An alternating copolymer containing trigonal planar homocoordinated copper(I) ions: catena-poly[[[bis­[μ-(E)-1,2-bis­(1-ethyl-1H-benzimidazol-2-yl)ethene-κ²N³:N^3′]dicopper(I)]-μ-(E)-1,2-bis­(1-ethyl-1H-benzimidazol-2-yl)ethene-κ²N³:N^3′] bis­(perchlorate) acetonitrile disolvate]

The structure of the title salt, {[Cu₂(C₂₀H₂₀N₄)₃](ClO₄)₂·2CH₃CN}_n, consists of linear [Cu^I₂L₃] polymer chains [L is (E)-1,2-bis­(1-ethyl-1H-benzimidazol-2-yl)ethene], which extend along the c cell direction, inter­spersed with disordered perchlorate ions and acetonitrile solvent mol­ecules. In a given chain, each Cu^I ion exhibits distorted trigonal planar coordination to three L ligands; two of these are linked to adjacent Cu^I ions to form dimeric units containing 14-membered rings that adopt a twisted-loop configuration, stabilized by π–π inter­actions between the ethene fragments of the two ligands. The dimeric units exhibit diad symmetry (twofold axis sites in I2/a) and are linked by a third, centrosymmetric, S-shaped L ligand (inversion centers in I2/a) to form the copolymer chain. When viewed along the b cell direction, the 14-membered rings appear as vacant ellipses that form channels parallel to the b axis. The walls of the channels are formed by the benzimidazole fragments of the dimeric units. This study of a novel alternating copolymer containing homocoordinated Cu^I ions demonstrates further the usefulness of bis(benzimidazoles) as versatile bidentate ligands.

S1. Comment

Our long-standing interest in the chemistry of bis(imidazoles), bis(benzimidazoles) and their complexes with metal ions has demonstrated the usefulness of these species as geometrically constraining ligands (Stibrany et al., 2004), proton sponges (Stibrany et al., 2002), polymerization catalysts (Stibrany et al., 2003; Stibrany & Kacker, 2002), and agents to study electron transfer (Knapp et al., 1990; Xie et al., 1999). An effort to prepare a coordination complex of Cu^II and L, where L is (E)-1,2-bis(1-ethylbenzimidazol-2-yl)ethene, yielded instead, via a redox reaction, an amorphous mass and a few low-quality crystals of the title salt, (I), [Cu^I₂L₃](ClO₄)₂(CH₃CN)_2. High-quality crystals, one of which was used for the structure determination reported here, were obtained in good yield by the direct reaction of Cu^I(ClO₄) and L in acetonitrile.

The structure of (I) consists of Cu^I₂L₂ dimeric units bridged by ligands L to form linear polymeric chains interspersed with disordered perchlorate counter-ions and with solvent acetonitrile molecules. In addition to a perchlorate ion and an acetonitrile solvent molecule, the asymmetric unit (Fig. 1) contains a Cu^I ion bonded to the imine N atoms N13 and N33 of two L ligands. Only half of the ligand containing N33 is unique, and the cation portion of the asymmetric unit can be viewed as containing a Cu^I ion and three half ligands (ethylbenzimidazole fragments containing one ethene atom), which we designate as etbzim1, etbzim2 and etbzim3 for the fragments containing N13, N23 and N33, respectively.

In forming the polymer chain, both ligands utilize crystallographic symmetry. Ligands L derived from etbzim3 are centrosymmetrically related (4d sites in I2/a), with the inversion centers located at the mid-points of the ethene fragments (atom C3 and its symmetry-related partner in Fig. 1), while ligands generated from etbzim1 and etbzim2 exhibit twofold symmetry (4e sites in space group I2/a). The result is the alternating copolymer chain sketched in the scheme and shown in Fig. 2. Partial removal of the benzimidazole fragments, as in Fig. 3, helps to clarify the connectivity and the linkage along a given chain. Thus, etbzim1 and etbzim2 are linked to adjacent Cu atoms by two S-shaped ligands L in a twisted-loop arrangement to yield dimeric units. The two symmetry-related Cu ions in the dimeric units are part of 14-membered rings, which are stabilized by π–π interactions (Janiak, 2000) between the ethene groups, as indicated by the C1···C1' and C2···C2' distances of 3.399 (3) and 3.351 (3) Å), respectively. A third S-shaped bidentate ligand links the dimers and completes the alternating copolymer cation chain.

At the unique Cu^I ion (Fig. 2), a distorted trigonal–planar coordination geometry is formed (Table 1), in which the Cu—N33 bond length to etbzim3 is substantially longer than the corresponding Cu—N(imine) bonds to etbzim1 and etbzim2, while the N13—Cu—N23 angle, involving etbzim1 and etbzim2, is substantially larger than those involving etbzim3. Excluding the methyl group atoms and the methylene H atoms, the atoms of a given benzimidazole fragment are essentially coplanar, as expected, and, as indicated by the metric data in Table 2, the geometric parameters of the three ligands compare well with one another and with those of the unique, centrosymmetric benzimidazole fragments in two structures that contain the free ligand L (La: Stibrany et al., 2005; Lb: Stibrany & Potenza, 2006).

In the crystal structure (Fig. 4), the polymer strands extend along the c cell direction and form layers centered about the planes x = 1/4 and 3/4. With crystallographic symmetry taken into account, the repeat unit in the solid state is seen to consist of two dimers and two single-ligand linkers. In Fig. 4, the S-shaped centrosymmetric ligands are clearly seen, while the 14-membered rings, viewed along their diad axes, appear as jagged ellipses. The ellipses outline vacant channels along the b cell direction, each with a cross section area of approximately 14 Ų, with the major and minor axes of the ellipses taken as the Cu···Cu' and ethene–ethene π overlap distances, respectively. The perchlorate counter-ions are centered about the planes x = 0 and 1/2, midway between the polymer strands. Along these planes, the perchlorate anions alternate with benzimidazole fragments from bzim3, which extend from the polymer chains along the a cell direction. In contrast, the benzimidazole fragments bzim1 and bzim2 extend along the b cell direction and form the walls of the channels noted above. The perchlorate ions are stabilized somewhat in the crystal structure by several weak C—H···O hydrogen bonds with the benzimidazole fragments. The solvent acetonitrile molecules are associated closely with a given chain (Fig. 4), with the cyano group located near the N(amine) and C(methylene) atoms, N33 and C32, respectively, of bzim3.

Knowledge of the structure is helpful in suggesting a possible path for the formation and termination of the copolymer chains. In acetonitrile, CuClO₄ forms Cu(NCCH₃)₄⁺ ions. Stepwise replacement of acetonitrile by the stronger imine bases of the bulky ligand L could produce the copolymer chains, which may be terminated at Cu by having one or two acetonitrile ligands complete the coordination of a terminal dimer. In support of this possibility, we note that a structure containing trigonal Cu^I(bbil)(NCCH₃) and tetrahedral Cu^I(bbil)(NCCH₃)₂ cations in the same crystal, where bbil is a bis(benzimidazole) ligand similar to L, has recently been reported (Stibrany & Potenza, 2006).

Structurally characterized polymeric complexes containing trigonally coordinated copper(I) ions are rare. We are aware of four such systems, one with alternating trigonal CuCl₃ and tetrahedral CuCl₄ units (Andersson & Jagner, 1988), one with N, S and Cl coordination to Cu^I (Devillanova et al., 1998), and two organometallic complexes with trigonal coordination of Cu^I by an olefin and two chloride ions (Baenziger et al., 1964; Goreshnik et al., 2005). In the four complexes noted above, the Cu^I—Cl and Cu^I—S linkages, formed with the relatively soft Cl and S ligands, range from 2.215 (2) to 2.288 (2) Å, all substantially larger than the Cu^I—N distances in the title complex, which are derived from the hard (stronger) imine bases in the benzimidazole fragments. The lone Cu—N(imine) distance of 1.929 Å in one of the complexes above (Devillanova et al., 1998) compares favorably with those in the title complex.

Lastly, we note that, owing to the steric bulk and limited flexibility of ligands such as L, it would seem possible to prepare a variety of polymers similar to that of the title complex with Cu^I and with other metals, such as Ag^I, known to accommodate trigonal coordination easily.

S2. Experimental

A colorless solution of 50 mg of [Cu(CH₃CN)₄](ClO₄) (0.15 mmol) was prepared in 10 ml of acetonitrile and 1 ml of methanol. Addition of 73 mg of (E)-1,2-bis(1-ethylbenzimidazol-2-yl)ethene (0.22 mmol) yielded a green solution, which was sealed in a jar containing diethyl ether to allow slow vapor diffusion. Orange crystalline prisms formed over a period of several days. The crystals exhibited yellow–green dichroism (yield 62 mg, 59.9%).

S3. Refinement

H atoms were positioned geometrically and were refined using a riding model, with C—H distances of 0.93–0.97 Å and U_iso(H) values of 1.5 U_eq(C) for the methyl H atoms and 1.2 U_eq(C) for all others. The perchlorate group exhibited large thermal parameters and was modeled assuming a three-site disorder about a threefold axis; the occupancy factors for the three components were allowed to vary and their summation was set to 1.00. A total of 26 restraints was employed to ensure convergence of this model.

Computing details

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEPIII (Burnett & Johnson, 1996) and ORTEP-32 (Farrugia, 1997); software used to prepare material for publication: SHELXTL (Version 6.10; Sheldrick, 2008).

Figures

	Fig. 1. A view of the asymmetric unit, showing 30% probability displacement ellipsoids and the atom-numbering scheme. Only the major component of the disordered perchlorate ion is shown. [Symmetry code: (iii) –x + 1/2, −y + 1/2, −z + 3/2.]
	Fig. 2. The repeat unit of the cationic, alternating copolymer chain in (I). H atoms have been omitted for clarity. [Symmetry codes: (ii) −x + 1/2, y, −z + 1; (iii) −x + 1/2, −y + 1/2, −z + 3/2; (iv) x, −y + 1/2, z + 1/2.]
	Fig. 3. The repeat unit showing only the connectivity of the Cu^I ions. The view is approximately normal to the twofold axis of the 14-membered ring. Displacement ellipsoids are shown at the 30% probability level. [Symmetry codes: (ii) −x + 1/2, y, −z + 1; (iii) −x + 1/2, −y + 1/2, −z + 3/2; (iv): x, −y + 1/2, z + 1/2.]
	Fig. 4. A projection of the structure along the b axis constructed by using the repeat unit in Fig. 3, augmented by the ethyl groups of the ligand.

catena-poly[[[bis[µ-(E)-1,2-bis(1-ethyl-1H-benzimidazol-2-yl)ethene-κ²N³:N^3']dicopper(I)]-µ-(E)-1,2-bis(1-ethyl-1H-benzimidazol-2-yl)ethene-κ²N³:N^3'] bis(perchlorate) acetonitrile disolvate]

Crystal data

[Cu2(C20H20N4)3](ClO4)2·2C2H3N	F(000) = 2816
Mr = 678.64	Dx = 1.367 Mg m^−3
Monoclinic, I2/a	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -I 2ya	Cell parameters from 1014 reflections
a = 21.834 (6) Å	θ = 2.4–25.2°
b = 12.948 (4) Å	µ = 0.79 mm^−1
c = 23.502 (10) Å	T = 297 K
β = 97.039 (4)°	Prism, orange
V = 6594 (4) Å^3	0.47 × 0.25 × 0.15 mm
Z = 8

Data collection

Bruker SMART CCD area-detector diffractometer	6478 independent reflections
Radiation source: fine-focus sealed tube	5414 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.023
ϕ and ω scans	θmax = 26.0°, θmin = 2.4°
Absorption correction: multi-scan (SADABS; Blessing, 1995)	h = −26→26
Tmin = 0.757, Tmax = 1.00	k = −15→15
30631 measured reflections	l = −28→28

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)] = 0.033	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.096	H-atom parameters constrained
S = 1.00	w = 1/[σ^2(Fo^2) + (0.0645P)^2 + 2.91P] where P = (Fo^2 + 2Fc^2)/3
6478 reflections	(Δ/σ)max = 0.002
469 parameters	Δρmax = 0.41 e Å^−3
26 restraints	Δρmin = −0.21 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	Occ. (<1)
Cu1	0.290850 (9)	0.282786 (15)	0.617923 (8)	0.03564 (9)
N11	0.16281 (7)	0.49507 (10)	0.54648 (6)	0.0364 (3)
N13	0.23106 (6)	0.39187 (10)	0.59648 (6)	0.0345 (3)
N23	0.18214 (6)	0.15744 (11)	0.41895 (6)	0.0348 (3)
N21	0.15085 (6)	0.04506 (11)	0.48138 (6)	0.0352 (3)
N31	0.39076 (7)	0.25593 (15)	0.78175 (7)	0.0490 (4)
N33	0.34544 (7)	0.29116 (12)	0.69369 (6)	0.0392 (3)
C1	0.17362 (7)	0.32091 (13)	0.50766 (7)	0.0344 (3)
H1	0.1595	0.3422	0.4706	0.041*
C2	0.17790 (8)	0.22007 (12)	0.51753 (7)	0.0338 (3)
H2	0.1867	0.1978	0.5553	0.041*
C3	0.27702 (8)	0.24514 (16)	0.76595 (8)	0.0414 (4)
H3	0.2768	0.2243	0.8038	0.050*
C11	0.18837 (8)	0.55167 (13)	0.59280 (7)	0.0387 (4)
C12	0.18933 (7)	0.40004 (12)	0.55032 (7)	0.0326 (3)
C13	0.23097 (8)	0.48698 (13)	0.62415 (7)	0.0373 (4)
C14	0.26569 (9)	0.52153 (16)	0.67409 (8)	0.0484 (5)
H14	0.2943	0.4791	0.6953	0.058*
C15	0.25561 (11)	0.62187 (17)	0.69073 (9)	0.0596 (6)
H15	0.2784	0.6478	0.7236	0.072*
C16	0.21214 (12)	0.68520 (16)	0.65945 (10)	0.0608 (6)
H16	0.2064	0.7519	0.6725	0.073*
C17	0.17763 (10)	0.65250 (14)	0.61011 (9)	0.0507 (5)
H17	0.1487	0.6950	0.5893	0.061*
C18	0.11490 (9)	0.53181 (15)	0.50168 (8)	0.0464 (4)
H18A	0.0883	0.5803	0.5184	0.056*
H18B	0.0898	0.4737	0.4869	0.056*
C19	0.14148 (14)	0.5832 (2)	0.45331 (11)	0.0803 (8)
H19A	0.1689	0.6374	0.4681	0.120*
H19B	0.1087	0.6118	0.4270	0.120*
H19C	0.1639	0.5334	0.4337	0.120*
C21	0.15102 (8)	−0.00746 (13)	0.43050 (8)	0.0374 (4)
C22	0.16961 (7)	0.14295 (12)	0.47263 (7)	0.0324 (3)
C23	0.17065 (8)	0.06296 (13)	0.39174 (7)	0.0372 (4)
C24	0.17902 (10)	0.03166 (16)	0.33650 (8)	0.0502 (5)
H24	0.1925	0.0776	0.3103	0.060*
C25	0.16656 (11)	−0.06967 (17)	0.32229 (10)	0.0590 (5)
H25	0.1719	−0.0926	0.2857	0.071*
C26	0.14611 (10)	−0.13884 (16)	0.36108 (10)	0.0572 (5)
H26	0.1380	−0.2067	0.3497	0.069*
C27	0.13755 (9)	−0.10983 (14)	0.41581 (9)	0.0479 (4)
H27	0.1235	−0.1560	0.4416	0.057*
C28	0.13061 (9)	0.00225 (14)	0.53360 (8)	0.0449 (4)
H28A	0.0940	−0.0396	0.5235	0.054*
H28B	0.1197	0.0583	0.5578	0.054*
C29	0.18003 (12)	−0.0629 (2)	0.56642 (11)	0.0763 (7)
H29A	0.1915	−0.1176	0.5423	0.114*
H29B	0.1647	−0.0917	0.5995	0.114*
H29C	0.2155	−0.0208	0.5784	0.114*
C31	0.43703 (9)	0.27983 (17)	0.74982 (9)	0.0503 (5)
C32	0.33633 (8)	0.26430 (14)	0.74665 (7)	0.0387 (4)
C33	0.40860 (9)	0.30155 (16)	0.69479 (8)	0.0446 (4)
C34	0.44357 (10)	0.3284 (2)	0.65143 (10)	0.0617 (6)
H34	0.4251	0.3432	0.6146	0.074*
C35	0.50635 (11)	0.3323 (3)	0.66515 (12)	0.0783 (8)
H35	0.5308	0.3496	0.6368	0.094*
C36	0.53447 (11)	0.3112 (3)	0.72012 (13)	0.0838 (9)
H36	0.5772	0.3155	0.7277	0.101*
C37	0.50084 (10)	0.2841 (2)	0.76379 (11)	0.0717 (7)
H37	0.5197	0.2694	0.8005	0.086*
C38	0.40102 (11)	0.2191 (2)	0.84102 (9)	0.0706 (8)
H38A	0.3635	0.2278	0.8587	0.085*
H38B	0.4331	0.2603	0.8624	0.085*
C39	0.41966 (14)	0.1076 (3)	0.84414 (14)	0.1008 (11)
H39A	0.3867	0.0660	0.8254	0.151*
H39B	0.4282	0.0870	0.8836	0.151*
H39C	0.4560	0.0982	0.8254	0.151*
N6	0.3841 (2)	0.5218 (5)	0.7969 (2)	0.194 (2)
C6	0.4325 (2)	0.5296 (4)	0.8181 (2)	0.1262 (14)
C7	0.4933 (2)	0.5380 (4)	0.8462 (2)	0.1360 (16)
H7A	0.5067	0.4720	0.8616	0.204*
H7B	0.4943	0.5875	0.8767	0.204*
H7C	0.5203	0.5603	0.8193	0.204*
Cl1	0.50228 (2)	0.23206 (4)	0.49950 (3)	0.05883 (15)
O1	0.56385 (7)	0.22805 (12)	0.52523 (8)	0.0722 (5)
O2	0.4636 (3)	0.1939 (14)	0.5391 (3)	0.099 (6)	0.278 (17)
O2A	0.4673 (3)	0.1629 (7)	0.5295 (5)	0.121 (5)	0.559 (19)
O2B	0.5213 (7)	0.2831 (16)	0.4364 (4)	0.099 (7)	0.165 (10)
O3	0.4956 (4)	0.1681 (11)	0.4506 (4)	0.074 (4)	0.278 (17)
O3A	0.4987 (4)	0.2028 (11)	0.4420 (2)	0.166 (7)	0.559 (19)
O3B	0.4760 (6)	0.1496 (10)	0.4800 (8)	0.117 (8)	0.165 (10)
O4	0.4852 (6)	0.3337 (5)	0.4842 (9)	0.132 (9)	0.278 (17)
O4A	0.4785 (3)	0.3324 (4)	0.5044 (6)	0.112 (4)	0.559 (19)
O4B	0.4711 (6)	0.3147 (14)	0.5154 (7)	0.087 (8)	0.165 (10)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.04165 (14)	0.03298 (13)	0.03171 (13)	0.00657 (8)	0.00219 (9)	0.00009 (8)
N11	0.0419 (8)	0.0288 (7)	0.0375 (7)	0.0054 (6)	0.0014 (6)	0.0006 (6)
N13	0.0417 (8)	0.0298 (7)	0.0315 (7)	0.0055 (6)	0.0018 (6)	−0.0026 (5)
N23	0.0415 (8)	0.0288 (7)	0.0334 (7)	−0.0054 (6)	0.0023 (6)	−0.0012 (6)
N21	0.0384 (7)	0.0281 (7)	0.0398 (8)	−0.0019 (5)	0.0076 (6)	0.0015 (6)
N31	0.0378 (8)	0.0742 (11)	0.0327 (8)	−0.0005 (8)	−0.0049 (6)	0.0020 (8)
N33	0.0374 (8)	0.0481 (9)	0.0315 (7)	0.0027 (6)	0.0015 (6)	−0.0021 (6)
C1	0.0382 (9)	0.0332 (8)	0.0309 (8)	0.0018 (7)	0.0007 (6)	0.0014 (7)
C2	0.0377 (9)	0.0320 (8)	0.0314 (8)	−0.0003 (6)	0.0037 (7)	0.0010 (6)
C3	0.0399 (9)	0.0546 (11)	0.0292 (8)	0.0032 (8)	0.0028 (7)	−0.0009 (8)
C11	0.0457 (9)	0.0317 (8)	0.0385 (9)	0.0019 (7)	0.0047 (7)	−0.0023 (7)
C12	0.0374 (8)	0.0285 (8)	0.0324 (8)	0.0026 (6)	0.0055 (6)	0.0009 (6)
C13	0.0455 (9)	0.0321 (8)	0.0344 (8)	0.0032 (7)	0.0047 (7)	−0.0032 (7)
C14	0.0578 (12)	0.0437 (10)	0.0412 (10)	0.0066 (9)	−0.0040 (8)	−0.0066 (8)
C15	0.0784 (15)	0.0490 (12)	0.0488 (11)	0.0002 (11)	−0.0024 (10)	−0.0173 (10)
C16	0.0862 (16)	0.0358 (10)	0.0592 (13)	0.0069 (10)	0.0044 (12)	−0.0134 (9)
C17	0.0636 (12)	0.0313 (9)	0.0566 (12)	0.0089 (8)	0.0044 (9)	−0.0031 (8)
C18	0.0481 (10)	0.0394 (10)	0.0488 (11)	0.0101 (8)	−0.0061 (8)	0.0031 (8)
C19	0.100 (2)	0.0823 (18)	0.0588 (14)	0.0253 (15)	0.0088 (13)	0.0297 (13)
C21	0.0357 (8)	0.0317 (8)	0.0448 (10)	−0.0025 (7)	0.0041 (7)	−0.0037 (7)
C22	0.0333 (8)	0.0282 (8)	0.0353 (8)	−0.0002 (6)	0.0028 (6)	0.0024 (6)
C23	0.0387 (9)	0.0338 (8)	0.0384 (9)	−0.0037 (7)	0.0017 (7)	−0.0033 (7)
C24	0.0626 (12)	0.0465 (11)	0.0416 (10)	−0.0097 (9)	0.0070 (9)	−0.0066 (8)
C25	0.0737 (14)	0.0535 (12)	0.0503 (12)	−0.0076 (11)	0.0090 (10)	−0.0196 (10)
C26	0.0671 (13)	0.0374 (10)	0.0668 (14)	−0.0096 (9)	0.0070 (11)	−0.0174 (10)
C27	0.0508 (11)	0.0323 (9)	0.0608 (12)	−0.0076 (8)	0.0077 (9)	−0.0038 (8)
C28	0.0523 (11)	0.0357 (9)	0.0487 (10)	−0.0061 (8)	0.0150 (8)	0.0059 (8)
C29	0.0752 (16)	0.0803 (17)	0.0708 (16)	−0.0030 (13)	−0.0017 (13)	0.0351 (14)
C31	0.0388 (10)	0.0672 (14)	0.0434 (10)	−0.0036 (9)	−0.0014 (8)	−0.0055 (9)
C32	0.0353 (9)	0.0479 (10)	0.0317 (8)	0.0023 (7)	−0.0007 (7)	−0.0044 (7)
C33	0.0384 (9)	0.0539 (11)	0.0409 (10)	−0.0015 (8)	0.0023 (7)	−0.0034 (8)
C34	0.0500 (12)	0.0855 (17)	0.0506 (12)	−0.0084 (11)	0.0103 (9)	0.0032 (11)
C35	0.0516 (13)	0.117 (2)	0.0694 (16)	−0.0179 (14)	0.0196 (12)	−0.0016 (16)
C36	0.0382 (12)	0.132 (3)	0.0812 (18)	−0.0165 (14)	0.0057 (12)	−0.0113 (18)
C37	0.0389 (11)	0.113 (2)	0.0604 (14)	−0.0078 (12)	−0.0054 (10)	−0.0036 (14)
C38	0.0470 (12)	0.128 (3)	0.0338 (10)	−0.0007 (13)	−0.0069 (9)	0.0113 (12)
C39	0.084 (2)	0.128 (3)	0.091 (2)	0.0118 (19)	0.0113 (16)	0.056 (2)
N6	0.123 (3)	0.257 (6)	0.192 (5)	0.020 (4)	−0.025 (3)	−0.069 (4)
C6	0.112 (3)	0.134 (4)	0.127 (3)	0.020 (3)	−0.005 (3)	−0.030 (3)
C7	0.111 (3)	0.125 (3)	0.165 (4)	0.010 (3)	−0.014 (3)	−0.015 (3)
Cl1	0.0380 (3)	0.0537 (3)	0.0823 (4)	0.0017 (2)	−0.0025 (2)	−0.0063 (3)
O1	0.0446 (8)	0.0576 (10)	0.1089 (14)	0.0038 (7)	−0.0129 (9)	−0.0113 (9)
O2	0.052 (5)	0.193 (18)	0.055 (6)	−0.018 (6)	0.021 (4)	−0.013 (7)
O2A	0.092 (4)	0.076 (4)	0.200 (12)	−0.034 (3)	0.034 (5)	0.027 (5)
O2B	0.090 (10)	0.126 (16)	0.078 (9)	0.008 (10)	−0.007 (7)	0.029 (9)
O3	0.070 (6)	0.102 (8)	0.045 (5)	−0.009 (5)	−0.007 (4)	−0.022 (5)
O3A	0.195 (12)	0.217 (14)	0.074 (4)	0.099 (10)	−0.032 (5)	−0.005 (6)
O3B	0.105 (12)	0.134 (14)	0.110 (17)	−0.079 (11)	0.014 (11)	−0.062 (13)
O4	0.064 (8)	0.084 (9)	0.24 (2)	0.013 (6)	−0.017 (11)	0.047 (10)
O4A	0.069 (4)	0.048 (3)	0.225 (11)	0.016 (3)	0.041 (6)	0.008 (4)
O4B	0.071 (12)	0.109 (17)	0.083 (11)	0.054 (12)	0.021 (9)	0.002 (11)

Geometric parameters (Å, º)

Cu1—N13	1.9473 (14)	C26—H26	0.9300
Cu1—N23^i	1.9642 (14)	C27—H27	0.9300
Cu1—N33	2.0206 (16)	C28—C29	1.505 (3)
N11—C12	1.358 (2)	C28—H28A	0.9700
N11—C11	1.373 (2)	C28—H28B	0.9700
N11—C18	1.470 (2)	C29—H29A	0.9600
N13—C12	1.333 (2)	C29—H29B	0.9600
N13—C13	1.393 (2)	C29—H29C	0.9600
N23—C22	1.336 (2)	C31—C37	1.393 (3)
N23—C23	1.389 (2)	C31—C33	1.393 (3)
N23—Cu1^i	1.9642 (14)	C33—C34	1.390 (3)
N21—C22	1.355 (2)	C34—C35	1.370 (3)
N21—C21	1.376 (2)	C34—H34	0.9300
N21—C28	1.463 (2)	C35—C36	1.388 (4)
N31—C32	1.366 (2)	C35—H35	0.9300
N31—C31	1.366 (3)	C36—C37	1.379 (4)
N31—C38	1.463 (3)	C36—H36	0.9300
N33—C32	1.330 (2)	C37—H37	0.9300
N33—C33	1.383 (2)	C38—C39	1.500 (5)
C1—C2	1.327 (2)	C38—H38A	0.9700
C1—C12	1.445 (2)	C38—H38B	0.9700
C1—H1	0.9300	C39—H39A	0.9600
C2—C22	1.448 (2)	C39—H39B	0.9600
C2—H2	0.9300	C39—H39C	0.9600
C3—C3^ii	1.324 (4)	N6—C6	1.115 (5)
C3—C32	1.445 (3)	C6—C7	1.413 (6)
C3—H3	0.9300	C7—H7A	0.9600
C11—C13	1.393 (2)	C7—H7B	0.9600
C11—C17	1.396 (2)	C7—H7C	0.9600
C13—C14	1.391 (3)	Cl1—O3B	1.271 (9)
C14—C15	1.382 (3)	Cl1—O4B	1.345 (10)
C14—H14	0.9300	Cl1—O3A	1.396 (4)
C15—C16	1.394 (3)	Cl1—O4	1.403 (4)
C15—H15	0.9300	Cl1—O1	1.4059 (16)
C16—C17	1.370 (3)	Cl1—O4A	1.409 (4)
C16—H16	0.9300	Cl1—O3	1.409 (4)
C17—H17	0.9300	Cl1—O2	1.419 (4)
C18—C19	1.495 (3)	Cl1—O2A	1.420 (4)
C18—H18A	0.9700	Cl1—O2B	1.719 (10)
C18—H18B	0.9700	O2—O3B	1.56 (2)
C19—H19A	0.9600	O2—O4B	1.67 (2)
C19—H19B	0.9600	O2A—O3B	1.214 (19)
C19—H19C	0.9600	O2B—O3A	1.165 (19)
C21—C27	1.392 (2)	O2B—O4	1.59 (3)
C21—C23	1.393 (2)	O2B—O3	1.64 (2)
C23—C24	1.393 (3)	O3—O3A	0.50 (2)
C24—C25	1.373 (3)	O3—O3B	0.89 (2)
C24—H24	0.9300	O3A—O3B	1.276 (19)
C25—C26	1.390 (3)	O4—O4A	0.51 (3)
C25—H25	0.9300	O4—O4B	0.86 (3)
C26—C27	1.375 (3)
N13—Cu1—N23^i	135.49 (6)	C35—C34—C33	117.4 (2)
N13—Cu1—N33	119.57 (6)	C35—C34—H34	121.3
N23—Cu1—N33^i	104.87 (6)	C33—C34—H34	121.3
C12—N11—C11	107.61 (14)	C34—C35—C36	121.8 (2)
C12—N11—C18	126.95 (15)	C34—C35—H35	119.1
C11—N11—C18	125.44 (15)	C36—C35—H35	119.1
C12—N13—C13	105.66 (13)	C37—C36—C35	121.9 (2)
C12—N13—Cu1	129.65 (11)	C37—C36—H36	119.1
C13—N13—Cu1	124.04 (11)	C35—C36—H36	119.1
C22—N23—C23	105.34 (14)	C36—C37—C31	116.3 (2)
C22—N23—Cu1^i	129.77 (11)	C36—C37—H37	121.8
C23—N23—Cu1^i	124.87 (12)	C31—C37—H37	121.8
C22—N21—C21	107.29 (14)	N31—C38—C39	111.7 (2)
C22—N21—C28	127.54 (15)	N31—C38—H38A	109.3
C21—N21—C28	125.09 (15)	C39—C38—H38A	109.3
C32—N31—C31	107.31 (16)	N31—C38—H38B	109.3
C32—N31—C38	128.41 (18)	C39—C38—H38B	109.3
C31—N31—C38	124.03 (17)	H38A—C38—H38B	107.9
C32—N33—C33	105.72 (15)	C38—C39—H39A	109.5
C32—N33—Cu1	132.12 (13)	C38—C39—H39B	109.5
C33—N33—Cu1	120.07 (12)	H39A—C39—H39B	109.5
C2—C1—C12	124.79 (15)	C38—C39—H39C	109.5
C2—C1—H1	117.6	H39A—C39—H39C	109.5
C12—C1—H1	117.6	H39B—C39—H39C	109.5
C1—C2—C22	123.44 (15)	N6—C6—C7	178.6 (7)
C1—C2—H2	118.3	C6—C7—H7A	109.5
C22—C2—H2	118.3	C6—C7—H7B	109.5
C3^ii—C3—C32	125.2 (2)	H7A—C7—H7B	109.5
C3^ii—C3—H3	117.4	C6—C7—H7C	109.5
C32—C3—H3	117.4	H7A—C7—H7C	109.5
N11—C11—C13	106.17 (15)	H7B—C7—H7C	109.5
N11—C11—C17	131.60 (17)	O3B—Cl1—O4B	123.1 (5)
C13—C11—C17	122.23 (17)	O3B—Cl1—O3A	56.9 (9)
N13—C12—N11	111.68 (14)	O4B—Cl1—O3A	120.9 (8)
N13—C12—C1	126.08 (15)	O3B—Cl1—O4	127.0 (8)
N11—C12—C1	122.23 (15)	O3A—Cl1—O4	91.4 (10)
C14—C13—N13	130.29 (16)	O3B—Cl1—O1	119.3 (7)
C14—C13—C11	120.82 (16)	O4B—Cl1—O1	113.6 (6)
N13—C13—C11	108.89 (15)	O3A—Cl1—O1	110.1 (3)
C15—C14—C13	116.86 (18)	O4—Cl1—O1	110.8 (4)
C15—C14—H14	121.6	O3B—Cl1—O4A	130.5 (8)
C13—C14—H14	121.6	O3A—Cl1—O4A	110.6 (4)
C14—C15—C16	121.71 (19)	O1—Cl1—O4A	110.0 (3)
C14—C15—H15	119.1	O4B—Cl1—O3	133.5 (8)
C16—C15—H15	119.1	O4—Cl1—O3	110.1 (5)
C17—C16—C15	122.20 (19)	O1—Cl1—O3	109.1 (3)
C17—C16—H16	118.9	O4A—Cl1—O3	127.3 (7)
C15—C16—H16	118.9	O3B—Cl1—O2	70.4 (11)
C16—C17—C11	116.17 (19)	O4B—Cl1—O2	74.5 (11)
C16—C17—H17	121.9	O3A—Cl1—O2	124.9 (6)
C11—C17—H17	121.9	O4—Cl1—O2	109.5 (9)
N11—C18—C19	112.36 (18)	O1—Cl1—O2	108.6 (4)
N11—C18—H18A	109.1	O4A—Cl1—O2	90.7 (8)
C19—C18—H18A	109.1	O3—Cl1—O2	108.6 (4)
N11—C18—H18B	109.1	O3B—Cl1—O2A	53.3 (9)
C19—C18—H18B	109.1	O4B—Cl1—O2A	92.4 (10)
H18A—C18—H18B	107.9	O3A—Cl1—O2A	109.9 (4)
C18—C19—H19A	109.5	O4—Cl1—O2A	125.2 (8)
C18—C19—H19B	109.5	O1—Cl1—O2A	107.9 (3)
H19A—C19—H19B	109.5	O4A—Cl1—O2A	108.3 (4)
C18—C19—H19C	109.5	O3—Cl1—O2A	91.5 (7)
H19A—C19—H19C	109.5	O3B—Cl1—O2B	99.1 (6)
H19B—C19—H19C	109.5	O4B—Cl1—O2B	96.8 (6)
N21—C21—C27	131.53 (17)	O4—Cl1—O2B	60.2 (12)
N21—C21—C23	106.17 (15)	O1—Cl1—O2B	93.7 (4)
C27—C21—C23	122.27 (17)	O4A—Cl1—O2B	81.2 (8)
N23—C22—N21	112.04 (14)	O3—Cl1—O2B	62.3 (9)
N23—C22—C2	124.70 (14)	O2—Cl1—O2B	157.6 (6)
N21—C22—C2	123.19 (15)	O2A—Cl1—O2B	150.7 (6)
N23—C23—C21	109.16 (15)	Cl1—O2—O3B	50.3 (5)
N23—C23—C24	130.41 (17)	Cl1—O2—O4B	50.7 (5)
C21—C23—C24	120.32 (17)	O3B—O2—O4B	90.8 (8)
C25—C24—C23	117.38 (19)	O3B—O2A—Cl1	57.1 (5)
C25—C24—H24	121.3	O3A—O2B—O4	91.9 (10)
C23—C24—H24	121.3	O4—O2B—O3	91.1 (8)
C24—C25—C26	121.8 (2)	O3A—O2B—Cl1	53.8 (4)
C24—C25—H25	119.1	O4—O2B—Cl1	50.0 (5)
C26—C25—H25	119.1	O3—O2B—Cl1	49.5 (4)
C27—C26—C25	121.93 (18)	O3A—O3—O3B	131.1 (18)
C27—C26—H26	119.0	O3A—O3—Cl1	78.2 (7)
C25—C26—H26	119.0	O3B—O3—Cl1	62.4 (7)
C26—C27—C21	116.32 (19)	O3B—O3—O2B	127.7 (12)
C26—C27—H27	121.8	Cl1—O3—O2B	68.2 (7)
C21—C27—H27	121.8	O3—O3A—O2B	157.9 (14)
N21—C28—C29	111.76 (17)	O2B—O3A—O3B	140.1 (10)
N21—C28—H28A	109.3	O3—O3A—Cl1	81.3 (7)
C29—C28—H28A	109.3	O2B—O3A—Cl1	83.8 (7)
N21—C28—H28B	109.3	O3B—O3A—Cl1	56.6 (5)
C29—C28—H28B	109.3	O3—O3B—O2A	148.6 (9)
H28A—C28—H28B	107.9	O3—O3B—Cl1	79.3 (9)
C28—C29—H29A	109.5	O2A—O3B—Cl1	69.7 (8)
C28—C29—H29B	109.5	O2A—O3B—O3A	135.6 (10)
H29A—C29—H29B	109.5	Cl1—O3B—O3A	66.5 (6)
C28—C29—H29C	109.5	O3—O3B—O2	138.3 (10)
H29A—C29—H29C	109.5	Cl1—O3B—O2	59.3 (8)
H29B—C29—H29C	109.5	O3A—O3B—O2	123.4 (10)
N31—C31—C37	131.7 (2)	O4A—O4—Cl1	80.2 (9)
N31—C31—C33	106.29 (17)	O4B—O4—Cl1	68.1 (9)
C37—C31—C33	122.0 (2)	O4A—O4—O2B	149.4 (8)
N33—C32—N31	111.54 (16)	O4B—O4—O2B	137.7 (11)
N33—C32—C3	125.52 (16)	Cl1—O4—O2B	69.8 (8)
N31—C32—C3	122.94 (17)	O4—O4A—Cl1	78.8 (7)
N33—C33—C34	130.29 (18)	O4—O4B—Cl1	75.3 (10)
N33—C33—C31	109.13 (17)	O4—O4B—O2	127.4 (13)
C34—C33—C31	120.58 (19)	Cl1—O4B—O2	54.8 (7)
N23^i—Cu1—N13—C12	6.50 (19)	O2A—Cl1—O3—O2B	166.4 (6)
N33—Cu1—N13—C12	−177.10 (13)	O4—O2B—O3—O3A	98 (5)
N23^i—Cu1—N13—C13	−162.85 (12)	Cl1—O2B—O3—O3A	128 (5)
N33—Cu1—N13—C13	13.54 (16)	O3A—O2B—O3—O3B	−109 (5)
N13—Cu1—N33—C32	83.63 (18)	O4—O2B—O3—O3B	−10.9 (14)
N23^i—Cu1—N33—C32	−98.98 (17)	Cl1—O2B—O3—O3B	19.6 (13)
N13—Cu1—N33—C33	−115.37 (14)	O3A—O2B—O3—Cl1	−128 (5)
N23^i—Cu1—N33—C33	62.02 (15)	O4—O2B—O3—Cl1	−30.5 (4)
C12—C1—C2—C22	−171.62 (16)	O3B—O3—O3A—O2B	84 (6)
C12—N11—C11—C13	0.07 (19)	Cl1—O3—O3A—O2B	48 (4)
C18—N11—C11—C13	179.41 (16)	Cl1—O3—O3A—O3B	−35.8 (17)
C12—N11—C11—C17	−179.2 (2)	O2B—O3—O3A—O3B	−84 (6)
C18—N11—C11—C17	0.1 (3)	O3B—O3—O3A—Cl1	35.8 (17)
C13—N13—C12—N11	0.48 (19)	O2B—O3—O3A—Cl1	−48 (4)
Cu1—N13—C12—N11	−170.37 (12)	O4—O2B—O3A—O3	−82 (5)
C13—N13—C12—C1	179.08 (16)	Cl1—O2B—O3A—O3	−48 (4)
Cu1—N13—C12—C1	8.2 (2)	O4—O2B—O3A—O3B	−27.8 (19)
C11—N11—C12—N13	−0.35 (19)	O3—O2B—O3A—O3B	55 (4)
C18—N11—C12—N13	−179.68 (16)	Cl1—O2B—O3A—O3B	6.9 (15)
C11—N11—C12—C1	−179.02 (15)	O4—O2B—O3A—Cl1	−34.7 (6)
C18—N11—C12—C1	1.7 (3)	O3—O2B—O3A—Cl1	48 (4)
C2—C1—C12—N13	28.6 (3)	O3B—Cl1—O3A—O3	−21.6 (16)
C2—C1—C12—N11	−152.96 (17)	O4B—Cl1—O3A—O3	−133.3 (17)
C12—N13—C13—C14	−179.57 (19)	O4—Cl1—O3A—O3	−156.2 (17)
Cu1—N13—C13—C14	−8.1 (3)	O1—Cl1—O3A—O3	91.0 (15)
C12—N13—C13—C11	−0.42 (19)	O4A—Cl1—O3A—O3	−147.3 (15)
Cu1—N13—C13—C11	171.08 (12)	O2—Cl1—O3A—O3	−41.1 (17)
N11—C11—C13—C14	179.46 (17)	O2A—Cl1—O3A—O3	−27.7 (16)
C17—C11—C13—C14	−1.1 (3)	O2B—Cl1—O3A—O3	163.7 (19)
N11—C11—C13—N13	0.2 (2)	O3B—Cl1—O3A—O2B	174.7 (13)
C17—C11—C13—N13	179.62 (17)	O4B—Cl1—O3A—O2B	63.0 (10)
N13—C13—C14—C15	179.3 (2)	O4—Cl1—O3A—O2B	40.2 (10)
C11—C13—C14—C15	0.2 (3)	O1—Cl1—O3A—O2B	−72.7 (9)
C13—C14—C15—C16	0.8 (3)	O4A—Cl1—O3A—O2B	49.1 (10)
C14—C15—C16—C17	−1.0 (4)	O3—Cl1—O3A—O2B	−163.7 (19)
C15—C16—C17—C11	0.1 (3)	O2—Cl1—O3A—O2B	155.3 (10)
N11—C11—C17—C16	−179.8 (2)	O2A—Cl1—O3A—O2B	168.6 (9)
C13—C11—C17—C16	1.0 (3)	O4B—Cl1—O3A—O3B	−111.7 (8)
C12—N11—C18—C19	−91.8 (2)	O4—Cl1—O3A—O3B	−134.6 (11)
C11—N11—C18—C19	89.0 (2)	O1—Cl1—O3A—O3B	112.6 (8)
C22—N21—C21—C27	178.06 (19)	O4A—Cl1—O3A—O3B	−125.7 (10)
C28—N21—C21—C27	−4.9 (3)	O3—Cl1—O3A—O3B	21.6 (16)
C22—N21—C21—C23	0.13 (18)	O2—Cl1—O3A—O3B	−19.5 (11)
C28—N21—C21—C23	177.12 (16)	O2A—Cl1—O3A—O3B	−6.2 (10)
C23—N23—C22—N21	0.03 (19)	O2B—Cl1—O3A—O3B	−174.7 (13)
Cu1^i—N23—C22—N21	178.63 (11)	O3A—O3—O3B—O2A	−49 (5)
C23—N23—C22—C2	176.96 (15)	Cl1—O3—O3B—O2A	−9 (3)
Cu1^i—N23—C22—C2	−4.4 (2)	O2B—O3—O3B—O2A	−29 (4)
C21—N21—C22—N23	−0.10 (19)	O3A—O3—O3B—Cl1	−40 (2)
C28—N21—C22—N23	−176.99 (15)	O2B—O3—O3B—Cl1	−20.6 (13)
C21—N21—C22—C2	−177.09 (15)	Cl1—O3—O3B—O3A	40 (2)
C28—N21—C22—C2	6.0 (3)	O2B—O3—O3B—O3A	19.6 (15)
C1—C2—C22—N23	29.2 (3)	O3A—O3—O3B—O2	−34 (3)
C1—C2—C22—N21	−154.17 (17)	Cl1—O3—O3B—O2	6.3 (16)
C22—N23—C23—C21	0.06 (19)	O2B—O3—O3B—O2	−14 (3)
Cu1^i—N23—C23—C21	−178.63 (11)	Cl1—O2A—O3B—O3	9 (3)
C22—N23—C23—C24	−176.12 (19)	Cl1—O2A—O3B—O3A	−9.5 (13)
Cu1^i—N23—C23—C24	5.2 (3)	Cl1—O2A—O3B—O2	−38 (2)
N21—C21—C23—N23	−0.12 (19)	O4B—Cl1—O3B—O3	119.9 (14)
C27—C21—C23—N23	−178.29 (17)	O3A—Cl1—O3B—O3	12.0 (10)
N21—C21—C23—C24	176.51 (16)	O4—Cl1—O3B—O3	75.1 (16)
C27—C21—C23—C24	−1.7 (3)	O1—Cl1—O3B—O3	−84.0 (13)
N23—C23—C24—C25	176.5 (2)	O4A—Cl1—O3B—O3	101.8 (15)
C21—C23—C24—C25	0.7 (3)	O2—Cl1—O3B—O3	175.2 (13)
C23—C24—C25—C26	0.3 (3)	O2A—Cl1—O3B—O3	−175.2 (16)
C24—C25—C26—C27	−0.4 (4)	O2B—Cl1—O3B—O3	15.6 (13)
C25—C26—C27—C21	−0.6 (3)	O4B—Cl1—O3B—O2A	−64.9 (14)
N21—C21—C27—C26	−176.09 (19)	O3A—Cl1—O3B—O2A	−172.8 (11)
C23—C21—C27—C26	1.6 (3)	O4—Cl1—O3B—O2A	−109.7 (14)
C22—N21—C28—C29	−102.9 (2)	O1—Cl1—O3B—O2A	91.3 (9)
C21—N21—C28—C29	80.7 (2)	O4A—Cl1—O3B—O2A	−83.0 (10)
C32—N31—C31—C37	179.7 (3)	O3—Cl1—O3B—O2A	175.2 (16)
C38—N31—C31—C37	−5.5 (4)	O2—Cl1—O3B—O2A	−9.6 (8)
C32—N31—C31—C33	−0.6 (2)	O2B—Cl1—O3B—O2A	−169.2 (8)
C38—N31—C31—C33	174.2 (2)	O4B—Cl1—O3B—O3A	107.9 (12)
C33—N33—C32—N31	−0.6 (2)	O4—Cl1—O3B—O3A	63.0 (17)
Cu1—N33—C32—N31	162.41 (14)	O1—Cl1—O3B—O3A	−96.0 (7)
C33—N33—C32—C3	179.80 (18)	O4A—Cl1—O3B—O3A	89.7 (11)
Cu1—N33—C32—C3	−17.2 (3)	O3—Cl1—O3B—O3A	−12.0 (10)
C31—N31—C32—N33	0.7 (2)	O2—Cl1—O3B—O3A	163.1 (9)
C38—N31—C32—N33	−173.8 (2)	O2A—Cl1—O3B—O3A	172.8 (11)
C31—N31—C32—C3	−179.63 (19)	O2B—Cl1—O3B—O3A	3.6 (9)
C38—N31—C32—C3	5.9 (3)	O4B—Cl1—O3B—O2	−55.2 (13)
C3^ii—C3—C32—N33	−2.3 (4)	O3A—Cl1—O3B—O2	−163.1 (9)
C3^ii—C3—C32—N31	178.1 (3)	O4—Cl1—O3B—O2	−100.1 (14)
C32—N33—C33—C34	−179.9 (2)	O1—Cl1—O3B—O2	100.9 (8)
Cu1—N33—C33—C34	14.6 (3)	O4A—Cl1—O3B—O2	−73.4 (11)
C32—N33—C33—C31	0.2 (2)	O3—Cl1—O3B—O2	−175.2 (13)
Cu1—N33—C33—C31	−165.28 (13)	O2A—Cl1—O3B—O2	9.6 (8)
N31—C31—C33—N33	0.2 (2)	O2B—Cl1—O3B—O2	−159.6 (7)
C37—C31—C33—N33	180.0 (2)	O2B—O3A—O3B—O3	−144 (3)
N31—C31—C33—C34	−179.6 (2)	Cl1—O3A—O3B—O3	−136 (2)
C37—C31—C33—C34	0.1 (4)	O3—O3A—O3B—O2A	146 (3)
N33—C33—C34—C35	−179.8 (2)	O2B—O3A—O3B—O2A	2 (3)
C31—C33—C34—C35	0.1 (4)	Cl1—O3A—O3B—O2A	9.7 (13)
C33—C34—C35—C36	−0.5 (5)	O3—O3A—O3B—Cl1	136 (2)
C34—C35—C36—C37	0.7 (5)	O2B—O3A—O3B—Cl1	−8.2 (18)
C35—C36—C37—C31	−0.5 (5)	O3—O3A—O3B—O2	154 (2)
N31—C31—C37—C36	179.8 (3)	O2B—O3A—O3B—O2	9 (2)
C33—C31—C37—C36	0.1 (4)	Cl1—O3A—O3B—O2	17.4 (8)
C32—N31—C38—C39	96.9 (3)	Cl1—O2—O3B—O3	−7.2 (19)
C31—N31—C38—C39	−76.8 (3)	O4B—O2—O3B—O3	26 (2)
O4B—Cl1—O2—O3B	134.5 (7)	Cl1—O2—O3B—O2A	138 (2)
O3A—Cl1—O2—O3B	17.2 (10)	O4B—O2—O3B—O2A	171 (2)
O4—Cl1—O2—O3B	123.5 (9)	O4B—O2—O3B—Cl1	33.5 (4)
O1—Cl1—O2—O3B	−115.4 (7)	Cl1—O2—O3B—O3A	−18.6 (8)
O4A—Cl1—O2—O3B	133.2 (8)	O4B—O2—O3B—O3A	15.0 (10)
O3—Cl1—O2—O3B	3.2 (9)	O3B—Cl1—O4—O4A	108 (2)
O2A—Cl1—O2—O3B	−24.2 (17)	O4B—Cl1—O4—O4A	10.2 (17)
O2B—Cl1—O2—O3B	65 (2)	O3A—Cl1—O4—O4A	156.2 (16)
O3B—Cl1—O2—O4B	−134.5 (7)	O1—Cl1—O4—O4A	−91.6 (17)
O3A—Cl1—O2—O4B	−117.2 (9)	O3—Cl1—O4—O4A	147.5 (15)
O4—Cl1—O2—O4B	−11.0 (9)	O2—Cl1—O4—O4A	28.2 (17)
O1—Cl1—O2—O4B	110.1 (7)	O2A—Cl1—O4—O4A	40.5 (18)
O4A—Cl1—O2—O4B	−1.3 (8)	O2B—Cl1—O4—O4A	−173.7 (19)
O3—Cl1—O2—O4B	−131.3 (8)	O3B—Cl1—O4—O4B	97.7 (15)
O2A—Cl1—O2—O4B	−158.7 (19)	O3A—Cl1—O4—O4B	146.1 (13)
O2B—Cl1—O2—O4B	−69 (2)	O1—Cl1—O4—O4B	−101.8 (13)
O4B—Cl1—O2A—O3B	130.7 (8)	O4A—Cl1—O4—O4B	−10.2 (17)
O3A—Cl1—O2A—O3B	6.4 (10)	O3—Cl1—O4—O4B	137.4 (12)
O4—Cl1—O2A—O3B	113.1 (12)	O2—Cl1—O4—O4B	18.0 (14)
O1—Cl1—O2A—O3B	−113.6 (9)	O2A—Cl1—O4—O4B	30.4 (15)
O4A—Cl1—O2A—O3B	127.3 (9)	O2B—Cl1—O4—O4B	176.1 (15)
O3—Cl1—O2A—O3B	−3.0 (10)	O3B—Cl1—O4—O2B	−78.4 (12)
O2—Cl1—O2A—O3B	151 (2)	O4B—Cl1—O4—O2B	−176.1 (15)
O2B—Cl1—O2A—O3B	22.3 (16)	O3A—Cl1—O4—O2B	−30.0 (7)
O3B—Cl1—O2B—O3A	−4.5 (11)	O1—Cl1—O4—O2B	82.1 (7)
O4B—Cl1—O2B—O3A	−129.7 (10)	O4A—Cl1—O4—O2B	173.7 (19)
O4—Cl1—O2B—O3A	−132.0 (10)	O3—Cl1—O4—O2B	−38.7 (8)
O1—Cl1—O2B—O3A	116.0 (7)	O2—Cl1—O4—O2B	−158.1 (7)
O4A—Cl1—O2B—O3A	−134.3 (8)	O2A—Cl1—O4—O2B	−145.7 (7)
O3—Cl1—O2B—O3A	6.4 (8)	O3A—O2B—O4—O4A	49 (4)
O2—Cl1—O2B—O3A	−64 (3)	O3—O2B—O4—O4A	43 (4)
O2A—Cl1—O2B—O3A	−22.4 (18)	Cl1—O2B—O4—O4A	12 (4)
O3B—Cl1—O2B—O4	127.6 (9)	O3A—O2B—O4—O4B	31 (2)
O4B—Cl1—O2B—O4	2.3 (9)	O3—O2B—O4—O4B	25 (2)
O3A—Cl1—O2B—O4	132.0 (10)	Cl1—O2B—O4—O4B	−5 (2)
O1—Cl1—O2B—O4	−111.9 (5)	O3A—O2B—O4—Cl1	36.9 (6)
O4A—Cl1—O2B—O4	−2.3 (7)	O3—O2B—O4—Cl1	30.3 (4)
O3—Cl1—O2B—O4	138.4 (7)	O4B—O4—O4A—Cl1	38 (4)
O2—Cl1—O2B—O4	68 (3)	O2B—O4—O4A—Cl1	−12 (3)
O2A—Cl1—O2B—O4	109.7 (14)	O3B—Cl1—O4A—O4	−89 (2)
O3B—Cl1—O2B—O3	−10.9 (9)	O4B—Cl1—O4A—O4	−158 (3)
O4B—Cl1—O2B—O3	−136.1 (8)	O3A—Cl1—O4A—O4	−25.5 (18)
O3A—Cl1—O2B—O3	−6.4 (8)	O1—Cl1—O4A—O4	96.3 (16)
O4—Cl1—O2B—O3	−138.4 (7)	O3—Cl1—O4A—O4	−39.3 (18)
O1—Cl1—O2B—O3	109.6 (5)	O2—Cl1—O4A—O4	−153.6 (16)
O4A—Cl1—O2B—O3	−140.7 (6)	O2A—Cl1—O4A—O4	−146.0 (16)
O2—Cl1—O2B—O3	−71 (3)	O2B—Cl1—O4A—O4	5.5 (16)
O2A—Cl1—O2B—O3	−28.8 (15)	O4A—O4—O4B—Cl1	−140 (4)
O3B—Cl1—O3—O3A	150 (2)	O2B—O4—O4B—Cl1	5 (2)
O4B—Cl1—O3—O3A	59 (2)	O4A—O4—O4B—O2	−158 (5)
O4—Cl1—O3—O3A	25.5 (18)	Cl1—O4—O4B—O2	−18.1 (11)
O1—Cl1—O3—O3A	−96.4 (15)	O2B—O4—O4B—O2	−13 (3)
O4A—Cl1—O3—O3A	39.5 (17)	O3B—Cl1—O4B—O4	−109.0 (16)
O2—Cl1—O3—O3A	145.4 (15)	O3A—Cl1—O4B—O4	−40.6 (16)
O2A—Cl1—O3—O3A	154.0 (15)	O1—Cl1—O4B—O4	93.7 (12)
O2B—Cl1—O3—O3A	−12.4 (15)	O4A—Cl1—O4B—O4	13 (2)
O4B—Cl1—O3—O3B	−90.9 (15)	O3—Cl1—O4B—O4	−61.2 (18)
O3A—Cl1—O3—O3B	−150 (2)	O2—Cl1—O4B—O4	−162.4 (13)
O4—Cl1—O3—O3B	−124.7 (13)	O2A—Cl1—O4B—O4	−155.6 (12)
O1—Cl1—O3—O3B	113.4 (12)	O2B—Cl1—O4B—O4	−3.4 (13)
O4A—Cl1—O3—O3B	−110.7 (15)	O3B—Cl1—O4B—O2	53.4 (13)
O2—Cl1—O3—O3B	−4.8 (13)	O3A—Cl1—O4B—O2	121.8 (8)
O2A—Cl1—O3—O3B	3.8 (13)	O4—Cl1—O4B—O2	162.4 (13)
O2B—Cl1—O3—O3B	−162.5 (14)	O1—Cl1—O4B—O2	−103.9 (5)
O3B—Cl1—O3—O2B	162.5 (14)	O4A—Cl1—O4B—O2	176 (3)
O4B—Cl1—O3—O2B	71.6 (11)	O3—Cl1—O4B—O2	101.2 (10)
O3A—Cl1—O3—O2B	12.4 (15)	O2A—Cl1—O4B—O2	6.8 (6)
O4—Cl1—O3—O2B	37.8 (10)	O2B—Cl1—O4B—O2	159.0 (6)
O1—Cl1—O3—O2B	−84.0 (6)	Cl1—O2—O4B—O4	21.6 (14)
O4A—Cl1—O3—O2B	51.8 (8)	O3B—O2—O4B—O4	−11.7 (15)
O2—Cl1—O3—O2B	157.7 (7)	O3B—O2—O4B—Cl1	−33.3 (4)

Symmetry codes: (i) −x+1/2, y, −z+1; (ii) −x+1/2, −y+1/2, −z+3/2.