N,N'-Di­thio­bisphthal­imide-nitro­benzene (2/1): a Pn solvate with localized solvent mol­ecules ordered head-to-tail in channels

N,N'-Di­thio­bisphthal­imide crystallizes from nitro­benzene solution as a solvate, 2C₁₆H₈N₂O₄S₂·C₆H₅NO₂, having space group Pn. The bisphthal­imide mol­ecules are linked by C-H...O hydrogen bonds and by aromatic [pi]-[pi]-stacking interactions, forming a framework enclosing continuous channels running along the [100] direction and accounting for ca 20% of the unit-cell volume. The nitro­benzene mol­ecules lie in these channels, ordered in a head-to-tail fashion and linked to the bis­phthal­imide framework by C-H...O and C-H...[pi](arene) hydrogen bonds.

S1. Comment

We have recently described a number of solvates of N,N'-dithiobisphthalimide, as well as some solvent-free polymorphs (Skakle et al., 2001; Bowes et al., 2002; Farrell et al., 2002). In some of the solvates, the bisphthalimide molecules and the solvent are linked by C—H···O hydrogen bonds, while in other solvates the bisphthalimide molecules form structures containing either isolated cavities or continuous channels in which the solvent molecules reside without being hydrogen bonded to the bisphthalimide frameworks. Thus, for example, nitromethane forms a monosolvate, C₁₆H₈N₂O₄S₂·CH₃NO₂, in which the solvent molecules are linked to the bisphthalimide molecules not only via a conventional C—H···O hydrogen bond but also via a polarized multi-centre interaction involving all three C—H bonds of the solvent molecule (Farrell et al., 2002). On the other hand, in the chlorobenzene solvate, 2C₁₆H₈N₂O₄S₂·C₆H₅Cl, the solvent molecules lie in isolated cavities, while in the toluene solvate, 2C₁₆H₈N₂O₄S₂·C₇H₈, the solvent molecules lie within continuous channels (Farrell et al., 2002).

Seeking to combine the specific hydrogen-bonding capacity manifest in nitromethane with the steric requirements of aromatic solvent molecules, such as chlorobenzene and toluene, we have now prepared and structurally characterized the nitrobenzene solvate, 2C₁₆H₈N₂O₄S₂·C₆H₅NO₂, (I), which turns out to exhibit a channel structure containing fully ordered and bound solvent molecules.

Compound (I) (Fig. 1) crystallizes in space group Pn with four molecules of the bisphthalimide per unit cell, and these molecules, whose internal dimensions do not differ significantly from those observed in other polymorphs and solvates (Skakle et al., 2001; Bowes et al., 2002; Farrell et al., 2002), are linked by a combination of C—H···O hydrogen bonds (Table 1) and aromatic π–π-stacking interactions. The substructure formed by the bisphthalimide molecules alone is effectively centrosymmetric (100% fit to P2₁/n), but the presence of the nitrobenzene component precludes the higher symmetry. Each type of bisphthalimide molecule (type 1 contains S1 and S2; type 2 contains S3 and S4) forms chains by means of C—H···O hydrogen bonds reinforced by aromatic π–π-stacking interactions, but only one type of chain needs to be described, because of the pseudosymmetry.

Atom C15 in the type 1 molecule at (x, y, z) acts as hydrogen-bond donor to O11 in the type 1 molecule at (-0.5 + x, 1 - y, 0.5 + z), and propagation of this hydrogen bond produces a C(7) chain running parallel to the [101] direction, and generated by the n-glide plane at y = 0.5 (Fig. 2). At the same time, the C13–C18 aryl ring at (x, y, z) forms a π–π-stacking interaction with the C23–C28 ring at (-0.5 + x, 1 - y, 0.5 + z), so reinforcing the action of the C—H···O hydrogen bond (Fig. 2); the interplanar angle is only 0.6 (2)°, with a centroid separation of 3.598 (2) Å and an interplanar spacing of 3.361 (2) Å, giving a centroid offset of 1.284 (2) Å. The antiparallel [101] chains formed individually by the two types of bisphthalimide molecule are linked by further C—H···O hydrogen bonds involving both types. Atom C26 in the type 1 molecule at (x, y, z) acts as hydrogen-bond donor to O42 in the type 2 molecule at (0.5 + x, 1 - y, -0.5 + z), while C46 at (0.5 + x, 1 - y, -0.5 + z) acts as donor to O22 at (x, 1 + y, z), so forming a C²₂(14) chain running parallel to [010] (Fig. 3).

The bisphthalimide molecules occupy only ca 80% of the unit-cell volume [i.e. 20% solvent-accessible volume as estimated using PLATON (Spek, 2002)]; the remaining volume takes the form of continuous channels running along [100] (Fig. 4). There are two such channels passing through each unit cell, along the lines (x, 1/4, 0) and (x, 3/4, 1/2), and having mean diameter ca 5.4 Å, and it is in these channels that the nitrobenzene molecules lie, arranged in an ordered head-to-tail fashion.

The ordering of the nitrobenzene molecules contrasts with the disorder of the chlorobenzene and toluene molecules across centres of inversion in their respective solvates. The ordering in (I) is due to specific multi-point recognition between the bisphthalimide framework and the nitrobenzene solvate molecules, involving both C—H···O and C—H···π(arene) hydrogen bonds (Table 1). The nitrobenzene molecule at (x, y, z) accepts via O1 a rather weak hydrogen bond from C24 in the type 1 molecule at (x, y, z), while nitrobenzene C6 acts as donor to O42 in the type 2 molecule at (1 + x, y, -1 + z). In addition to these two C—H···O hydrogen bonds, there are two C—H···π(arene) hydrogen bonds, in which the C1–C6 nitrobenzene ring at (x, y, z), centroid Cg1, accepts C—H···π hydrogen bonds from C14 at (1 + x, y, -1 + z) and from C34 at (1 + x, y, z), with one such hydrogen bond on each face of the ring (Fig. 5).

In a recent study based on the Cambridge Structural Database (CSD: Allen & Kennard, 1993), Nangia & Desiraju (1999) analysed both the relative frequency of occurrence of the common organic solvents in solvated organic crystals, and the specific supramolecular synthons linking the solvent molecules to the host molecules. When normalized for the frequency of usage in crystal growth, 13 solvents were found to have a significantly higher than average tendency to be included in solvates. It is interesting to note that of the N,N'-bisphthalimide solvates so far analysed, the two solvents found to exhibit specific multi-point interactions (nitromethane and nitrobenzene) do not appear in the top 20 solvents in the normalized CSD-based list; indeed neither solvent is mentioned in Nangia & Desiraju's (1999) analysis.

S2. Experimental

A sample of N,N'-dithiobisphthalimide was purchased from Aldrich. Crystals of (I) suitable for single-crystal X-ray diffraction were grown by slow evaporation of a solution in nitrobenzene.

S3. Refinement

Compound (I) is monoclinic and the systematic absences permitted Pn and P2/n as possible space groups; Pn was selected and confirmed by the analysis. H atoms were treated as riding, with a C—H distance of 0.95 Å. The value of the Flack (1983) parameter [0.32 (9)] indicated racemic twinning and this was handled via the TWIN and BASF instructions in SHELXL97 (Sheldrick, 1997). Although PLATON (Spek, 2002) reports a 94% fit to P2₁/n (and indeed a 100% fit when the nitrobenzene component is omitted), careful inspection of the reflection file indicated several strong (0k0) reflections with k odd, which preclude the presence of a 2₁ screw axis. In addition to the structure for (I) discussed above, we had earlier located another solution, which refined to R = 0.0457, wR2 = 0.1087 and gave effectively the same supramolecular structure as that described above, but approximately related to it by the transformation (x, y, 1 - z). Our attention was drawn to the unsatisfactory nature of this initial solution by the PLATON (Spek, 2002) checking routines which flagged, in particular, the consistently low average C—C distance (ca 1.34 Å) in the phthalimide arene rings and the very large range (ca 0.16 Å) of the nitrobenzene C—C bond lengths; a detailed examination of the bond distances and angles then led to the decisive rejection of this solution. The lessons to be drawn from this are that, despite a satisfactory R and a satisfactory supramolecular arrangement, the warnings of the data-validation process must be heeded and investigated, and that all of the derived geometric parameters must be scrutinized critically.

Computing details

Data collection: KappaCCD Server Software (Nonius, 1997); cell refinement: DENZO–SMN (Otwinowski & Minor, 1997); data reduction: DENZO–SMN; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2002); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997) and PRPKAPPA (Ferguson, 1999).

Figures

	Fig. 1. The independent molecular components in (I), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. Stereoview of part of the crystal structure of (I), showing the formation of a [101] chain of type 1 molecules built from C—H···O hydrogen bonds and aromatic π–π-stacking interactions.
	Fig. 3. Part of the crystal structure of (I), showing the formation of a C^22(14) chain along [010]. Atoms marked with an asterisk (*), hash (#) or dollar sign ($) are at the symmetry positions (0.5 + x, 1 - y, -0.5 + z), (x, 1 + y, z) and (0.5 + x, -1 - y, -0.5 + z), respectively.
	Fig. 4. Space-filling representation of the bisphthalimide framework, showing the continuous channels along [100].
	Fig. 5. Part of the crystal structure of (I), showing the linking of the nitrobenzene to the bisphthalimide framework by C—H···π(arene) hydrogen bonds. For the sake of clarity, the unit-cell box has been omitted. Atoms marked with an asterisk (*) or hash (#) are at the symmetry positions (1 + x, y, -1 + z) and (1 + x, y, z) respectively.

N,N'-Dithiobisphthalimide–nitrobenzene (2/1)

Crystal data

2C16H8N2O4S2·C6H5NO2	F(000) = 856
Mr = 835.88	Dx = 1.570 Mg m^−3
Monoclinic, Pn	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P -2yac	Cell parameters from 7660 reflections
a = 7.7070 (2) Å	θ = 2.9–27.5°
b = 16.1001 (3) Å	µ = 0.34 mm^−1
c = 14.3067 (4) Å	T = 120 K
β = 95.077 (1)°	Block, colourless
V = 1768.26 (8) Å^3	0.22 × 0.10 × 0.08 mm
Z = 2

Data collection

Nonius KappaCCD diffractometer	7660 independent reflections
Radiation source: fine-focus sealed tube	5681 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.056
ϕ scans, and ω scans with κ offsets	θmax = 27.5°, θmin = 2.9°
Absorption correction: multi-scan (DENZO-SMN; Otwinowski & Minor, 1997)	h = −9→10
Tmin = 0.927, Tmax = 0.972	k = −20→20
19021 measured reflections	l = −18→18

Refinement

Refinement on F^2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.043	w = 1/[σ^2(Fo^2) + (0.0406P)^2] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.096	(Δ/σ)max < 0.001
S = 0.97	Δρmax = 0.37 e Å^−3
7660 reflections	Δρmin = −0.31 e Å^−3
516 parameters	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
2 restraints	Extinction coefficient: 0.0057 (7)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack (1983); 3603 Friedel pairs
Secondary atom site location: difference Fourier map	Absolute structure parameter: 0.32 (9)

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.

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

	x	y	z	Uiso*/Ueq
S1	0.84531 (12)	0.31916 (6)	0.55294 (7)	0.0220 (3)
S2	0.63911 (12)	0.32151 (6)	0.45398 (7)	0.0221 (2)
N11	0.7851 (4)	0.3782 (2)	0.6424 (2)	0.0195 (8)
C11	0.8211 (5)	0.4645 (2)	0.6525 (3)	0.0191 (9)
O11	0.8929 (4)	0.50588 (18)	0.5985 (2)	0.0243 (7)
C12	0.7030 (5)	0.3456 (3)	0.7193 (3)	0.0181 (9)
O12	0.6573 (4)	0.27387 (19)	0.7262 (2)	0.0285 (7)
C13	0.6877 (5)	0.4167 (3)	0.7837 (3)	0.0196 (9)
C14	0.6161 (5)	0.4200 (3)	0.8689 (3)	0.0219 (9)
H14	0.5704	0.3717	0.8959	0.026*
C15	0.6132 (5)	0.4963 (3)	0.9136 (3)	0.0242 (10)
H15	0.5662	0.5004	0.9726	0.029*
C16	0.6786 (5)	0.5669 (3)	0.8729 (3)	0.0225 (9)
H16	0.6736	0.6186	0.9046	0.027*
C17	0.7509 (5)	0.5642 (3)	0.7875 (3)	0.0212 (9)
H17	0.7960	0.6125	0.7603	0.025*
C18	0.7539 (5)	0.4869 (3)	0.7437 (3)	0.0182 (9)
N21	0.6825 (4)	0.3974 (2)	0.3787 (2)	0.0196 (8)
C21	0.6360 (5)	0.4837 (3)	0.3887 (3)	0.0219 (9)
O21	0.5710 (3)	0.51074 (18)	0.4545 (2)	0.0267 (7)
C22	0.7657 (5)	0.3841 (3)	0.2952 (3)	0.0201 (9)
O22	0.8218 (4)	0.31761 (17)	0.2724 (2)	0.0259 (7)
C23	0.7650 (5)	0.4648 (3)	0.2475 (3)	0.0191 (9)
C24	0.8289 (5)	0.4857 (3)	0.1635 (3)	0.0192 (9)
H24	0.8806	0.4452	0.1264	0.023*
C25	0.8150 (5)	0.5684 (3)	0.1350 (3)	0.0210 (9)
H25	0.8561	0.5848	0.0771	0.025*
C26	0.7408 (5)	0.6277 (3)	0.1911 (3)	0.0231 (10)
H26	0.7356	0.6840	0.1711	0.028*
C27	0.6746 (5)	0.6066 (3)	0.2752 (3)	0.0232 (10)
H27	0.6221	0.6468	0.3123	0.028*
C28	0.6891 (5)	0.5240 (3)	0.3024 (3)	0.0186 (9)
S3	0.15417 (12)	0.18431 (6)	0.44754 (7)	0.0224 (2)
S4	0.36143 (12)	0.17751 (6)	0.54561 (7)	0.0229 (2)
N31	0.2072 (4)	0.1232 (2)	0.3593 (2)	0.0193 (8)
C31	0.1715 (5)	0.0366 (3)	0.3522 (3)	0.0188 (9)
O31	0.1042 (4)	−0.00328 (18)	0.4107 (2)	0.0252 (7)
C32	0.2895 (5)	0.1522 (3)	0.2793 (3)	0.0210 (9)
O32	0.3377 (4)	0.22228 (18)	0.2702 (2)	0.0273 (7)
C33	0.3016 (5)	0.0781 (2)	0.2183 (3)	0.0172 (9)
C34	0.3685 (5)	0.0709 (3)	0.1330 (3)	0.0227 (9)
H34	0.4129	0.1178	0.1025	0.027*
C35	0.3687 (5)	−0.0082 (3)	0.0929 (3)	0.0221 (9)
H35	0.4135	−0.0151	0.0336	0.027*
C36	0.3055 (5)	−0.0765 (3)	0.1369 (3)	0.0231 (9)
H36	0.3084	−0.1294	0.1077	0.028*
C37	0.2370 (5)	−0.0692 (3)	0.2240 (3)	0.0197 (9)
H37	0.1942	−0.1160	0.2552	0.024*
C38	0.2347 (5)	0.0096 (3)	0.2624 (3)	0.0176 (9)
N41	0.3136 (4)	0.1005 (2)	0.6187 (2)	0.0215 (8)
C41	0.3618 (5)	0.0155 (3)	0.6101 (3)	0.0201 (9)
O41	0.4331 (3)	−0.01309 (18)	0.54575 (19)	0.0251 (7)
C42	0.2254 (5)	0.1149 (3)	0.7010 (3)	0.0192 (9)
O42	0.1635 (4)	0.17961 (17)	0.7215 (2)	0.0246 (7)
C43	0.2271 (5)	0.0326 (3)	0.7497 (3)	0.0180 (9)
C44	0.1626 (5)	0.0131 (3)	0.8339 (3)	0.0209 (9)
H44	0.1112	0.0539	0.8708	0.025*
C45	0.1769 (5)	−0.0699 (3)	0.8620 (3)	0.0247 (10)
H45	0.1330	−0.0862	0.9192	0.030*
C46	0.2534 (5)	−0.1288 (3)	0.8087 (3)	0.0261 (10)
H46	0.2628	−0.1846	0.8301	0.031*
C47	0.3171 (5)	−0.1071 (3)	0.7236 (3)	0.0217 (10)
H47	0.3681	−0.1477	0.6863	0.026*
C48	0.3040 (5)	−0.0258 (3)	0.6953 (3)	0.0188 (9)
N1	1.1273 (3)	0.30387 (16)	0.0296 (2)	0.0259 (6)
O1	1.1111 (3)	0.33860 (16)	0.10471 (18)	0.0411 (6)
O2	1.0053 (3)	0.29256 (15)	−0.03039 (18)	0.0381 (6)
C1	1.3017 (4)	0.2744 (2)	0.0111 (2)	0.0199 (8)
C2	1.4444 (5)	0.2961 (2)	0.0712 (3)	0.0243 (8)
H2	1.4323	0.3317	0.1231	0.029*
C3	1.6058 (5)	0.2645 (2)	0.0540 (3)	0.0250 (8)
H3	1.7065	0.2799	0.0933	0.030*
C4	1.6206 (5)	0.2108 (2)	−0.0199 (3)	0.0267 (8)
H4	1.7306	0.1874	−0.0298	0.032*
C5	1.4751 (5)	0.1909 (2)	−0.0798 (3)	0.0269 (8)
H5	1.4869	0.1550	−0.1316	0.032*
C6	1.3150 (4)	0.2222 (2)	−0.0650 (2)	0.0215 (7)
H6	1.2152	0.2085	−0.1059	0.026*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0287 (6)	0.0188 (6)	0.0188 (6)	0.0050 (4)	0.0045 (4)	−0.0013 (4)
S2	0.0291 (6)	0.0196 (6)	0.0182 (6)	−0.0050 (4)	0.0048 (4)	0.0018 (4)
N11	0.0238 (18)	0.0184 (19)	0.0173 (19)	0.0016 (15)	0.0078 (14)	−0.0039 (15)
C11	0.019 (2)	0.015 (2)	0.022 (2)	0.0035 (17)	0.0004 (16)	−0.0010 (18)
O11	0.0302 (16)	0.0237 (17)	0.0207 (16)	−0.0026 (13)	0.0110 (12)	0.0019 (12)
C12	0.020 (2)	0.018 (2)	0.016 (2)	0.0017 (17)	−0.0014 (15)	0.0000 (18)
O12	0.0391 (17)	0.0221 (17)	0.0253 (17)	−0.0015 (14)	0.0084 (12)	0.0026 (14)
C13	0.018 (2)	0.021 (2)	0.020 (2)	−0.0001 (16)	0.0018 (16)	0.0057 (18)
C14	0.023 (2)	0.024 (2)	0.019 (2)	0.0018 (16)	0.0042 (16)	0.0034 (17)
C15	0.021 (2)	0.035 (2)	0.017 (2)	0.0027 (16)	0.0061 (15)	0.0047 (17)
C16	0.022 (2)	0.026 (2)	0.019 (2)	0.0058 (16)	−0.0011 (16)	−0.0078 (17)
C17	0.0175 (19)	0.023 (2)	0.023 (2)	−0.0010 (16)	0.0026 (15)	0.0007 (17)
C18	0.0137 (19)	0.024 (2)	0.016 (2)	0.0066 (16)	−0.0010 (16)	−0.0047 (17)
N21	0.0268 (18)	0.0147 (18)	0.018 (2)	−0.0013 (14)	0.0056 (14)	0.0017 (15)
C21	0.017 (2)	0.024 (2)	0.024 (3)	0.0024 (18)	0.0009 (17)	−0.001 (2)
O21	0.0287 (16)	0.0243 (17)	0.0279 (19)	−0.0001 (13)	0.0068 (14)	−0.0053 (13)
C22	0.021 (2)	0.019 (3)	0.020 (2)	−0.0003 (18)	0.0015 (16)	0.0010 (19)
O22	0.0364 (16)	0.0182 (18)	0.0238 (17)	−0.0005 (12)	0.0069 (13)	−0.0031 (12)
C23	0.019 (2)	0.020 (2)	0.019 (2)	0.0001 (16)	0.0031 (17)	−0.0050 (18)
C24	0.021 (2)	0.022 (2)	0.015 (2)	−0.0016 (17)	0.0023 (16)	0.0021 (18)
C25	0.026 (2)	0.018 (2)	0.019 (2)	−0.0030 (18)	0.0018 (18)	0.0016 (18)
C26	0.027 (2)	0.013 (2)	0.028 (3)	−0.0011 (17)	−0.0029 (17)	0.004 (2)
C27	0.022 (2)	0.024 (2)	0.024 (3)	0.0000 (18)	0.0007 (18)	−0.0001 (19)
C28	0.019 (2)	0.015 (2)	0.021 (2)	−0.0042 (17)	−0.0008 (16)	0.0028 (17)
S3	0.0291 (6)	0.0208 (6)	0.0178 (6)	0.0039 (4)	0.0053 (4)	−0.0022 (4)
S4	0.0295 (5)	0.0204 (6)	0.0188 (6)	−0.0075 (4)	0.0033 (4)	−0.0013 (4)
N31	0.0258 (19)	0.019 (2)	0.0139 (19)	−0.0012 (15)	0.0033 (14)	0.0008 (15)
C31	0.018 (2)	0.020 (2)	0.019 (2)	−0.0021 (17)	0.0045 (16)	0.0015 (18)
O31	0.0302 (17)	0.0240 (17)	0.0225 (17)	−0.0033 (13)	0.0082 (12)	0.0007 (12)
C32	0.018 (2)	0.025 (3)	0.020 (2)	0.0014 (18)	0.0025 (15)	0.0059 (19)
O32	0.0373 (16)	0.0164 (16)	0.0289 (17)	−0.0026 (14)	0.0069 (12)	0.0024 (13)
C33	0.019 (2)	0.018 (2)	0.015 (2)	0.0008 (16)	0.0026 (15)	−0.0031 (17)
C34	0.0183 (19)	0.030 (2)	0.020 (2)	−0.0003 (16)	0.0035 (15)	0.0026 (18)
C35	0.0212 (19)	0.028 (2)	0.018 (2)	0.0023 (16)	0.0084 (15)	−0.0049 (17)
C36	0.018 (2)	0.024 (2)	0.027 (2)	−0.0013 (15)	0.0011 (16)	−0.0053 (17)
C37	0.0206 (19)	0.020 (2)	0.018 (2)	−0.0006 (16)	0.0011 (15)	−0.0016 (16)
C38	0.017 (2)	0.020 (2)	0.017 (2)	−0.0029 (16)	0.0037 (15)	0.0056 (16)
N41	0.0277 (19)	0.020 (2)	0.017 (2)	−0.0007 (15)	0.0040 (15)	0.0001 (15)
C41	0.021 (2)	0.020 (2)	0.018 (2)	−0.0049 (18)	−0.0033 (16)	−0.0059 (19)
O41	0.0273 (16)	0.0307 (18)	0.0181 (18)	0.0019 (13)	0.0057 (13)	−0.0057 (13)
C42	0.020 (2)	0.019 (3)	0.018 (2)	−0.0059 (17)	−0.0008 (16)	−0.0045 (18)
O42	0.0302 (15)	0.0194 (18)	0.0246 (18)	0.0000 (12)	0.0053 (12)	0.0006 (12)
C43	0.017 (2)	0.017 (2)	0.020 (2)	−0.0030 (16)	−0.0024 (16)	0.0053 (18)
C44	0.022 (2)	0.017 (2)	0.023 (2)	−0.0011 (17)	0.0013 (17)	−0.0039 (19)
C45	0.022 (2)	0.030 (3)	0.023 (3)	−0.0064 (19)	−0.0010 (18)	0.0056 (19)
C46	0.026 (2)	0.022 (3)	0.030 (3)	−0.0029 (19)	0.0007 (18)	0.008 (2)
C47	0.020 (2)	0.016 (2)	0.029 (3)	0.0014 (17)	−0.0024 (18)	−0.0024 (19)
C48	0.0132 (19)	0.024 (2)	0.018 (2)	−0.0007 (17)	−0.0021 (16)	−0.0041 (19)
N1	0.0268 (15)	0.0240 (14)	0.0280 (16)	0.0023 (12)	0.0088 (12)	0.0028 (13)
O1	0.0436 (14)	0.0472 (15)	0.0341 (15)	0.0174 (12)	0.0123 (11)	−0.0042 (12)
O2	0.0257 (14)	0.0406 (14)	0.0484 (16)	0.0007 (11)	0.0065 (12)	−0.0052 (12)
C1	0.0269 (18)	0.0176 (17)	0.0169 (17)	0.0017 (14)	0.0107 (14)	0.0030 (13)
C2	0.036 (2)	0.0157 (17)	0.022 (2)	0.0023 (16)	0.0102 (16)	0.0007 (15)
C3	0.0285 (19)	0.0201 (19)	0.0259 (19)	−0.0037 (15)	−0.0002 (15)	0.0017 (15)
C4	0.025 (2)	0.0226 (19)	0.033 (2)	0.0050 (16)	0.0081 (16)	0.0044 (17)
C5	0.036 (2)	0.023 (2)	0.0235 (19)	0.0013 (16)	0.0112 (16)	−0.0004 (15)
C6	0.0318 (19)	0.0166 (17)	0.0159 (17)	−0.0022 (14)	0.0012 (14)	0.0002 (13)

Geometric parameters (Å, º)

S1—N11	1.692 (4)	C32—O32	1.198 (5)
S1—S2	2.0330 (13)	C32—C33	1.486 (6)
S2—N21	1.682 (3)	C33—C34	1.372 (6)
N11—C12	1.418 (5)	C33—C38	1.392 (6)
N11—C11	1.422 (5)	C34—C35	1.398 (6)
C11—O11	1.193 (5)	C34—H34	0.9500
C11—C18	1.490 (6)	C35—C36	1.377 (6)
C12—O12	1.214 (5)	C35—H35	0.9500
C12—C13	1.480 (6)	C36—C37	1.401 (6)
C13—C14	1.382 (6)	C36—H36	0.9500
C13—C18	1.385 (6)	C37—C38	1.383 (6)
C14—C15	1.385 (6)	C37—H37	0.9500
C14—H14	0.9500	N41—C41	1.427 (5)
C15—C16	1.392 (6)	N41—C42	1.429 (5)
C15—H15	0.9500	C41—O41	1.204 (5)
C16—C17	1.388 (6)	C41—C48	1.490 (6)
C16—H16	0.9500	C42—O42	1.193 (5)
C17—C18	1.394 (6)	C42—C43	1.497 (6)
C17—H17	0.9500	C43—C44	1.379 (6)
N21—C22	1.421 (5)	C43—C48	1.387 (6)
N21—C21	1.445 (5)	C44—C45	1.397 (6)
C21—O21	1.188 (5)	C44—H44	0.9500
C21—C28	1.484 (6)	C45—C46	1.382 (6)
C22—O22	1.210 (5)	C45—H45	0.9500
C22—C23	1.468 (6)	C46—C47	1.396 (6)
C23—C24	1.382 (6)	C46—H46	0.9500
C23—C28	1.395 (5)	C47—C48	1.373 (6)
C24—C25	1.394 (6)	C47—H47	0.9500
C24—H24	0.9500	N1—O1	1.228 (3)
C25—C26	1.401 (6)	N1—O2	1.229 (3)
C25—H25	0.9500	N1—C1	1.471 (4)
C26—C27	1.390 (6)	C1—C2	1.379 (5)
C26—H26	0.9500	C1—C6	1.387 (5)
C27—C28	1.388 (6)	C2—C3	1.386 (5)
C27—H27	0.9500	C2—H2	0.9500
S3—N31	1.679 (4)	C3—C4	1.378 (5)
S3—S4	2.0335 (13)	C3—H3	0.9500
S4—N41	1.684 (4)	C4—C5	1.388 (5)
N31—C31	1.423 (5)	C4—H4	0.9500
N31—C32	1.435 (5)	C5—C6	1.366 (5)
C31—O31	1.207 (5)	C5—H5	0.9500
C31—C38	1.480 (6)	C6—H6	0.9500
N11—S1—S2	105.47 (13)	C34—C33—C38	121.3 (4)
N21—S2—S1	105.79 (13)	C34—C33—C32	129.7 (4)
C12—N11—C11	112.3 (3)	C38—C33—C32	109.0 (4)
C12—N11—S1	123.4 (3)	C33—C34—C35	117.2 (4)
C11—N11—S1	124.2 (3)	C33—C34—H34	121.4
O11—C11—N11	125.2 (4)	C35—C34—H34	121.4
O11—C11—C18	130.5 (4)	C36—C35—C34	121.8 (4)
N11—C11—C18	104.2 (3)	C36—C35—H35	119.1
O12—C12—N11	124.6 (4)	C34—C35—H35	119.1
O12—C12—C13	130.2 (4)	C35—C36—C37	121.1 (4)
N11—C12—C13	105.2 (3)	C35—C36—H36	119.5
C14—C13—C18	121.5 (4)	C37—C36—H36	119.5
C14—C13—C12	129.7 (4)	C38—C37—C36	116.7 (4)
C18—C13—C12	108.8 (4)	C38—C37—H37	121.7
C13—C14—C15	117.7 (4)	C36—C37—H37	121.7
C13—C14—H14	121.1	C37—C38—C33	122.0 (4)
C15—C14—H14	121.1	C37—C38—C31	129.1 (4)
C14—C15—C16	120.7 (4)	C33—C38—C31	108.9 (4)
C14—C15—H15	119.7	C41—N41—C42	112.0 (3)
C16—C15—H15	119.7	C41—N41—S4	125.4 (3)
C17—C16—C15	122.0 (4)	C42—N41—S4	122.6 (3)
C17—C16—H16	119.0	O41—C41—N41	125.0 (4)
C15—C16—H16	119.0	O41—C41—C48	130.2 (4)
C16—C17—C18	116.6 (4)	N41—C41—C48	104.9 (3)
C16—C17—H17	121.7	O42—C42—N41	125.1 (4)
C18—C17—H17	121.7	O42—C42—C43	130.1 (4)
C13—C18—C17	121.4 (4)	N41—C42—C43	104.8 (3)
C13—C18—C11	109.5 (4)	C44—C43—C48	122.8 (4)
C17—C18—C11	129.1 (4)	C44—C43—C42	128.3 (4)
C22—N21—C21	111.3 (3)	C48—C43—C42	109.0 (3)
C22—N21—S2	124.0 (3)	C43—C44—C45	116.4 (4)
C21—N21—S2	124.8 (3)	C43—C44—H44	121.8
O21—C21—N21	123.8 (4)	C45—C44—H44	121.8
O21—C21—C28	131.7 (4)	C46—C45—C44	121.6 (4)
N21—C21—C28	104.4 (3)	C46—C45—H45	119.2
O22—C22—N21	124.0 (4)	C44—C45—H45	119.2
O22—C22—C23	130.1 (4)	C45—C46—C47	120.7 (4)
N21—C22—C23	105.9 (3)	C45—C46—H46	119.6
C24—C23—C28	121.5 (4)	C47—C46—H46	119.6
C24—C23—C22	129.3 (4)	C48—C47—C46	118.2 (4)
C28—C23—C22	109.1 (3)	C48—C47—H47	120.9
C23—C24—C25	117.6 (4)	C46—C47—H47	120.9
C23—C24—H24	121.2	C47—C48—C43	120.3 (4)
C25—C24—H24	121.2	C47—C48—C41	130.3 (4)
C24—C25—C26	120.5 (4)	C43—C48—C41	109.3 (4)
C24—C25—H25	119.7	O1—N1—O2	123.2 (3)
C26—C25—H25	119.7	O1—N1—C1	118.0 (3)
C27—C26—C25	122.0 (4)	O2—N1—C1	118.8 (3)
C27—C26—H26	119.0	C2—C1—C6	122.2 (3)
C25—C26—H26	119.0	C2—C1—N1	119.8 (3)
C28—C27—C26	116.7 (4)	C6—C1—N1	118.0 (3)
C28—C27—H27	121.6	C1—C2—C3	118.4 (3)
C26—C27—H27	121.6	C1—C2—H2	120.8
C27—C28—C23	121.6 (4)	C3—C2—H2	120.8
C27—C28—C21	129.1 (4)	C4—C3—C2	120.2 (3)
C23—C28—C21	109.2 (4)	C4—C3—H3	119.9
N31—S3—S4	104.97 (13)	C2—C3—H3	119.9
N41—S4—S3	105.46 (13)	C3—C4—C5	120.1 (3)
C31—N31—C32	111.0 (3)	C3—C4—H4	119.9
C31—N31—S3	124.7 (3)	C5—C4—H4	119.9
C32—N31—S3	124.2 (3)	C6—C5—C4	120.7 (3)
O31—C31—N31	124.3 (4)	C6—C5—H5	119.6
O31—C31—C38	129.8 (4)	C4—C5—H5	119.6
N31—C31—C38	105.9 (3)	C5—C6—C1	118.4 (3)
O32—C32—N31	123.8 (4)	C5—C6—H6	120.8
O32—C32—C33	131.0 (4)	C1—C6—H6	120.8
N31—C32—C33	105.2 (3)
N11—S1—S2—N21	95.37 (19)	S3—N31—C31—C38	177.9 (3)
S2—S1—N11—C12	91.8 (3)	C31—N31—C32—O32	−177.5 (4)
S2—S1—N11—C11	−92.6 (3)	S3—N31—C32—O32	4.5 (6)
C12—N11—C11—O11	178.2 (4)	C31—N31—C32—C33	1.1 (4)
S1—N11—C11—O11	2.2 (6)	S3—N31—C32—C33	−176.9 (3)
C12—N11—C11—C18	−0.3 (4)	O32—C32—C33—C34	−1.7 (8)
S1—N11—C11—C18	−176.4 (3)	N31—C32—C33—C34	179.7 (4)
C11—N11—C12—O12	178.9 (4)	O32—C32—C33—C38	176.7 (4)
S1—N11—C12—O12	−5.1 (6)	N31—C32—C33—C38	−1.8 (4)
C11—N11—C12—C13	−0.7 (4)	C38—C33—C34—C35	−0.8 (6)
S1—N11—C12—C13	175.3 (3)	C32—C33—C34—C35	177.5 (4)
O12—C12—C13—C14	−0.3 (7)	C33—C34—C35—C36	−0.4 (6)
N11—C12—C13—C14	179.2 (4)	C34—C35—C36—C37	0.5 (6)
O12—C12—C13—C18	−178.0 (4)	C35—C36—C37—C38	0.6 (6)
N11—C12—C13—C18	1.6 (4)	C36—C37—C38—C33	−1.8 (6)
C18—C13—C14—C15	−0.3 (6)	C36—C37—C38—C31	−179.9 (4)
C12—C13—C14—C15	−177.7 (4)	C34—C33—C38—C37	1.9 (6)
C13—C14—C15—C16	0.8 (6)	C32—C33—C38—C37	−176.7 (4)
C14—C15—C16—C17	−0.9 (6)	C34—C33—C38—C31	−179.6 (3)
C15—C16—C17—C18	0.4 (6)	C32—C33—C38—C31	1.8 (5)
C14—C13—C18—C17	−0.1 (6)	O31—C31—C38—C37	−2.1 (7)
C12—C13—C18—C17	177.8 (4)	N31—C31—C38—C37	177.3 (4)
C14—C13—C18—C11	−179.7 (4)	O31—C31—C38—C33	179.6 (4)
C12—C13—C18—C11	−1.8 (4)	N31—C31—C38—C33	−1.0 (4)
C16—C17—C18—C13	0.1 (6)	S3—S4—N41—C41	92.3 (3)
C16—C17—C18—C11	179.6 (4)	S3—S4—N41—C42	−91.0 (3)
O11—C11—C18—C13	−177.1 (4)	C42—N41—C41—O41	177.8 (4)
N11—C11—C18—C13	1.4 (4)	S4—N41—C41—O41	−5.2 (6)
O11—C11—C18—C17	3.4 (7)	C42—N41—C41—C48	−1.9 (4)
N11—C11—C18—C17	−178.2 (4)	S4—N41—C41—C48	175.1 (3)
S1—S2—N21—C22	93.4 (3)	C41—N41—C42—O42	−175.7 (4)
S1—S2—N21—C21	−88.5 (3)	S4—N41—C42—O42	7.2 (6)
C22—N21—C21—O21	−177.1 (4)	C41—N41—C42—C43	3.0 (4)
S2—N21—C21—O21	4.6 (6)	S4—N41—C42—C43	−174.1 (3)
C22—N21—C21—C28	2.5 (4)	O42—C42—C43—C44	−3.3 (7)
S2—N21—C21—C28	−175.8 (3)	N41—C42—C43—C44	178.1 (4)
C21—N21—C22—O22	177.6 (4)	O42—C42—C43—C48	175.6 (4)
S2—N21—C22—O22	−4.0 (6)	N41—C42—C43—C48	−2.9 (4)
C21—N21—C22—C23	−2.7 (4)	C48—C43—C44—C45	−0.6 (6)
S2—N21—C22—C23	175.6 (3)	C42—C43—C44—C45	178.2 (4)
O22—C22—C23—C24	0.0 (7)	C43—C44—C45—C46	0.7 (6)
N21—C22—C23—C24	−179.6 (4)	C44—C45—C46—C47	−0.9 (7)
O22—C22—C23—C28	−178.6 (4)	C45—C46—C47—C48	1.0 (6)
N21—C22—C23—C28	1.8 (4)	C46—C47—C48—C43	−0.9 (6)
C28—C23—C24—C25	−0.1 (6)	C46—C47—C48—C41	178.9 (4)
C22—C23—C24—C25	−178.5 (4)	C44—C43—C48—C47	0.7 (6)
C23—C24—C25—C26	1.0 (6)	C42—C43—C48—C47	−178.3 (4)
C24—C25—C26—C27	−1.7 (6)	C44—C43—C48—C41	−179.1 (4)
C25—C26—C27—C28	1.5 (6)	C42—C43—C48—C41	1.9 (4)
C26—C27—C28—C23	−0.5 (6)	O41—C41—C48—C47	0.4 (8)
C26—C27—C28—C21	178.0 (4)	N41—C41—C48—C47	−179.9 (4)
C24—C23—C28—C27	−0.1 (6)	O41—C41—C48—C43	−179.8 (4)
C22—C23—C28—C27	178.6 (4)	N41—C41—C48—C43	−0.1 (4)
C24—C23—C28—C21	−179.0 (4)	O1—N1—C1—C2	−8.8 (4)
C22—C23—C28—C21	−0.3 (5)	O2—N1—C1—C2	171.3 (3)
O21—C21—C28—C27	−0.5 (8)	O1—N1—C1—C6	168.3 (3)
N21—C21—C28—C27	180.0 (4)	O2—N1—C1—C6	−11.6 (4)
O21—C21—C28—C23	178.2 (4)	C6—C1—C2—C3	0.3 (5)
N21—C21—C28—C23	−1.3 (4)	N1—C1—C2—C3	177.4 (3)
N31—S3—S4—N41	−92.93 (18)	C1—C2—C3—C4	−2.0 (5)
S4—S3—N31—C31	88.9 (3)	C2—C3—C4—C5	2.7 (5)
S4—S3—N31—C32	−93.4 (3)	C3—C4—C5—C6	−1.8 (5)
C32—N31—C31—O31	179.3 (4)	C4—C5—C6—C1	0.1 (5)
S3—N31—C31—O31	−2.7 (6)	C2—C1—C6—C5	0.6 (5)
C32—N31—C31—C38	−0.1 (4)	N1—C1—C6—C5	−176.5 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C15—H15···O11^i	0.95	2.34	3.267 (5)	166
C26—H26···O42^ii	0.95	2.39	3.196 (6)	142
C35—H35···O31^iii	0.95	2.41	3.311 (5)	159
C46—H46···O22^iv	0.95	2.35	3.136 (6)	139
C6—H6···O42^v	0.95	2.51	3.245 (4)	134
C24—H24···O1	0.95	2.51	3.372 (5)	151
C14—H14···Cg1^vi	0.95	2.69	3.633 (5)	172
C34—H34···Cg1^vii	0.95	2.58	3.510 (5)	166

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