Influence of chloro­form on crystalline products yielded in reactions of 5,10,15,20-tetra­phenyl­porphyrin with HCl and copper(II) salts

Chloro­form was found to occupy the lattice of the protonated porphyrin and to promote crystallization of a different poly­morphic form of a metalloporphyrin. The structure of 5,10,15,20-tetra­phenyl­porphyrin-21,23-diium dichloride chloro­form octa­solvate, C₄₄H₃₂N₄²⁺·2Cl⁻·8CHCl₃, (I), in the solid state is described and compared with related solvates. The porphyrin macrocycle displays a distorted saddle shape, with chloride anions above and below the ring. Seven chloro­form mol­ecules are bound via C—H...Cl hydrogen bonds, while the link with the eighth solvent mol­ecule is weaker. A new monoclinic polymorph of (5,10,15,20-tetra­phenyl­porphyrinato)copper(II), [Cu(C₄₄H₂₈N₄)], (II), crystallized from chloro­form, is also presented.

S1. Comment

Porphyrins and metalloporphyrins have been studied for many years because of their biochemical relevance as well as their applications. In biology, these tetrapyrrolic macrocycles fulfill such diverse roles as molecular binding, light harvesting, catalysis, and energy and/or electron transfer (Burrell et al., 2001). From the technological point of view, porphyrins have been useful in a range of applications, from molecular sensing to the development of dye-sensitized solar cells (Hagfeldt et al., 2010). Also, these compounds have been found to possess a rich macromolecular chemistry, i.a. promoting DNA cleavage (Börjesson et al., 2010), serving as the core for metallodendrimers (Newkome et al., 1999) or as the building blocks for other self-organized nanostructures (Harada & Kojima, 2005).

Much work has been devoted to 5,10,15,20-tetraphenylporphyrin and its derived metal complexes, which is understandable given the facile and rapid synthesis of this porphyrin. On some occasions, protonated porphyrins may be obtained in parallel with metal complexes. While they do not share the popularity of their free-base or coordinated relatives, porphyrin dications have been found very useful in elucidating the nature of the structural distortions of porphyrin derivatives.

The study of the geometrical distortion of porphyrins may give rise to interesting nanostructured materials. For instance, it has recently been demonstrated that the puckering of saddle-distorted porphyrins results in nanochannel materials in which photochemically induced electron transfer to guest molecules can be recorded (Kojima et al., 2007; Nakanishi et al., 2008).

Porphyrin molecules upon protonation become nonplanar largely because of the strain caused by the four H-atom interaction at the ring core (Stone & Fleischer, 1968). This behaviour is observed in several structures of protonated porphyrins, where the ring is forced to adopt a distorted geometry described as saddled, ruffled, domed, propellered [spelling correct?] or waved. Saddled is the most common (Senge & Kalisch, 1999). Data on selected structures of protonated porphyrins are presented in Table 1. The symmetry of the porphyrin macrocycle deformation was analysed by Stone & Fleischer (1968) in terms of irreducible representations of the point group D_4h. The distortions can be classified as: sad B_1u, ruf B_2u, dom A_2u, pro A_1u and wav(1) or wav(2) E_g, respectively. From the symbols one can infer that local symmetry of the porphyrin molecule can be 2 or 4 for the first two conformations. Local symmetry 4 is allowed only for dom and pro, whereas 1 is allowed only for the wav forms. Obviously, this is true only for porphrins with full D_4h symmetry. For an analysis of deformation in a less symmetric molecule, see Sun et al. (2012).

Generally, the presence of substituents on the β positions causes the porphyrins to deviate more from planarity than meso (i.e. 5,10,15,20-) substituents. Cheng et al. (1997) compared meso (Ph, mesityl and H) and β (Et, H) substitution in several diacid porphyrins. Their octaethyl β-substituted porphyrins were less distorted than Ph- or mesityl-substituted molecules in meso positions. They concluded that the stiffness of the substituent must also be taken into account as a factor influencing the distortion. Among the compounds in Table 1, the β substitution by stiff Ph groups inevitably leads to a strongly distorted conformation (Δ24 > 0.6 and dihedral angles between the opposite pyrrole rings close to 90°).

A general view of 5,10,15,20-tetraphenylporphyrin-21,23-diium dichloride chloroform octasolvate, (I), and the definition of the atom-labelling scheme are shown in Fig. 1. Two N—H bonds (from N1 and N3) are directed above the mean plane of the molecule and form hydrogen bonds with chloride ion Cl1 and the remaining N—H bonds point down to the second chloride ion (Cl2).

Three chloroform molecules bound by a C—H···Cl hydrogen bond to the Cl1 atom, as well as the stand-alone molecule are well ordered. However, the remaining four chloroform molecules, all linked to the Cl2 atom, display strong disorder (see Fig. 2). As the disordered chloroform molecules have a severe impact on R indices, building an appropriate disorder model was crucial. In our attempt, all the chloroform molecules were restrained to the geometry of a `regular' molecule. In order to define this, the Cambridge Structural Database (CSD; Allen, 2002) was queried for data on the mean chloroform geometry observed in crystals. A total of 4707 examples were found. These provided a statistically relevant estimation of the mean C—Cl bond length value (1.737 Å, with a sample standard uncertainty of 0.06 Å) and the mean 1,3 Cl···Cl distance (2.838 Å, with a sample standard uncertainty of 0.08 Å). All the disordered molecules were restrained to the above-mentioned values, while their standard uncertainties were shrunk to 0.002 Å. One molecule (C45—Cl3—Cl4—Cl5) had to be split over three positions, and the other three were disordered over two positions. It appears all four molecules have some degree of `orbiting rotational freedom' over the acceptor atom and may interchange, while still being linked to chloride atom Cl2.

Many similarities can be found in the structure of 5,10,15,20-tetrakis(4-methylphenyl)porphyrin-21,23-diium dichloride chloroform heptasolvate (Grubisha et al., 2008). Again, the porphyrin ring is distorted, which manifests in dihedral angles between opposite pyrrole rings of ca 120°. More interestingly, the chloroform molecules are bound to the chloride ions by C—H···Cl hydrogen bonds, four from one side of the porphyrin ring plane and three from the other (Fig. 2b), forming a similar pattern to that of the new structure.

meso-Tetraphenylporphyrindiium dichloride is known to form `binary' solvates with acetonitrile and water (Larsen et al., 2004). It forms a similar core with a saddledistorted porphyrin and Cl^- anions as acceptors for the N—H bonds from both sides of the porphyrin plane. The similarity ends there as the structure is further stabilized by O—H···Cl hydrogen bonds with water molecules and the remaining acetonitrile seems to play a space-filling role only.

Other structures with 22,24-dihydro-5,10,15,20-tetraphenylporphyrindiium dications contain a number of combinations of anions and solvents: porphyrin bis(hydrogen sulfate) methanol solvate (Senge & Kalisch, 1999), porphyrin diperchlorate benzene solvate (Cheng et al., 1997), porphyrin bis(tetrafluoroborate) chloroform solvate dihydrate (Rayati et al., 2008) and porphyrin diperchlorate methanol solvate (Senge et al., 1994; Senge & Kalisch, 1999).

In the case of 22,24-dihydro-5,10,15,20-tetraphenylporphyrin chloride ferrichloride, no solvent is trapped in the structure (Stone & Fleischer, 1968).

Two X-ray crystal structures for (5,10,15,20-tetraphenylporphyrinato)copper(II), (II), have been determined so far, viz. a tetragonal form crystallizing in I42d, determined twice [by Fleischer et al. (1964) at 295 K, d = 1.421 Mg m^-1, then by Zeller et al. (2004) at 100 K, d = 1.461 Mg m^-1], and another tetragonal form with symmetry I4/m [He (2007), d = 1.290 Mg m^-1 at 290 K]. Other structures of CuTPP contained additional guest molecules, such as benzene and C₇₈ fullerene (Epple et al., 2009), 4-picoline (Byrn et al., 1993) or m-xylene (Byrn et al., 1991), fullerene C₆₀ either alone or accompanied by toluene and C₂HCl₃ (Konarev et al., 2001). While the conformation of the 24-membered macrocycle is saddled (local 4) for TPPCu crystallizing in I42d, a flat core (local 4/m) is observed in the case of the I4/m space group. The present monoclinic structure (P2₁/n) has local symmetry 1 which only allows for the wave conformation (E_g-type representation). The deviation of the macrocycle from flatness is not strong (Δ₂₄ = 0.0428 Å), but clearly no fourfold symmetry is present (see Fig. 3). The same type of conformation with a local centre of symmetry is present in all the solvated structures mentioned above (excluding Konarev et al., 2001). Comparing the densities of known polymorphs with 1.394 Mg m^-1, we see that when CuTPP crystallizes from chloroform it does not present the most dense packing and probably it is not the most thermodynamically stable. It follows the Ostwald's rule of stages (Ostwald, 1897; Threlfall, 2003), which states that crystallization often favours the least stable polymorphs. Although the validity of this rule is questionable, the balance between kinetics and thermodynamics allows us to obtain the less dense monoclinic form of CuTPP. Chloroform is generally disregarded as a solvent, because of its tendency to form disordered structures. However, it is worth keeping in mind that chloroform may be helpful when trying to obtain less stable polymorphs as in the current case.

Related literature

For related literature, see: Adler et al. (1967); Börjesson et al. (2010); Burrell et al. (2001); Byrn et al. (1991, 1993); Cheng et al. (1997); Fleischer et al. (1964); Grubisha et al. (2008); Hagfeldt et al. (2010); Harada & Kojima (2005); He (2007); Kojima et al. (2007); Konarev et al. (2001); Larsen et al. (2004); Nakanishi et al. (2008); Newkome et al. (1999); Ostwald (1897); Rayati et al. (2008); Senge & Kalisch (1999); Senge et al. (1994); Stone & Fleischer (1968); Zeller et al. (2004).

S2. Experimental

meso-Tetraphenylporphyrin [H₂(TPP), from now on] was synthesized according to the extensively used method devised by Adler et al. (1967). Chloroform was dried over molecular sieves while methanol was dried over metallic Mg. Both solvents were distilled prior to use.

H₂(TPP) (120 mg, ~0.2 mmol) was dissolved in chloroform (8 ml). Then, a 2 M solution of HCl (0.5 ml) was added to methanol (2.5 ml) and poured into the porphyrin solution. The resulting green solution was stirred for 10 min and then left to slowly crystallize at 263 K. After a few days, a small quantity of [H₄(TPP)]Cl₂.8CHCl₃ single crystals, suitable for X-ray analysis, appeared on the bottom of the flask. This deep-blue product was extremely unstable at room temperature, redissolving after some minutes if left in the solution and becoming very brittle while turning completely opaque when dried, at which point no reflections could be taken with the diffractometer (we suspect this was caused by the loss of the most volatile chloroform moieties). Therefore, extreme caution had to be observed in order to pick a fresh and appropriate crystal.

(5,10,15,20-Tetraphenylporphyrinato)copper(II) (CuTPP for short), (II), was synthesized by refluxing CuCl₂.2H₂O (234 mg) in dimethylformamide (50 ml) in the presence of H₂(TPP) (425 mg) over a period of 2.5 h. The product was completely dried, washed twice with water and purified by chromatography on an alumina column, using chloroform as the eluent. The resulting red phase containing CuTPP was left open to the atmosphere at room temperature. After a few days, the chloroform had evaporated, leaving well formed crystals of CuTPP, (II).

S3. Refinement

All C- and N-bound H atoms were refined in isotropic approximation as riding on their parent atoms, with aromatic C—H = 0.95 Å, methine C—H = 1.00 Å and N—H = 0.88 Å, and with U_iso(H) = 1.2U_eq(C,N). The disorder in four of the eight chloroform molecules in (I) required a rather complex model. The solvent molecule containing atom C46 was ordered, but refined using isotropic Cl atoms. The three chloroform molecules containing atoms C47, C48 and C49, respectively, were fully ordered and were refined with anisotropic displacement parameters for the non-H atoms. The chloroform molecule containing atom C45 was refined as being disordered over three positions. The anisotropic displacement parameters of each disordered position for atom C45 were constrained to be equal, while isotropic displacement parameters were refined for the Cl atoms in all three orientations and constrained to be equal in one orientation. A SUMP restraint (Sheldrick, 2008) in the form of sof(1) + sof(2) + sof(3) = 1.000 (1) was applied and gave a final distribution of the parts as 0.734 (6)/0.191 (5)/0.077 (4). Notably, the omission of the third orientation of this chloroform molecule results in a substantial increase of the R1 index by ca 0.7%. The three solvent molecules containing atoms C50, C51 and C52, were found to be disordered and were refined as being split over two orientations with final occupation-factor ratios of 0.529 (19):0.471 (19), 0.904 (4):0.096 (4) and 0.587 (14):0.413 (14), respectively. Isotropic displacement parameters were refined for all non-H atoms of these solvent molecules, except for those of the Cl atoms of the minor orientation of the molecule containing atom C51, which were kept fixed at 0.04 Ų. In addition the isotropic displacement parameters of the two disordered C atom positions of each of these solvent molecules were constrained to be equal. The C—Cl and Cl···Cl distances in all of the disordered chloroform molecules were restrained to 1.737 (2) and 2.848 (2) Å, respectively, as described in the Comment. Despite the complex disorder model, the residual electron density (located in the disordered solvent region) is still high, indicating that the real structure is perhaps even more complex. This may be the main reason for the relatively large value of R1.

Computing details

For both compounds, data collection: CrysAlis PRO (Oxford Diffraction, 2006); cell refinement: CrysAlis PRO (Oxford Diffraction, 2006); data reduction: CrysAlis PRO (Oxford Diffraction, 2006); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: Mercury (Macrae et al., 2006); software used to prepare material for publication: WinGX (Farrugia, 1999), publCIF (Westrip, 2010) and PLATON (Spek, 2009).

Figures

	Fig. 1. The molecular structure of 5,10,15,20-tetraphenylporphyrin-21,23-diium dichloride. The chloroform solvent molecules have been omitted for clarity. Displacement ellipsoids are drawn at the 50% probability level. [Author: please provide revised figure with parentheses removed from atom labels and with labels not touching atoms or bonds]
	Fig. 2. A view of the hydrogen bonding of chloroform solvent molecules to the chloride anions in (a) 5,10,15,20-tetraphenylporphyrin-21,23-diium dichloride chloroform solvate and (b) 5,10,15,20-tetrakis(4-methylphenyl)porphyrin-21,23-diium dichloride chloroform solvate.
	Fig. 3. The linear display of the deviations of the 24 atoms of the macrocycle from their mean plane (a) for TPP*2HCl*8CHCl3 and (b) for CuTPP (the horizontal axis is not to scale).
	Fig. 4. The molecular structure of CuTPP, showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level. [Author: please provide revised figure with parentheses removed from atom labels and with labels not touching atoms or bonds]

(I) 5,10,15,20-tetraphenylporphyrin-21,23-diium dichloride chloroform octasolvate

Crystal data

C44H32N4^2+·2Cl^−·8CHCl3	Z = 2
Mr = 1642.58	F(000) = 1644
Triclinic, P1	Dx = 1.58 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 11.6031 (3) Å	Cell parameters from 11928 reflections
b = 12.6132 (3) Å	θ = 2.3–28.7°
c = 24.5118 (6) Å	µ = 1.06 mm^−1
α = 87.706 (2)°	T = 120 K
β = 82.025 (2)°	Prism, blue
γ = 76.356 (2)°	0.49 × 0.40 × 0.22 mm
V = 3452.31 (15) Å^3

Data collection

Oxford Diffraction Xcalibur Sapphire2 (large Be window) diffractometer	12824 independent reflections
Radiation source: Mo Ka radiation	9236 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.030
Detector resolution: 8.1883 pixels mm^-1	θmax = 25.5°, θmin = 2.3°
ω scans	h = −12→14
Absorption correction: analytical [CrysAlis PRO (Oxford Diffraction, 2006), a multifaceted crystal model based on expressions derived by Clark & Reid (1995)]	k = −15→15
Tmin = 0.705, Tmax = 0.823	l = −29→26
22549 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)] = 0.095	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.261	H-atom parameters constrained
S = 1.05	w = 1/[σ^2(Fo^2) + (0.1268P)^2 + 26.0222P] where P = (Fo^2 + 2Fc^2)/3
12824 reflections	(Δ/σ)max = 0.035
720 parameters	Δρmax = 3.32 e Å^−3
55 restraints	Δρmin = −2.09 e Å^−3

Special details

Experimental. CrysAlisPro (Oxford Diffraction, 2006), Analytical numeric absorption correction using a multifaceted crystal model based on expressions derived by R.C. Clark & J.S. Reid (Clark & Reid, 1995)

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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)
C1	0.3898 (6)	0.7809 (5)	0.1483 (3)	0.0195 (13)
C2	0.4636 (6)	0.7226 (5)	0.1020 (3)	0.0213 (14)
H2	0.4898	0.7537	0.0679	0.026*
C3	0.4892 (6)	0.6149 (5)	0.1157 (3)	0.0202 (13)
H3	0.536	0.5574	0.0927	0.024*
C4	0.4339 (6)	0.6030 (5)	0.1704 (3)	0.0194 (13)
C5	0.4387 (6)	0.5052 (5)	0.2010 (3)	0.0195 (13)
C6	0.5358 (6)	0.4088 (5)	0.1822 (3)	0.0208 (13)
C7	0.6507 (6)	0.4207 (6)	0.1650 (3)	0.0253 (15)
H7	0.6689	0.4899	0.1674	0.03*
C8	0.7402 (7)	0.3316 (7)	0.1441 (3)	0.0370 (19)
H8	0.8188	0.3402	0.1317	0.044*
C9	0.7138 (8)	0.2316 (7)	0.1415 (3)	0.040 (2)
H9	0.7745	0.1712	0.1268	0.048*
C10	0.6007 (9)	0.2176 (6)	0.1598 (3)	0.040 (2)
H10	0.5841	0.1476	0.1583	0.049*
C11	0.5111 (7)	0.3055 (5)	0.1804 (3)	0.0267 (15)
H11	0.4331	0.2958	0.1932	0.032*
C12	0.3558 (6)	0.4931 (5)	0.2472 (3)	0.0187 (13)
C13	0.3704 (6)	0.4106 (5)	0.2893 (3)	0.0235 (14)
H13	0.4409	0.3557	0.2925	0.028*
C14	0.2667 (6)	0.4246 (6)	0.3235 (3)	0.0250 (15)
H14	0.2515	0.3809	0.3549	0.03*
C15	0.1834 (6)	0.5164 (5)	0.3045 (3)	0.0213 (14)
C16	0.0635 (6)	0.5578 (6)	0.3267 (3)	0.0233 (14)
C17	0.0007 (6)	0.4843 (6)	0.3623 (3)	0.0260 (15)
C18	−0.0001 (7)	0.3814 (6)	0.3438 (3)	0.0316 (17)
H18	0.0429	0.3568	0.309	0.038*
C19	−0.0626 (7)	0.3144 (7)	0.3754 (4)	0.0390 (19)
H19	−0.0625	0.2445	0.3623	0.047*
C20	−0.1251 (7)	0.3501 (7)	0.4262 (4)	0.042 (2)
H20	−0.1684	0.3047	0.448	0.05*
C21	−0.1246 (8)	0.4519 (7)	0.4451 (3)	0.044 (2)
H21	−0.1668	0.4756	0.4802	0.053*
C22	−0.0631 (7)	0.5192 (6)	0.4135 (3)	0.0346 (18)
H22	−0.0643	0.5893	0.4266	0.042*
C23	−0.0028 (6)	0.6644 (6)	0.3173 (3)	0.0222 (14)
C24	−0.1291 (6)	0.7035 (6)	0.3255 (3)	0.0269 (15)
H24	−0.1857	0.6614	0.3378	0.032*
C25	−0.1552 (6)	0.8116 (6)	0.3126 (3)	0.0244 (14)
H25	−0.2331	0.858	0.3143	0.029*
C26	−0.0445 (6)	0.8431 (5)	0.2959 (3)	0.0205 (13)
C27	−0.0292 (6)	0.9477 (5)	0.2809 (3)	0.0223 (14)
C28	−0.1286 (6)	1.0417 (6)	0.3007 (3)	0.0241 (14)
C29	−0.1843 (6)	1.0444 (6)	0.3550 (3)	0.0236 (14)
H29	−0.1568	0.9868	0.3796	0.028*
C30	−0.2790 (7)	1.1295 (6)	0.3737 (3)	0.0298 (16)
H30	−0.317	1.1292	0.4106	0.036*
C31	−0.3184 (6)	1.2151 (6)	0.3386 (3)	0.0284 (16)
H31	−0.3833	1.2738	0.3513	0.034*
C32	−0.2621 (7)	1.2144 (6)	0.2846 (3)	0.0325 (17)
H32	−0.2881	1.2735	0.2605	0.039*
C33	−0.1693 (7)	1.1291 (6)	0.2658 (3)	0.0288 (16)
H33	−0.1323	1.1294	0.2287	0.035*
C34	0.0729 (6)	0.9683 (5)	0.2493 (3)	0.0218 (14)
C35	0.1117 (6)	1.0682 (5)	0.2450 (3)	0.0238 (14)
H35	0.0727	1.1339	0.2639	0.029*
C36	0.2142 (7)	1.0529 (6)	0.2089 (3)	0.0253 (15)
H36	0.2588	1.1062	0.198	0.03*
C37	0.2431 (6)	0.9433 (5)	0.1902 (3)	0.0208 (14)
C38	0.3416 (6)	0.8949 (5)	0.1516 (3)	0.0195 (13)
C39	0.3982 (6)	0.9664 (5)	0.1134 (3)	0.0211 (14)
C40	0.3253 (7)	1.0549 (5)	0.0875 (3)	0.0284 (16)
H40	0.2407	1.0653	0.0938	0.034*
C41	0.3756 (8)	1.1260 (6)	0.0532 (3)	0.0353 (18)
H41	0.326	1.1848	0.0359	0.042*
C42	0.4981 (8)	1.1113 (6)	0.0443 (3)	0.0331 (18)
H42	0.5328	1.1612	0.0214	0.04*
C43	0.5707 (7)	1.0251 (6)	0.0682 (3)	0.0318 (17)
H43	0.6551	1.0152	0.0612	0.038*
C44	0.5212 (6)	0.9520 (6)	0.1028 (3)	0.0242 (14)
H44	0.572	0.8924	0.119	0.029*
N1	0.3737 (5)	0.7053 (4)	0.1884 (2)	0.0174 (11)
H1	0.3311	0.72	0.2209	0.021*
N2	0.2419 (5)	0.5558 (4)	0.2586 (2)	0.0173 (11)
H2A	0.2108	0.613	0.2393	0.021*
N3	0.0456 (5)	0.7509 (4)	0.2987 (2)	0.0189 (11)
H3A	0.1225	0.7477	0.29	0.023*
N4	0.1567 (5)	0.8948 (4)	0.2160 (2)	0.0191 (11)
H4	0.155	0.8262	0.2119	0.023*
Cl1	0.30940 (15)	0.76859 (13)	0.31206 (6)	0.0231 (4)
Cl2	0.10941 (14)	0.68414 (13)	0.16279 (7)	0.0242 (4)
C45	−0.1730 (9)	0.6478 (8)	0.1828 (4)	0.031 (2)*	0.734 (6)
H45	−0.1218	0.6986	0.189	0.038*	0.734 (6)
Cl3	−0.3208 (3)	0.7083 (3)	0.21054 (16)	0.0321 (10)*	0.734 (6)
Cl4	−0.1675 (3)	0.6305 (4)	0.11151 (13)	0.0391 (9)*	0.734 (6)
Cl5	−0.1208 (2)	0.5219 (2)	0.21636 (11)	0.0347 (8)*	0.734 (6)
C45A	−0.128 (3)	0.570 (3)	0.1860 (10)	0.031 (2)*	0.077 (4)
H45A	−0.0678	0.6112	0.1934	0.038*	0.077 (4)
Cl3A	−0.2618 (15)	0.6348 (14)	0.2249 (7)	0.017 (4)*	0.077 (4)
Cl4A	−0.1435 (18)	0.5924 (18)	0.1166 (6)	0.017 (4)*	0.077 (4)
Cl5A	−0.0727 (15)	0.4374 (13)	0.2060 (7)	0.017 (4)*	0.077 (4)
C45B	−0.202 (2)	0.7166 (18)	0.1783 (8)	0.031 (2)*	0.191 (5)
H45B	−0.1278	0.6771	0.1935	0.038*	0.191 (5)
Cl3B	−0.3256 (8)	0.6935 (8)	0.2219 (4)	0.012 (3)*	0.191 (5)
Cl4B	−0.1951 (12)	0.6719 (11)	0.1108 (4)	0.038 (3)*	0.191 (5)
Cl5B	−0.2041 (7)	0.8556 (6)	0.1744 (3)	0.021 (2)*	0.191 (5)
C46	0.5163 (8)	0.5804 (7)	0.3777 (4)	0.043 (2)
H46	0.4485	0.6244	0.3594	0.052*
Cl6	0.5736 (3)	0.6682 (3)	0.41431 (13)	0.0693 (7)*
Cl7	0.6284 (2)	0.5122 (2)	0.32691 (10)	0.0544 (6)*
Cl8	0.4635 (3)	0.4836 (2)	0.42229 (11)	0.0625 (7)*
C47	0.2978 (7)	0.1794 (7)	0.4729 (3)	0.0349 (18)
H47	0.2985	0.1151	0.4502	0.042*
Cl9	0.4284 (2)	0.2243 (2)	0.45121 (10)	0.0591 (7)
Cl10	0.2918 (2)	0.1384 (2)	0.54240 (9)	0.0552 (6)
Cl11	0.1719 (2)	0.2815 (2)	0.46321 (9)	0.0515 (6)
C48	0.1570 (7)	0.8937 (7)	0.4277 (3)	0.0354 (18)
H48	0.2163	0.8529	0.3978	0.043*
Cl12	0.2284 (3)	0.8918 (3)	0.48634 (11)	0.0700 (8)
Cl13	0.1083 (2)	1.0289 (2)	0.40557 (12)	0.0595 (7)
Cl14	0.0374 (2)	0.8291 (2)	0.44134 (10)	0.0518 (6)
C49	0.4190 (7)	1.0040 (6)	0.3108 (3)	0.0316 (17)
H49	0.3581	0.9621	0.3058	0.038*
Cl15	0.3467 (2)	1.14431 (16)	0.31629 (9)	0.0436 (5)
Cl16	0.4794 (2)	0.95855 (19)	0.37185 (10)	0.0517 (6)
Cl17	0.5289 (2)	0.9820 (2)	0.25393 (11)	0.0647 (7)
C50	0.2417 (13)	0.6847 (13)	0.0267 (10)	0.044 (2)*	0.529 (19)
H50	0.2451	0.6599	0.0658	0.052*	0.529 (19)
Cl18	0.2011 (8)	0.8325 (7)	0.0277 (5)	0.081 (3)*	0.529 (19)
Cl19	0.1258 (3)	0.6338 (5)	0.00320 (16)	0.0278 (16)*	0.529 (19)
Cl20	0.3702 (6)	0.6075 (5)	−0.0120 (2)	0.0337 (18)*	0.529 (19)
C50A	0.2432 (14)	0.6698 (13)	0.0220 (11)	0.044 (2)*	0.471 (19)
H50A	0.2516	0.6539	0.0618	0.052*	0.471 (19)
Cl1D	0.2185 (4)	0.8172 (4)	0.0141 (2)	0.0214 (17)*	0.471 (19)
Cl2D	0.1357 (9)	0.5966 (12)	0.0055 (4)	0.086 (3)*	0.471 (19)
Cl3D	0.3877 (5)	0.6204 (5)	−0.0149 (2)	0.0217 (16)*	0.471 (19)
C51	−0.0601 (9)	0.9125 (8)	0.1040 (4)	0.045 (2)*	0.904 (4)
H51	0.0005	0.844	0.1106	0.054*	0.904 (4)
Cl21	0.0059 (2)	1.0208 (2)	0.10610 (10)	0.0393 (6)*	0.904 (4)
Cl22	−0.1815 (2)	0.9244 (2)	0.15746 (10)	0.0464 (7)*	0.904 (4)
Cl23	−0.1045 (3)	0.9033 (2)	0.03786 (12)	0.0491 (7)*	0.904 (4)
C51A	−0.070 (3)	0.880 (3)	0.0899 (11)	0.045 (2)*	0.096 (4)
H51A	−0.016	0.8141	0.1043	0.054*	0.096 (4)
Cl1E	−0.0145 (19)	0.9938 (19)	0.0991 (9)	0.04*	0.096 (4)
Cl2E	−0.2132 (17)	0.8943 (17)	0.1256 (8)	0.04*	0.096 (4)
Cl3E	−0.069 (2)	0.8634 (19)	0.0200 (7)	0.04*	0.096 (4)
C52	0.1672 (15)	0.4057 (17)	0.1222 (6)	0.050 (3)*	0.587 (14)
H52	0.1178	0.4817	0.1284	0.06*	0.587 (14)
Cl24	0.3081 (5)	0.4220 (5)	0.0767 (4)	0.0664 (18)*	0.587 (14)
Cl25	0.1775 (5)	0.3459 (4)	0.1919 (2)	0.0315 (15)*	0.587 (14)
Cl26	0.0694 (5)	0.3325 (5)	0.0963 (4)	0.0650 (16)*	0.587 (14)
C52A	0.1483 (18)	0.418 (2)	0.1231 (7)	0.050 (3)*	0.413 (14)
H52A	0.1009	0.4944	0.1306	0.06*	0.413 (14)
Cl1C	0.2977 (4)	0.4144 (4)	0.0929 (2)	0.0175 (16)*	0.413 (14)
Cl2C	0.1657 (8)	0.3424 (7)	0.1835 (4)	0.047 (3)*	0.413 (14)
Cl3C	0.0861 (4)	0.3516 (4)	0.0772 (3)	0.0228 (17)*	0.413 (14)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.019 (3)	0.019 (3)	0.021 (3)	−0.006 (3)	−0.004 (3)	0.001 (3)
C2	0.024 (3)	0.018 (3)	0.021 (3)	−0.005 (3)	0.001 (3)	−0.002 (3)
C3	0.021 (3)	0.015 (3)	0.023 (3)	−0.001 (3)	−0.004 (3)	−0.002 (3)
C4	0.015 (3)	0.015 (3)	0.028 (3)	−0.003 (2)	−0.005 (3)	0.000 (3)
C5	0.021 (3)	0.018 (3)	0.023 (3)	−0.008 (3)	−0.007 (3)	−0.001 (3)
C6	0.023 (3)	0.020 (3)	0.018 (3)	0.002 (3)	−0.008 (3)	0.000 (3)
C7	0.025 (4)	0.023 (3)	0.023 (3)	0.002 (3)	−0.003 (3)	0.005 (3)
C8	0.031 (4)	0.042 (5)	0.028 (4)	0.010 (4)	0.000 (3)	0.006 (3)
C9	0.044 (5)	0.037 (5)	0.024 (4)	0.020 (4)	−0.004 (3)	0.000 (3)
C10	0.064 (6)	0.020 (4)	0.033 (4)	0.007 (4)	−0.022 (4)	−0.006 (3)
C11	0.030 (4)	0.017 (3)	0.031 (4)	0.001 (3)	−0.011 (3)	0.000 (3)
C12	0.019 (3)	0.014 (3)	0.023 (3)	−0.003 (3)	−0.005 (3)	0.000 (2)
C13	0.026 (4)	0.017 (3)	0.028 (4)	−0.005 (3)	−0.007 (3)	0.007 (3)
C14	0.025 (4)	0.022 (3)	0.028 (4)	−0.007 (3)	−0.003 (3)	0.007 (3)
C15	0.026 (4)	0.013 (3)	0.025 (3)	−0.005 (3)	−0.004 (3)	0.000 (3)
C16	0.024 (4)	0.024 (3)	0.023 (3)	−0.008 (3)	0.000 (3)	−0.003 (3)
C17	0.025 (4)	0.026 (4)	0.029 (4)	−0.013 (3)	0.001 (3)	0.005 (3)
C18	0.027 (4)	0.031 (4)	0.037 (4)	−0.008 (3)	−0.001 (3)	0.002 (3)
C19	0.037 (5)	0.029 (4)	0.054 (5)	−0.015 (4)	−0.008 (4)	0.012 (4)
C20	0.035 (4)	0.042 (5)	0.051 (5)	−0.019 (4)	−0.005 (4)	0.023 (4)
C21	0.046 (5)	0.049 (5)	0.033 (4)	−0.013 (4)	0.010 (4)	0.010 (4)
C22	0.042 (5)	0.025 (4)	0.034 (4)	−0.010 (3)	0.009 (3)	0.001 (3)
C23	0.026 (4)	0.023 (3)	0.018 (3)	−0.009 (3)	0.001 (3)	−0.001 (3)
C24	0.023 (4)	0.029 (4)	0.027 (4)	−0.008 (3)	0.002 (3)	−0.001 (3)
C25	0.018 (3)	0.030 (4)	0.024 (3)	−0.002 (3)	−0.003 (3)	−0.002 (3)
C26	0.018 (3)	0.024 (3)	0.016 (3)	0.001 (3)	−0.001 (2)	0.000 (3)
C27	0.029 (4)	0.022 (3)	0.016 (3)	−0.004 (3)	−0.007 (3)	−0.001 (3)
C28	0.022 (3)	0.026 (4)	0.022 (3)	−0.003 (3)	−0.001 (3)	−0.001 (3)
C29	0.023 (3)	0.025 (4)	0.019 (3)	0.000 (3)	−0.002 (3)	0.001 (3)
C30	0.026 (4)	0.033 (4)	0.026 (4)	0.001 (3)	0.002 (3)	−0.003 (3)
C31	0.021 (4)	0.026 (4)	0.032 (4)	0.005 (3)	−0.001 (3)	−0.004 (3)
C32	0.041 (4)	0.025 (4)	0.026 (4)	0.002 (3)	−0.006 (3)	0.004 (3)
C33	0.032 (4)	0.030 (4)	0.022 (3)	−0.004 (3)	−0.003 (3)	0.002 (3)
C34	0.025 (4)	0.018 (3)	0.017 (3)	0.005 (3)	−0.001 (3)	−0.002 (3)
C35	0.030 (4)	0.016 (3)	0.021 (3)	0.001 (3)	−0.001 (3)	0.000 (3)
C36	0.030 (4)	0.018 (3)	0.025 (3)	−0.004 (3)	0.001 (3)	0.003 (3)
C37	0.021 (3)	0.019 (3)	0.019 (3)	0.001 (3)	−0.003 (3)	0.004 (3)
C38	0.021 (3)	0.019 (3)	0.019 (3)	−0.005 (3)	−0.005 (3)	0.000 (3)
C39	0.024 (3)	0.019 (3)	0.018 (3)	−0.003 (3)	0.000 (3)	0.002 (3)
C40	0.034 (4)	0.017 (3)	0.030 (4)	−0.001 (3)	0.001 (3)	0.002 (3)
C41	0.053 (5)	0.026 (4)	0.027 (4)	−0.011 (4)	−0.006 (3)	0.006 (3)
C42	0.057 (5)	0.029 (4)	0.022 (3)	−0.027 (4)	−0.006 (3)	0.004 (3)
C43	0.035 (4)	0.039 (4)	0.026 (4)	−0.020 (4)	0.001 (3)	−0.001 (3)
C44	0.031 (4)	0.022 (3)	0.021 (3)	−0.009 (3)	−0.003 (3)	0.000 (3)
N1	0.016 (3)	0.016 (3)	0.018 (3)	−0.002 (2)	0.000 (2)	0.001 (2)
N2	0.019 (3)	0.014 (3)	0.019 (3)	−0.003 (2)	−0.002 (2)	0.002 (2)
N3	0.016 (3)	0.019 (3)	0.019 (3)	−0.003 (2)	0.003 (2)	0.000 (2)
N4	0.022 (3)	0.012 (3)	0.020 (3)	0.000 (2)	0.000 (2)	0.002 (2)
Cl1	0.0243 (8)	0.0225 (8)	0.0220 (8)	−0.0042 (6)	−0.0033 (6)	−0.0018 (6)
Cl2	0.0215 (8)	0.0254 (8)	0.0244 (8)	−0.0008 (6)	−0.0056 (6)	−0.0014 (6)
C46	0.044 (5)	0.037 (5)	0.051 (5)	−0.008 (4)	−0.017 (4)	0.000 (4)
C47	0.036 (4)	0.043 (5)	0.029 (4)	−0.017 (4)	−0.002 (3)	−0.002 (3)
Cl9	0.0474 (13)	0.0858 (19)	0.0497 (13)	−0.0359 (13)	0.0124 (10)	−0.0109 (12)
Cl10	0.0698 (16)	0.0734 (16)	0.0369 (11)	−0.0422 (14)	−0.0189 (11)	0.0205 (11)
Cl11	0.0483 (13)	0.0555 (14)	0.0441 (12)	−0.0036 (11)	−0.0007 (10)	0.0076 (10)
C48	0.041 (5)	0.044 (5)	0.024 (4)	−0.018 (4)	0.003 (3)	−0.003 (3)
Cl12	0.091 (2)	0.0820 (19)	0.0587 (15)	−0.0491 (17)	−0.0434 (15)	0.0284 (14)
Cl13	0.0626 (16)	0.0467 (13)	0.0759 (17)	−0.0191 (12)	−0.0258 (13)	0.0159 (12)
Cl14	0.0542 (14)	0.0619 (15)	0.0488 (12)	−0.0336 (12)	−0.0065 (10)	0.0067 (11)
C49	0.040 (4)	0.024 (4)	0.031 (4)	−0.009 (3)	−0.002 (3)	0.000 (3)
Cl15	0.0518 (13)	0.0266 (10)	0.0506 (12)	−0.0008 (9)	−0.0137 (10)	−0.0065 (9)
Cl16	0.0687 (16)	0.0411 (12)	0.0484 (13)	−0.0106 (11)	−0.0247 (11)	0.0091 (10)
Cl17	0.0527 (15)	0.0761 (18)	0.0526 (14)	−0.0016 (13)	0.0158 (11)	−0.0079 (13)

Geometric parameters (Å, º)

C1—N1	1.367 (8)	C37—C38	1.411 (9)
C1—C38	1.417 (9)	C38—C39	1.470 (9)
C1—C2	1.436 (9)	C39—C44	1.384 (10)
C2—C3	1.359 (9)	C39—C40	1.419 (10)
C2—H2	0.95	C40—C41	1.378 (10)
C3—C4	1.423 (9)	C40—H40	0.95
C3—H3	0.95	C41—C42	1.377 (12)
C4—N1	1.371 (8)	C41—H41	0.95
C4—C5	1.411 (9)	C42—C43	1.375 (11)
C5—C12	1.409 (9)	C42—H42	0.95
C5—C6	1.488 (9)	C43—C44	1.396 (10)
C6—C7	1.383 (10)	C43—H43	0.95
C6—C11	1.402 (10)	C44—H44	0.95
C7—C8	1.398 (10)	N1—H1	0.88
C7—H7	0.95	N2—H2A	0.88
C8—C9	1.373 (13)	N3—H3A	0.88
C8—H8	0.95	N4—H4	0.88
C9—C10	1.376 (13)	C45—Cl3	1.756 (10)
C9—H9	0.95	C45—Cl4	1.761 (9)
C10—C11	1.386 (11)	C45—Cl5	1.773 (10)
C10—H10	0.95	C45—H45	1
C11—H11	0.95	C45A—Cl5A	1.72 (2)
C12—N2	1.368 (8)	C45A—Cl4A	1.74 (2)
C12—C13	1.432 (9)	C45A—Cl3A	1.74 (2)
C13—C14	1.346 (10)	C45A—H45A	1
C13—H13	0.95	C45B—Cl3B	1.741 (19)
C14—C15	1.430 (9)	C45B—Cl5B	1.747 (19)
C14—H14	0.95	C45B—Cl4B	1.754 (19)
C15—N2	1.369 (8)	C45B—H45	0.9755
C15—C16	1.406 (10)	C45B—H45B	1
C16—C23	1.411 (10)	C46—Cl6	1.751 (9)
C16—C17	1.492 (9)	C46—Cl7	1.758 (10)
C17—C18	1.394 (11)	C46—Cl8	1.767 (9)
C17—C22	1.397 (10)	C46—H46	1
C18—C19	1.386 (11)	C47—Cl11	1.742 (9)
C18—H18	0.95	C47—Cl9	1.748 (8)
C19—C20	1.387 (13)	C47—Cl10	1.756 (8)
C19—H19	0.95	C47—H47	1
C20—C21	1.384 (13)	C48—Cl12	1.752 (8)
C20—H20	0.95	C48—Cl13	1.755 (9)
C21—C22	1.382 (11)	C48—Cl14	1.756 (8)
C21—H21	0.95	C48—H48	1
C22—H22	0.95	C49—Cl17	1.737 (8)
C23—N3	1.375 (8)	C49—Cl16	1.759 (8)
C23—C24	1.420 (10)	C49—Cl15	1.772 (8)
C24—C25	1.359 (10)	C49—H49	1
C24—H24	0.95	C50—Cl20	1.752 (15)
C25—C26	1.434 (10)	C50—Cl19	1.790 (16)
C25—H25	0.95	C50—Cl18	1.811 (15)
C26—N3	1.375 (8)	C50—H50	1
C26—C27	1.401 (9)	C50A—Cl3D	1.774 (16)
C27—C34	1.394 (10)	C50A—Cl2D	1.813 (16)
C27—C28	1.489 (10)	C50A—Cl1D	1.820 (16)
C28—C29	1.396 (9)	C50A—H50A	1
C28—C33	1.400 (10)	C51—Cl21	1.722 (9)
C29—C30	1.382 (10)	C51—Cl22	1.768 (9)
C29—H29	0.95	C51—Cl23	1.784 (9)
C30—C31	1.383 (10)	C51—H51	1
C30—H30	0.95	C51A—Cl3E	1.73 (2)
C31—C32	1.393 (10)	C51A—Cl2E	1.74 (2)
C31—H31	0.95	C51A—Cl1E	1.74 (2)
C32—C33	1.373 (10)	C51A—H51A	1
C32—H32	0.95	C52—Cl26	1.812 (15)
C33—H33	0.95	C52—Cl25	1.847 (14)
C34—N4	1.374 (8)	C52—Cl24	1.896 (14)
C34—C35	1.431 (10)	C52—H52	1
C35—C36	1.359 (10)	C52A—Cl2C	1.738 (18)
C35—H35	0.95	C52A—Cl3C	1.754 (18)
C36—C37	1.421 (10)	C52A—Cl1C	1.779 (18)
C36—H36	0.95	C52A—H52A	1
C37—N4	1.364 (9)
N1—C1—C38	126.4 (6)	C1—C38—C39	118.3 (6)
N1—C1—C2	107.0 (5)	C44—C39—C40	118.4 (6)
C38—C1—C2	126.6 (6)	C44—C39—C38	122.1 (6)
C3—C2—C1	107.6 (6)	C40—C39—C38	119.5 (6)
C3—C2—H2	126.2	C41—C40—C39	120.8 (7)
C1—C2—H2	126.2	C41—C40—H40	119.6
C2—C3—C4	108.4 (6)	C39—C40—H40	119.6
C2—C3—H3	125.8	C42—C41—C40	119.6 (7)
C4—C3—H3	125.8	C42—C41—H41	120.2
N1—C4—C5	125.8 (6)	C40—C41—H41	120.2
N1—C4—C3	107.0 (5)	C43—C42—C41	120.6 (7)
C5—C4—C3	127.2 (6)	C43—C42—H42	119.7
C12—C5—C4	123.9 (6)	C41—C42—H42	119.7
C12—C5—C6	118.4 (6)	C42—C43—C44	120.5 (7)
C4—C5—C6	117.6 (6)	C42—C43—H43	119.8
C7—C6—C11	119.3 (6)	C44—C43—H43	119.8
C7—C6—C5	120.2 (6)	C39—C44—C43	120.0 (7)
C11—C6—C5	120.4 (6)	C39—C44—H44	120
C6—C7—C8	120.3 (7)	C43—C44—H44	120
C6—C7—H7	119.8	C1—N1—C4	109.9 (5)
C8—C7—H7	119.8	C1—N1—H1	125
C9—C8—C7	119.6 (8)	C4—N1—H1	125
C9—C8—H8	120.2	C12—N2—C15	110.1 (5)
C7—C8—H8	120.2	C12—N2—H2A	124.9
C8—C9—C10	120.9 (7)	C15—N2—H2A	124.9
C8—C9—H9	119.6	C23—N3—C26	109.5 (5)
C10—C9—H9	119.6	C23—N3—H3A	125.2
C9—C10—C11	120.1 (8)	C26—N3—H3A	125.2
C9—C10—H10	120	C37—N4—C34	110.3 (5)
C11—C10—H10	120	C37—N4—H4	124.9
C10—C11—C6	119.8 (7)	C34—N4—H4	124.9
C10—C11—H11	120.1	Cl3—C45—Cl4	108.9 (5)
C6—C11—H11	120.1	Cl3—C45—Cl5	110.7 (5)
N2—C12—C5	125.7 (6)	Cl4—C45—Cl5	111.5 (5)
N2—C12—C13	106.7 (5)	Cl3—C45—H45	107.8
C5—C12—C13	127.5 (6)	Cl4—C45—H45	109.1
C14—C13—C12	108.1 (6)	Cl5—C45—H45	108.8
C14—C13—H13	126	Cl5A—C45A—Cl4A	116.7 (19)
C12—C13—H13	126	Cl5A—C45A—Cl3A	114.1 (18)
C13—C14—C15	108.5 (6)	Cl4A—C45A—Cl3A	108.4 (16)
C13—C14—H14	125.8	Cl5A—C45A—H45A	105.6
C15—C14—H14	125.8	Cl4A—C45A—H45A	105.6
N2—C15—C16	125.7 (6)	Cl3A—C45A—H45A	105.6
N2—C15—C14	106.6 (6)	Cl3B—C45B—Cl5B	110.8 (13)
C16—C15—C14	127.7 (6)	Cl3B—C45B—Cl4B	113.1 (13)
C15—C16—C23	124.4 (6)	Cl5B—C45B—Cl4B	107.2 (12)
C15—C16—C17	118.3 (6)	Cl3B—C45B—H45	122
C23—C16—C17	117.3 (6)	Cl5B—C45B—H45	91.8
C18—C17—C22	118.7 (6)	Cl4B—C45B—H45	109.2
C18—C17—C16	120.5 (6)	Cl3B—C45B—H45B	108.5
C22—C17—C16	120.7 (6)	Cl5B—C45B—H45B	108.5
C19—C18—C17	121.1 (7)	Cl4B—C45B—H45B	108.5
C19—C18—H18	119.4	H45—C45B—H45B	17.9
C17—C18—H18	119.4	Cl6—C46—Cl7	109.7 (5)
C18—C19—C20	119.5 (8)	Cl6—C46—Cl8	110.8 (5)
C18—C19—H19	120.3	Cl7—C46—Cl8	109.4 (5)
C20—C19—H19	120.3	Cl6—C46—H46	108.9
C21—C20—C19	120.0 (7)	Cl7—C46—H46	108.9
C21—C20—H20	120	Cl8—C46—H46	108.9
C19—C20—H20	120	Cl11—C47—Cl9	110.5 (5)
C22—C21—C20	120.6 (8)	Cl11—C47—Cl10	110.3 (4)
C22—C21—H21	119.7	Cl9—C47—Cl10	110.7 (4)
C20—C21—H21	119.7	Cl11—C47—H47	108.4
C21—C22—C17	120.2 (8)	Cl9—C47—H47	108.4
C21—C22—H22	119.9	Cl10—C47—H47	108.4
C17—C22—H22	119.9	Cl12—C48—Cl13	109.6 (5)
N3—C23—C16	125.1 (6)	Cl12—C48—Cl14	110.7 (4)
N3—C23—C24	107.3 (6)	Cl13—C48—Cl14	111.3 (5)
C16—C23—C24	127.6 (6)	Cl12—C48—H48	108.4
C25—C24—C23	108.4 (6)	Cl13—C48—H48	108.4
C25—C24—H24	125.8	Cl14—C48—H48	108.4
C23—C24—H24	125.8	Cl17—C49—Cl16	111.2 (5)
C24—C25—C26	107.9 (6)	Cl17—C49—Cl15	110.5 (4)
C24—C25—H25	126.1	Cl16—C49—Cl15	109.7 (4)
C26—C25—H25	126.1	Cl17—C49—H49	108.5
N3—C26—C27	125.8 (6)	Cl16—C49—H49	108.5
N3—C26—C25	106.9 (6)	Cl15—C49—H49	108.5
C27—C26—C25	127.3 (6)	Cl20—C50—Cl19	101.9 (9)
C34—C27—C26	124.1 (6)	Cl20—C50—Cl18	124.2 (12)
C34—C27—C28	118.8 (6)	Cl19—C50—Cl18	110.0 (10)
C26—C27—C28	117.1 (6)	Cl20—C50—H50	106.5
C29—C28—C33	118.1 (6)	Cl19—C50—H50	106.5
C29—C28—C27	120.3 (6)	Cl18—C50—H50	106.5
C33—C28—C27	121.6 (6)	Cl3D—C50A—Cl2D	112.4 (10)
C30—C29—C28	121.1 (6)	Cl3D—C50A—Cl1D	103.5 (10)
C30—C29—H29	119.5	Cl2D—C50A—Cl1D	121.8 (13)
C28—C29—H29	119.5	Cl3D—C50A—H50A	106
C29—C30—C31	120.1 (7)	Cl2D—C50A—H50A	106
C29—C30—H30	120	Cl1D—C50A—H50A	106
C31—C30—H30	120	Cl21—C51—Cl22	109.8 (5)
C30—C31—C32	119.4 (7)	Cl21—C51—Cl23	110.7 (5)
C30—C31—H31	120.3	Cl22—C51—Cl23	112.1 (5)
C32—C31—H31	120.3	Cl21—C51—H51	108
C33—C32—C31	120.5 (7)	Cl22—C51—H51	108
C33—C32—H32	119.7	Cl23—C51—H51	108
C31—C32—H32	119.7	Cl3E—C51A—Cl2E	111.3 (17)
C32—C33—C28	120.8 (7)	Cl3E—C51A—Cl1E	108.6 (17)
C32—C33—H33	119.6	Cl2E—C51A—Cl1E	110.6 (17)
C28—C33—H33	119.6	Cl3E—C51A—H51A	108.7
N4—C34—C27	126.0 (6)	Cl2E—C51A—H51A	108.8
N4—C34—C35	106.3 (6)	Cl1E—C51A—H51A	108.7
C27—C34—C35	127.7 (6)	Cl26—C52—Cl25	101.6 (8)
C36—C35—C34	108.1 (6)	Cl26—C52—Cl24	119.3 (9)
C36—C35—H35	126	Cl25—C52—Cl24	119.7 (9)
C34—C35—H35	126	Cl26—C52—H52	104.9
C35—C36—C37	108.2 (6)	Cl25—C52—H52	104.9
C35—C36—H36	125.9	Cl24—C52—H52	104.9
C37—C36—H36	125.9	Cl2C—C52A—Cl3C	110.7 (12)
N4—C37—C38	126.7 (6)	Cl2C—C52A—Cl1C	103.7 (11)
N4—C37—C36	107.0 (6)	Cl3C—C52A—Cl1C	106.5 (11)
C38—C37—C36	126.2 (6)	Cl2C—C52A—H52A	111.8
C37—C38—C1	123.3 (6)	Cl3C—C52A—H52A	111.8
C37—C38—C39	118.5 (6)	Cl1C—C52A—H52A	111.8
N1—C1—C2—C3	0.0 (8)	C25—C26—C27—C28	21.5 (10)
C38—C1—C2—C3	−179.3 (6)	C34—C27—C28—C29	−135.1 (7)
C1—C2—C3—C4	−0.6 (8)	C26—C27—C28—C29	44.4 (9)
C2—C3—C4—N1	0.9 (8)	C34—C27—C28—C33	45.1 (10)
C2—C3—C4—C5	−179.2 (6)	C26—C27—C28—C33	−135.4 (7)
N1—C4—C5—C12	19.8 (10)	C33—C28—C29—C30	1.6 (11)
C3—C4—C5—C12	−160.1 (7)	C27—C28—C29—C30	−178.2 (7)
N1—C4—C5—C6	−161.8 (6)	C28—C29—C30—C31	−1.4 (12)
C3—C4—C5—C6	18.3 (10)	C29—C30—C31—C32	0.2 (12)
C12—C5—C6—C7	−139.4 (6)	C30—C31—C32—C33	0.8 (12)
C4—C5—C6—C7	42.1 (9)	C31—C32—C33—C28	−0.6 (12)
C12—C5—C6—C11	42.4 (9)	C29—C28—C33—C32	−0.6 (11)
C4—C5—C6—C11	−136.1 (7)	C27—C28—C33—C32	179.2 (7)
C11—C6—C7—C8	2.3 (10)	C26—C27—C34—N4	19.2 (11)
C5—C6—C7—C8	−175.9 (6)	C28—C27—C34—N4	−161.3 (6)
C6—C7—C8—C9	−1.0 (11)	C26—C27—C34—C35	−160.7 (7)
C7—C8—C9—C10	−0.7 (11)	C28—C27—C34—C35	18.8 (10)
C8—C9—C10—C11	1.1 (12)	N4—C34—C35—C36	1.4 (8)
C9—C10—C11—C6	0.3 (11)	C27—C34—C35—C36	−178.7 (7)
C7—C6—C11—C10	−2.0 (10)	C34—C35—C36—C37	−0.7 (8)
C5—C6—C11—C10	176.3 (6)	C35—C36—C37—N4	−0.3 (8)
C4—C5—C12—N2	22.8 (10)	C35—C36—C37—C38	178.7 (7)
C6—C5—C12—N2	−155.6 (6)	N4—C37—C38—C1	−23.6 (11)
C4—C5—C12—C13	−161.1 (7)	C36—C37—C38—C1	157.6 (7)
C6—C5—C12—C13	20.5 (10)	N4—C37—C38—C39	157.4 (6)
N2—C12—C13—C14	0.9 (8)	C36—C37—C38—C39	−21.4 (10)
C5—C12—C13—C14	−175.7 (7)	N1—C1—C38—C37	−18.9 (11)
C12—C13—C14—C15	−0.3 (8)	C2—C1—C38—C37	160.3 (7)
C13—C14—C15—N2	−0.4 (8)	N1—C1—C38—C39	160.1 (6)
C13—C14—C15—C16	177.7 (7)	C2—C1—C38—C39	−20.7 (10)
N2—C15—C16—C23	−22.0 (11)	C37—C38—C39—C44	134.7 (7)
C14—C15—C16—C23	160.3 (7)	C1—C38—C39—C44	−44.4 (9)
N2—C15—C16—C17	157.3 (6)	C37—C38—C39—C40	−43.7 (9)
C14—C15—C16—C17	−20.4 (11)	C1—C38—C39—C40	137.2 (7)
C15—C16—C17—C18	−52.3 (10)	C44—C39—C40—C41	−1.1 (11)
C23—C16—C17—C18	127.0 (8)	C38—C39—C40—C41	177.4 (7)
C15—C16—C17—C22	130.8 (8)	C39—C40—C41—C42	−0.3 (11)
C23—C16—C17—C22	−49.9 (10)	C40—C41—C42—C43	1.4 (11)
C22—C17—C18—C19	−0.1 (12)	C41—C42—C43—C44	−1.1 (11)
C16—C17—C18—C19	−177.0 (7)	C40—C39—C44—C43	1.5 (10)
C17—C18—C19—C20	−0.2 (12)	C38—C39—C44—C43	−177.0 (6)
C18—C19—C20—C21	−0.2 (13)	C42—C43—C44—C39	−0.4 (11)
C19—C20—C21—C22	0.7 (14)	C38—C1—N1—C4	179.9 (6)
C20—C21—C22—C17	−1.0 (14)	C2—C1—N1—C4	0.6 (7)
C18—C17—C22—C21	0.6 (12)	C5—C4—N1—C1	179.1 (6)
C16—C17—C22—C21	177.6 (8)	C3—C4—N1—C1	−1.0 (7)
C15—C16—C23—N3	−18.9 (11)	C5—C12—N2—C15	175.5 (6)
C17—C16—C23—N3	161.8 (6)	C13—C12—N2—C15	−1.2 (7)
C15—C16—C23—C24	162.1 (7)	C16—C15—N2—C12	−177.1 (6)
C17—C16—C23—C24	−17.2 (11)	C14—C15—N2—C12	1.0 (7)
N3—C23—C24—C25	−0.6 (8)	C16—C23—N3—C26	−178.0 (6)
C16—C23—C24—C25	178.5 (7)	C24—C23—N3—C26	1.2 (7)
C23—C24—C25—C26	−0.1 (8)	C27—C26—N3—C23	177.3 (6)
C24—C25—C26—N3	0.8 (8)	C25—C26—N3—C23	−1.3 (7)
C24—C25—C26—C27	−177.7 (7)	C38—C37—N4—C34	−177.8 (6)
N3—C26—C27—C34	22.8 (11)	C36—C37—N4—C34	1.2 (7)
C25—C26—C27—C34	−158.9 (7)	C27—C34—N4—C37	178.5 (6)
N3—C26—C27—C28	−156.7 (6)	C35—C34—N4—C37	−1.6 (7)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···Cl1	0.88	2.30	3.110 (5)	152
N3—H3A···Cl1	0.88	2.38	3.183 (6)	152
N2—H2A···Cl2	0.88	2.38	3.167 (5)	148
N4—H4···Cl2	0.88	2.40	3.198 (6)	152
C45—H45···Cl2	1.00	2.64	3.382 (10)	132
C46—H46···Cl1	1.00	2.50	3.474 (9)	166
C48—H48···Cl1	1.00	2.39	3.362 (8)	164
C49—H49···Cl1	1.00	2.63	3.492 (8)	145
C50—H50···Cl2	1.00	2.65	3.47 (2)	140
C51—H51···Cl2	1.00	2.52	3.467 (10)	158
C52—H52···Cl2	1.00	2.70	3.57 (2)	146

(II) (5,10,15,20-tetraphenylporphyrinato)copper(II)

Crystal data

[Cu(C44H28N4)]	F(000) = 698
Mr = 676.24	Dx = 1.394 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 11910 reflections
a = 14.5813 (12) Å	θ = 2.3–26.0°
b = 8.6068 (5) Å	µ = 0.72 mm^−1
c = 14.6191 (11) Å	T = 120 K
β = 118.56 (1)°	Plate, blue
V = 1611.4 (2) Å^3	0.53 × 0.23 × 0.02 mm
Z = 2

Data collection

KM-4-CCD Sapphire2 (large Be window) diffractometer	3167 independent reflections
Graphite monochromator	2288 reflections with I > 2σ(I)
Detector resolution: 8.1883 pixels mm^-1	Rint = 0.052
ω scans	θmax = 26.0°, θmin = 2.7°
Absorption correction: analytical [CrysAlis PRO (Oxford Diffraction, 2006), a multifaceted crystal model based on expressions derived by Clark & Reid (1995)]	h = −17→16
Tmin = 0.777, Tmax = 0.992	k = −10→10
11911 measured reflections	l = −17→18

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)] = 0.052	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.147	H-atom parameters constrained
S = 0.96	w = 1/[σ^2(Fo^2) + (0.1054P)^2] where P = (Fo^2 + 2Fc^2)/3
3167 reflections	(Δ/σ)max < 0.001
223 parameters	Δρmax = 0.63 e Å^−3
0 restraints	Δρmin = −0.48 e Å^−3

Special details

Experimental. CrysAlisPro, Oxford Diffraction Ltd., Analytical numeric absorption correction using a multifaceted crystal model based on expressions derived by R.C. Clark & J.S. Reid. (Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887-897)

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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
Cu1	0	0	0	0.02046 (19)
N1	−0.13381 (19)	0.0220 (3)	0.00558 (19)	0.0185 (5)
N2	0.08109 (19)	0.0314 (3)	0.15490 (19)	0.0189 (6)
C1	−0.2336 (2)	0.0143 (3)	−0.0767 (2)	0.0181 (6)
C2	−0.3075 (3)	0.0505 (4)	−0.0407 (2)	0.0243 (7)
H2	−0.3813	0.0535	−0.0821	0.029*
C3	−0.2532 (2)	0.0792 (4)	0.0618 (2)	0.0244 (7)
H3	−0.2811	0.1079	0.1063	0.029*
C4	−0.1448 (2)	0.0583 (4)	0.0913 (2)	0.0198 (6)
C5	−0.0640 (2)	0.0744 (4)	0.1933 (2)	0.0204 (6)
C6	−0.0919 (2)	0.1097 (4)	0.2774 (2)	0.0239 (7)
C7	−0.0763 (3)	0.2575 (4)	0.3195 (3)	0.0319 (8)
H7	−0.0496	0.3375	0.2941	0.038*
C8	−0.1001 (3)	0.2881 (5)	0.3995 (3)	0.0403 (9)
H8	−0.0886	0.3894	0.4287	0.048*
C9	−0.1392 (3)	0.1763 (5)	0.4365 (3)	0.0443 (10)
H9	−0.1529	0.1987	0.4924	0.053*
C10	−0.1593 (4)	0.0289 (5)	0.3923 (3)	0.0504 (11)
H10	−0.1892	−0.0491	0.4158	0.06*
C11	−0.1347 (3)	−0.0027 (4)	0.3130 (3)	0.0381 (9)
H11	−0.1477	−0.1035	0.2829	0.046*
C12	0.0413 (2)	0.0612 (4)	0.2208 (2)	0.0198 (6)
C13	0.1251 (2)	0.0847 (4)	0.3255 (2)	0.0245 (7)
H13	0.1182	0.105	0.3859	0.029*
C14	0.2145 (3)	0.0721 (4)	0.3208 (2)	0.0239 (7)
H14	0.2831	0.0838	0.3774	0.029*
C15	0.1879 (2)	0.0378 (3)	0.2149 (2)	0.0194 (7)
C16	0.2610 (2)	0.0169 (3)	0.1798 (2)	0.0177 (6)
C17	0.3745 (2)	0.0278 (3)	0.2577 (2)	0.0200 (6)
C18	0.4207 (2)	−0.0821 (3)	0.3356 (2)	0.0208 (7)
H18	0.3798	−0.1647	0.3399	0.025*
C19	0.5257 (2)	−0.0737 (4)	0.4074 (2)	0.0248 (7)
H19	0.5565	−0.151	0.4598	0.03*
C20	0.5855 (3)	0.0466 (4)	0.4029 (3)	0.0271 (7)
H20	0.6575	0.0531	0.4523	0.033*
C21	0.5403 (3)	0.1570 (4)	0.3265 (3)	0.0327 (8)
H21	0.5816	0.2402	0.3235	0.039*
C22	0.4354 (3)	0.1493 (4)	0.2535 (3)	0.0276 (7)
H22	0.4053	0.2264	0.2009	0.033*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.0218 (3)	0.0221 (3)	0.0147 (3)	0.0007 (2)	0.0064 (2)	−0.0008 (2)
N1	0.0177 (13)	0.0233 (14)	0.0128 (12)	0.0015 (10)	0.0060 (11)	−0.0011 (10)
N2	0.0178 (13)	0.0229 (14)	0.0134 (12)	−0.0012 (10)	0.0053 (11)	−0.0008 (10)
C1	0.0196 (15)	0.0178 (14)	0.0142 (14)	0.0017 (11)	0.0060 (12)	0.0015 (11)
C2	0.0194 (17)	0.0292 (16)	0.0209 (16)	0.0001 (12)	0.0069 (14)	−0.0005 (14)
C3	0.0240 (17)	0.0287 (17)	0.0221 (16)	0.0013 (13)	0.0125 (14)	0.0008 (14)
C4	0.0211 (16)	0.0204 (14)	0.0164 (14)	−0.0006 (12)	0.0079 (13)	−0.0012 (12)
C5	0.0251 (17)	0.0201 (15)	0.0155 (14)	0.0005 (12)	0.0092 (13)	−0.0003 (12)
C6	0.0202 (16)	0.0339 (17)	0.0152 (14)	0.0016 (13)	0.0066 (13)	−0.0026 (13)
C7	0.0284 (19)	0.0383 (19)	0.0302 (18)	−0.0034 (15)	0.0151 (16)	−0.0078 (16)
C8	0.035 (2)	0.049 (2)	0.039 (2)	−0.0018 (17)	0.0190 (19)	−0.0199 (18)
C9	0.047 (2)	0.069 (3)	0.0242 (18)	0.001 (2)	0.0232 (19)	−0.0110 (19)
C10	0.066 (3)	0.062 (3)	0.041 (2)	−0.007 (2)	0.040 (2)	−0.003 (2)
C11	0.054 (2)	0.039 (2)	0.034 (2)	−0.0051 (17)	0.031 (2)	−0.0081 (17)
C12	0.0218 (17)	0.0192 (14)	0.0147 (14)	0.0002 (12)	0.0059 (13)	−0.0004 (12)
C13	0.0282 (18)	0.0299 (18)	0.0117 (14)	0.0011 (13)	0.0066 (14)	−0.0024 (13)
C14	0.0242 (18)	0.0260 (16)	0.0133 (14)	0.0040 (13)	0.0025 (13)	−0.0008 (13)
C15	0.0243 (17)	0.0177 (15)	0.0119 (14)	0.0008 (11)	0.0052 (13)	−0.0003 (11)
C16	0.0176 (15)	0.0157 (14)	0.0132 (13)	0.0012 (11)	0.0020 (12)	0.0018 (11)
C17	0.0193 (16)	0.0242 (16)	0.0143 (14)	0.0013 (11)	0.0062 (13)	−0.0036 (12)
C18	0.0220 (17)	0.0182 (15)	0.0182 (15)	−0.0013 (12)	0.0063 (14)	−0.0025 (12)
C19	0.0236 (18)	0.0258 (16)	0.0188 (16)	0.0046 (13)	0.0051 (14)	−0.0006 (14)
C20	0.0184 (17)	0.0360 (18)	0.0202 (16)	−0.0016 (13)	0.0038 (14)	−0.0031 (14)
C21	0.0298 (19)	0.0315 (18)	0.0309 (18)	−0.0094 (14)	0.0097 (16)	0.0013 (15)
C22	0.0284 (19)	0.0235 (16)	0.0243 (17)	0.0003 (13)	0.0073 (15)	0.0033 (14)

Geometric parameters (Å, º)

Cu1—N1^i	2.000 (2)	C9—H9	0.95
Cu1—N1	2.000 (2)	C10—C11	1.394 (5)
Cu1—N2	2.010 (2)	C10—H10	0.95
Cu1—N2^i	2.010 (2)	C11—H11	0.95
N1—C4	1.373 (4)	C12—C13	1.445 (4)
N1—C1	1.377 (4)	C13—C14	1.344 (5)
N2—C12	1.366 (4)	C13—H13	0.95
N2—C15	1.376 (4)	C14—C15	1.436 (4)
C1—C16^i	1.390 (4)	C14—H14	0.95
C1—C2	1.440 (4)	C15—C16	1.396 (4)
C2—C3	1.341 (4)	C16—C1^i	1.390 (4)
C2—H2	0.95	C16—C17	1.498 (4)
C3—C4	1.438 (4)	C17—C18	1.383 (4)
C3—H3	0.95	C17—C22	1.392 (4)
C4—C5	1.397 (4)	C18—C19	1.383 (4)
C5—C12	1.393 (4)	C18—H18	0.95
C5—C6	1.499 (4)	C19—C20	1.375 (5)
C6—C11	1.381 (5)	C19—H19	0.95
C6—C7	1.384 (5)	C20—C21	1.372 (5)
C7—C8	1.395 (5)	C20—H20	0.95
C7—H7	0.95	C21—C22	1.386 (5)
C8—C9	1.356 (6)	C21—H21	0.95
C8—H8	0.95	C22—H22	0.95
C9—C10	1.389 (6)
N1^i—Cu1—N1	180.00 (14)	C9—C10—C11	118.9 (4)
N1^i—Cu1—N2	89.94 (10)	C9—C10—H10	120.5
N1—Cu1—N2	90.06 (10)	C11—C10—H10	120.5
N1^i—Cu1—N2^i	90.06 (10)	C6—C11—C10	121.3 (3)
N1—Cu1—N2^i	89.94 (10)	C6—C11—H11	119.4
N2—Cu1—N2^i	180.00 (14)	C10—C11—H11	119.4
C4—N1—C1	105.8 (2)	N2—C12—C5	126.4 (3)
C4—N1—Cu1	126.9 (2)	N2—C12—C13	110.2 (3)
C1—N1—Cu1	127.2 (2)	C5—C12—C13	123.4 (3)
C12—N2—C15	106.1 (2)	C14—C13—C12	106.5 (3)
C12—N2—Cu1	126.9 (2)	C14—C13—H13	126.7
C15—N2—Cu1	126.9 (2)	C12—C13—H13	126.7
N1—C1—C16^i	126.3 (3)	C13—C14—C15	107.7 (3)
N1—C1—C2	109.5 (3)	C13—C14—H14	126.2
C16^i—C1—C2	124.2 (3)	C15—C14—H14	126.2
C3—C2—C1	107.7 (3)	N2—C15—C16	126.2 (3)
C3—C2—H2	126.2	N2—C15—C14	109.6 (3)
C1—C2—H2	126.2	C16—C15—C14	124.2 (3)
C2—C3—C4	106.8 (3)	C1^i—C16—C15	123.3 (3)
C2—C3—H3	126.6	C1^i—C16—C17	118.4 (3)
C4—C3—H3	126.6	C15—C16—C17	118.2 (3)
N1—C4—C5	126.2 (3)	C18—C17—C22	118.7 (3)
N1—C4—C3	110.2 (3)	C18—C17—C16	120.6 (3)
C5—C4—C3	123.6 (3)	C22—C17—C16	120.7 (3)
C12—C5—C4	123.4 (3)	C19—C18—C17	121.1 (3)
C12—C5—C6	118.3 (3)	C19—C18—H18	119.5
C4—C5—C6	118.3 (3)	C17—C18—H18	119.5
C11—C6—C7	119.0 (3)	C20—C19—C18	120.0 (3)
C11—C6—C5	121.1 (3)	C20—C19—H19	120
C7—C6—C5	120.0 (3)	C18—C19—H19	120
C6—C7—C8	119.5 (3)	C21—C20—C19	119.5 (3)
C6—C7—H7	120.2	C21—C20—H20	120.3
C8—C7—H7	120.2	C19—C20—H20	120.3
C9—C8—C7	121.4 (4)	C20—C21—C22	121.1 (3)
C9—C8—H8	119.3	C20—C21—H21	119.4
C7—C8—H8	119.3	C22—C21—H21	119.4
C8—C9—C10	119.9 (3)	C21—C22—C17	119.6 (3)
C8—C9—H9	120.1	C21—C22—H22	120.2
C10—C9—H9	120.1	C17—C22—H22	120.2
N2—Cu1—N1—C4	4.6 (2)	C5—C6—C11—C10	179.0 (4)
N2^i—Cu1—N1—C4	−175.4 (2)	C9—C10—C11—C6	−0.5 (7)
N2—Cu1—N1—C1	179.9 (2)	C15—N2—C12—C5	176.6 (3)
N2^i—Cu1—N1—C1	−0.1 (2)	Cu1—N2—C12—C5	0.6 (5)
N1^i—Cu1—N2—C12	177.7 (3)	C15—N2—C12—C13	−0.9 (3)
N1—Cu1—N2—C12	−2.3 (3)	Cu1—N2—C12—C13	−176.94 (19)
N1^i—Cu1—N2—C15	2.5 (2)	C4—C5—C12—N2	−0.1 (5)
N1—Cu1—N2—C15	−177.5 (2)	C6—C5—C12—N2	−179.3 (3)
C4—N1—C1—C16^i	178.9 (3)	C4—C5—C12—C13	177.2 (3)
Cu1—N1—C1—C16^i	2.9 (4)	C6—C5—C12—C13	−2.0 (5)
C4—N1—C1—C2	1.4 (3)	N2—C12—C13—C14	1.4 (4)
Cu1—N1—C1—C2	−174.7 (2)	C5—C12—C13—C14	−176.2 (3)
N1—C1—C2—C3	−0.2 (3)	C12—C13—C14—C15	−1.2 (3)
C16^i—C1—C2—C3	−177.8 (3)	C12—N2—C15—C16	−178.9 (3)
C1—C2—C3—C4	−1.1 (4)	Cu1—N2—C15—C16	−3.0 (4)
C1—N1—C4—C5	178.3 (3)	C12—N2—C15—C14	0.2 (3)
Cu1—N1—C4—C5	−5.6 (4)	Cu1—N2—C15—C14	176.19 (19)
C1—N1—C4—C3	−2.1 (3)	C13—C14—C15—N2	0.7 (4)
Cu1—N1—C4—C3	174.00 (19)	C13—C14—C15—C16	179.8 (3)
C2—C3—C4—N1	2.0 (4)	N2—C15—C16—C1^i	−0.2 (5)
C2—C3—C4—C5	−178.3 (3)	C14—C15—C16—C1^i	−179.2 (3)
N1—C4—C5—C12	2.7 (5)	N2—C15—C16—C17	−179.8 (3)
C3—C4—C5—C12	−176.9 (3)	C14—C15—C16—C17	1.2 (4)
N1—C4—C5—C6	−178.1 (3)	C1^i—C16—C17—C18	−112.7 (3)
C3—C4—C5—C6	2.3 (5)	C15—C16—C17—C18	66.9 (4)
C12—C5—C6—C11	−107.3 (4)	C1^i—C16—C17—C22	67.6 (4)
C4—C5—C6—C11	73.4 (4)	C15—C16—C17—C22	−112.8 (3)
C12—C5—C6—C7	73.7 (4)	C22—C17—C18—C19	−0.9 (5)
C4—C5—C6—C7	−105.5 (4)	C16—C17—C18—C19	179.5 (3)
C11—C6—C7—C8	2.6 (5)	C17—C18—C19—C20	0.9 (5)
C5—C6—C7—C8	−178.4 (3)	C18—C19—C20—C21	−0.4 (5)
C6—C7—C8—C9	−0.6 (6)	C19—C20—C21—C22	−0.2 (5)
C7—C8—C9—C10	−1.9 (6)	C20—C21—C22—C17	0.2 (5)
C8—C9—C10—C11	2.5 (7)	C18—C17—C22—C21	0.3 (5)
C7—C6—C11—C10	−2.0 (6)	C16—C17—C22—C21	179.9 (3)

Symmetry code: (i) −x, −y, −z.