{2,2′-[1,1′-(4-Aza­heptane-1,7-diyl­dinitrilo)diethyl­idyne]­diphenolato}­copper(II)

The quinquedentate ligand 2,2′-[1,1′-(4-aza­heptane-1,7-diyl­dinitrilo)diethyl­idyne]diphenol in the title compound, [Cu(C₂₂H₂₇N₃O₂)], furnishes an N₃O₂ donor set, which results in a distorted square-pyramidal coordination; the two O and two imine N atoms lie in the basal plane, while the secondary amine N atom of the ligand occupies the axial position. The axial Cu—N bond is 0.33 Å longer than the average of the equatorial bonds, and the O atoms are trans. The symmetry of the mol­ecule is lowered by the twist–boat and chair conformations adopted by the two CuNN chelate rings. The complex contains two intra­molecular C—H...O inter­actions, and two mol­ecules of the complex are linked into a dimer by means of moderate N—H...O hydrogen bonds. Spectroscopic evidence supports the presence of hydrogen bonds.

S1. Comment

Cu^II complexes have been studied widely, because of their flexibility and ability to stabilize unusual oxidation states (Xifra et al., 2005), and for their rôle in mimicking peculiar geometries around the metal atom, leading to very interesting spectroscopic properties and varied reactivities (Adman, 1991; Kitajima, 1992; Fenton, 1999). The complexity of the stereochemistry of Cu^II complexes is well known (Gažo et al., 1982; Hathaway, 1984; Murphy, 1993). The structures of such complexes are controlled by the type of donor atoms and the steric constraints in the ligands. For instance, five-coordinated Cu^II complexes, in most cases, take on many different geometries between square-pyramidal and trigonal–bipyramidal (Hathaway, 1987).

The majority of pentadentate ligands studied have been derived from the Schiff base condensation of 2 mol of an aldehyde or ketone with 1 mol of an amine containing three donor atoms. 2,2'-[1,1'-(4-Azaheptane-1,7-diyldinitrilo)diethylidyne]diphenol [(Me-sal)₂dpt] is a ligand which is formed by the condensation of 2 mol of 2-hydroxyacetophenone and 1 mol of dipropylenetriamine. This ligand yields metal complexes showing distorted structures intermediate between trigonal–bipyramidal and square-pyramidal. The effect of altering the metal atom, bonded to identical ligands, can also be observed in the structures of these metal complexes. It is in this context that we have reported the nickel complexes obtained from this ligand under different experimental conditions (Amirnasr et al., 2005), and we report here the synthesis and structural characterization of the title compound, [(Me-sal)₂dpt]Cu, (I).

The Cu^II atom of (I) is coordinated to three N and two O atoms, and the coordination geometry around the Cu^II atom is distorted square-pyramidal. Two imino N atoms and two phenolic O atoms reside in the basal plane, while the secondary amine N atom occupies the axial position. Bond lengths in the coordination polyhedron are in agreement with values from analogous structures. The Cu—O [1.9533 (16) and 1.9578 (16) Å], Cu—N_imine [1.9832 (19) and 1.9850 (19) Å] and Cu—N3 [2.309 (2) Å] bond lengths are in good agreement with the Cu—O [1.925 (5) and 1.951 (5) Å], Cu—N_imine [1.951 (5) and 1.983 (5) Å] and Cu—N3 [2.374 (10) Å] bond lengths found in N,N'-bis[(2-hydroxy-5-methylphenyl)phenylmethylene]-4-azaheptane-1,7-diaminato(2-)copper(II) (Healy et al., 1975). The Cu—N3 bond in (I) is considerably longer than the corresponding Ni—N3 bond [2.0505 (12) Å] in the analogous Ni complex (Amirnasr et al., 2005) and reflects a weaker axial interaction which is typical of Jahn–Teller-sensitive copper(II) complexes. In the conformation adopted by the (Me-sal)₂dpt ligand, the phenyl rings are bent unsymmetrically away from the axial position occupied by atom N3, owing to the difference in the conformations of the six-membered rings linking the salycilidene rings to the secondary amine atom N3. The angles between the normal to the equatorial plane defined by atoms Cu/O11/O21/N11/N21 and the normals to the C11–C16 and C21–C26 phenyl rings are 50.55 (10) and 60.47 (11)°, respectively.

Within the ligand, all refined distances and angles are well within the accepted ranges (Reference for standard values?). The C11–C16 phenyl ring (mean deviation 0.006 Å) and indeed the whole O11/C11–C16/C17 group (mean deviation 0.014 Å), is quite flat. The C21–C26 ring is slightly twisted (mean deviation 0.022 Å), and the O21/C21–C26/C27 group (mean deviation 0.039 Å, greatest deviation 0.059 Å for atom C27) is even more warped. Atom C27 links to the twist–boat Cu/N3/C211/C210/C29/N21 ring [topological D₂ symmetry, puckering parameters (Cremer & Pople 1975) θ = 87.0 (2)° and ϕ = 273.61 (17)°]. As shown below, the fact that the O21–C27 group is more warped than the analogous O11–C17 group is a consequence of a packing impossibility. The other chelate ring is in an approximate chair conformation (Fig. 1). This is in contrast with [Ni(Me-sal)₂dpt] (Amirnasr et al., 2005) and [Co((Me-sal)₂dpt))(benzylamine)]PF₆ (Amirnasr et al., 2006), in which a clear chair and a neat boat conformation, as well as rigorously flat O/C11–C16/C17 rings, were observed.

The shape of the title complex resembles a chubby angle-iron. On its convex side it is decorated with a Lissajous-like bulge of H atoms, within the loop of which are embedded the phenyl rings. Two of these irons are held together by means of two moderate intermolecular N—H···O hydrogen bonds [Table 1, in which normalized H-atom positions are used (Jeffrey & Saenger 1991)], to form centrosymmetric dimers vaguely reminiscent of an X-shaped branding-iron. These dimers then build up the structure according to van der Waals considerations and C—H···π interactions (Fig. 2) (Hunter & Sanders 1990). Indeed, almost the whole of the surface of this branding-iron consists of hydrogen. During the build-up of the structural edifice, the bulges of the complexes fit into the dips of neighbouring complexes in such a way that a rather compact structure is obtained (Fig. 2). This is certainly so when viewed along the a and c axes, but there are four tiny (roughly 2 Å wide) channels per unit cell along the b axis. These are the places where a methylene group stands perpendicular to the C21–C26 phenyl ring (shortest contacts ≈ 1.8 Å). In these instances, there is obviously a steric compromise to tolerate the channels mentioned above.

It is interesting to note that the N—H.·O hydrogen bond is corroborated by IR spectroscopy. Indeed, the sharp band corresponding to the amine ν(N—H) stretching vibrations of free H₂(Me-sal)₂dpt appears at 3295 cm⁻¹, but the band is shifted by about 83 cm⁻¹ in (I) relative to the uncoordinated amine and becomes relatively broad, owing to intermolecular hydrogen bonding. These data thus confirm the attribution of the N—H.·O hydrogen bonds. The same behaviour was also observed in [Co((Me-sal)₂dpt))(benzylamine)]PF₆ (Amirnasr et al., 2006), in which the H···O distances are even shorter. These hydrogen bonds are further corroborated by the chemical shift of the H_c atoms on the C—N groups. In the free ligand, the chemical shift of the H atom NHCH₂CH₂CH₂—N═C is 3.63 (4H, t, H_c), and that of NHCH₂CH₂CH₂N═C is 2.15 (1H, br, N—H). The H_c atom is even more deshielded in metal complexes. For example, the chemical shifts of H_c protons in [Co((Me-sal)₂dpt))(benzylamine)]PF₆ are in the range 3.65–5.20 p.p.m. The H_c protons are therefore capable of forming intramolecular hydrogen bonds with the O atom. It is also interesting to note that the broad band characteristic of the OH group of the free H2(Me-sal)₂dpt ligand (3300–3400 cm⁻¹) is absent in the IR spectrum of the Title? complex, indicating that the equatorial ligand is coordinated in its deprotonated form.

Furthermore, there are two intramolecular C—H···O hydrogen bonds in the complex (Table 1). Again, the lengths and angles of all hydrogen bonds fall perfectly in the ranges given by Jeffrey & Saenger (1991) or Desiraju & Steiner (1999). These weakish hydrogen bonds manifest themselves in the IR spectrum as a splitting of the ν(C—H) band at 3052 cm⁻¹ in the free ligand into two bands at 3046 and 3013 cm⁻¹. The same situation also occurs in the Co complex.

S2. Experimental

H₂(Me-sal)₂dpt was prepared as reported elsewhere (Amirnasr et al., 2005). To a boiling solution of H₂(Me-sal)₂dpt (367 mg, 1 mmol) in dichloromethane (10 ml), a solution of Cu(OAc)₂·4H₂O (253.7 mg 1 mmol) in methanol (10 ml) was added slowly and the mixture stirred until the dichloromethane had evaporated. Solid KOH (112 mg, 2 mmol) was then added to the remaining solution and the mixture was stirred for an additional 5 min. A green precipitate was finally obtained. The reaction mixture was cooled to room temperature and the green precipitate was filtered off and washed with methanol. Green crystals of [Cu(Me-sal)₂dpt], (I), suitable for X-ray crystallography were grown by slow evaporation of a hot toluene solution of the complex at 351 K. Analysis calculated for C₂₂H₂₇CuN₃O₂: C 61.6, H 6.34, N 9.80%; found: C 61.3, H 6.30, N 9.70%. We have actually recorded data from two crystals of (I). The first was bounded by a {111} dipyramid, an {012} prism and an {001} pinacoid, but on the second one - from which the data of this report stem - these forms were only partially developed and were completed by appropriate fracture planes to close the polyhedron.

S3. Refinement

All H atoms were made to ride on their carrier atoms, with C—H = 0.93–0.97 Å and N—H = 0.91 Å, and with U_iso(H) = 1.2U_eq(C,N) or 1.5U_eq(C_methyl). [Please check added text] Torsional degrees of freedom were allowed for the methyl groups. The somewhat high R_int value might be due to the presence of some concave regions in the measured crystal. Since we measured two different crystals on two different diffractometers, a few comparative items from the other, unpublished, crystal might be of interest. Its cell was: a = 18.118 (4), b = 11.327 (2) and c = 19.826 (4) Å, and V = 4068.8 (14) ų. The Cu—N3 bond was 2.3068 (18) Å. The N3···O11 hydrogen bond had parameters of 2.17 Å, 3.152 (2) Å and 165°. Finally, the dihedral angles between the equatorial plane and the phenyl rings were 50.45 (7) and 60.53 (6)°, respectively.

Computing details

Data collection: X-AREA (Stoe & Cie, 2005); cell refinement: X-AREA; data reduction: X-RED (Stoe & Cie, 2005); program(s) used to solve structure: DIRDIF96 (Beurskens et al., 1996); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Sheldrick, 1996); software used to prepare material for publication: SHELXL97, PLATON (Spek, 2003) and X-RED.

Figures

	Fig. 1. A view of (I), with the atom-numbering scheme and intramolecular hydrogen bonds (dashed lines). Displacement ellipsoids are drawn at the 20% probability level. Most H atoms have been omitted for clarity.
	Fig. 2. A stereoview, showing the N—H···O and C—H···π intermolecular interactions (dashed lines) in (I). Most H atoms have been omitted for clarity.

{2,2'-[1,1'-(4-Azaheptane-1,7-diyldinitrilo)diethylidyne]diphenolato}copper(II)

Crystal data

[Cu(C22H27N3O2)]	F(000) = 1800
Mr = 429.01	Dx = 1.405 Mg m^−3
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 26946 reflections
a = 18.120 (4) Å	θ = 2.1–29.5°
b = 11.317 (2) Å	µ = 1.10 mm^−1
c = 19.777 (4) Å	T = 293 K
V = 4055.6 (14) Å^3	Fractured dipyramid, blue–green
Z = 8	0.4 × 0.2 × 0.12 mm

Data collection

Stoe IPDS-2 diffractometer	5497 independent reflections
Radiation source: fine-focus sealed tube	4147 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.080
Detector resolution: 6.67 pixels mm^-1	θmax = 29.3°, θmin = 2.1°
ω scans	h = −24→24
Absorption correction: integration (X-RED; Stoe & Cie, 2005)	k = −15→15
Tmin = 0.824, Tmax = 0.903	l = −27→25
36949 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)] = 0.047	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.097	H-atom parameters constrained
S = 1.09	w = 1/[σ^2(Fo^2) + (0.0415P)^2 + 1.2681P] where P = (Fo^2 + 2Fc^2)/3
5497 reflections	(Δ/σ)max = 0.001
255 parameters	Δρmax = 0.32 e Å^−3
0 restraints	Δρmin = −0.43 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
Cu	0.412757 (14)	0.56012 (2)	0.113790 (12)	0.03529 (8)
O11	0.38409 (10)	0.55066 (15)	0.01873 (8)	0.0463 (4)
C11	0.31948 (12)	0.50527 (19)	0.00426 (10)	0.0360 (4)
C12	0.27829 (14)	0.5548 (2)	−0.04932 (11)	0.0455 (5)
H12	0.2973	0.6196	−0.0724	0.055*
C13	0.21117 (15)	0.5103 (3)	−0.06835 (13)	0.0541 (6)
H13	0.1852	0.5459	−0.1034	0.065*
C14	0.18151 (15)	0.4130 (3)	−0.03590 (14)	0.0584 (7)
H14	0.1356	0.3835	−0.0485	0.070*
C15	0.22097 (13)	0.3606 (2)	0.01521 (13)	0.0477 (6)
H15	0.2016	0.2940	0.0363	0.057*
C16	0.28970 (12)	0.40421 (19)	0.03690 (10)	0.0349 (4)
C17	0.33021 (12)	0.34112 (18)	0.09031 (11)	0.0360 (4)
N11	0.37899 (10)	0.39469 (16)	0.12624 (9)	0.0368 (4)
C18	0.31289 (16)	0.2114 (2)	0.10016 (14)	0.0537 (6)
H18A	0.3575	0.1694	0.1105	0.080*
H18B	0.2917	0.1801	0.0595	0.080*
H18C	0.2785	0.2025	0.1367	0.080*
C19	0.41936 (14)	0.3328 (2)	0.18015 (13)	0.0475 (5)
H19A	0.3948	0.2587	0.1901	0.057*
H19B	0.4187	0.3806	0.2209	0.057*
C110	0.49912 (15)	0.3082 (3)	0.16009 (15)	0.0585 (7)
H11A	0.5179	0.2448	0.1882	0.070*
H11B	0.4999	0.2807	0.1136	0.070*
C111	0.54965 (15)	0.4119 (3)	0.16621 (15)	0.0629 (8)
H11C	0.5457	0.4431	0.2117	0.075*
H11D	0.6000	0.3846	0.1602	0.075*
N3	0.53594 (10)	0.50848 (19)	0.11815 (11)	0.0467 (5)
H3	0.5512	0.4860	0.0762	0.056*
C211	0.57754 (14)	0.6134 (3)	0.13921 (17)	0.0633 (8)
H21A	0.6278	0.5900	0.1493	0.076*
H21B	0.5559	0.6440	0.1805	0.076*
C210	0.57926 (15)	0.7104 (3)	0.08752 (19)	0.0699 (9)
H21C	0.6162	0.6911	0.0538	0.084*
H21D	0.5946	0.7829	0.1096	0.084*
C29	0.50617 (16)	0.7330 (3)	0.05163 (14)	0.0604 (7)
H29A	0.5070	0.8107	0.0309	0.073*
H29B	0.4993	0.6749	0.0161	0.073*
C28	0.4500 (2)	0.9398 (2)	0.12135 (16)	0.0663 (8)
H28A	0.5024	0.9368	0.1142	0.099*
H28B	0.4396	0.9875	0.1603	0.099*
H28C	0.4266	0.9737	0.0823	0.099*
N21	0.44466 (11)	0.72593 (17)	0.09970 (10)	0.0413 (4)
C27	0.42087 (13)	0.8160 (2)	0.13258 (12)	0.0437 (5)
C26	0.36359 (12)	0.7996 (2)	0.18425 (12)	0.0396 (5)
C25	0.31391 (15)	0.8916 (2)	0.19930 (14)	0.0528 (6)
H25	0.3172	0.9618	0.1750	0.063*
C24	0.26119 (16)	0.8816 (3)	0.24804 (17)	0.0645 (8)
H24	0.2270	0.9418	0.2549	0.077*
C23	0.25943 (16)	0.7806 (3)	0.28702 (16)	0.0639 (8)
H23	0.2254	0.7746	0.3221	0.077*
C22	0.30711 (15)	0.6888 (2)	0.27481 (13)	0.0528 (6)
H22	0.3055	0.6225	0.3026	0.063*
C21	0.35865 (13)	0.6923 (2)	0.22116 (11)	0.0405 (5)
O21	0.39974 (10)	0.59915 (15)	0.20949 (8)	0.0463 (4)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu	0.03731 (13)	0.03430 (13)	0.03426 (13)	−0.00091 (11)	0.00027 (11)	−0.00070 (11)
O11	0.0531 (9)	0.0494 (9)	0.0362 (8)	−0.0162 (8)	−0.0044 (7)	0.0054 (7)
C11	0.0413 (11)	0.0351 (10)	0.0315 (10)	0.0048 (9)	0.0011 (9)	−0.0036 (8)
C12	0.0566 (14)	0.0423 (12)	0.0375 (11)	0.0083 (11)	−0.0005 (10)	0.0028 (10)
C13	0.0543 (15)	0.0663 (17)	0.0418 (13)	0.0176 (13)	−0.0087 (11)	0.0000 (12)
C14	0.0409 (13)	0.082 (2)	0.0520 (15)	−0.0036 (13)	−0.0088 (11)	−0.0033 (14)
C15	0.0419 (12)	0.0560 (14)	0.0452 (13)	−0.0054 (11)	0.0014 (10)	0.0006 (11)
C16	0.0356 (10)	0.0364 (10)	0.0326 (10)	0.0030 (8)	0.0026 (8)	−0.0025 (8)
C17	0.0381 (10)	0.0320 (10)	0.0379 (10)	0.0018 (8)	0.0045 (9)	0.0008 (8)
N11	0.0386 (9)	0.0370 (9)	0.0349 (9)	0.0022 (8)	−0.0014 (7)	0.0043 (7)
C18	0.0676 (16)	0.0348 (12)	0.0585 (16)	−0.0035 (11)	−0.0061 (13)	0.0015 (11)
C19	0.0495 (13)	0.0475 (13)	0.0456 (12)	0.0021 (11)	−0.0068 (11)	0.0115 (10)
C110	0.0561 (15)	0.0615 (16)	0.0579 (15)	0.0165 (13)	−0.0077 (13)	0.0117 (13)
C111	0.0407 (13)	0.087 (2)	0.0605 (17)	0.0101 (14)	−0.0071 (12)	0.0105 (15)
N3	0.0358 (9)	0.0560 (12)	0.0483 (11)	0.0005 (9)	0.0021 (8)	−0.0081 (10)
C211	0.0376 (13)	0.0727 (19)	0.080 (2)	−0.0035 (12)	0.0020 (12)	−0.0267 (16)
C210	0.0469 (15)	0.0609 (17)	0.102 (2)	−0.0153 (13)	0.0285 (16)	−0.0262 (17)
C29	0.0734 (18)	0.0526 (15)	0.0554 (15)	−0.0184 (14)	0.0249 (14)	−0.0066 (12)
C28	0.084 (2)	0.0401 (13)	0.075 (2)	−0.0084 (14)	0.0089 (17)	0.0012 (14)
N21	0.0447 (10)	0.0396 (10)	0.0396 (10)	−0.0054 (8)	0.0053 (8)	−0.0020 (8)
C27	0.0477 (13)	0.0365 (11)	0.0470 (12)	−0.0031 (10)	−0.0046 (10)	0.0013 (9)
C26	0.0387 (11)	0.0373 (11)	0.0428 (11)	0.0020 (9)	−0.0048 (9)	−0.0060 (9)
C25	0.0552 (14)	0.0437 (13)	0.0594 (16)	0.0088 (12)	−0.0099 (13)	−0.0108 (12)
C24	0.0491 (15)	0.0639 (18)	0.080 (2)	0.0106 (14)	−0.0021 (14)	−0.0324 (16)
C23	0.0517 (15)	0.0718 (19)	0.0681 (18)	−0.0134 (14)	0.0182 (13)	−0.0339 (15)
C22	0.0632 (16)	0.0487 (14)	0.0464 (13)	−0.0138 (12)	0.0107 (12)	−0.0136 (11)
C21	0.0439 (11)	0.0418 (12)	0.0357 (11)	−0.0011 (10)	−0.0018 (9)	−0.0086 (9)
O21	0.0636 (11)	0.0398 (8)	0.0353 (8)	0.0089 (8)	0.0025 (7)	0.0004 (6)

Geometric parameters (Å, º)

Cu—O11	1.9533 (16)	C111—H11C	0.9700
Cu—O21	1.9578 (16)	C111—H11D	0.9700
Cu—N21	1.9832 (19)	N3—C211	1.467 (3)
Cu—N11	1.9850 (19)	N3—H3	0.9100
Cu—N3	2.309 (2)	C211—C210	1.501 (5)
O11—C11	1.310 (3)	C211—H21A	0.9700
C11—C12	1.412 (3)	C211—H21B	0.9700
C11—C16	1.420 (3)	C210—C29	1.524 (4)
C12—C13	1.369 (4)	C210—H21C	0.9700
C12—H12	0.9300	C210—H21D	0.9700
C13—C14	1.383 (4)	C29—N21	1.467 (3)
C13—H13	0.9300	C29—H29A	0.9700
C14—C15	1.373 (4)	C29—H29B	0.9700
C14—H14	0.9300	C28—C27	1.514 (3)
C15—C16	1.407 (3)	C28—H28A	0.9600
C15—H15	0.9300	C28—H28B	0.9600
C16—C17	1.471 (3)	C28—H28C	0.9600
C17—N11	1.286 (3)	N21—C27	1.284 (3)
C17—C18	1.513 (3)	C27—C26	1.468 (3)
N11—C19	1.471 (3)	C26—C25	1.408 (3)
C18—H18A	0.9600	C26—C21	1.419 (3)
C18—H18B	0.9600	C25—C24	1.362 (4)
C18—H18C	0.9600	C25—H25	0.9300
C19—C110	1.524 (4)	C24—C23	1.380 (5)
C19—H19A	0.9700	C24—H24	0.9300
C19—H19B	0.9700	C23—C22	1.373 (4)
C110—C111	1.493 (4)	C23—H23	0.9300
C110—H11A	0.9700	C22—C21	1.414 (3)
C110—H11B	0.9700	C22—H22	0.9300
C111—N3	1.470 (4)	C21—O21	1.312 (3)
O11—Cu—O21	155.61 (8)	C110—C111—H11D	108.4
O11—Cu—N21	89.67 (7)	H11C—C111—H11D	107.5
O21—Cu—N21	87.56 (7)	C211—N3—C111	109.4 (2)
O11—Cu—N11	89.18 (7)	C211—N3—Cu	107.61 (16)
O21—Cu—N11	93.20 (7)	C111—N3—Cu	112.07 (15)
N21—Cu—N11	178.64 (8)	C211—N3—H3	109.2
O11—Cu—N3	106.21 (8)	C111—N3—H3	109.2
O21—Cu—N3	97.90 (7)	Cu—N3—H3	109.2
N21—Cu—N3	87.88 (8)	N3—C211—C210	114.2 (3)
N11—Cu—N3	93.13 (8)	N3—C211—H21A	108.7
C11—O11—Cu	117.99 (14)	C210—C211—H21A	108.7
O11—C11—C12	118.7 (2)	N3—C211—H21B	108.7
O11—C11—C16	123.79 (19)	C210—C211—H21B	108.7
C12—C11—C16	117.4 (2)	H21A—C211—H21B	107.6
C13—C12—C11	122.0 (2)	C211—C210—C29	115.0 (2)
C13—C12—H12	119.0	C211—C210—H21C	108.5
C11—C12—H12	119.0	C29—C210—H21C	108.5
C12—C13—C14	120.7 (2)	C211—C210—H21D	108.5
C12—C13—H13	119.7	C29—C210—H21D	108.5
C14—C13—H13	119.7	H21C—C210—H21D	107.5
C15—C14—C13	118.9 (2)	N21—C29—C210	110.4 (2)
C15—C14—H14	120.6	N21—C29—H29A	109.6
C13—C14—H14	120.6	C210—C29—H29A	109.6
C14—C15—C16	122.3 (2)	N21—C29—H29B	109.6
C14—C15—H15	118.8	C210—C29—H29B	109.6
C16—C15—H15	118.8	H29A—C29—H29B	108.1
C15—C16—C11	118.7 (2)	C27—C28—H28A	109.5
C15—C16—C17	119.4 (2)	C27—C28—H28B	109.5
C11—C16—C17	121.86 (19)	H28A—C28—H28B	109.5
N11—C17—C16	120.72 (19)	C27—C28—H28C	109.5
N11—C17—C18	121.9 (2)	H28A—C28—H28C	109.5
C16—C17—C18	117.4 (2)	H28B—C28—H28C	109.5
C17—N11—C19	121.2 (2)	C27—N21—C29	122.7 (2)
C17—N11—Cu	126.02 (15)	C27—N21—Cu	125.61 (16)
C19—N11—Cu	112.69 (15)	C29—N21—Cu	111.35 (16)
C17—C18—H18A	109.5	N21—C27—C26	119.3 (2)
C17—C18—H18B	109.5	N21—C27—C28	122.9 (2)
H18A—C18—H18B	109.5	C26—C27—C28	117.8 (2)
C17—C18—H18C	109.5	C25—C26—C21	118.9 (2)
H18A—C18—H18C	109.5	C25—C26—C27	120.4 (2)
H18B—C18—H18C	109.5	C21—C26—C27	120.7 (2)
N11—C19—C110	111.7 (2)	C24—C25—C26	122.5 (3)
N11—C19—H19A	109.3	C24—C25—H25	118.8
C110—C19—H19A	109.3	C26—C25—H25	118.8
N11—C19—H19B	109.3	C25—C24—C23	118.7 (3)
C110—C19—H19B	109.3	C25—C24—H24	120.6
H19A—C19—H19B	107.9	C23—C24—H24	120.6
C111—C110—C19	114.6 (2)	C22—C23—C24	121.0 (3)
C111—C110—H11A	108.6	C22—C23—H23	119.5
C19—C110—H11A	108.6	C24—C23—H23	119.5
C111—C110—H11B	108.6	C23—C22—C21	121.8 (3)
C19—C110—H11B	108.6	C23—C22—H22	119.1
H11A—C110—H11B	107.6	C21—C22—H22	119.1
N3—C111—C110	115.4 (2)	O21—C21—C22	119.0 (2)
N3—C111—H11C	108.4	O21—C21—C26	124.2 (2)
C110—C111—H11C	108.4	C22—C21—C26	116.9 (2)
N3—C111—H11D	108.4	C21—O21—Cu	114.83 (14)
O21—Cu—O11—C11	−49.8 (3)	O11—Cu—N3—C111	−125.89 (18)
N21—Cu—O11—C11	−133.12 (17)	O21—Cu—N3—C111	57.84 (19)
N11—Cu—O11—C11	46.17 (17)	N21—Cu—N3—C111	145.08 (19)
N3—Cu—O11—C11	139.19 (16)	N11—Cu—N3—C111	−35.83 (19)
Cu—O11—C11—C12	142.65 (17)	C111—N3—C211—C210	169.2 (2)
Cu—O11—C11—C16	−41.1 (3)	Cu—N3—C211—C210	−68.8 (2)
O11—C11—C12—C13	178.4 (2)	N3—C211—C210—C29	41.9 (3)
C16—C11—C12—C13	1.9 (3)	C211—C210—C29—N21	40.7 (3)
C11—C12—C13—C14	−0.9 (4)	C210—C29—N21—C27	90.0 (3)
C12—C13—C14—C15	−0.8 (4)	C210—C29—N21—Cu	−83.6 (2)
C13—C14—C15—C16	1.6 (4)	O11—Cu—N21—C27	123.2 (2)
C14—C15—C16—C11	−0.6 (4)	O21—Cu—N21—C27	−32.6 (2)
C14—C15—C16—C17	−177.8 (2)	N3—Cu—N21—C27	−130.6 (2)
O11—C11—C16—C15	−177.5 (2)	O11—Cu—N21—C29	−63.43 (18)
C12—C11—C16—C15	−1.1 (3)	O21—Cu—N21—C29	140.81 (18)
O11—C11—C16—C17	−0.3 (3)	N3—Cu—N21—C29	42.80 (18)
C12—C11—C16—C17	176.0 (2)	C29—N21—C27—C26	−174.5 (2)
C15—C16—C17—N11	−157.4 (2)	Cu—N21—C27—C26	−1.8 (3)
C11—C16—C17—N11	25.4 (3)	C29—N21—C27—C28	4.6 (4)
C15—C16—C17—C18	23.5 (3)	Cu—N21—C27—C28	177.3 (2)
C11—C16—C17—C18	−153.6 (2)	N21—C27—C26—C25	−151.5 (2)
C16—C17—N11—C19	179.5 (2)	C28—C27—C26—C25	29.3 (3)
C18—C17—N11—C19	−1.5 (3)	N21—C27—C26—C21	30.3 (3)
C16—C17—N11—Cu	−4.3 (3)	C28—C27—C26—C21	−148.9 (2)
C18—C17—N11—Cu	174.74 (17)	C21—C26—C25—C24	0.0 (4)
O11—Cu—N11—C17	−25.17 (19)	C27—C26—C25—C24	−178.2 (2)
O21—Cu—N11—C17	130.54 (19)	C26—C25—C24—C23	4.2 (4)
N3—Cu—N11—C17	−131.36 (19)	C25—C24—C23—C22	−3.5 (4)
O11—Cu—N11—C19	151.34 (16)	C24—C23—C22—C21	−1.5 (4)
O21—Cu—N11—C19	−52.95 (16)	C23—C22—C21—O21	−176.0 (2)
N3—Cu—N11—C19	45.16 (16)	C23—C22—C21—C26	5.6 (4)
C17—N11—C19—C110	106.8 (3)	C25—C26—C21—O21	176.9 (2)
Cu—N11—C19—C110	−69.9 (2)	C27—C26—C21—O21	−4.9 (3)
N11—C19—C110—C111	78.8 (3)	C25—C26—C21—C22	−4.8 (3)
C19—C110—C111—N3	−68.1 (3)	C27—C26—C21—C22	173.4 (2)
C110—C111—N3—C211	167.5 (2)	C22—C21—O21—Cu	138.55 (18)
C110—C111—N3—Cu	48.2 (3)	C26—C21—O21—Cu	−43.2 (3)
O11—Cu—N3—C211	113.84 (18)	O11—Cu—O21—C21	−31.4 (3)
O21—Cu—N3—C211	−62.43 (19)	N21—Cu—O21—C21	52.43 (17)
N21—Cu—N3—C211	24.81 (19)	N11—Cu—O21—C21	−126.44 (17)
N11—Cu—N3—C211	−156.10 (19)	N3—Cu—O21—C21	139.95 (16)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3···O11^i	1.01	2.16	3.143 (3)	165
C19—H19B···O21	1.09	2.45	3.090 (3)	116
C29—H29B···O11	1.09	2.46	3.094 (3)	116

Symmetry code: (i) −x+1, −y+1, −z.