1,2-Diphenyl-2-(phenyldiazenyl)-2-tosylethanone, an example of a fungicide containing a sulfonyl group

The mol­ecule of the title compound, C₂₇H₂₂N₂O₃S, adopts an irregular propeller shape with the tetrahedral C1 atom pivotal. The α-azo­phenyl and α-phenyl moieties are approximately coplanar. Electrostatic attraction of the oppositely charged atoms generates several short intramolecular contacts involving the sulfonyl, azo and carbonyl groups. Characteristic bond-length distribution of the central part of the mol­ecule indicates that the Coulombic charge transfer is supplemented by hyperconjugation involving donation of electron density from the azo moiety towards the sulfonyl and carbonyl groups.

S1. Comment

The title compound, (I), represents a new group of α-phenylazo-β-keto sulfones characterized by a substantial antimycotic activity (Zakrzewski & Kacała, 1998; Zakrzewski, 1999) which arises from the photodynamic degradation of a fungicide. In the presence of daylight the original compound splits into fragments which are toxic to the fungal mycellium. The present work is part of a larger project carried out in collaboration with A. Zakrzewski (Technical and Agricultural Academy, Bydgoszcz, Poland). Our aim is to identify molecular features which are responsible for the antymycotic activity and to prepare the best fungicide (Wolf, 1999). \sch

Conformation of β-ketosulfones and β-ketosulfoxides is very often controlled by the mutual stereoelectronic charge transfers between the sulfonyl and β-carbonyl groups (Distefano et al., 1996; Olivato et al., 2000, and references therein). These interactions reduce the large positive charge present on the sulfur atom and partially counteract the strong electron-withdrawing capacity of the phenylsulfonyl group. The latter is confirmed by the highly positive value of its Hammett's σ_p constant, 0.70 (Hansch & Leo, 1979). Attractive Coulombic interactions prompt the oppositely charged atoms to be positioned closer than the sums of their van der Waals radii. Indeed, short intramolecular contacts have been often observed in β-ketosulfones and in β-ketosulfoxides (Kucsman & Kapovits, 1985).

A view of compound (I) with the atom-numbering scheme is shown in Fig. 1. Selected geometric parameters are in Table 1. The molecule adopts irregular propeller shape with the pivotal tetrahedral C1 atom. The α-azophenyl and α-phenyl moieties are approximately coplanar.

The electrostatic potential derived atomic charge distribution (S 1.18, O1 − 0.59, O2 − 0.60, O3 − 0.45, N1 − 0.14, N2 − 0.27, C1 − 0.07, C2 0.46 e) clearly shows that within the central part of a molecule the positive charges are located on the S and carbonyl C2 atoms only. Electrostatic attraction of the oppositely charged atoms generates several short intramolecular contacts as listed in the Table 2. In particular, the sulfonyl-S atom forms a short contact with the carbonyl O3 atom [2.946 (2) Å], and the carbonyl C2 atom is positioned close to the azo N2 atom [2.693 (2) Å]. Respective van der Waals radii are 3.32 and 3.25 Å (Bondi, 1964). Shortening of the former distance has been often observed in α,α-unsubstituted-β-ketosulfones and additionally to the electrostatic charge transfer it is also attributed to the anomeric overlapping of the π^*(C2═O3)–σ(S—C1) and π(C2═O3)–σ^*(S—C1) pairs of bonding and non-bonding molecular orbitals (Distefano et al., 1991; Dal Colle et al., 1995). By analogy, the short intramolecular S···N2 contact existing in (I) can be influenced by the π^*(N1═N2)–σ(C1—C2) and π(N1═N2)–σ^*(C1—C2) cross interactions. Anomeric effect is most effective when interacting polar bonds are positioned gauche in respect to each other (Juaristi & Cuevas, 1995, and references therein). Indeed, 12 out of 14 non-cyclic α,α-unsubstituted β-ketosulfones which are reported in the Cambridge Structural Data Base (Allen et al., 1979) adopt conformations which are dominated by gauche arrangements of their S—C1—C2═O3 moieties. In compound (I), the S—C1 and C2═O3 bonds are almost syn-periplanar while conformation of the N1═N2 and C1—C2 bonds is much closer to gauche [the S—C1—C2═O3 and N2═N1—C1—C2 torsion angles are −13.9 (2), 39.8 (2)°, respectively]. It suggests that the latter system is more affected by the anomeric effect while interactions between the S—C1 and C2═O3 bonds are dominated by the non-stereospecific electrostatic Coulombic interactions.

The azo moiety adopts trans conformation. The N1═N2 bond [1.2445 (18) Å] is slightly longer than the similar bond reported in International Tables for Crystallography (Allen et al., 1992) (1.222 Å). The C1—N1 [1.474 (2) Å] is shorter than respective bond in the standard Csp³—-N═N system (1.493 Å). A very long S—C1 [1.8875 (17) Å] is accompanied by a stretched C1—C2 bond [1.539 (2) Å]. The former is much longer than the typical single S—C bond, 1.78 Å. The latter exceeds the single C—C bond as has been found in the aliphatic ketones, C—C(O)—C (1.511 Å). These systematic bond differences resemble the characteristic pattern of bond length changes induced by an anomeric effect (Kirby, 1983; Graczyk & Mikołajczyk, 1994). This effect is partially responsible for the donation of electron density from the azo–N2 towards S and carbonyl–C2 atoms. The resulting hyperconjugative (March, 1992) increase of π character of the C1—N1 bond can be stabilized by conjugation with the α-phenyl ring borne by the C1 atom (Wolf, 2000). It explains the odd conformation of a molecule as characterized by an approximate coplanarity of the opposite located α-phenyl and α-phenylazo fragments.

The azo and carbonyl groups are approximately coplanar with their parent phenyl rings. The C2—C3 bond length [1.501 (2) Å] is closer to a value reported for the Csp³—C_aryl [1.506 Å] than the Csp²—C_aryl (1.470 Å). The N2—C16 [1.430 (2) Å] is very similar to the C_aryl—N═N bond (1.431 Å). The terminal phenyl rings endocyclic bond lengths and valency angles distribution is uniform and doesn't resemble quinoid type structures (Domenicano, 1992). This indicate that the stereoelectronic and the π electrons delocalization involving carbonyl and azo groups are directed towards the central part of a molecule. An influence of the terminal phenyl rings is restricted to the small inductive effect only. All typical bond lengths quoted throughout this paper are taken from Allen et al. (1992).

Examination of intermolecular distances shows that the packing arrangement is not significantly influenced by steric interactions as indentified by sums of the respective van der Waals radii (Bondi, 1964).

S2. Experimental

The title compound was synthesized by reaction of the benzoylphenylmethyl p-tolyl sulfone with phenyldiazonium chloride in the alkaline ethyl alcohol solution (Zakrzewski, 1996). Crystal used for the data collection was obtained by a vapour diffusion. A sample of (I) dissolved in the 2:1 mixture of chloroform and isopropyl alcohol was equilibrated at room temperature against pure isopropyl alcohol for 10 d.

S3. Refinement

All H atoms were located on a difference Fourier map calculated after three cycles of anisotropic refinement. Their positional and isotropic displacement parameters were allowed to refine freely, only the C19—H19 distance was restrained to 1.00 (1) Å. Electrostatic potential derived atomic charges were calculated with Turbomole (MSI, 1996) at the HF/6–31G** level, for the X-ray determined coordinates. The van der Waals fit has been applied.

Computing details

Data collection: KM-4 (Kuma Diffraction, 1991); cell refinement: KM-4; data reduction: DATAPROC 9.0 (Gałdecki et al., 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: InsightII (MSI, 1997) and XP (Siemens, 1990); software used to prepare material for publication: SHELXL97.

Figures

Fig. 1. Molecular structure of the title compound. Displacement ellipsoids are drawn at the 50% probability level.

1,2-Diphenyl-2-(phenyldiazenyl)-2-tosylethanone

Crystal data

C27H22N2O3S	F(000) = 952
Mr = 454.53	Dx = 1.295 Mg m^−3
Monoclinic, P21/c	Cu Kα radiation, λ = 1.54178 Å
a = 11.824 (2) Å	Cell parameters from 80 reflections
b = 17.573 (2) Å	θ = 5–12°
c = 11.960 (2) Å	µ = 1.49 mm^−1
β = 110.24 (1)°	T = 292 K
V = 2331.6 (6) Å^3	Ellipsoidal shape, yellow
Z = 4	0.49 × 0.41 × 0.32 × 0.40 (radius) mm

Data collection

KUMA Diffraction KM-4 diffractometer	3880 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.026
Graphite monochromator	θmax = 80.9°, θmin = 4.0°
ω–2θ scans	h = −15→15
Absorption correction: ψ scan (XEMP; Siemens, 1991)	k = −22→0
Tmin = 0.522, Tmax = 0.621	l = −15→15
9632 measured reflections	3 standard reflections every 100 reflections
5074 independent reflections	intensity decay: 4%

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.042	All H-atom parameters refined
wR(F^2) = 0.133	Calculated w = 1/[σ^2(Fo^2) + (0.0684P)^2 + 0.292P] where P = (Fo^2 + 2Fc^2)/3
S = 1.03	(Δ/σ)max = 0.034
5074 reflections	Δρmax = 0.41 e Å^−3
387 parameters	Δρmin = −0.27 e Å^−3
1 restraint	Extinction correction: SHELXL97 (Sheldrick, 1997), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0011 (2)

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
S	0.78755 (4)	0.52542 (2)	0.23253 (4)	0.06357 (15)
O1	0.69550 (13)	0.58248 (7)	0.20191 (13)	0.0810 (4)
O2	0.90939 (12)	0.54712 (8)	0.29966 (12)	0.0787 (4)
O3	0.57601 (12)	0.42405 (9)	0.16234 (12)	0.0817 (4)
N1	0.85936 (12)	0.40872 (7)	0.38671 (12)	0.0591 (3)
N2	0.86875 (13)	0.35693 (8)	0.31949 (12)	0.0618 (3)
C1	0.74904 (14)	0.45400 (9)	0.33170 (15)	0.0574 (4)
C2	0.63939 (15)	0.40512 (10)	0.26158 (16)	0.0616 (4)
C3	0.60950 (15)	0.33617 (9)	0.32008 (16)	0.0613 (4)
C4	0.51634 (18)	0.29000 (12)	0.2497 (2)	0.0762 (5)
C5	0.4823 (2)	0.22636 (13)	0.2980 (2)	0.0885 (6)
C6	0.5403 (2)	0.20792 (13)	0.4162 (3)	0.0904 (7)
C7	0.6326 (2)	0.25307 (13)	0.4863 (2)	0.0847 (6)
C8	0.66797 (18)	0.31691 (11)	0.43899 (17)	0.0697 (4)
C9	0.78794 (16)	0.48216 (10)	0.10040 (16)	0.0643 (4)
C10	0.6896 (2)	0.49046 (14)	−0.00316 (19)	0.0803 (5)
C11	0.6945 (3)	0.45938 (16)	−0.1069 (2)	0.0957 (7)
C12	0.7920 (3)	0.41947 (14)	−0.1115 (2)	0.0926 (7)
C13	0.8893 (3)	0.41264 (15)	−0.0091 (2)	0.0938 (7)
C14	0.8891 (2)	0.44430 (13)	0.0975 (2)	0.0788 (5)
C15	0.7913 (7)	0.3819 (3)	−0.2261 (4)	0.1394 (15)
C16	0.97414 (16)	0.31105 (9)	0.36939 (16)	0.0625 (4)
C17	1.04274 (19)	0.30953 (12)	0.48927 (19)	0.0766 (5)
C18	1.1425 (2)	0.26263 (15)	0.5278 (2)	0.0954 (7)
C19	1.1743 (2)	0.21860 (14)	0.4476 (3)	0.0983 (7)
C20	1.1061 (2)	0.22078 (13)	0.3291 (3)	0.0950 (7)
C21	1.0053 (2)	0.26624 (11)	0.2890 (2)	0.0797 (5)
C22	0.72284 (16)	0.50199 (9)	0.42575 (15)	0.0612 (4)
C23	0.6102 (2)	0.53355 (15)	0.4019 (2)	0.0928 (7)
C24	0.5854 (3)	0.57897 (18)	0.4851 (3)	0.1071 (8)
C25	0.6716 (3)	0.59363 (15)	0.5914 (3)	0.0953 (7)
C26	0.7841 (2)	0.56275 (15)	0.6160 (2)	0.0922 (7)
C27	0.81084 (19)	0.51762 (12)	0.53385 (18)	0.0737 (5)
H4	0.4732 (19)	0.3038 (12)	0.167 (2)	0.084 (6)*
H5	0.415 (2)	0.1985 (14)	0.246 (2)	0.095 (7)*
H6	0.516 (2)	0.1645 (16)	0.444 (2)	0.105 (8)*
H7	0.672 (2)	0.2387 (16)	0.569 (2)	0.108 (8)*
H8	0.7263 (18)	0.3481 (12)	0.4853 (18)	0.075 (6)*
H10	0.624 (2)	0.5172 (14)	0.005 (2)	0.088 (7)*
H11	0.627 (3)	0.4647 (16)	−0.175 (3)	0.114 (9)*
H13	0.958 (3)	0.385 (2)	−0.011 (3)	0.147 (12)*
H14	0.960 (2)	0.4390 (13)	0.168 (2)	0.091 (7)*
H151	0.745 (3)	0.403 (2)	−0.282 (3)	0.146 (16)*
H152	0.763 (4)	0.327 (3)	−0.221 (4)	0.20 (2)*
H153	0.864 (5)	0.379 (3)	−0.242 (5)	0.22 (3)*
H17	1.0227 (19)	0.3377 (13)	0.5418 (19)	0.082 (6)*
H18	1.193 (3)	0.2673 (18)	0.614 (3)	0.124 (9)*
H19	1.2476 (15)	0.1825 (11)	0.4878 (19)	0.096 (7)*
H20	1.131 (2)	0.1922 (18)	0.276 (3)	0.122 (9)*
H21	0.9407 (17)	0.2634 (11)	0.1886 (18)	0.077 (5)*
H23	0.552 (2)	0.5261 (15)	0.328 (3)	0.107 (9)*
H24	0.502 (3)	0.5994 (19)	0.455 (3)	0.137 (11)*
H25	0.658 (2)	0.6237 (16)	0.652 (2)	0.116 (9)*
H26	0.842 (2)	0.5717 (16)	0.693 (2)	0.110 (9)*
H27	0.892 (2)	0.4975 (13)	0.5479 (18)	0.084 (6)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S	0.0729 (3)	0.0483 (2)	0.0692 (3)	0.00178 (17)	0.0243 (2)	0.00298 (17)
O1	0.0977 (9)	0.0562 (7)	0.0930 (9)	0.0208 (6)	0.0379 (8)	0.0120 (6)
O2	0.0809 (8)	0.0703 (8)	0.0802 (8)	−0.0203 (7)	0.0221 (7)	−0.0026 (6)
O3	0.0744 (8)	0.0847 (9)	0.0723 (8)	−0.0059 (7)	0.0078 (6)	0.0125 (7)
N1	0.0610 (7)	0.0481 (7)	0.0665 (8)	0.0031 (5)	0.0198 (6)	−0.0038 (6)
N2	0.0718 (8)	0.0522 (7)	0.0617 (8)	0.0068 (6)	0.0235 (7)	−0.0023 (6)
C1	0.0604 (8)	0.0475 (7)	0.0625 (9)	0.0036 (6)	0.0191 (7)	0.0001 (6)
C2	0.0608 (9)	0.0565 (9)	0.0654 (9)	0.0017 (7)	0.0191 (8)	−0.0018 (7)
C3	0.0637 (9)	0.0528 (8)	0.0696 (9)	−0.0030 (7)	0.0260 (8)	−0.0055 (7)
C4	0.0747 (11)	0.0693 (11)	0.0819 (13)	−0.0106 (9)	0.0237 (10)	−0.0095 (10)
C5	0.0916 (15)	0.0674 (12)	0.1089 (17)	−0.0229 (11)	0.0376 (13)	−0.0147 (12)
C6	0.1061 (17)	0.0629 (11)	0.1153 (19)	−0.0149 (11)	0.0550 (15)	0.0009 (12)
C7	0.1030 (15)	0.0731 (12)	0.0848 (14)	−0.0066 (11)	0.0413 (12)	0.0070 (11)
C8	0.0782 (12)	0.0632 (10)	0.0697 (10)	−0.0088 (9)	0.0281 (9)	−0.0034 (8)
C9	0.0702 (10)	0.0568 (9)	0.0651 (9)	0.0033 (7)	0.0224 (8)	0.0081 (7)
C10	0.0802 (13)	0.0847 (13)	0.0692 (11)	0.0141 (11)	0.0172 (10)	0.0076 (10)
C11	0.1025 (17)	0.1071 (18)	0.0653 (12)	0.0079 (14)	0.0135 (12)	0.0039 (11)
C12	0.128 (2)	0.0799 (13)	0.0738 (13)	0.0116 (13)	0.0406 (13)	0.0051 (10)
C13	0.1079 (17)	0.0954 (16)	0.0893 (15)	0.0289 (14)	0.0483 (14)	0.0127 (12)
C14	0.0756 (12)	0.0901 (14)	0.0715 (11)	0.0167 (10)	0.0266 (10)	0.0117 (10)
C15	0.210 (5)	0.127 (3)	0.090 (2)	0.026 (3)	0.063 (3)	−0.008 (2)
C16	0.0706 (10)	0.0506 (8)	0.0680 (9)	0.0064 (7)	0.0258 (8)	−0.0023 (7)
C17	0.0825 (12)	0.0746 (12)	0.0702 (11)	0.0177 (10)	0.0232 (9)	−0.0052 (9)
C18	0.0893 (15)	0.1004 (17)	0.0848 (14)	0.0312 (13)	0.0152 (12)	0.0016 (12)
C19	0.0924 (15)	0.0830 (14)	0.1152 (19)	0.0315 (12)	0.0304 (14)	0.0036 (13)
C20	0.1109 (17)	0.0754 (13)	0.1045 (17)	0.0272 (12)	0.0448 (15)	−0.0122 (12)
C21	0.0974 (14)	0.0615 (10)	0.0806 (12)	0.0141 (10)	0.0313 (11)	−0.0098 (9)
C22	0.0658 (9)	0.0514 (8)	0.0685 (9)	0.0018 (7)	0.0258 (8)	−0.0013 (7)
C23	0.0762 (13)	0.1053 (17)	0.0926 (15)	0.0244 (12)	0.0238 (12)	−0.0168 (13)
C24	0.0961 (17)	0.114 (2)	0.121 (2)	0.0289 (15)	0.0500 (16)	−0.0173 (16)
C25	0.1140 (19)	0.0822 (14)	0.1095 (18)	0.0025 (13)	0.0639 (16)	−0.0222 (13)
C26	0.0970 (16)	0.0952 (16)	0.0879 (15)	−0.0097 (13)	0.0365 (13)	−0.0309 (13)
C27	0.0724 (11)	0.0726 (11)	0.0764 (11)	−0.0022 (9)	0.0264 (9)	−0.0154 (9)

Geometric parameters (Å, º)

S—O1	1.4311 (13)	C20—C21	1.376 (3)
S—O2	1.4371 (14)	C22—C27	1.378 (3)
S—C9	1.7551 (19)	C22—C23	1.379 (3)
S—C1	1.8875 (17)	C23—C24	1.383 (3)
O3—C2	1.211 (2)	C24—C25	1.352 (4)
N1—N2	1.2445 (18)	C25—C26	1.371 (4)
N1—C1	1.474 (2)	C26—C27	1.382 (3)
N2—C16	1.430 (2)	C4—H4	0.97 (2)
C1—C22	1.521 (2)	C5—H5	0.96 (2)
C1—C2	1.539 (2)	C6—H6	0.91 (3)
C2—C3	1.501 (2)	C7—H7	0.97 (3)
C3—C8	1.391 (3)	C8—H8	0.90 (2)
C3—C4	1.392 (3)	C10—H10	0.94 (2)
C4—C5	1.381 (3)	C11—H11	0.93 (3)
C5—C6	1.380 (4)	C13—H13	0.95 (4)
C6—C7	1.375 (3)	C14—H14	0.97 (2)
C7—C8	1.385 (3)	C15—H151	0.80 (4)
C9—C14	1.379 (3)	C15—H152	1.03 (5)
C9—C10	1.383 (3)	C15—H153	0.94 (5)
C10—C11	1.375 (3)	C17—H17	0.89 (2)
C11—C12	1.368 (4)	C18—H18	1.00 (3)
C12—C13	1.365 (4)	C19—H19	1.05 (1)
C12—C15	1.519 (4)	C20—H20	0.94 (3)
C13—C14	1.392 (3)	C21—H21	1.18 (2)
C16—C17	1.382 (3)	C23—H23	0.92 (3)
C16—C21	1.387 (3)	C24—H24	0.99 (3)
C17—C18	1.381 (3)	C25—H25	0.95 (3)
C18—C19	1.381 (3)	C26—H26	0.95 (3)
C19—C20	1.368 (4)	C27—H27	0.99 (2)
O1—S—O2	118.93 (9)	C24—C25—C26	119.1 (2)
O1—S—C9	108.16 (9)	C25—C26—C27	121.2 (2)
O2—S—C9	107.67 (9)	C22—C27—C26	119.8 (2)
O1—S—C1	107.41 (8)	C5—C4—H4	120.0 (13)
O2—S—C1	103.80 (8)	C3—C4—H4	119.7 (13)
C9—S—C1	110.74 (8)	C6—C5—H5	123.4 (15)
N2—N1—C1	111.68 (13)	C4—C5—H5	116.2 (15)
N1—N2—C16	113.73 (14)	C7—C6—H6	122.7 (16)
N1—C1—C22	110.14 (13)	C5—C6—H6	117.4 (16)
N1—C1—C2	112.97 (13)	C6—C7—H7	117.9 (16)
C22—C1—C2	111.32 (13)	C8—C7—H7	121.6 (16)
N1—C1—S	105.71 (11)	C7—C8—H8	121.0 (13)
C22—C1—S	104.55 (10)	C3—C8—H8	118.9 (13)
C2—C1—S	111.69 (11)	C11—C10—H10	126.1 (14)
O3—C2—C3	120.87 (16)	C9—C10—H10	115.1 (14)
O3—C2—C1	119.98 (16)	C12—C11—H11	120.2 (18)
C3—C2—C1	119.09 (14)	C10—C11—H11	117.1 (18)
C8—C3—C4	119.06 (17)	C12—C13—H13	119 (2)
C8—C3—C2	123.99 (16)	C14—C13—H13	120 (2)
C4—C3—C2	116.95 (17)	C9—C14—H14	121.7 (14)
C5—C4—C3	120.2 (2)	C13—C14—H14	118.8 (14)
C6—C5—C4	120.4 (2)	C12—C15—H151	110 (3)
C7—C6—C5	119.8 (2)	C12—C15—H152	105 (3)
C6—C7—C8	120.4 (2)	H151—C15—H152	110 (4)
C7—C8—C3	120.1 (2)	C12—C15—H153	119 (4)
C14—C9—C10	119.8 (2)	H151—C15—H153	105 (4)
C14—C9—S	120.26 (15)	H152—C15—H153	107 (4)
C10—C9—S	119.83 (16)	C18—C17—H17	120.0 (14)
C11—C10—C9	118.8 (2)	C16—C17—H17	121.0 (14)
C12—C11—C10	122.7 (2)	C19—C18—H18	123.8 (17)
C13—C12—C11	118.0 (2)	C17—C18—H18	115.3 (17)
C13—C12—C15	120.8 (3)	C20—C19—H19	126.1 (13)
C11—C12—C15	121.2 (3)	C18—C19—H19	113.7 (13)
C12—C13—C14	121.2 (2)	C19—C20—H20	118.4 (17)
C9—C14—C13	119.5 (2)	C21—C20—H20	121.2 (18)
C17—C16—C21	120.44 (17)	C20—C21—H21	120.5 (10)
C17—C16—N2	123.92 (16)	C16—C21—H21	119.7 (10)
C21—C16—N2	115.64 (16)	C22—C23—H23	118.9 (17)
C18—C17—C16	119.0 (2)	C24—C23—H23	120.2 (17)
C19—C18—C17	120.6 (2)	C25—C24—H24	127.0 (18)
C20—C19—C18	120.0 (2)	C23—C24—H24	112.3 (18)
C19—C20—C21	120.4 (2)	C24—C25—H25	123.4 (16)
C20—C21—C16	119.6 (2)	C26—C25—H25	117.5 (17)
C27—C22—C23	118.42 (19)	C25—C26—H26	117.6 (17)
C27—C22—C1	121.57 (16)	C27—C26—H26	121.1 (17)
C23—C22—C1	119.96 (17)	C22—C27—H27	117.7 (13)
C22—C23—C24	120.9 (2)	C26—C27—H27	122.4 (13)
C25—C24—C23	120.6 (2)
S—C1—C2—O3	−13.9 (2)	N1—C1—C2—O3	−132.90 (18)
S—C1—N1—N2	−82.65 (14)	N1—C1—C2—C3	49.9 (2)
S—C1—C2—C3	168.87 (12)	N2—N1—C1—C22	164.95 (14)
O1—S—C1—C2	71.48 (13)	N2—N1—C1—C2	39.8 (2)
O1—S—C1—N1	−165.28 (11)	C9—S—C1—N1	76.81 (12)
O1—S—C1—C22	−49.01 (12)	C1—N1—N2—C16	−179.60 (13)
O2—S—C1—C2	−161.72 (12)	C9—S—C1—C22	−166.92 (11)
O2—S—C1—N1	−38.48 (12)	C9—S—C1—C2	−46.42 (13)
O2—S—C1—C22	77.78 (12)	C22—C1—C2—O3	102.57 (19)