Triple ring contraction of a [2+2] macrocyclic ligand

Schiff base condensation of 2,6-di­formyl­pyridine and 1,3-di­amino­propan-2-ol in the presence of a Ba^II template ion yields a complex containing a [2+2] macrocycle, [Ba₂(μ_1,2-ClO₄)₂(H₂L1)₂], where H₂L1 is 3,7,15,19,25,26-hexaaza­tri­cyclo­[19.3.1.1^9,13]hexa­cosa-1(25),2,7,9(26),10,12,14,19,21,23-deca­ene-5,17-diol. On transmetallation with Cu^II cations, the macrocycle undergoes three successive ring contractions, yielding crystals of (acetato-κO)[26,28-dioxa-3,7,15,19,25,27-hexaazahexacyclo[19.3.1.1^2,5.1^9,13.1^17,10.0^3,8]octacosa-1(25),9(27),10,12,14,21,23-heptaene-κ⁵N]copper(II) perchlorate, [Cu(CH₃COO)(C₂₀H₂₂N₆O₂)]ClO₄ or [Cu(CH₃COO)(L2)]ClO₄, in which the macrocycle ring size has been reduced from 20 members in H₂L1 to 16 in L2.

S1. Introduction

The ease and versatility of Schiff base condensation has led to its extensive use over many years in coordination chemistry (Tamburini et al., 2004; Vigato et al., 2012). Recently, the reversibility of Schiff base condensation has led to its exploitation in studies of dynamic covalent chemistry (Hafezi & Lehn, 2012; Nitschke, 2007) and to renewed inter­est in the mechanisms of self-assembly in Schiff base reactions, with a view to improving control and manipulation of the product assembly (Akine & Nabeshima, 2009).

S2. Experimental

S2.1. Synthesis and crystallization

[Ba₂(µ_1,2-ClO₄)₂(H₂L1)₂](ClO₄)₂, (1), was prepared as described previously (James et al., 2011). In the transmetallation reaction, the barium complex (0.194 g, 0.271 mmol) was dissolved in aceto­nitrile (15 ml) and heated to reflux. Copper acetate monohydrate (0.109 g, 0.545 mmol) dissolved in aceto­nitrile (10 ml) was added to the refluxing solution with stirring. The resulting dark-blue solution was refluxed for 6 h, after which time a brown, as yet unidentified, precipitate (yield 0.160 g) was removed by filtration. Green crystals of [Cu(CH₃COO)(L2)]ClO₄, (2), grew in the dark-blue filtrate on standing overnight and were collected by filtration (yield 0.028 g, 0.047 mmol, 17%). Elemental analysis, calculated for (2): C 44.0, H 4.2, N 14.0%; found: C 43.5, H 4.1, N 13.9%.

S2.2. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1. C-bound H atoms were inserted at calculated positions riding on their carrier atoms, with C—H = 0.95, 0.98, 0.99 and 1.00 Å for aryl, methyl, methyl­ene and tertiary H atoms, respectively. N-bound H atoms were located from difference maps and their coordinates refined. The H atoms of the aryl, methyl­ene and tertiary C—H groups had U_iso(H) = 1.2U_eq(C), and those of the methyl or N—H groups had U_iso(H) = 1.5U_eq(C,N).

S3. Results and discussion

The [2+2] Schiff base macrocycle L1 (Scheme 1) is conveniently obtained as the Ba^II complex, [Ba₂(µ_1,2-ClO₄)₂(H₂L1)₂](ClO₄)₂, (1), by condensation of 2,6-di­formyl­pyridine and 1,3-di­amino­propan-2-ol in the presence of a Ba^II template ion (James et al., 2011). Complexes of this type are often considered as synthetic equivalents of the free [2+2] macrocycles, as the Ba^II cation can be readily transmetallated by transition metal ions with hard–soft acid–base (HSAB) properties better matched to those of the ligand. Since the transition metal ions are generally smaller than the Ba^II cation, dinuclear complexes often result (Brooker & McKee, 1989; Bailey et al., 1987). In other cases, where the radius of the metal ion and the size of the macrocyclic cavity are poorly compatable, the macrocycle may undergo ring-contraction (Adams et al. 1987; Bailey et al., 1983) or ring-expansion (Brooker et al. 1987) reactions. In this paper, we report a new derivative of L1 obtained via three successive ring-contraction reactions on a Cu^II template ion to give the title complex, (2), of the new macrocycle L2 [systematic name: 26,28-dioxa-3,7,15,19,25,27-hexa­aza­hexa­cyclo­[19.3.1.1^2,5.1^9,13.1^17,20.0^3,8]o­cta­cosa-1(25),9(27),10,12,14,21,23-hepta­ene­; see Schemes 1 and 2].

Transmetallation of Ba^II complex (1) using copper(II) acetate in aceto­nitrile yielded well formed green crystals of [Cu(L2)(CH₃COO)]ClO₄, (2); the formula unit is shown Scheme 2 and the structure of the cation is shown in Fig. 1. The Cu^II cation is six-coordinate, bonded to five N atoms of the macrocycle and to one O atom of the acetate anion. A long inter­action with the second O atom of the acetate ligand might suggest it has some bidentate character [Cu—O22 = 2.946 (2) Å]. The angular geometry at the metal ion is irregular (Table 2), and the bond lengths cover a range including three normal Cu—N bonds, two somewhat longer bonds and one very long bond to the imine N atom [Cu1—N6 = 2.532 (2) Å].

The macrocycle has undergone three distinct ring-contraction processes (shown in Scheme 1). First, both pendant alcohol groups have attacked the imine carbon centres at the same pyridine group, forming two perhydro­pyrimidine groups. One of the newly formed secondary amine groups then attacks one of the remaining imine C atoms, forming an oxazolidine ring and resulting in an overall ring contraction from a 20-membered ring to a 16-membered macrocycle. The ligand has a distinct fold [N1—Cu1—N4 = 103.57 (7)°], imposed primarily by the geometry of the fused perhydro­pyrimidine and oxazolidine rings at atom N2. The monodentate acetate anions link pairs of cations via hydrogen bonding [N5···O22ⁱ = 2.843 (3) Å; symmetry code: (i) -x, -y, -z + 2; Table 3 and Fig. 2]. The perchlorate anions are also linked to the cations via hydrogen bonds involving the uncoordinated N atom of the perhydro­pyrimidine ring [N3···O12 = 3.111 (3) Å]. There are no other particularly striking inter­molecular inter­actions. The hydrogen-bonded dimers lie with the Cu···Cu vector parallel to the c axis (Fig. 3).

The behaviour of (2) contrasts with the analogous system derived from 2,6-di­acetyl­pyridine, where a very similar barium complex of the [2+2] complex (H₂L3) can be prepared (Adams et al., 1987). This ketone-derived system is less susceptible to ring-contraction reactions than the aldehyde-derived equivalent L1, due to the increased steric hindrance and decreased polarity of the C═N bond, and transmetallation with Cu^II in methanol yields a dicopper(II) complex of the same [2+2] macrocycle, (3) (Fig. 4; Bailey et al., 1987). In the absence of ring-contraction reactions, transmetallation of (1) with copper(II) acetate would be expected to yield a structurally similar analogue of complex (3).

The driving force for macrocyclic ring-contraction reactions is usually ascribed to an improved fit between the radius of the metal ion and the macrocycle cavity (Drew et al., 1981). It is not immediately obvious from the structures of (2) and (3) (Figs. 1 and 4) that the ring contraction has resulted in an improved fit in this case, since (3) shows a reasonably conventional tetra­gonal-based geometry at the Cu^II cation, with unexceptional bond lengths. Instead, the situation should be viewed as a dynamic chemical system (Lehn, 2007), in which the solvent, counter-ions, ligation available to those Cu^II cations not coordinated to the macrocyclic ligand, covalent bond formation etc. all influence the structure of the macrocyclic product isolated.

Related literature

For related literature, see: Adams et al. (1987); Akine & Nabeshima (2009); Bailey et al. (1983, 1987); Brooker & McKee (1989); Brooker et al. (1987); Drew et al. (1981); Hafezi & Lehn (2012); James et al. (2011); Lehn (2007); Nitschke (2007); Tamburini et al. (2004); Vigato et al. (2012).

Computing details

Data collection: APEX2 (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT (Bruker, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2012 (Sheldrick, 2012); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures

	Fig. 1. A perspective view of (2), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. The long bond to the imine N atom is shown unfilled. H atoms and the (well behaved) perchlorate anion have been omitted for clarity.
	Fig. 2. A perspective view of (2), showing the hydrogen bonding as dashed lines. Primed atoms are generated by the symmetry operator (?, ?, ?) [Please complete].
	Fig. 3. A packing diagram for (2), viewed down the a axis. Hydrogen bonds are shown as dashed lines and H atoms have been omitted for clarity.
	Fig. 4. A perspective view of the [Cu2(HL3)(CH3CN)(H2O]^3+ cation (Bailey et al., 1987). H atoms have been omitted for clarity. Bonds to the Cu atom are in the range 1.967 (11)–2.116 (11) Å, except for Cu1—N7 and Cu2—O3 [2.276 (7) and 2.346 (11) Å, respectively]. The cis bond angles in the Cu basal planes are in the range 77.4 (4)–112.1 (9)°.

(Acetato-κO)[26,28-dioxa-3,7,15,19,25,27-hexaazahexacyclo[19.3.1.1^2,5.1^9,13.1^17,20.0^3,8]octacosa-1(25),9(27),10,12,14,21,23-heptaene-κ⁵N]copper(II) perchlorate

Crystal data

[Cu(C2H3O2)(C20H22N6O2)]ClO4	F(000) = 1236
Mr = 600.47	Dx = 1.637 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 8.9252 (8) Å	Cell parameters from 7293 reflections
b = 16.9606 (15) Å	θ = 2.4–28.0°
c = 16.5461 (14) Å	µ = 1.07 mm^−1
β = 103.350 (1)°	T = 150 K
V = 2437.0 (4) Å^3	Block, green
Z = 4	0.37 × 0.33 × 0.27 mm

Data collection

Bruker APEXII CCD area-detector diffractometer	5050 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.033
ω rotation with narrow frames scans	θmax = 28.4°, θmin = 1.7°
Absorption correction: multi-scan (SADABS; Sheldrick, 2009)	h = −11→11
Tmin = 0.639, Tmax = 0.746	k = −22→22
24778 measured reflections	l = −22→22
6075 independent 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)] = 0.041	Hydrogen site location: mixed
wR(F^2) = 0.115	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ^2(Fo^2) + (0.058P)^2 + 2.621P] where P = (Fo^2 + 2Fc^2)/3
6075 reflections	(Δ/σ)max = 0.001
350 parameters	Δρmax = 1.53 e Å^−3
0 restraints	Δρmin = −1.10 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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Cu1	0.00676 (3)	0.01697 (2)	0.81242 (2)	0.01841 (9)
N1	−0.0850 (2)	0.04068 (11)	0.67681 (12)	0.0200 (4)
C1	0.0001 (3)	0.07678 (15)	0.63030 (15)	0.0256 (5)
C2	−0.0615 (3)	0.09853 (18)	0.54831 (16)	0.0356 (6)
H2	0.0016	0.1212	0.5154	0.043*
C3	−0.2176 (3)	0.08638 (17)	0.51575 (17)	0.0358 (6)
H3	−0.2632	0.1018	0.4603	0.043*
C4	−0.3060 (3)	0.05184 (15)	0.56404 (16)	0.0283 (5)
H4	−0.4135	0.0444	0.5431	0.034*
C5	−0.2345 (3)	0.02793 (13)	0.64434 (15)	0.0211 (5)
C6	−0.3209 (3)	−0.01375 (14)	0.70116 (15)	0.0209 (4)
H6	−0.3680	0.0277	0.7305	0.025*
N2	−0.2054 (2)	−0.05758 (11)	0.76516 (11)	0.0177 (4)
N3	−0.4449 (2)	−0.06170 (13)	0.65356 (14)	0.0262 (4)
H3A	−0.416 (4)	−0.086 (2)	0.616 (2)	0.039*
C7	−0.5055 (3)	−0.11883 (16)	0.70521 (17)	0.0288 (5)
H7A	−0.5635	−0.1604	0.6690	0.035*
H7B	−0.5779	−0.0916	0.7330	0.035*
C8	−0.3775 (3)	−0.15712 (15)	0.77105 (16)	0.0267 (5)
H8	−0.4187	−0.1974	0.8043	0.032*
C9	−0.2858 (3)	−0.09337 (15)	0.82580 (15)	0.0235 (5)
H9A	−0.3537	−0.0550	0.8449	0.028*
H9B	−0.2123	−0.1160	0.8744	0.028*
O1	−0.2626 (2)	−0.19016 (10)	0.73131 (11)	0.0256 (4)
C10	−0.1551 (3)	−0.12867 (13)	0.72681 (14)	0.0196 (4)
H10	−0.1547	−0.1178	0.6675	0.023*
C11	0.0045 (3)	−0.15142 (13)	0.77419 (14)	0.0204 (4)
C12	0.0607 (3)	−0.22789 (14)	0.77751 (16)	0.0264 (5)
H12	0.0008	−0.2691	0.7471	0.032*
C13	0.2073 (3)	−0.24281 (15)	0.82651 (18)	0.0306 (6)
H13	0.2508	−0.2941	0.8281	0.037*
C14	0.2892 (3)	−0.18215 (14)	0.87298 (16)	0.0264 (5)
H14	0.3866	−0.1919	0.9093	0.032*
C15	0.2265 (3)	−0.10703 (13)	0.86550 (14)	0.0205 (4)
N4	0.0887 (2)	−0.09210 (11)	0.81478 (11)	0.0180 (4)
C16	0.3014 (3)	−0.03686 (14)	0.91445 (15)	0.0207 (4)
H16	0.3551	−0.0532	0.9719	0.025*
O2	0.40728 (19)	−0.00096 (10)	0.87330 (11)	0.0247 (4)
C17	0.3967 (3)	0.08382 (14)	0.87928 (15)	0.0221 (5)
H17	0.4982	0.1056	0.9097	0.026*
C18	0.2766 (3)	0.09766 (14)	0.93034 (15)	0.0233 (5)
H18A	0.3261	0.1056	0.9898	0.028*
H18B	0.2114	0.1439	0.9096	0.028*
N5	0.1857 (2)	0.02381 (11)	0.91742 (13)	0.0191 (4)
H5	0.147 (4)	0.0143 (18)	0.959 (2)	0.029*
C19	0.3540 (3)	0.11819 (14)	0.79237 (15)	0.0240 (5)
H19A	0.3566	0.1765	0.7953	0.029*
H19B	0.4291	0.1008	0.7604	0.029*
N6	0.1993 (2)	0.09167 (12)	0.75073 (12)	0.0217 (4)
C20	0.1598 (3)	0.09575 (16)	0.67273 (16)	0.0293 (5)
H20	0.2322	0.1109	0.6416	0.035*
O21	−0.0892 (2)	0.11513 (10)	0.83097 (10)	0.0243 (4)
O22	−0.1335 (3)	0.06843 (13)	0.94826 (14)	0.0459 (6)
C21	−0.1343 (3)	0.12219 (14)	0.89891 (16)	0.0238 (5)
C22	−0.1870 (4)	0.20378 (17)	0.9163 (2)	0.0422 (7)
H22A	−0.2533	0.2002	0.9558	0.063*
H22B	−0.2447	0.2275	0.8644	0.063*
H22C	−0.0971	0.2365	0.9399	0.063*
Cl1	−0.34875 (7)	−0.19938 (4)	0.48008 (4)	0.03087 (15)
O11	−0.2261 (3)	−0.24779 (15)	0.46888 (19)	0.0631 (8)
O12	−0.2962 (3)	−0.12426 (13)	0.51353 (14)	0.0457 (6)
O13	−0.4472 (3)	−0.18456 (15)	0.39730 (14)	0.0481 (6)
O14	−0.4383 (2)	−0.23729 (13)	0.53157 (13)	0.0381 (5)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.02038 (15)	0.01567 (14)	0.01789 (15)	0.00440 (10)	0.00181 (10)	−0.00089 (10)
N1	0.0195 (9)	0.0201 (9)	0.0195 (9)	0.0015 (7)	0.0026 (7)	0.0022 (7)
C1	0.0251 (12)	0.0284 (12)	0.0218 (11)	−0.0020 (10)	0.0028 (9)	0.0068 (9)
C2	0.0370 (15)	0.0447 (16)	0.0226 (13)	−0.0115 (12)	0.0019 (11)	0.0114 (11)
C3	0.0401 (15)	0.0382 (15)	0.0227 (12)	−0.0077 (12)	−0.0060 (11)	0.0113 (11)
C4	0.0283 (13)	0.0233 (12)	0.0275 (12)	−0.0018 (10)	−0.0056 (10)	0.0041 (10)
C5	0.0218 (11)	0.0176 (10)	0.0220 (11)	0.0007 (8)	0.0012 (9)	0.0010 (8)
C6	0.0161 (10)	0.0224 (11)	0.0229 (11)	0.0018 (8)	0.0019 (9)	−0.0003 (9)
N2	0.0179 (9)	0.0180 (9)	0.0177 (9)	0.0012 (7)	0.0047 (7)	0.0004 (7)
N3	0.0216 (10)	0.0299 (11)	0.0250 (11)	−0.0058 (8)	0.0012 (8)	−0.0009 (9)
C7	0.0201 (11)	0.0345 (14)	0.0315 (13)	−0.0082 (10)	0.0052 (10)	0.0006 (11)
C8	0.0266 (12)	0.0269 (12)	0.0279 (12)	−0.0050 (10)	0.0091 (10)	0.0019 (10)
C9	0.0245 (12)	0.0275 (12)	0.0200 (11)	−0.0016 (9)	0.0081 (9)	0.0025 (9)
O1	0.0265 (9)	0.0193 (8)	0.0312 (9)	−0.0061 (7)	0.0070 (7)	−0.0023 (7)
C10	0.0227 (11)	0.0158 (10)	0.0201 (10)	−0.0015 (8)	0.0047 (9)	−0.0022 (8)
C11	0.0247 (11)	0.0173 (10)	0.0208 (11)	0.0009 (8)	0.0081 (9)	0.0005 (8)
C12	0.0323 (13)	0.0167 (10)	0.0317 (13)	0.0008 (9)	0.0103 (10)	−0.0025 (9)
C13	0.0340 (14)	0.0179 (11)	0.0416 (15)	0.0085 (10)	0.0118 (12)	0.0022 (10)
C14	0.0251 (12)	0.0227 (11)	0.0323 (13)	0.0067 (9)	0.0082 (10)	0.0055 (10)
C15	0.0204 (11)	0.0206 (11)	0.0218 (11)	0.0035 (8)	0.0075 (9)	0.0041 (9)
N4	0.0207 (9)	0.0151 (8)	0.0185 (9)	0.0026 (7)	0.0050 (7)	0.0019 (7)
C16	0.0181 (10)	0.0213 (10)	0.0218 (11)	0.0028 (8)	0.0029 (9)	0.0050 (9)
O2	0.0195 (8)	0.0218 (8)	0.0345 (10)	0.0027 (6)	0.0095 (7)	0.0042 (7)
C17	0.0179 (10)	0.0204 (10)	0.0257 (11)	−0.0011 (8)	0.0005 (9)	0.0019 (9)
C18	0.0231 (11)	0.0216 (11)	0.0238 (11)	−0.0036 (9)	0.0030 (9)	−0.0033 (9)
N5	0.0197 (9)	0.0191 (9)	0.0189 (9)	−0.0001 (7)	0.0055 (7)	0.0004 (7)
C19	0.0180 (11)	0.0250 (11)	0.0280 (12)	−0.0003 (9)	0.0037 (9)	0.0066 (9)
N6	0.0179 (9)	0.0243 (10)	0.0225 (10)	0.0008 (7)	0.0041 (7)	0.0036 (8)
C20	0.0248 (12)	0.0381 (14)	0.0249 (12)	−0.0045 (10)	0.0056 (10)	0.0108 (11)
O21	0.0313 (9)	0.0191 (8)	0.0240 (8)	0.0075 (7)	0.0094 (7)	0.0030 (6)
O22	0.0664 (15)	0.0365 (11)	0.0461 (13)	0.0160 (10)	0.0363 (11)	0.0180 (9)
C21	0.0238 (11)	0.0216 (11)	0.0280 (12)	0.0023 (9)	0.0104 (10)	0.0016 (9)
C22	0.059 (2)	0.0289 (14)	0.0479 (18)	0.0102 (13)	0.0310 (15)	−0.0012 (13)
Cl1	0.0327 (3)	0.0236 (3)	0.0407 (4)	−0.0064 (2)	0.0174 (3)	−0.0033 (2)
O11	0.0666 (17)	0.0455 (14)	0.091 (2)	0.0156 (12)	0.0464 (16)	0.0182 (14)
O12	0.0669 (15)	0.0354 (11)	0.0379 (11)	−0.0225 (10)	0.0188 (11)	−0.0131 (9)
O13	0.0501 (13)	0.0599 (15)	0.0333 (11)	−0.0184 (11)	0.0075 (10)	−0.0022 (10)
O14	0.0365 (11)	0.0436 (12)	0.0369 (11)	−0.0104 (9)	0.0139 (9)	0.0040 (9)

Geometric parameters (Å, º)

Cu1—O21	1.9290 (16)	C11—N4	1.339 (3)
Cu1—N4	1.9861 (18)	C11—C12	1.387 (3)
Cu1—N5	2.074 (2)	C12—C13	1.394 (4)
Cu1—N1	2.2402 (19)	C12—H12	0.9500
Cu1—N2	2.2611 (19)	C13—C14	1.387 (4)
Cu1—N6	2.532 (2)	C13—H13	0.9500
Cu1—O22	2.946 (2)	C14—C15	1.386 (3)
N1—C5	1.336 (3)	C14—H14	0.9500
N1—C1	1.347 (3)	C15—N4	1.343 (3)
C1—C2	1.391 (3)	C15—C16	1.507 (3)
C1—C20	1.471 (3)	C16—O2	1.423 (3)
C2—C3	1.388 (4)	C16—N5	1.467 (3)
C2—H2	0.9500	C16—H16	1.0000
C3—C4	1.377 (4)	O2—C17	1.446 (3)
C3—H3	0.9500	C17—C19	1.517 (3)
C4—C5	1.395 (3)	C17—C18	1.528 (3)
C4—H4	0.9500	C17—H17	1.0000
C5—C6	1.521 (3)	C18—N5	1.481 (3)
C6—N3	1.451 (3)	C18—H18A	0.9900
C6—N2	1.494 (3)	C18—H18B	0.9900
C6—H6	1.0000	N5—H5	0.85 (3)
N2—C10	1.480 (3)	C19—N6	1.464 (3)
N2—C9	1.491 (3)	C19—H19A	0.9900
N3—C7	1.475 (3)	C19—H19B	0.9900
N3—H3A	0.84 (3)	N6—C20	1.259 (3)
C7—C8	1.530 (4)	C20—H20	0.9500
C7—H7A	0.9900	O21—C21	1.284 (3)
C7—H7B	0.9900	O22—C21	1.223 (3)
C8—O1	1.452 (3)	C21—C22	1.510 (3)
C8—C9	1.522 (3)	C22—H22A	0.9800
C8—H8	1.0000	C22—H22B	0.9800
C9—H9A	0.9900	C22—H22C	0.9800
C9—H9B	0.9900	Cl1—O11	1.415 (2)
O1—C10	1.431 (3)	Cl1—O12	1.425 (2)
C10—C11	1.509 (3)	Cl1—O14	1.446 (2)
C10—H10	1.0000	Cl1—O13	1.468 (2)
O21—Cu1—N4	167.34 (7)	N2—C10—C11	109.22 (18)
O21—Cu1—N5	95.90 (7)	O1—C10—H10	109.9
N4—Cu1—N5	80.03 (8)	N2—C10—H10	109.9
O21—Cu1—N1	86.06 (7)	C11—C10—H10	109.9
N4—Cu1—N1	103.57 (7)	N4—C11—C12	121.8 (2)
N5—Cu1—N1	149.52 (8)	N4—C11—C10	114.90 (19)
O21—Cu1—N2	99.81 (7)	C12—C11—C10	123.3 (2)
N4—Cu1—N2	76.17 (7)	C11—C12—C13	118.4 (2)
N5—Cu1—N2	137.94 (7)	C11—C12—H12	120.8
N1—Cu1—N2	70.77 (7)	C13—C12—H12	120.8
O21—Cu1—N6	89.99 (7)	C14—C13—C12	119.4 (2)
N4—Cu1—N6	101.13 (7)	C14—C13—H13	120.3
N5—Cu1—N6	81.18 (7)	C12—C13—H13	120.3
N1—Cu1—N6	68.39 (7)	C15—C14—C13	118.8 (2)
N2—Cu1—N6	137.11 (7)	C15—C14—H14	120.6
O21—Cu1—O22	48.74 (6)	C13—C14—H14	120.6
N4—Cu1—O22	118.70 (7)	N4—C15—C14	121.5 (2)
N5—Cu1—O22	74.04 (7)	N4—C15—C16	114.56 (19)
N1—Cu1—O22	126.12 (7)	C14—C15—C16	123.9 (2)
N2—Cu1—O22	87.72 (7)	C11—N4—C15	119.9 (2)
N6—Cu1—O22	127.36 (7)	C11—N4—Cu1	121.91 (15)
C5—N1—C1	119.1 (2)	C15—N4—Cu1	117.88 (15)
C5—N1—Cu1	118.31 (15)	O2—C16—N5	105.45 (18)
C1—N1—Cu1	121.98 (16)	O2—C16—C15	110.01 (19)
N1—C1—C2	122.0 (2)	N5—C16—C15	110.10 (18)
N1—C1—C20	116.0 (2)	O2—C16—H16	110.4
C2—C1—C20	121.9 (2)	N5—C16—H16	110.4
C3—C2—C1	118.3 (2)	C15—C16—H16	110.4
C3—C2—H2	120.8	C16—O2—C17	109.36 (17)
C1—C2—H2	120.8	O2—C17—C19	108.9 (2)
C4—C3—C2	119.8 (2)	O2—C17—C18	104.83 (18)
C4—C3—H3	120.1	C19—C17—C18	114.24 (19)
C2—C3—H3	120.1	O2—C17—H17	109.6
C3—C4—C5	118.6 (2)	C19—C17—H17	109.6
C3—C4—H4	120.7	C18—C17—H17	109.6
C5—C4—H4	120.7	N5—C18—C17	102.77 (18)
N1—C5—C4	122.1 (2)	N5—C18—H18A	111.2
N1—C5—C6	115.4 (2)	C17—C18—H18A	111.2
C4—C5—C6	122.6 (2)	N5—C18—H18B	111.2
N3—C6—N2	114.89 (19)	C17—C18—H18B	111.2
N3—C6—C5	110.92 (19)	H18A—C18—H18B	109.1
N2—C6—C5	107.72 (18)	C16—N5—C18	103.40 (18)
N3—C6—H6	107.7	C16—N5—Cu1	110.17 (14)
N2—C6—H6	107.7	C18—N5—Cu1	117.29 (15)
C5—C6—H6	107.7	C16—N5—H5	108 (2)
C10—N2—C9	101.40 (17)	C18—N5—H5	111 (2)
C10—N2—C6	109.23 (17)	Cu1—N5—H5	106 (2)
C9—N2—C6	108.63 (17)	N6—C19—C17	109.34 (19)
C10—N2—Cu1	106.92 (13)	N6—C19—H19A	109.8
C9—N2—Cu1	119.32 (14)	C17—C19—H19A	109.8
C6—N2—Cu1	110.63 (13)	N6—C19—H19B	109.8
C6—N3—C7	112.9 (2)	C17—C19—H19B	109.8
C6—N3—H3A	110 (2)	H19A—C19—H19B	108.3
C7—N3—H3A	109 (2)	C20—N6—C19	118.4 (2)
N3—C7—C8	112.21 (19)	C20—N6—Cu1	112.66 (16)
N3—C7—H7A	109.2	C19—N6—Cu1	128.17 (14)
C8—C7—H7A	109.2	N6—C20—C1	119.2 (2)
N3—C7—H7B	109.2	N6—C20—H20	120.4
C8—C7—H7B	109.2	C1—C20—H20	120.4
H7A—C7—H7B	107.9	C21—O21—Cu1	117.40 (15)
O1—C8—C9	101.82 (19)	O22—C21—O21	124.1 (2)
O1—C8—C7	109.3 (2)	O22—C21—C22	120.7 (2)
C9—C8—C7	109.4 (2)	O21—C21—C22	115.2 (2)
O1—C8—H8	111.9	C21—C22—H22A	109.5
C9—C8—H8	111.9	C21—C22—H22B	109.5
C7—C8—H8	111.9	H22A—C22—H22B	109.5
N2—C9—C8	99.49 (18)	C21—C22—H22C	109.5
N2—C9—H9A	111.9	H22A—C22—H22C	109.5
C8—C9—H9A	111.9	H22B—C22—H22C	109.5
N2—C9—H9B	111.9	O11—Cl1—O12	111.98 (17)
C8—C9—H9B	111.9	O11—Cl1—O14	111.64 (14)
H9A—C9—H9B	109.6	O12—Cl1—O14	110.25 (13)
C10—O1—C8	107.12 (17)	O11—Cl1—O13	106.96 (17)
O1—C10—N2	107.34 (17)	O12—Cl1—O13	106.37 (14)
O1—C10—C11	110.53 (18)	O14—Cl1—O13	109.42 (13)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3A···O12	0.84 (3)	2.29 (4)	3.111 (3)	165 (3)
N5—H5···O22	0.85 (3)	2.63 (3)	3.102 (3)	116 (2)
N5—H5···O22^i	0.85 (3)	2.11 (3)	2.843 (3)	145 (3)

Symmetry code: (i) −x, −y, −z+2.