Ethyl 2-{[2-(3-nitro­phenyl)-5-phenyl-1H-imidazol-4-yl]­sulfanyl}acetate: synthesis via a microwave-mediated combinatorial chemistry approach

The orange title compound, C₁₉H₁₇N₃O₄S, can be synthesized either via microwave-mediated combinatorial chemistry strategies or conventional synthetic procedures. The phenyl and meta-nitro­phenyl C₆ rings are essentially coplanar with the central imidazolyl ring, with interplanar angles of 0.87 (5) and 0.97 (4)°, respectively, resulting in optimum conjugation (SCH₂ moiety included); [lambda]_max = 281 nm in CH₃CN. The principal intermolecular interactions are N_imid-H...O_nitro and N_imid-H...O=C [N...O = 3.058 (2) and 3.432 (3) Å, and N-H...O = 128 and 153°, respectively]. The closest H...S distance is an intramolecular C-H...S contact, with H...S = 2.54 Å and C-H...S = 136°.

S1. Comment

The development of high-throughput biological screening has lead to dramatic changes in the drug-discovery process. The generation of large numbers of new drug-like molecules has been achieved in a combinatorial manner rather than in a traditional sequential fashion. The exploitation of microwave irradiation for organic synthesis has gained in popularity with dramatic reduction in reaction times being reported for a wide range of organic reactions (Caddick, 1995; Strauss & Trainor, 1995; Galema, 1997). Clearly, the ability of microwave technology to rapidly synthesize organic compounds would be of significant benefit for combinatorial library generation and its potential as a future tool for drug-discovery programs has recently been identified (Larhed & Hallberg, 2001).

Substituted 4(5)-sulfanyl-imidazoles have been synthesized in a three-component reaction of an aldehyde, alkyl bromide, 2-oxo-thioacetamide and ammonium acetate. Parallel libraries have been generated using both conventional and a new microwave approaches: full synthetic details for compound (I), C₁₉H₁₇N₃O₄S, via both routes are described in the experimental section. The principal benefit of the microwave facilitated procedure over the conventional procedure was a reduction in the overall library generation time from 12 h to 16 minutes. The microwave library generation was achieved utilized an array of expandable reaction vessels which can accommodate the increased pressure during the reaction (Coleman et al., 2001).

The molecular structure of (I) is depicted with the atomic numbering scheme in Fig. 1, with selected geometric dimensions in Table 1. Bond lengths are in accord with the anticipated values (Orpen et al., 1994). Comparisons with a related monosubstituted 2-imidazol-2-yl derivative (Gallagher et al., 1998) indicate that the imidazolyl bond lengths expand slightly in (I) on extra substitution. A para-fluorophenyl acetamide analogue has been deposited as a private communication on the CSD (Gallagher et al., 2001).

In (I) the phenyl and meta-nitrophenyl C₆ rings are essentially coplanar with the central imidazolyl ring, 0.87 (5) and 0.97 (4)°, respectively, resulting in an optimum conjugation in the system (–SCH₂– moiety included, Figure 1): the λ_max = 281 nm in CH₃CN solution. Two principal intermolecular interactions are present in the crystal structure of (I) and both involve the imidazolyl N2—H2 donor as (i) the N2—H2···O21 interaction which generates a one-dimensional chain along [101] in combination with (ii) the longer N2—H2···O2ⁱ interaction which further impacts on the overall hydrogen bonding network by forming π···π stacked aromatic columns (where symmetry code: i = 1 - x,-y,1 - z) (Table 2).

Thus, the central imidazolyl ring core stacks about inversion centres along the b axis with the centroids Cg1···Cg1ⁱ 3.56 Å apart and a perpendicular separation of 3.36 Å (i = 1 - x,-y,1 - z) (Figure 2). For the three coplanar aromatic rings, the perpendicular stacking distance between planes is between 3.35 and 3.43 Å, with a dihedral angle between the stacked planes of < 2°. This is similar in nature to the π-π stacking in graphite where the interplanar spacing is 3.35 Å (Wells, 1984).

A search of the Cambridge Structural Database (Allen & Kennard, 1993) using CONQUEST version 1.2 (April 2001) for systems containing the 2-(3-nitrophenyl)-1H-imidazolyl group reveals eight structures, most of which contain two para-methoxyphenyl groups attached at the remaining two imidazolyl C atoms. Compound 4,5-bis(4-methoxyphenyl)-2-(3-nitrophenyl)-1H-imidazole, (II) CIZMUT01 (Inouye & Sakaino, 2000) is representative. From a series of solvates, different coloured crystals of (II) were obtained and the resulting bathochromic shifts explained by molecular planarity and charge transfer effects. A related search for the S—C₃N₂H moiety revealed six structures quite different to (I) where the sulfur has been incorporated in a heterocyclic ring or is part of a metal complex: a wider search for 2-thioimidazolyl, S—C₃N₂, yielded a total of 41 compounds. For comparison with (I) 1-benzyl-5-methoxycarbonylmethylthio-4-nitroimidazole, C₁₃H₁₃N₃O₄S, (Saadeh et al., 1995) contains _imidC—S—C_ester bond lengths of 1.740 and 1.799 Å, C—S—C 101.14° and C—S—C—C of -72.1 ° and similar to the data for (I) in Table 1. The related S—C—C_imid and S—C—N_imid angles are 134.8 and 122.0°.

Previous biological screening of substituted sulfanyl-imidazoles have shown their potential as acyl-CoA:cholesterol acyltransferase inhibitors, analgesic agents and angiotensin II receptor antagonists, (Higley et al., 1994; Sharpe et al., 1985; Deprez et al., 1995).

S2. Experimental

2-Oxo-2-phenyl-thioacetamides were prepared according to literature methods (Asinger & Gentz, 1963). The combinatorial library was generated using an Argonaut first mate synthesiser with reaction components, aldehyde (0.15 mmol), ammonium acetate (0.15 mmol), 2-oxo-2-aryl-thioacetamide (0.15 mmol) loaded into each reaction vessel with 2 ml of C₂H₅OH. The library was heated for 12 h, cooled and products precipitated with 1M HCl (5 ml), filtered, dried, to give average library purity and yield of 78% and 63%. An identical library was generated using microwave irradiation to give average library purity and yield of 76% and 67%.

An alternative but conventional synthesis for [2-(3-nitrophenyl)-5-phenyl-1H-imidazol-4-yl]sulfanyl]acetic acid ethyl ester is as follows: A mixture of 2-oxo-2-phenyl-thioacetamide (1.04 g, 6.3 mmol), sodium carbonate (0.67 g, 6.3 mmol), ammonium acetate (0.59 g, 6.3 mmol), ethyl bromoacetate (1.05 g, 6.3 mmol) and 3-nitrobenzaldehyde (0.95 g, 6.3 mmol) in ethanol (50 ml) was heated under reflux for 7 h under nitrogen. The reaction mixture was concentrated to half its volume and an orange/yellow solid precipitated. Further purification using dry flash chromatography on silica gel with a gradient of ether:hexane:methanol (2:8:1) to (8:2:1) gave the pure product (1.59 g, 78%): m.p. 462 - 464 K:

Orange crystals were obtained by slow evaporation of a methanol solution. Uv-Vis λ_max = 281, 315 nm. IR, (ν_C═O cm^-1), 1728 (KBr). ¹H NMR data (300 MHz) (δ, d₆ DMSO), 1.07 (t, 3H), 3.82 (s, 2H), 3.95 (q, 2H), 7.37 (m, 1H), 7.48 (m, 2H), 7.80 (m, 1H), 7.90 (m, 2H), 8.24 (m, 1H), 8.47 (m, 1H), 8.92 (m, 1H). HRMS calc. 383.0940, found 383.0932. Anal. calc. for C₁₉H₁₇N₃O₄S, C. 59.58: H, 4.47: N, 10.97: S, 8.37: Found C. 59.39: H, 4.39: N, 10.92: S, 8.87.

S3. Refinement

In (I), all H atoms bound to C were treated as riding, with the SHELXL97 (Sheldrick, 1997) defaults for C—H lengths and with U_iso(H) = 1.5U_eq(C) for methylene H atoms, 1.2U_eq(C) for the remainder. Examination of the structure with PLATON (Spek, 1998) showed that there were no solvent accessible voids in the crystal lattice.

Computing details

Data collection: XSCANS (Siemens, 1994); cell refinement: XSCANS (Siemens, 1994); data reduction: XSCANS (Siemens, 1994); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 1998); software used to prepare material for publication: SHELXL97 and PREP8 (Ferguson, 1998).

Figures

	Fig. 1. A view of (I) with the atomic numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. A view of the interactions and π···π stacking in the crystal structure. The phenyl ring C6H5 H atoms have been removed for clarity.

Ethyl 2-{[2-(3-nitrophenyl)-5-phenyl-1H-imidazol-4-yl]sulfanyl}acetate

Crystal data

C19H17N3O4S	F(000) = 800
Mr = 383.42	Dx = 1.406 Mg m^−3
Monoclinic, P21/n	Melting point: 463 K
Hall symbol: -P 2yn	Mo Kα radiation, λ = 0.71073 Å
a = 10.5606 (13) Å	Cell parameters from 70 reflections
b = 12.1254 (9) Å	θ = 5.4–15.6°
c = 14.8196 (10) Å	µ = 0.21 mm^−1
β = 107.389 (6)°	T = 292 K
V = 1810.9 (3) Å^3	Block, orange
Z = 4	0.45 × 0.35 × 0.18 mm

Data collection

Bruker-AXS P4 diffractometer	Rint = 0.016
Radiation source: X-ray tube	θmax = 26.0°, θmin = 2.1°
Graphite monochromator	h = −1→13
ω scans	k = −1→14
4517 measured reflections	l = −18→17
3524 independent reflections	4 standard reflections every 296 reflections
2569 reflections with I > 2σ(I)	intensity decay: variation 1%

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)] = 0.042	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.110	H-atom parameters constrained
S = 1.03	w = 1/[σ^2(Fo^2) + (0.0496P)^2 + 0.459P] where P = (Fo^2 + 2Fc^2)/3
3524 reflections	(Δ/σ)max < 0.001
245 parameters	Δρmax = 0.21 e Å^−3
0 restraints	Δρmin = −0.18 e Å^−3

Special details

Geometry. Mean plane data ex-SHELXL97 for molecule (I) ############################################

Least-squares planes (x,y,z in crystal coordinates) and deviations from them (* indicates atom used to define plane)

-1.3989(0.0116)x + 11.9754(0.0025)y + 1.7733(0.0141)z = 1.8670(0.0113)

* -0.0037 (0.0016) C31 * -0.0001 (0.0018) C32 * 0.0043 (0.0019) C33 * -0.0049 (0.0018) C34 * 0.0010 (0.0018) C35 * 0.0032 (0.0017) C36 - 0.0254 (0.0048) S1 0.1798 (0.0067) C11 0.0341 (0.0064) C21 - 0.0037 (0.0016) C31

Rms deviation of fitted atoms = 0.0033

-1.1984(0.0095)x + 11.9941(0.0022)y + 1.8194(0.0128)z = 2.0286(0.0057)

Angle to previous plane (with approximate e.s.d.) = 1.21 (4)

* -0.0026 (0.0015) C21 * 0.0024 (0.0014) C22 * 0.0011 (0.0015) C23 * -0.0044 (0.0016) C24 * 0.0041 (0.0017) C25 * -0.0006 (0.0016) C26 - 0.1222 (0.0057) S1 0.0557 (0.0060) C11 - 0.0026 (0.0015) C21 - 0.0279 (0.0058) C31

Rms deviation of fitted atoms = 0.0029

-1.3645(0.0110)x + 11.9640(0.0026)y + 1.9689(0.0157)z = 1.9828(0.0077)

Angle to previous plane (with approximate e.s.d.) = 0.97 (4)

* -0.0024 (0.0012) C1 * 0.0024 (0.0012) C2 * 0.0036 (0.0012) C3 * 0.0000 (0.0012) N1 * -0.0037 (0.0012) N2 - 0.0265 (0.0033) S1 0.1519 (0.0044) C11 0.0077 (0.0035) C21 0.0348 (0.0036) C31

Rms deviation of fitted atoms = 0.0028

-1.3989(0.0116)x + 11.9754(0.0025)y + 1.7733(0.0141)z = 1.8670(0.0113)

Angle to previous plane (with approximate e.s.d.) = 0.87 (5)

* -0.0037 (0.0016) C31 * -0.0001 (0.0018) C32 * 0.0043 (0.0019) C33 * -0.0049 (0.0018) C34 * 0.0010 (0.0018) C35 * 0.0032 (0.0017) C36 - 0.0254 (0.0048) S1 0.1798 (0.0067) C11 0.0341 (0.0064) C21 - 0.0037 (0.0016) C31

Rms deviation of fitted atoms = 0.0033

-0.1379(0.0212)x + 12.1129(0.0023)y + 0.6731(0.0477)z = 2.3016(0.0106)

Angle to previous plane (with approximate e.s.d.) = 7.26 (6)

* 0.0000 (0.0000) N23 * 0.0000 (0.0000) O21 * 0.0000 (0.0000) O22 0.0172 (0.0080) C23 - 0.1330 (0.0163) C21

Rms deviation of fitted atoms = 0.0000

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

	x	y	z	Uiso*/Ueq
S1	0.18564 (5)	0.09268 (5)	0.55909 (4)	0.04748 (18)
O1	0.12588 (18)	−0.06314 (14)	0.38695 (11)	0.0589 (4)
O2	0.00941 (17)	0.06410 (15)	0.28649 (11)	0.0646 (5)
C11	0.0745 (2)	0.11400 (19)	0.44312 (15)	0.0453 (5)
C12	0.0764 (2)	0.0267 (2)	0.37148 (15)	0.0443 (5)
C13	−0.0079 (4)	−0.0100 (3)	0.20684 (18)	0.0947 (11)
C14	−0.0799 (5)	0.0444 (4)	0.1220 (2)	0.1380 (18)
C1	0.33841 (19)	0.11568 (17)	0.53746 (13)	0.0357 (4)
N1	0.34275 (15)	0.13124 (14)	0.44714 (11)	0.0384 (4)
C2	0.47011 (19)	0.14464 (16)	0.45516 (13)	0.0357 (4)
N2	0.54564 (15)	0.13775 (14)	0.54627 (10)	0.0389 (4)
C3	0.46281 (19)	0.11972 (17)	0.60215 (13)	0.0361 (4)
C21	0.52093 (19)	0.16416 (16)	0.37448 (13)	0.0355 (4)
C22	0.4301 (2)	0.16912 (16)	0.28463 (13)	0.0374 (5)
C23	0.4771 (2)	0.18528 (17)	0.20842 (13)	0.0400 (5)
C24	0.6102 (2)	0.19680 (19)	0.21716 (15)	0.0476 (5)
C25	0.6989 (2)	0.1928 (2)	0.30645 (15)	0.0509 (6)
C26	0.6554 (2)	0.17621 (18)	0.38473 (14)	0.0443 (5)
N23	0.38144 (19)	0.18805 (16)	0.11352 (12)	0.0484 (5)
O21	0.26298 (16)	0.18710 (15)	0.10629 (10)	0.0619 (5)
O22	0.42414 (18)	0.19232 (16)	0.04549 (10)	0.0687 (5)
C31	0.5123 (2)	0.11105 (16)	0.70503 (13)	0.0371 (4)
C32	0.6466 (2)	0.1199 (2)	0.75322 (15)	0.0522 (6)
C33	0.6920 (2)	0.1111 (2)	0.85078 (15)	0.0610 (7)
C34	0.6052 (3)	0.0926 (2)	0.90191 (15)	0.0548 (6)
C35	0.4727 (3)	0.0844 (2)	0.85609 (15)	0.0562 (6)
C36	0.4260 (2)	0.0936 (2)	0.75863 (14)	0.0502 (6)
H11A	−0.0150	0.1192	0.4478	0.054*
H11B	0.0954	0.1843	0.4198	0.054*
H13A	0.0781	−0.0329	0.2025	0.114*
H13B	−0.0558	−0.0753	0.2158	0.114*
H14A	−0.1685	0.0592	0.1235	0.207*
H14B	−0.0830	−0.0018	0.0688	0.207*
H14C	−0.0366	0.1127	0.1165	0.207*
H2	0.6306	0.1435	0.5663	0.047*
H22	0.3396	0.1617	0.2762	0.045*
H24	0.6390	0.2069	0.1643	0.057*
H25	0.7890	0.2014	0.3143	0.061*
H26	0.7166	0.1731	0.4446	0.053*
H32	0.7069	0.1319	0.7195	0.063*
H33	0.7822	0.1178	0.8819	0.073*
H34	0.6364	0.0857	0.9673	0.066*
H35	0.4134	0.0726	0.8906	0.067*
H36	0.3353	0.0880	0.7284	0.060*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0363 (3)	0.0709 (4)	0.0383 (3)	−0.0029 (3)	0.0159 (2)	−0.0012 (3)
O1	0.0691 (11)	0.0490 (10)	0.0541 (9)	0.0068 (9)	0.0114 (8)	0.0014 (8)
O2	0.0725 (11)	0.0719 (12)	0.0425 (9)	0.0189 (9)	0.0068 (8)	0.0026 (8)
C11	0.0333 (11)	0.0527 (14)	0.0497 (12)	0.0034 (10)	0.0120 (9)	0.0022 (10)
C12	0.0366 (11)	0.0546 (14)	0.0414 (12)	−0.0014 (10)	0.0110 (9)	0.0036 (10)
C13	0.119 (3)	0.107 (3)	0.0454 (15)	0.024 (2)	0.0050 (17)	−0.0149 (16)
C14	0.173 (4)	0.153 (4)	0.0558 (19)	0.043 (3)	−0.015 (2)	−0.008 (2)
C1	0.0363 (10)	0.0400 (11)	0.0328 (9)	0.0001 (9)	0.0133 (8)	−0.0004 (8)
N1	0.0359 (9)	0.0482 (10)	0.0319 (8)	−0.0008 (8)	0.0110 (7)	0.0020 (7)
C2	0.0351 (10)	0.0419 (11)	0.0299 (9)	−0.0014 (9)	0.0093 (8)	0.0014 (8)
N2	0.0316 (8)	0.0548 (11)	0.0302 (8)	−0.0063 (8)	0.0090 (7)	0.0018 (8)
C3	0.0389 (10)	0.0392 (11)	0.0316 (9)	−0.0030 (9)	0.0126 (8)	−0.0001 (8)
C21	0.0382 (10)	0.0382 (11)	0.0313 (10)	−0.0002 (9)	0.0124 (8)	0.0030 (8)
C22	0.0369 (10)	0.0426 (12)	0.0343 (10)	0.0024 (9)	0.0129 (8)	0.0028 (8)
C23	0.0470 (12)	0.0426 (12)	0.0305 (10)	0.0074 (10)	0.0114 (9)	0.0068 (9)
C24	0.0517 (13)	0.0562 (14)	0.0425 (12)	0.0044 (11)	0.0253 (10)	0.0123 (10)
C25	0.0390 (11)	0.0668 (16)	0.0508 (13)	−0.0020 (11)	0.0193 (10)	0.0096 (12)
C26	0.0399 (11)	0.0567 (14)	0.0348 (10)	−0.0039 (10)	0.0088 (9)	0.0042 (10)
N23	0.0563 (12)	0.0564 (12)	0.0325 (9)	0.0135 (9)	0.0131 (8)	0.0062 (8)
O21	0.0502 (10)	0.0885 (14)	0.0418 (9)	0.0135 (9)	0.0058 (7)	0.0090 (8)
O22	0.0795 (12)	0.0984 (14)	0.0324 (8)	0.0168 (11)	0.0232 (8)	0.0084 (9)
C31	0.0440 (11)	0.0367 (11)	0.0311 (9)	−0.0001 (9)	0.0119 (8)	0.0001 (8)
C32	0.0463 (13)	0.0725 (17)	0.0371 (11)	−0.0034 (12)	0.0114 (10)	0.0023 (11)
C33	0.0527 (14)	0.0831 (19)	0.0393 (12)	−0.0013 (13)	0.0018 (10)	0.0004 (12)
C34	0.0726 (17)	0.0595 (15)	0.0291 (10)	0.0036 (13)	0.0102 (11)	−0.0010 (10)
C35	0.0682 (16)	0.0701 (17)	0.0363 (11)	−0.0018 (13)	0.0247 (11)	0.0007 (11)
C36	0.0473 (12)	0.0700 (16)	0.0357 (11)	−0.0007 (12)	0.0163 (9)	0.0004 (11)

Geometric parameters (Å, º)

S1—C1	1.759 (2)	C31—C32	1.388 (3)
S1—C11	1.787 (2)	C31—C36	1.393 (3)
O1—C12	1.201 (3)	C32—C33	1.385 (3)
O2—C12	1.326 (3)	C33—C34	1.371 (3)
O2—C13	1.451 (3)	C34—C35	1.364 (3)
N1—C1	1.366 (2)	C35—C36	1.384 (3)
N1—C2	1.324 (2)	N2—H2	0.8600
N2—C2	1.350 (2)	C11—H11A	0.9700
N2—C3	1.390 (2)	C11—H11B	0.9700
C1—C3	1.376 (3)	C13—H13A	0.9700
C2—C21	1.469 (3)	C13—H13B	0.9700
C3—C31	1.460 (3)	C14—H14A	0.9600
C11—C12	1.503 (3)	C14—H14B	0.9600
C13—C14	1.422 (4)	C14—H14C	0.9600
C21—C22	1.391 (3)	C22—H22	0.9300
C21—C26	1.390 (3)	C24—H24	0.9300
C22—C23	1.377 (3)	C25—H25	0.9300
C23—C24	1.379 (3)	C26—H26	0.9300
C23—N23	1.467 (3)	C32—H32	0.9300
C24—C25	1.375 (3)	C33—H33	0.9300
C25—C26	1.384 (3)	C34—H34	0.9300
N23—O22	1.222 (2)	C35—H35	0.9300
N23—O21	1.223 (2)	C36—H36	0.9300
C1—S1—C11	100.18 (9)	C35—C36—C31	121.1 (2)
C12—O2—C13	117.6 (2)	S1—C11—H11A	108.4
S1—C11—C12	115.70 (15)	S1—C11—H11B	108.4
O1—C12—O2	124.7 (2)	C2—N2—H2	125.8
O1—C12—C11	126.9 (2)	C3—N2—H2	125.8
O2—C12—C11	108.31 (19)	O2—C13—H13A	109.7
O2—C13—C14	109.6 (3)	O2—C13—H13B	109.7
S1—C1—N1	120.12 (14)	C12—C11—H11A	108.4
S1—C1—C3	127.98 (15)	C12—C11—H11B	108.4
N1—C1—C3	111.90 (17)	C14—C13—H13A	109.7
C1—N1—C2	105.05 (16)	C14—C13—H13B	109.7
N1—C2—N2	111.27 (16)	C13—C14—H14A	109.5
N1—C2—C21	123.72 (17)	C13—C14—H14B	109.5
N2—C2—C21	125.01 (17)	C13—C14—H14C	109.5
C2—N2—C3	108.46 (15)	H11A—C11—H11B	107.4
C1—C3—N2	103.31 (16)	H13A—C13—H13B	108.2
C1—C3—C31	133.95 (18)	H14A—C14—H14B	109.5
N2—C3—C31	122.73 (17)	H14A—C14—H14C	109.5
C2—C21—C22	118.09 (17)	H14B—C14—H14C	109.5
C2—C21—C26	122.55 (17)	C21—C22—H22	120.8
C22—C21—C26	119.36 (18)	C23—C22—H22	120.8
C21—C22—C23	118.45 (18)	C23—C24—H24	121.0
C22—C23—C24	123.01 (19)	C25—C24—H24	121.0
C22—C23—N23	118.39 (19)	C24—C25—H25	119.6
C24—C23—N23	118.59 (18)	C26—C25—H25	119.6
C23—C24—C25	117.95 (19)	C21—C26—H26	119.7
C24—C25—C26	120.7 (2)	C25—C26—H26	119.7
C21—C26—C25	120.51 (19)	C31—C32—H32	119.6
O21—N23—O22	123.21 (18)	C33—C32—H32	119.6
O21—N23—C23	118.52 (17)	C32—C33—H33	119.7
O22—N23—C23	118.26 (19)	C34—C33—H33	119.7
C3—C31—C32	121.57 (18)	C33—C34—H34	120.2
C3—C31—C36	121.00 (18)	C35—C34—H34	120.2
C32—C31—C36	117.44 (18)	C34—C35—H35	119.8
C31—C32—C33	120.8 (2)	C36—C35—H35	119.8
C32—C33—C34	120.7 (2)	C31—C36—H36	119.4
C33—C34—C35	119.5 (2)	C35—C36—H36	119.4
C34—C35—C36	120.4 (2)
C1—S1—C11—C12	70.19 (18)	C2—C21—C22—C23	−178.78 (18)
C13—O2—C12—O1	1.6 (4)	C21—C22—C23—C24	0.0 (3)
C13—O2—C12—C11	−176.5 (2)	C21—C22—C23—N23	178.66 (18)
S1—C11—C12—O1	13.9 (3)	C22—C23—C24—C25	−0.6 (3)
S1—C11—C12—O2	−168.09 (15)	N23—C23—C24—C25	−179.3 (2)
C12—O2—C13—C14	−179.1 (3)	C23—C24—C25—C26	0.9 (4)
C11—S1—C1—N1	−6.30 (19)	C24—C25—C26—C21	−0.5 (4)
C11—S1—C1—C3	174.3 (2)	C22—C21—C26—C25	−0.1 (3)
C3—C1—N1—C2	0.2 (2)	C2—C21—C26—C25	179.0 (2)
S1—C1—N1—C2	−179.23 (15)	C22—C23—N23—O22	−173.5 (2)
C1—N1—C2—N2	0.2 (2)	C24—C23—N23—O22	5.3 (3)
C1—N1—C2—C21	−179.90 (18)	C22—C23—N23—O21	7.3 (3)
N1—C2—N2—C3	−0.6 (2)	C24—C23—N23—O21	−174.0 (2)
C21—C2—N2—C3	179.53 (19)	C1—C3—C31—C32	−179.1 (2)
N1—C1—C3—N2	−0.6 (2)	N2—C3—C31—C32	−0.3 (3)
S1—C1—C3—N2	178.83 (15)	C1—C3—C31—C36	0.9 (4)
N1—C1—C3—C31	178.3 (2)	N2—C3—C31—C36	179.6 (2)
S1—C1—C3—C31	−2.3 (4)	C36—C31—C32—C33	0.3 (3)
C2—N2—C3—C1	0.7 (2)	C3—C31—C32—C33	−179.8 (2)
C2—N2—C3—C31	−178.37 (19)	C31—C32—C33—C34	0.5 (4)
N1—C2—C21—C26	−178.9 (2)	C32—C33—C34—C35	−0.9 (4)
N2—C2—C21—C26	0.9 (3)	C33—C34—C35—C36	0.6 (4)
N1—C2—C21—C22	0.2 (3)	C34—C35—C36—C31	0.1 (4)
N2—C2—C21—C22	−179.98 (19)	C32—C31—C36—C35	−0.6 (3)
C26—C21—C22—C23	0.4 (3)	C3—C31—C36—C35	179.5 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O21^i	0.86	2.46	3.058 (2)	128
N2—H2···O1^ii	0.86	2.64	3.432 (3)	153
C36—H36···S1	0.93	2.54	3.271 (2)	136

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