(±)-6-Benzyl-3,3-di­methyl­morpholine-2,5-dione and its 5-mono­thio and 2,5-di­thio derivatives

The morpholine ring of the title dione, C₁₃H₁₅NO₃, shows a boat conformation that is distorted towards a twist-boat, with the boat ends being the two Csp³ atoms of the ring. The benzyl substituent is in the favoured `exo' position. In the mono­thione derivative, (±)-6-benzyl-3,3-di­methyl-5-thioxo­morpholin-2-one, C<sub>13</sub>H<sub>15</sub>NO<sub>2</sub>S, this ring has a much flatter conformation that is midway between a boat and an envelope, with the di­methyl end being almost planar. The orientation of the benzyl group is `endo'. The di­thione derivative, (±)-6-benzyl-3,3-di­methyl­morpholine-2,5-di­thione, C₁₃H₁₅N­OS₂, has two symmetry-independent mol­ecules, which show different puckering of the morpholine ring. One mol­ecule has a flattened envelope conformation distorted towards a screw-boat, while the conformation in the other mol­ecule is similar to that in the mono­thione derivative. Intermolecular hydrogen bonds link the mol­ecules in the three compounds, respectively, into centrosymmetric dimers, infinite chains, and dimers made up of one of each of the symmetry-independent mol­ecules.

S1. Comment

Some years ago, we showed that diamides akin to compound (III) (see Scheme), which are conveniently prepared by the reaction of hydroxy acids with 3-amino-2H-azirines, can be cyclized by treatment with HCl gas in a non-nucleophilic solvent (Obrecht & Heimgartner, 1984, 1987; Heimgartner, 1991a; Heimgartner et al., 1999). This method, the so-called 'direct amide cyclization', has been used widely to prepare cyclic depsipeptides by lactone formation (Obrecht & Heimgartner, 1984, 1990; Magirius, 1995; Koch & Heimgartner, 2000; Koch et al., 2000). In the case of larger rings, the cyclization occurs via 1,3-oxazol-5(4H)-ones as intermediates and ring enlargement by intramolecular nucleophilic attack of the hydroxy group at the oxazolone C═ O group (Heimgartner et al., 1999). On the other hand, a mechanism via an intermediate oxonium ion is more likely for the formation of the six-membered morpholine-2,5-diones.

In connection with our investigations of 1,3-dipolar cycloadditions with thiocarbonyl compounds (cf. Heimgartner, 1986, 1991b; Linden et al., 1999; Mloston & Heimgartner, 2000), we also became interested in the thioanalogues of morpholinediones as C═S dipolarophiles. The mono- and dithioanalogues are attractive models for the study of the chemoselectivity (dipolarophilicity) of different π-systems in 1,3-dipolar cycloadditions. The racemic morpholine-2,5-dione (IV) was prepared by following the described protocol (Obrecht & Heimgartner, 1987). Subsequent successive thionation with Lawesson reagent (LR) led almost quantitatively to the monothione (V) and then to the morpholine-2,5-dithione (VI), although the latter reaction was sluggish with a low yield. As part of the full characterization of compounds (IV), (V), and (VI), their low-temperature crystal structures have been determined. \sch

In each compound, the bond lengths and angles are generally within normal ranges. The amide C═O and thioamide C═S bonds in the dione, (IV), and the dithione, (VI), respectively, are longer than the corresponding ester C═O and thioester C═S bonds (Tables 1 and 3). This reflects the expected greater π-electron delocalization in (thio)amide groups compared with (thio)ester groups and is consistent with the trends for such groups derived from an examination of the Cambridge Structural Database (CSD, October 2000 release; Allen & Kennard, 1993). The angles at the O and N atoms of the morpholine rings (Tables 1, 3 and 5) are significantly larger than 120°, particularly in the presence of the ring flattening observed in the monothione, (V), and dithione, (VI), derivatives, as described below.

The morpholine ring of the dione, (IV), has puckering parameters (Cremer & Pople, 1975) of Q = 0.463 (2) Å, θ = 92.4 (2)° and ϕ = 133.4 (2)°, which represent a conformation midway between a boat (nearest ideal values: θ = 90, ϕ = 120°) and a twist-boat (θ = 90, ϕ = 150°) (Boeyens, 1978), where the boat ends are the two sp³ C atoms of the ring (Fig. 1) and the twist results from a slight non-planarity of the four atoms constituting the base of the boat. The r.m.s. deviation of O1, C2, N4 and C5 from their mean plane is 0.053 Å, while C3 and C6 deviate from this plane by 0.363 (3) and 0.416 (3) Å, respectively. The benzyl substituent is in the favoured 'exo' position.

The morpholine ring of the monothione derivative, (V), has a much flatter and less twisted boat conformation (Fig. 2). The two sp³ C atoms of the ring again form the ends of the boat, but the dimethyl end is almost co-planar with the base of the boat, so that the ring is distorted towards an envelope conformation. This is borne out by the ring puckering parameters of Q = 0.139 (2) Å, θ = 75.2 (8)° and ϕ = 298.3 (10)°. The value of ϕ is appropriate for either an envelope or boat conformation (nearest ideal value is 300°) (Boeyens, 1978), while θ lies approximately midway between the ideal values for the boat (90°) and envelope (54.7°) conformations. The r.m.s. deviation of O1, C2, N4 and C5 from their mean plane is only 0.002 Å, while C3 and C6 deviate from this plane by 0.069 (3) and 0.162 (3) Å, respectively. The orientation of the benzyl group is 'endo', which brings the phenyl ring into a position above the body of the morpholine ring.

The asymmetric unit of the dithione derivative, (VI), has two symmetry-independent molecules (Fig. 3) and PLATON (Spek, 2001) confirmed that there was no additional overlooked symmetry, although the molecules are approximately related by a non-crystallographic twofold axis. The two molecules have different puckering of the morpholine ring and the orientation of the phenyl ring about the C9—C10 bond (C29—C30 in molecule B) also differs by a twist of about 17°. The morpholine ring of molecule A has puckering parameters of Q = 0.185 (2) Å, θ = 62.8 (7)° and ϕ = 75.2 (8)°, which represent a conformation midway between that of a slightly flattened envelope (nearest ideal values: θ = 54.7, ϕ = 60°) and a screw-boat (θ = 67.5, ϕ = 90°) (Boeyens, 1978). In contrast to compounds (IV) and (V), it is not an sp³ C atom that is out of the plane, but the thioester C atom, C2. The r.m.s. deviation of O1, C3, N4, C5 and C6 from their mean plane is 0.022 Å, while C2 deviates from this plane by 0.250 (3) Å. The phenyl ring is positioned above the morpholine ring.

The morpholine ring in molecule B of (VI) has a flattened boat conformation distorted towards an envelope, similar to, but even flatter than the conformation observed in compound (V). The ring puckering parameters are Q = 0.097 (2) Å, θ = 101.6 (12)° and ϕ = 120.5 (12)°. Using the inverted molecule, which is also present in this racemic compound, θ = 78.4 (12)° and ϕ = 300.5 (12)°, which indicate a conformation similar to that observed for compound (V). As in (V), the two sp³ C atoms of the ring form the ends of the boat, with the dimethyl end being almost co-planar with the base of the boat. The r.m.s. deviation of O21, C22, N24 and C25 from their mean plane is only 0.0004 Å, while C23 and C26 deviate from this plane by 0.056 (3) and 0.108 (3) Å, respectively. The orientation of the benzyl group is 'endo', with the phenyl ring again being positioned above the morpholine ring.

There are only two structure reports cited in the CSD of compounds containing a morpholine-2,5-dione moiety, while there are no reports of any structures involving 5-thioxomorpholin-2-one or morpholine-2,5-dithione moieties. Both reported structures are simply substituted morpholine derivatives. The morpholine ring in 3-benzyl-6-isopropylmorpholine-2,5-dione was reported as having a boat conformation with the sp³ C atoms forming the boat ends (Bolte & Egert, 1994). However, a closer examination of the puckering parameters [Q = 0.494 (2) Å, θ = 93.1 (2)° and ϕ = 129.3 (2)°] shows that the ring has an unflattened conformation that lies midway between a boat and a twist-boat, and which is virtually identical to that in compound (IV). Conversely, in 3-benzyl-3-hydroxy-6-methylamino-6-(2-methylpropyl)morpholine-2,5-dione (Iijima et al., 1992), the morpholine ring has an almost completely flattened boat conformation with the two sp³ C atoms being only 0.086 and 0.078 Å from the plane defined by the other four ring atoms, which are all 0.002 Å from their mean plane.

While a comparison of the structures of compounds (IV), (V) and (VI) might induce one to conclude that an increasing number of thione substituents in the morpholine ring leads to a greater flattening of the ring, the two previously reported structures of morpholine-2,5-dione derivatives contradict this hypothesis and suggest that the cause of the ring flattening is not necessarily related to the degree of thione substitution, but to other effects which cannot readily be deduced from the small number of determined structures of this class.

The amide N—H of compound (IV) forms an intermolecular hydrogen bond with the amide O atom of an adjacent molecule (Table 2). This acceptor molecule then donates back to the first molecule, thereby linking pairs of molecules into centrosymmetric dimers whose interactions can be described by the graph set motif (Bernstein et al., 1995) of R²₂(8). In the monothione derivative, (V), a simple change from the ester group of (IV) to a thioester group has dramatically altered the hydrogen bonding pattern (Table 4). The acceptor atom is now the morpholine ring O atom of a neighbouring molecule and the intermolecular interactions link the molecules of (V) into infinite one-dimensional chains which run parallel to the [010] direction and have a graph set motif of C(5). In compound (VI), the hydrogen bonding pattern is similar to that in compound (IV). The acceptor atom is the thioamide S atom of the other symmetry-independent molecule in the asymmetric unit. This acceptor molecule then donates back to the first molecule, thus forming hydrogen-bonded dimers comprised of one of each of the symmetry-independent molecules (Table 6, Fig. 3). These interactions can again be described by the graph set motif of R²₂(8).

Related literature

For related literature, see: Allen & Kennard (1993); Bernstein et al. (1995); Boeyens (1978); Bolte & Egert (1994); Cremer & Pople (1975); Heimgartner (1986, 1991a, 1991b); Heimgartner et al. (1999); Iijima et al. (1992); Koch & Heimgartner (2000); Koch, Linden & Heimgartner (2000); Linden et al. (1999); Magirius (1995); Mloston & Heimgartner (2000); Obrecht & Heimgartner (1984, 1987, 1990); Scheibye et al. (1978); Spek (2001).

S2. Experimental

Compound (III) was obtained in 92% yield by the reaction of D,L-phenyllactic acid, (I) (408 mg, 2.46 mmol), and 2,2,N-trimethyl-N-phenyl-2H-azirin-3-amine, (II) (472 mg, 2.71 mmol), in acetonitrile (20 ml) at room temperature following a known protocol (Obrecht & Heimgartner, 1987). Treatment of a solution of (III) (2.19 g, 6.44 mmol) in toluene (300 ml) at 373 K with dry HCl gas for 15 min yielded, after chromatography (silica gel, dichloromethane/diethylether 6:1) and crystallization from diethylether, compound (IV) in 27% yield as colourless plates (m.p. 437–438 K). Lawesson reagent (Scheibye et al., 1978) (240 mg, 0.59 mmol) was added to a solution of (IV) (276 mg, 1.19 mmol) in toluene (15 ml), and the mixture was heated to 373 K for 30 min. After chromatography (silica gel, dichloromethane/hexane 3:2) and crystallization from dichloromethane/diethylether, compound (V) was obtained in 96% yield as colourless needles (m.p. 448–449 K). Heating a mixture of (V) (95 mg, 0.38 mmol) and Lawesson reagent (3.84 mg, 0.95 mmol) in toluene (10 ml) for 2 d under reflux led, after chromatographic separation (silica gel, dichloromethane/hexane 1:1), to compound (VI) in 28% yield as yellow prisms (m.p. 396–397 K). Suitable single crystals of (VI) were obtained by recrystallization from diethylether/dichloromethane/hexane.

S3. Refinement

For each compound, the methyl H atoms were constrained to an ideal geometry with U_iso(H) = 1.5U_eq(C), but were allowed to rotate freely about the C—C bonds. The positions of the amino H atoms were refined freely along with individual isotropic displacement parameters. All other H atoms were placed in geometrically idealized positions and constrained to ride on their parent atoms with U_iso(H) = 1.2U_eq(C). For (V), the ψ-scans for three reflections showed a more severe absorption profile than that which is theoretically predicted and this is attributed to the anisotropic shape of the crystal. A test refinement using uncorrected reflection data produced virtually identical results.

Computing details

For all compounds, data collection: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1991); cell refinement: MSC/AFC Diffractometer Control Software; data reduction: TEXSAN (Molecular Structure Corporation, 1999). Program(s) used to solve structure: SHELXS97 (Sheldrick, 1997) for (IV); SIR92 (Altomare et al., 1994) for (V), (VI). For all compounds, program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2001).

Figures

	Fig. 1. The molecular structure of (IV) showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. The molecular structure of (V) showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 3. The molecular structure of both symmetry-independent molecules of (VI) showing the atom-labelling scheme and the hydrogen bonds (dashed lines). Molecule A is on the left. Displacement ellipsoids are drawn at the 30% probability level. H atoms are represented by circles of arbitrary size.

(IV) 6-benzyl-3,3-dimethylmorpholine-2,5-dione

Crystal data

C13H15NO3	F(000) = 248
Mr = 233.27	Dx = 1.281 Mg m^−3
Triclinic, P1	Melting point = 437–438 K
a = 5.699 (2) Å	Mo Kα radiation, λ = 0.71069 Å
b = 10.347 (3) Å	Cell parameters from 25 reflections
c = 11.327 (4) Å	θ = 19.0–20.0°
α = 67.51 (2)°	µ = 0.09 mm^−1
β = 80.38 (3)°	T = 173 K
γ = 80.35 (3)°	Plate, colourless
V = 604.5 (4) Å^3	0.50 × 0.38 × 0.12 mm
Z = 2

Data collection

Rigaku AFC-5R diffractometer	Rint = 0.025
Radiation source: Rigaku rotating anode generator	θmax = 27.5°, θmin = 3.4°
Graphite monochromator	h = −7→7
ω–2θ scans	k = −13→0
2927 measured reflections	l = −14→13
2773 independent reflections	3 standard reflections every 150 reflections
1859 reflections with I > 2σ(I)	intensity decay: none

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)] = 0.047	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.130	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	w = 1/[σ^2(Fo^2) + (0.053P)^2 + 0.1854P] where P = (Fo^2 + 2Fc^2)/3
2773 reflections	(Δ/σ)max = 0.001
160 parameters	Δρmax = 0.27 e Å^−3
0 restraints	Δρmin = −0.23 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
O1	0.4371 (2)	0.10417 (12)	0.63704 (12)	0.0321 (3)
O2	0.7608 (2)	0.11627 (14)	0.50074 (14)	0.0411 (4)
O5	−0.0837 (3)	0.34956 (14)	0.63550 (14)	0.0520 (5)
N4	0.2406 (3)	0.36142 (15)	0.48846 (14)	0.0283 (3)
H4	0.194 (4)	0.451 (2)	0.447 (2)	0.043 (6)*
C2	0.5594 (3)	0.16503 (17)	0.52203 (17)	0.0273 (4)
C3	0.4341 (3)	0.29250 (17)	0.42359 (16)	0.0244 (4)
C5	0.1008 (3)	0.29338 (18)	0.59202 (17)	0.0331 (4)
C6	0.1783 (3)	0.13724 (18)	0.65703 (17)	0.0307 (4)
H6	0.0985	0.0827	0.6221	0.037*
C7	0.3359 (3)	0.24227 (19)	0.33272 (17)	0.0322 (4)
H71	0.2569	0.3232	0.2676	0.048*
H72	0.2199	0.1755	0.3820	0.048*
H73	0.4680	0.1959	0.2904	0.048*
C8	0.6138 (3)	0.39764 (19)	0.34989 (19)	0.0357 (4)
H81	0.7442	0.3541	0.3042	0.054*
H82	0.6793	0.4253	0.4103	0.054*
H83	0.5335	0.4811	0.2878	0.054*
C9	0.1099 (4)	0.0907 (2)	0.80091 (18)	0.0471 (6)
H91	0.1972	0.1411	0.8354	0.057*
H92	−0.0636	0.1186	0.8177	0.057*
C10	0.1624 (3)	−0.06485 (18)	0.87193 (16)	0.0308 (4)
C11	0.3570 (4)	−0.1186 (2)	0.94168 (18)	0.0372 (5)
H11	0.4629	−0.0565	0.9410	0.045*
C12	0.4007 (4)	−0.2604 (2)	1.01209 (19)	0.0421 (5)
H12	0.5341	−0.2951	1.0603	0.050*
C13	0.2510 (4)	−0.3511 (2)	1.01230 (19)	0.0422 (5)
H13	0.2787	−0.4488	1.0614	0.051*
C14	0.0603 (4)	−0.2996 (2)	0.9409 (2)	0.0468 (5)
H14	−0.0417	−0.3626	0.9393	0.056*
C15	0.0158 (4)	−0.1580 (2)	0.87165 (19)	0.0399 (5)
H15	−0.1173	−0.1240	0.8232	0.048*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0329 (7)	0.0264 (6)	0.0288 (6)	0.0042 (5)	−0.0046 (5)	−0.0038 (5)
O2	0.0263 (7)	0.0353 (7)	0.0512 (9)	0.0046 (6)	−0.0026 (6)	−0.0083 (7)
O5	0.0594 (10)	0.0288 (7)	0.0400 (8)	0.0160 (7)	0.0195 (7)	−0.0009 (6)
N4	0.0347 (8)	0.0184 (7)	0.0246 (7)	0.0050 (6)	0.0020 (6)	−0.0055 (6)
C2	0.0266 (9)	0.0239 (8)	0.0309 (9)	0.0000 (7)	−0.0052 (7)	−0.0098 (7)
C3	0.0246 (8)	0.0210 (8)	0.0249 (8)	0.0010 (6)	0.0002 (6)	−0.0080 (6)
C5	0.0395 (10)	0.0242 (9)	0.0271 (9)	0.0068 (8)	0.0030 (8)	−0.0070 (7)
C6	0.0341 (9)	0.0236 (8)	0.0272 (9)	0.0050 (7)	0.0033 (7)	−0.0077 (7)
C7	0.0367 (10)	0.0311 (9)	0.0288 (9)	−0.0010 (8)	−0.0038 (7)	−0.0119 (8)
C8	0.0339 (10)	0.0283 (9)	0.0399 (10)	−0.0055 (8)	0.0006 (8)	−0.0081 (8)
C9	0.0725 (15)	0.0259 (10)	0.0300 (10)	0.0051 (10)	0.0101 (10)	−0.0068 (8)
C10	0.0408 (10)	0.0243 (8)	0.0212 (8)	0.0009 (7)	0.0062 (7)	−0.0075 (7)
C11	0.0461 (11)	0.0377 (10)	0.0317 (10)	−0.0124 (9)	−0.0005 (8)	−0.0153 (9)
C12	0.0435 (11)	0.0463 (12)	0.0305 (10)	0.0010 (9)	−0.0109 (8)	−0.0074 (9)
C13	0.0525 (13)	0.0257 (9)	0.0352 (10)	−0.0007 (9)	0.0001 (9)	−0.0003 (8)
C14	0.0499 (13)	0.0371 (11)	0.0535 (13)	−0.0173 (10)	−0.0045 (10)	−0.0120 (10)
C15	0.0341 (10)	0.0427 (11)	0.0376 (10)	−0.0007 (8)	−0.0090 (8)	−0.0081 (9)

Geometric parameters (Å, º)

O1—C2	1.340 (2)	C8—H82	0.9800
O1—C6	1.457 (2)	C8—H83	0.9800
O2—C2	1.199 (2)	C9—C10	1.502 (3)
O5—C5	1.236 (2)	C9—H91	0.9900
N4—C5	1.323 (2)	C9—H92	0.9900
N4—C3	1.460 (2)	C10—C15	1.378 (3)
N4—H4	0.88 (2)	C10—C11	1.383 (3)
C2—C3	1.522 (2)	C11—C12	1.378 (3)
C3—C8	1.524 (2)	C11—H11	0.9500
C3—C7	1.530 (3)	C12—C13	1.369 (3)
C5—C6	1.519 (2)	C12—H12	0.9500
C6—C9	1.513 (3)	C13—C14	1.374 (3)
C6—H6	1.0000	C13—H13	0.9500
C7—H71	0.9800	C14—C15	1.375 (3)
C7—H72	0.9800	C14—H14	0.9500
C7—H73	0.9800	C15—H15	0.9500
C8—H81	0.9800
C2—O1—C6	120.53 (13)	C3—C8—H82	109.5
C5—N4—C3	124.06 (14)	H81—C8—H82	109.5
C5—N4—H4	117.3 (14)	C3—C8—H83	109.5
C3—N4—H4	117.2 (14)	H81—C8—H83	109.5
O2—C2—O1	118.81 (16)	H82—C8—H83	109.5
O2—C2—C3	122.98 (16)	C10—C9—C6	114.08 (16)
O1—C2—C3	118.20 (14)	C10—C9—H91	108.7
N4—C3—C2	110.10 (13)	C6—C9—H91	108.7
N4—C3—C8	108.03 (14)	C10—C9—H92	108.7
C2—C3—C8	108.97 (14)	C6—C9—H92	108.7
N4—C3—C7	110.62 (14)	H91—C9—H92	107.6
C2—C3—C7	108.25 (14)	C15—C10—C11	118.01 (17)
C8—C3—C7	110.87 (15)	C15—C10—C9	121.09 (19)
O5—C5—N4	123.78 (16)	C11—C10—C9	120.89 (19)
O5—C5—C6	120.30 (16)	C12—C11—C10	121.43 (19)
N4—C5—C6	115.92 (15)	C12—C11—H11	119.3
O1—C6—C9	106.64 (16)	C10—C11—H11	119.3
O1—C6—C5	111.79 (15)	C13—C12—C11	119.72 (19)
C9—C6—C5	110.50 (15)	C13—C12—H12	120.1
O1—C6—H6	109.3	C11—C12—H12	120.1
C9—C6—H6	109.3	C12—C13—C14	119.49 (19)
C5—C6—H6	109.3	C12—C13—H13	120.3
C3—C7—H71	109.5	C14—C13—H13	120.3
C3—C7—H72	109.5	C13—C14—C15	120.7 (2)
H71—C7—H72	109.5	C13—C14—H14	119.7
C3—C7—H73	109.5	C15—C14—H14	119.7
H71—C7—H73	109.5	C14—C15—C10	120.63 (19)
H72—C7—H73	109.5	C14—C15—H15	119.7
C3—C8—H81	109.5	C10—C15—H15	119.7
C6—O1—C2—O2	−165.28 (16)	N4—C5—C6—O1	28.5 (2)
C6—O1—C2—C3	14.0 (2)	O5—C5—C6—C9	−33.3 (3)
C5—N4—C3—C2	−37.3 (2)	N4—C5—C6—C9	147.15 (19)
C5—N4—C3—C8	−156.18 (18)	O1—C6—C9—C10	−62.9 (2)
C5—N4—C3—C7	82.3 (2)	C5—C6—C9—C10	175.40 (18)
O2—C2—C3—N4	−156.84 (17)	C6—C9—C10—C15	−77.5 (3)
O1—C2—C3—N4	23.9 (2)	C6—C9—C10—C11	103.7 (2)
O2—C2—C3—C8	−38.5 (2)	C15—C10—C11—C12	−1.8 (3)
O1—C2—C3—C8	142.19 (16)	C9—C10—C11—C12	176.93 (18)
O2—C2—C3—C7	82.1 (2)	C10—C11—C12—C13	0.9 (3)
O1—C2—C3—C7	−97.14 (18)	C11—C12—C13—C14	0.8 (3)
C3—N4—C5—O5	−168.91 (19)	C12—C13—C14—C15	−1.4 (3)
C3—N4—C5—C6	10.6 (3)	C13—C14—C15—C10	0.4 (3)
C2—O1—C6—C9	−162.18 (16)	C11—C10—C15—C14	1.2 (3)
C2—O1—C6—C5	−41.3 (2)	C9—C10—C15—C14	−177.55 (19)
O5—C5—C6—O1	−151.95 (18)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N4—H4···O5^i	0.88 (2)	1.95 (2)	2.833 (2)	176 (2)

Symmetry code: (i) −x, −y+1, −z+1.

(V) 6-benzyl-3,3-dimethyl-5-thioxomorpholin-2-one

Crystal data

C13H15NO2S	Dx = 1.335 Mg m^−3
Mr = 249.33	Melting point = 448–449 K
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71069 Å
a = 13.901 (4) Å	Cell parameters from 24 reflections
b = 5.843 (6) Å	θ = 18.0–20.0°
c = 16.559 (5) Å	µ = 0.25 mm^−1
β = 112.70 (2)°	T = 173 K
V = 1240.7 (13) Å^3	Needle, colourless
Z = 4	0.50 × 0.20 × 0.15 mm
F(000) = 528

Data collection

Rigaku AFC-5R diffractometer	1926 reflections with I > 2σ(I)
Radiation source: Rigaku rotating anode generator	Rint = 0.034
Graphite monochromator	θmax = 27.5°, θmin = 2.7°
ω–2θ scans	h = 0→18
Absorption correction: ψ scan (North et al., 1968)	k = 0→7
Tmin = 0.696, Tmax = 0.963	l = −21→19
3261 measured reflections	3 standard reflections every 150 reflections
2854 independent reflections	intensity decay: none

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)] = 0.052	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.151	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ^2(Fo^2) + (0.082P)^2] where P = (Fo^2 + 2Fc^2)/3
2854 reflections	(Δ/σ)max = 0.001
160 parameters	Δρmax = 0.53 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
S5	0.62224 (5)	−0.06702 (12)	0.63839 (4)	0.0320 (2)
O1	0.81373 (12)	0.4508 (3)	0.64124 (10)	0.0253 (4)
O2	0.98048 (14)	0.4688 (3)	0.66856 (13)	0.0366 (5)
N4	0.81735 (15)	−0.0209 (3)	0.65326 (13)	0.0234 (4)
H4	0.8240 (18)	−0.173 (5)	0.6609 (15)	0.022 (6)*
C2	0.90599 (18)	0.3483 (4)	0.65683 (15)	0.0250 (5)
C3	0.91534 (17)	0.0890 (4)	0.66001 (15)	0.0230 (5)
C5	0.72653 (17)	0.0749 (4)	0.63857 (14)	0.0233 (5)
C6	0.71576 (17)	0.3293 (4)	0.62064 (15)	0.0237 (5)
H6	0.6811	0.3960	0.6581	0.028*
C7	1.00011 (18)	0.0211 (4)	0.74852 (15)	0.0267 (5)
H81	1.0087	−0.1455	0.7510	0.040*
H82	0.9795	0.0716	0.7960	0.040*
H83	1.0662	0.0940	0.7550	0.040*
C8	0.94441 (19)	0.0124 (4)	0.58386 (16)	0.0276 (5)
H71	1.0094	0.0875	0.5884	0.041*
H72	0.8885	0.0548	0.5283	0.041*
H73	0.9540	−0.1540	0.5861	0.041*
C9	0.64598 (18)	0.3850 (4)	0.52460 (15)	0.0278 (5)
H91	0.5773	0.3104	0.5099	0.033*
H92	0.6343	0.5524	0.5187	0.033*
C10	0.69169 (18)	0.3079 (4)	0.45982 (15)	0.0255 (5)
C11	0.66486 (18)	0.0969 (4)	0.41769 (15)	0.0269 (5)
H11	0.6179	−0.0010	0.4303	0.032*
C12	0.7063 (2)	0.0288 (5)	0.35738 (15)	0.0328 (6)
H12	0.6869	−0.1146	0.3286	0.039*
C13	0.7756 (2)	0.1693 (5)	0.33920 (16)	0.0369 (7)
H13	0.8040	0.1217	0.2982	0.044*
C14	0.8036 (2)	0.3788 (5)	0.38066 (17)	0.0367 (6)
H14	0.8516	0.4748	0.3685	0.044*
C15	0.7611 (2)	0.4480 (5)	0.44020 (16)	0.0300 (6)
H15	0.7796	0.5929	0.4679	0.036*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S5	0.0266 (3)	0.0407 (4)	0.0339 (4)	−0.0049 (3)	0.0176 (3)	0.0004 (3)
O1	0.0260 (8)	0.0238 (8)	0.0272 (8)	0.0013 (7)	0.0115 (7)	−0.0012 (7)
O2	0.0316 (10)	0.0290 (10)	0.0511 (11)	−0.0073 (8)	0.0181 (9)	0.0009 (8)
N4	0.0254 (10)	0.0197 (10)	0.0273 (10)	−0.0001 (8)	0.0127 (8)	−0.0007 (8)
C2	0.0287 (12)	0.0260 (12)	0.0223 (11)	0.0009 (10)	0.0121 (9)	0.0002 (9)
C3	0.0212 (11)	0.0253 (12)	0.0253 (11)	−0.0023 (9)	0.0121 (9)	−0.0020 (9)
C5	0.0250 (11)	0.0327 (13)	0.0147 (10)	−0.0003 (10)	0.0105 (9)	−0.0017 (9)
C6	0.0227 (11)	0.0300 (12)	0.0221 (11)	0.0000 (10)	0.0125 (9)	−0.0021 (9)
C7	0.0267 (12)	0.0306 (13)	0.0233 (11)	0.0011 (10)	0.0101 (10)	−0.0003 (9)
C8	0.0276 (12)	0.0330 (13)	0.0258 (12)	0.0027 (10)	0.0141 (10)	0.0010 (10)
C9	0.0240 (11)	0.0343 (14)	0.0263 (12)	0.0069 (10)	0.0110 (10)	0.0015 (10)
C10	0.0235 (11)	0.0318 (13)	0.0203 (11)	0.0055 (10)	0.0074 (9)	0.0071 (9)
C11	0.0254 (11)	0.0323 (14)	0.0220 (11)	0.0002 (10)	0.0081 (9)	0.0036 (10)
C12	0.0345 (14)	0.0387 (15)	0.0202 (12)	0.0067 (11)	0.0049 (10)	−0.0033 (10)
C13	0.0347 (14)	0.0563 (18)	0.0218 (12)	0.0131 (13)	0.0132 (11)	0.0028 (12)
C14	0.0293 (13)	0.0540 (18)	0.0301 (13)	0.0018 (13)	0.0152 (11)	0.0131 (13)
C15	0.0320 (13)	0.0327 (13)	0.0236 (12)	−0.0006 (11)	0.0088 (10)	0.0035 (10)

Geometric parameters (Å, º)

S5—C5	1.669 (2)	C8—H72	0.9800
O1—C2	1.347 (3)	C8—H73	0.9800
O1—C6	1.455 (3)	C9—C10	1.511 (3)
O2—C2	1.204 (3)	C9—H91	0.9900
N4—C3	1.470 (3)	C9—H92	0.9900
N4—C5	1.315 (3)	C10—C11	1.394 (4)
N4—H4	0.90 (3)	C10—C15	1.396 (4)
C2—C3	1.520 (4)	C11—C12	1.389 (4)
C3—C7	1.536 (3)	C11—H11	0.9500
C3—C8	1.532 (3)	C12—C13	1.385 (4)
C5—C6	1.512 (4)	C12—H12	0.9500
C6—C9	1.544 (3)	C13—C14	1.384 (4)
C6—H6	1.0000	C13—H13	0.9500
C7—H81	0.9800	C14—C15	1.391 (4)
C7—H82	0.9800	C14—H14	0.9500
C7—H83	0.9800	C15—H15	0.9500
C8—H71	0.9800
C2—O1—C6	124.30 (19)	C3—C8—H72	109.5
C5—N4—C3	128.6 (2)	H71—C8—H72	109.5
C5—N4—H4	119.2 (16)	C3—C8—H73	109.5
C3—N4—H4	112.3 (16)	H71—C8—H73	109.5
O2—C2—O1	117.8 (2)	H72—C8—H73	109.5
O2—C2—C3	121.4 (2)	C10—C9—C6	113.52 (19)
O1—C2—C3	120.8 (2)	C10—C9—H91	108.9
N4—C3—C2	111.61 (19)	C6—C9—H91	108.9
N4—C3—C8	109.92 (19)	C10—C9—H92	108.9
C2—C3—C8	107.99 (19)	C6—C9—H92	108.9
N4—C3—C7	107.86 (18)	H91—C9—H92	107.7
C2—C3—C7	108.32 (19)	C11—C10—C15	118.5 (2)
C8—C3—C7	111.15 (19)	C11—C10—C9	120.9 (2)
N4—C5—C6	118.0 (2)	C15—C10—C9	120.5 (2)
N4—C5—S5	124.1 (2)	C12—C11—C10	120.5 (2)
C6—C5—S5	117.90 (17)	C12—C11—H11	119.7
O1—C6—C5	114.91 (19)	C10—C11—H11	119.7
O1—C6—C9	107.32 (18)	C13—C12—C11	120.2 (2)
C5—C6—C9	112.62 (19)	C13—C12—H12	119.9
O1—C6—H6	107.2	C11—C12—H12	119.9
C5—C6—H6	107.2	C14—C13—C12	120.2 (2)
C9—C6—H6	107.2	C14—C13—H13	119.9
C3—C7—H81	109.5	C12—C13—H13	119.9
C3—C7—H82	109.5	C13—C14—C15	119.6 (3)
H81—C7—H82	109.5	C13—C14—H14	120.2
C3—C7—H83	109.5	C15—C14—H14	120.2
H81—C7—H83	109.5	C14—C15—C10	121.0 (3)
H82—C7—H83	109.5	C14—C15—H15	119.5
C3—C8—H71	109.5	C10—C15—H15	119.5
C6—O1—C2—O2	176.1 (2)	S5—C5—C6—O1	166.56 (14)
C6—O1—C2—C3	−4.3 (3)	N4—C5—C6—C9	109.8 (2)
C5—N4—C3—C2	5.8 (3)	S5—C5—C6—C9	−70.1 (2)
C5—N4—C3—C8	−114.0 (2)	O1—C6—C9—C10	61.4 (3)
C5—N4—C3—C7	124.7 (2)	C5—C6—C9—C10	−66.0 (3)
O2—C2—C3—N4	173.9 (2)	C6—C9—C10—C11	94.7 (3)
O1—C2—C3—N4	−5.7 (3)	C6—C9—C10—C15	−86.0 (3)
O2—C2—C3—C8	−65.2 (3)	C15—C10—C11—C12	−0.2 (3)
O1—C2—C3—C8	115.2 (2)	C9—C10—C11—C12	179.2 (2)
O2—C2—C3—C7	55.3 (3)	C10—C11—C12—C13	0.7 (4)
O1—C2—C3—C7	−124.3 (2)	C11—C12—C13—C14	−0.3 (4)
C3—N4—C5—C6	4.0 (3)	C12—C13—C14—C15	−0.5 (4)
C3—N4—C5—S5	−176.09 (17)	C13—C14—C15—C10	0.9 (4)
C2—O1—C6—C5	14.0 (3)	C11—C10—C15—C14	−0.6 (3)
C2—O1—C6—C9	−112.1 (2)	C9—C10—C15—C14	−180.0 (2)
N4—C5—C6—O1	−13.5 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N4—H4···O1^i	0.90 (3)	2.22 (3)	3.092 (4)	164 (2)

Symmetry code: (i) x, y−1, z.

(VI) 6-benzyl-3,3-dimethylmorpholine-2,5-dithione

Crystal data

C13H15NOS2	F(000) = 560
Mr = 265.39	Dx = 1.327 Mg m^−3
Triclinic, P1	Melting point = 396–397 K
a = 8.6915 (13) Å	Mo Kα radiation, λ = 0.71069 Å
b = 11.896 (3) Å	Cell parameters from 25 reflections
c = 13.661 (4) Å	θ = 19.0–20.0°
α = 75.62 (2)°	µ = 0.38 mm^−1
β = 76.211 (16)°	T = 173 K
γ = 84.971 (18)°	Prism, yellow
V = 1328.2 (6) Å^3	0.48 × 0.40 × 0.30 mm
Z = 4

Data collection

Rigaku AFC-5R diffractometer	4424 reflections with I > 2σ(I)
Radiation source: Rigaku rotating anode generator	Rint = 0.021
Graphite monochromator	θmax = 27.5°, θmin = 2.6°
ω–2θ scans	h = −11→11
Absorption correction: ψ scan (North et al., 1968)	k = −15→0
Tmin = 0.781, Tmax = 0.891	l = −17→17
6399 measured reflections	3 standard reflections every 150 reflections
6101 independent reflections	intensity decay: none

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)] = 0.049	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.142	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ^2(Fo^2) + (0.0823P)^2 + 0.0825P] where P = (Fo^2 + 2Fc^2)/3
6101 reflections	(Δ/σ)max = 0.001
319 parameters	Δρmax = 0.54 e Å^−3
0 restraints	Δρmin = −0.41 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
S2	1.31149 (7)	0.61456 (6)	0.69359 (6)	0.04615 (19)
S5	0.78907 (7)	0.39220 (5)	0.58055 (6)	0.03978 (18)
O1	1.02831 (18)	0.60055 (13)	0.67956 (16)	0.0411 (4)
N4	1.0494 (2)	0.37797 (15)	0.65169 (16)	0.0297 (4)
H4	1.064 (4)	0.310 (3)	0.634 (2)	0.057 (9)*
C2	1.1665 (3)	0.54387 (19)	0.68373 (19)	0.0322 (5)
C3	1.1772 (2)	0.41325 (18)	0.69084 (19)	0.0296 (5)
C5	0.9228 (2)	0.43916 (18)	0.62984 (19)	0.0318 (5)
C6	0.8992 (3)	0.56035 (19)	0.6472 (2)	0.0381 (6)
H6	0.8919	0.6136	0.5791	0.046*
C7	1.3348 (3)	0.3776 (2)	0.6257 (2)	0.0355 (5)
H71	1.3472	0.4220	0.5537	0.053*
H72	1.3354	0.2945	0.6283	0.053*
H73	1.4225	0.3935	0.6535	0.053*
C8	1.1591 (3)	0.3487 (2)	0.8052 (2)	0.0429 (6)
H81	1.1635	0.2648	0.8109	0.064*
H82	1.0570	0.3709	0.8457	0.064*
H83	1.2452	0.3693	0.8320	0.064*
C9	0.7450 (3)	0.5789 (2)	0.7248 (3)	0.0504 (8)
H91	0.7367	0.6612	0.7288	0.060*
H92	0.6547	0.5646	0.6974	0.060*
C10	0.7289 (3)	0.5037 (2)	0.8330 (2)	0.0474 (7)
C11	0.6270 (3)	0.4108 (2)	0.8676 (3)	0.0544 (8)
H11	0.5719	0.3923	0.8217	0.065*
C12	0.6056 (4)	0.3452 (3)	0.9691 (3)	0.0633 (9)
H12	0.5350	0.2825	0.9919	0.076*
C13	0.6837 (4)	0.3690 (3)	1.0358 (3)	0.0679 (10)
H13	0.6681	0.3234	1.1050	0.082*
C14	0.7868 (4)	0.4606 (3)	1.0026 (3)	0.0729 (11)
H14	0.8426	0.4777	1.0488	0.088*
C15	0.8079 (3)	0.5266 (3)	0.9026 (3)	0.0617 (9)
H15	0.8783	0.5894	0.8806	0.074*
S22	0.51036 (7)	−0.14157 (5)	0.71819 (7)	0.0507 (2)
S25	1.14229 (6)	0.11719 (5)	0.57744 (5)	0.03136 (15)
O21	0.80999 (16)	−0.12851 (12)	0.68707 (13)	0.0299 (3)
N24	0.83142 (19)	0.10772 (15)	0.62064 (14)	0.0252 (4)
H24	0.838 (3)	0.186 (2)	0.598 (2)	0.039 (7)*
C22	0.6729 (2)	−0.06953 (18)	0.68532 (18)	0.0283 (4)
C23	0.6698 (2)	0.06227 (17)	0.65390 (16)	0.0246 (4)
C25	0.9671 (2)	0.05103 (18)	0.62203 (16)	0.0246 (4)
C26	0.9652 (2)	−0.07851 (18)	0.66533 (18)	0.0278 (4)
H26	1.0381	−0.1152	0.6126	0.033*
C27	0.5915 (3)	0.10592 (19)	0.56134 (18)	0.0303 (5)
H271	0.5911	0.1910	0.5416	0.045*
H272	0.4823	0.0796	0.5806	0.045*
H273	0.6511	0.0751	0.5027	0.045*
C28	0.5812 (3)	0.11054 (19)	0.74677 (17)	0.0302 (5)
H281	0.4702	0.0881	0.7657	0.045*
H282	0.5862	0.1954	0.7283	0.045*
H283	0.6306	0.0789	0.8057	0.045*
C29	1.0253 (3)	−0.11551 (19)	0.76561 (18)	0.0310 (5)
H291	1.0276	−0.2013	0.7880	0.037*
H292	1.1352	−0.0895	0.7517	0.037*
C30	0.9237 (3)	−0.06613 (19)	0.85260 (17)	0.0295 (5)
C31	0.9515 (3)	0.0432 (2)	0.86368 (18)	0.0340 (5)
H31	1.0376	0.0862	0.8173	0.041*
C32	0.8556 (3)	0.0904 (2)	0.94128 (19)	0.0393 (5)
H32	0.8760	0.1652	0.9475	0.047*
C33	0.7303 (3)	0.0285 (2)	1.00955 (19)	0.0388 (5)
H33	0.6640	0.0609	1.0624	0.047*
C34	0.7020 (3)	−0.0810 (2)	1.00048 (19)	0.0401 (6)
H34	0.6169	−0.1241	1.0479	0.048*
C35	0.7973 (3)	−0.1280 (2)	0.92259 (19)	0.0356 (5)
H35	0.7765	−0.2028	0.9168	0.043*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S2	0.0322 (3)	0.0366 (3)	0.0781 (5)	−0.0035 (3)	−0.0174 (3)	−0.0235 (3)
S5	0.0270 (3)	0.0261 (3)	0.0668 (4)	−0.0026 (2)	−0.0219 (3)	−0.0006 (3)
O1	0.0221 (7)	0.0232 (8)	0.0799 (13)	0.0028 (6)	−0.0092 (8)	−0.0189 (8)
N4	0.0234 (9)	0.0205 (8)	0.0481 (11)	0.0019 (7)	−0.0135 (8)	−0.0090 (8)
C2	0.0234 (10)	0.0277 (11)	0.0460 (13)	0.0001 (8)	−0.0065 (9)	−0.0110 (10)
C3	0.0228 (10)	0.0238 (10)	0.0456 (13)	0.0021 (8)	−0.0126 (9)	−0.0108 (9)
C5	0.0189 (10)	0.0218 (10)	0.0509 (14)	−0.0010 (8)	−0.0090 (9)	−0.0007 (9)
C6	0.0209 (10)	0.0210 (10)	0.0709 (17)	0.0007 (8)	−0.0136 (11)	−0.0051 (10)
C7	0.0224 (10)	0.0320 (11)	0.0557 (15)	0.0054 (9)	−0.0137 (10)	−0.0140 (11)
C8	0.0488 (15)	0.0337 (12)	0.0492 (15)	−0.0037 (11)	−0.0192 (12)	−0.0063 (11)
C9	0.0236 (11)	0.0232 (11)	0.098 (2)	0.0060 (9)	−0.0030 (13)	−0.0142 (13)
C10	0.0250 (11)	0.0292 (12)	0.084 (2)	0.0027 (9)	0.0073 (12)	−0.0268 (13)
C11	0.0348 (14)	0.0382 (14)	0.090 (2)	−0.0054 (11)	−0.0092 (14)	−0.0185 (15)
C12	0.0495 (17)	0.0443 (16)	0.092 (3)	−0.0110 (14)	0.0005 (17)	−0.0217 (17)
C13	0.065 (2)	0.061 (2)	0.073 (2)	−0.0064 (17)	0.0126 (17)	−0.0337 (18)
C14	0.064 (2)	0.086 (3)	0.076 (2)	−0.0168 (19)	0.0122 (18)	−0.054 (2)
C15	0.0458 (16)	0.0567 (18)	0.085 (2)	−0.0176 (14)	0.0164 (16)	−0.0460 (18)
S22	0.0257 (3)	0.0275 (3)	0.0941 (6)	−0.0038 (2)	−0.0092 (3)	−0.0085 (3)
S25	0.0180 (2)	0.0334 (3)	0.0425 (3)	−0.0014 (2)	−0.0002 (2)	−0.0147 (2)
O21	0.0208 (7)	0.0213 (7)	0.0493 (9)	0.0018 (6)	−0.0092 (7)	−0.0110 (6)
N24	0.0186 (8)	0.0228 (9)	0.0340 (10)	−0.0014 (7)	−0.0042 (7)	−0.0077 (7)
C22	0.0200 (9)	0.0234 (10)	0.0427 (12)	0.0025 (8)	−0.0063 (9)	−0.0117 (9)
C23	0.0160 (9)	0.0231 (10)	0.0341 (11)	0.0008 (7)	−0.0032 (8)	−0.0086 (8)
C25	0.0201 (9)	0.0279 (10)	0.0277 (10)	0.0015 (8)	−0.0027 (8)	−0.0133 (8)
C26	0.0160 (9)	0.0274 (10)	0.0419 (12)	0.0043 (8)	−0.0044 (8)	−0.0154 (9)
C27	0.0246 (10)	0.0324 (11)	0.0355 (12)	0.0038 (8)	−0.0079 (9)	−0.0113 (9)
C28	0.0281 (11)	0.0288 (11)	0.0321 (11)	0.0035 (9)	−0.0028 (9)	−0.0094 (9)
C29	0.0247 (10)	0.0265 (10)	0.0422 (13)	0.0065 (8)	−0.0088 (9)	−0.0099 (9)
C30	0.0246 (10)	0.0307 (11)	0.0338 (12)	0.0053 (8)	−0.0104 (9)	−0.0072 (9)
C31	0.0313 (12)	0.0359 (12)	0.0353 (12)	−0.0018 (9)	−0.0101 (10)	−0.0065 (10)
C32	0.0421 (13)	0.0390 (13)	0.0411 (13)	0.0007 (11)	−0.0126 (11)	−0.0148 (11)
C33	0.0395 (13)	0.0455 (14)	0.0319 (12)	0.0045 (11)	−0.0071 (10)	−0.0130 (11)
C34	0.0346 (12)	0.0462 (14)	0.0343 (13)	−0.0032 (11)	−0.0025 (10)	−0.0042 (11)
C35	0.0324 (12)	0.0310 (11)	0.0416 (13)	−0.0002 (9)	−0.0084 (10)	−0.0053 (10)

Geometric parameters (Å, º)

S2—C2	1.624 (2)	S22—C22	1.628 (2)
S5—C5	1.670 (2)	S25—C25	1.685 (2)
O1—C2	1.331 (3)	O21—C22	1.331 (2)
O1—C6	1.455 (3)	O21—C26	1.458 (2)
N4—C5	1.319 (3)	N24—C25	1.308 (3)
N4—C3	1.473 (3)	N24—C23	1.476 (2)
N4—H4	0.89 (3)	N24—H24	0.91 (3)
C2—C3	1.529 (3)	C22—C23	1.519 (3)
C3—C7	1.534 (3)	C23—C28	1.533 (3)
C3—C8	1.538 (3)	C23—C27	1.534 (3)
C5—C6	1.507 (3)	C25—C26	1.507 (3)
C6—C9	1.534 (3)	C26—C29	1.531 (3)
C6—H6	1.0000	C26—H26	1.0000
C7—H71	0.9800	C27—H271	0.9800
C7—H72	0.9800	C27—H272	0.9800
C7—H73	0.9800	C27—H273	0.9800
C8—H81	0.9800	C28—H281	0.9800
C8—H82	0.9800	C28—H282	0.9800
C8—H83	0.9800	C28—H283	0.9800
C9—C10	1.508 (4)	C29—C30	1.514 (3)
C9—H91	0.9900	C29—H291	0.9900
C9—H92	0.9900	C29—H292	0.9900
C10—C15	1.386 (4)	C30—C31	1.394 (3)
C10—C11	1.393 (3)	C30—C35	1.398 (3)
C11—C12	1.389 (5)	C31—C32	1.388 (3)
C11—H11	0.9500	C31—H31	0.9500
C12—C13	1.352 (5)	C32—C33	1.383 (3)
C12—H12	0.9500	C32—H32	0.9500
C13—C14	1.389 (5)	C33—C34	1.387 (4)
C13—H13	0.9500	C33—H33	0.9500
C14—C15	1.375 (5)	C34—C35	1.387 (3)
C14—H14	0.9500	C34—H34	0.9500
C15—H15	0.9500	C35—H35	0.9500
C2—O1—C6	124.91 (18)	C22—O21—C26	126.03 (16)
C5—N4—C3	128.14 (19)	C25—N24—C23	128.93 (18)
C5—N4—H4	115 (2)	C25—N24—H24	115.1 (17)
C3—N4—H4	117 (2)	C23—N24—H24	115.9 (17)
O1—C2—C3	119.02 (19)	O21—C22—C23	120.13 (18)
O1—C2—S2	117.96 (17)	O21—C22—S22	118.61 (15)
C3—C2—S2	122.68 (16)	C23—C22—S22	121.26 (15)
N4—C3—C2	110.90 (17)	N24—C23—C22	111.51 (16)
N4—C3—C7	107.16 (18)	N24—C23—C28	108.02 (17)
C2—C3—C7	111.39 (18)	C22—C23—C28	109.37 (18)
N4—C3—C8	108.33 (18)	N24—C23—C27	106.60 (17)
C2—C3—C8	108.7 (2)	C22—C23—C27	110.35 (18)
C7—C3—C8	110.28 (19)	C28—C23—C27	110.96 (17)
N4—C5—C6	118.2 (2)	N24—C25—C26	118.26 (18)
N4—C5—S5	124.03 (18)	N24—C25—S25	122.55 (16)
C6—C5—S5	117.72 (16)	C26—C25—S25	119.19 (15)
O1—C6—C5	114.97 (18)	O21—C26—C25	114.31 (16)
O1—C6—C9	107.5 (2)	O21—C26—C29	106.92 (17)
C5—C6—C9	113.86 (19)	C25—C26—C29	112.68 (17)
O1—C6—H6	106.6	O21—C26—H26	107.5
C5—C6—H6	106.6	C25—C26—H26	107.5
C9—C6—H6	106.6	C29—C26—H26	107.5
C3—C7—H71	109.5	C23—C27—H271	109.5
C3—C7—H72	109.5	C23—C27—H272	109.5
H71—C7—H72	109.5	H271—C27—H272	109.5
C3—C7—H73	109.5	C23—C27—H273	109.5
H71—C7—H73	109.5	H271—C27—H273	109.5
H72—C7—H73	109.5	H272—C27—H273	109.5
C3—C8—H81	109.5	C23—C28—H281	109.5
C3—C8—H82	109.5	C23—C28—H282	109.5
H81—C8—H82	109.5	H281—C28—H282	109.5
C3—C8—H83	109.5	C23—C28—H283	109.5
H81—C8—H83	109.5	H281—C28—H283	109.5
H82—C8—H83	109.5	H282—C28—H283	109.5
C10—C9—C6	115.5 (2)	C30—C29—C26	112.80 (17)
C10—C9—H91	108.4	C30—C29—H291	109.0
C6—C9—H91	108.4	C26—C29—H291	109.0
C10—C9—H92	108.4	C30—C29—H292	109.0
C6—C9—H92	108.4	C26—C29—H292	109.0
H91—C9—H92	107.5	H291—C29—H292	107.8
C15—C10—C11	117.8 (3)	C31—C30—C35	118.2 (2)
C15—C10—C9	122.0 (2)	C31—C30—C29	120.9 (2)
C11—C10—C9	120.2 (3)	C35—C30—C29	120.8 (2)
C12—C11—C10	120.3 (3)	C32—C31—C30	121.1 (2)
C12—C11—H11	119.9	C32—C31—H31	119.4
C10—C11—H11	119.9	C30—C31—H31	119.4
C13—C12—C11	121.1 (3)	C33—C32—C31	120.0 (2)
C13—C12—H12	119.5	C33—C32—H32	120.0
C11—C12—H12	119.5	C31—C32—H32	120.0
C12—C13—C14	119.5 (4)	C32—C33—C34	119.7 (2)
C12—C13—H13	120.2	C32—C33—H33	120.2
C14—C13—H13	120.2	C34—C33—H33	120.2
C15—C14—C13	119.8 (4)	C33—C34—C35	120.4 (2)
C15—C14—H14	120.1	C33—C34—H34	119.8
C13—C14—H14	120.1	C35—C34—H34	119.8
C14—C15—C10	121.5 (3)	C34—C35—C30	120.6 (2)
C14—C15—H15	119.2	C34—C35—H35	119.7
C10—C15—H15	119.2	C30—C35—H35	119.7
C6—O1—C2—C3	−21.4 (4)	C26—O21—C22—C23	2.9 (3)
C6—O1—C2—S2	165.11 (19)	C26—O21—C22—S22	−176.68 (16)
C5—N4—C3—C2	−11.8 (3)	C25—N24—C23—C22	−4.9 (3)
C5—N4—C3—C7	−133.6 (2)	C25—N24—C23—C28	115.3 (2)
C5—N4—C3—C8	107.4 (3)	C25—N24—C23—C27	−125.4 (2)
O1—C2—C3—N4	22.2 (3)	O21—C22—C23—N24	4.4 (3)
S2—C2—C3—N4	−164.59 (17)	S22—C22—C23—N24	−176.09 (16)
O1—C2—C3—C7	141.5 (2)	O21—C22—C23—C28	−115.0 (2)
S2—C2—C3—C7	−45.3 (3)	S22—C22—C23—C28	64.5 (2)
O1—C2—C3—C8	−96.8 (3)	O21—C22—C23—C27	122.6 (2)
S2—C2—C3—C8	76.4 (2)	S22—C22—C23—C27	−57.8 (2)
C3—N4—C5—C6	−1.0 (4)	C23—N24—C25—C26	−1.8 (3)
C3—N4—C5—S5	177.11 (19)	C23—N24—C25—S25	178.19 (16)
C2—O1—C6—C5	7.2 (4)	C22—O21—C26—C25	−9.6 (3)
C2—O1—C6—C9	135.2 (2)	C22—O21—C26—C29	115.9 (2)
N4—C5—C6—O1	4.6 (3)	N24—C25—C26—O21	8.7 (3)
S5—C5—C6—O1	−173.61 (17)	S25—C25—C26—O21	−171.28 (14)
N4—C5—C6—C9	−120.1 (3)	N24—C25—C26—C29	−113.6 (2)
S5—C5—C6—C9	61.7 (3)	S25—C25—C26—C29	66.4 (2)
O1—C6—C9—C10	−67.7 (3)	O21—C26—C29—C30	−64.3 (2)
C5—C6—C9—C10	60.9 (3)	C25—C26—C29—C30	62.1 (2)
C6—C9—C10—C15	77.1 (3)	C26—C29—C30—C31	−86.9 (3)
C6—C9—C10—C11	−105.8 (3)	C26—C29—C30—C35	91.7 (2)
C15—C10—C11—C12	0.7 (4)	C35—C30—C31—C32	−0.7 (3)
C9—C10—C11—C12	−176.6 (3)	C29—C30—C31—C32	178.0 (2)
C10—C11—C12—C13	−0.6 (5)	C30—C31—C32—C33	0.3 (4)
C11—C12—C13—C14	0.1 (5)	C31—C32—C33—C34	0.5 (4)
C12—C13—C14—C15	0.4 (5)	C32—C33—C34—C35	−0.8 (4)
C13—C14—C15—C10	−0.3 (5)	C33—C34—C35—C30	0.4 (4)
C11—C10—C15—C14	−0.2 (4)	C31—C30—C35—C34	0.3 (3)
C9—C10—C15—C14	177.0 (3)	C29—C30—C35—C34	−178.3 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N4—H4···S25	0.89 (3)	2.58 (3)	3.469 (2)	173 (3)
N24—H24···S5	0.91 (3)	2.42 (3)	3.293 (2)	163 (2)