu dimer component in the network and the trigonal Cu component.

Table 1

Selected bond lengths (Å)

Cu1—C2	1.892 (3)	Cu2—C3ii	2.022 (3)
Cu1—N1	1.946 (3)	Cu2—C3iii	2.221 (3)
Cu1—N3	1.945 (2)	N1—C1	1.151 (4)
Cu2—C1	1.944 (3)	N2—C2	1.141 (4)
Cu2—N2i	1.986 (2)	N3—C3	1.135 (4)

Symmetry codes: (i) ; (ii) ; (iii) .

The cation forms a roughly spherical shape. There may be an intra­molecular hydrogen bond between the N—H bond and the hydroxyl O atom. Possible disordering in the cation is discussed below. We were not able to locate the hydroxyl H atom. The hydroxyl O atom is 2.907 (4) Å from Cu1, lying above the trigonal coordination plane in an approximately axial position. We do not consider the O atom bonded to Cu1, however.

We inter­pret the structure as a CuI complex, not the mixed-valn class="Chemical">ence compound that was expected. In support of this, we cite the pale-yellow color of the compound, and also the silence in the electron spin resonance (esr) measurement (Bender, 2015 ▸). This inter­pretation requires the amine base to be protonated, for charge balance. There is indeed very clear evidence for protonation of the base N atom in the difference Fourier maps and in successful refinement of this as an unrestrained H atom. The syntheses were carried out at an initial pH of 12.4, higher than the pKa of the conjugate acid of the ethano­lamine base, which we measured by titration at 9.9–10.2, depending on the ionic strength. The protonated base at this pH would be a minor component of the mixture, evidently selected by the need for charge balance as the solid polymer crystallizes.

CuI framework structures with inter­calated nitro­gn class="Chemical">en-base cations are well known [see, for example: Liu et al. (2005 ▸); Qin et al. (2011 ▸)]. Jian et al. (2012 ▸) describe a mixed-valence complex, {CuIICuI(μ-CN)3}, which appears to be closely related to the present structure: it has similar unit-cell dimensions, the same space group, the same color, and the same CuCN network topology, with Cu positions close to those found here. These authors report a tri­ethyl­amine solvent mol­ecule in the network cavities. In light of the present work, we suggest that the tri­ethyl­amine mol­ecules in Jian et al. (2012 ▸) might be protonated. Their complex would in that case be a CuI anionic network complex similar to that reported here, rather than the mixed-valence complex they report.

Supra­molecular features

The packing arrangement in the unit cell is shown in a projection down the a axis in Fig. 3 ▸, and down the c axis in Fig. 4 ▸. Atom n class="Chemical">Cu1 is trigonally coordinated by three CN groups, C1≡N1, C2≡N2, and C3≡N3. C1≡N1 also bonds with Cu2, one of the dimer Cu atoms, while C3≡N3 coordinates to Cu2 atoms in both a dimer at (x, y, z) and at (x + 1, y, z), thus linking the dimers into a column along the a axis. C2≡N2 forms a bridge to a Cu2 dimer atom related by the n glide plane, linking the columns into a three-dimensional network. Topology around Cu1 involves one 12-membered ring and two 18-membered rings.

Figure 3

Projection of the structure down the a axis.

Figure 4

Projection of the structure down the c axis, showing the columns along a. The guest cation at (x,y,z) is shown, almost eclipsed by a {CuCNCu} chain.

There is a short contact of 3.130 (4) Å between the n class="Chemical">amine N13 and cyanide N1 atom, with H13⋯N1 = 2.35 Å and an angle N13—H13⋯N1 = 143.1°. In addition, the O10⋯N3 distance is 3.185 (5) Å. The inter­actions implied by these parameters may partially explain the overall ordering found for the CN orientations, as well as the distortions from linear geometry at N1 and N3, with Cu1—N1—C1 = 167.5 (3)° and Cu1—N3—C3 = 170.0 (3)°.

The cation hydroxide groups approach close to one another across the center of symmetry at (, 0, ), with O10⋯O10(1 − x, −y, 1 − z) = 2.964 (6) Å. These hydroxide groups are discussed further in the Refinement section.

Database survey

Searches of the Cambridge Structure Database (CSD, Version 5.35; Groom et al., 2016 ▸) yielded 35 structures containing the Cu(Cn class="Chemical">N)2Cu fragment with two CN groups bridging the two Cu atoms via the C atom. To this list we added the structures of inorganic compounds CuCN·NH3 (Cromer et al., 1965 ▸), which contains the first example determined for this unit, and [CuCN]3·H2O (Kildea et al., 1985 ▸). Cu⋯Cu distances averaged 2.53 Å, with a range of 2.31–2.69 Å. The corresponding distance in the present work is 2.5171 (7) Å, close to the observed mean. The Cu—C distances to the bridging C atom of the CN group are almost always significantly different. The shorter distance averages 2.00 Å with a limited range of 1.90–2.13 Å. The longer one ranges from 2.10 to 2.52 Å, with an average of 2.25 Å. The Cu—C distances of 2.022 (3) and 2.221 (3) Å in the present work again fall very close to these averages. There is a rough correlation between the Cu⋯Cu distance and the longer Cu—C distance, as noted by Stocker et al. (1999 ▸).

Synthesis and crystallization

The compound studied was synthesized as follows: CuCN (23 mmol) and n class="Chemical">NaCN (39 mmol) were stirred in 8 ml of water until all solids dissolved. 40 mmol of N,N-(di­ethyl­amino)­ethanol in 6 ml of water were added. The solution turned orange and slow evaporation yielded yellow crystals after several days (a green powder was also obtained in some preparations). We also prepared the compound by reduction of CuII: 2 mmol CuSO4·5H2O and 40 mmol N,N-(di­ethyl­amino)­ethanol were dissolved in 15 ml of water, and 5 mmol of NaCN in 10 ml water were added. Needle-like crystals up to 2 mm long were yielded through slow evaporation.

Infra-red spectra obtained with both a Nicolet iS50 FT–IR and a Buck 550 machine showed three bands in the Cn class="Chemical">N stretching region, with bands at 2072, 2099, and 2122 cm−1. In addition, there is a strong, broad band at 3430 cm−1, reflecting the presence of the OH group. This band is present also in the IR spectrum of neat N,N-di­ethyl­ethano­lamine, as well as in that of the corresponding hydro­chloride salt.

A ground-up sample of the compound was shown to be esr silent (Bender, 2015 ▸), confirming the absence of CuII species in the structure.

Refinement details

Crystal data, data collection and structure refinement details are summarized in Table 2 ▸. Intn class="Chemical">ensities of three standard reflections were measured every two h during the 114 h of data collection. A small overall decay of 2.1 (5)% in standard intensity was noted; no correction was made for this decay.

Table 2

Experimental details

Crystal data
Chemical formula	(C6H16NO)[Cu2(CN)3]
M r	323.34
Crystal system, space group	Monoclinic, P21/n
Temperature (K)	298
a, b, c (Å)	8.3560 (11), 13.7347 (13), 11.2928 (12)
β (°)	93.991 (9)
V (Å3)	1292.9 (3)
Z	4
Radiation type	Mo Kα
μ (mm−1)	3.27
Crystal size (mm)	0.5 × 0.3 × 0.3
Data collection
Diffractometer	Enraf–Nonius CAD-4
Absorption correction	Gaussian (Busing & Levy, 1957 ▸)
T min, T max	0.404, 0.548
No. of measured, independent and observed [I > 2σ(I)] reflections	7241, 2534, 2160
R int	0.029
(sin θ/λ)max (Å−1)	0.616
Refinement
R[F 2 > 2σ(F 2)], wR(F 2), S	0.027, 0.082, 1.05
No. of reflections	2534
No. of parameters	148
H-atom treatment	H-atom parameters constrained
Δρmax, Δρmin (e Å−3)	0.41, −0.37

Computer programs: CAD-4 (Enraf–Nonius, 1994 ▸), SHELXS97 and SHELXL97 (Sheldrick, 2008 ▸) and ORTEPIII (Burnett & Johnson, 1996 ▸). Data reduction followed procedures in Corfield et al. (1973 ▸); data were averaged with a local version of SORTAV (Blessing, 1989 ▸).

C-bound hydrogen atoms were constrained to idealized positions with C—H distances of 0.97 Å for CH2 groups and 0.96 Å for CH3 groups, and U eq values fixed at 1.2 times the U iso of their bonded C atoms. The methyl torsional angles were refined. The n class="Chemical">N-bound hydrogen atom was independently refined.

After convergence in initial refinemn class="Chemical">ents, we observed considerable anisotropy in the displacement ellipsoid for O10, in the substituted ethano­lamine cation, indicating a possible disorder. This disorder hindered unambiguous detection of the hydroxyl H atom in difference Fourier maps. We have made extensive attempts to model the disorder without success. The models invariably led to poor geometry without improving the agreement between calculated and observed structure factors. If the geometry was restrained to reasonable values, the agreement became even poorer. Refinements of non-centric models were also carried out in light of the close approach between hydroxyl groups related by the center of symmetry at (, 0, ). These were also unsuccessful. In an attempt to improve the electron density around the hydroxyl group, the intensity data were smoothed by a 12 parameter model with XABS2 (Parkin et al., 1995 ▸). The smoothing did improve the electron density and lowered the R-factor slightly, but did not improve refinements of the disordered models. The final model does not include any disorder in the cation.

The cyanide groups are mainly ordered, as indicated by refinemn class="Chemical">ent of C and N occupancy factors. Results clearly indicated that C3 bridges the two Cu2 atoms, not N3, and C3≡N3 was refined as ordered. Refined occupancies for the other cyanide groups were 77.8(1.4)% for C1≡N1 and 89.7(1.4)% for C2≡N2, indicating a favored orientation. Although these occupancies were significantly different from 100%, we chose to use ordered cyanide groups in our final model.

Crystal structure: contains datablock(s) I. DOI: 10.1107/S2056989016008781/wm5295sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989016008781/wm5295Isup2.hkl

CCDC reference: 1482622

Additional supporting information: crystallographic information; 3D view; checkCIF report

(C6H16NO)[Cu2(CN)3]	F(000) = 656
Mr = 323.34	Dx = 1.661 Mg m−3Dm = 1.667 (2) Mg m−3Dm measured by Flotation in 1,2-dibromopropane/1,2,3-trichloropropane mixtures. Three independent determinations were made.
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 8.3560 (11) Å	Cell parameters from 25 reflections
b = 13.7347 (13) Å	θ = 7.2–21.2°
c = 11.2928 (12) Å	µ = 3.27 mm−1
β = 93.991 (9)°	T = 298 K
V = 1292.9 (3) Å3	Rod, pale yellow
Z = 4	0.5 × 0.3 × 0.3 mm

Enraf–Nonius CAD-4 diffractometer	2160 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.029
Oriented graphite 200 reflection monochromator	θmax = 26.0°, θmin = 2.3°
θ/2θ scans	h = 0→10
Absorption correction: gaussian (Busing & Levy, 1957)	k = 0→16
Tmin = 0.404, Tmax = 0.548	l = −13→13
7241 measured reflections	3 standard reflections every 120 min
2534 independent reflections	intensity decay: −2.1(5)

Refinement on F2	Primary atom site location: heavy-atom method
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.027	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.082	H-atom parameters constrained
S = 1.05	w = 1/[σ2(Fo2) + 0.370P] where P = (Fo2 + 2Fc2)/3
2534 reflections	(Δ/σ)max = 0.001
148 parameters	Δρmax = 0.41 e Å−3
0 restraints	Δρmin = −0.37 e Å−3

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

	x	y	z	Uiso*/Ueq
Cu1	0.57241 (4)	0.14558 (3)	0.76249 (3)	0.04445 (13)
Cu2	0.08692 (4)	0.07242 (2)	0.98109 (3)	0.03959 (12)
N1	0.3754 (3)	0.10097 (19)	0.8273 (2)	0.0507 (6)
C1	0.2650 (3)	0.08775 (19)	0.8807 (2)	0.0375 (6)
N2	0.5860 (3)	0.31586 (18)	0.5927 (2)	0.0477 (6)
C2	0.5850 (3)	0.2498 (2)	0.6540 (2)	0.0403 (6)
N3	0.7582 (3)	0.08232 (19)	0.8423 (2)	0.0524 (6)
C3	0.8645 (3)	0.0553 (2)	0.9013 (3)	0.0443 (6)
O10	0.6123 (6)	−0.0187 (3)	0.6049 (3)	0.1317 (16)
C11	0.6313 (5)	−0.1172 (4)	0.6251 (4)	0.0935 (15)
H11A	0.7086	−0.1272	0.6921	0.112*
H11B	0.6733	−0.1475	0.5561	0.112*
C12	0.4794 (7)	−0.1640 (3)	0.6495 (4)	0.0886 (15)
H12A	0.4998	−0.2316	0.6704	0.106*
H12B	0.4082	−0.1628	0.5779	0.106*
N13	0.3985 (3)	−0.11628 (18)	0.7466 (2)	0.0477 (6)
H13	0.4166	−0.0513	0.7388	0.050 (9)*
C14	0.4660 (5)	−0.1430 (3)	0.8694 (3)	0.0690 (10)
H14A	0.5798	−0.1284	0.8758	0.083*
H14B	0.4154	−0.1027	0.9266	0.083*
C15	0.4435 (8)	−0.2471 (3)	0.9010 (5)	0.1138 (19)
H15A	0.3332	−0.2650	0.8839	0.137*
H15B	0.4721	−0.2563	0.9840	0.137*
H15C	0.5106	−0.2871	0.8554	0.137*
C16	0.2193 (5)	−0.1287 (3)	0.7354 (4)	0.0782 (12)
H16A	0.1758	−0.1098	0.8095	0.094*
H16B	0.1940	−0.1968	0.7214	0.094*
C17	0.1404 (6)	−0.0684 (4)	0.6354 (5)	0.1070 (18)
H17A	0.1726	−0.0016	0.6451	0.128*
H17B	0.0260	−0.0730	0.6368	0.128*
H17C	0.1728	−0.0922	0.5608	0.128*

	U11	U22	U33	U12	U13	U23
Cu1	0.0404 (2)	0.0412 (2)	0.0514 (2)	0.00079 (14)	0.00088 (15)	0.01524 (15)
Cu2	0.0390 (2)	0.03404 (19)	0.0458 (2)	−0.00008 (13)	0.00321 (14)	−0.00375 (13)
N1	0.0452 (14)	0.0433 (13)	0.0637 (15)	−0.0007 (11)	0.0045 (12)	0.0131 (12)
C1	0.0386 (14)	0.0305 (13)	0.0442 (13)	−0.0044 (11)	0.0083 (11)	−0.0003 (10)
N2	0.0525 (14)	0.0391 (13)	0.0526 (14)	0.0017 (11)	0.0100 (11)	0.0088 (11)
C2	0.0370 (13)	0.0369 (14)	0.0476 (14)	0.0020 (11)	0.0073 (11)	0.0084 (12)
N3	0.0388 (13)	0.0529 (15)	0.0646 (16)	0.0003 (11)	−0.0026 (12)	0.0224 (13)
C3	0.0398 (15)	0.0438 (15)	0.0487 (15)	0.0063 (12)	−0.0007 (12)	−0.0005 (12)
O10	0.194 (4)	0.106 (3)	0.103 (3)	−0.061 (3)	0.068 (3)	−0.013 (2)
C11	0.063 (3)	0.139 (5)	0.082 (3)	0.010 (3)	0.025 (2)	−0.015 (3)
C12	0.130 (4)	0.058 (2)	0.084 (3)	−0.007 (2)	0.052 (3)	−0.019 (2)
N13	0.0570 (15)	0.0349 (13)	0.0524 (14)	−0.0089 (11)	0.0121 (11)	−0.0068 (10)
C14	0.091 (3)	0.054 (2)	0.062 (2)	0.0026 (19)	0.0043 (19)	0.0008 (16)
C15	0.166 (6)	0.065 (3)	0.110 (4)	0.003 (3)	0.008 (4)	0.034 (3)
C16	0.067 (2)	0.074 (3)	0.095 (3)	−0.028 (2)	0.015 (2)	−0.015 (2)
C17	0.072 (3)	0.140 (5)	0.104 (4)	−0.007 (3)	−0.028 (3)	−0.028 (3)

Cu1—C2	1.892 (3)	C11—H11B	0.9700
Cu1—N1	1.946 (3)	C12—N13	1.480 (4)
Cu1—N3	1.945 (2)	C12—H12A	0.9700
Cu1—O10	2.907 (4)	C12—H12B	0.9700
Cu2—C1	1.944 (3)	N13—C16	1.503 (5)
Cu2—N2i	1.986 (2)	N13—C14	1.505 (4)
Cu2—C3ii	2.022 (3)	N13—H13	0.9100
Cu2—C3iii	2.221 (3)	C14—C15	1.488 (5)
Cu2—Cu2iv	2.5171 (7)	C14—H14A	0.9700
N1—C1	1.151 (4)	C14—H14B	0.9700
N2—C2	1.141 (4)	C15—H15A	0.9600
N2—Cu2v	1.986 (2)	C15—H15B	0.9600
N3—C3	1.135 (4)	C15—H15C	0.9600
C3—Cu2vi	2.022 (3)	C16—C17	1.514 (7)
C3—Cu2iii	2.221 (3)	C16—H16A	0.9700
O10—C11	1.380 (6)	C16—H16B	0.9700
O10—O10vii	2.962 (10)	C17—H17A	0.9600
C11—C12	1.465 (6)	C17—H17B	0.9600
C11—H11A	0.9700	C17—H17C	0.9600
C2—Cu1—N1	124.64 (11)	O10—C11—H11B	109.3
C2—Cu1—N3	124.01 (11)	C12—C11—H11B	109.3
N1—Cu1—N3	110.73 (11)	H11A—C11—H11B	107.9
C2—Cu1—O10	100.18 (11)	C11—C12—N13	113.1 (4)
N1—Cu1—O10	97.00 (11)	C11—C12—H12A	109.0
N3—Cu1—O10	79.35 (14)	N13—C12—H12A	109.0
C2—Cu1—Cu2	123.78 (8)	C11—C12—H12B	109.0
N1—Cu1—Cu2	9.50 (8)	N13—C12—H12B	109.0
N3—Cu1—Cu2	109.32 (8)	H12A—C12—H12B	107.8
O10—Cu1—Cu2	106.14 (7)	C12—N13—C16	113.0 (3)
C1—Cu2—N2i	108.86 (11)	C12—N13—C14	114.4 (3)
C1—Cu2—C3ii	118.03 (12)	C16—N13—C14	110.9 (3)
N2i—Cu2—C3ii	109.16 (11)	C12—N13—H13	105.9
C1—Cu2—C3iii	108.59 (11)	C16—N13—H13	105.9
N2i—Cu2—C3iii	103.87 (11)	C14—N13—H13	105.9
C3ii—Cu2—C3iii	107.39 (9)	C15—C14—N13	114.2 (4)
C1—Cu2—Cu2iv	131.21 (8)	C15—C14—H14A	108.7
N2i—Cu2—Cu2iv	118.37 (8)	N13—C14—H14A	108.7
C3ii—Cu2—Cu2iv	57.35 (9)	C15—C14—H14B	108.7
C3iii—Cu2—Cu2iv	50.04 (8)	N13—C14—H14B	108.7
C1—Cu2—Cu1	7.72 (8)	H14A—C14—H14B	107.6
N2i—Cu2—Cu1	101.38 (7)	C14—C15—H15A	109.5
C3ii—Cu2—Cu1	123.79 (8)	C14—C15—H15B	109.5
C3iii—Cu2—Cu1	109.48 (7)	H15A—C15—H15B	109.5
Cu2iv—Cu2—Cu1	137.808 (18)	C14—C15—H15C	109.5
C1—N1—Cu1	167.5 (3)	H15A—C15—H15C	109.5
N1—C1—Cu2	175.2 (3)	H15B—C15—H15C	109.5
C2—N2—Cu2v	178.0 (3)	N13—C16—C17	112.4 (3)
N2—C2—Cu1	175.6 (3)	N13—C16—H16A	109.1
C3—N3—Cu1	170.0 (3)	C17—C16—H16A	109.1
N3—C3—Cu2vi	151.8 (3)	N13—C16—H16B	109.1
N3—C3—Cu2iii	135.4 (2)	C17—C16—H16B	109.1
Cu2vi—C3—Cu2iii	72.61 (9)	H16A—C16—H16B	107.9
C11—O10—Cu1	132.6 (3)	C16—C17—H17A	109.5
C11—O10—O10vii	111.2 (3)	C16—C17—H17B	109.5
Cu1—O10—O10vii	105.2 (2)	H17A—C17—H17B	109.5
O10—C11—C12	111.7 (4)	C16—C17—H17C	109.5
O10—C11—H11A	109.3	H17A—C17—H17C	109.5
C12—C11—H11A	109.3	H17B—C17—H17C	109.5