5-Methyl-1,3-phenyl-ene bis-[5-(di-methyl-amino)-naphthalene-1-sulfonate]: crystal structure and DFT calculations.

The title compound, C31H30N2S2O6, possesses crystallographically imposed twofold symmetry with the two C atoms of the central benzene ring and the C atom of its methyl substituent lying on the twofold rotation axis. The two dansyl groups are twisted away from the plane of methyl-phenyl bridging unit in opposite directions. The three-dimensional arrangement in the crystal is mainly stabilized by weak hydrogen bonds between the sulfonyl oxygen atoms and the hydrogen atoms from the N-methyl groups. Stacking of the dansyl group is not observed. From the DFT calculations, the HOMO-LUMO energy gap was found to be 2.99 eV and indicates n→π* and π→π* transitions within the mol-ecule.

Chemical context

Dansyl probes play important roles in many fields, including their use as industrial tracers and labelled biological tags (Tondi et al., 2005 ▸; Li et al., 2006 ▸; Liu et al., 2016 ▸). Dansyl derivatives have been employed to identify some diseases within cells and to detect DNA-duplex sequences. For example, modified oligonucleotides that contain a dansyl fluoro­phore and (S)-2, 3-dihy­droxy propyl carbamates linked to guanine residues result in an enhancement of the fluorescence. Such modified oligonucleotides can be used to prepare and detect the sequence of fluoro­genic probes in DNA (Suzuki et al., 2013 ▸). Cu-labelled dansyl mol­ecules have been designed and synthesized as fluorescence probes for membrane tags on apoptosis cells. These compounds can also be used for PET imaging of the apoptosis in vivo (Han et al., 2016 ▸). Furthermore, the development of dansyl fluoro­genic receptors for cations, anions and neutral mol­ecules has attracted much attention because of their ability to turn fluorescence ‘on’ or ‘off’ through a number of mechanisms including ICT, PET and ET processes (Chen & Chen, 2005 ▸; Praveen et al., 2010 ▸; Dinake et al. 2012 ▸; Jeong et al. 2016 ▸). In this paper, we report the synthesis, mol­ecular structure and crystal packing of 5-methyl-1,3-phenyl­ene bis­[5-(di­methyl­amino)­naphthalene-1-sulfonate]. The results of DFT calculations on the mol­ecule are also reported.

Structural commentary

The title compound crystallizes in the space group C2/c. The mol­ecule lies on a crystallographic twofold axis running through atoms C1, C2 and C5 of the methyl­phenyl unit so that the asymmetric unit comprises one half-mol­ecule (Fig. 1 ▸). The hydrogen atoms of the C1 methyl group are therefore disordered over two equivalent positions. Intra­molecular C14—H14—O3 hydrogen bonds enclose S(6) rings, Fig. 1 ▸. The mol­ecular structure comprises two O-dansyl groups on either side of a bridging methyl­phenyl ring that is essentially planar. The S1—O1—C4—C3 torsion angle is 72.98 (16)° with the methyl­phenyl ring plane. The S1 sulfur atoms have distorted tetra­hedral geometries, with an O2—S1—C6 bond angle of 109.18 (8)°. The two naphthalene units in each dansyl group are inclined to one another at an angle of 52.29 (6)°; however, no stacking of the naphthalene units is observed.

Figure 1

The mol­ecular structure of the title compound with displacement ellipsoids are drawn at the 50% probability level. Intra­molecular hydrogen bonds are shown as red dashed lines.

Supra­molecular features

In the crystal structure, the supra­molecular packing is dominated by weak C—H⋯O hydrogen bonds, Table 1 ▸. C9—H9—O1 contacts form dimers enclosing (22) rings and generate chains of mol­ecules along the c-axis direction, Fig. 2 ▸. C1—H1B—O3 and C16—H16C—O2 contacts further link the mol­ecules into sheets in the ab plane, Fig. 3 ▸. These contacts combine to stack rows of mol­ecules arranged in an obverse fashion along the a-axis direction, Fig. 4 ▸.

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C14—H14⋯O3	0.93	2.49	3.116 (2)	125
C1—H1B⋯O3i	0.96	2.70	3.528 (2)	145
C9—H9⋯O1ii	0.93	2.60	3.486 (2)	158
C16—H16C⋯O2iii	0.96	2.63	3.475 (2)	147

Symmetry codes: (i) ; (ii) ; (iii) .

Figure 2

Chains of dimers of the title compound along the c axis. Dashed lines represent the C—H⋯O hydrogen bonds.

Figure 3

Sheets of mol­ecules of the title compound formed in the ab plane.

Figure 4

The overall packing of the title compound viewed along the a-axis direction.

Computational study

The Density Functional Theory (DFT) calculations were performed at the CAM-B3LYP/6-311G (d,p) level as implemented in the GAUSSIAN09 program package (Frisch et al., 2009 ▸). The DFT structure optimization of the compound was performed starting from the X-ray geometry. The experimental values of the bond lengths and bond angles match reasonably well with the theoretical values in most cases. However, the lengths of bonds to O atoms involved in hydrogen bonding fit less well, Table 2 ▸. The important features such as conjugation and aromaticity are well illustrated by frontier mol­ecular orbitals. The ionization potential of the mol­ecule is determined from the energy of the highest occupied mol­ecular orbital (HOMO) and the electron affinity is calculated from the energy of the lowest unoccupied mol­ecular orbital (LUMO). The frontier mol­ecular orbital energies, E HOMO and E LUMO are −8.24 and −5.25 eV, respectively. Insights into the kinetic stability and chemical reactivity of a mol­ecule can be determined from the energy difference between the HOMO and LUMO orbitals, the so-called HOMO–LUMO energy gap. This gap was found here to be 2.99 eV. The HOMO–LUMO energy levels indicate n→π* and π→π* transitions and are shown in Fig. 5 ▸. The HOMO is mainly localized on the nitro­gen atom of di­methyl­amine group as well as on the C=C segments of the naphthalene ring systems while the LUMO is located again on the di­methyl­amine substituent and also on the aromatic rings of the naphthalene systems. In Fig. 5 ▸, the negative and positive phases are represented by green and red colours, respectively.

Table 2

Comparison of selected experimental (XRD) bond lengths and angles (Å, °) with those from DFT calculations

Bond/angle	XRD	DFT
S1—O1	1.6006 (12)	1.647
S1—O3	1.4223 (13)	1.453
S1—C6	1.7552 (16)	1.768
O1—C4	1.4166 (17)	1.394
N1—C11	1.413 (2)	1.406
O1—S1—C6	103.11 (7)	103.46
O2—S1—O1	108.81 (7)	108.93
O2—S1—O3	119.32 (9)	119.85
C4—O1—S1	119.05 (9)	119.08
O2—S1—C6	109.18 (8)	109.04

Figure 5

Frontier mol­ecular orbitals of the title compound.

Database survey

There are many crystal structures of dansyl derivatives that are similar to the title compound. Two categories of crystal structures of dansyl derivatives are found. The first types are simple organic mol­ecules that pack in the solid state through the many types of inter­molecular inter­actions. For example, in 2-[5-(di­methyl­amino)­naphthalene-1-sulfonamido]­phenyl 5-(di­methyl­amino)­naphthalene-1-sulfonate [CSD (Groom et al., 2016 ▸) refcode NUQDOU; Chainok et al., 2015 ▸), there are two dansyl units connecting to the amine and hydroxyl groups of a 2-amino­phenol, while weak C—H⋯O hydrogen bonds stabilize the crystal structure. In N-cyclo­dodecyl-5-(di­methyl­amino)­naphthalene-1-sulfonamide (HODDOU; Fischer et al., 2008 ▸) a cyclo­dodecyl­amine linked to the dansyl substituent adopts a U-shaped conformation, and the crystal packing is stabilized by N—H⋯O hydrogen bonds and C—H⋯π inter­actions between neighbouring mol­ecules. In 8-quinolyl 5-(di­methyl­amino)­naphthalene-1-sulfonate, (DUVFOQ; Xiao & Zhan, 2010 ▸) with an 8-hy­droxy­quinoline ring, C—H⋯O hydrogen bonds and π–π inter­actions between pairs of chains link adjacent mol­ecules. In the crystal structure of N-(2-amino­eth­yl)-5-(di­methyl­amino)­naphthalene-1-sulfonamide (BOVBOE; Zhang et al., 2009 ▸) a dansyl compound with a 2-amino­ethyl group, layers are formed through N—H⋯N and weak C—H⋯O hydrogen bonds. In 5,5′-bis­(di­methyl­amino)-N,N′-(3-methyl-3-aza­pentane-1,5-di­yl)di(naphthalene-1-sulf­onamide) (DABSEH; Horne et al., 2015 ▸), packing in the crystal structure relies on N—H⋯O and C—H⋯O inter­actions.

Metal–dansyl complexes form the second class of common dansyl derivatives. The crystal structures of the di- and trinuclear gold(I) complexes [5-(di­methyl­amino)­naphthalene-1-sulfonamido]­bis­(tri­phenyl­phosphine)digold (UZEJAL) and [5-(di­methyl­amino)­naphthalene-1-sulfonamido]­tris­(tri­phenyl­phosphine)trigold perchlorate (UZEJEP) (Cho et al., 2011 ▸) display weak Au⋯Au inter­actions and C—H⋯π contacts within the mol­ecule. The Pb2+ complex 26,28-dibut­oxy-25,27-bis­(N-dansylcarbamoylmeth­oxy)-5,11,17,23-tetra­kis(1,1-di­methyl­eth­yl)calix[4]arene (NOJRAG; Buie et al., 2008 ▸), where the calix[4]arene bears two dansylcarboxamide groups, was found to be highly selective and sensitive for the recognition of and coordination to the Pb2+ ion.

Synthesis and crystallization

The title compound was synthesized by mixing 3,5-di­hydroxy­toluene (1.05 g, 8.46 mmol) and dansyl chloride (4.55g, 17 mmol) using potassium carbonate(2.34g, 17 mmol) as a base in aceto­nitrile solvent (40 ml). The reaction mixture was heated at 363 K and stirred under an N2 atmosphere for 24 h. The solvent was removed with a rotary evaporator. The residue was added to water (15 ml) and extracted with di­chloro­methane (3 × 25ml). The organic layer was dried with anhydrous Na2SO4 and the product was purified by column chromatography using CH2Cl2 as the eluent. The di­chloro­methane was slowly evaporated to afford a green solid in 65% yield. Light-green block-like crystals were grown in chloro­form at room temperature.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 3 ▸. All H atoms on C were refined using a riding model with d(C—H) = 0.95 Å and U iso(H) = 1.2U eq(C) for aromatic and d(C—H) = 0.98 Å, U iso(H) = 1.5U eq(C) for methyl H atoms. As atom Cl lies on a twofold rotation axis, the H atoms of the Cl methyl group are disordered with occupancies fixed at 0.5.

Table 3

Experimental details

Crystal data
Chemical formula	C31H30N2O6S2
M r	590.69
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	296
a, b, c (Å)	15.5072 (6), 12.3504 (5), 16.3017 (5)
β (°)	114.868 (1)
V (Å3)	2832.62 (18)
Z	4
Radiation type	Mo Kα
μ (mm−1)	0.24
Crystal size (mm)	0.44 × 0.44 × 0.4
Data collection
Diffractometer	Bruker D8 QUEST CMOS
Absorption correction	Multi-scan (SADABS; Bruker, 2014 ▸)
T min, T max	0.710, 0.745
No. of measured, independent and observed [I > 2σ(I)] reflections	18169, 2857, 2437
R int	0.025
(sin θ/λ)max (Å−1)	0.625
Refinement
R[F 2 > 2σ(F 2)], wR(F 2), S	0.037, 0.106, 1.04
No. of reflections	2857
No. of parameters	190
H-atom treatment	H-atom parameters constrained
Δρmax, Δρmin (e Å−3)	0.23, −0.33

Computer programs: APEX CCD and SAINT (Bruker, 2013 ▸), SHELXT (Sheldrick, 2015a ▸), SHELXL2014 (Sheldrick, 2015b ▸), OLEX2 (Dolomanov et al., 2009 ▸) and Mercury (Macrae et al., 2008 ▸).

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989019009058/sj5573sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989019009058/sj5573Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S2056989019009058/sj5573Isup3.cml

CCDC reference: 1535824

Additional supporting information: crystallographic information; 3D view; checkCIF report

C31H30N2O6S2	F(000) = 1240
Mr = 590.69	Dx = 1.385 Mg m−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 15.5072 (6) Å	Cell parameters from 8490 reflections
b = 12.3504 (5) Å	θ = 3.0–26.4°
c = 16.3017 (5) Å	µ = 0.24 mm−1
β = 114.868 (1)°	T = 296 K
V = 2832.62 (18) Å3	Block, light green
Z = 4	0.44 × 0.44 × 0.4 mm

Bruker D8 QUEST CMOS diffractometer	2857 independent reflections
Radiation source: sealed tube	2437 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.025
φ and ω scans	θmax = 26.4°, θmin = 3.0°
Absorption correction: multi-scan (SADABS; Bruker, 2014)	h = −19→19
Tmin = 0.710, Tmax = 0.745	k = −15→15
18169 measured reflections	l = −20→20

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.037	H-atom parameters constrained
wR(F2) = 0.106	w = 1/[σ2(Fo2) + (0.0573P)2 + 1.5124P] where P = (Fo2 + 2Fc2)/3
S = 1.04	(Δ/σ)max < 0.001
2857 reflections	Δρmax = 0.23 e Å−3
190 parameters	Δρmin = −0.33 e Å−3
0 restraints

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

	x	y	z	Uiso*/Ueq	Occ. (<1)
S1	0.24891 (3)	0.59066 (4)	0.67336 (3)	0.04868 (15)
O1	0.35036 (8)	0.59425 (9)	0.75828 (7)	0.0458 (3)
O2	0.21860 (9)	0.69851 (11)	0.64561 (10)	0.0632 (4)
O3	0.19426 (9)	0.52398 (12)	0.70474 (10)	0.0675 (4)
N1	0.43181 (10)	0.25203 (12)	0.48853 (10)	0.0535 (4)
C6	0.27383 (10)	0.52632 (13)	0.58976 (11)	0.0424 (4)
C7	0.25296 (12)	0.58335 (13)	0.51133 (12)	0.0483 (4)
H7	0.2260	0.6519	0.5041	0.058*
C8	0.27244 (12)	0.53779 (15)	0.44241 (12)	0.0526 (4)
H8	0.2545	0.5739	0.3876	0.063*
C9	0.31748 (12)	0.44083 (14)	0.45540 (11)	0.0473 (4)
H9	0.3316	0.4125	0.4096	0.057*
C10	0.34350 (10)	0.38180 (12)	0.53666 (10)	0.0400 (3)
C11	0.39393 (11)	0.28115 (13)	0.55059 (11)	0.0458 (4)
C12	0.40220 (13)	0.21854 (14)	0.62272 (14)	0.0586 (5)
H12	0.4305	0.1507	0.6302	0.070*
C13	0.36883 (15)	0.25495 (16)	0.68541 (14)	0.0644 (5)
H13	0.3740	0.2096	0.7328	0.077*
C14	0.32938 (13)	0.35391 (15)	0.67920 (12)	0.0532 (4)
H14	0.3114	0.3778	0.7238	0.064*
C15	0.31559 (10)	0.42115 (12)	0.60409 (10)	0.0405 (3)
C16	0.51087 (14)	0.32132 (16)	0.49436 (14)	0.0616 (5)
H16A	0.4915	0.3958	0.4888	0.092*
H16B	0.5289	0.3032	0.4465	0.092*
H16C	0.5640	0.3103	0.5516	0.092*
C17	0.45713 (16)	0.13831 (16)	0.48903 (16)	0.0728 (6)
H17A	0.5091	0.1212	0.5457	0.109*
H17B	0.4755	0.1250	0.4406	0.109*
H17C	0.4034	0.0939	0.4812	0.109*
C4	0.42508 (10)	0.65401 (13)	0.75150 (10)	0.0400 (3)
C3	0.42371 (11)	0.76504 (14)	0.75244 (11)	0.0459 (4)
H3	0.3723	0.8016	0.7547	0.055*
C2	0.5000	0.82262 (19)	0.7500	0.0490 (5)
C5	0.5000	0.59523 (18)	0.7500	0.0398 (5)
H5	0.5000	0.5199	0.7500	0.048*
C1	0.5000	0.9447 (2)	0.7500	0.0765 (9)
H1A	0.4591	0.9706	0.6908	0.115*	0.5
H1B	0.5635	0.9706	0.7663	0.115*	0.5
H1C	0.4774	0.9706	0.7929	0.115*	0.5

	U11	U22	U33	U12	U13	U23
S1	0.0324 (2)	0.0582 (3)	0.0573 (3)	−0.00268 (16)	0.02067 (19)	−0.00729 (18)
O1	0.0378 (6)	0.0558 (7)	0.0467 (6)	−0.0065 (5)	0.0208 (5)	−0.0008 (5)
O2	0.0455 (6)	0.0600 (8)	0.0765 (9)	0.0133 (6)	0.0182 (6)	−0.0078 (6)
O3	0.0482 (7)	0.0864 (10)	0.0816 (9)	−0.0191 (7)	0.0407 (7)	−0.0157 (7)
N1	0.0461 (8)	0.0486 (8)	0.0618 (9)	0.0003 (6)	0.0189 (7)	−0.0103 (7)
C6	0.0325 (7)	0.0458 (9)	0.0473 (9)	−0.0036 (6)	0.0153 (6)	−0.0010 (7)
C7	0.0429 (8)	0.0426 (9)	0.0548 (10)	0.0020 (7)	0.0158 (8)	0.0066 (7)
C8	0.0509 (9)	0.0554 (10)	0.0452 (9)	0.0027 (8)	0.0142 (8)	0.0142 (7)
C9	0.0451 (9)	0.0538 (10)	0.0411 (8)	−0.0015 (7)	0.0163 (7)	0.0013 (7)
C10	0.0336 (7)	0.0395 (8)	0.0423 (8)	−0.0059 (6)	0.0114 (6)	0.0000 (6)
C11	0.0375 (8)	0.0397 (8)	0.0531 (9)	−0.0052 (6)	0.0121 (7)	−0.0032 (7)
C12	0.0564 (10)	0.0414 (9)	0.0743 (13)	0.0032 (8)	0.0241 (10)	0.0119 (8)
C13	0.0662 (12)	0.0583 (11)	0.0700 (12)	−0.0002 (9)	0.0300 (10)	0.0265 (10)
C14	0.0517 (10)	0.0575 (11)	0.0545 (10)	−0.0016 (8)	0.0264 (8)	0.0113 (8)
C15	0.0336 (7)	0.0425 (8)	0.0433 (8)	−0.0062 (6)	0.0141 (6)	0.0029 (6)
C16	0.0507 (10)	0.0686 (12)	0.0671 (12)	0.0000 (9)	0.0263 (9)	−0.0005 (9)
C17	0.0682 (13)	0.0544 (11)	0.0892 (15)	0.0032 (10)	0.0266 (12)	−0.0176 (10)
C4	0.0332 (7)	0.0499 (9)	0.0360 (8)	−0.0049 (6)	0.0136 (6)	−0.0008 (6)
C3	0.0373 (8)	0.0487 (9)	0.0518 (9)	0.0027 (6)	0.0186 (7)	−0.0020 (7)
C2	0.0446 (12)	0.0440 (12)	0.0577 (14)	0.000	0.0208 (11)	0.000
C5	0.0372 (10)	0.0432 (12)	0.0363 (11)	0.000	0.0129 (9)	0.000
C1	0.0671 (18)	0.0455 (15)	0.124 (3)	0.000	0.0475 (19)	0.000

S1—O1	1.6006 (12)	C13—H13	0.9300
S1—O2	1.4215 (14)	C13—C14	1.352 (3)
S1—O3	1.4223 (13)	C14—H14	0.9300
S1—C6	1.7552 (16)	C14—C15	1.419 (2)
O1—C4	1.4166 (17)	C16—H16A	0.9600
N1—C11	1.413 (2)	C16—H16B	0.9600
N1—C16	1.465 (2)	C16—H16C	0.9600
N1—C17	1.458 (2)	C17—H17A	0.9600
C6—C7	1.374 (2)	C17—H17B	0.9600
C6—C15	1.426 (2)	C17—H17C	0.9600
C7—H7	0.9300	C4—C3	1.372 (2)
C7—C8	1.399 (3)	C4—C5	1.3789 (19)
C8—H8	0.9300	C3—H3	0.9300
C8—C9	1.357 (2)	C3—C2	1.395 (2)
C9—H9	0.9300	C2—C3i	1.395 (2)
C9—C10	1.414 (2)	C2—C1	1.507 (3)
C10—C11	1.435 (2)	C5—C4i	1.3789 (19)
C10—C15	1.426 (2)	C5—H5	0.9300
C11—C12	1.367 (3)	C1—H1A	0.9600
C12—H12	0.9300	C1—H1B	0.9600
C12—C13	1.400 (3)	C1—H1C	0.9600
O1—S1—C6	103.11 (7)	C13—C14—C15	119.53 (17)
O2—S1—O1	108.81 (7)	C15—C14—H14	120.2
O2—S1—O3	119.32 (9)	C10—C15—C6	116.65 (14)
O2—S1—C6	109.18 (8)	C14—C15—C6	124.57 (15)
O3—S1—O1	102.86 (8)	C14—C15—C10	118.77 (15)
O3—S1—C6	112.10 (8)	N1—C16—H16A	109.5
C4—O1—S1	119.05 (9)	N1—C16—H16B	109.5
C11—N1—C16	113.17 (14)	N1—C16—H16C	109.5
C11—N1—C17	115.68 (16)	H16A—C16—H16B	109.5
C17—N1—C16	110.26 (16)	H16A—C16—H16C	109.5
C7—C6—S1	116.60 (13)	H16B—C16—H16C	109.5
C7—C6—C15	122.16 (15)	N1—C17—H17A	109.5
C15—C6—S1	121.22 (12)	N1—C17—H17B	109.5
C6—C7—H7	120.1	N1—C17—H17C	109.5
C6—C7—C8	119.70 (15)	H17A—C17—H17B	109.5
C8—C7—H7	120.1	H17A—C17—H17C	109.5
C7—C8—H8	120.0	H17B—C17—H17C	109.5
C9—C8—C7	120.03 (15)	C3—C4—O1	120.20 (13)
C9—C8—H8	120.0	C3—C4—C5	122.93 (15)
C8—C9—H9	119.1	C5—C4—O1	116.74 (14)
C8—C9—C10	121.77 (16)	C4—C3—H3	120.3
C10—C9—H9	119.1	C4—C3—C2	119.48 (16)
C9—C10—C11	121.12 (15)	C2—C3—H3	120.3
C9—C10—C15	119.14 (14)	C3—C2—C3i	118.7 (2)
C15—C10—C11	119.69 (14)	C3i—C2—C1	120.64 (11)
N1—C11—C10	118.03 (15)	C3—C2—C1	120.65 (11)
C12—C11—N1	123.69 (16)	C4—C5—C4i	116.5 (2)
C12—C11—C10	118.28 (16)	C4—C5—H5	121.8
C11—C12—H12	119.5	C4i—C5—H5	121.8
C11—C12—C13	121.09 (17)	C2—C1—H1A	109.5
C13—C12—H12	119.5	C2—C1—H1B	109.5
C12—C13—H13	119.0	C2—C1—H1C	109.5
C14—C13—C12	122.05 (17)	H1A—C1—H1B	109.5
C14—C13—H13	119.0	H1A—C1—H1C	109.5
C13—C14—H14	120.2	H1B—C1—H1C	109.5
S1—O1—C4—C3	72.98 (16)	C9—C10—C11—N1	11.1 (2)
S1—O1—C4—C5	−111.07 (11)	C9—C10—C11—C12	−168.50 (16)
S1—C6—C7—C8	178.93 (13)	C9—C10—C15—C6	−8.3 (2)
S1—C6—C15—C10	−172.59 (11)	C9—C10—C15—C14	170.72 (15)
S1—C6—C15—C14	8.4 (2)	C10—C11—C12—C13	−4.8 (3)
O1—S1—C6—C7	−121.15 (13)	C11—C10—C15—C6	174.23 (13)
O1—S1—C6—C15	57.51 (13)	C11—C10—C15—C14	−6.7 (2)
O1—C4—C3—C2	176.99 (11)	C11—C12—C13—C14	−1.7 (3)
O1—C4—C5—C4i	−176.50 (14)	C12—C13—C14—C15	4.0 (3)
O2—S1—O1—C4	−53.02 (13)	C13—C14—C15—C6	179.28 (16)
O2—S1—C6—C7	−5.58 (15)	C13—C14—C15—C10	0.3 (2)
O2—S1—C6—C15	173.07 (12)	C15—C6—C7—C8	0.3 (2)
O3—S1—O1—C4	179.51 (11)	C15—C10—C11—N1	−171.45 (13)
O3—S1—C6—C7	128.91 (14)	C15—C10—C11—C12	8.9 (2)
O3—S1—C6—C15	−52.44 (15)	C16—N1—C11—C10	68.68 (19)
N1—C11—C12—C13	175.62 (17)	C16—N1—C11—C12	−111.71 (19)
C6—S1—O1—C4	62.80 (12)	C17—N1—C11—C10	−162.74 (15)
C6—C7—C8—C9	−4.3 (3)	C17—N1—C11—C12	16.9 (2)
C7—C6—C15—C10	6.0 (2)	C4—C3—C2—C3i	−0.62 (10)
C7—C6—C15—C14	−172.98 (16)	C4—C3—C2—C1	179.38 (10)
C7—C8—C9—C10	1.8 (3)	C3—C4—C5—C4i	−0.66 (11)
C8—C9—C10—C11	−177.88 (15)	C5—C4—C3—C2	1.3 (2)
C8—C9—C10—C15	4.7 (2)

D—H···A	D—H	H···A	D···A	D—H···A
C14—H14···O3	0.93	2.49	3.116 (2)	125
C1—H1B···O3ii	0.96	2.70	3.528 (2)	145
C9—H9···O1iii	0.93	2.60	3.486 (2)	158
C16—H16C···O2iv	0.96	2.63	3.475 (2)	147