Poly­sulfonyl­amines. CXLV. N-Diethyl­carbamoyl-o-benzene­di­sul­fon­imide, a urea with non-planar geometry at nitro­gen and an amide single bond

The prominent features in the molecular structure of the title compound (alternative name: 2-diethyl­carbamoyl-1,1,3,3-tetraoxo-1,3,2-benzodi­thia­zole), C₁₁H₁₄N₂O₅S₂, arise in the urea moiety S₂N—C(O)—N′C₂: the sum of the angles at N is 332.3 (1)°, the N—C(O)—N′C₂ unit is planar, and distances N—C(O) = 1.494 (3) Å, N′—C(O) = 1.325 (2) Å and C—O = 1.215 (2) Å. The mol­ecules are associated via five C—H...O hydrogen bonds to form layers parallel to the yz plane. This compound and its di­methyl homologue, which were synthesized by treating the silver salt of o-benzene­disulfon­imide with carbamoyl chlorides, are prone to rapid hydro­lysis at the weak N—C(O) bond. For both mol­ecules, the rotational barrier about the partial N′—C(O) double bond is ca 50 kJ mol⁻¹ at 250 K (from dynamic ¹H NMR experiments).

S1. Comment

The syntheses of the cyclic 1,1-disulfonylureas (I) and (II), and the structure elucidation of (II) form part of a programme aimed at derivatives of o-benzenedisulfonimide, HN(SO₂)₂C₆H₄ (HZ), including metal complexes of the N-deprotonated species Z^- (e.g. Moers et al., 2001b; Jones et al., 1997) and covalently N-substituted molecules X—Z (Pröhl et al., 1999; Hamann et al., 1998; Jones et al., 1995). The novel ureas, obtained by treating AgZ with the appropriate carbamoyl chlorides in acetonitrile, are moisture-sensitive and readily hydrolyze to give the respective ammonium salts, [R₂NH₂]Z, and carbon dioxide. Crystals of (II) could be mounted in inert oil despite their sensitivity, but compound (I) proved impossible to mount because it is not wetted by the oil or by its own mother liquor (acetonitrile) Compound (II) and its acyclic congener (MeSO₂)₂N—C(O)—NMe₂ [(III); Dalluhn et al., 2001] appear to be the first crystallographically authenticated 1,1-disulfonylureas. No entry for any urea displaying an (SO₂)₂N—C(O) group was found in the April 2001 release of the Cambridge Structural Database (Allen & Kennard, 1993).

The molecular structure of (II) with the atomic labelling is shown in Fig. 1 and Table 1 summarizes important bond lengths, bond angles and torsion angles. The most notable features are the degree of pyramidality of the ring N atom (N1), despite its being part of a urea, and the astoundingly elongated amide N1—C1 bond.

In the bicyclic moiety, which possesses approximate mirror symmetry, bond lengths and angles are as expected. The six-membered carbocycle and the two S atoms are coplanar (r.m.s. deviation of eight atoms = 0.0045 Å). The five-membered heterocycle adopts an envelope conformation, with N1 lying 0.619 (2) Å out of the plane of the other eight ring atoms. The sulfonyl O atoms are located above or below the S11—N1—S12 plane, whereby O11 and O13 occupy the equatorial positions [e.g. O11—S11—C11—C12 133.61 (16)° and O12—S11—C11—C12 - 90.21 (16)°]. The greater part of the urea grouping, as defined by the ring N1 atom, the carbonyl C1—O1 function and the C21—N2—C22 fragment, is typically planar, with C1 and N2 deviating by only 0.001 (2) and -0.002 (2) Å from the respective planes formed by their three bonded neighbours; the corresponding torsion angles are included in Table 1.

The striking aspects arise at the disulfonylated N1 centre. Firstly, the sum of angles at this atom is 332.3 (1)°, which correlates with a distance of 0.5054 (17) Å between N1 and the plane defined by C1, S11 and S12. Secondly, in order to reduce steric hindrance, the Et₂N—C(O) moiety is rotated about N1—C1 in such a way that O1—C1 and N2—C1 adopt an asymmetrically staggered orientation relative to the N—S bonds (the torsion angles sre given in Table 1). Thirdly, the N1—C1 amide bond exhibits a length of 1.494 (3) Å and must accordingly be regarded as a covalent single bond devoid of electron delocalization via pπ–pπ bonding. It is even longer than the Nsp²—Csp³ bonds in the Et₂N group and exceeds by 0.13 Å the mean for Nsp²—Csp² bonds in tetrasubstituted ureas, and by 0.03 Å the mean for Nsp³—Csp³ bonds in tertiary aliphatic amines (Allen et al., 1987). Consistent with the established interdependence of C—N and C—O bond lengths in ureas (Blessing, 1983), the adjacent N2—C1 and O1—C1 bonds are shortened to 1.325 (2) and 1.215 (2) Å, thus closely approaching the low end of the range associated with related distances in urea molecules (Allen et al. 1987). It should be emphasized that the abnormal electronic properties of (II) are not exclusively induced by N1 being part of a five-membered heterocycle; a similar geometry has been detected for the acyclic urea (III), where the sum of angles at the disulfonylated N atom amounts to 351.3 (1)° and the (SO₂)₂N—C(O) bond length is 1.486 (3) Å (Dalluhn et al., 2001). The high tendency of the compounds to hydrolyse reflects a high degree of electrophilic activation of the carbonyl C atom that can be traced back to the low order of the (SO₂)₂N—C(O) bond.

¹H and ¹³C NMR data for (I) and (II) show that rotation around the N2—C1 amide multiple bond is not hindered in solution at ambient temperature. On cooling, decoalescence of the alkyl ¹H signals starts at 250 K and is completed at 230 K. Using the conventional Eyring equation, a rotational barrier of ΔG^#_c ≈ 50 kJ mol^-1 at T_c = 250 K was obtained for both molecules. In contrast to these results, the Me₂N group in urea (III) gave rise to distinct ¹H and ¹³C NMR signals at room temperature, the barrier to rotation amounting to ΔG^#_c ≈ 80 kJ mol^-1 at T_c = 380 K (Dalluhn et al., 2001). The high values of the activation parameters and the large discrepancy between the acyclic and cyclic cases probably stem from intramolecular steric hindrance, which, according to simulation experiments on rigid-rotator models, is more pronounced in (III) than in the cyclic urea (II). In any case, it should be borne in mind that the currently known rotational barriers about C—N bonds in ureas are generally lower than 50 kJ mol^-1 [see, for example, Wawer & Koleva (1995), and references therein].

The packing of (II) involves six C—H···O interactions that may reasonably be classified as hydrogen bonds (Table 2). The first five of these link the molecules to form thick layers parallel to the yz plane (Fig. 2) with one layer per x axis repeat distance. The end faces of the layers are formed by the six-membered rings, which are linked by bifurcated C13—H13···O12···H15—C15 hydrogen-bond systems. Prominent in the centre of the layers are short C21—H21B···O1 interactions. The layers are linked by the sixth hydrogen bond, i.e. C14—H14···O14.

S2. Experimental

The silver salt, AgZ, used to synthesize compounds (I) and (II) was prepared and dehydrated as described elsewhere (Blaschette et al., 1993). Compounds (I) and (II) are moisture sensitive and are best handled within glove-bags or within a dry box. For the preparation of compound (I), dimethylcarbamoyl c hloride (1.07 g, 10.0 mmol) was dissolved in anhydrous acetonitrile (20 ml) and the solution added dropwise to a stirred solution of AgZ (3.26 g, 10.0 mmol) in the same solvent (50 ml). After stirring for 48 h at room temperature in the dark, AgCl was removed by filtration and washed with dichloromethane (30 ml). The combined liquid phases were evaporated to dryness under reduced pressure and the crude product was recrystallized from dichloromethane/petrol ether (3/1) [yield 72% (2.1 g), m.p. 415 K]. ¹H NMR (CD₂Cl₂, 200 MHz, 300 K, p.p.m.): δ 3.14 (s, 6H, Me₂N), 7.85–7.98 (4H, C_arH). ¹H NMR (CD₂Cl₂, 200 MHz, 230 K, p.p.m.): δ 3.00 (s, 3H, MeN), 3.22 (s, 3H, MeN), 7.90–8.05 (4H, C_arH). ¹³C NMR (CD₂Cl₂, 50 MHz, 300 K, p.p.m.): δ 38.47 (Me₂N), 122.73, 135.42, 138.88 (all C_ar), 147.94 (CO). For the preparation of compound (II), the same procedure was employed as for (I), but using diethylcarbamoyl chloride (1.36 g, 10.0 mmol) and AgZ (3.26 g, 10.0 mmol) [yield 91% (2.9 g), m.p. 458 K]. ¹H NMR (CD₂Cl₂, 200 MHz, 300 K, p.p.m.): δ 1.24 [t, 6H, 2 × Me, ³J(H—H) = 7.2 Hz], 3.51 [q, 4H, 2 × CH₂, ³J(H—H) = 7.2 Hz], 7.87–8.01 (4H, C_arH). ¹H NMR (CD₂Cl₂, 200 MHz, 230 K, p.p.m.): δ 1.05–1.32 (t + t, 2 × Me, spectral resolution poor), 3.34 [q, 2H, CH₂, ³J(H—H) = 6.8 Hz], 3.57 [q, 2H, CH₂, ³J(H—H) = 7.0 Hz], 7.90–8.10 (4H, C_arH). ¹³C NMR (CDCl₃, 50 MHz, 300 K, p.p.m.): δ 13.43 (2 × Me), 44.04 (2 × CH₂), 122.57, 134.64, 139.78 (all C_ar), 148.00 (CO). Satisfactory elemental analyses were obtained for both compounds. For (I), found: C 36.97, H 3.54, N 9.53, S 21.99%; calculated for C₉H₁₀N₂O₅S₂: C 37.23, H 3.47, N 9.65, S 22.09%; for (II), found: C 41.71, H 4.44, N 8.78, S 20.16%; calculated for C₁₁H₁₄N₂O₅S₂: C 41.50, H 4.43, N 8.80, S 20.14%. Crystals of (II) suitable for X-ray diffraction were grown at room temperature by vapour diffusion of petrol ether into a dichloromethane solution of the compound.

S3. Refinement

Methyl groups were refined as rigid groups allowed to rotate but not tip; the starting positions were obtained from difference syntheses. Other H atoms were refined using a riding model starting from calculated positions. The fixed C—H distances were methyl 0.98 Å, methylene 0.99 Å and aromatic 0.95 Å.

Computing details

Data collection: DIF4 (Stoe & Cie, 1992); cell refinement: DIF4; data reduction: REDU4 (Stoe & Cie, 1992); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP (Siemens, 1994); software used to prepare material for publication: SHELXL97.

Figures

Fig. 1. The molecule of compound (II) in the crystal. Ellipsoids represent 50% probability levels. H-atom radii are arbitrary.

Fig. 2. Packing diagram of compound (II) viewed parallel to the z axis. Atoms are identified as follows: circles with crosses – S; dotted – N; with diagonal lines — O; with slight shading – C; small open circles – H. Hydrogen bonds are indicated by thick dashed lines. Normalized H···O distances (C—H = 1.08 Å, cf. Table 2) are H13···O12^i 2.55, H15···O12^ii 2.51, H21B···O1^iii 2.38, H22B···O1^iv 2.46, H23A···O13^v 2.52 and H14···O14^vi 2.51 Å.

(II)

Crystal data

C11H14N2O5S2	F(000) = 664
Mr = 318.36	Dx = 1.546 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 14.393 (5) Å	Cell parameters from 54 reflections
b = 8.201 (2) Å	θ = 10–11.5°
c = 12.606 (4) Å	µ = 0.41 mm^−1
β = 113.17 (2)°	T = 143 K
V = 1368.0 (7) Å^3	Prism, colourless
Z = 4	0.6 × 0.5 × 0.4 mm

Data collection

Stoe Stadi-4 diffractometer	Rint = 0.059
Radiation source: fine-focus sealed tube	θmax = 27.6°, θmin = 3.0°
Graphite monochromator	h = 0→18
ω/θ scans	k = −1→10
3327 measured reflections	l = −16→15
3148 independent reflections	3 standard reflections every 60 min
2663 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)] = 0.040	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.109	H-atom parameters constrained
S = 1.04	w = 1/[σ^2(Fo^2) + (0.0554P)^2 + 0.9893P] where P = (Fo^2 + 2Fc^2)/3
3148 reflections	(Δ/σ)max < 0.001
183 parameters	Δρmax = 0.55 e Å^−3
0 restraints	Δρmin = −0.54 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
N1	0.24106 (12)	0.6992 (2)	0.08380 (14)	0.0200 (3)
S11	0.19650 (4)	0.50867 (6)	0.03680 (4)	0.02337 (14)
S12	0.16513 (4)	0.78269 (6)	0.14448 (4)	0.02120 (14)
O11	0.27952 (13)	0.4113 (2)	0.04090 (15)	0.0359 (4)
O12	0.11009 (12)	0.5256 (2)	−0.06853 (13)	0.0315 (4)
O13	0.22294 (12)	0.89650 (19)	0.22951 (15)	0.0333 (4)
O14	0.07488 (12)	0.8340 (2)	0.05270 (14)	0.0314 (4)
O1	0.37525 (11)	0.6333 (2)	0.25868 (12)	0.0293 (4)
N2	0.40942 (13)	0.7615 (2)	0.11781 (14)	0.0217 (3)
C11	0.15706 (15)	0.4629 (2)	0.14922 (17)	0.0225 (4)
C12	0.14171 (14)	0.6009 (2)	0.20397 (16)	0.0207 (4)
C13	0.11047 (15)	0.5892 (3)	0.29436 (18)	0.0291 (5)
H13	0.0999	0.6836	0.3319	0.035*
C14	0.09523 (17)	0.4344 (4)	0.3278 (2)	0.0392 (6)
H14	0.0736	0.4222	0.3895	0.047*
C15	0.11067 (18)	0.2970 (3)	0.2735 (2)	0.0408 (6)
H15	0.1001	0.1924	0.2992	0.049*
C16	0.14131 (17)	0.3085 (3)	0.1821 (2)	0.0325 (5)
H16	0.1510	0.2141	0.1439	0.039*
C1	0.35004 (15)	0.6945 (2)	0.16365 (16)	0.0209 (4)
C21	0.51892 (15)	0.7620 (3)	0.18623 (18)	0.0281 (5)
H21A	0.5316	0.7564	0.2692	0.034*
H21B	0.5479	0.8655	0.1727	0.034*
C22	0.37466 (15)	0.8374 (3)	0.00295 (16)	0.0243 (4)
H22A	0.3111	0.7845	−0.0486	0.029*
H22B	0.4259	0.8194	−0.0301	0.029*
C23	0.57116 (19)	0.6206 (3)	0.1559 (3)	0.0432 (6)
H23A	0.6440	0.6269	0.2018	0.052*
H23B	0.5584	0.6252	0.0737	0.052*
H23C	0.5449	0.5178	0.1726	0.052*
C24	0.35701 (19)	1.0178 (3)	0.0081 (2)	0.0345 (5)
H24A	0.3365	1.0648	−0.0693	0.041*
H24B	0.4195	1.0701	0.0603	0.041*
H24C	0.3036	1.0357	0.0366	0.041*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0228 (8)	0.0204 (8)	0.0212 (8)	0.0002 (6)	0.0134 (7)	0.0009 (6)
S11	0.0285 (3)	0.0219 (3)	0.0221 (2)	0.0014 (2)	0.0125 (2)	−0.00446 (19)
S12	0.0253 (3)	0.0171 (2)	0.0268 (3)	0.00109 (18)	0.0163 (2)	−0.00021 (18)
O11	0.0406 (9)	0.0314 (9)	0.0402 (9)	0.0073 (7)	0.0208 (8)	−0.0088 (7)
O12	0.0335 (9)	0.0366 (9)	0.0225 (7)	−0.0009 (7)	0.0090 (7)	−0.0068 (6)
O13	0.0401 (9)	0.0237 (8)	0.0433 (9)	−0.0071 (7)	0.0242 (8)	−0.0124 (7)
O14	0.0305 (8)	0.0320 (8)	0.0370 (8)	0.0111 (7)	0.0190 (7)	0.0098 (7)
O1	0.0335 (8)	0.0369 (9)	0.0209 (7)	0.0043 (7)	0.0144 (6)	0.0084 (6)
N2	0.0224 (8)	0.0269 (9)	0.0188 (8)	0.0020 (7)	0.0112 (6)	0.0039 (7)
C11	0.0223 (10)	0.0206 (10)	0.0241 (9)	−0.0034 (8)	0.0085 (8)	0.0003 (7)
C12	0.0206 (9)	0.0230 (10)	0.0196 (8)	−0.0029 (8)	0.0092 (7)	0.0012 (7)
C13	0.0213 (10)	0.0466 (14)	0.0212 (9)	−0.0049 (9)	0.0103 (8)	0.0003 (9)
C14	0.0254 (11)	0.0651 (18)	0.0263 (11)	−0.0126 (11)	0.0093 (9)	0.0135 (11)
C15	0.0291 (12)	0.0435 (15)	0.0402 (13)	−0.0118 (11)	0.0033 (10)	0.0215 (12)
C16	0.0289 (11)	0.0234 (11)	0.0379 (12)	−0.0064 (9)	0.0053 (9)	0.0049 (9)
C1	0.0236 (10)	0.0226 (10)	0.0197 (9)	0.0024 (8)	0.0120 (8)	0.0006 (7)
C21	0.0229 (10)	0.0344 (12)	0.0269 (10)	−0.0011 (9)	0.0096 (8)	0.0044 (9)
C22	0.0231 (10)	0.0351 (11)	0.0181 (9)	−0.0016 (8)	0.0118 (8)	0.0055 (8)
C23	0.0335 (13)	0.0392 (14)	0.0602 (17)	0.0089 (11)	0.0220 (12)	0.0077 (12)
C24	0.0362 (12)	0.0345 (13)	0.0341 (12)	−0.0002 (10)	0.0151 (10)	0.0113 (10)

Geometric parameters (Å, º)

N1—S11	1.7041 (18)	C15—C16	1.390 (4)
N1—S12	1.7048 (17)	C21—C23	1.511 (3)
N1—C1	1.494 (3)	C22—C24	1.507 (3)
O1—C1	1.215 (2)	C13—H13	0.9500
N2—C1	1.325 (2)	C14—H14	0.9500
N2—C21	1.469 (3)	C15—H15	0.9500
N2—C22	1.471 (2)	C16—H16	0.9500
S11—O11	1.4211 (17)	C21—H21A	0.9900
S11—O12	1.4246 (17)	C21—H21B	0.9900
S11—C11	1.762 (2)	C22—H22A	0.9900
S12—O13	1.4180 (16)	C22—H22B	0.9900
S12—O14	1.4215 (17)	C23—H23A	0.9800
S12—C12	1.760 (2)	C23—H23B	0.9800
C11—C16	1.379 (3)	C23—H23C	0.9800
C11—C12	1.388 (3)	C24—H24A	0.9800
C12—C13	1.383 (3)	C24—H24B	0.9800
C13—C14	1.382 (4)	C24—H24C	0.9800
C14—C15	1.381 (4)
S11—N1—S12	107.72 (9)	N2—C22—C24	111.75 (18)
C1—N1—S11	111.24 (13)	C14—C13—H13	121.4
C1—N1—S12	113.36 (12)	C12—C13—H13	121.4
N2—C1—N1	112.45 (16)	C15—C14—H14	119.2
O1—C1—N1	120.13 (17)	C13—C14—H14	119.2
O1—C1—N2	127.42 (19)	C14—C15—H15	119.3
C21—N2—C22	116.59 (16)	C16—C15—H15	119.3
C1—N2—C21	118.17 (17)	C11—C16—H16	121.5
C1—N2—C22	125.24 (17)	C15—C16—H16	121.5
O11—S11—O12	120.12 (10)	N2—C21—H21A	109.2
O11—S11—N1	107.85 (10)	C23—C21—H21A	109.2
O12—S11—N1	107.82 (9)	N2—C21—H21B	109.2
O11—S11—C11	112.55 (10)	C23—C21—H21B	109.2
O12—S11—C11	109.33 (10)	H21A—C21—H21B	107.9
N1—S11—C11	96.41 (9)	N2—C22—H22A	109.3
O13—S12—O14	119.79 (11)	C24—C22—H22A	109.3
O13—S12—N1	108.33 (9)	N2—C22—H22B	109.3
O14—S12—N1	107.19 (9)	C24—C22—H22B	109.3
O13—S12—C12	112.91 (10)	H22A—C22—H22B	107.9
O14—S12—C12	109.32 (10)	C21—C23—H23A	109.5
N1—S12—C12	96.60 (9)	C21—C23—H23B	109.5
C16—C11—C12	121.5 (2)	H23A—C23—H23B	109.5
C16—C11—S11	125.47 (18)	C21—C23—H23C	109.5
C12—C11—S11	113.03 (15)	H23A—C23—H23C	109.5
C13—C12—C11	121.3 (2)	H23B—C23—H23C	109.5
C13—C12—S12	126.07 (17)	C22—C24—H24A	109.5
C11—C12—S12	112.59 (14)	C22—C24—H24B	109.5
C14—C13—C12	117.2 (2)	H24A—C24—H24B	109.5
C15—C14—C13	121.5 (2)	C22—C24—H24C	109.5
C14—C15—C16	121.4 (2)	H24A—C24—H24C	109.5
C11—C16—C15	117.0 (2)	H24B—C24—H24C	109.5
N2—C21—C23	112.04 (19)
C1—N1—S11—O11	−26.38 (15)	N1—S12—C12—C13	158.61 (18)
S12—N1—S11—O11	−151.18 (10)	O13—S12—C12—C11	−135.09 (15)
C1—N1—S11—O12	−157.46 (12)	O14—S12—C12—C11	88.88 (16)
S12—N1—S11—O12	77.73 (11)	N1—S12—C12—C11	−21.97 (16)
C1—N1—S11—C11	89.83 (13)	C11—C12—C13—C14	0.0 (3)
S12—N1—S11—C11	−34.97 (11)	S12—C12—C13—C14	179.38 (16)
C1—N1—S12—O13	28.59 (16)	C12—C13—C14—C15	0.1 (3)
S11—N1—S12—O13	152.11 (10)	C13—C14—C15—C16	−0.6 (4)
C1—N1—S12—O14	159.16 (14)	C12—C11—C16—C15	−0.8 (3)
S11—N1—S12—O14	−77.32 (11)	S11—C11—C16—C15	179.67 (16)
C1—N1—S12—C12	−88.23 (14)	C14—C15—C16—C11	1.0 (3)
S11—N1—S12—C12	35.29 (11)	C21—N2—C1—N1	−178.70 (17)
O11—S11—C11—C16	−46.9 (2)	C22—N2—C1—N1	1.6 (3)
O12—S11—C11—C16	89.3 (2)	C21—N2—C1—O1	1.1 (3)
N1—S11—C11—C16	−159.23 (19)	C22—N2—C1—O1	−178.6 (2)
O11—S11—C11—C12	133.61 (16)	S11—N1—C1—O1	−68.8 (2)
O12—S11—C11—C12	−90.21 (16)	S12—N1—C1—O1	52.8 (2)
N1—S11—C11—C12	21.24 (16)	S11—N1—C1—N2	111.08 (16)
C16—C11—C12—C13	0.4 (3)	S12—N1—C1—N2	−127.36 (15)
S11—C11—C12—C13	179.93 (16)	C1—N2—C21—C23	96.0 (2)
C16—C11—C12—S12	−179.08 (17)	C22—N2—C21—C23	−84.3 (2)
S11—C11—C12—S12	0.48 (19)	C1—N2—C22—C24	92.0 (2)
O13—S12—C12—C13	45.5 (2)	C21—N2—C22—C24	−87.7 (2)
O14—S12—C12—C13	−90.54 (19)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C13—H13···O12^i	0.95	2.67	3.602 (3)	166
C15—H15···O12^ii	0.95	2.41	3.313 (3)	159
C21—H21B···O1^iii	0.99	2.46	3.353 (3)	150
C22—H22B···O1^iv	0.99	2.50	3.092 (2)	118
C23—H23A···O13^v	0.98	2.58	3.298 (3)	130
C14—H14···O14^vi	0.95	2.62	3.442 (3)	145

Symmetry codes: (i) x, −y+3/2, z+1/2; (ii) x, −y+1/2, z+1/2; (iii) −x+1, y+1/2, −z+1/2; (iv) x, −y+3/2, z−1/2; (v) −x+1, y−1/2, −z+1/2; (vi) −x, y−1/2, −z+1/2.