2,4,6-Tri­methyl-1,3,5-tris(4-methyl­thia­zol-2-yl­sulfanyl­methyl)­benzene

The title compound, C₂₄H₂₇N₃S₆, crystallizes in the monoclinic space group P2₁/n. All of the 4-methyl­thia­zol-2-yl­sulfanyl groups point to the same side of the central benzene ring, resulting in a tripodal arrangement.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.006 Å
• R factor = 0.059
• wR factor = 0.114
• Data-to-parameter ratio = 13.3

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT026_ALERT_3_C Ratio Observed / Unique Reflections too Low ..         49 Perc.
PLAT220_ALERT_2_C Large Non-Solvent    C     Ueq(max)/Ueq(min) .       2.63 Ratio
PLAT241_ALERT_2_C Check High   U(eq) as Compared to Neighbors ..           S1
PLAT241_ALERT_2_C Check High   U(eq) as Compared to Neighbors ..           S3
PLAT241_ALERT_2_C Check High   U(eq) as Compared to Neighbors ..           S4
PLAT241_ALERT_2_C Check High   U(eq) as Compared to Neighbors ..           S5
PLAT241_ALERT_2_C Check High   U(eq) as Compared to Neighbors ..          S6'
PLAT241_ALERT_2_C Check High   U(eq) as Compared to Neighbors ..           S6
PLAT242_ALERT_2_C Check Low    U(eq) as Compared to Neighbors ..          C16
PLAT242_ALERT_2_C Check Low    U(eq) as Compared to Neighbors ..          C18
PLAT242_ALERT_2_C Check Low    U(eq) as Compared to Neighbors ..         C21'
PLAT242_ALERT_2_C Check Low    U(eq) as Compared to Neighbors ..          C21
PLAT301_ALERT_3_C Main Residue  Disorder .......................      15.00 Perc.
PLAT322_ALERT_2_C Check Hybridisation of  S2     in Main Residue          ?
PLAT322_ALERT_2_C Check Hybridisation of  S4     in Main Residue          ?
PLAT340_ALERT_3_C Low Bond Precision on C-C bonds (x 1000) Ang..          6
PLAT380_ALERT_4_C Incorrectly Oriented X(sp2)-Methyl Moiety ....           C14
PLAT413_ALERT_2_C Short Inter XH3 .. XHn  : H10B    .. H24B    =       2.11 Ang.
PLAT779_ALERT_2_C Suspect or Irrelevant (Bond) Angle in CIF ....       7.00 Deg.
              C21  -S5   -C21'    1.555   1.555   1.555

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
  19 ALERT level C = Check and explain
   0 ALERT level G = General alerts; check

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
  15 ALERT type 2 Indicator that the structure model may be wrong or deficient
   3 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion

---

S1. Comment

We were presently involved in the synthesis of the multithiazoles, because thiazole and its derivatives are of considerable interest due to the fact that they exhibit remarkable bioactivities (Tian et al., 1996; Sasaki, 1994, 1996) and act as potential donors to transition metals for the generation of one-, two- and three-dimensional coordination networks (Liu et al., 2001; Sun et al., 1997; Fisher et al., 1985). Thus, we were prompted to explore new compounds containing two or more thiazolyl groups using different linkages. The selection of the linkages is crucial; the existing functions of linkages and the availability of the starting materials from commercial sources are two aspects of primary consideration. Herein we report the synthesis and the structure of a new flexible ligand containing three thiazolyl groups, namely 2,4,6-trimethyl-1,3,5-tris(4-methylthiazol-2-ylsulfanylmethyl)benzene, (I).

As shown in Fig. 1, the tripodal arrangement of all 4-methylthiazol-2-ylsulfanyl groups gives a conformation with all S atoms ready for facile coordination with a metal ion. The methyl and methylene groups bonded to the benzene ring are nearly coplanar with the benzene plane, with the largest deviation of 0.1504 (8) Å for atom C10. Similar situations have been found between the methyl groups and the bonded thiazole rings in the 4-methylthiazol-2-yl groups. Three exocyclic S atoms (viz. S1, S3 and S5) are approximately equidistant from the benzene ring, forming an angle of 2.2 (9)° between plane defined as S1/S3/S5 and the benzene plane.

S2. Experimental

2,4,6-Trimethyl-1,3,5-tris(bromomethyl)benzene was prepared according to a reported method (van der Made & van der Made, 1993). The title compound was synthesized according to a reported procedure (Zhang et al., 2003) by the reaction of 2,4,6-trimethyl-1,3,5-tris(bromomethyl)benzene and potassium 4-methylthiazolylthiolate in EtOH at 323–333 K; yield 87.4%; m.p. 388–389 K; IR (KBr) 3111 (w), 2960 (w), 2916 (w), 1527 (ms), 1414 (s), 1414 (s), 1372 (ms), 1289 (s), 1032 (versus), 723 (w), 706 (ms) cm⁻¹; ¹H NMR (CDCl₃) δ 6.81 (3H, s), 4.49 (6H, s), 2.49 (9H, s), 2.45 (9H, s) p.p.m.; elemental analysis calculated for C₂₄H₂₇N₃S₆ C 52.40, H 4.90, N 7.63%; found C 52.40, H 4.88, N 7.47%. The single crystals of (I), suitable for X-ray analysis, were obtained by slow diffusion of acetone into the chloroform solution of (I).

S3. Refinement

In the disorderd thiazolyl ring, the bonds S6—C21, S6–22, S6'-C21', S6'-C22' were restrained to 1.71 (1) Å and the angles C21—S6—C22, C21'-S6'-C22' to 89 (1)°; other C—C and C—N bond parameters were restrained to appropriate values. The primed atoms have occupancy 0.53 (3) and the unprimed 0.47 (3).

Computing details

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

Figures

Fig. 1. The molecular structure of (I), showing the atom-numbering scheme and displacement ellipsoids at the 30% probability level.

2,4,6-Trimethyl-1,3,5-tris(4-methylthiazol-2-ylsulfanylmethyl)benzene

Crystal data

C24H27N3S6	F(000) = 1152
Mr = 549.91	Dx = 1.343 Mg m^−3
Monoclinic, P21/n	Melting point = 388–389 K
Hall symbol: -P 2yn	Mo Kα radiation, λ = 0.71073 Å
a = 12.216 (4) Å	Cell parameters from 992 reflections
b = 17.801 (5) Å	θ = 2.5–21.4°
c = 12.528 (4) Å	µ = 0.52 mm^−1
β = 93.420 (6)°	T = 293 K
V = 2719.4 (15) Å^3	Prism, colorless
Z = 4	0.25 × 0.20 × 0.15 mm

Data collection

Bruker SMART CCD area-detector diffractometer	4780 independent reflections
Radiation source: fine-focus sealed tube	2335 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.069
ϕ and ω scans	θmax = 25.0°, θmin = 2.0°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −14→13
Tmin = 0.880, Tmax = 0.927	k = −17→21
12608 measured reflections	l = −10→14

Refinement

Refinement on F^2	252 restraints
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F^2 > 2σ(F^2)] = 0.059	w = 1/[σ^2(Fo^2) + (0.0343P)^2 + 0.7831P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.114	(Δ/σ)max = 0.003
S = 1.00	Δρmax = 0.25 e Å^−3
4772 reflections	Δρmin = −0.19 e Å^−3
360 parameters

Special details

Experimental. The corresponding bond distances and angles of the disorderd thiazolyl ring S6'-C21'-C22'-C23'-N3'-C24' were restrained to that of S6—C21—C22—C23—N3—C24. i.e. the bond lengths S6—C21, S6–22, S6'-C21', S6'-C22' are restrained to 1.71 (1) Å, and the angles C21—S6—C22, C21'-S6'-C22' are restrained to 89 (1)°, other C—C and C—N bond parameters are restrained to appropriate values.

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 > 2σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
S1	0.58944 (9)	0.04420 (6)	0.72001 (10)	0.0737 (4)
S2	0.38138 (9)	0.11800 (7)	0.78092 (10)	0.0697 (4)
S3	0.89432 (12)	−0.22489 (6)	0.57718 (9)	0.0802 (4)
S4	0.87887 (13)	−0.38177 (7)	0.49189 (14)	0.1094 (5)
S5	1.07953 (10)	0.01463 (6)	0.89455 (9)	0.0730 (4)
S6	1.2236 (12)	0.0415 (6)	1.0833 (12)	0.092 (3)	0.47 (3)
C21	1.167 (2)	0.0760 (10)	0.9661 (14)	0.047 (5)	0.47 (3)
C22	1.2816 (17)	0.1276 (9)	1.1064 (14)	0.084 (6)	0.47 (3)
H22	1.3261	0.1399	1.1667	0.101*	0.47 (3)
C23	1.2551 (16)	0.1748 (8)	1.0272 (14)	0.063 (6)	0.47 (3)
N3	1.188 (3)	0.1450 (11)	0.9446 (14)	0.051 (6)	0.47 (3)
C24	1.290 (2)	0.2560 (9)	1.018 (2)	0.090 (9)	0.47 (3)
H24A	1.3399	0.2687	1.0774	0.135*	0.47 (3)
H24B	1.2269	0.2880	1.0178	0.135*	0.47 (3)
H24C	1.3261	0.2629	0.9525	0.135*	0.47 (3)
S6'	1.1851 (12)	0.0650 (9)	1.1088 (7)	0.089 (3)	0.53 (3)
C21'	1.154 (2)	0.0802 (9)	0.9754 (12)	0.052 (5)	0.53 (3)
C22'	1.2543 (15)	0.1484 (10)	1.1150 (12)	0.076 (5)	0.53 (3)
H22A	1.2900	0.1682	1.1763	0.092*	0.53 (3)
C23'	1.2495 (13)	0.1812 (6)	1.0192 (13)	0.053 (5)	0.53 (3)
N3'	1.192 (2)	0.1422 (9)	0.9379 (13)	0.050 (5)	0.53 (3)
C24'	1.3007 (19)	0.2557 (7)	0.9911 (18)	0.069 (5)	0.53 (3)
H24D	1.3365	0.2773	1.0541	0.103*	0.53 (3)
H24E	1.2445	0.2892	0.9630	0.103*	0.53 (3)
H24F	1.3534	0.2478	0.9384	0.103*	0.53 (3)
N1	0.5027 (3)	0.17344 (19)	0.6409 (3)	0.0618 (10)
N2	0.9259 (3)	−0.27008 (19)	0.3751 (3)	0.0674 (10)
C1	0.7899 (3)	0.0318 (2)	0.6336 (3)	0.0470 (10)
C2	0.8783 (3)	0.0609 (2)	0.6969 (3)	0.0469 (10)
C3	0.9793 (3)	0.0248 (2)	0.6980 (3)	0.0442 (9)
C4	0.9924 (3)	−0.0414 (2)	0.6398 (3)	0.0468 (10)
C5	0.9029 (3)	−0.0700 (2)	0.5779 (3)	0.0494 (10)
C6	0.8012 (3)	−0.0347 (2)	0.5771 (3)	0.0513 (10)
C7	0.7034 (3)	−0.0687 (2)	0.5134 (4)	0.0808 (14)
H7A	0.6371	−0.0552	0.5461	0.121*
H7B	0.7105	−0.1224	0.5126	0.121*
H7C	0.7010	−0.0500	0.4415	0.121*
C8	1.1015 (3)	−0.0820 (2)	0.6446 (3)	0.0711 (13)
H8A	1.0892	−0.1352	0.6403	0.107*
H8B	1.1417	−0.0702	0.7106	0.107*
H8C	1.1429	−0.0663	0.5857	0.107*
C9	0.8637 (3)	0.1293 (2)	0.7669 (3)	0.0690 (13)
H9A	0.9000	0.1716	0.7373	0.103*
H9B	0.8949	0.1195	0.8377	0.103*
H9C	0.7870	0.1401	0.7701	0.103*
C10	0.6835 (3)	0.0744 (2)	0.6222 (3)	0.0615 (12)
H10A	0.6500	0.0666	0.5509	0.074*
H10B	0.6980	0.1277	0.6311	0.074*
C11	0.4942 (3)	0.1174 (2)	0.7055 (3)	0.0546 (11)
C12	0.3422 (4)	0.2001 (2)	0.7194 (4)	0.0697 (13)
H12	0.2786	0.2264	0.7326	0.084*
C13	0.4142 (4)	0.2216 (2)	0.6503 (4)	0.0656 (12)
C14	0.4099 (4)	0.2905 (3)	0.5811 (4)	0.1088 (19)
H14A	0.4074	0.2759	0.5072	0.163*
H14B	0.4741	0.3206	0.5973	0.163*
H14C	0.3456	0.3192	0.5945	0.163*
C15	0.9189 (3)	−0.13771 (19)	0.5068 (3)	0.0620 (12)
H15A	0.9932	−0.1377	0.4834	0.074*
H15B	0.8689	−0.1344	0.4438	0.074*
C16	0.9039 (4)	−0.2878 (2)	0.4713 (4)	0.0675 (13)
C17	0.8996 (5)	−0.3966 (3)	0.3602 (5)	0.110 (2)
H17	0.8946	−0.4434	0.3273	0.132*
C18	0.9241 (4)	−0.3330 (3)	0.3096 (5)	0.0823 (15)
C19	0.9500 (5)	−0.3251 (3)	0.1959 (4)	0.117 (2)
H19A	0.9079	−0.2846	0.1638	0.175*
H19B	0.9322	−0.3709	0.1585	0.175*
H19C	1.0268	−0.3146	0.1919	0.175*
C20	1.0758 (3)	0.0581 (2)	0.7634 (3)	0.0566 (11)
H20A	1.0671	0.1120	0.7697	0.068*
H20B	1.1435	0.0481	0.7293	0.068*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0582 (8)	0.0782 (8)	0.0866 (9)	0.0139 (6)	0.0210 (7)	0.0264 (7)
S2	0.0516 (7)	0.0878 (9)	0.0703 (8)	0.0050 (6)	0.0096 (6)	−0.0024 (7)
S3	0.1171 (11)	0.0646 (8)	0.0590 (8)	−0.0089 (7)	0.0061 (7)	−0.0015 (6)
S4	0.1386 (14)	0.0576 (9)	0.1305 (15)	−0.0007 (8)	−0.0041 (11)	0.0015 (8)
S5	0.0888 (9)	0.0709 (8)	0.0571 (8)	−0.0337 (7)	−0.0151 (7)	0.0128 (6)
S6	0.097 (5)	0.092 (4)	0.080 (4)	−0.016 (3)	−0.049 (3)	0.023 (3)
C21	0.041 (10)	0.061 (11)	0.040 (9)	−0.008 (9)	0.009 (8)	−0.002 (9)
C22	0.075 (10)	0.106 (11)	0.067 (9)	−0.019 (9)	−0.034 (8)	0.016 (8)
C23	0.061 (11)	0.071 (11)	0.056 (11)	−0.010 (10)	−0.012 (10)	−0.008 (10)
N3	0.056 (11)	0.061 (11)	0.034 (9)	0.007 (10)	−0.007 (9)	−0.010 (9)
C24	0.120 (17)	0.099 (14)	0.049 (12)	0.014 (11)	−0.009 (10)	0.010 (10)
S6'	0.098 (5)	0.108 (5)	0.058 (3)	−0.050 (4)	−0.026 (3)	0.032 (3)
C21'	0.034 (8)	0.065 (10)	0.055 (10)	−0.011 (7)	−0.009 (8)	0.010 (8)
C22'	0.071 (9)	0.088 (9)	0.066 (8)	−0.039 (8)	−0.029 (7)	0.008 (7)
C23'	0.045 (9)	0.061 (9)	0.052 (9)	−0.003 (8)	0.009 (8)	−0.005 (8)
N3'	0.056 (10)	0.043 (9)	0.053 (10)	−0.013 (8)	0.007 (8)	−0.002 (8)
C24'	0.097 (11)	0.057 (8)	0.054 (11)	−0.037 (8)	0.014 (8)	−0.036 (6)
N1	0.055 (2)	0.062 (2)	0.068 (3)	0.006 (2)	0.0016 (19)	0.003 (2)
N2	0.076 (3)	0.061 (2)	0.063 (3)	0.0150 (19)	−0.014 (2)	−0.015 (2)
C1	0.043 (3)	0.057 (3)	0.042 (2)	−0.002 (2)	0.009 (2)	0.008 (2)
C2	0.059 (3)	0.046 (2)	0.037 (2)	−0.006 (2)	0.009 (2)	−0.0013 (19)
C3	0.045 (3)	0.051 (2)	0.038 (2)	−0.008 (2)	0.0060 (19)	0.0013 (19)
C4	0.048 (3)	0.052 (3)	0.042 (2)	0.000 (2)	0.010 (2)	0.002 (2)
C5	0.060 (3)	0.051 (2)	0.038 (2)	−0.007 (2)	0.009 (2)	−0.002 (2)
C6	0.048 (3)	0.064 (3)	0.042 (3)	−0.011 (2)	0.001 (2)	0.000 (2)
C7	0.067 (3)	0.100 (4)	0.072 (3)	−0.013 (3)	−0.016 (3)	−0.020 (3)
C8	0.064 (3)	0.074 (3)	0.076 (3)	0.012 (2)	0.007 (3)	−0.005 (2)
C9	0.080 (3)	0.062 (3)	0.066 (3)	0.005 (2)	0.008 (3)	−0.008 (2)
C10	0.050 (3)	0.073 (3)	0.062 (3)	0.005 (2)	0.010 (2)	0.012 (2)
C11	0.045 (3)	0.065 (3)	0.053 (3)	0.001 (2)	0.001 (2)	−0.002 (2)
C12	0.055 (3)	0.081 (3)	0.072 (3)	0.012 (3)	−0.004 (3)	−0.021 (3)
C13	0.067 (4)	0.058 (3)	0.070 (3)	0.010 (3)	−0.010 (3)	−0.011 (3)
C14	0.121 (5)	0.074 (4)	0.132 (5)	0.027 (3)	0.009 (4)	0.016 (3)
C15	0.077 (3)	0.062 (3)	0.047 (3)	0.000 (2)	0.002 (2)	−0.005 (2)
C16	0.073 (3)	0.055 (3)	0.072 (3)	0.002 (2)	−0.012 (3)	−0.007 (3)
C17	0.134 (5)	0.074 (4)	0.120 (5)	0.013 (3)	−0.018 (4)	−0.035 (4)
C18	0.081 (4)	0.075 (4)	0.087 (4)	0.018 (3)	−0.026 (3)	−0.024 (3)
C19	0.138 (5)	0.126 (5)	0.083 (5)	0.043 (4)	−0.021 (4)	−0.040 (4)
C20	0.061 (3)	0.058 (3)	0.050 (3)	−0.012 (2)	0.000 (2)	0.005 (2)

Geometric parameters (Å, º)

S1—C11	1.748 (4)	C1—C10	1.503 (5)
S1—C10	1.811 (4)	C2—C3	1.392 (5)
S2—C12	1.708 (5)	C2—C9	1.518 (5)
S2—C11	1.717 (4)	C3—C4	1.398 (5)
S3—C16	1.745 (5)	C3—C20	1.516 (5)
S3—C15	1.819 (4)	C4—C5	1.398 (5)
S4—C17	1.705 (6)	C4—C8	1.515 (5)
S4—C16	1.724 (4)	C5—C6	1.392 (5)
S5—C21	1.736 (10)	C5—C15	1.518 (5)
S5—C21'	1.763 (9)	C6—C7	1.521 (5)
S5—C20	1.814 (4)	C7—H7A	0.9600
S6—C21	1.702 (12)	C7—H7B	0.9600
S6—C22	1.706 (11)	C7—H7C	0.9600
C21—N3	1.286 (10)	C8—H8A	0.9600
C22—C23	1.325 (12)	C8—H8B	0.9600
C22—H22	0.9300	C8—H8C	0.9600
C23—N3	1.389 (10)	C9—H9A	0.9600
C23—C24	1.516 (8)	C9—H9B	0.9600
C24—H24A	0.9600	C9—H9C	0.9600
C24—H24B	0.9600	C10—H10A	0.9700
C24—H24C	0.9600	C10—H10B	0.9700
S6'—C22'	1.707 (9)	C12—C13	1.326 (6)
S6'—C21'	1.713 (10)	C12—H12	0.9300
C21'—N3'	1.296 (9)	C13—C14	1.502 (6)
C22'—C23'	1.332 (10)	C14—H14A	0.9600
C22'—H22A	0.9300	C14—H14B	0.9600
C23'—N3'	1.388 (9)	C14—H14C	0.9600
C23'—C24'	1.517 (8)	C15—H15A	0.9700
C24'—H24D	0.9600	C15—H15B	0.9700
C24'—H24E	0.9600	C17—C18	1.341 (6)
C24'—H24F	0.9600	C17—H17	0.9300
N1—C11	1.293 (4)	C18—C19	1.483 (7)
N1—C13	1.391 (5)	C19—H19A	0.9600
N2—C16	1.289 (5)	C19—H19B	0.9600
N2—C18	1.388 (5)	C19—H19C	0.9600
C1—C6	1.392 (5)	C20—H20A	0.9700
C1—C2	1.399 (5)	C20—H20B	0.9700
C11—S1—C10	98.84 (19)	C4—C8—H8A	109.5
C12—S2—C11	88.3 (2)	C4—C8—H8B	109.5
C16—S3—C15	99.1 (2)	H8A—C8—H8B	109.5
C17—S4—C16	88.1 (3)	C4—C8—H8C	109.5
C21—S5—C21'	7 (2)	H8A—C8—H8C	109.5
C21—S5—C20	100.4 (5)	H8B—C8—H8C	109.5
C21'—S5—C20	102.8 (4)	C2—C9—H9A	109.5
C21—S6—C22	88.1 (6)	C2—C9—H9B	109.5
N3—C21—S6	116.6 (7)	H9A—C9—H9B	109.5
N3—C21—S5	128.1 (11)	C2—C9—H9C	109.5
S6—C21—S5	115.2 (8)	H9A—C9—H9C	109.5
C23—C22—S6	111.2 (8)	H9B—C9—H9C	109.5
C23—C22—H22	124.4	C1—C10—S1	111.4 (3)
S6—C22—H22	124.4	C1—C10—H10A	109.3
C22—C23—N3	115.1 (8)	S1—C10—H10A	109.3
C22—C23—C24	127.2 (10)	C1—C10—H10B	109.3
N3—C23—C24	117.7 (10)	S1—C10—H10B	109.3
C21—N3—C23	109.0 (8)	H10A—C10—H10B	108.0
C22'—S6'—C21'	89.3 (5)	N1—C11—S2	115.9 (3)
N3'—C21'—S6'	115.1 (7)	N1—C11—S1	124.2 (3)
N3'—C21'—S5	122.7 (9)	S2—C11—S1	119.9 (3)
S6'—C21'—S5	122.2 (7)	C13—C12—S2	111.2 (3)
C23'—C22'—S6'	110.2 (7)	C13—C12—H12	124.4
C23'—C22'—H22A	124.9	S2—C12—H12	124.4
S6'—C22'—H22A	124.9	C12—C13—N1	115.3 (4)
C22'—C23'—N3'	115.8 (7)	C12—C13—C14	127.7 (4)
C22'—C23'—C24'	126.6 (9)	N1—C13—C14	117.0 (5)
N3'—C23'—C24'	117.6 (8)	C13—C14—H14A	109.5
C21'—N3'—C23'	109.7 (7)	C13—C14—H14B	109.5
C23'—C24'—H24D	109.5	H14A—C14—H14B	109.5
C23'—C24'—H24E	109.5	C13—C14—H14C	109.5
H24D—C24'—H24E	109.5	H14A—C14—H14C	109.5
C23'—C24'—H24F	109.5	H14B—C14—H14C	109.5
H24D—C24'—H24F	109.5	C5—C15—S3	111.2 (3)
H24E—C24'—H24F	109.5	C5—C15—H15A	109.4
C11—N1—C13	109.3 (4)	S3—C15—H15A	109.4
C16—N2—C18	111.1 (4)	C5—C15—H15B	109.4
C6—C1—C2	120.4 (4)	S3—C15—H15B	109.4
C6—C1—C10	119.4 (4)	H15A—C15—H15B	108.0
C2—C1—C10	120.1 (4)	N2—C16—S4	115.2 (3)
C3—C2—C1	119.3 (3)	N2—C16—S3	125.6 (3)
C3—C2—C9	120.0 (4)	S4—C16—S3	119.2 (3)
C1—C2—C9	120.7 (4)	C18—C17—S4	112.1 (4)
C2—C3—C4	120.8 (3)	C18—C17—H17	123.9
C2—C3—C20	119.1 (3)	S4—C17—H17	123.9
C4—C3—C20	120.1 (4)	C17—C18—N2	113.4 (5)
C5—C4—C3	119.1 (4)	C17—C18—C19	126.9 (5)
C5—C4—C8	120.3 (3)	N2—C18—C19	119.7 (5)
C3—C4—C8	120.6 (4)	C18—C19—H19A	109.5
C6—C5—C4	120.5 (3)	C18—C19—H19B	109.5
C6—C5—C15	120.0 (4)	H19A—C19—H19B	109.5
C4—C5—C15	119.4 (4)	C18—C19—H19C	109.5
C1—C6—C5	119.7 (3)	H19A—C19—H19C	109.5
C1—C6—C7	120.5 (4)	H19B—C19—H19C	109.5
C5—C6—C7	119.8 (4)	C3—C20—S5	107.4 (2)
C6—C7—H7A	109.5	C3—C20—H20A	110.2
C6—C7—H7B	109.5	S5—C20—H20A	110.2
H7A—C7—H7B	109.5	C3—C20—H20B	110.2
C6—C7—H7C	109.5	S5—C20—H20B	110.2
H7A—C7—H7C	109.5	H20A—C20—H20B	108.5
H7B—C7—H7C	109.5
C22—S6—C21—N3	0.02 (17)	C8—C4—C5—C15	−6.1 (5)
C22—S6—C21—S5	−176 (2)	C2—C1—C6—C5	−4.2 (5)
C21'—S5—C21—N3	−89 (8)	C10—C1—C6—C5	172.9 (3)
C20—S5—C21—N3	22.8 (14)	C2—C1—C6—C7	176.5 (4)
C21'—S5—C21—S6	87 (7)	C10—C1—C6—C7	−6.5 (5)
C20—S5—C21—S6	−161.7 (16)	C4—C5—C6—C1	3.6 (6)
C21—S6—C22—C23	0.03 (16)	C15—C5—C6—C1	−173.3 (3)
S6—C22—C23—N3	−0.1 (3)	C4—C5—C6—C7	−177.1 (4)
S6—C22—C23—C24	−179.9 (3)	C15—C5—C6—C7	6.1 (5)
S6—C21—N3—C23	−0.1 (3)	C6—C1—C10—S1	89.9 (4)
S5—C21—N3—C23	175 (3)	C2—C1—C10—S1	−93.0 (4)
C22—C23—N3—C21	0.1 (4)	C11—S1—C10—C1	166.6 (3)
C24—C23—N3—C21	179.9 (3)	C13—N1—C11—S2	0.2 (4)
C22'—S6'—C21'—N3'	0.02 (17)	C13—N1—C11—S1	−179.3 (3)
C22'—S6'—C21'—S5	178 (2)	C12—S2—C11—N1	0.5 (3)
C21—S5—C21'—N3'	70 (7)	C12—S2—C11—S1	179.9 (3)
C20—S5—C21'—N3'	0.0 (11)	C10—S1—C11—N1	−1.1 (4)
C21—S5—C21'—S6'	−108 (8)	C10—S1—C11—S2	179.5 (2)
C20—S5—C21'—S6'	−178.2 (16)	C11—S2—C12—C13	−1.0 (3)
C21'—S6'—C22'—C23'	0.05 (15)	S2—C12—C13—N1	1.3 (5)
S6'—C22'—C23'—N3'	−0.1 (3)	S2—C12—C13—C14	−179.6 (4)
S6'—C22'—C23'—C24'	−179.9 (3)	C11—N1—C13—C12	−1.0 (5)
S6'—C21'—N3'—C23'	−0.1 (3)	C11—N1—C13—C14	179.9 (4)
S5—C21'—N3'—C23'	−178 (2)	C6—C5—C15—S3	−92.4 (4)
C22'—C23'—N3'—C21'	0.1 (4)	C4—C5—C15—S3	90.7 (4)
C24'—C23'—N3'—C21'	179.9 (3)	C16—S3—C15—C5	173.7 (3)
C6—C1—C2—C3	3.5 (5)	C18—N2—C16—S4	−0.1 (5)
C10—C1—C2—C3	−173.5 (3)	C18—N2—C16—S3	−178.2 (3)
C6—C1—C2—C9	−174.2 (3)	C17—S4—C16—N2	−0.2 (4)
C10—C1—C2—C9	8.8 (5)	C17—S4—C16—S3	178.1 (3)
C1—C2—C3—C4	−2.3 (5)	C15—S3—C16—N2	1.7 (5)
C9—C2—C3—C4	175.5 (3)	C15—S3—C16—S4	−176.3 (3)
C1—C2—C3—C20	177.8 (3)	C16—S4—C17—C18	0.4 (4)
C9—C2—C3—C20	−4.5 (5)	S4—C17—C18—N2	−0.6 (6)
C2—C3—C4—C5	1.6 (5)	S4—C17—C18—C19	178.2 (4)
C20—C3—C4—C5	−178.4 (3)	C16—N2—C18—C17	0.4 (6)
C2—C3—C4—C8	−177.7 (3)	C16—N2—C18—C19	−178.5 (4)
C20—C3—C4—C8	2.2 (5)	C2—C3—C20—S5	92.4 (4)
C3—C4—C5—C6	−2.3 (5)	C4—C3—C20—S5	−87.6 (4)
C8—C4—C5—C6	177.1 (4)	C21—S5—C20—C3	−164.4 (11)
C3—C4—C5—C15	174.6 (3)	C21'—S5—C20—C3	−157.9 (10)