17,18-Dibromo-8-methyl-4,12-ditosyl-3,4,5,6,7,8,9,10,11,12,13,14-dodeca­hydro-2H-benzo[b][1,4,7,11,15]dioxatriaza­cyclo­hepta­decine

Abstract

In the title compound, C₃₁H₃₉Br₂N₃O₆S₂, a 17-membered aza-macrocyclic ligand containing two ether O and three aza N atoms, the three pendant aromatic rings form an ‘E’ shape. The dihedral angles between the central benzene ring and the side ones are 17.8 (3) and 7.4 (3)°, and the dihedral angle between the tosyl rings is 10.6 (3)°. The methyl group is disordered over two orientations, with occupancies of 0.52 (15) and 0.48 (15).

Related literature

For general background to aza-macrocyclic ligands, see: Fry et al. (1997 ▶); Xu et al. (1997 ▶); Canales et al. (2000 ▶); Shishkina et al. (2007 ▶). For related structures, see: Hökelek et al. (2001 ▶, 2004 ▶); Işik et al. (1999 ▶). For further synthetic details, see: Notni et al. (2006 ▶); Koçak et al. (1994 ▶).

Experimental

Crystal data

• C₃₁H₃₉Br₂N₃O₆S₂

• M _r = 773.59

• Monoclinic,

• a = 18.7520 (9) Å

• b = 10.6864 (4) Å

• c = 19.9527 (9) Å

• β = 121.416 (3)°

• V = 3412.2 (3) ų

• Z = 4

• Mo Kα radiation

• μ = 2.54 mm⁻¹

• T = 296 K

• 0.60 × 0.52 × 0.37 mm

Data collection

• Stoe IPDS 2 diffractometer

• Absorption correction: integration (X-RED32; Stoe & Cie, 2002 ▶) T _min = 0.260, T _max = 0.425

• 24321 measured reflections

• 7243 independent reflections

• 4640 reflections with I > 2σ(I)

• R _int = 0.049

Refinement

• R[F ² > 2σ(F ²)] = 0.062

• wR(F ²) = 0.152

• S = 1.02

• 7243 reflections

• 409 parameters

• H-atom parameters constrained

• Δρ_max = 1.31 e Å⁻³

• Δρ_min = −1.17 e Å⁻³

Data collection: X-AREA (Stoe & Cie, 2002 ▶); cell refinement: X-AREA; data reduction: X-RED32 (Stoe & Cie, 2002 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Supplementary Material

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

supplementary crystallographic information

Comment

The synthesis and characterization of coordination compounds with aza-macrocyclic ligands has evolved during the last years as one of the main research areas in coordination chemistry (Fry et al.,1997; Xu et al., 1997). By the end of the last century the macrocyclic polyethers (crown ethers) had became one of the most popular chemical reagents with a very wide area of applications. They are used successfully in chemistry of 'host–guest' complexes, extraction, phase transfer catalysis, organic synthesis, analytical chemistry, biology, medicine, ecology, etc. (Shishkina et al., 2007). In addition, aza-macrocyclic ligands, as well as their coordination and organometallic compounds play important roles in catalysis in the activation of small molecules, showing catalytic activity in electrochemically assisted reactions with several substrates (Canales et al., 2000).

We have investigated the title structure of macrocyclic multidentate O₂N₃ donor-type ligand (Fig. 1). The 17-membered macrocyclic ring contains two ether O and three aza N atoms. The ligand cavity for macrocyclic ring plays an important role in metal-ion selectivity (Hökelek et al.,2004; Hökelek et al., 2001).

The 17-membered macro-cyclic molecule with O₂N₃ type ring, the deviations from the least-squares plane defined by atoms O1, O2, N1, N2 and N3 are -0.661 (4)Å (O1), 0.363 (3)Å (O2), -0.352 (3)(N1) and 0.806 (3)Å (N2) and C29 shows the maximum r.m.s deviation from the plane as 1.067 (3).

The dihedral angle between the tosyl rings A(C18—C23, C24, S2) and B(C11—C16, C17, S1) is 10.6 (3)° [both nearly planar with r.m.s. deviations of 0.11 (3) Å for S1 and -0.06 (3) Å for S2, from the mean planes]. The geometry at the S atoms is distorted from the tetrahedral configuration [the largest angle is 120.3 (3)° for O3—S1—O4] and agree with the corresponding angle 120.4 (3)° in 10,11-Dibromo-3,6-ditosyl-3,6-diazabicyclo-[6.4.0]dodeca-1 (8),9,11-triene (Işik et al., 1999).

The benzene rings C(C1—C6), D(C11—C16) and E(C18—C23) are planar with the maximum r.m.s. deviation from the mean plane as 0.021 (4) Å for C13. The dihedral angles between these benzene rings are C/D = 17.8 (3)°, D/E = 10.9 (3)° and C/E = 7.4 (3)°. The conformation of the title compound's macrocyclic ring can be given by the torsion angles. The optimum values of the torsion angles in a macrocyclic ring are 180° (anti) and 60° (gauche). In the compound (I), seven torsion angles are seems to be anti and five ones as gauche (Table 1). There is no classic hydrogen bonds in (I) and van der Waals interactions are effective in the molecular packing.

Experimental

N,N'-(3,3'-(methylazanediyl)bis(propane-3,1-diyl))bis(4-methyl benzenesulfonamide) (Notni et al., 2006) (1 g, 2.21 mmol) was dissolved in dry acetonitrile (50 ml) containing finely ground anhydrous Cs₂CO₃ (2.16 g, 6.63 mmol) and purged under nitrogen in a Schlenk system. This solution was stirred at 50 °C and a solution 1,2-bis(2-iodo-ethoxy) -4,5-dibromobenzene (Koçak et al., 1994) (1.27 g, 2.21 mmol) in dry acetonitrile (30 ml) was added dropwise over a period of 3 h at reflux temperature (90 °C). The reaction was monitored by TLC using hexane/ethyl acetate (1:1) and was complete in 8 days at the reflux temperature. At the end of this period the solvent was removed under reduced pressure, mixed with water (50 ml) and then extracted with chloroform (3 times 50). The combine extract was washed with water, dried over Na₂SO₄ and filtered and evaporated to dryness. The product was chromatographed on silica gel with hexane/ethyl acetate (2:3). Finally the white solid product was obtained. This product was crystallized from chloroform/hexane to yield colourless prisms of (I). This compound is soluble in chloroform, dichloromethane, dimethyl formamide. Yield: 0.65 g (%38). IR(KBr pellets): 3026 (Ar–H), 2926–2854 (Aliph. C–H), 1642, 1597, 1493, 1335, 1251, 1156, 815. 1H NMR (CDCl3): 7.67 (d, 4H, Ar–Ts—H), 7.22 (d, 4H, Ar–Ts—H), 6.81 (s, 2H, Ar–H), 3.97 (t, 4H, O–CH2), 3.66 (t, 4H, N–CH2), 3.45 (t, 4H, N–CH2), 2.37 (t, 4H, N–CH2), 2.21 (s, 6H, CH3), 2.08 (s, 3H, N—CH3), 1.70 (m, 4H, CH2). ¹³C NMR (CDCl3): 148.15 (Ar–C), 148.61 (Ar–C), 137.93 (Ar–C), 129.86 (Ar–C),127.06 (Ar–C), 117.47 (Ar–C), 115.25 (Ar–C), 69.21 (O–CH2), 54.26 (N–CH2), 48.58 (N–CH2), 47.96 (N–CH2), 41.56 (N–CH2), 26.98 (CH2), 21.77 (CH3).

Refinement

All H atoms were positioned with idealized geometry using a riding model [C—H = 0.93—0.97 Å]. All H atoms were refined with isotropic displacement parameters (set to 1.2 and 1.5 times of the U_eq of the parent atom). The methyl group is disordered over two orientations, with occupancies of 0.52 (15) and O.48 (15).

Figures

Fig. 1.

A view of (I), showing 30% probability displacement ellipsoids. Only the major disorder component of the methyl group is shown.

Crystal data

C31H39Br2N3O6S2	F(000) = 1584
Mr = 773.59	Dx = 1.506 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 22517 reflections
a = 18.7520 (9) Å	θ = 1.2–27.3°
b = 10.6864 (4) Å	µ = 2.54 mm−1
c = 19.9527 (9) Å	T = 296 K
β = 121.416 (3)°	Prism, colorless
V = 3412.2 (3) Å3	0.60 × 0.52 × 0.37 mm
Z = 4

Data collection

Stoe IPDS 2 diffractometer	7243 independent reflections
Radiation source: fine-focus sealed tube	4640 reflections with I > 2σ(I)
graphite	Rint = 0.049
Detector resolution: 6.67 pixels mm-1	θmax = 26.8°, θmin = 2.0°
rotation method scans	h = −23→21
Absorption correction: integration (X-RED32; Stoe & Cie, 2002)	k = −13→13
Tmin = 0.260, Tmax = 0.425	l = −25→25
24321 measured reflections

Refinement

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.062	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.152	H-atom parameters constrained
S = 1.02	w = 1/[σ2(Fo2) + (0.0629P)2 + 3.5929P] where P = (Fo2 + 2Fc2)/3
7243 reflections	(Δ/σ)max = 0.001
409 parameters	Δρmax = 1.31 e Å−3
0 restraints	Δρmin = −1.17 e Å−3

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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	0.7001 (3)	0.3914 (4)	0.5560 (2)	0.0486 (10)
C2	0.6569 (3)	0.2996 (4)	0.5022 (3)	0.0632 (12)
H2	0.6427	0.2263	0.5176	0.076*
C3	0.6341 (3)	0.3154 (4)	0.4237 (3)	0.0655 (13)
C4	0.6564 (3)	0.4214 (5)	0.4013 (2)	0.0585 (11)
C5	0.6994 (3)	0.5155 (4)	0.4557 (2)	0.0556 (11)
H5	0.7138	0.5883	0.4400	0.067*
C6	0.7208 (3)	0.5021 (4)	0.5325 (2)	0.0468 (9)
C7	0.7871 (3)	0.7025 (4)	0.5702 (3)	0.0573 (11)
H7A	0.7425	0.7350	0.5203	0.069*
H7B	0.8351	0.6855	0.5656	0.069*
C8	0.8097 (3)	0.7969 (4)	0.6346 (3)	0.0579 (11)
H8A	0.8537	0.7617	0.6838	0.069*
H8B	0.8322	0.8707	0.6238	0.069*
C9	0.7245 (3)	0.2609 (4)	0.6628 (3)	0.0564 (11)
H9A	0.7463	0.2000	0.6419	0.068*
H9B	0.6681	0.2367	0.6474	0.068*
C10	0.7790 (3)	0.2666 (5)	0.7508 (2)	0.0569 (11)
H10A	0.7519	0.3193	0.7706	0.068*
H10B	0.7832	0.1831	0.7716	0.068*
C11	0.5504 (3)	0.7378 (6)	0.5204 (3)	0.0806 (15)
H11	0.5552	0.7363	0.5692	0.097*
C12	0.4984 (3)	0.6531 (6)	0.4624 (4)	0.0842 (17)
H12	0.4678	0.5964	0.4729	0.101*
C13	0.4909 (3)	0.6504 (5)	0.3900 (3)	0.0723 (14)
C14	0.5329 (3)	0.7394 (6)	0.3749 (3)	0.0813 (16)
H14	0.5267	0.7422	0.3256	0.098*
C15	0.5846 (3)	0.8260 (5)	0.4315 (3)	0.0790 (16)
H15	0.6126	0.8857	0.4199	0.095*
C16	0.5944 (3)	0.8236 (5)	0.5051 (3)	0.0645 (12)
C17	0.4383 (4)	0.5511 (6)	0.3308 (4)	0.098 (2)
H17A	0.3818	0.5570	0.3189	0.118*
H17B	0.4603	0.4699	0.3521	0.118*
H17C	0.4394	0.5633	0.2836	0.118*
C18	0.9238 (3)	0.2680 (4)	0.6840 (3)	0.0580 (11)
C19	0.8771 (4)	0.1928 (5)	0.6181 (4)	0.0787 (16)
H19	0.8517	0.1203	0.6215	0.094*
C20	0.8690 (4)	0.2273 (6)	0.5484 (4)	0.0888 (19)
H20	0.8380	0.1763	0.5048	0.107*
C21	0.9045 (3)	0.3334 (5)	0.5398 (3)	0.0692 (13)
C22	0.9515 (3)	0.4052 (5)	0.6057 (3)	0.0694 (13)
H22	0.9773	0.4770	0.6021	0.083*
C23	0.9614 (3)	0.3740 (5)	0.6772 (3)	0.0631 (12)
H23	0.9934	0.4245	0.7208	0.076*
C24	0.8933 (5)	0.3707 (7)	0.4621 (4)	0.106 (2)
H24A	0.9469	0.3748	0.4669	0.128*
H24B	0.8668	0.4511	0.4470	0.128*
H24C	0.8590	0.3098	0.4230	0.128*
C25	0.7356 (3)	0.7777 (5)	0.7079 (3)	0.0642 (12)
H25A	0.7467	0.6888	0.7092	0.077*
H25B	0.6793	0.7876	0.6975	0.077*
C26	0.7965 (4)	0.8339 (5)	0.7868 (3)	0.0759 (15)
H26A	0.7847	0.9225	0.7857	0.091*
H26B	0.8527	0.8256	0.7966	0.091*
C27	0.7927 (5)	0.7729 (5)	0.8533 (3)	0.0908 (19)
H27A	0.8327	0.8134	0.9022	0.109*
H27B	0.7374	0.7858	0.8450	0.109*
C28	0.8987 (4)	0.6155 (6)	0.8929 (3)	0.101 (2)
H28A	0.9289	0.6346	0.9486	0.122*
H28B	0.9193	0.6707	0.8681	0.122*
C29	0.9159 (4)	0.4810 (6)	0.8816 (3)	0.094 (2)
H29A	0.9758	0.4678	0.9086	0.113*
H29B	0.8937	0.4256	0.9048	0.113*
C30	0.8775 (3)	0.4486 (4)	0.7963 (3)	0.0644 (12)
H30A	0.8245	0.4920	0.7662	0.077*
H30B	0.9138	0.4782	0.7786	0.077*
C31A	0.797 (8)	0.589 (5)	0.919 (6)	0.14 (2)	0.52 (15)
H31A	0.8063	0.4999	0.9222	0.205*	0.52 (15)
H31B	0.7410	0.6057	0.9052	0.205*	0.52 (15)
H31C	0.8357	0.6266	0.9684	0.205*	0.52 (15)
C31B	0.758 (5)	0.570 (6)	0.890 (4)	0.118 (12)	0.48 (15)
H31D	0.7627	0.4809	0.8864	0.178*	0.48 (15)
H31E	0.7007	0.5943	0.8591	0.178*	0.48 (15)
H31F	0.7797	0.5918	0.9443	0.178*	0.48 (15)
N1	0.7410 (2)	0.8354 (3)	0.6445 (2)	0.0543 (9)
N2	0.8634 (2)	0.3142 (3)	0.7806 (2)	0.0545 (9)
N3	0.8103 (4)	0.6388 (4)	0.8600 (3)	0.0798 (13)
O1	0.72458 (19)	0.3840 (3)	0.63322 (15)	0.0562 (7)
O2	0.76047 (19)	0.5906 (3)	0.58982 (16)	0.0551 (7)
O3	0.7025 (3)	0.9994 (3)	0.5462 (2)	0.0861 (12)
O4	0.6274 (3)	0.9787 (4)	0.6179 (3)	0.0931 (12)
O5	0.9052 (3)	0.1027 (3)	0.7685 (3)	0.0910 (12)
O6	1.0111 (2)	0.2702 (4)	0.8347 (2)	0.0906 (12)
S1	0.66723 (9)	0.92262 (11)	0.58044 (8)	0.0680 (3)
S2	0.93076 (8)	0.23094 (12)	0.77324 (8)	0.0643 (3)
Br1	0.56928 (5)	0.18578 (6)	0.35290 (3)	0.1104 (3)
Br2	0.62827 (4)	0.44795 (6)	0.29617 (3)	0.0819 (2)

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
C1	0.050 (2)	0.046 (2)	0.043 (2)	0.0069 (19)	0.0199 (18)	0.0034 (17)
C2	0.079 (3)	0.044 (2)	0.055 (2)	−0.001 (2)	0.026 (2)	0.0036 (19)
C3	0.077 (3)	0.051 (3)	0.050 (2)	0.002 (2)	0.021 (2)	−0.004 (2)
C4	0.063 (3)	0.064 (3)	0.045 (2)	0.005 (2)	0.026 (2)	0.001 (2)
C5	0.063 (3)	0.053 (3)	0.049 (2)	−0.002 (2)	0.028 (2)	0.0026 (19)
C6	0.048 (2)	0.044 (2)	0.046 (2)	0.0026 (18)	0.0217 (18)	−0.0010 (17)
C7	0.060 (3)	0.052 (3)	0.060 (2)	−0.008 (2)	0.031 (2)	0.001 (2)
C8	0.057 (3)	0.051 (3)	0.060 (3)	−0.010 (2)	0.026 (2)	−0.001 (2)
C9	0.059 (3)	0.047 (2)	0.059 (2)	0.004 (2)	0.028 (2)	0.012 (2)
C10	0.057 (3)	0.062 (3)	0.056 (2)	0.012 (2)	0.032 (2)	0.020 (2)
C11	0.068 (3)	0.096 (4)	0.069 (3)	−0.011 (3)	0.030 (3)	0.004 (3)
C12	0.058 (3)	0.093 (4)	0.095 (4)	−0.017 (3)	0.035 (3)	0.004 (3)
C13	0.045 (3)	0.078 (4)	0.072 (3)	0.002 (2)	0.016 (2)	0.003 (3)
C14	0.070 (3)	0.094 (4)	0.057 (3)	0.000 (3)	0.018 (3)	0.011 (3)
C15	0.073 (4)	0.074 (3)	0.067 (3)	−0.010 (3)	0.020 (3)	0.021 (3)
C16	0.056 (3)	0.060 (3)	0.065 (3)	0.010 (2)	0.022 (2)	0.014 (2)
C17	0.068 (4)	0.103 (5)	0.100 (4)	−0.011 (3)	0.027 (3)	−0.015 (4)
C18	0.055 (3)	0.048 (2)	0.078 (3)	0.003 (2)	0.039 (2)	−0.005 (2)
C19	0.095 (4)	0.053 (3)	0.117 (5)	−0.020 (3)	0.075 (4)	−0.031 (3)
C20	0.099 (4)	0.088 (4)	0.095 (4)	−0.034 (4)	0.062 (4)	−0.054 (3)
C21	0.070 (3)	0.074 (3)	0.071 (3)	−0.004 (3)	0.042 (3)	−0.018 (3)
C22	0.083 (4)	0.061 (3)	0.073 (3)	−0.013 (3)	0.046 (3)	−0.007 (2)
C23	0.065 (3)	0.060 (3)	0.063 (3)	−0.014 (2)	0.032 (2)	−0.012 (2)
C24	0.127 (6)	0.128 (6)	0.073 (4)	0.000 (5)	0.058 (4)	−0.016 (4)
C25	0.071 (3)	0.058 (3)	0.063 (3)	−0.001 (2)	0.035 (3)	0.005 (2)
C26	0.105 (4)	0.058 (3)	0.066 (3)	0.004 (3)	0.045 (3)	−0.003 (2)
C27	0.142 (6)	0.070 (4)	0.073 (3)	0.020 (4)	0.065 (4)	0.003 (3)
C28	0.117 (6)	0.080 (4)	0.059 (3)	0.009 (4)	0.013 (3)	−0.016 (3)
C29	0.100 (4)	0.082 (4)	0.056 (3)	0.022 (3)	0.010 (3)	−0.005 (3)
C30	0.076 (3)	0.057 (3)	0.057 (3)	0.010 (2)	0.033 (2)	0.006 (2)
C31A	0.23 (6)	0.092 (18)	0.16 (4)	0.02 (3)	0.15 (4)	0.03 (2)
C31B	0.18 (3)	0.12 (2)	0.10 (2)	−0.02 (2)	0.11 (2)	0.002 (16)
N1	0.055 (2)	0.049 (2)	0.0530 (19)	0.0003 (17)	0.0237 (17)	0.0008 (16)
N2	0.054 (2)	0.052 (2)	0.057 (2)	0.0107 (17)	0.0285 (18)	0.0106 (16)
N3	0.121 (4)	0.067 (3)	0.068 (3)	0.017 (3)	0.060 (3)	0.009 (2)
O1	0.071 (2)	0.0450 (16)	0.0431 (14)	0.0023 (14)	0.0232 (14)	0.0057 (12)
O2	0.0665 (19)	0.0474 (16)	0.0483 (15)	−0.0081 (14)	0.0277 (14)	−0.0018 (13)
O3	0.098 (3)	0.0517 (19)	0.084 (2)	−0.0102 (19)	0.030 (2)	0.0179 (18)
O4	0.089 (3)	0.072 (2)	0.113 (3)	0.022 (2)	0.049 (2)	−0.010 (2)
O5	0.104 (3)	0.0483 (19)	0.143 (4)	0.023 (2)	0.080 (3)	0.030 (2)
O6	0.055 (2)	0.121 (3)	0.082 (2)	0.018 (2)	0.0259 (19)	0.027 (2)
S1	0.0714 (8)	0.0436 (6)	0.0742 (8)	0.0055 (6)	0.0275 (7)	0.0053 (5)
S2	0.0548 (7)	0.0589 (7)	0.0799 (8)	0.0187 (6)	0.0355 (6)	0.0218 (6)
Br1	0.1618 (7)	0.0672 (4)	0.0607 (3)	−0.0270 (4)	0.0290 (4)	−0.0158 (3)
Br2	0.1014 (5)	0.0923 (4)	0.0486 (3)	−0.0089 (3)	0.0368 (3)	−0.0056 (3)

Geometric parameters (Å, °)

C1—O1	1.361 (5)	C19—H19	0.9300
C1—C2	1.366 (6)	C20—C21	1.370 (8)
C1—C6	1.400 (6)	C20—H20	0.9300
C2—C3	1.401 (6)	C21—C22	1.374 (7)
C2—H2	0.9300	C21—C24	1.504 (8)
C3—C4	1.361 (7)	C22—C23	1.379 (7)
C3—Br1	1.898 (5)	C22—H22	0.9300
C4—C5	1.388 (6)	C23—H23	0.9300
C4—Br2	1.899 (4)	C24—H24A	0.9600
C5—C6	1.374 (5)	C24—H24B	0.9600
C5—H5	0.9300	C24—H24C	0.9600
C6—O2	1.368 (5)	C25—N1	1.456 (6)
C7—O2	1.427 (5)	C25—C26	1.506 (7)
C7—C8	1.510 (6)	C25—H25A	0.9700
C7—H7A	0.9700	C25—H25B	0.9700
C7—H7B	0.9700	C26—C27	1.513 (7)
C8—N1	1.462 (6)	C26—H26A	0.9700
C8—H8A	0.9700	C26—H26B	0.9700
C8—H8B	0.9700	C27—N3	1.462 (7)
C9—O1	1.442 (5)	C27—H27A	0.9700
C9—C10	1.503 (6)	C27—H27B	0.9700
C9—H9A	0.9700	C28—N3	1.451 (8)
C9—H9B	0.9700	C28—C29	1.516 (8)
C10—N2	1.461 (6)	C28—H28A	0.9700
C10—H10A	0.9700	C28—H28B	0.9700
C10—H10B	0.9700	C29—C30	1.501 (7)
C11—C16	1.371 (7)	C29—H29A	0.9700
C11—C12	1.390 (8)	C29—H29B	0.9700
C11—H11	0.9300	C30—N2	1.465 (6)
C12—C13	1.376 (8)	C30—H30A	0.9700
C12—H12	0.9300	C30—H30B	0.9700
C13—C14	1.365 (8)	C31A—N3	1.42 (4)
C13—C17	1.511 (8)	C31A—H31A	0.9600
C14—C15	1.389 (8)	C31A—H31B	0.9600
C14—H14	0.9300	C31A—H31C	0.9600
C15—C16	1.380 (7)	C31B—N3	1.58 (6)
C15—H15	0.9300	C31B—H31D	0.9600
C16—S1	1.762 (5)	C31B—H31E	0.9600
C17—H17A	0.9600	C31B—H31F	0.9600
C17—H17B	0.9600	N1—S1	1.604 (4)
C17—H17C	0.9600	N2—S2	1.613 (4)
C18—C23	1.377 (7)	O3—S1	1.432 (4)
C18—C19	1.392 (7)	O4—S1	1.434 (4)
C18—S2	1.762 (5)	O5—S2	1.439 (4)
C19—C20	1.370 (8)	O6—S2	1.423 (4)
O1—C1—C2	124.1 (4)	C23—C22—H22	119.1
O1—C1—C6	116.1 (4)	C18—C23—C22	120.0 (5)
C2—C1—C6	119.8 (4)	C18—C23—H23	120.0
C1—C2—C3	120.2 (4)	C22—C23—H23	120.0
C1—C2—H2	119.9	C21—C24—H24A	109.5
C3—C2—H2	119.9	C21—C24—H24B	109.5
C4—C3—C2	120.0 (4)	H24A—C24—H24B	109.5
C4—C3—Br1	123.4 (3)	C21—C24—H24C	109.5
C2—C3—Br1	116.6 (4)	H24A—C24—H24C	109.5
C3—C4—C5	120.0 (4)	H24B—C24—H24C	109.5
C3—C4—Br2	122.1 (3)	N1—C25—C26	112.4 (4)
C5—C4—Br2	117.9 (4)	N1—C25—H25A	109.1
C6—C5—C4	120.6 (4)	C26—C25—H25A	109.1
C6—C5—H5	119.7	N1—C25—H25B	109.1
C4—C5—H5	119.7	C26—C25—H25B	109.1
O2—C6—C5	125.2 (4)	H25A—C25—H25B	107.9
O2—C6—C1	115.4 (3)	C25—C26—C27	112.8 (5)
C5—C6—C1	119.4 (4)	C25—C26—H26A	109.0
O2—C7—C8	108.0 (3)	C27—C26—H26A	109.0
O2—C7—H7A	110.1	C25—C26—H26B	109.0
C8—C7—H7A	110.1	C27—C26—H26B	109.0
O2—C7—H7B	110.1	H26A—C26—H26B	107.8
C8—C7—H7B	110.1	N3—C27—C26	113.0 (4)
H7A—C7—H7B	108.4	N3—C27—H27A	109.0
N1—C8—C7	115.3 (4)	C26—C27—H27A	109.0
N1—C8—H8A	108.5	N3—C27—H27B	109.0
C7—C8—H8A	108.5	C26—C27—H27B	109.0
N1—C8—H8B	108.5	H27A—C27—H27B	107.8
C7—C8—H8B	108.5	N3—C28—C29	112.1 (5)
H8A—C8—H8B	107.5	N3—C28—H28A	109.2
O1—C9—C10	107.2 (4)	C29—C28—H28A	109.2
O1—C9—H9A	110.3	N3—C28—H28B	109.2
C10—C9—H9A	110.3	C29—C28—H28B	109.2
O1—C9—H9B	110.3	H28A—C28—H28B	107.9
C10—C9—H9B	110.3	C30—C29—C28	112.0 (5)
H9A—C9—H9B	108.5	C30—C29—H29A	109.2
N2—C10—C9	115.0 (4)	C28—C29—H29A	109.2
N2—C10—H10A	108.5	C30—C29—H29B	109.2
C9—C10—H10A	108.5	C28—C29—H29B	109.2
N2—C10—H10B	108.5	H29A—C29—H29B	107.9
C9—C10—H10B	108.5	N2—C30—C29	113.3 (4)
H10A—C10—H10B	107.5	N2—C30—H30A	108.9
C16—C11—C12	119.5 (5)	C29—C30—H30A	108.9
C16—C11—H11	120.2	N2—C30—H30B	108.9
C12—C11—H11	120.2	C29—C30—H30B	108.9
C13—C12—C11	122.0 (6)	H30A—C30—H30B	107.7
C13—C12—H12	119.0	N3—C31A—H31A	109.5
C11—C12—H12	119.0	N3—C31A—H31B	109.5
C14—C13—C12	117.6 (5)	N3—C31A—H31C	109.5
C14—C13—C17	122.2 (6)	N3—C31B—H31D	109.5
C12—C13—C17	120.2 (6)	N3—C31B—H31E	109.5
C13—C14—C15	121.5 (5)	H31D—C31B—H31E	109.5
C13—C14—H14	119.3	N3—C31B—H31F	109.5
C15—C14—H14	119.3	H31D—C31B—H31F	109.5
C16—C15—C14	120.2 (5)	H31E—C31B—H31F	109.5
C16—C15—H15	119.9	C25—N1—C8	117.6 (4)
C14—C15—H15	119.9	C25—N1—S1	121.2 (3)
C11—C16—C15	119.1 (5)	C8—N1—S1	120.7 (3)
C11—C16—S1	120.0 (4)	C10—N2—C30	117.7 (4)
C15—C16—S1	120.7 (4)	C10—N2—S2	120.3 (3)
C13—C17—H17A	109.5	C30—N2—S2	119.9 (3)
C13—C17—H17B	109.5	C31A—N3—C28	102 (5)
H17A—C17—H17B	109.5	C31A—N3—C27	109 (2)
C13—C17—H17C	109.5	C28—N3—C27	111.2 (5)
H17A—C17—H17C	109.5	C28—N3—C31B	122 (3)
H17B—C17—H17C	109.5	C27—N3—C31B	110 (2)
C23—C18—C19	119.0 (5)	C1—O1—C9	116.4 (3)
C23—C18—S2	120.8 (4)	C6—O2—C7	117.8 (3)
C19—C18—S2	120.2 (4)	O3—S1—O4	120.3 (3)
C20—C19—C18	119.0 (5)	O3—S1—N1	107.0 (2)
C20—C19—H19	120.5	O4—S1—N1	107.1 (2)
C18—C19—H19	120.5	O3—S1—C16	106.4 (2)
C21—C20—C19	123.1 (5)	O4—S1—C16	108.2 (3)
C21—C20—H20	118.4	N1—S1—C16	107.1 (2)
C19—C20—H20	118.4	O6—S2—O5	120.3 (3)
C20—C21—C22	116.9 (5)	O6—S2—N2	106.7 (2)
C20—C21—C24	122.1 (5)	O5—S2—N2	106.3 (2)
C22—C21—C24	120.9 (5)	O6—S2—C18	106.9 (2)
C21—C22—C23	121.9 (5)	O5—S2—C18	107.5 (2)
C21—C22—H22	119.1	N2—S2—C18	108.7 (2)
O1—C1—C2—C3	179.8 (4)	C26—C25—N1—S1	−110.2 (4)
C6—C1—C2—C3	0.6 (7)	C7—C8—N1—C25	100.3 (5)
C1—C2—C3—C4	1.4 (8)	C7—C8—N1—S1	−71.1 (5)
C1—C2—C3—Br1	−176.8 (4)	C9—C10—N2—C30	92.1 (5)
C2—C3—C4—C5	−2.2 (8)	C9—C10—N2—S2	−71.1 (5)
Br1—C3—C4—C5	175.9 (4)	C29—C30—N2—C10	99.7 (5)
C2—C3—C4—Br2	179.4 (4)	C29—C30—N2—S2	−97.0 (5)
Br1—C3—C4—Br2	−2.5 (6)	C29—C28—N3—C31A	79 (4)
C3—C4—C5—C6	0.9 (7)	C29—C28—N3—C27	−165.4 (5)
Br2—C4—C5—C6	179.4 (3)	C29—C28—N3—C31B	62 (3)
C4—C5—C6—O2	−177.6 (4)	C26—C27—N3—C31A	−174 (6)
C4—C5—C6—C1	1.1 (7)	C26—C27—N3—C28	74.0 (7)
O1—C1—C6—O2	−2.3 (5)	C26—C27—N3—C31B	−147 (3)
C2—C1—C6—O2	177.0 (4)	C2—C1—O1—C9	17.1 (6)
O1—C1—C6—C5	178.9 (4)	C6—C1—O1—C9	−163.6 (4)
C2—C1—C6—C5	−1.8 (6)	C10—C9—O1—C1	161.3 (4)
O2—C7—C8—N1	−62.9 (5)	C5—C6—O2—C7	−4.6 (6)
O1—C9—C10—N2	−54.1 (5)	C1—C6—O2—C7	176.7 (4)
C16—C11—C12—C13	1.4 (9)	C8—C7—O2—C6	166.7 (4)
C11—C12—C13—C14	−3.7 (9)	C25—N1—S1—O3	159.0 (3)
C11—C12—C13—C17	175.8 (6)	C8—N1—S1—O3	−30.0 (4)
C12—C13—C14—C15	3.1 (9)	C25—N1—S1—O4	28.7 (4)
C17—C13—C14—C15	−176.5 (5)	C8—N1—S1—O4	−160.3 (3)
C13—C14—C15—C16	−0.1 (9)	C25—N1—S1—C16	−87.3 (4)
C12—C11—C16—C15	1.6 (8)	C8—N1—S1—C16	83.8 (4)
C12—C11—C16—S1	−174.5 (4)	C11—C16—S1—O3	179.6 (4)
C14—C15—C16—C11	−2.2 (8)	C15—C16—S1—O3	3.5 (5)
C14—C15—C16—S1	173.8 (4)	C11—C16—S1—O4	−49.8 (5)
C23—C18—C19—C20	−0.7 (8)	C15—C16—S1—O4	134.2 (5)
S2—C18—C19—C20	176.5 (4)	C11—C16—S1—N1	65.4 (5)
C18—C19—C20—C21	−0.4 (9)	C15—C16—S1—N1	−110.6 (4)
C19—C20—C21—C22	1.4 (9)	C10—N2—S2—O6	−154.2 (3)
C19—C20—C21—C24	−178.7 (6)	C30—N2—S2—O6	42.9 (4)
C20—C21—C22—C23	−1.2 (8)	C10—N2—S2—O5	−24.7 (4)
C24—C21—C22—C23	178.8 (5)	C30—N2—S2—O5	172.5 (3)
C19—C18—C23—C22	0.9 (8)	C10—N2—S2—C18	90.8 (3)
S2—C18—C23—C22	−176.4 (4)	C30—N2—S2—C18	−72.0 (4)
C21—C22—C23—C18	0.1 (8)	C23—C18—S2—O6	−35.0 (5)
N1—C25—C26—C27	−178.9 (4)	C19—C18—S2—O6	147.8 (4)
C25—C26—C27—N3	59.2 (7)	C23—C18—S2—O5	−165.5 (4)
N3—C28—C29—C30	64.1 (8)	C19—C18—S2—O5	17.3 (5)
C28—C29—C30—N2	−157.2 (6)	C23—C18—S2—N2	79.8 (4)
C26—C25—N1—C8	78.5 (5)	C19—C18—S2—N2	−97.4 (4)