2,3,12,13-Tetra­bromo-5,10,15,20-tetra­kis(4-butoxy­phen­yl)porphyrin 1,2-dichloro­ethane solvate

Nonmesogenic 2,3,12,13-tetra­bromo-5,10,15,20-tetra­kis(4-butoxy­phenyl)­porphyrin crystallizes as the title 1,2-dichloro­ethane solvate, C₆₀H₅₈Br₄N₄O₄·C₂H₄Cl₂. The porphyrin ring shows a nonplanar conformation, with an average mean plane displacement of the [beta]-pyrrole C atoms from the 24-atom (C₂₀N₄) core of ±0.50 (3) Å. The 1,2-dichloro­ethane solvent is incorporated between the porphyrin units and induces the formation of one-dimensional chains via inter­halogen Cl...Br and butyl-aryl C-H...[pi] inter­actions. These chains are oriented along the unit-cell a axis, with the macrocyclic ring planes lying almost parallel to the (010) plane. The chains are arranged in an offset fashion by aligning the butoxy chains approximately above or below the faces of the adjacent porphyrin core, resulting in decreased inter­porphyrin [pi]-[pi] inter­actions, and they are held together by weak inter­molecular (C-Br...[pi], C-H...[pi] and C-H...Br) inter­actions. The nonplanar geometry of the macrocyclic ring is probably due to the weak inter­porphyrin inter­actions induced by the solvent mol­ecule and the peripheral butoxy groups. The nonplanarity of the mesogens could influence the mesogenic behaviour differently relative to planar porphyrin mesogens.

S1. Comment

Porphyrins and metalloporphyrins have been widely used as molecular scaffolds for the formation of clathrates by incorporating a wide range of guests (Byrn et al., 1993). Sterically crowded porphyrins have been developed as model compounds of nonplanar conformations of tetrapyrrole pigments in nature (Shelnutt et al., 1998). The variation in nonplanarity of the macrocyclic ring has been attributed to the degree of steric crowding around the periphery of the porphyrin (Senge, 2000). The crystal structure of 2,3,12,13-tetrabromo-5,10,15,20-tetraphenylporphyrin (TPPBr₄) exhibits a nearly planar geometry of the porphyrin ring (Zou et al., 1995). In this study, the effect of substitution at the phenyl rings on the stereochemistry and intermolecular interactions of 2,3,12,13-tetrabromo-5,10,15,20-tetrakis[4-(1-butoxyphenyl)]porphyrin has been examined through the structure of the title 1,2-dichloroethane solvate, H₂T(4-OC₄P)PBr₄.C₂H₄Cl₂, (I), which reveals a nonplanar conformation of the macrocycle.

The nonplanarity of the macrocycle in (I) (Fig. 1a) is evidenced from the side-on view in Fig. 1(b), as well as from the diagram of the mean-plane deviations of the 24-atom core (Fig. 1c). The average deviation of the β-pyrrole C atoms is ±0.50 (3) Å, while the mean deviation of the meso C atoms is ±0.038 (3) Å. Interestingly, the β-pyrrole C atoms of the brominated pyrroles show a greater mean-plane displacement than their counterparts in the unbrominated pyrroles. The pyrrole groups themselves are alternately displaced up and down from the mean plane formed by the 24-atom core, indicating that the distortion of the ring is more of a saddle-shaped conformation combined with a gently ruffled conformation (Senge, 2000). This shows an enhanced distortion of the 24-atom core in (I) compared with the nearly planar free H₂TPPBr₄ molecule (Zou et al., 1995) and it is also greater than the distortion reported for the five-coordinated ZnTPPBr₄(CH₃OH).DMF structure (Terazono et al., 2002). The Cβ···Cβ distance along the transannular brominated pyrrole groups in (I) [8.48 (2) Å] is longer than the corresponding distance along the unbrominated pyrroles [8.25 (5) Å]. Similarly, the N···N distance along the brominated pyrroles [4.19 (1) Å] is longer than that in the opposite direction [4.07 (3) Å]. The corresponding Cβ···Cβ and N···N distances in H₂TPPBr₄ are slightly longer, as expected from the flattening of the macrocycle. An increase in the mean value of the torsion angles N—Cα—C_m—Cα' = 9.0 (8)° (e.g. N1—C4—C5—C6) and Cα—N—Cα—C_b = 3.0 (8)° is observed in (I), in contrast with the corresponding values of 4.9 and 0.7°, respectively, for H₂TPPBr₄. [Please define subscripts m and b]

Similar trends in behaviour were reported for the solvate-free structures H₂TPPR₄ (R = C₆H₅ or CH₃) (Chan et al., 1994; Bhyrappa et al., 2007). The relaxation of the steric strain in the macrocyclic ring is reflected in the elongation of the core along the substituted pyrrole direction (Scheidt, 2000). In the case of (I), the meso-aryl and pyrrole groups make average dihedral angles of 68.1 (5) and 12.3 (7)°, respectively, with the mean plane of the 24-atom core. It is anticipated that the extent of steric crowding around the periphery of the porphyrin in (I) is comparable with that in the non-solvated structures H₂TTPPR₄ (R = CH₃, Br or C₆H₅), since the alkoxy groups are farther away from the core. However, the presence of the solvent molecule and the weak interporphyrin interactions (see below) seem to have a greater influence on the nonplanar geometry of (I) (Krupitsky et al., 1994).

Notably, the solvate complex in (I) forms a one-dimensional array oriented approximately along the unit-cell a axis, with the macrocyclic ring planes lying almost parallel to the (010) plane. Atom Cl1 of the 1,2-dichloroethane solvate bridges two porphyrin molecules via Cl···Br and C—H···π interactions to form a one-dimensional array (Fig. 2). The short interhalogen contacts are Br1···Cl1ⁱ = 3.496 (2) Å, Br3···Cl1ⁱⁱ = 3.458 (2) Å and C—H···π (H60C···C45ⁱⁱⁱ = 2.70 Å) [symmetry codes: (i) x, -y + 1/2, z + 1/2; (ii) x + 1, -y + 1/2, z + 1/2; (iii) x - 1, y, z]. Such interhalogen and C—H ···π interactions are known to generate interesting structural motifs (Freytag & Jones, 2000; Desiraju & Steiner, 1999). These one-dimensional chains are stabilized further by weak intermolecular interactions. Selected intermolecular hydrogen-bonding distances are listed in Table 1. These chains are bridged by closest arrays from above and below the plane in a slipped stack fashion and are held together by C—H···Br [H52···Br2^iv and H49B···Br3^iv] and C—H···π [H56···C14^v and H47A···C11^iv] interactions (Table 1) [symmetry codes: (iv) x, -y + 1/2, z - 1/2; (v) -x + 1, -y, -z + 1]. These hydrogen-bonding distances are indicative of weak intermolecular interactions (Desiraju & Steiner, 1999). In addition, a weak intermolecular C—Br···π [Br4···C32ⁱ = 3.414 (5) Å] short contact is also observed. Fig. 3 shows the relative orientation of the one-dimensional chains, with the butoxy groups lying approximately on the faces of the other adjacent porphyrins, leading to decreased intermolecular π–π interactions that perhaps partly influence the distortion of the macrocyclic ring.

The structure of (I) shows decreased intermolecular π–π interactions and enhanced nonplanar geometry of the 24-atom core, in contrast with that found in unbrominated 5,10,15,20-tetrakis[4-(1-hexyloxyphenyl)]porphyrin (Walawalkar et al., 1993) and 5,10,15,20-tetrakis[4-(1-octyloxyphenyl)]porphinato zinc(II) (Chiaroni et al., 1988), suggesting that the Br atoms, alkoxy chains and solvate influence the conformational behaviour in this system.

S2. Experimental

Compound (I) was prepared by bromination of 5,10,15,20-tetrakis[4-(1-butoxyphenyl)]porphyrin using the procedure of Kumar et al. (2003) (yield 70%). UV–Vis data [CH₂Cl₂, λ_max, nm (log ε)]: 447 (5.65), 545 (4.40), 595 (3.90), 625 (sh), 704 (4.10); ¹H NMR (CDCl₃, δ, p.p.m.): 8.70 (s, 4H, β-pyrrole-H), 8.09 (d, 8H, J = 8.56 Hz, o-phenyl-H), 7.32 (d, 8H, J = 8.56 Hz, m-phenyl-H), 4.26 (t, 8H, J = 6.52 Hz, α-CH₂), 1.97 (qnt, 8H, J = 7.50 Hz, β-CH₂), 1.65 (qnt, 8H, J = 7.49 Hz, γ-CH₂), 1.10 (t, 12H,J = 7.38 Hz, –CH₃), -2.71 (s, 2H, imino-H); MALDI-TOF mass spectrum in α-cyano-4-hydroxycinnamic acid as the matrix: m/z calculated for C₆₀H₅₈N₄O₄Br₄: 1218.76; found 1220.36; analysis, calculated for C₆₀H₅₈N₄O₄Br₄: C 59.14, H 4.82, N 4.61%; found: C 59.31, H 4.81, N 4.33%. Single crystals of (I) suitable for X-ray analysis were obtained by slow vapour diffusion of hexane into a 1,2-dichloroethane solution of the porphyrin over a period of 4 d.

S3. Refinement

All H atoms were placed in constrained positions, with C—H = 0.93–0.98 Å, and refined using a riding model, with U_iso(H) = 1.2U_eq(C). Terminal atom C60 of one of the alkyl chains exhibits positional disorder and was refined with split positions of occupancy 0.52(s.u.?) and 0.48(s.u.?) [0.59 (15) and 0.41 (15) in CIF tables?]

Computing details

Data collection: APEX2 (Bruker, 2004); cell refinement: APEX2 (Bruker, 2004); data reduction: XPREP (Bruker, 2003); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-32 (Farrugia, 1997) and Mercury (Bruno et al., 2002); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures

	Fig. 1. (a) A diagram of the H2T(4-OC4Ph)Br4.C2H4Cl2 complex, (I). Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii. [Please check added text] (b) A side-on view of the complex. Displacement ellipsoids are drawn at the 50% probability level. The meso-aryl groups and H atoms have been omitted for clarity. (c) The deviation of the core atoms from the mean plane formed by the 24-atom core. The deviations are in Å with s.u.s of 0.004 Å.
	Fig. 2. A molecular packing diagram for (I), viewed approximately down the unit-cell b axis. Intermolecular Br···Cl···Br and C—H···π short contacts are shown as dotted lines. [Symmetry codes: (i) 1+x, y, z; (ii) 1+x, 1/2-y, 1/2+z.]
	Fig. 3. A projection diagram of the packing in (I) along the b axis. Heavy molecules are in front and are oriented in a slipped stack fashion relative to the lighter molecules, which are at the back. Intermolecular Cl···Br and C—Br···π interactions are shown as dotted lines.

2,3,12,13-Tetrabromo-5,10,15,20-tetrakis(4-butoxyphenyl)porphyrin 1,2-dichloroethane solvate

Crystal data

C60H58Br4N4O4·C2H4Cl2	F(000) = 2672
Mr = 1317.70	Dx = 1.506 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 7087 reflections
a = 18.8426 (4) Å	θ = 2.0–28.3°
b = 17.1996 (4) Å	µ = 2.91 mm^−1
c = 18.0722 (4) Å	T = 176 K
β = 97.080 (1)°	Plate, brown
V = 5812.3 (2) Å^3	0.31 × 0.24 × 0.20 mm
Z = 4

Data collection

Bruker APEXII CCD area-detector diffractometer	10251 independent reflections
Radiation source: fine-focus sealed tube	7087 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.037
ω and ϕ scans	θmax = 25.0°, θmin = 1.1°
Absorption correction: multi-scan (SADABS; Bruker, 2003)	h = −20→22
Tmin = 0.445, Tmax = 0.554	k = −18→20
65317 measured reflections	l = −16→21

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)] = 0.051	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.145	H-atom parameters constrained
S = 1.07	w = 1/[σ^2(Fo^2) + (0.0531P)^2 + 16.8948P] where P = (Fo^2 + 2Fc^2)/3
10251 reflections	(Δ/σ)max < 0.001
693 parameters	Δρmax = 1.10 e Å^−3
4 restraints	Δρmin = −0.71 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)
C1	0.3904 (3)	0.1304 (3)	0.5815 (3)	0.0366 (12)
C2	0.3356 (3)	0.1527 (3)	0.6281 (3)	0.0385 (12)
C3	0.3686 (3)	0.1551 (3)	0.6986 (3)	0.0384 (12)
C4	0.4438 (3)	0.1361 (3)	0.6967 (3)	0.0385 (12)
C5	0.4965 (3)	0.1285 (3)	0.7579 (3)	0.0392 (12)
C6	0.5698 (3)	0.1231 (3)	0.7532 (3)	0.0392 (12)
C7	0.6248 (3)	0.1159 (3)	0.8143 (3)	0.0464 (14)
H7	0.6178	0.1091	0.8639	0.056*
C8	0.6887 (3)	0.1205 (3)	0.7883 (3)	0.0445 (13)
H8	0.7331	0.1183	0.8171	0.053*
C9	0.6769 (3)	0.1294 (3)	0.7092 (3)	0.0361 (12)
C10	0.7304 (3)	0.1377 (3)	0.6628 (3)	0.0375 (12)
C11	0.7185 (3)	0.1436 (3)	0.5846 (3)	0.0336 (11)
C12	0.7728 (3)	0.1606 (3)	0.5352 (3)	0.0343 (11)
C13	0.7376 (3)	0.1615 (3)	0.4654 (3)	0.0374 (12)
C14	0.6634 (3)	0.1409 (3)	0.4698 (3)	0.0363 (12)
C15	0.6122 (3)	0.1222 (3)	0.4100 (3)	0.0365 (12)
C16	0.5403 (3)	0.1063 (3)	0.4157 (3)	0.0373 (12)
C17	0.4878 (3)	0.0817 (3)	0.3574 (3)	0.0488 (14)
H17	0.4962	0.0694	0.3091	0.059*
C18	0.4233 (3)	0.0791 (3)	0.3835 (3)	0.0488 (14)
H18	0.3802	0.0647	0.3564	0.059*
C19	0.4333 (3)	0.1023 (3)	0.4594 (3)	0.0387 (12)
C20	0.3787 (3)	0.1133 (3)	0.5048 (3)	0.0369 (12)
C21	0.4768 (3)	0.1212 (3)	0.8351 (3)	0.0412 (13)
C22	0.4498 (3)	0.0522 (3)	0.8584 (3)	0.0407 (12)
H22	0.4435	0.0107	0.8253	0.049*
C23	0.4321 (3)	0.0431 (3)	0.9295 (3)	0.0440 (13)
H23	0.4141	−0.0041	0.9440	0.053*
C24	0.4410 (3)	0.1043 (3)	0.9793 (3)	0.0448 (13)
C25	0.4688 (3)	0.1735 (3)	0.9582 (3)	0.0546 (16)
H25	0.4758	0.2145	0.9919	0.065*
C26	0.4865 (3)	0.1816 (3)	0.8867 (3)	0.0580 (17)
H26	0.5052	0.2286	0.8726	0.070*
C27	0.4237 (4)	0.1514 (4)	1.1003 (3)	0.0631 (17)
H27A	0.3989	0.1967	1.0781	0.076*
H27B	0.4730	0.1655	1.1164	0.076*
C28	0.3879 (3)	0.1224 (4)	1.1658 (3)	0.0581 (16)
H28A	0.4129	0.0765	1.1864	0.070*
H28B	0.3919	0.1620	1.2043	0.070*
C29	0.3102 (3)	0.1028 (4)	1.1447 (3)	0.0609 (17)
H29A	0.3068	0.0577	1.1122	0.073*
H29B	0.2871	0.1459	1.1166	0.073*
C30	0.2703 (4)	0.0861 (4)	1.2103 (4)	0.079 (2)
H30A	0.2928	0.0435	1.2386	0.118*
H30B	0.2217	0.0726	1.1927	0.118*
H30C	0.2710	0.1314	1.2414	0.118*
C31	0.8042 (3)	0.1398 (3)	0.7041 (3)	0.0392 (12)
C32	0.8348 (3)	0.2084 (3)	0.7341 (3)	0.0521 (15)
H32	0.8107	0.2553	0.7250	0.063*
C33	0.9017 (3)	0.2071 (4)	0.7781 (3)	0.0586 (17)
H33	0.9223	0.2532	0.7975	0.070*
C34	0.9367 (3)	0.1376 (4)	0.7924 (3)	0.0573 (16)
C35	0.9072 (3)	0.0712 (4)	0.7631 (3)	0.0556 (15)
H35	0.9317	0.0245	0.7722	0.067*
C36	0.8421 (3)	0.0712 (3)	0.7205 (3)	0.0462 (14)
H36	0.8227	0.0244	0.7019	0.055*
C37	1.0306 (4)	0.1920 (5)	0.8754 (5)	0.094 (3)
H37A	0.9961	0.2139	0.9052	0.113*
H37B	1.0429	0.2313	0.8407	0.113*
C38	1.0983 (4)	0.1647 (5)	0.9261 (5)	0.090 (2)
H38A	1.1200	0.2095	0.9525	0.108*
H38B	1.0838	0.1291	0.9630	0.108*
C39	1.1533 (4)	0.1258 (5)	0.8868 (4)	0.085 (2)
H39A	1.1622	0.1570	0.8442	0.102*
H39B	1.1351	0.0757	0.8683	0.102*
C40	1.2247 (4)	0.1135 (4)	0.9382 (4)	0.077 (2)
H40A	1.2459	0.1631	0.9516	0.115*
H40B	1.2569	0.0835	0.9123	0.115*
H40C	1.2156	0.0864	0.9825	0.115*
C41	0.6335 (3)	0.1136 (3)	0.3334 (3)	0.0361 (11)
C42	0.6149 (3)	0.1678 (3)	0.2773 (3)	0.0456 (13)
H42	0.5866	0.2100	0.2870	0.055*
C43	0.6371 (3)	0.1607 (3)	0.2071 (3)	0.0435 (13)
H43	0.6239	0.1976	0.1703	0.052*
C44	0.6795 (3)	0.0977 (3)	0.1928 (3)	0.0416 (13)
C45	0.6960 (3)	0.0418 (3)	0.2464 (3)	0.0476 (14)
H45	0.7223	−0.0017	0.2358	0.057*
C46	0.6739 (3)	0.0498 (3)	0.3161 (3)	0.0454 (13)
H46	0.6862	0.0119	0.3521	0.054*
C47	0.6945 (4)	0.1424 (3)	0.0696 (3)	0.0602 (17)
H47A	0.7141	0.1918	0.0882	0.072*
H47B	0.6439	0.1490	0.0534	0.072*
C48	0.7325 (4)	0.1145 (4)	0.0057 (3)	0.0645 (19)
H48A	0.7114	0.0656	−0.0127	0.077*
H48B	0.7250	0.1520	−0.0346	0.077*
C49	0.8118 (4)	0.1030 (4)	0.0267 (4)	0.074 (2)
H49A	0.8194	0.0624	0.0641	0.089*
H49B	0.8324	0.1506	0.0486	0.089*
C50	0.8505 (5)	0.0808 (5)	−0.0403 (4)	0.100 (3)
H50A	0.8282	0.0357	−0.0643	0.150*
H50B	0.8998	0.0696	−0.0234	0.150*
H50C	0.8478	0.1232	−0.0750	0.150*
C51	0.3046 (3)	0.1067 (3)	0.4670 (3)	0.0371 (12)
C52	0.2763 (3)	0.1628 (3)	0.4163 (3)	0.0501 (14)
H52	0.3058	0.2023	0.4027	0.060*
C53	0.2060 (3)	0.1611 (4)	0.3857 (3)	0.0566 (16)
H53	0.1882	0.1998	0.3526	0.068*
C54	0.1612 (3)	0.1016 (3)	0.4041 (3)	0.0481 (14)
C55	0.1893 (3)	0.0429 (3)	0.4510 (3)	0.0494 (14)
H55	0.1606	0.0015	0.4620	0.059*
C56	0.2599 (3)	0.0459 (3)	0.4813 (3)	0.0434 (13)
H56	0.2784	0.0057	0.5124	0.052*
C57	0.0424 (4)	0.0524 (4)	0.3977 (5)	0.077 (2)
H57A	0.0433	0.0553	0.4514	0.093*
H57B	0.0538	−0.0003	0.3842	0.093*
C58	−0.0300 (4)	0.0761 (6)	0.3591 (7)	0.134 (4)
H58A	−0.0276	0.0823	0.3061	0.160*
H58B	−0.0438	0.1256	0.3787	0.160*
C59	−0.0852 (6)	0.0154 (7)	0.3711 (8)	0.185 (6)
H59A	−0.1095	0.0296	0.4134	0.222*
H59B	−0.0622	−0.0345	0.3815	0.222*
C60A	−0.1385 (13)	0.010 (2)	0.3017 (12)	0.156 (7)	0.412 (15)
H60A	−0.1727	−0.0302	0.3081	0.234*	0.412 (15)
H60B	−0.1139	−0.0026	0.2598	0.234*	0.412 (15)
H60C	−0.1628	0.0586	0.2931	0.234*	0.412 (15)
C60B	−0.0919 (12)	−0.0252 (14)	0.2966 (10)	0.156 (7)	0.588 (15)
H60D	−0.1250	−0.0676	0.2966	0.234*	0.588 (15)
H60E	−0.0460	−0.0446	0.2877	0.234*	0.588 (15)
H60F	−0.1090	0.0110	0.2580	0.234*	0.588 (15)
C61	0.0631 (7)	0.2619 (10)	0.1665 (6)	0.150 (5)
H61A	0.1022	0.2893	0.1952	0.180*
H61B	0.0198	0.2745	0.1880	0.180*
C62	0.0762 (8)	0.1780 (11)	0.1757 (9)	0.196 (7)
H62A	0.0791	0.1654	0.2283	0.236*
H62B	0.1221	0.1659	0.1595	0.236*
N1	0.4547 (2)	0.1246 (2)	0.6242 (2)	0.0360 (10)
N2	0.6045 (2)	0.1295 (2)	0.6905 (2)	0.0379 (10)
H2	0.5833	0.1331	0.6457	0.045*
N3	0.6538 (2)	0.1341 (2)	0.5436 (2)	0.0347 (9)
N4	0.5051 (2)	0.1161 (2)	0.4776 (2)	0.0373 (10)
H4	0.5251	0.1290	0.5212	0.045*
O1	0.4204 (2)	0.0894 (2)	1.04804 (19)	0.0546 (10)
O2	1.0029 (3)	0.1279 (3)	0.8379 (3)	0.0824 (14)
O3	0.7054 (2)	0.0845 (2)	0.12650 (19)	0.0543 (10)
O4	0.0921 (2)	0.1063 (3)	0.3726 (2)	0.0696 (12)
Br1	0.24014 (3)	0.18090 (4)	0.60184 (3)	0.05624 (18)
Br2	0.32209 (3)	0.18440 (4)	0.78014 (3)	0.05624 (19)
Br3	0.87065 (3)	0.17805 (3)	0.55693 (3)	0.04762 (16)
Br4	0.78050 (3)	0.19637 (3)	0.38306 (3)	0.04771 (17)
Cl1	0.05423 (12)	0.29781 (18)	0.07614 (15)	0.1196 (9)
Cl2	0.0120 (4)	0.1203 (3)	0.1274 (3)	0.276 (3)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.045 (3)	0.032 (3)	0.036 (3)	0.001 (2)	0.016 (3)	0.000 (2)
C2	0.043 (3)	0.033 (3)	0.042 (3)	−0.001 (2)	0.019 (3)	−0.002 (2)
C3	0.045 (3)	0.036 (3)	0.039 (3)	−0.001 (2)	0.026 (3)	−0.004 (2)
C4	0.050 (3)	0.037 (3)	0.032 (3)	−0.007 (2)	0.018 (3)	−0.005 (2)
C5	0.050 (3)	0.039 (3)	0.032 (3)	−0.008 (2)	0.018 (3)	−0.003 (2)
C6	0.052 (3)	0.039 (3)	0.030 (3)	−0.008 (2)	0.020 (3)	−0.002 (2)
C7	0.057 (4)	0.055 (3)	0.030 (3)	−0.005 (3)	0.019 (3)	−0.001 (2)
C8	0.048 (3)	0.056 (3)	0.030 (3)	−0.006 (3)	0.009 (3)	−0.003 (2)
C9	0.041 (3)	0.038 (3)	0.031 (3)	−0.003 (2)	0.012 (2)	−0.005 (2)
C10	0.049 (3)	0.032 (3)	0.034 (3)	−0.002 (2)	0.014 (2)	−0.005 (2)
C11	0.039 (3)	0.033 (3)	0.031 (3)	0.000 (2)	0.013 (2)	−0.002 (2)
C12	0.032 (3)	0.033 (3)	0.041 (3)	−0.004 (2)	0.015 (2)	−0.001 (2)
C13	0.048 (3)	0.034 (3)	0.035 (3)	0.002 (2)	0.021 (3)	0.001 (2)
C14	0.046 (3)	0.030 (2)	0.036 (3)	0.005 (2)	0.020 (3)	0.001 (2)
C15	0.048 (3)	0.037 (3)	0.027 (3)	0.004 (2)	0.014 (2)	0.000 (2)
C16	0.044 (3)	0.040 (3)	0.030 (3)	0.005 (2)	0.011 (2)	−0.002 (2)
C17	0.051 (3)	0.066 (4)	0.032 (3)	0.001 (3)	0.015 (3)	−0.011 (3)
C18	0.043 (3)	0.066 (4)	0.037 (3)	0.002 (3)	0.009 (3)	−0.009 (3)
C19	0.042 (3)	0.043 (3)	0.033 (3)	0.003 (2)	0.012 (2)	−0.002 (2)
C20	0.044 (3)	0.032 (3)	0.038 (3)	0.001 (2)	0.015 (2)	0.000 (2)
C21	0.044 (3)	0.047 (3)	0.037 (3)	−0.011 (2)	0.020 (2)	−0.006 (2)
C22	0.048 (3)	0.040 (3)	0.036 (3)	−0.005 (2)	0.015 (2)	−0.006 (2)
C23	0.056 (4)	0.038 (3)	0.042 (3)	0.000 (2)	0.024 (3)	0.004 (2)
C24	0.054 (3)	0.051 (3)	0.034 (3)	0.001 (3)	0.022 (3)	0.003 (2)
C25	0.065 (4)	0.059 (4)	0.045 (3)	−0.019 (3)	0.029 (3)	−0.016 (3)
C26	0.085 (5)	0.051 (3)	0.045 (3)	−0.025 (3)	0.034 (3)	−0.008 (3)
C27	0.081 (5)	0.074 (4)	0.039 (3)	−0.018 (4)	0.025 (3)	−0.015 (3)
C28	0.078 (5)	0.068 (4)	0.031 (3)	−0.003 (3)	0.021 (3)	−0.004 (3)
C29	0.072 (4)	0.063 (4)	0.051 (4)	0.005 (3)	0.022 (3)	0.002 (3)
C30	0.093 (5)	0.075 (5)	0.076 (5)	−0.009 (4)	0.043 (4)	−0.003 (4)
C31	0.039 (3)	0.050 (3)	0.031 (3)	−0.009 (2)	0.014 (2)	−0.008 (2)
C32	0.062 (4)	0.052 (3)	0.047 (3)	−0.005 (3)	0.025 (3)	−0.014 (3)
C33	0.051 (4)	0.075 (4)	0.052 (4)	−0.025 (3)	0.017 (3)	−0.030 (3)
C34	0.041 (4)	0.085 (5)	0.047 (4)	−0.005 (3)	0.013 (3)	−0.016 (3)
C35	0.047 (4)	0.067 (4)	0.053 (4)	−0.004 (3)	0.009 (3)	−0.003 (3)
C36	0.045 (3)	0.047 (3)	0.048 (3)	−0.006 (3)	0.015 (3)	0.000 (3)
C37	0.079 (6)	0.095 (6)	0.110 (7)	0.002 (5)	0.022 (5)	−0.023 (5)
C38	0.059 (5)	0.117 (7)	0.089 (6)	−0.004 (4)	−0.002 (4)	−0.003 (5)
C39	0.088 (6)	0.109 (6)	0.060 (5)	−0.022 (5)	0.022 (4)	−0.024 (4)
C40	0.065 (5)	0.086 (5)	0.076 (5)	0.003 (4)	−0.002 (4)	0.018 (4)
C41	0.037 (3)	0.042 (3)	0.031 (3)	−0.002 (2)	0.010 (2)	−0.003 (2)
C42	0.052 (3)	0.043 (3)	0.045 (3)	0.010 (3)	0.017 (3)	0.001 (2)
C43	0.058 (4)	0.046 (3)	0.027 (3)	−0.002 (3)	0.009 (3)	0.001 (2)
C44	0.061 (4)	0.037 (3)	0.031 (3)	−0.011 (2)	0.020 (3)	−0.007 (2)
C45	0.073 (4)	0.035 (3)	0.040 (3)	0.000 (3)	0.023 (3)	−0.006 (2)
C46	0.069 (4)	0.034 (3)	0.037 (3)	0.003 (3)	0.022 (3)	0.003 (2)
C47	0.099 (5)	0.048 (3)	0.039 (3)	−0.010 (3)	0.032 (3)	−0.003 (3)
C48	0.109 (6)	0.054 (4)	0.037 (3)	−0.014 (4)	0.031 (4)	−0.003 (3)
C49	0.090 (6)	0.079 (5)	0.060 (4)	−0.026 (4)	0.034 (4)	−0.012 (4)
C50	0.115 (7)	0.121 (7)	0.074 (5)	0.002 (5)	0.056 (5)	0.006 (5)
C51	0.038 (3)	0.044 (3)	0.031 (3)	0.005 (2)	0.011 (2)	−0.002 (2)
C52	0.051 (4)	0.055 (3)	0.047 (3)	0.005 (3)	0.015 (3)	0.017 (3)
C53	0.057 (4)	0.065 (4)	0.048 (4)	0.019 (3)	0.009 (3)	0.018 (3)
C54	0.049 (4)	0.056 (3)	0.037 (3)	0.010 (3)	−0.001 (3)	−0.004 (3)
C55	0.050 (4)	0.041 (3)	0.057 (4)	0.004 (3)	0.007 (3)	−0.003 (3)
C56	0.050 (4)	0.036 (3)	0.045 (3)	0.008 (2)	0.011 (3)	0.000 (2)
C57	0.060 (4)	0.065 (4)	0.102 (6)	−0.001 (4)	−0.006 (4)	−0.007 (4)
C58	0.066 (6)	0.104 (7)	0.224 (13)	−0.017 (5)	−0.012 (7)	0.043 (8)
C59	0.166 (13)	0.160 (13)	0.227 (18)	0.004 (10)	0.018 (12)	0.008 (12)
C60A	0.130 (16)	0.185 (19)	0.156 (15)	0.024 (12)	0.033 (13)	−0.075 (13)
C60B	0.130 (16)	0.185 (19)	0.156 (15)	0.024 (12)	0.033 (13)	−0.075 (13)
C61	0.121 (9)	0.247 (16)	0.089 (8)	−0.045 (10)	0.044 (7)	−0.017 (9)
C62	0.154 (13)	0.25 (2)	0.170 (15)	0.001 (13)	−0.055 (11)	0.040 (14)
N1	0.040 (3)	0.041 (2)	0.030 (2)	−0.0015 (18)	0.014 (2)	−0.0029 (18)
N2	0.042 (3)	0.045 (2)	0.028 (2)	−0.0041 (19)	0.015 (2)	−0.0013 (18)
N3	0.042 (3)	0.037 (2)	0.028 (2)	0.0002 (18)	0.014 (2)	−0.0013 (17)
N4	0.041 (3)	0.043 (2)	0.030 (2)	−0.0004 (19)	0.0116 (19)	−0.0032 (18)
O1	0.081 (3)	0.053 (2)	0.036 (2)	0.003 (2)	0.030 (2)	0.0005 (17)
O2	0.067 (3)	0.100 (4)	0.078 (3)	−0.014 (3)	0.003 (3)	−0.028 (3)
O3	0.094 (3)	0.043 (2)	0.033 (2)	−0.006 (2)	0.033 (2)	−0.0030 (16)
O4	0.053 (3)	0.080 (3)	0.071 (3)	0.007 (2)	−0.013 (2)	0.008 (2)
Br1	0.0461 (3)	0.0681 (4)	0.0576 (4)	0.0121 (3)	0.0189 (3)	−0.0105 (3)
Br2	0.0616 (4)	0.0668 (4)	0.0464 (4)	0.0101 (3)	0.0311 (3)	−0.0068 (3)
Br3	0.0412 (3)	0.0604 (3)	0.0442 (3)	−0.0087 (2)	0.0172 (3)	0.0001 (3)
Br4	0.0522 (3)	0.0582 (3)	0.0371 (3)	−0.0055 (3)	0.0232 (3)	0.0047 (2)
Cl1	0.0763 (15)	0.162 (2)	0.122 (2)	−0.0025 (15)	0.0185 (14)	0.0052 (17)
Cl2	0.394 (8)	0.223 (5)	0.189 (4)	−0.092 (5)	−0.046 (5)	0.067 (4)

Geometric parameters (Å, º)

C1—N1	1.358 (6)	C37—O2	1.364 (9)
C1—C20	1.408 (7)	C37—C38	1.549 (11)
C1—C2	1.463 (6)	C37—H37A	0.9700
C2—C3	1.347 (7)	C37—H37B	0.9700
C2—Br1	1.867 (5)	C38—C39	1.486 (10)
C3—C4	1.459 (7)	C38—H38A	0.9700
C3—Br2	1.874 (4)	C38—H38B	0.9700
C4—N1	1.365 (6)	C39—C40	1.554 (10)
C4—C5	1.399 (7)	C39—H39A	0.9700
C5—C6	1.397 (7)	C39—H39B	0.9700
C5—C21	1.492 (6)	C40—H40A	0.9600
C6—N2	1.381 (6)	C40—H40B	0.9600
C6—C7	1.424 (8)	C40—H40C	0.9600
C7—C8	1.348 (7)	C41—C42	1.390 (7)
C7—H7	0.9300	C41—C46	1.393 (7)
C8—C9	1.427 (7)	C42—C43	1.389 (7)
C8—H8	0.9300	C42—H42	0.9300
C9—N2	1.365 (6)	C43—C44	1.389 (7)
C9—C10	1.396 (6)	C43—H43	0.9300
C10—C11	1.407 (7)	C44—O3	1.366 (5)
C10—C31	1.496 (7)	C44—C45	1.374 (7)
C11—N3	1.356 (6)	C45—C46	1.381 (7)
C11—C12	1.467 (6)	C45—H45	0.9300
C12—C13	1.351 (7)	C46—H46	0.9300
C12—Br3	1.861 (5)	C47—O3	1.427 (7)
C13—C14	1.454 (7)	C47—C48	1.511 (7)
C13—Br4	1.877 (5)	C47—H47A	0.9700
C14—N3	1.374 (6)	C47—H47B	0.9700
C14—C15	1.395 (7)	C48—C49	1.509 (9)
C15—C16	1.397 (7)	C48—H48A	0.9700
C15—C41	1.496 (6)	C48—H48B	0.9700
C16—N4	1.380 (6)	C49—C50	1.538 (9)
C16—C17	1.419 (7)	C49—H49A	0.9700
C17—C18	1.357 (7)	C49—H49B	0.9700
C17—H17	0.9300	C50—H50A	0.9600
C18—C19	1.417 (7)	C50—H50B	0.9600
C18—H18	0.9300	C50—H50C	0.9600
C19—N4	1.373 (6)	C51—C56	1.387 (7)
C19—C20	1.405 (6)	C51—C52	1.390 (7)
C20—C51	1.482 (7)	C52—C53	1.372 (8)
C21—C22	1.378 (7)	C52—H52	0.9300
C21—C26	1.393 (7)	C53—C54	1.393 (8)
C22—C23	1.376 (7)	C53—H53	0.9300
C22—H22	0.9300	C54—O4	1.358 (7)
C23—C24	1.381 (7)	C54—C55	1.380 (8)
C23—H23	0.9300	C55—C56	1.376 (8)
C24—O1	1.370 (6)	C55—H55	0.9300
C24—C25	1.374 (7)	C56—H56	0.9300
C25—C26	1.382 (7)	C57—O4	1.431 (8)
C25—H25	0.9300	C57—C58	1.509 (10)
C26—H26	0.9300	C57—H57A	0.9700
C27—O1	1.421 (7)	C57—H57B	0.9700
C27—C28	1.518 (7)	C58—C59	1.508 (15)
C27—H27A	0.9700	C58—H58A	0.9700
C27—H27B	0.9700	C58—H58B	0.9700
C28—C29	1.505 (8)	C59—C60B	1.509 (2)
C28—H28A	0.9700	C59—C60A	1.510 (2)
C28—H28B	0.9700	C59—H59A	0.9700
C29—C30	1.509 (8)	C59—H59B	0.9700
C29—H29A	0.9700	C60A—H60A	0.9600
C29—H29B	0.9700	C60A—H60B	0.9600
C30—H30A	0.9600	C60A—H60C	0.9600
C30—H30B	0.9600	C60B—H60D	0.9600
C30—H30C	0.9600	C60B—H60E	0.9600
C31—C36	1.392 (7)	C60B—H60F	0.9600
C31—C32	1.392 (7)	C61—C62	1.470 (18)
C32—C33	1.406 (9)	C61—Cl1	1.734 (12)
C32—H32	0.9300	C61—H61A	0.9700
C33—C34	1.376 (9)	C61—H61B	0.9700
C33—H33	0.9300	C62—Cl2	1.717 (16)
C34—C35	1.349 (8)	C62—H62A	0.9700
C34—O2	1.416 (8)	C62—H62B	0.9700
C35—C36	1.366 (8)	N2—H2	0.8600
C35—H35	0.9300	N4—H4	0.8600
C36—H36	0.9300
N1—C1—C20	124.5 (4)	H38A—C38—H38B	107.5
N1—C1—C2	109.6 (4)	C38—C39—C40	112.3 (6)
C20—C1—C2	125.9 (5)	C38—C39—H39A	109.1
C3—C2—C1	106.0 (4)	C40—C39—H39A	109.1
C3—C2—Br1	123.4 (4)	C38—C39—H39B	109.1
C1—C2—Br1	130.4 (4)	C40—C39—H39B	109.1
C2—C3—C4	107.9 (4)	H39A—C39—H39B	107.9
C2—C3—Br2	123.1 (4)	C39—C40—H40A	109.5
C4—C3—Br2	128.9 (4)	C39—C40—H40B	109.5
N1—C4—C5	124.6 (5)	H40A—C40—H40B	109.5
N1—C4—C3	108.5 (4)	C39—C40—H40C	109.5
C5—C4—C3	126.9 (4)	H40A—C40—H40C	109.5
C6—C5—C4	124.7 (4)	H40B—C40—H40C	109.5
C6—C5—C21	114.4 (5)	C42—C41—C46	117.5 (4)
C4—C5—C21	120.8 (4)	C42—C41—C15	122.5 (4)
N2—C6—C5	128.1 (5)	C46—C41—C15	120.1 (4)
N2—C6—C7	105.7 (4)	C43—C42—C41	121.9 (5)
C5—C6—C7	126.1 (4)	C43—C42—H42	119.0
C8—C7—C6	108.7 (5)	C41—C42—H42	119.0
C8—C7—H7	125.7	C42—C43—C44	119.0 (5)
C6—C7—H7	125.7	C42—C43—H43	120.5
C7—C8—C9	108.7 (5)	C44—C43—H43	120.5
C7—C8—H8	125.7	O3—C44—C45	115.4 (5)
C9—C8—H8	125.7	O3—C44—C43	124.6 (5)
N2—C9—C10	128.6 (5)	C45—C44—C43	120.0 (4)
N2—C9—C8	106.0 (4)	C44—C45—C46	120.4 (5)
C10—C9—C8	125.3 (5)	C44—C45—H45	119.8
C9—C10—C11	125.0 (5)	C46—C45—H45	119.8
C9—C10—C31	113.4 (4)	C45—C46—C41	121.1 (5)
C11—C10—C31	121.5 (4)	C45—C46—H46	119.4
N3—C11—C10	124.1 (4)	C41—C46—H46	119.4
N3—C11—C12	109.9 (4)	O3—C47—C48	106.9 (5)
C10—C11—C12	126.1 (5)	O3—C47—H47A	110.3
C13—C12—C11	105.8 (4)	C48—C47—H47A	110.3
C13—C12—Br3	123.7 (4)	O3—C47—H47B	110.3
C11—C12—Br3	130.6 (4)	C48—C47—H47B	110.3
C12—C13—C14	108.1 (4)	H47A—C47—H47B	108.6
C12—C13—Br4	122.3 (4)	C49—C48—C47	113.3 (5)
C14—C13—Br4	129.2 (4)	C49—C48—H48A	108.9
N3—C14—C15	124.8 (4)	C47—C48—H48A	108.9
N3—C14—C13	108.5 (4)	C49—C48—H48B	108.9
C15—C14—C13	126.3 (4)	C47—C48—H48B	108.9
C14—C15—C16	124.9 (4)	H48A—C48—H48B	107.7
C14—C15—C41	120.0 (4)	C48—C49—C50	112.7 (6)
C16—C15—C41	115.0 (4)	C48—C49—H49A	109.1
N4—C16—C15	127.2 (5)	C50—C49—H49A	109.1
N4—C16—C17	106.1 (4)	C48—C49—H49B	109.1
C15—C16—C17	126.6 (4)	C50—C49—H49B	109.1
C18—C17—C16	108.9 (5)	H49A—C49—H49B	107.8
C18—C17—H17	125.6	C49—C50—H50A	109.5
C16—C17—H17	125.6	C49—C50—H50B	109.5
C17—C18—C19	108.1 (5)	H50A—C50—H50B	109.5
C17—C18—H18	126.0	C49—C50—H50C	109.5
C19—C18—H18	126.0	H50A—C50—H50C	109.5
N4—C19—C20	127.3 (5)	H50B—C50—H50C	109.5
N4—C19—C18	106.8 (4)	C56—C51—C52	117.1 (5)
C20—C19—C18	125.7 (5)	C56—C51—C20	122.1 (5)
C19—C20—C1	124.5 (5)	C52—C51—C20	120.8 (5)
C19—C20—C51	115.9 (4)	C53—C52—C51	121.6 (5)
C1—C20—C51	119.6 (4)	C53—C52—H52	119.2
C22—C21—C26	117.4 (4)	C51—C52—H52	119.2
C22—C21—C5	120.2 (4)	C52—C53—C54	120.1 (5)
C26—C21—C5	122.4 (4)	C52—C53—H53	119.9
C23—C22—C21	121.7 (5)	C54—C53—H53	119.9
C23—C22—H22	119.2	O4—C54—C55	125.2 (6)
C21—C22—H22	119.2	O4—C54—C53	115.6 (5)
C22—C23—C24	119.9 (5)	C55—C54—C53	119.1 (5)
C22—C23—H23	120.1	C56—C55—C54	119.7 (5)
C24—C23—H23	120.1	C56—C55—H55	120.1
O1—C24—C25	125.0 (5)	C54—C55—H55	120.1
O1—C24—C23	115.0 (5)	C55—C56—C51	122.2 (5)
C25—C24—C23	120.0 (5)	C55—C56—H56	118.9
C24—C25—C26	119.4 (5)	C51—C56—H56	118.9
C24—C25—H25	120.3	O4—C57—C58	105.6 (6)
C26—C25—H25	120.3	O4—C57—H57A	110.6
C25—C26—C21	121.6 (5)	C58—C57—H57A	110.6
C25—C26—H26	119.2	O4—C57—H57B	110.6
C21—C26—H26	119.2	C58—C57—H57B	110.6
O1—C27—C28	106.5 (5)	H57A—C57—H57B	108.7
O1—C27—H27A	110.4	C57—C58—C59	110.3 (9)
C28—C27—H27A	110.4	C57—C58—H58A	109.6
O1—C27—H27B	110.4	C59—C58—H58A	109.6
C28—C27—H27B	110.4	C57—C58—H58B	109.6
H27A—C27—H27B	108.6	C59—C58—H58B	109.6
C29—C28—C27	112.8 (5)	H58A—C58—H58B	108.1
C29—C28—H28A	109.0	C58—C59—C60B	100.1 (13)
C27—C28—H28A	109.0	C58—C59—C60A	108.9 (16)
C29—C28—H28B	109.0	C58—C59—H59A	109.9
C27—C28—H28B	109.0	C60B—C59—H59A	145.6
H28A—C28—H28B	107.8	C60A—C59—H59A	109.9
C28—C29—C30	114.0 (5)	C58—C59—H59B	109.9
C28—C29—H29A	108.7	C60B—C59—H59B	75.5
C30—C29—H29A	108.7	C60A—C59—H59B	109.9
C28—C29—H29B	108.7	H59A—C59—H59B	108.3
C30—C29—H29B	108.7	C59—C60A—H60A	109.5
H29A—C29—H29B	107.6	C59—C60A—H60B	109.5
C29—C30—H30A	109.5	H60A—C60A—H60B	109.5
C29—C30—H30B	109.5	C59—C60A—H60C	109.5
H30A—C30—H30B	109.5	H60A—C60A—H60C	109.5
C29—C30—H30C	109.5	H60B—C60A—H60C	109.5
H30A—C30—H30C	109.5	C59—C60B—H60D	109.5
H30B—C30—H30C	109.5	C59—C60B—H60E	109.5
C36—C31—C32	117.3 (5)	H60D—C60B—H60E	109.5
C36—C31—C10	120.4 (5)	C59—C60B—H60F	109.5
C32—C31—C10	122.0 (5)	H60D—C60B—H60F	109.5
C31—C32—C33	120.4 (6)	H60E—C60B—H60F	109.5
C31—C32—H32	119.8	C62—C61—Cl1	116.9 (11)
C33—C32—H32	119.8	C62—C61—H61A	108.1
C34—C33—C32	119.7 (5)	Cl1—C61—H61A	108.1
C34—C33—H33	120.1	C62—C61—H61B	108.1
C32—C33—H33	120.1	Cl1—C61—H61B	108.1
C35—C34—C33	119.9 (6)	H61A—C61—H61B	107.3
C35—C34—O2	114.8 (6)	C61—C62—Cl2	114.3 (10)
C33—C34—O2	125.3 (6)	C61—C62—H62A	108.7
C34—C35—C36	121.2 (6)	Cl2—C62—H62A	108.7
C34—C35—H35	119.4	C61—C62—H62B	108.7
C36—C35—H35	119.4	Cl2—C62—H62B	108.7
C35—C36—C31	121.5 (5)	H62A—C62—H62B	107.6
C35—C36—H36	119.3	C1—N1—C4	107.8 (4)
C31—C36—H36	119.3	C9—N2—C6	110.9 (4)
O2—C37—C38	106.6 (7)	C9—N2—H2	124.6
O2—C37—H37A	110.4	C6—N2—H2	124.6
C38—C37—H37A	110.4	C11—N3—C14	107.6 (4)
O2—C37—H37B	110.4	C19—N4—C16	110.1 (4)
C38—C37—H37B	110.4	C19—N4—H4	125.0
H37A—C37—H37B	108.6	C16—N4—H4	125.0
C39—C38—C37	115.3 (7)	C24—O1—C27	117.9 (4)
C39—C38—H38A	108.5	C37—O2—C34	116.7 (6)
C37—C38—H38A	108.5	C44—O3—C47	118.7 (4)
C39—C38—H38B	108.5	C54—O4—C57	117.4 (5)
C37—C38—H38B	108.5
N1—C1—C2—C3	−3.5 (5)	O1—C27—C28—C29	−62.5 (7)
C20—C1—C2—C3	173.4 (5)	C27—C28—C29—C30	−170.8 (6)
N1—C1—C2—Br1	172.1 (4)	C9—C10—C31—C36	88.1 (6)
C20—C1—C2—Br1	−11.0 (7)	C11—C10—C31—C36	−91.8 (6)
C1—C2—C3—C4	1.1 (5)	C9—C10—C31—C32	−85.3 (6)
Br1—C2—C3—C4	−174.9 (3)	C11—C10—C31—C32	94.7 (6)
C1—C2—C3—Br2	177.8 (3)	C36—C31—C32—C33	0.9 (7)
Br1—C2—C3—Br2	1.8 (6)	C10—C31—C32—C33	174.5 (5)
C2—C3—C4—N1	1.5 (5)	C31—C32—C33—C34	−0.9 (8)
Br2—C3—C4—N1	−174.9 (3)	C32—C33—C34—C35	1.1 (9)
C2—C3—C4—C5	−176.9 (5)	C32—C33—C34—O2	−177.5 (5)
Br2—C3—C4—C5	6.7 (8)	C33—C34—C35—C36	−1.3 (9)
N1—C4—C5—C6	13.1 (8)	O2—C34—C35—C36	177.4 (5)
C3—C4—C5—C6	−168.7 (5)	C34—C35—C36—C31	1.3 (8)
N1—C4—C5—C21	−163.6 (4)	C32—C31—C36—C35	−1.1 (7)
C3—C4—C5—C21	14.6 (8)	C10—C31—C36—C35	−174.8 (5)
C4—C5—C6—N2	4.9 (8)	O2—C37—C38—C39	56.6 (10)
C21—C5—C6—N2	−178.2 (5)	C37—C38—C39—C40	169.7 (7)
C4—C5—C6—C7	179.6 (5)	C14—C15—C41—C42	−108.4 (6)
C21—C5—C6—C7	−3.6 (7)	C16—C15—C41—C42	74.6 (6)
N2—C6—C7—C8	2.0 (6)	C14—C15—C41—C46	71.3 (6)
C5—C6—C7—C8	−173.7 (5)	C16—C15—C41—C46	−105.7 (6)
C6—C7—C8—C9	−1.1 (6)	C46—C41—C42—C43	−2.0 (8)
C7—C8—C9—N2	−0.2 (6)	C15—C41—C42—C43	177.6 (5)
C7—C8—C9—C10	178.7 (5)	C41—C42—C43—C44	−0.2 (8)
N2—C9—C10—C11	−3.9 (8)	C42—C43—C44—O3	−179.4 (5)
C8—C9—C10—C11	177.5 (5)	C42—C43—C44—C45	2.9 (8)
N2—C9—C10—C31	176.2 (5)	O3—C44—C45—C46	178.7 (5)
C8—C9—C10—C31	−2.4 (7)	C43—C44—C45—C46	−3.4 (8)
C9—C10—C11—N3	−7.0 (8)	C44—C45—C46—C41	1.0 (9)
C31—C10—C11—N3	172.9 (4)	C42—C41—C46—C45	1.6 (8)
C9—C10—C11—C12	173.1 (5)	C15—C41—C46—C45	−178.1 (5)
C31—C10—C11—C12	−7.0 (7)	O3—C47—C48—C49	−60.2 (7)
N3—C11—C12—C13	0.7 (5)	C47—C48—C49—C50	−175.5 (6)
C10—C11—C12—C13	−179.4 (5)	C19—C20—C51—C56	111.4 (5)
N3—C11—C12—Br3	−179.1 (3)	C1—C20—C51—C56	−69.1 (6)
C10—C11—C12—Br3	0.8 (7)	C19—C20—C51—C52	−69.7 (6)
C11—C12—C13—C14	−3.3 (5)	C1—C20—C51—C52	109.8 (5)
Br3—C12—C13—C14	176.5 (3)	C56—C51—C52—C53	4.6 (8)
C11—C12—C13—Br4	170.0 (3)	C20—C51—C52—C53	−174.3 (5)
Br3—C12—C13—Br4	−10.2 (6)	C51—C52—C53—C54	−1.2 (9)
C12—C13—C14—N3	4.9 (5)	C52—C53—C54—O4	178.2 (5)
Br4—C13—C14—N3	−167.7 (3)	C52—C53—C54—C55	−2.6 (9)
C12—C13—C14—C15	−168.2 (5)	O4—C54—C55—C56	−178.0 (5)
Br4—C13—C14—C15	19.1 (7)	C53—C54—C55—C56	2.9 (8)
N3—C14—C15—C16	11.3 (8)	C54—C55—C56—C51	0.6 (8)
C13—C14—C15—C16	−176.7 (5)	C52—C51—C56—C55	−4.3 (7)
N3—C14—C15—C41	−165.4 (4)	C20—C51—C56—C55	174.6 (5)
C13—C14—C15—C41	6.6 (7)	O4—C57—C58—C59	170.5 (9)
C14—C15—C16—N4	9.3 (8)	C57—C58—C59—C60B	−102.4 (14)
C41—C15—C16—N4	−173.9 (5)	C57—C58—C59—C60A	−144.7 (15)
C14—C15—C16—C17	−175.2 (5)	Cl1—C61—C62—Cl2	−57.3 (16)
C41—C15—C16—C17	1.7 (7)	C20—C1—N1—C4	−172.5 (4)
N4—C16—C17—C18	1.6 (6)	C2—C1—N1—C4	4.5 (5)
C15—C16—C17—C18	−174.7 (5)	C5—C4—N1—C1	174.7 (5)
C16—C17—C18—C19	0.2 (7)	C3—C4—N1—C1	−3.7 (5)
C17—C18—C19—N4	−1.8 (6)	C10—C9—N2—C6	−177.3 (5)
C17—C18—C19—C20	174.5 (5)	C8—C9—N2—C6	1.5 (5)
N4—C19—C20—C1	−9.7 (8)	C5—C6—N2—C9	173.4 (5)
C18—C19—C20—C1	174.7 (5)	C7—C6—N2—C9	−2.1 (5)
N4—C19—C20—C51	169.8 (5)	C10—C11—N3—C14	−177.6 (4)
C18—C19—C20—C51	−5.8 (7)	C12—C11—N3—C14	2.4 (5)
N1—C1—C20—C19	−12.5 (8)	C15—C14—N3—C11	168.9 (4)
C2—C1—C20—C19	171.0 (5)	C13—C14—N3—C11	−4.4 (5)
N1—C1—C20—C51	168.0 (4)	C20—C19—N4—C16	−173.4 (5)
C2—C1—C20—C51	−8.5 (7)	C18—C19—N4—C16	2.9 (6)
C6—C5—C21—C22	−101.6 (6)	C15—C16—N4—C19	173.5 (5)
C4—C5—C21—C22	75.4 (7)	C17—C16—N4—C19	−2.7 (5)
C6—C5—C21—C26	76.4 (7)	C25—C24—O1—C27	4.2 (9)
C4—C5—C21—C26	−106.6 (6)	C23—C24—O1—C27	−175.9 (5)
C26—C21—C22—C23	0.9 (9)	C28—C27—O1—C24	171.7 (5)
C5—C21—C22—C23	179.0 (5)	C38—C37—O2—C34	174.8 (6)
C21—C22—C23—C24	0.2 (8)	C35—C34—O2—C37	−172.7 (6)
C22—C23—C24—O1	178.8 (5)	C33—C34—O2—C37	6.0 (9)
C22—C23—C24—C25	−1.3 (9)	C45—C44—O3—C47	−175.9 (5)
O1—C24—C25—C26	−178.9 (6)	C43—C44—O3—C47	6.3 (8)
C23—C24—C25—C26	1.2 (9)	C48—C47—O3—C44	176.4 (5)
C24—C25—C26—C21	−0.1 (10)	C55—C54—O4—C57	9.1 (8)
C22—C21—C26—C25	−1.0 (9)	C53—C54—O4—C57	−171.8 (6)
C5—C21—C26—C25	−179.0 (6)	C58—C57—O4—C54	174.7 (7)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C52—H52···Br2^i	0.93	3.00	3.772 (5)	142
C49—H49B···Br3^i	0.97	3.03	3.945 (5)	157
C56—H56···C14^ii	0.93	2.75	3.588 (7)	151
C47—H47A···C11^i	0.97	2.83	3.714 (7)	151
C60A—H60C···C45^iii	0.97	2.70	3.202 (5)	113

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