An unexpected TTFAQ donor-fluorene acceptor reaction resulting in a novel salt: 2,6-di­hexyl­oxy-9,10-bis(4,5-di­methyl-1,3-di­thiol-2-yl­ium)-anthracene bis(2,5,7-tri­nitro-4-bromo-9-cyano­fluorenide) dioxane trisolvate

Reaction of the electron acceptor 2,5,7-tri­nitro-4-bromo-9-di­cyano­methyl­enefluorene (1) and the electron donor 2,6-di­hexyl­oxy-9,10-bis(4,5-di­methyl-1,3-di­thiol-2-yl­idene)-9,10-di­hydro­anthracene (2) in dioxane resulted in the formation of a novel type of salt with the previously unknown 2,5,7-tri­nitro-4-bromo-9-cyano­fluorenide anion (3^-): (2)²⁺·(3^-)₂·3C₄H₈O₂.

Key indicators

• Single-crystal X-ray study
• T = 100 K
• Mean [sigma](C-C) = 0.007 Å
• R factor = 0.058
• wR factor = 0.186
• Data-to-parameter ratio = 20.0

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry


 Alert Level C:



PLAT_371  Alert C Long   C(sp2)-C(sp1) Bond  C(59)  -   C(64)  =       1.42 Ang.


 0 Alert Level A = Potentially serious problem

 0 Alert Level B = Potential problem

 1 Alert Level C = Please check

---

S1. Comment

π-Extended quinoid electron donors of the tetrathiafulvalene family (TTFAQ) are known to form stable dication salts (Bryce et al., 1990, 2000; Triki et al., 1993). In the course of our investigations on radical ion salts formed between electron acceptors of the fluorene series and TTFAQ (Perepichka et al., 2002) we obtained a novel type of fluorene-TTFAQ salt [(3^-)₂.(2²⁺)], containing the previously unknown 2,5,7-trinitro-4-bromo-9-cyanofluorenide anion (3^-). This salt was unexpectedly isolated from crystallization of a mixture of 2,5,7-trinitro-4-bromo-9-dicyanomethylenefluorene (1) as an electron acceptor and 2,6-dihexyloxy-9,10-bis(4,5-dimethyl-1,3-dithiol-2- ylidene)-9,10-dihydroanthracene (2) as an electron donor, in dioxane.

Recently we isolated the first crystalline complex for acceptor (1) (A) and the TTFAQ derivative (D) (Perepichka et al., 2002), which has been shown to be a radical ion salt of the type 2 A^.-·D²⁺·2MeCN, in contrast to charge-transfer complexes of fluorene acceptors with TTF donors, which are essentially neutral or have only partial charge transfer in the ground state (Perepichka et al., 1998, 2000, 2001; Bryce et al., 1999; Batsanov et al., 2001; Kuz'mina et al., 2002). Continuing these studies, attempts to obtain crystals of a radical salt using (1) as an acceptor and (2) as a donor in dioxane gave no solid during 1.5 months (although the greenish colour of the solution could indicate a charge transfer interaction between the donor and the acceptor). After leaving this solution to stand for 10 months, a few black crystals were isolated. X-Ray analysis revealed that the crystals contained the anion (3^-), instead of the expected anion radical (1^.-), and the composition of the salt is (2²⁺).(3^-)₂·3C₄H₈O₂.

The origin of anion (3^-) in the salt 2²⁺.(3^-)₂ is not clear, and we found no evidence for its presence in the starting sample of (1) [which was prepared from the corresponding 9-fluorenone precursor and malononitrile (Perepichka et al., 2002)]. Some speculations to explain the formation of (3^-) are as follows, with reference to the Scheme below.

Strong electron acceptors of the fluorenone and 9-dicyanomethylenefluorene series, in addition to charge-transfer interaction with electron donors (or a single electron transfer process in the case of strong donors) are known to undergo nucleophilic substitution reactions of the nitro and cyano groups by nucleophiles (Perepichka et al., 2000; Semidetko et al., 1987; Chetkina et al., 1985; Andrievskii et al., 1982). Generally, nucleophilic attack on activated 9-methylenefluorenes can occur at different sites (particularly, attack on sp²-hybridized C-9 and C-α atoms), depending on the structures of the substrate and nucleophile, solvent properties, etc. (Hoz et al., 1981, 1985; Hoz & Perach, 1982; Hoz & Speizman, 1983; Hoz, 1993; Perepichka et al., 1996). Thus, the key reaction for the transformation of (1) into (3^-) is nucleophilic addition of HCN (or CN^-) to (1), resulting in compound (4), further oxidative transformation of which produces anion (3^-).

Different reactions could be a source of HCN in the system: (i) nucleophilic attack of water on the C-α atom of compound (1), resulting in substitution of a CN group by an OH group (5); (ii) hydrolysis of (1) to fluorenone (6), after which malonodinitrile could generate HCN. Charge-transfer interaction between (1) and (2), resulting in reversible formation of (1^.-) and (2²⁺) in solution, could facilitate formation of (3^-) through additional redox processes in the system (for example, expulsion of CN^- from (1^.-) or, alternatively, generation of CN^- by the reaction of (1^.-) with water).

Consequently, although we have no clear mechanism for the transformation of (1) into (3^-), two key reactions shown in the Scheme, which explain the generation of cyanide ion and its attack at position (9) of the activated fluorene system, have precedents in the literature.

The asymmetric unit of (2²⁺).(3^-)₂·3C₄H₈O₂ comprises two anions and three dioxane molecules in general positions, and the halves of two cations, which are located at crystallographic inversion centres (Figs. 1 and 2). The cation is structurally similar to its analogues studied earlier (Bryce et al., 1990, 2000; Christensen et al., 2001; Jones et al., 2001; Triki et al., 1993): the central anthracene moiety is planar, and the dithiolium rings are also planar and nearly perpendicular to the former [interplanar angles 88.2 (1) and 85.8 (1)° in the two independent cations]. Bond lengths in the anthracene moiety are essentially the same as in anthracene itself (Brock & Dunitz, 1990), indicating a neutral aromatic system. The dithiolium heterocyclesin (2⁺) has a similar geometry to the dication of tetrathiafulvalene (Shibaeva, 1984). Thus, each heterocycle carries a charge of +1, as can be deduced from charge/bond-distance correlations, well established by Reith et al. (1988) and Clemente & Marzotto (1996). In both cations, hexyl chains adopt almost ideal all-trans conformations and are roughly coplanar with the anthracene moieties. The deviations from the anthracene plane range from 0.11 to 0.46 Å for the atoms C13 to C18, and from 0.12 to 0.26 Å for C31 to C36.

The fluorene moieties of both (3^-) anions adopt a somewhat twisted conformation, similar to that of molecule (1) (Perepichka et al., 2002), due to steric repulsion between the bromo- and nitro-substituents in positions 4 and 5. These substituents are tilted out of the fluorene plane in opposite directions, and the adjacent carbon atoms follow their tilt. Thus the average deviation of the 13 fluorene carbon atoms from their mean plane is 0.09 and 0.10 Å in the two (3^-) anions, the strongest deviations being shown by C40 (0.16 Å), C41 (-0.18 Å), C54 (-0.18 Å) and C55 (0.23 Å). For the same reason, the twist of the nitro groups (compared to the eclipsed conformation) around the C41—N2 and C55—N6 bonds [38.8 (5)° and 47.8 (5)°, respectively] is stronger than for other, sterically unencumbered, nitro groups, viz. C38—N1 13.7 (8), C43—N3 10.1 (6), C52—N5 9(1), C57—N7 3.1 (9)°. In all previously studied structures containing molecules of (1), the bromo- and nitro-substituents were disordered between positions 4 and 5; no significant disorder is found here in the (3^-) anions (see Experimental section).

The twist does not disturb the aromaticity of the fluorene system of the (3^-) anions, the bond distances of which are close to those in the unsubstituted fluorenide anion (Buchholz, Harms, Massa & Boche, 1989). In (3^-), the cyano group actively participates in π-conjugation and hence in the negative charge delocalization, as indicated by the shortening of the C—CN bond [average 1.414 (6) Å] and lengthening of the C≡N bond [average 1.153 (6) Å] compared to the average values [1.443 (8) and 1.138 (7) Å, respectively] for C(aryl)—C≡N moieties (Allen et al., 1987). The central (five-membered) ring of (3^-) shows a less aromatic distribution of bond distances than in the fluorenide anion. Although each of these differences individually is of marginal statistical significance, they are mutually consistent and suggest a substantial contribution of the C(fluorene)═C═ N^- structure. In this structure, (3^-) can be compared to the 1,2,4-tricyanocyclopentadienide anion in the crystal structure of its ammonium salt (Buchholz, Harms, Marsch et al., 1989).

The crystal packing of (2²⁺).(3^-)₂·3C₄H₈O₂ can be described as a succession of alternating layers of dications and anions (Fig. 3), the dioxane molecules occupying the gaps in and between the layers. Thus, no segregated stacks of similarly-charged ions exist. On the other hand, the twisted conformation of the (2²⁺) dication, with the positively charged heterocycles oriented normally to the rest of the cation, forbids an effective cation-anion stacking, such as is usual for charge-transfer complexes. As one can see from Fig. 4, the anion overlaps mainly with the side-chain of the dication. In fact, the packing is dominated by short contacts between the sulfur atoms of the dications (i.e. the main centres of positive charge) and the (negatively charged) Br, nitro O and cyano N atoms of the anions. There are nine crystallographically independent S···O contacts shorter than the sum (3.39 Å) of their van der Waals radii (Rowland & Taylor, 1996). The shortest of these, S4···O14 at 3.075 (5) Å, falls within the range characteristic for weak donor-acceptor interactions (Kucsman & Kapovits, 1985). Both cyano groups participate in short contacts with sulfur atoms [S2···N4 3.111 (5) and S3···N8 2.982 (5) Å, cf. the sum of the van der Waals radii, 3.45 Å], as do both bromine atoms [S1···Br2 3.541 (1) and S4···Br1 3.447 (1) Å, cf. the sum of the van der Waals radii, 3.69 Å].

S2. Experimental

Acceptor (1) (Perepichka et al., 2002) (1.4 mg, 3.2 mmol) and donor (2) (Bryce et al., 2000) (1.0 mg, 1.6 mmol) were dissolved together in 1,4-dioxane (0.3 ml), with heating at 353 K for 5 min. The greenish solution was stored in a closed tube in the dark at 293 K. After 1.5 months, no further changes in colour and no precipitation were observed, whereas, after 10 months, a few black (or dark green) crystals were isolated from the bulk amorphous product.

S3. Refinement

The crystal was a pseudo-merohedral twin, with the twinning law 0 1 0 /1 0 0 / 0 0 1, associated with the pseudo-monoclinic C-centred cell a=24.539, b=14.245, c=22.382 Å, α=90.61, β=103.65, γ=89.53°. The second crystal contribution was refined to 0.1026 (7). Without a twinning correction, R = 0.100.

The H atoms of the methyl groups were found by the circular Fourier method and refined in the rigid-body model (C—H 0.978 Å); a riding model was used for other H atoms, with C(sp²)—H 0.948 and C(methylene)—H 0.988 Å.

The highest peak of residual electron density lies 2.66 Å from Br1 and in the close proximity of the adjacent nitro-group, and the largest hole is 0.45 Å from Br1. These features may indicate some minor disorder of the bromo and nitro-substituents between positions 4 and 5 of the fluorene, which could not be resolved.

Computing details

Data collection: SMART (Bruker, 1999); cell refinement: SMART; data reduction: SAINT (Bruker, 1999); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1998); software used to prepare material for publication: SHELXTL.

Figures

	Fig. 1. Cations and solvent molecules in (2^2+).(3^-)2·3C4H8O2. Atoms generated by inversion centres are primed. Atomic displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. Anions in (2^2+).(3^-)2·3C4H8O2. Atomic displacement ellipsoids are drawn at the 50% probability level.
	Fig. 3. Layers of dications (top) and anions (bottom), projected on the (110) plane.
	Fig. 4. Overlap between the adjacent layers; projection on the (110) plane.

2,6-dihexyloxy-9,10-bis(4,5-dimethyl-1,3-dithiolium)-anthracene bis-[2,4,7-trinitro-5-bromo-9-cyanofluorenide], 1,4-dioxane trisolvate

Crystal data

C36H44O2S4^2+·2C14H4BrN4O6^−·3C4H8O2	Z = 2
Mr = 1709.51	F(000) = 1764
Triclinic, P1	Dx = 1.493 Mg m^−3
a = 14.136 (4) Å	Mo Kα radiation, λ = 0.71073 Å
b = 14.244 (4) Å	Cell parameters from 976 reflections
c = 22.383 (8) Å	θ = 12.0–22.8°
α = 77.92 (2)°	µ = 1.26 mm^−1
β = 78.49 (2)°	T = 100 K
γ = 60.26 (2)°	Block, black
V = 3802 (2) Å^3	0.32 × 0.28 × 0.13 mm

Data collection

SMART 1K CCD area-detector diffractometer	19938 independent reflections
Radiation source: fine-focus sealed tube	15653 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.041
Detector resolution: 8 pixels mm^-1	θmax = 29.0°, θmin = 1.7°
ω scans	h = −19→19
Absorption correction: integration (XPREP in SHELXTL; Bruker, 1998)	k = −19→18
Tmin = 0.695, Tmax = 0.894	l = −30→30
42220 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)] = 0.058	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.186	H-atom parameters constrained
S = 1.08	w = 1/[σ^2(Fo^2) + (0.0951P)^2 + 6.2761P] where P = (Fo^2 + 2Fc^2)/3
19938 reflections	(Δ/σ)max < 0.001
998 parameters	Δρmax = 1.49 e Å^−3
0 restraints	Δρmin = −1.63 e Å^−3

Special details

Experimental. The data collection nominally covered full sphere of reciprocal space, by a combination of 5 sets of ω scans; each set at different φ and/or 2θ angles and each scan (15 sec exposure) covering 0.3° in ω. Crystal to detector distance 4.54 cm.

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. Methyl groups refined as rigid bodies, other H atoms in riding model.

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

	x	y	z	Uiso*/Ueq
Br1	0.44217 (4)	0.33603 (4)	0.601348 (19)	0.01951 (10)
Br2	0.30979 (4)	0.41389 (4)	0.098100 (19)	0.02195 (11)
S1	0.56656 (9)	0.22832 (9)	0.02844 (5)	0.01630 (19)
S2	0.75830 (9)	0.02550 (9)	0.03293 (5)	0.0181 (2)
S3	0.02747 (9)	0.75800 (9)	0.52269 (5)	0.0182 (2)
S4	0.22858 (9)	0.56559 (9)	0.53655 (5)	0.0197 (2)
O1	0.4730 (3)	−0.0414 (3)	0.23262 (13)	0.0178 (6)
O2	−0.0398 (3)	0.4729 (3)	0.73231 (13)	0.0192 (6)
O3	0.1344 (3)	0.1352 (3)	0.59622 (16)	0.0307 (8)
O4	0.1908 (3)	0.2249 (3)	0.51992 (15)	0.0304 (8)
O5	0.2940 (3)	0.5242 (3)	0.68010 (15)	0.0263 (7)
O6	0.4540 (3)	0.4764 (3)	0.70515 (16)	0.0325 (8)
O7	0.3979 (3)	0.4015 (3)	0.93237 (15)	0.0295 (8)
O8	0.3469 (3)	0.2777 (3)	0.97212 (14)	0.0298 (8)
O9	0.1151 (3)	0.0853 (3)	0.14561 (18)	0.0354 (9)
O10	0.1774 (3)	0.1465 (3)	0.05901 (17)	0.0340 (8)
O11	0.5146 (3)	0.2744 (3)	0.16648 (14)	0.0228 (7)
O12	0.4944 (3)	0.4288 (3)	0.18282 (15)	0.0268 (7)
O13	0.4034 (3)	0.4575 (4)	0.40337 (17)	0.0362 (9)
O14	0.3153 (4)	0.3769 (4)	0.46024 (15)	0.0388 (10)
O15	0.8503 (3)	0.1318 (3)	0.30293 (16)	0.0330 (8)
O16	0.7643 (3)	0.2266 (3)	0.18878 (16)	0.0290 (8)
O17	0.7657 (3)	0.0996 (3)	0.71358 (15)	0.0280 (7)
O18	0.8271 (3)	0.2083 (4)	0.60433 (16)	0.0345 (9)
O19	0.7371 (3)	0.2295 (3)	0.90271 (15)	0.0283 (7)
O20	0.8079 (3)	0.2818 (3)	0.77893 (16)	0.0354 (9)
N1	0.1773 (3)	0.1944 (3)	0.57510 (17)	0.0215 (8)
N2	0.3718 (3)	0.4667 (3)	0.71084 (16)	0.0207 (7)
N3	0.3633 (3)	0.3378 (3)	0.92832 (17)	0.0230 (8)
N4	0.1196 (4)	0.1241 (4)	0.8548 (2)	0.0306 (9)
N5	0.1633 (3)	0.1347 (4)	0.11584 (19)	0.0264 (8)
N6	0.4721 (3)	0.3555 (3)	0.19402 (16)	0.0184 (7)
N7	0.3582 (3)	0.4012 (3)	0.41048 (17)	0.0232 (8)
N8	0.1619 (4)	0.1056 (4)	0.39260 (19)	0.0312 (10)
C1	0.5212 (3)	0.0051 (3)	0.12420 (17)	0.0145 (7)
H1	0.5626	0.0360	0.1322	0.017*
C2	0.4700 (3)	−0.0379 (3)	0.17219 (17)	0.0146 (7)
C3	0.4064 (4)	−0.0834 (3)	0.16042 (18)	0.0161 (8)
H3	0.3711	−0.1120	0.1938	0.019*
C4	0.3963 (3)	−0.0868 (3)	0.10188 (18)	0.0147 (7)
H4	0.3542	−0.1179	0.0951	0.018*
C5	0.4485 (3)	−0.0441 (3)	0.05023 (17)	0.0134 (7)
C6	0.5113 (3)	0.0030 (3)	0.06209 (17)	0.0135 (7)
C7	0.5620 (3)	0.0450 (3)	0.01084 (17)	0.0128 (7)
C8	0.6260 (3)	0.0952 (3)	0.02186 (17)	0.0147 (7)
C9	0.6800 (4)	0.2303 (4)	0.04375 (18)	0.0180 (8)
C10	0.7720 (4)	0.1324 (4)	0.04644 (19)	0.0191 (8)
C11	0.6692 (4)	0.3376 (4)	0.0504 (2)	0.0237 (9)
H111	0.6997	0.3305	0.0877	0.036*
H112	0.5917	0.3921	0.0533	0.036*
H113	0.7090	0.3605	0.0146	0.036*
C12	0.8828 (4)	0.1104 (4)	0.0584 (2)	0.0238 (9)
H121	0.9236	0.1229	0.0195	0.036*
H122	0.9235	0.0348	0.0769	0.036*
H123	0.8732	0.1596	0.0864	0.036*
C13	0.5268 (4)	0.0115 (4)	0.24936 (18)	0.0160 (8)
H131	0.4929	0.0894	0.2322	0.021*
H132	0.6053	−0.0233	0.2333	0.021*
C14	0.5142 (3)	−0.0004 (3)	0.31922 (17)	0.0150 (7)
H141	0.5492	−0.0785	0.3359	0.020*
H142	0.4356	0.0324	0.3349	0.020*
C15	0.5672 (4)	0.0565 (4)	0.34076 (18)	0.0168 (8)
H151	0.6455	0.0241	0.3242	0.022*
H152	0.5318	0.1345	0.3238	0.022*
C16	0.5576 (4)	0.0475 (4)	0.41094 (18)	0.0177 (8)
H161	0.5924	−0.0304	0.4281	0.023*
H162	0.4793	0.0809	0.4276	0.023*
C17	0.6128 (4)	0.1025 (4)	0.43143 (19)	0.0217 (9)
H171	0.6889	0.0745	0.4112	0.028*
H172	0.5731	0.1817	0.4178	0.028*
C18	0.6135 (5)	0.0843 (5)	0.5012 (2)	0.0298 (11)
H181	0.5382	0.1153	0.5214	0.045*
H182	0.6511	0.1195	0.5119	0.045*
H183	0.6520	0.0060	0.5150	0.045*
C19	0.0065 (3)	0.5200 (3)	0.62365 (18)	0.0158 (8)
H19	0.0394	0.5596	0.6315	0.019*
C20	−0.0387 (3)	0.4716 (4)	0.67162 (18)	0.0157 (8)
C21	−0.0891 (4)	0.4123 (4)	0.66056 (18)	0.0178 (8)
H21	−0.1209	0.3802	0.6941	0.021*
C22	−0.0928 (3)	0.4028 (3)	0.60218 (18)	0.0162 (8)
H22	−0.1272	0.3637	0.5955	0.019*
C23	−0.0459 (3)	0.4506 (3)	0.55002 (17)	0.0139 (7)
C24	0.0032 (3)	0.5114 (3)	0.56181 (18)	0.0138 (7)
C25	0.0484 (3)	0.5589 (3)	0.51064 (18)	0.0143 (7)
C26	0.0983 (3)	0.6232 (3)	0.52162 (17)	0.0147 (7)
C27	0.1301 (4)	0.7748 (4)	0.54096 (18)	0.0185 (8)
C28	0.2270 (4)	0.6827 (4)	0.54723 (19)	0.0199 (9)
C29	0.1074 (5)	0.8873 (4)	0.5471 (2)	0.0278 (10)
H291	0.1427	0.8833	0.5816	0.042*
H292	0.0283	0.9345	0.5545	0.042*
H293	0.1368	0.9173	0.5092	0.042*
C30	0.3306 (4)	0.6753 (4)	0.5604 (2)	0.0270 (10)
H301	0.3619	0.7055	0.5235	0.041*
H302	0.3830	0.5988	0.5717	0.041*
H303	0.3146	0.7166	0.5942	0.041*
C31	0.0150 (4)	0.5253 (4)	0.74818 (18)	0.0168 (8)
H311	−0.0201	0.6035	0.7316	0.022*
H312	0.0929	0.4914	0.7309	0.022*
C32	0.0048 (4)	0.5122 (4)	0.81804 (18)	0.0169 (8)
H321	0.0397	0.4338	0.8341	0.022*
H322	−0.0735	0.5450	0.8347	0.022*
C33	0.0601 (3)	0.5664 (4)	0.83941 (19)	0.0177 (8)
H331	0.1392	0.5303	0.8246	0.023*
H332	0.0285	0.6436	0.8208	0.023*
C34	0.0457 (4)	0.5621 (4)	0.90922 (18)	0.0181 (8)
H341	0.0820	0.4850	0.9277	0.024*
H342	−0.0332	0.5936	0.9244	0.024*
C35	0.0939 (4)	0.6235 (4)	0.9305 (2)	0.0222 (9)
H351	0.0643	0.6983	0.9082	0.029*
H352	0.1743	0.5865	0.9199	0.029*
C36	0.0669 (5)	0.6296 (5)	0.9999 (2)	0.0294 (11)
H361	−0.0125	0.6711	1.0100	0.044*
H362	0.1026	0.6657	1.0118	0.044*
H363	0.0936	0.5558	1.0220	0.044*
C37	0.1848 (4)	0.2121 (4)	0.68027 (19)	0.0181 (8)
H37	0.1386	0.1797	0.6953	0.022*
C38	0.2154 (4)	0.2289 (4)	0.61856 (19)	0.0181 (8)
C39	0.2871 (3)	0.2729 (3)	0.59416 (19)	0.0175 (8)
H39	0.3092	0.2800	0.5513	0.021*
C40	0.3251 (3)	0.3046 (3)	0.63379 (18)	0.0159 (8)
C41	0.3600 (4)	0.3858 (4)	0.75963 (19)	0.0182 (8)
C42	0.3780 (4)	0.3913 (4)	0.81664 (19)	0.0196 (8)
H42	0.4125	0.4314	0.8216	0.024*
C43	0.3434 (4)	0.3333 (4)	0.86782 (18)	0.0176 (8)
C44	0.2887 (3)	0.2783 (4)	0.86328 (18)	0.0176 (8)
H44	0.2638	0.2434	0.8988	0.021*
C45	0.2142 (3)	0.2285 (3)	0.78598 (19)	0.0166 (8)
C46	0.2244 (3)	0.2440 (3)	0.72083 (19)	0.0158 (8)
C47	0.2896 (3)	0.2985 (3)	0.69762 (18)	0.0155 (7)
C48	0.3135 (3)	0.3238 (3)	0.74997 (18)	0.0150 (7)
C49	0.2712 (3)	0.2746 (3)	0.80434 (18)	0.0155 (8)
C50	0.1611 (4)	0.1725 (4)	0.8243 (2)	0.0213 (9)
C51	0.2002 (4)	0.1606 (4)	0.2113 (2)	0.0212 (9)
H51	0.1690	0.1161	0.2333	0.025*
C52	0.2072 (4)	0.1816 (4)	0.1482 (2)	0.0218 (9)
C53	0.2466 (4)	0.2518 (4)	0.1132 (2)	0.0217 (9)
H53	0.2457	0.2669	0.0699	0.026*
C54	0.2864 (4)	0.2977 (4)	0.14319 (19)	0.0189 (8)
C55	0.3937 (3)	0.3536 (3)	0.24946 (18)	0.0156 (8)
C56	0.4049 (4)	0.3857 (4)	0.30018 (19)	0.0178 (8)
H56	0.4464	0.4225	0.2972	0.021*
C57	0.3513 (4)	0.3621 (4)	0.35679 (19)	0.0185 (8)
C58	0.2956 (4)	0.3034 (4)	0.36448 (19)	0.0181 (8)
H58	0.2654	0.2843	0.4039	0.022*
C59	0.2350 (4)	0.2099 (4)	0.30520 (19)	0.0177 (8)
C60	0.2397 (4)	0.2088 (4)	0.24159 (19)	0.0179 (8)
C61	0.2908 (3)	0.2732 (4)	0.20714 (19)	0.0172 (8)
C62	0.3265 (3)	0.3052 (3)	0.25135 (18)	0.0157 (8)
C63	0.2852 (3)	0.2724 (4)	0.31174 (19)	0.0175 (8)
C64	0.1928 (4)	0.1545 (4)	0.3537 (2)	0.0218 (9)
C65	0.8597 (5)	0.2227 (4)	0.2675 (2)	0.0312 (11)
H651	0.9296	0.1968	0.2402	0.041*
H652	0.8603	0.2679	0.2953	0.041*
C66	0.7658 (5)	0.2902 (4)	0.2292 (2)	0.0303 (11)
H661	0.6959	0.3191	0.2564	0.039*
H662	0.7740	0.3527	0.2048	0.039*
C67	0.7537 (5)	0.1352 (4)	0.2246 (2)	0.0309 (11)
H671	0.7535	0.0892	0.1972	0.040*
H672	0.6835	0.1620	0.2516	0.040*
C68	0.8463 (5)	0.0684 (4)	0.2631 (3)	0.0332 (11)
H681	0.8379	0.0065	0.2880	0.043*
H682	0.9160	0.0386	0.2359	0.043*
C70	0.6922 (5)	0.1644 (5)	0.6688 (2)	0.0377 (14)
H701	0.6165	0.1983	0.6896	0.049*
H702	0.6964	0.1186	0.6397	0.049*
C71	0.8748 (4)	0.0540 (4)	0.6844 (2)	0.0297 (10)
H711	0.8845	0.0048	0.6559	0.039*
H712	0.9259	0.0106	0.7159	0.039*
C72	0.9010 (4)	0.1424 (5)	0.6495 (2)	0.0297 (11)
H721	0.8966	0.1885	0.6785	0.039*
H722	0.9767	0.1091	0.6287	0.039*
C73	0.8506 (5)	0.1893 (6)	0.8817 (3)	0.0435 (15)
H731	0.8920	0.1166	0.9047	0.057*
H732	0.8763	0.2381	0.8898	0.057*
C69	0.7189 (5)	0.2528 (5)	0.6343 (3)	0.0375 (13)
H691	0.6669	0.2980	0.6035	0.049*
H692	0.7109	0.3006	0.6633	0.049*
C74	0.8716 (5)	0.1792 (5)	0.8133 (2)	0.0373 (13)
H741	0.9503	0.1539	0.7992	0.049*
H742	0.8527	0.1248	0.8059	0.049*
C75	0.6948 (4)	0.3189 (4)	0.7999 (2)	0.0307 (11)
H751	0.6725	0.2668	0.7927	0.040*
H752	0.6507	0.3903	0.7764	0.040*
C76	0.6737 (5)	0.3304 (5)	0.8675 (2)	0.0335 (11)
H761	0.6908	0.3867	0.8741	0.044*
H762	0.5952	0.3545	0.8815	0.044*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Br1	0.0191 (2)	0.0260 (2)	0.01698 (18)	−0.01448 (18)	−0.00129 (15)	−0.00059 (16)
Br2	0.0249 (2)	0.0226 (2)	0.01720 (19)	−0.01103 (18)	−0.00319 (16)	−0.00030 (16)
S1	0.0204 (5)	0.0173 (5)	0.0165 (4)	−0.0126 (4)	−0.0018 (4)	−0.0032 (4)
S2	0.0194 (5)	0.0199 (5)	0.0212 (5)	−0.0126 (4)	−0.0054 (4)	−0.0033 (4)
S3	0.0209 (5)	0.0195 (5)	0.0196 (5)	−0.0124 (4)	−0.0035 (4)	−0.0046 (4)
S4	0.0196 (5)	0.0208 (5)	0.0253 (5)	−0.0142 (4)	−0.0080 (4)	0.0013 (4)
O1	0.0258 (16)	0.0234 (16)	0.0116 (12)	−0.0175 (14)	−0.0019 (11)	−0.0018 (11)
O2	0.0257 (16)	0.0296 (17)	0.0121 (13)	−0.0208 (14)	−0.0016 (11)	−0.0021 (12)
O3	0.038 (2)	0.046 (2)	0.0267 (17)	−0.0333 (19)	−0.0029 (15)	−0.0061 (16)
O4	0.041 (2)	0.044 (2)	0.0195 (15)	−0.0298 (18)	−0.0078 (14)	−0.0014 (14)
O5	0.0357 (19)	0.0249 (17)	0.0215 (15)	−0.0177 (15)	−0.0061 (14)	0.0020 (13)
O6	0.040 (2)	0.048 (2)	0.0250 (17)	−0.0354 (19)	−0.0002 (15)	0.0016 (16)
O7	0.040 (2)	0.039 (2)	0.0216 (16)	−0.0253 (18)	−0.0090 (14)	−0.0042 (14)
O8	0.043 (2)	0.035 (2)	0.0148 (14)	−0.0228 (18)	−0.0023 (14)	−0.0007 (13)
O9	0.040 (2)	0.042 (2)	0.040 (2)	−0.0290 (19)	−0.0077 (17)	−0.0089 (17)
O10	0.040 (2)	0.040 (2)	0.0282 (18)	−0.0194 (18)	−0.0075 (16)	−0.0132 (16)
O11	0.0224 (16)	0.0275 (17)	0.0200 (14)	−0.0127 (14)	0.0011 (12)	−0.0072 (13)
O12	0.0313 (19)	0.0269 (18)	0.0244 (16)	−0.0188 (16)	0.0042 (14)	−0.0014 (13)
O13	0.050 (2)	0.057 (3)	0.0274 (17)	−0.045 (2)	0.0074 (16)	−0.0159 (17)
O14	0.077 (3)	0.049 (2)	0.0121 (14)	−0.049 (2)	0.0007 (16)	−0.0020 (15)
O15	0.042 (2)	0.038 (2)	0.0258 (17)	−0.0247 (18)	−0.0110 (16)	0.0051 (15)
O16	0.037 (2)	0.0309 (19)	0.0240 (16)	−0.0205 (17)	−0.0069 (14)	0.0032 (14)
O17	0.0243 (17)	0.039 (2)	0.0234 (16)	−0.0200 (16)	−0.0009 (13)	0.0035 (14)
O18	0.046 (2)	0.059 (3)	0.0190 (15)	−0.044 (2)	0.0035 (15)	−0.0026 (16)
O19	0.0284 (18)	0.037 (2)	0.0187 (15)	−0.0182 (16)	0.0022 (13)	−0.0001 (14)
O20	0.048 (2)	0.047 (2)	0.0220 (16)	−0.035 (2)	0.0099 (16)	−0.0056 (16)
N1	0.0217 (19)	0.026 (2)	0.0228 (18)	−0.0143 (16)	−0.0051 (15)	−0.0046 (15)
N2	0.030 (2)	0.0209 (19)	0.0187 (16)	−0.0171 (17)	−0.0043 (15)	−0.0028 (14)
N3	0.026 (2)	0.024 (2)	0.0182 (17)	−0.0108 (17)	−0.0037 (15)	−0.0044 (15)
N4	0.035 (2)	0.037 (2)	0.027 (2)	−0.025 (2)	−0.0084 (18)	0.0061 (18)
N5	0.024 (2)	0.026 (2)	0.030 (2)	−0.0085 (17)	−0.0084 (16)	−0.0087 (17)
N6	0.0126 (16)	0.0247 (19)	0.0164 (15)	−0.0049 (15)	−0.0027 (13)	−0.0093 (14)
N7	0.032 (2)	0.025 (2)	0.0182 (17)	−0.0173 (18)	−0.0028 (15)	−0.0038 (15)
N8	0.049 (3)	0.036 (2)	0.0243 (19)	−0.034 (2)	0.0108 (18)	−0.0141 (17)
C1	0.0183 (19)	0.019 (2)	0.0116 (16)	−0.0127 (17)	−0.0034 (14)	−0.0010 (14)
C2	0.019 (2)	0.0143 (19)	0.0119 (16)	−0.0089 (16)	−0.0016 (14)	−0.0030 (14)
C3	0.023 (2)	0.019 (2)	0.0128 (17)	−0.0152 (18)	0.0007 (15)	−0.0011 (14)
C4	0.0178 (19)	0.0170 (19)	0.0141 (17)	−0.0129 (17)	0.0003 (14)	−0.0015 (14)
C5	0.0158 (18)	0.0166 (19)	0.0115 (16)	−0.0107 (16)	−0.0011 (14)	−0.0017 (14)
C6	0.0172 (19)	0.0160 (19)	0.0109 (16)	−0.0107 (16)	−0.0009 (14)	−0.0021 (14)
C7	0.0168 (19)	0.0154 (19)	0.0122 (16)	−0.0117 (16)	−0.0027 (14)	−0.0017 (14)
C8	0.0172 (19)	0.021 (2)	0.0131 (16)	−0.0140 (17)	−0.0018 (14)	−0.0018 (14)
C9	0.027 (2)	0.028 (2)	0.0111 (16)	−0.023 (2)	−0.0001 (15)	−0.0033 (15)
C10	0.025 (2)	0.028 (2)	0.0171 (18)	−0.022 (2)	−0.0028 (16)	−0.0035 (16)
C11	0.036 (3)	0.026 (2)	0.022 (2)	−0.025 (2)	−0.0020 (19)	−0.0037 (18)
C12	0.022 (2)	0.030 (3)	0.027 (2)	−0.018 (2)	−0.0019 (18)	−0.0065 (18)
C13	0.022 (2)	0.018 (2)	0.0139 (17)	−0.0127 (17)	−0.0036 (15)	−0.0020 (14)
C14	0.0181 (19)	0.018 (2)	0.0116 (16)	−0.0108 (17)	−0.0008 (14)	−0.0026 (14)
C15	0.020 (2)	0.018 (2)	0.0161 (17)	−0.0116 (17)	−0.0039 (15)	−0.0018 (15)
C16	0.024 (2)	0.023 (2)	0.0128 (17)	−0.0164 (18)	−0.0034 (15)	−0.0013 (15)
C17	0.033 (2)	0.027 (2)	0.0165 (18)	−0.024 (2)	−0.0037 (17)	−0.0012 (16)
C18	0.047 (3)	0.041 (3)	0.019 (2)	−0.034 (3)	−0.005 (2)	−0.003 (2)
C19	0.019 (2)	0.018 (2)	0.0149 (17)	−0.0125 (17)	−0.0025 (15)	−0.0016 (15)
C20	0.0168 (19)	0.021 (2)	0.0138 (17)	−0.0117 (17)	−0.0009 (14)	−0.0048 (15)
C21	0.023 (2)	0.023 (2)	0.0151 (17)	−0.0172 (18)	−0.0029 (15)	0.0016 (15)
C22	0.019 (2)	0.020 (2)	0.0170 (18)	−0.0148 (17)	−0.0025 (15)	−0.0007 (15)
C23	0.0151 (18)	0.0171 (19)	0.0141 (17)	−0.0114 (16)	−0.0018 (14)	−0.0011 (14)
C24	0.0155 (19)	0.0145 (19)	0.0149 (17)	−0.0097 (16)	−0.0034 (14)	−0.0005 (14)
C25	0.0150 (18)	0.0147 (19)	0.0183 (18)	−0.0102 (16)	−0.0036 (15)	−0.0020 (14)
C26	0.0187 (19)	0.020 (2)	0.0112 (16)	−0.0140 (17)	−0.0010 (14)	−0.0022 (14)
C27	0.027 (2)	0.024 (2)	0.0140 (17)	−0.0197 (19)	−0.0043 (16)	−0.0011 (15)
C28	0.028 (2)	0.028 (2)	0.0160 (18)	−0.023 (2)	−0.0065 (16)	0.0026 (16)
C29	0.040 (3)	0.023 (2)	0.032 (2)	−0.021 (2)	−0.009 (2)	−0.0049 (19)
C30	0.030 (2)	0.033 (3)	0.032 (2)	−0.025 (2)	−0.012 (2)	0.004 (2)
C31	0.019 (2)	0.020 (2)	0.0159 (17)	−0.0129 (17)	−0.0027 (15)	−0.0021 (15)
C32	0.019 (2)	0.022 (2)	0.0133 (17)	−0.0128 (18)	−0.0001 (15)	−0.0041 (15)
C33	0.0161 (19)	0.022 (2)	0.0180 (18)	−0.0106 (17)	−0.0008 (15)	−0.0046 (16)
C34	0.021 (2)	0.024 (2)	0.0158 (18)	−0.0147 (18)	−0.0028 (15)	−0.0046 (16)
C35	0.029 (2)	0.028 (2)	0.0196 (19)	−0.020 (2)	−0.0029 (17)	−0.0037 (17)
C36	0.041 (3)	0.043 (3)	0.018 (2)	−0.030 (3)	−0.0053 (19)	−0.003 (2)
C37	0.020 (2)	0.018 (2)	0.0191 (19)	−0.0120 (17)	−0.0018 (16)	−0.0002 (15)
C38	0.020 (2)	0.015 (2)	0.0210 (19)	−0.0091 (17)	−0.0064 (16)	−0.0013 (15)
C39	0.018 (2)	0.017 (2)	0.0172 (18)	−0.0092 (17)	−0.0030 (15)	0.0002 (15)
C40	0.0156 (19)	0.0146 (19)	0.0169 (18)	−0.0084 (16)	−0.0015 (15)	0.0022 (15)
C41	0.020 (2)	0.022 (2)	0.0171 (18)	−0.0139 (18)	−0.0034 (15)	−0.0001 (16)
C42	0.022 (2)	0.024 (2)	0.0185 (19)	−0.0148 (19)	−0.0039 (16)	−0.0013 (16)
C43	0.020 (2)	0.019 (2)	0.0145 (17)	−0.0093 (17)	−0.0037 (15)	−0.0010 (15)
C44	0.017 (2)	0.017 (2)	0.0139 (17)	−0.0062 (17)	−0.0009 (15)	−0.0001 (15)
C45	0.0164 (19)	0.0153 (19)	0.0194 (19)	−0.0099 (16)	−0.0012 (15)	0.0009 (15)
C46	0.0142 (19)	0.0139 (19)	0.0197 (18)	−0.0078 (16)	−0.0017 (15)	−0.0002 (15)
C47	0.0157 (19)	0.0137 (19)	0.0154 (17)	−0.0064 (16)	−0.0026 (14)	0.0007 (14)
C48	0.0140 (18)	0.0121 (18)	0.0180 (18)	−0.0058 (15)	−0.0043 (14)	0.0010 (14)
C49	0.0142 (19)	0.0149 (19)	0.0165 (18)	−0.0069 (16)	−0.0023 (14)	0.0006 (14)
C50	0.022 (2)	0.025 (2)	0.0193 (19)	−0.0133 (19)	−0.0042 (16)	0.0007 (17)
C51	0.019 (2)	0.021 (2)	0.025 (2)	−0.0099 (18)	−0.0027 (17)	−0.0069 (17)
C52	0.016 (2)	0.025 (2)	0.026 (2)	−0.0073 (18)	−0.0030 (17)	−0.0107 (18)
C53	0.019 (2)	0.024 (2)	0.0183 (19)	−0.0058 (18)	−0.0046 (16)	−0.0058 (17)
C54	0.018 (2)	0.018 (2)	0.0168 (18)	−0.0055 (17)	−0.0009 (15)	−0.0047 (15)
C55	0.0180 (19)	0.0150 (19)	0.0133 (17)	−0.0082 (16)	−0.0003 (14)	−0.0011 (14)
C56	0.019 (2)	0.018 (2)	0.0191 (19)	−0.0107 (17)	−0.0027 (16)	−0.0028 (15)
C57	0.024 (2)	0.020 (2)	0.0149 (18)	−0.0123 (18)	−0.0047 (16)	−0.0020 (15)
C58	0.018 (2)	0.020 (2)	0.0162 (18)	−0.0088 (17)	−0.0005 (15)	−0.0024 (15)
C59	0.021 (2)	0.018 (2)	0.0164 (18)	−0.0114 (17)	0.0007 (15)	−0.0035 (15)
C60	0.018 (2)	0.017 (2)	0.0182 (18)	−0.0073 (17)	−0.0004 (15)	−0.0057 (15)
C61	0.0166 (19)	0.018 (2)	0.0169 (18)	−0.0079 (17)	−0.0014 (15)	−0.0044 (15)
C62	0.0171 (19)	0.0152 (19)	0.0157 (17)	−0.0082 (16)	0.0003 (15)	−0.0043 (14)
C63	0.016 (2)	0.020 (2)	0.0178 (18)	−0.0100 (17)	−0.0009 (15)	−0.0029 (15)
C64	0.025 (2)	0.025 (2)	0.021 (2)	−0.0146 (19)	0.0035 (17)	−0.0103 (17)
C65	0.041 (3)	0.032 (3)	0.030 (2)	−0.024 (2)	−0.008 (2)	−0.004 (2)
C66	0.037 (3)	0.024 (2)	0.034 (3)	−0.019 (2)	−0.004 (2)	0.000 (2)
C67	0.039 (3)	0.029 (3)	0.033 (3)	−0.023 (2)	−0.012 (2)	0.004 (2)
C68	0.039 (3)	0.023 (3)	0.040 (3)	−0.017 (2)	−0.012 (2)	0.006 (2)
C70	0.030 (3)	0.061 (4)	0.027 (2)	−0.032 (3)	−0.006 (2)	0.015 (2)
C71	0.028 (3)	0.032 (3)	0.035 (3)	−0.019 (2)	0.002 (2)	−0.010 (2)
C72	0.028 (2)	0.039 (3)	0.031 (2)	−0.022 (2)	0.001 (2)	−0.010 (2)
C73	0.027 (3)	0.076 (5)	0.026 (2)	−0.022 (3)	−0.001 (2)	−0.012 (3)
C69	0.037 (3)	0.049 (3)	0.029 (2)	−0.029 (3)	−0.007 (2)	0.015 (2)
C74	0.029 (3)	0.056 (4)	0.022 (2)	−0.016 (3)	0.001 (2)	−0.011 (2)
C75	0.034 (3)	0.022 (2)	0.025 (2)	−0.008 (2)	0.001 (2)	−0.0002 (18)
C76	0.039 (3)	0.029 (3)	0.026 (2)	−0.014 (2)	0.004 (2)	−0.004 (2)

Geometric parameters (Å, º)

Br1—C40	1.893 (4)	C14—C15	1.537 (5)
Br2—C54	1.892 (4)	C15—C16	1.533 (5)
S1—C8	1.676 (4)	C16—C17	1.528 (5)
S1—C9	1.720 (4)	C17—C18	1.530 (6)
S2—C8	1.669 (4)	C19—C20	1.375 (5)
S2—C10	1.720 (4)	C19—C24	1.427 (5)
S3—C26	1.671 (4)	C20—C21	1.427 (5)
S3—C27	1.718 (4)	C21—C22	1.355 (6)
S4—C26	1.676 (4)	C22—C23	1.440 (5)
S4—C28	1.722 (4)	C23—C25^ii	1.401 (5)
O1—C2	1.351 (5)	C23—C24	1.437 (5)
O1—C13	1.444 (5)	C24—C25	1.411 (5)
O2—C20	1.360 (5)	C25—C23^ii	1.401 (5)
O2—C31	1.440 (5)	C25—C26	1.484 (5)
O3—N1	1.237 (5)	C27—C28	1.355 (7)
O4—N1	1.230 (5)	C27—C29	1.501 (6)
O5—N2	1.235 (5)	C28—C30	1.499 (6)
O6—N2	1.216 (5)	C31—C32	1.522 (5)
O7—N3	1.249 (5)	C32—C33	1.530 (5)
O8—N3	1.226 (5)	C33—C34	1.527 (6)
O9—N5	1.225 (6)	C34—C35	1.534 (6)
O10—N5	1.236 (5)	C35—C36	1.533 (6)
O11—N6	1.240 (5)	C37—C38	1.371 (6)
O12—N6	1.199 (5)	C37—C46	1.404 (6)
O13—N7	1.222 (5)	C38—C39	1.409 (6)
O14—N7	1.227 (5)	C39—C40	1.370 (6)
O15—C65	1.421 (6)	C40—C47	1.416 (5)
O15—C68	1.422 (7)	C41—C42	1.375 (6)
O16—C66	1.418 (6)	C41—C48	1.405 (5)
O16—C67	1.438 (6)	C42—C43	1.419 (6)
O17—C71	1.417 (6)	C43—C44	1.375 (6)
O17—C70	1.419 (6)	C44—C49	1.406 (6)
O18—C69	1.413 (7)	C45—C50	1.410 (6)
O18—C72	1.431 (7)	C45—C46	1.417 (6)
O19—C76	1.421 (6)	C45—C49	1.422 (5)
O19—C73	1.422 (7)	C46—C47	1.439 (5)
O20—C75	1.422 (7)	C47—C48	1.439 (6)
O20—C74	1.428 (7)	C48—C49	1.448 (5)
N1—C38	1.466 (5)	C51—C52	1.375 (6)
N2—C41	1.463 (5)	C51—C60	1.402 (6)
N3—C43	1.457 (5)	C52—C53	1.406 (7)
N4—C50	1.152 (6)	C53—C54	1.376 (6)
N5—C52	1.466 (6)	C54—C61	1.407 (6)
N6—C55	1.495 (5)	C55—C56	1.372 (6)
N7—C57	1.465 (5)	C55—C62	1.415 (6)
N8—C64	1.153 (6)	C56—C57	1.408 (6)
C1—C2	1.381 (5)	C57—C58	1.374 (6)
C1—C6	1.433 (5)	C58—C63	1.401 (6)
C2—C3	1.428 (5)	C59—C60	1.415 (6)
C3—C4	1.359 (5)	C59—C64	1.417 (6)
C4—C5	1.436 (5)	C59—C63	1.428 (6)
C5—C7^i	1.408 (5)	C60—C61	1.449 (6)
C5—C6	1.438 (5)	C61—C62	1.434 (6)
C6—C7	1.413 (5)	C62—C63	1.441 (6)
C7—C5^i	1.408 (5)	C65—C66	1.504 (7)
C7—C8	1.482 (5)	C67—C68	1.494 (7)
C9—C10	1.356 (7)	C70—C69	1.508 (7)
C9—C11	1.495 (6)	C71—C72	1.506 (7)
C10—C12	1.505 (6)	C73—C74	1.523 (7)
C13—C14	1.521 (5)	C75—C76	1.511 (7)
C8—S1—C9	97.6 (2)	C30—C28—S4	118.7 (4)
C8—S2—C10	97.6 (2)	O2—C31—C32	107.0 (3)
C26—S3—C27	97.4 (2)	C31—C32—C33	110.8 (3)
C26—S4—C28	97.2 (2)	C34—C33—C32	112.9 (3)
C2—O1—C13	118.0 (3)	C33—C34—C35	113.0 (3)
C20—O2—C31	117.6 (3)	C36—C35—C34	112.1 (4)
C65—O15—C68	109.4 (4)	C38—C37—C46	117.9 (4)
C66—O16—C67	108.8 (4)	C37—C38—C39	123.4 (4)
C71—O17—C70	109.5 (4)	C37—C38—N1	119.3 (4)
C69—O18—C72	108.5 (4)	C39—C38—N1	117.3 (4)
C76—O19—C73	110.5 (4)	C40—C39—C38	118.6 (4)
C75—O20—C74	109.5 (4)	C39—C40—C47	121.2 (4)
O4—N1—O3	123.8 (4)	C39—C40—Br1	116.7 (3)
O4—N1—C38	118.4 (4)	C47—C40—Br1	121.4 (3)
O3—N1—C38	117.8 (4)	C42—C41—C48	123.5 (4)
O6—N2—O5	124.6 (4)	C42—C41—N2	114.4 (4)
O6—N2—C41	118.5 (4)	C48—C41—N2	120.9 (4)
O5—N2—C41	116.8 (4)	C41—C42—C43	116.9 (4)
O8—N3—O7	123.8 (4)	C44—C43—C42	123.6 (4)
O8—N3—C43	118.2 (4)	C44—C43—N3	119.2 (4)
O7—N3—C43	118.0 (4)	C42—C43—N3	117.2 (4)
O9—N5—O10	122.7 (4)	C43—C44—C49	118.0 (4)
O9—N5—C52	119.4 (4)	C50—C45—C46	125.1 (4)
O10—N5—C52	118.0 (4)	C50—C45—C49	127.3 (4)
O12—N6—O11	126.0 (4)	C46—C45—C49	107.5 (3)
O12—N6—C55	118.7 (4)	C37—C46—C45	130.1 (4)
O11—N6—C55	115.0 (4)	C37—C46—C47	120.6 (4)
O13—N7—O14	123.8 (4)	C45—C46—C47	109.3 (3)
O13—N7—C57	119.0 (4)	C40—C47—C46	117.8 (4)
O14—N7—C57	117.2 (4)	C40—C47—C48	134.7 (4)
C2—C1—C6	119.6 (3)	C46—C47—C48	107.1 (3)
O1—C2—C1	125.6 (4)	C41—C48—C47	136.3 (4)
O1—C2—C3	113.8 (3)	C41—C48—C49	116.6 (4)
C1—C2—C3	120.6 (3)	C47—C48—C49	107.0 (3)
C4—C3—C2	120.9 (4)	C44—C49—C45	130.4 (4)
C3—C4—C5	120.9 (4)	C44—C49—C48	120.8 (4)
C7^i—C5—C4	122.2 (3)	C45—C49—C48	108.8 (3)
C7^i—C5—C6	119.6 (3)	N4—C50—C45	178.0 (6)
C4—C5—C6	118.2 (3)	C52—C51—C60	117.3 (4)
C7—C6—C1	122.6 (3)	C51—C52—C53	123.9 (4)
C7—C6—C5	117.6 (3)	C51—C52—N5	118.2 (4)
C1—C6—C5	119.8 (3)	C53—C52—N5	117.8 (4)
C5^i—C7—C6	122.7 (3)	C54—C53—C52	118.3 (4)
C5^i—C7—C8	118.6 (3)	C53—C54—C61	121.4 (4)
C6—C7—C8	118.6 (3)	C53—C54—Br2	117.1 (3)
C7—C8—S2	124.0 (3)	C61—C54—Br2	120.6 (3)
C7—C8—S1	121.3 (3)	C56—C55—C62	123.1 (4)
S2—C8—S1	114.6 (2)	C56—C55—N6	115.0 (4)
C10—C9—C11	126.9 (4)	C62—C55—N6	121.1 (3)
C10—C9—S1	115.0 (3)	C55—C56—C57	117.0 (4)
C11—C9—S1	118.1 (4)	C58—C57—C56	124.0 (4)
C9—C10—C12	126.4 (4)	C58—C57—N7	118.8 (4)
C9—C10—S2	115.2 (3)	C56—C57—N7	117.2 (4)
C12—C10—S2	118.4 (4)	C57—C58—C63	117.4 (4)
O1—C13—C14	107.2 (3)	C60—C59—C64	125.9 (4)
C13—C14—C15	110.4 (3)	C60—C59—C63	107.8 (4)
C16—C15—C14	113.1 (3)	C64—C59—C63	126.2 (4)
C17—C16—C15	112.3 (3)	C51—C60—C59	130.1 (4)
C16—C17—C18	112.6 (3)	C51—C60—C61	120.9 (4)
C20—C19—C24	119.8 (4)	C59—C60—C61	109.0 (4)
O2—C20—C19	125.5 (4)	C54—C61—C62	135.4 (4)
O2—C20—C21	113.5 (3)	C54—C61—C60	117.7 (4)
C19—C20—C21	121.0 (4)	C62—C61—C60	106.6 (3)
C22—C21—C20	120.1 (4)	C55—C62—C61	136.0 (4)
C21—C22—C23	121.6 (4)	C55—C62—C63	116.0 (4)
C25^ii—C23—C24	119.9 (3)	C61—C62—C63	107.9 (4)
C25^ii—C23—C22	122.4 (3)	C58—C63—C59	130.4 (4)
C24—C23—C22	117.7 (3)	C58—C63—C62	121.4 (4)
C25—C24—C19	122.6 (3)	C59—C63—C62	108.2 (4)
C25—C24—C23	117.6 (3)	N8—C64—C59	177.4 (5)
C19—C24—C23	119.8 (3)	O15—C65—C66	110.7 (4)
C23^ii—C25—C24	122.5 (3)	O16—C66—C65	110.4 (4)
C23^ii—C25—C26	118.9 (3)	O16—C67—C68	110.4 (4)
C24—C25—C26	118.6 (3)	O15—C68—C67	111.3 (4)
C25—C26—S3	122.5 (3)	O17—C70—C69	110.2 (4)
C25—C26—S4	122.5 (3)	O17—C71—C72	110.7 (4)
S3—C26—S4	114.9 (2)	O18—C72—C71	111.0 (4)
C28—C27—C29	125.8 (4)	O19—C73—C74	110.5 (4)
C28—C27—S3	115.3 (3)	O18—C69—C70	111.3 (5)
C29—C27—S3	118.9 (4)	O20—C74—C73	110.6 (5)
C27—C28—C30	126.1 (4)	O20—C75—C76	110.0 (5)
C27—C28—S4	115.2 (3)	O19—C76—C75	111.0 (4)

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