Two (E)-2-aryl­idene-1,4-di-p-tosyl-1,2,3,4-tetra­hydro­quinoxaline compounds: supra­molecular frameworks built with C-H...O and C-H...[pi](arene) hydrogen bonds and [pi]-[pi] stacking inter­actions

The pyrazine ring in two N-substituted quinoxaline derivatives, namely (E)-2-(2-methoxy­benzyl­idene)-1,4-di-p-tosyl-1,2,3,4-tetra­hydro­quin­oxaline, C₃₀H₂₈N₂S₂O₅, (II), and (E)-methyl 2-[(1,4-di-p-tosyl-1,2,3,4-tetra­hydro­quinoxalin-2-yli­dene)methyl]benzoate, C₃₁H₂₈N₂S₂O₆, (III), assumes a half-chair conformation and is shielded by the terminal tosyl groups. In the mol­ecular packing of the compounds, inter­molecular C-H...O hydrogen bonds between centrosymmetrically related mol­ecules generate dimeric rings, viz. R₂²(22) in (II) and R₂²(26) in (III), which are further connected through C-H...[pi](arene) hydrogen bonds and [pi]-[pi] stacking inter­actions into novel supra­molecular frameworks.

S1. Comment

The quinoxaline heterocycle, (I), has been an integral part in many natural products (Dell et al., 1975). Several quinoxaline derivatives have been successfully used in the pharmaceutical industry as synthetic precursors of antihypertensives, analgesics and neurotransmitter antagonists (Fuente et al., 2000; Kher et al., 1995). Furthermore, the in vitro anticancer activity of quinoxaline compounds has recently emerged as a promising modality against cancer and allied diseases (Lorgia et al., 1995; Bonnett, 1995). The DNA photocleaving property of quinoxaline-based compounds with substitutions at the C-positions of the pyrazine ring has been attributed to the conjugated C═N bond in these systems (Toshima et al., 2002). Although the syntheses and crystal structure analyses of different C-substituted quinoxalines have been reported (Dobrzańska & Lloyd, 2005; Zhao & Du, 2003; Sessler et al., 2002; Chowdhury et al., 2001), the corresponding study of N-substituted quinoxalines has been rather sparse (Banerjee et al., 2001). As part of an ongoing programme on the synthesis and structural characterization of novel N-substituted quinoxalines, we synthesized two 2-alkylidene-1,4-di-p-tosyl-1,2,3,4-tetrahydroquinoxalines via palladium-catalyzed heteroannulation of N-substituted phenylamines. In order to establish the regio- and stereospecificities of the reaction and to build up a hierarchy for such systems, X-ray analyses of 2-(2-methoxyphenylmethylidene)-1,4-di-p-tosyl-1,2,3,4-tetrahydroquinoxaline, (II), and 2-(2-carbomethoxyphenylmethylidene)-1,4-di-p-tosyl-1,2,3,4-tetrahydroquinoxaline, (III), were undertaken.

The title compounds (Figs. 1 and 2) consist of a quinoxaline ring system with two p-tosyl and one substituted phenylmethylidene groups at the 1-, 4- and 2-positions, respectively. The E configuration of the molecules of (II) and (III), as established from the ³J_C—H coupling constant (Moreau et al., 1991; Cabiddu et al., 1986) value of 7.76 Hz for both compounds, is confirmed by the N1—C22—C23—C24 torsion angles of −172.0 (1)° for (II) and 171.7 (2)° for (III). The pyrazine ring B (N1/C8/C13/N2/C21/C22) fused to the phenyl ring A (C8–C13) in both compounds assumes a half-chair conformation. with ring-puckering parameters (Cremer & Pople, 1975) Q, θ and ϕ of 0.413 (1) Å, 49.7 (2)° and 264.5 (2)°, respectively, for (II), and 0.413 (2) Å, 132.0 (3)° and 77.8 (3)°, respectively, for (III). The deviations of atom C21 from the corresponding least-squares planes through the remaining endocyclic atoms of the C₄N₂ ring are 0.543 (2) and −0.557 (2) Å, respectively, for (II) and (III).

The molecular geometries of (II) and (III) (Tables 1 and 2) agree well with the corresponding values reported for similar N-substituted quinoxaline compounds (Banerjee et al., 2001). The sums of the valence angles at the two N atoms (N1 and N2) of the pyrazine ring are 349.1 (1) and 348.5 (1)°, respectively, for (II), and 348.2 (1) and 347.8 (1)°, respectively, for (III), deviating significantly from 360°, and thus these atoms display pyramidal distortion. The conformation of the molecules can be described by the torsion angles C6—S1—N1—C8 and C14—S2—N2—C21, which are −91.8 (1) and 84.8 (1)°, respectively, in (II), and 84.8 (2) and −77.3 (1)°, respectively, in (III). These values indicate that the tosyl groups in the compounds adopt folded conformations, with the phenyl rings C (C1–C6) and D (C14–C19) shielding the central quinoxaline moiety. The dihedral angles between the essentially planar phenyl rings C and D are 7.3 (1)° in (II) and 4.7 (1)° in (III). The S═O bond distances in the compounds are in the range 1.427 (1)–1.434 (1) Å (Tables 1 and 2) and are consistent with those found in structures containing sulfonyl groups (Ghosh et al., 2006; Wardell et al., 2005). However, the angular disposition of the bonds about atoms S1 and S2 in the two compounds deviates considerably from that of a regular tetrahedron; the largest and the smallest angles are O1—S1—O2 = 119.5 (1)° and N1—S1—C6 = 104.1 (1)°, respectively, in (II). Similar distortion in sulfonyl geometry has been reported in the literature (Chumakov et al., 2005; Sonar et al., 2004) and can be attributed to the repulsive interaction between the short S═O bonds. Although both compounds (II) and (III) contain four essentially planar phenyl rings (A, C, D and E), the lack of π-bonding in the branches between the phenyl rings precludes any possible π conjugation across the whole molecules. The aromatic nature of the rings is therefore localized within the rings and on their direct substituents.

The similarity of the lattice parameters and space groups between (II) and other N-substituted quinoxaline compounds reported earlier by Banerjee et al. (2001), namely 2-(4-methylbenzylidene)-1,4-di-p-tosyl-1,2,3,4-tetrahydroquinoxaline, 2-(4-methoxybenzylidene)-1,4-di-p-tosyl-1,2,3,4-tetrahydroquinoxaline and 2-(3-chlorobenzylidene)-1,4-di-p-tosyl-1,2,3,4-tetrahydroquinoxaline, hereinafter referred to as (IV), (V) and (VI), respectively, suggests some degree of isostructurality among the compounds. The results of the calculation (Table 5) of the unit-cell similarity descriptor π (Kálmán et al., 1993), the isostructurality index I_i (Kálmán et al., 1993) and the volumetric isostructurality index I_v (Fábián & Kálmán, 1999) reveal a high degree of isostructurality between compounds (II) and (VI). The volumetric index of isostructurality between compounds (II) and (VI) amounts to 77% for the whole unit cell, with four molecules indicating significant packing similarity of the two structures. The large values of the isostructurality index I_i(61) between (II) and (IV) and (II) and (V) (Table 5) indicate that compound (II) is not isostructural with compound (IV) or (V). This is probably a consequence of the exchange of cell-axis lengths in compound (II) compared with those in (IV) and (V), which results in different packing arrangements in these compounds.

Despite the close similarity between compounds (II) and (III) in terms of their overall constitutions and detailed molecular geometries, there are some significant differences in the nature of their supramolecular aggregation. The molecules of (II) are linked into a three-dimensional framework by a combination of C—H···O and C—H···π(arene) hydrogen bonds (Table 3), and π–π stacking interactions. It is convenient to consider the substructures generated by each type of hydrogen bond acting individually, and then the combination of substructures to build up the resulting assembly. The molecules in (II) related by inversion, with phenyl atom C2 in the molecule at (x, y, z) acting as a donor to sulfonamide atom O4 in the molecule at (1 − x, 1 − y, 1 − z), generate a centrosymmetric R₂²(22) (Bernstein et al., 1995) dimeric ring centred at (1/2, 1/2, 1/2). Propagation of these dimers through C—H···π(arene) hydrogen bonds (Table 3) produces two chains, the first running parallel to the [010] direction and generated by the 2₁ screw axis along (0, y, 1/4) and the second running parallel to the [001] direction and generated by the c-glide plane at y = 1/4. The combination of [010] and [001] chains in (II) produces a complex sheet parallel to (100). Finally, the interconnection of molecular sheets through a π–π stacking interaction (Table 3) between the C1–C6 and C14–C19 aryl rings of the molecules at (x, y, z) and (1 + x, y, z), respectively, forms a three-dimensional supramolecular assembly (Fig. 3) in (II).

In (III), a pair of intermolecular C—H···O hydrogen bonds between centrosymmetrically related molecules involving the tosyl group atom C16 at (x, y, z) and the carbomethoxy atom O5 at (1 − x, −y, −z) generates an R₂²(26) dimeric ring centred at (1/2, 0, 0). Propagation of these R₂²(26) rings along the [100] direction forms a C(11) chain via another type of intermolecular C—H···O hydrogen bond between the phenyl atom C18 and the sulfonamide atom O1 (Table 4). The molecular packing in (III) is such that the π–π stacking interactions between the aryl rings in the carbomethoxyphenyl groups of adjacent polymeric chains are optimized. The phenyl rings C24–C29 of the molecules at (x, y, z) and (1 − x, 1 − y, −z) are strictly parallel, with an interplanar spacing of 3.417 Å, and a ring centroid separation of 3.938 (1) Å, corresponding to a ring offset of 1.96 Å. The combination of C—H···O hydrogen bonds and π–π interactions results in a two-dimensional supramolecular framework in (III) (Fig. 4).

S2. Experimental

A mixture of aryl iodide [2-methoxy-iodobenzene (0.268 g, 1.14 mmol) for (II); 2-carbomethoxy iodobenzene (0.30 g, 1.14 mmol) for (III)], palladium(II) acetate [Pd(OAc)₂] (0.009 g, 5 mmol%), anhydrous potassium carbonate (0.304 g, 2.2 mmol) and tetrabutylammonium bromide (TBAB) (0.142 g, 0.44 mmol) was stirred in dimethylformamide (DMF; 10 ml) under a nitrogen atomosphere at room temperature (300 K) for 1 h. The acetylenic compound N-(prop-2'-ynyl)-N,N'-1,2-phenylenedi-p-tosylamide (0.4 g, 0.88 mmol) was added to the mixture, followed by stirring for a further 24 h at room temperature. After the usual work-up, the crude product was purified by column chromatography through silica gel (60–120 mesh) using chloroform as eluant, affording the title compounds, (II) (yield 47%) and (III) (yield 50%). Single crystals of (II) and (III) suitable for X-ray analyses were obtained from a chloroform–light petroleum (333–353 K) mixture (1:1 v/v). Compound (II): m.p. 442 (2) K; analysis found: C 64.32, H 4.96, N 5.02%; calculated for C₃₀H₂₈N₂S₂O₅: C 64.28, H 5.00, N 5.00%. Spectroscopic analysis: ¹H NMR (300 MHz, CDCl₃, δ, p.p.m.): 2.33 (s, 3H, Ar—CH₃), 2.42 (s, 3H, Ar—CH₃), 3.84 (s, 3H, –OCH₃), 4.05 (s, 2H, –CH₂), 6.92 (s, 1H, ═CH), 6.94–7.83 (m, 16H, Ar—H); ¹³C NMR (75 MHz, CDCl₃, δ, p.p.m.): 21.5 (Ar—CH₃), 21.53 (Ar—CH₃), 21.6 (Ar—OCH₃), 43.5 (—CH₂–), 55.25 (═CH–). Compound (III): m.p. 441 (2) K; analysis found: C 62.88, H 4.80, N 4.67%; calculated for C₃₁H₂₈N₂S₂O₆: C 63.26, H 4.76, N 4.76%. Spectroscopic analysis: ¹H NMR (300 MHz, CDCl₃, δ, p.p.m.): 2.35 (s, 3H, Ar—CH₃), 2.46 (s, 3H, Ar—CH₃) 3.87 (s, 3H, –COOCH₃), 4.15 (s, 2H, –CH₂), 7.10 (s, 1H, ═CH), 7.12–8.09 (m, 16H, Ar—H); ¹³C NMR (75 MHz, CDCl₃, δ, p.p.m.): 21.5 (Ar—CH₃), 21.6 (–COOCH₃), 44.5 (–CH₂–), 52.1 (═ CH–).

S3. Refinement

H atoms were positioned geometrically and treated as riding, with C—H = 0.93–0.97 Å and with U_iso(H) = 1.5–1.8U_eq(C). [Please check added text and correct as necessary]

Computing details

For both compounds, data collection: SMART (Bruker, 1998); cell refinement: SMART; data reduction: SMART; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Version 1.06; Farrugia, 1997) and CAMERON (Watkin et al., 1993); software used to prepare material for publication: SHELXL97 and PARST 95 (Nardelli, 1995).

Figures

	Fig. 1. A view of (II), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 40% probability level and H atoms are shown as small spheres of arbritary radii.
	Fig. 2. A view of (III), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 40% probability level and H atoms are shown as small spheres of arbritary radii.
	Fig. 3. The three-dimensional supramolecular framework in (II) formed by C—H···O and C—H···π(arene) hydrogen bonds and π–π stacking interactions. [Symmetry codes: (i) 1 − x, 1 − y, 1 − z; (ii) x, 1/2 − y, −1/2 + z; (iii) −1 + x, y, z.]
	Fig. 4. The two-dimensional supramolecular architecture in (III). H atoms not involved in hydrogen bonding have been omitted. [Symmetry codes: (i) 1 − x, −y, −z; (ii) 1 + x, y, z; (iii) 1 − x, 1 − y, −z; (iv) x − 1, y, z.]

(II) (E)-2-(2-methoxybenzylidene)-1,4-di-p-tosyl-1,2,3,4-tetrahydroquinoxaline

Crystal data

C30H28N2O5S2	F(000) = 1176
Mr = 560.66	Dx = 1.451 Mg m^−3
Monoclinic, P21/c	Melting point: 442 K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 10.4081 (5) Å	Cell parameters from 9506 reflections
b = 24.0202 (11) Å	θ = 2.6–26.4°
c = 10.2842 (5) Å	µ = 0.25 mm^−1
β = 93.314 (10)°	T = 100 K
V = 2566.8 (2) Å^3	Block, colourless
Z = 4	0.50 × 0.50 × 0.40 mm

Data collection

Bruker SMART CCD area-detector diffractometer	5223 independent reflections
Radiation source: fine-focus sealed tube	4688 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.030
ϕ and ω scans	θmax = 26.4°, θmin = 2.0°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −12→13
Tmin = 0.887, Tmax = 0.908	k = −17→29
14680 measured reflections	l = −12→12

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)] = 0.032	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.090	H-atom parameters constrained
S = 1.07	w = 1/[σ^2(Fo^2) + (0.0517P)^2 + 0.8776P] where P = (Fo^2 + 2Fc^2)/3
5223 reflections	(Δ/σ)max = 0.001
352 parameters	Δρmax = 0.44 e Å^−3
0 restraints	Δρmin = −0.36 e Å^−3

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
S1	0.62971 (3)	0.305435 (14)	0.24029 (3)	0.01438 (10)
S2	0.17251 (3)	0.377587 (14)	0.48384 (3)	0.01757 (10)
O1	0.65777 (9)	0.24748 (4)	0.25798 (10)	0.0188 (2)
O2	0.65163 (9)	0.33134 (4)	0.11846 (9)	0.0196 (2)
O3	0.11113 (10)	0.34710 (5)	0.58191 (10)	0.0245 (2)
O4	0.18676 (10)	0.43673 (4)	0.49690 (10)	0.0228 (2)
O5	0.27924 (10)	0.45069 (4)	−0.01747 (9)	0.0187 (2)
N1	0.47210 (11)	0.31503 (5)	0.26630 (11)	0.0140 (2)
N2	0.32243 (11)	0.35246 (5)	0.47786 (11)	0.0161 (2)
C1	0.75481 (13)	0.39671 (6)	0.33998 (14)	0.0174 (3)
H1	0.7454	0.4114	0.2563	0.031*
C2	0.81261 (13)	0.42776 (6)	0.44046 (14)	0.0186 (3)
H2	0.8422	0.4634	0.4238	0.034*
C3	0.82709 (13)	0.40621 (6)	0.56645 (14)	0.0170 (3)
C4	0.78144 (13)	0.35263 (6)	0.58967 (14)	0.0176 (3)
H4	0.7902	0.3380	0.6734	0.032*
C5	0.72344 (13)	0.32094 (6)	0.49043 (13)	0.0165 (3)
H5	0.6933	0.2853	0.5068	0.030*
C6	0.71103 (12)	0.34348 (6)	0.36530 (13)	0.0145 (3)
C7	0.89080 (15)	0.44016 (6)	0.67470 (14)	0.0221 (3)
H7A	0.9445	0.4680	0.6386	0.033*
H7B	0.9424	0.4163	0.7314	0.033*
H7C	0.8262	0.4579	0.7232	0.033*
C8	0.40703 (12)	0.27614 (6)	0.34536 (13)	0.0148 (3)
C9	0.40765 (13)	0.21966 (6)	0.31317 (14)	0.0181 (3)
H9	0.4516	0.2078	0.2420	0.033*
C10	0.34383 (14)	0.18123 (6)	0.38572 (15)	0.0211 (3)
H10	0.3445	0.1437	0.3631	0.038*
C11	0.27876 (14)	0.19864 (6)	0.49226 (15)	0.0215 (3)
H11	0.2381	0.1726	0.5428	0.039*
C12	0.27415 (13)	0.25442 (6)	0.52360 (14)	0.0190 (3)
H12	0.2301	0.2658	0.5952	0.034*
C13	0.33505 (13)	0.29413 (6)	0.44883 (13)	0.0156 (3)
C14	0.09300 (13)	0.36270 (6)	0.33195 (14)	0.0180 (3)
C15	0.03889 (14)	0.31029 (6)	0.30990 (15)	0.0216 (3)
H15	0.0420	0.2837	0.3758	0.039*
C16	−0.01969 (14)	0.29810 (6)	0.18858 (16)	0.0229 (3)
H16	−0.0548	0.2629	0.1733	0.041*
C17	−0.02683 (13)	0.33776 (6)	0.08912 (15)	0.0204 (3)
C18	0.02633 (14)	0.39022 (6)	0.11502 (14)	0.0206 (3)
H18	0.0205	0.4174	0.0504	0.037*
C19	0.08752 (14)	0.40287 (6)	0.23433 (14)	0.0192 (3)
H19	0.1245	0.4377	0.2491	0.035*
C20	−0.08725 (15)	0.32439 (7)	−0.04338 (15)	0.0263 (3)
H20A	−0.0227	0.3255	−0.1063	0.039*
H20B	−0.1530	0.3513	−0.0662	0.039*
H20C	−0.1247	0.2879	−0.0423	0.039*
C21	0.41718 (13)	0.38918 (6)	0.41902 (13)	0.0158 (3)
H21A	0.4984	0.3872	0.4700	0.028*
H21B	0.3870	0.4274	0.4212	0.028*
C22	0.43789 (12)	0.37299 (5)	0.28065 (13)	0.0144 (3)
C23	0.42993 (12)	0.40538 (6)	0.17546 (13)	0.0155 (3)
H23	0.4363	0.3875	0.0959	0.028*
C24	0.41222 (13)	0.46625 (6)	0.17024 (13)	0.0158 (3)
C25	0.47475 (13)	0.50299 (6)	0.25836 (13)	0.0179 (3)
H25	0.5235	0.4888	0.3295	0.032*
C26	0.46544 (14)	0.56034 (6)	0.24173 (14)	0.0199 (3)
H26	0.5073	0.5842	0.3015	0.036*
C27	0.39376 (14)	0.58176 (6)	0.13609 (14)	0.0197 (3)
H27	0.3884	0.6201	0.1244	0.036*
C28	0.32938 (13)	0.54639 (6)	0.04694 (14)	0.0179 (3)
H28	0.2805	0.5610	−0.0235	0.032*
C29	0.33861 (13)	0.48906 (6)	0.06398 (13)	0.0162 (3)
C30	0.21005 (15)	0.47027 (6)	−0.13207 (14)	0.0225 (3)
H30A	0.1745	0.4392	−0.1805	0.034*
H30B	0.2673	0.4904	−0.1848	0.034*
H30C	0.1417	0.4944	−0.1081	0.034*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.01544 (17)	0.01446 (18)	0.01324 (17)	0.00140 (12)	0.00087 (12)	−0.00078 (12)
S2	0.01635 (18)	0.01824 (19)	0.01835 (18)	0.00308 (13)	0.00308 (13)	−0.00037 (13)
O1	0.0198 (5)	0.0146 (5)	0.0218 (5)	0.0038 (4)	0.0005 (4)	−0.0031 (4)
O2	0.0204 (5)	0.0242 (5)	0.0143 (5)	0.0009 (4)	0.0025 (4)	0.0003 (4)
O3	0.0215 (5)	0.0292 (6)	0.0236 (5)	0.0047 (4)	0.0074 (4)	0.0034 (4)
O4	0.0240 (5)	0.0188 (5)	0.0256 (5)	0.0040 (4)	0.0030 (4)	−0.0053 (4)
O5	0.0227 (5)	0.0159 (5)	0.0170 (5)	−0.0008 (4)	−0.0042 (4)	0.0013 (4)
N1	0.0154 (6)	0.0121 (5)	0.0146 (5)	0.0012 (4)	0.0009 (4)	0.0011 (4)
N2	0.0158 (6)	0.0154 (6)	0.0171 (6)	0.0013 (4)	0.0014 (4)	0.0007 (4)
C1	0.0186 (7)	0.0168 (7)	0.0170 (6)	0.0016 (5)	0.0028 (5)	0.0029 (5)
C2	0.0197 (7)	0.0138 (7)	0.0226 (7)	−0.0014 (5)	0.0034 (5)	0.0007 (5)
C3	0.0138 (6)	0.0174 (7)	0.0199 (7)	0.0014 (5)	0.0018 (5)	−0.0021 (5)
C4	0.0181 (7)	0.0186 (7)	0.0161 (6)	0.0013 (5)	0.0002 (5)	0.0019 (5)
C5	0.0171 (7)	0.0145 (7)	0.0180 (7)	−0.0001 (5)	0.0009 (5)	0.0019 (5)
C6	0.0132 (6)	0.0149 (6)	0.0152 (6)	0.0020 (5)	0.0002 (5)	−0.0021 (5)
C7	0.0237 (7)	0.0211 (7)	0.0216 (7)	−0.0036 (6)	0.0006 (6)	−0.0043 (6)
C8	0.0138 (6)	0.0157 (7)	0.0145 (6)	−0.0006 (5)	−0.0029 (5)	0.0031 (5)
C9	0.0182 (7)	0.0166 (7)	0.0191 (7)	0.0018 (5)	−0.0022 (5)	0.0005 (5)
C10	0.0201 (7)	0.0141 (7)	0.0286 (8)	−0.0003 (5)	−0.0034 (6)	0.0033 (6)
C11	0.0158 (7)	0.0195 (7)	0.0290 (8)	−0.0008 (5)	−0.0009 (6)	0.0101 (6)
C12	0.0142 (6)	0.0229 (7)	0.0198 (7)	0.0016 (5)	0.0000 (5)	0.0056 (6)
C13	0.0140 (6)	0.0151 (7)	0.0170 (6)	0.0013 (5)	−0.0034 (5)	0.0016 (5)
C14	0.0130 (6)	0.0191 (7)	0.0218 (7)	0.0027 (5)	0.0009 (5)	0.0006 (6)
C15	0.0173 (7)	0.0187 (7)	0.0285 (8)	0.0005 (5)	−0.0010 (6)	0.0057 (6)
C16	0.0170 (7)	0.0186 (7)	0.0328 (8)	−0.0010 (6)	−0.0005 (6)	0.0000 (6)
C17	0.0141 (6)	0.0229 (7)	0.0242 (7)	0.0039 (6)	0.0027 (5)	−0.0020 (6)
C18	0.0192 (7)	0.0212 (7)	0.0218 (7)	0.0034 (6)	0.0044 (6)	0.0032 (6)
C19	0.0179 (7)	0.0162 (7)	0.0238 (7)	0.0016 (5)	0.0037 (5)	0.0003 (6)
C20	0.0227 (8)	0.0299 (9)	0.0261 (8)	0.0031 (6)	0.0005 (6)	−0.0038 (7)
C21	0.0160 (6)	0.0148 (7)	0.0165 (7)	−0.0003 (5)	0.0009 (5)	−0.0001 (5)
C22	0.0128 (6)	0.0129 (6)	0.0174 (7)	0.0000 (5)	0.0002 (5)	−0.0011 (5)
C23	0.0137 (6)	0.0163 (7)	0.0162 (6)	−0.0008 (5)	−0.0004 (5)	−0.0008 (5)
C24	0.0160 (6)	0.0150 (7)	0.0167 (6)	0.0008 (5)	0.0040 (5)	0.0021 (5)
C25	0.0181 (7)	0.0192 (7)	0.0164 (6)	−0.0005 (5)	0.0015 (5)	0.0016 (5)
C26	0.0226 (7)	0.0178 (7)	0.0195 (7)	−0.0032 (6)	0.0033 (6)	−0.0032 (5)
C27	0.0233 (7)	0.0139 (7)	0.0226 (7)	0.0008 (5)	0.0065 (6)	0.0017 (5)
C28	0.0191 (7)	0.0172 (7)	0.0176 (7)	0.0022 (5)	0.0029 (5)	0.0034 (5)
C29	0.0164 (6)	0.0169 (7)	0.0157 (6)	−0.0008 (5)	0.0035 (5)	−0.0006 (5)
C30	0.0235 (7)	0.0230 (8)	0.0201 (7)	0.0018 (6)	−0.0051 (6)	0.0023 (6)

Geometric parameters (Å, º)

S1—O2	1.4291 (10)	C12—C13	1.400 (2)
S1—O1	1.4318 (10)	C12—H12	0.9300
S1—N1	1.6930 (11)	C14—C19	1.391 (2)
S1—C6	1.7545 (14)	C14—C15	1.392 (2)
S2—O3	1.4269 (11)	C15—C16	1.388 (2)
S2—O4	1.4340 (11)	C15—H15	0.9300
S2—N2	1.6774 (12)	C16—C17	1.397 (2)
S2—C14	1.7617 (15)	C16—H16	0.9300
O5—C29	1.3686 (17)	C17—C18	1.396 (2)
O5—C30	1.4250 (17)	C17—C20	1.502 (2)
N1—C8	1.4339 (17)	C18—C19	1.383 (2)
N1—C22	1.4466 (17)	C18—H18	0.9300
N2—C13	1.4403 (17)	C19—H19	0.9300
N2—C21	1.4784 (17)	C20—H20A	0.9600
C1—C2	1.384 (2)	C20—H20B	0.9600
C1—C6	1.3873 (19)	C20—H20C	0.9600
C1—H1	0.9300	C21—C22	1.5027 (18)
C2—C3	1.395 (2)	C21—H21A	0.9700
C2—H2	0.9300	C21—H21B	0.9700
C3—C4	1.3972 (19)	C22—C23	1.3312 (19)
C3—C7	1.5029 (19)	C23—C24	1.4742 (19)
C4—C5	1.384 (2)	C23—H23	0.9300
C4—H4	0.9300	C24—C25	1.398 (2)
C5—C6	1.3952 (19)	C24—C29	1.4087 (19)
C5—H5	0.9300	C25—C26	1.391 (2)
C7—H7A	0.9600	C25—H25	0.9300
C7—H7B	0.9600	C26—C27	1.381 (2)
C7—H7C	0.9600	C26—H26	0.9300
C8—C9	1.3966 (19)	C27—C28	1.393 (2)
C8—C13	1.4044 (19)	C27—H27	0.9300
C9—C10	1.381 (2)	C28—C29	1.3909 (19)
C9—H9	0.9300	C28—H28	0.9300
C10—C11	1.385 (2)	C30—H30A	0.9600
C10—H10	0.9300	C30—H30B	0.9600
C11—C12	1.380 (2)	C30—H30C	0.9600
C11—H11	0.9300
O2—S1—O1	119.54 (6)	C19—C14—C15	120.68 (13)
O2—S1—N1	106.53 (6)	C19—C14—S2	119.77 (11)
O1—S1—N1	107.74 (6)	C15—C14—S2	119.53 (11)
O2—S1—C6	108.72 (6)	C16—C15—C14	119.33 (14)
O1—S1—C6	109.09 (6)	C16—C15—H15	120
N1—S1—C6	104.13 (6)	C14—C15—H15	120
O3—S2—O4	119.36 (6)	C15—C16—C17	121.09 (14)
O3—S2—N2	107.26 (6)	C15—C16—H16	119
O4—S2—N2	105.58 (6)	C17—C16—H16	119
O3—S2—C14	108.42 (7)	C18—C17—C16	118.19 (14)
O4—S2—C14	108.96 (7)	C18—C17—C20	120.44 (14)
N2—S2—C14	106.54 (6)	C16—C17—C20	121.35 (14)
C29—O5—C30	118.20 (11)	C19—C18—C17	121.65 (14)
C8—N1—C22	116.23 (11)	C19—C18—H18	119
C8—N1—S1	119.64 (9)	C17—C18—H18	119
C22—N1—S1	113.18 (9)	C18—C19—C14	119.04 (14)
C13—N2—C21	115.12 (11)	C18—C19—H19	120
C13—N2—S2	116.99 (9)	C14—C19—H19	120
C21—N2—S2	116.38 (9)	C17—C20—H20A	109
C2—C1—C6	119.34 (13)	C17—C20—H20B	109
C2—C1—H1	120	H20A—C20—H20B	109
C6—C1—H1	120	C17—C20—H20C	109
C1—C2—C3	120.84 (13)	H20A—C20—H20C	109
C1—C2—H2	120	H20B—C20—H20C	109
C3—C2—H2	120	N2—C21—C22	111.64 (11)
C2—C3—C4	118.74 (13)	N2—C21—H21A	109
C2—C3—C7	120.39 (13)	C22—C21—H21A	109
C4—C3—C7	120.87 (13)	N2—C21—H21B	109
C5—C4—C3	121.26 (13)	C22—C21—H21B	109
C5—C4—H4	119	H21A—C21—H21B	108
C3—C4—H4	119	C23—C22—N1	118.92 (12)
C4—C5—C6	118.69 (13)	C23—C22—C21	127.79 (12)
C4—C5—H5	120	N1—C22—C21	113.28 (11)
C6—C5—H5	120	C22—C23—C24	127.66 (12)
C1—C6—C5	121.13 (12)	C22—C23—H23	116
C1—C6—S1	119.49 (10)	C24—C23—H23	116
C5—C6—S1	119.26 (10)	C25—C24—C29	117.98 (13)
C3—C7—H7A	109	C25—C24—C23	123.35 (12)
C3—C7—H7B	109	C29—C24—C23	118.37 (12)
H7A—C7—H7B	109	C26—C25—C24	121.26 (13)
C3—C7—H7C	109	C26—C25—H25	119
H7A—C7—H7C	109	C24—C25—H25	119
H7B—C7—H7C	109	C27—C26—C25	119.75 (13)
C9—C8—C13	119.24 (12)	C27—C26—H26	120
C9—C8—N1	119.32 (12)	C25—C26—H26	120
C13—C8—N1	121.29 (12)	C26—C27—C28	120.53 (13)
C10—C9—C8	120.82 (13)	C26—C27—H27	120
C10—C9—H9	119.6	C28—C27—H27	120
C8—C9—H9	120	C29—C28—C27	119.60 (13)
C9—C10—C11	119.86 (14)	C29—C28—H28	120
C9—C10—H10	120	C27—C28—H28	120
C11—C10—H10	120	O5—C29—C28	124.35 (12)
C12—C11—C10	120.20 (13)	O5—C29—C24	114.77 (12)
C12—C11—H11	120	C28—C29—C24	120.88 (13)
C10—C11—H11	120	O5—C30—H30A	109
C11—C12—C13	120.70 (14)	O5—C30—H30B	109
C11—C12—H12	120	H30A—C30—H30B	109
C13—C12—H12	120	O5—C30—H30C	109
C12—C13—C8	119.01 (13)	H30A—C30—H30C	109
C12—C13—N2	119.96 (12)	H30B—C30—H30C	109
C8—C13—N2	121.02 (12)
N1—C22—C23—C24	−172.0 (1)	S1—N1—C22—C23	73.8 (1)
N2—C21—C22—C23	127.2 (1)	C14—S2—N2—C21	84.8 (1)
C6—S1—N1—C8	−91.8 (1)

(III) (E)-methyl 2-[(1,4-di-p-tosyl-1,2,3,4-tetrahydroquinoxalin-2-ylidene)methyl]benzoate

Crystal data

C31H28N2O6S2	Z = 2
Mr = 588.67	F(000) = 616
Triclinic, P1	Dx = 1.450 Mg m^−3
Hall symbol: -P 1	Melting point: 441 K
a = 10.1431 (7) Å	Mo Kα radiation, λ = 0.71073 Å
b = 11.7721 (4) Å	Cell parameters from 4963 reflections
c = 11.8879 (9) Å	θ = 2.4–26.3°
α = 101.093 (1)°	µ = 0.25 mm^−1
β = 103.928 (2)°	T = 100 K
γ = 91.248 (3)°	Block, colourless
V = 1348.55 (15) Å^3	0.45 × 0.45 × 0.40 mm

Data collection

Bruker SMART CCD area-detector diffractometer	4625 independent reflections
Radiation source: fine-focus sealed tube	4153 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.027
ϕ and ω scans	θmax = 25.0°, θmin = 1.8°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −11→12
Tmin = 0.897, Tmax = 0.907	k = −13→13
9605 measured reflections	l = −13→13

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)] = 0.036	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.094	H-atom parameters constrained
S = 1.04	w = 1/[σ^2(Fo^2) + (0.0405P)^2 + 0.9284P] where P = (Fo^2 + 2Fc^2)/3
4625 reflections	(Δ/σ)max < 0.001
370 parameters	Δρmax = 0.35 e Å^−3
0 restraints	Δρmin = −0.35 e Å^−3

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
S1	0.08193 (4)	0.27896 (4)	0.10050 (4)	0.01639 (12)
S2	0.54542 (4)	0.24880 (4)	0.47822 (4)	0.01615 (13)
N1	0.22339 (15)	0.23010 (13)	0.18022 (13)	0.0158 (3)
N2	0.38448 (15)	0.27713 (12)	0.42298 (13)	0.0158 (3)
O1	−0.02637 (13)	0.19212 (11)	0.07954 (11)	0.0210 (3)
O2	0.11751 (13)	0.31297 (11)	0.00200 (11)	0.0209 (3)
O3	0.54273 (13)	0.18077 (11)	0.56543 (11)	0.0215 (3)
O4	0.62193 (13)	0.35885 (11)	0.51281 (11)	0.0216 (3)
O5	0.54019 (14)	0.22762 (12)	−0.01423 (12)	0.0271 (3)
O6	0.72143 (13)	0.31911 (11)	−0.04071 (11)	0.0206 (3)
C1	0.09944 (19)	0.51271 (16)	0.18985 (18)	0.0229 (4)
H1	0.1476	0.5215	0.1343	0.034*
C2	0.0770 (2)	0.60805 (17)	0.26909 (18)	0.0255 (4)
H2	0.1126	0.6810	0.2676	0.038*
C3	0.0023 (2)	0.59778 (17)	0.35109 (17)	0.0233 (4)
C4	−0.0489 (2)	0.48755 (17)	0.35234 (17)	0.0232 (4)
H4	−0.1008	0.4792	0.4054	0.035*
C5	−0.02450 (19)	0.39028 (16)	0.27664 (16)	0.0205 (4)
H5	−0.0567	0.3169	0.2805	0.031*
C6	0.04909 (18)	0.40359 (16)	0.19437 (16)	0.0177 (4)
C7	−0.0229 (2)	0.70366 (18)	0.43458 (19)	0.0312 (5)
H7A	−0.0810	0.6817	0.4808	0.056*
H7B	−0.0659	0.7585	0.3900	0.056*
H7C	0.0623	0.7383	0.4862	0.056*
C8	0.20792 (18)	0.15653 (15)	0.26057 (16)	0.0162 (4)
C9	0.12101 (18)	0.05552 (16)	0.21971 (17)	0.0202 (4)
H9	0.0762	0.0349	0.1399	0.030*
C10	0.10067 (19)	−0.01407 (16)	0.29600 (18)	0.0235 (4)
H10	0.0412	−0.0803	0.2676	0.035*
C11	0.1686 (2)	0.01447 (17)	0.41483 (18)	0.0240 (4)
H11	0.1528	−0.0310	0.4668	0.036*
C12	0.25986 (19)	0.11074 (16)	0.45551 (17)	0.0207 (4)
H12	0.3063	0.1292	0.5350	0.031*
C13	0.28362 (17)	0.18105 (15)	0.37916 (16)	0.0159 (4)
C14	0.59961 (17)	0.16309 (15)	0.36214 (15)	0.0161 (4)
C15	0.56057 (19)	0.04530 (15)	0.32920 (16)	0.0189 (4)
H15	0.5078	0.0112	0.3695	0.028*
C16	0.60124 (19)	−0.02064 (16)	0.23567 (17)	0.0209 (4)
H16	0.5747	−0.0995	0.2128	0.031*
C17	0.68126 (18)	0.02893 (16)	0.17495 (16)	0.0194 (4)
C18	0.71951 (19)	0.14693 (16)	0.21036 (17)	0.0209 (4)
H18	0.7734	0.1810	0.1710	0.031*
C19	0.67901 (18)	0.21473 (16)	0.30302 (17)	0.0196 (4)
H19	0.7046	0.2938	0.3254	0.029*
C20	0.7231 (2)	−0.04244 (17)	0.07159 (18)	0.0270 (5)
H20A	0.7495	−0.1161	0.0894	0.049*
H20B	0.7985	−0.0023	0.0567	0.049*
H20C	0.6480	−0.0545	0.0027	0.049*
C21	0.36741 (18)	0.36796 (15)	0.35095 (16)	0.0161 (4)
H21A	0.4498	0.4191	0.3739	0.024*
H21B	0.2932	0.4140	0.3666	0.024*
C22	0.33779 (17)	0.31632 (15)	0.22057 (16)	0.0153 (4)
C23	0.40004 (18)	0.34132 (15)	0.14055 (16)	0.0164 (4)
H23	0.3733	0.2940	0.0655	0.025*
C24	0.50588 (18)	0.43464 (15)	0.15655 (15)	0.0161 (4)
C25	0.50153 (19)	0.54244 (15)	0.22961 (16)	0.0178 (4)
H25	0.4343	0.5525	0.2711	0.027*
C26	0.59472 (19)	0.63431 (16)	0.24160 (16)	0.0198 (4)
H26	0.5904	0.7046	0.2917	0.030*
C27	0.69420 (19)	0.62196 (16)	0.17936 (16)	0.0198 (4)
H27	0.7565	0.6838	0.1869	0.030*
C28	0.70038 (18)	0.51690 (16)	0.10582 (16)	0.0183 (4)
H28	0.7674	0.5087	0.0641	0.027*
C29	0.60818 (18)	0.42322 (15)	0.09311 (15)	0.0164 (4)
C30	0.61616 (18)	0.31296 (16)	0.00907 (16)	0.0175 (4)
C31	0.7330 (2)	0.21694 (17)	−0.12621 (17)	0.0230 (4)
H31A	0.8216	0.2198	−0.1415	0.041*
H31B	0.6646	0.2142	−0.1985	0.041*
H31C	0.7204	0.1489	−0.0955	0.041*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0151 (2)	0.0190 (2)	0.0159 (2)	0.00112 (17)	0.00476 (17)	0.00459 (18)
S2	0.0179 (2)	0.0161 (2)	0.0137 (2)	0.00183 (17)	0.00360 (17)	0.00150 (17)
N1	0.0144 (7)	0.0172 (8)	0.0168 (8)	0.0009 (6)	0.0058 (6)	0.0037 (6)
N2	0.0166 (8)	0.0157 (7)	0.0165 (8)	0.0020 (6)	0.0058 (6)	0.0046 (6)
O1	0.0173 (7)	0.0232 (7)	0.0218 (7)	−0.0012 (5)	0.0037 (5)	0.0046 (5)
O2	0.0207 (7)	0.0266 (7)	0.0176 (7)	0.0018 (5)	0.0059 (5)	0.0079 (5)
O3	0.0251 (7)	0.0241 (7)	0.0159 (7)	0.0053 (6)	0.0046 (5)	0.0063 (5)
O4	0.0219 (7)	0.0193 (7)	0.0203 (7)	−0.0002 (5)	0.0026 (5)	−0.0008 (5)
O5	0.0275 (8)	0.0233 (7)	0.0306 (8)	−0.0058 (6)	0.0159 (6)	−0.0044 (6)
O6	0.0205 (7)	0.0213 (7)	0.0222 (7)	0.0025 (5)	0.0115 (5)	0.0023 (5)
C1	0.0232 (10)	0.0229 (10)	0.0275 (11)	0.0052 (8)	0.0114 (8)	0.0107 (8)
C2	0.0300 (11)	0.0189 (10)	0.0302 (11)	0.0031 (8)	0.0086 (9)	0.0095 (8)
C3	0.0238 (10)	0.0224 (10)	0.0221 (10)	0.0058 (8)	0.0021 (8)	0.0045 (8)
C4	0.0221 (10)	0.0296 (11)	0.0190 (10)	0.0019 (8)	0.0074 (8)	0.0047 (8)
C5	0.0197 (9)	0.0211 (10)	0.0208 (10)	−0.0011 (8)	0.0049 (8)	0.0049 (8)
C6	0.0153 (9)	0.0206 (9)	0.0179 (9)	0.0039 (7)	0.0039 (7)	0.0053 (7)
C7	0.0384 (12)	0.0272 (11)	0.0267 (11)	0.0088 (9)	0.0080 (9)	0.0020 (9)
C8	0.0166 (9)	0.0148 (9)	0.0206 (10)	0.0048 (7)	0.0092 (7)	0.0053 (7)
C9	0.0178 (9)	0.0187 (9)	0.0233 (10)	0.0014 (7)	0.0054 (8)	0.0022 (8)
C10	0.0212 (10)	0.0164 (9)	0.0343 (12)	−0.0013 (8)	0.0089 (8)	0.0066 (8)
C11	0.0265 (10)	0.0213 (10)	0.0304 (11)	0.0037 (8)	0.0126 (9)	0.0129 (8)
C12	0.0221 (10)	0.0214 (10)	0.0215 (10)	0.0052 (8)	0.0083 (8)	0.0078 (8)
C13	0.0160 (9)	0.0138 (9)	0.0196 (9)	0.0036 (7)	0.0083 (7)	0.0022 (7)
C14	0.0141 (9)	0.0168 (9)	0.0166 (9)	0.0040 (7)	0.0026 (7)	0.0032 (7)
C15	0.0211 (9)	0.0169 (9)	0.0207 (10)	0.0013 (7)	0.0077 (8)	0.0058 (7)
C16	0.0255 (10)	0.0147 (9)	0.0223 (10)	0.0001 (8)	0.0070 (8)	0.0021 (8)
C17	0.0189 (9)	0.0196 (9)	0.0199 (10)	0.0023 (7)	0.0059 (7)	0.0027 (7)
C18	0.0192 (9)	0.0227 (10)	0.0227 (10)	−0.0012 (8)	0.0090 (8)	0.0050 (8)
C19	0.0188 (9)	0.0160 (9)	0.0235 (10)	−0.0007 (7)	0.0062 (8)	0.0020 (7)
C20	0.0292 (11)	0.0251 (10)	0.0271 (11)	−0.0014 (8)	0.0141 (9)	−0.0021 (8)
C21	0.0179 (9)	0.0133 (9)	0.0185 (9)	0.0013 (7)	0.0060 (7)	0.0043 (7)
C22	0.0151 (9)	0.0132 (8)	0.0180 (9)	0.0021 (7)	0.0047 (7)	0.0036 (7)
C23	0.0162 (9)	0.0162 (9)	0.0173 (9)	0.0022 (7)	0.0055 (7)	0.0032 (7)
C24	0.0160 (9)	0.0198 (9)	0.0127 (9)	0.0019 (7)	0.0026 (7)	0.0053 (7)
C25	0.0216 (10)	0.0187 (9)	0.0159 (9)	0.0030 (7)	0.0086 (7)	0.0054 (7)
C26	0.0256 (10)	0.0163 (9)	0.0164 (10)	0.0010 (8)	0.0035 (8)	0.0028 (7)
C27	0.0195 (9)	0.0185 (9)	0.0211 (10)	−0.0034 (7)	0.0028 (8)	0.0070 (8)
C28	0.0171 (9)	0.0232 (10)	0.0166 (9)	0.0012 (7)	0.0052 (7)	0.0076 (7)
C29	0.0176 (9)	0.0204 (9)	0.0117 (9)	0.0030 (7)	0.0023 (7)	0.0058 (7)
C30	0.0150 (9)	0.0231 (10)	0.0154 (9)	0.0009 (8)	0.0032 (7)	0.0070 (7)
C31	0.0244 (10)	0.0268 (10)	0.0189 (10)	0.0046 (8)	0.0099 (8)	0.0014 (8)

Geometric parameters (Å, º)

S1—O1	1.4267 (13)	C12—C13	1.397 (3)
S1—O2	1.4279 (13)	C12—H12	0.9300
S1—N1	1.6967 (15)	C14—C15	1.387 (2)
S1—C6	1.7547 (18)	C14—C19	1.389 (3)
S2—O4	1.4309 (13)	C15—C16	1.383 (3)
S2—O3	1.4314 (13)	C15—H15	0.9300
S2—N2	1.6731 (15)	C16—C17	1.394 (3)
S2—C14	1.7545 (18)	C16—H16	0.9300
N1—C8	1.439 (2)	C17—C18	1.389 (3)
N1—C22	1.449 (2)	C17—C20	1.505 (3)
N2—C13	1.436 (2)	C18—C19	1.383 (3)
N2—C21	1.482 (2)	C18—H18	0.9300
O5—C30	1.198 (2)	C19—H19	0.9300
O6—C30	1.346 (2)	C20—H20A	0.9600
O6—C31	1.444 (2)	C20—H20B	0.9600
C1—C2	1.381 (3)	C20—H20C	0.9600
C1—C6	1.387 (3)	C21—C22	1.506 (2)
C1—H1	0.9300	C21—H21A	0.9700
C2—C3	1.391 (3)	C21—H21B	0.9700
C2—H2	0.9300	C22—C23	1.334 (2)
C3—C4	1.392 (3)	C23—C24	1.472 (2)
C3—C7	1.505 (3)	C23—H23	0.9300
C4—C5	1.380 (3)	C24—C25	1.401 (2)
C4—H4	0.9300	C24—C29	1.417 (2)
C5—C6	1.394 (3)	C25—C26	1.384 (3)
C5—H5	0.9300	C25—H25	0.9300
C7—H7A	0.9600	C26—C27	1.382 (3)
C7—H7B	0.9600	C26—H26	0.9300
C7—H7C	0.9600	C27—C28	1.383 (3)
C8—C9	1.398 (2)	C27—H27	0.9300
C8—C13	1.405 (3)	C28—C29	1.392 (2)
C9—C10	1.380 (3)	C28—H28	0.9300
C9—H9	0.9300	C29—C30	1.495 (2)
C10—C11	1.386 (3)	C31—H31A	0.9600
C10—H10	0.9300	C31—H31B	0.9600
C11—C12	1.379 (3)	C31—H31C	0.9600
C11—H11	0.9300
O1—S1—O2	119.25 (8)	C15—C14—S2	119.69 (14)
O1—S1—N1	107.07 (7)	C19—C14—S2	119.38 (13)
O2—S1—N1	107.06 (7)	C16—C15—C14	119.07 (17)
O1—S1—C6	109.11 (8)	C16—C15—H15	120.5
O2—S1—C6	108.48 (8)	C14—C15—H15	120.5
N1—S1—C6	104.95 (8)	C15—C16—C17	121.21 (17)
O4—S2—O3	119.36 (8)	C15—C16—H16	119.4
O4—S2—N2	105.58 (8)	C17—C16—H16	119.4
O3—S2—N2	106.90 (8)	C18—C17—C16	118.45 (17)
O4—S2—C14	109.05 (8)	C18—C17—C20	120.38 (17)
O3—S2—C14	108.25 (8)	C16—C17—C20	121.16 (17)
N2—S2—C14	107.07 (8)	C19—C18—C17	121.31 (17)
C8—N1—C22	116.56 (14)	C19—C18—H18	119.3
C8—N1—S1	118.71 (11)	C17—C18—H18	119.3
C22—N1—S1	112.88 (11)	C18—C19—C14	119.04 (17)
C13—N2—C21	114.38 (14)	C18—C19—H19	120.5
C13—N2—S2	117.94 (11)	C14—C19—H19	120.5
C21—N2—S2	115.49 (11)	C17—C20—H20A	109.5
C30—O6—C31	115.02 (14)	C17—C20—H20B	109.5
C2—C1—C6	118.99 (18)	H20A—C20—H20B	109.5
C2—C1—H1	120.5	C17—C20—H20C	109.5
C6—C1—H1	120.5	H20A—C20—H20C	109.5
C1—C2—C3	121.72 (18)	H20B—C20—H20C	109.5
C1—C2—H2	119.1	N2—C21—C22	111.73 (14)
C3—C2—H2	119.1	N2—C21—H21A	109.3
C2—C3—C4	118.07 (18)	C22—C21—H21A	109.3
C2—C3—C7	120.44 (18)	N2—C21—H21B	109.3
C4—C3—C7	121.49 (18)	C22—C21—H21B	109.3
C5—C4—C3	121.47 (18)	H21A—C21—H21B	107.9
C5—C4—H4	119.3	C23—C22—N1	117.92 (16)
C3—C4—H4	119.3	C23—C22—C21	128.83 (16)
C4—C5—C6	119.07 (17)	N1—C22—C21	113.23 (14)
C4—C5—H5	120.5	C22—C23—C24	127.90 (16)
C6—C5—H5	120.5	C22—C23—H23	116.1
C1—C6—C5	120.64 (17)	C24—C23—H23	116.1
C1—C6—S1	120.77 (14)	C25—C24—C29	117.56 (16)
C5—C6—S1	118.55 (14)	C25—C24—C23	120.00 (16)
C3—C7—H7A	109.5	C29—C24—C23	122.26 (16)
C3—C7—H7B	109.5	C26—C25—C24	121.66 (17)
H7A—C7—H7B	109.5	C26—C25—H25	119.2
C3—C7—H7C	109.5	C24—C25—H25	119.2
H7A—C7—H7C	109.5	C27—C26—C25	120.19 (17)
H7B—C7—H7C	109.5	C27—C26—H26	119.9
C9—C8—C13	118.64 (16)	C25—C26—H26	119.9
C9—C8—N1	119.99 (16)	C26—C27—C28	119.47 (17)
C13—C8—N1	121.30 (15)	C26—C27—H27	120.3
C10—C9—C8	121.01 (18)	C28—C27—H27	120.3
C10—C9—H9	119.5	C27—C28—C29	121.24 (17)
C8—C9—H9	119.5	C27—C28—H28	119.4
C9—C10—C11	120.16 (17)	C29—C28—H28	119.4
C9—C10—H10	119.9	C28—C29—C24	119.87 (16)
C11—C10—H10	119.9	C28—C29—C30	119.07 (16)
C12—C11—C10	119.57 (17)	C24—C29—C30	121.03 (16)
C12—C11—H11	120.2	O5—C30—O6	122.04 (17)
C10—C11—H11	120.2	O5—C30—C29	126.13 (16)
C11—C12—C13	121.06 (18)	O6—C30—C29	111.83 (15)
C11—C12—H12	119.5	O6—C31—H31A	109.5
C13—C12—H12	119.5	O6—C31—H31B	109.5
C12—C13—C8	119.25 (16)	H31A—C31—H31B	109.5
C12—C13—N2	119.66 (16)	O6—C31—H31C	109.5
C8—C13—N2	121.09 (15)	H31A—C31—H31C	109.5
C15—C14—C19	120.92 (17)	H31B—C31—H31C	109.5
N1—C22—C23—C24	171.7 (2)	S1—N1—C22—C23	−72.5 (2)
N2—C21—C22—C23	−128.1 (2)	C14—S2—N2—C21	−77.3 (1)
C6—S1—N1—C8	84.8 (2)