2-Naphthyl 4-toluene­sulfonate: supramolecular aggregation through C—H...O and C—H...π interactions

In the title compound, C₁₇H₁₄O₃S, there are two independent mol­ecules and the intramolecular dihedral angles between the mean planes of the 4-tolyl and the 2-naphthyl rings are 55.11 (7)° and 65.10 (7)°. C—H...O interactions generate rings of graph-set motif S(5), S(6), R²₁(4), R¹₂(6), R¹₂(8) and R¹₂(9). The supramolecular aggregation is completed by the presence of several C—H...π interactions.

Key indicators

• Single-crystal X-ray study
• T = 120 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.047
• wR factor = 0.112
• Data-to-parameter ratio = 17.0

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry


 Alert Level C:



ABSTM_02  Alert C The ratio of expected to reported Tmax/Tmin(RR') is < 0.90
          Tmin and Tmax reported:      0.699     0.930
          Tmin' and Tmax expected:      0.884     0.940
          RR' =      0.800
          Please check that your absorption correction is appropriate.

General Notes



REFLT_03
         From the CIF: _diffrn_reflns_theta_max           27.49
         From the CIF: _reflns_number_total               6450
         Count of symmetry unique reflns         3253
         Completeness (_total/calc)            198.28%
         TEST3: Check Friedels for noncentro structure
         Estimate of Friedel pairs measured      3197
         Fraction of Friedel pairs measured     0.983
         Are heavy atom types Z>Si present          yes
          Please check that the estimate of the number of Friedel pairs is
          correct. If it is not, please give the correct count in the
          _publ_section_exptl_refinement section of the submitted CIF.


 0 Alert Level A = Potentially serious problem

 0 Alert Level B = Potential problem

 1 Alert Level C = Please check

---

S1. Comment

p-Toluene sulfonates are used in monitoring the merging of lipids (Yachi et al., 1989), studying membrane fusion during acrosome reactions (Spungin et al., 1992), development of immuno-affinity chromatography for the purification of human coagulation factor (Tharakan et al., 1992), chemical studies on viruses (Alford et al., 1991), development of technology for linking photosensitizers to model monoclonal antibodies (Jiang et al., 1990) and chemical modification of sigma sub-units of the E-coli RNA polymerase (Narayanan & Krakow, 1983). An X-ray study of the title compound, (I), was undertaken in order to determine its crystal and molecular structure because of the biological importance of its analogues.

The dihedral angle between the mean planes of the 4-tolyl and 2-naphthyl rings is 65.10 (7)° for the molecule involving S1, and 55.11 (7)° for the molecule involving S2 (Fig. 1 and Table 1). This shows their non-coplanar orientation, similar to that found between the 4-tolyl and 2-chlorophenyl rings in 2-chlorophenyl 4-toluenesulfonate (Vembu, Nallu, Garrison & Youngs, 2003b) and the 4-tolyl and quinoline rings in 8-tosyloxyquinoline (Vembu, Nallu, Garrison & Youngs, 2003c) and in contrast to the near coplanar orientation of the 4-tolyl and 2,4-dinitrophenyl rings in 2,4-dinitrophenyl 4-toluenesulfonate (Vembu, Nallu, Garrison & Youngs, 2003a) and 4-tolyl and 4-methoxyphenyl rings in 4-methoxyphenyl 4-toluenesulfonate (Vembu, Nallu, Garrison, Hindi & Youngs, 2003).

The crystal structure of (I) is stabilized by weak C—H···O interactions. The range of H···O distances (Table 2) agrees with that found for weak C—H···O bonds (Desiraju & Steiner, 1999). The C4—H4···O2, C6—H6···O1, C15—H15···O2 (Fig.2), C21—H21···O4, C23—H23···O5 and C26—H26···O5 intramolecular interactions generate rings of graph-set motif (Etter, 1990; Bernstein et al., 1995) S(5), S(5), S(6), S(5), S(5) and S(6), respectively. The C3—H3···O1^vii and C3—H3···O3^vii interactions constitute a pair of bifurcated donor bonds, generating a ring of graph set R²₁(4). The H3···O1^vii and H3···O3^vii distances differ only by 0.04 Å. The resulting configuration is best regarded as a three-centered symmetrical hydrogen-bonded chelate motif (Desiraju, 1989) and is also observed in similar structures (Vembu, Nallu, Garrison & Youngs, 2003b, 2003c, 2003 d,2003 e, 2003f, 2003 g; Vembu, Nallu, Garrison, Hindi & Youngs 2003). The C3—H3···O3^vii and C1—H1A···O3^vii interactions constitute a pair of bifurcated acceptor bonds, generating a ring of graph set R¹₂(6). The C3—H3···O1^vii and C1—H1A···O3^vii interactions together generate a ring of graph set R¹₂(8). The R²₁(4) chelate motif and the R¹₂(6) ring motif are present within the R¹₂(8) ring motif. The C21—H21···O5^iv and C32—H32···O5^iv interactions constitute a pair of bifurcated acceptor bonds, generating a ring of graph set R¹₂(9). The C24—H24···O4ⁱ and C24—H24···O6ⁱ (Fig.3) interactions constitute a pair of bifurcated donor bonds, forming another symmetrical three[centered hydrogen-bonded chelate motif of graph set R²₁(4). The H24···O4ⁱ and H24···O6ⁱ distances differ by 0.07 Å. There are several other weak C—H···O bonds (Table 2, Fig. 3), which contribute to the aggregation of the title compound in the crystal lattice. The supramolecular aggregation is completed by the presence of ten C—H···π interactions (Table 2), where Cg1–Cg6 are the centroids of the rings C2—C7, C8—C9/C14—C17, C10—C13/C16—C17, C19—C24, C25—C26/C31—C34 and C27—C30/C33—C34, respectively. The details of these C—H···π interactions were calculated using PLATON (Spek, 1998).

S2. Experimental

4-Toluenesulfonyl chloride (4.7 mmol) dissolved in acetone (4 ml) was added dropwise to 2-naphthol (5.5 mmol) in aqueous NaOH (2.5 ml, 10%) with constant shaking. The precipitated compound, (I), (3.3 mmol, yield 70%) was filtered off and recrystallized from ethyl acetate.

Computing details

Data collection: SMART-NT (Bruker, 1998); cell refinement: SMART-NT; data reduction: SAINT-NT (Bruker, 1998); program(s) used to solve structure: SHELXTL (Sheldrick, 1998); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Figures

	Fig. 1. The structure of the two independent molecules of (I), showing 50% probability displacement ellipsoids.
	Fig. 2. Diagram showing the intramolecular hydrogen bonds in (I).
	Fig. 3. View of the crystal structure along the c axis, showing the intermolecular hydrogen bonds.

2-naphthyl 4-toluenesulfonate

Crystal data

C17H14O3S	F(000) = 624
Mr = 298.34	Dx = 1.405 Mg m^−3
Monoclinic, Pc	Melting point = 393–394 K
Hall symbol: P -2yc	Mo Kα radiation, λ = 0.71073 Å
a = 7.9315 (6) Å	Cell parameters from 942 reflections
b = 29.130 (2) Å	θ = 2.9–27.4°
c = 6.1111 (5) Å	µ = 0.24 mm^−1
β = 92.383 (3)°	T = 120 K
V = 1410.73 (19) Å^3	Block, colourless
Z = 4	0.51 × 0.45 × 0.26 mm

Data collection

Bruker SMART 6K CCD area-detector diffractometer	6450 independent reflections
Radiation source: fine-focus sealed tube	5907 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.045
Detector resolution: 8 pixels mm^-1	θmax = 27.5°, θmin = 0.7°
ω scans	h = −10→10
Absorption correction: multi-scan (SADABS; Sheldrick, 1998)	k = −37→37
Tmin = 0.699, Tmax = 0.930	l = −7→7
20999 measured reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.047	H-atom parameters constrained
wR(F^2) = 0.112	w = 1/[σ^2(Fo^2) + (0.0541P)^2 + 0.7718P] where P = (Fo^2 + 2Fc^2)/3
S = 1.04	(Δ/σ)max = 0.001
6450 reflections	Δρmax = 0.34 e Å^−3
379 parameters	Δρmin = −0.32 e Å^−3
2 restraints	Absolute structure: Flack (1983), 3197 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.03 (7)

Special details

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

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

	x	y	z	Uiso*/Ueq
S1	0.33101 (9)	0.91865 (2)	0.62202 (12)	0.02686 (17)
O1	0.2236 (3)	0.95769 (8)	0.6089 (5)	0.0413 (6)
O2	0.3813 (3)	0.89919 (8)	0.8286 (4)	0.0358 (5)
O3	0.2264 (2)	0.88092 (6)	0.4804 (3)	0.0242 (4)
C1	0.9502 (4)	0.95299 (11)	0.1037 (5)	0.0317 (7)
H1A	1.0503	0.9427	0.1893	0.048*
H1B	0.9608	0.9858	0.0712	0.048*
H1C	0.9403	0.9357	−0.0337	0.048*
C2	0.7955 (3)	0.94512 (9)	0.2330 (5)	0.0231 (6)
C3	0.8098 (3)	0.92597 (10)	0.4410 (5)	0.0257 (6)
H3	0.9185	0.9188	0.5026	0.031*
C4	0.6674 (3)	0.91706 (9)	0.5620 (5)	0.0218 (6)
H4	0.6780	0.9035	0.7032	0.026*
C5	0.5103 (3)	0.92863 (9)	0.4700 (5)	0.0240 (6)
C6	0.4923 (3)	0.94926 (9)	0.2658 (5)	0.0227 (6)
H6	0.3840	0.9579	0.2075	0.027*
C7	0.6353 (4)	0.95703 (9)	0.1487 (5)	0.0250 (6)
H7	0.6240	0.9708	0.0079	0.030*
C8	0.2725 (3)	0.83400 (9)	0.5049 (5)	0.0236 (6)
C9	0.3566 (3)	0.81356 (10)	0.3416 (5)	0.0250 (6)
H9	0.3932	0.8310	0.2209	0.030*
C10	0.4719 (4)	0.74204 (10)	0.1904 (5)	0.0285 (6)
H10	0.5111	0.7585	0.0684	0.034*
C11	0.4966 (4)	0.69572 (11)	0.2046 (6)	0.0348 (7)
H11	0.5515	0.6802	0.0909	0.042*
C12	0.4414 (4)	0.67065 (10)	0.3860 (6)	0.0345 (7)
H12	0.4598	0.6385	0.3939	0.041*
C13	0.3616 (4)	0.69257 (11)	0.5505 (5)	0.0327 (7)
H13	0.3254	0.6756	0.6726	0.039*
C14	0.2474 (4)	0.76440 (11)	0.7044 (5)	0.0292 (6)
H14	0.2116	0.7479	0.8282	0.035*
C15	0.2160 (4)	0.81022 (10)	0.6890 (5)	0.0275 (6)
H15	0.1575	0.8258	0.7994	0.033*
C16	0.3889 (3)	0.76536 (10)	0.3555 (5)	0.0239 (6)
C17	0.3324 (3)	0.74101 (11)	0.5395 (5)	0.0258 (6)
S2	0.96993 (8)	0.58200 (2)	1.05639 (10)	0.02009 (15)
O4	1.0857 (3)	0.54516 (7)	1.0349 (4)	0.0304 (5)
O5	0.9319 (3)	0.59901 (7)	1.2672 (3)	0.0277 (4)
O6	1.0545 (2)	0.62248 (6)	0.9197 (3)	0.0218 (4)
C18	0.3206 (4)	0.54824 (11)	0.5314 (6)	0.0311 (7)
H18A	0.3437	0.5479	0.3751	0.037*
H18B	0.2410	0.5730	0.5608	0.037*
H18C	0.2717	0.5187	0.5725	0.037*
C19	0.4829 (3)	0.55605 (9)	0.6635 (5)	0.0228 (5)
C20	0.6370 (4)	0.54245 (10)	0.5829 (5)	0.0228 (6)
H20	0.6394	0.5279	0.4439	0.027*
C21	0.7874 (3)	0.54989 (9)	0.7032 (4)	0.0209 (5)
H21	0.8921	0.5408	0.6468	0.025*
C22	0.7821 (3)	0.57082 (9)	0.9063 (4)	0.0176 (5)
C23	0.6300 (3)	0.58404 (9)	0.9924 (5)	0.0198 (5)
H23	0.6280	0.5980	1.1329	0.024*
C24	0.4813 (3)	0.57660 (9)	0.8703 (5)	0.0235 (6)
H24	0.3768	0.5856	0.9279	0.028*
C25	0.9723 (3)	0.66556 (9)	0.9072 (5)	0.0214 (5)
C26	0.9920 (3)	0.69604 (9)	1.0728 (5)	0.0214 (5)
H26	1.0553	0.6880	1.2026	0.026*
C27	0.9356 (4)	0.77356 (10)	1.2172 (5)	0.0273 (6)
H27	0.9988	0.7666	1.3483	0.033*
C28	0.8630 (4)	0.81556 (11)	1.1897 (6)	0.0345 (7)
H28	0.8764	0.8379	1.3025	0.041*
C29	0.7676 (4)	0.82664 (10)	0.9956 (5)	0.0339 (7)
H29	0.7162	0.8560	0.9810	0.041*
C30	0.7493 (4)	0.79588 (11)	0.8314 (5)	0.0304 (7)
H30	0.6866	0.8039	0.7010	0.036*
C31	0.8066 (4)	0.71786 (10)	0.6864 (5)	0.0251 (6)
H31	0.7431	0.7249	0.5555	0.030*
C32	0.8800 (3)	0.67557 (10)	0.7110 (5)	0.0248 (6)
H32	0.8688	0.6533	0.5977	0.030*
C33	0.9165 (3)	0.74073 (10)	1.0508 (5)	0.0218 (5)
C34	0.8242 (3)	0.75096 (10)	0.8527 (4)	0.0235 (6)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0179 (3)	0.0275 (4)	0.0356 (4)	−0.0036 (3)	0.0065 (3)	−0.0112 (3)
O1	0.0259 (12)	0.0293 (12)	0.0698 (18)	0.0012 (9)	0.0137 (11)	−0.0172 (11)
O2	0.0303 (12)	0.0499 (13)	0.0275 (11)	−0.0133 (10)	0.0051 (9)	−0.0088 (10)
O3	0.0152 (9)	0.0219 (9)	0.0352 (11)	0.0010 (7)	−0.0010 (8)	−0.0048 (8)
C1	0.0234 (16)	0.0359 (16)	0.0364 (19)	−0.0058 (12)	0.0080 (13)	0.0011 (13)
C2	0.0201 (13)	0.0205 (12)	0.0291 (15)	−0.0044 (10)	0.0050 (11)	−0.0032 (11)
C3	0.0148 (12)	0.0298 (15)	0.0323 (15)	0.0010 (10)	−0.0009 (11)	0.0015 (12)
C4	0.0204 (13)	0.0262 (14)	0.0185 (13)	−0.0003 (10)	−0.0024 (10)	0.0041 (10)
C5	0.0183 (13)	0.0201 (12)	0.0340 (16)	−0.0010 (10)	0.0057 (11)	−0.0072 (11)
C6	0.0176 (12)	0.0236 (13)	0.0267 (14)	0.0026 (10)	−0.0033 (11)	−0.0047 (11)
C7	0.0278 (15)	0.0219 (13)	0.0254 (15)	−0.0023 (11)	0.0007 (11)	0.0002 (11)
C8	0.0141 (12)	0.0238 (13)	0.0326 (15)	−0.0010 (10)	−0.0034 (11)	−0.0039 (11)
C9	0.0186 (13)	0.0298 (14)	0.0268 (15)	−0.0042 (11)	0.0020 (11)	−0.0013 (11)
C10	0.0277 (15)	0.0311 (15)	0.0269 (15)	−0.0039 (12)	0.0057 (12)	0.0008 (12)
C11	0.0358 (18)	0.0282 (15)	0.0409 (19)	0.0013 (13)	0.0090 (14)	−0.0018 (13)
C12	0.0365 (18)	0.0218 (14)	0.046 (2)	0.0013 (12)	0.0098 (15)	0.0010 (14)
C13	0.0321 (17)	0.0344 (16)	0.0321 (16)	−0.0036 (13)	0.0064 (13)	0.0041 (13)
C14	0.0247 (15)	0.0390 (16)	0.0244 (15)	−0.0043 (12)	0.0052 (11)	0.0020 (13)
C15	0.0180 (13)	0.0366 (16)	0.0282 (15)	−0.0032 (11)	0.0023 (11)	−0.0033 (12)
C16	0.0196 (13)	0.0293 (14)	0.0229 (14)	−0.0041 (11)	0.0024 (10)	0.0008 (11)
C17	0.0163 (13)	0.0349 (16)	0.0266 (15)	−0.0047 (11)	0.0060 (11)	−0.0001 (12)
S2	0.0150 (3)	0.0223 (3)	0.0228 (3)	0.0003 (2)	−0.0006 (2)	0.0012 (3)
O4	0.0197 (10)	0.0248 (11)	0.0464 (14)	0.0060 (8)	−0.0022 (9)	0.0037 (9)
O5	0.0258 (10)	0.0322 (11)	0.0250 (10)	−0.0045 (9)	0.0003 (8)	0.0006 (8)
O6	0.0143 (9)	0.0217 (9)	0.0299 (10)	0.0000 (7)	0.0064 (7)	−0.0009 (8)
C18	0.0245 (15)	0.0320 (16)	0.0360 (17)	−0.0044 (12)	−0.0093 (13)	0.0061 (14)
C19	0.0221 (13)	0.0201 (13)	0.0259 (14)	−0.0035 (10)	−0.0010 (11)	0.0050 (11)
C20	0.0267 (15)	0.0210 (14)	0.0210 (14)	−0.0028 (10)	0.0041 (11)	0.0000 (10)
C21	0.0242 (13)	0.0223 (13)	0.0167 (13)	0.0005 (10)	0.0084 (10)	0.0031 (10)
C22	0.0131 (11)	0.0194 (12)	0.0201 (13)	−0.0014 (9)	−0.0031 (9)	0.0053 (10)
C23	0.0179 (13)	0.0204 (12)	0.0216 (13)	0.0013 (9)	0.0064 (10)	−0.0028 (10)
C24	0.0152 (12)	0.0251 (13)	0.0305 (15)	0.0027 (10)	0.0045 (11)	0.0023 (11)
C25	0.0136 (12)	0.0216 (12)	0.0298 (15)	−0.0026 (9)	0.0089 (10)	0.0024 (11)
C26	0.0158 (13)	0.0264 (13)	0.0221 (13)	−0.0027 (10)	0.0029 (10)	0.0020 (11)
C27	0.0283 (15)	0.0277 (15)	0.0260 (15)	−0.0030 (12)	0.0039 (12)	0.0014 (12)
C28	0.0434 (19)	0.0257 (15)	0.0350 (18)	−0.0017 (13)	0.0066 (15)	−0.0004 (13)
C29	0.0425 (19)	0.0222 (14)	0.0375 (18)	0.0048 (12)	0.0092 (15)	0.0074 (12)
C30	0.0324 (16)	0.0316 (15)	0.0274 (16)	−0.0014 (12)	0.0051 (13)	0.0056 (12)
C31	0.0233 (14)	0.0340 (15)	0.0179 (13)	−0.0038 (11)	−0.0006 (10)	0.0029 (11)
C32	0.0219 (14)	0.0298 (14)	0.0230 (14)	−0.0048 (11)	0.0050 (11)	−0.0002 (11)
C33	0.0154 (12)	0.0293 (14)	0.0211 (13)	−0.0050 (10)	0.0044 (10)	0.0015 (11)
C34	0.0194 (13)	0.0311 (14)	0.0204 (14)	−0.0038 (11)	0.0059 (10)	0.0044 (11)

Geometric parameters (Å, º)

S1—O1	1.421 (2)	S2—O4	1.422 (2)
S1—O2	1.426 (2)	S2—O5	1.424 (2)
S1—O3	1.608 (2)	S2—O6	1.6076 (19)
S1—C5	1.755 (3)	S2—C22	1.747 (3)
O3—C8	1.421 (3)	O6—C25	1.415 (3)
C1—C2	1.504 (4)	C18—C19	1.508 (4)
C1—H1A	0.9800	C18—H18A	0.9800
C1—H1B	0.9800	C18—H18B	0.9800
C1—H1C	0.9800	C18—H18C	0.9800
C2—C3	1.389 (4)	C19—C20	1.394 (4)
C2—C7	1.395 (4)	C19—C24	1.399 (4)
C3—C4	1.399 (4)	C20—C21	1.392 (4)
C3—H3	0.9500	C20—H20	0.9500
C4—C5	1.387 (4)	C21—C22	1.385 (4)
C4—H4	0.9500	C21—H21	0.9500
C5—C6	1.387 (4)	C22—C23	1.391 (4)
C6—C7	1.385 (4)	C23—C24	1.386 (4)
C6—H6	0.9500	C23—H23	0.9500
C7—H7	0.9500	C24—H24	0.9500
C8—C9	1.360 (4)	C25—C26	1.350 (4)
C8—C15	1.410 (4)	C25—C32	1.409 (4)
C9—C16	1.429 (4)	C26—C33	1.437 (4)
C9—H9	0.9500	C26—H26	0.9500
C10—C11	1.366 (4)	C27—C28	1.360 (4)
C10—C16	1.403 (4)	C27—C33	1.399 (4)
C10—H10	0.9500	C27—H27	0.9500
C11—C12	1.413 (5)	C28—C29	1.417 (5)
C11—H11	0.9500	C28—H28	0.9500
C12—C13	1.368 (4)	C29—C30	1.349 (5)
C12—H12	0.9500	C29—H29	0.9500
C13—C17	1.431 (4)	C30—C34	1.441 (4)
C13—H13	0.9500	C30—H30	0.9500
C14—C15	1.361 (4)	C31—C32	1.368 (4)
C14—C17	1.411 (4)	C31—C34	1.403 (4)
C14—H14	0.9500	C31—H31	0.9500
C15—H15	0.9500	C32—H32	0.9500
C16—C17	1.418 (4)	C33—C34	1.420 (4)
O1—S1—O2	120.88 (16)	O4—S2—O5	120.52 (14)
O1—S1—O3	102.82 (13)	O4—S2—O6	102.75 (12)
O2—S1—O3	108.90 (12)	O5—S2—O6	108.85 (11)
O1—S1—C5	109.55 (14)	O4—S2—C22	110.52 (13)
O2—S1—C5	109.36 (15)	O5—S2—C22	109.39 (12)
O3—S1—C5	103.87 (12)	O6—S2—C22	103.24 (11)
C8—O3—S1	118.41 (17)	C25—O6—S2	118.53 (15)
C2—C1—H1A	109.5	C19—C18—H18A	109.5
C2—C1—H1B	109.5	C19—C18—H18B	109.5
H1A—C1—H1B	109.5	H18A—C18—H18B	109.5
C2—C1—H1C	109.5	C19—C18—H18C	109.5
H1A—C1—H1C	109.5	H18A—C18—H18C	109.5
H1B—C1—H1C	109.5	H18B—C18—H18C	109.5
C3—C2—C7	118.4 (3)	C20—C19—C24	118.8 (3)
C3—C2—C1	120.3 (3)	C20—C19—C18	120.6 (3)
C7—C2—C1	121.3 (3)	C24—C19—C18	120.5 (3)
C2—C3—C4	121.4 (3)	C21—C20—C19	120.9 (3)
C2—C3—H3	119.3	C21—C20—H20	119.5
C4—C3—H3	119.3	C19—C20—H20	119.5
C5—C4—C3	118.2 (3)	C22—C21—C20	119.0 (2)
C5—C4—H4	120.9	C22—C21—H21	120.5
C3—C4—H4	120.9	C20—C21—H21	120.5
C6—C5—C4	121.8 (3)	C21—C22—C23	121.4 (2)
C6—C5—S1	119.5 (2)	C21—C22—S2	119.7 (2)
C4—C5—S1	118.6 (2)	C23—C22—S2	118.9 (2)
C7—C6—C5	118.7 (3)	C24—C23—C22	119.0 (2)
C7—C6—H6	120.7	C24—C23—H23	120.5
C5—C6—H6	120.7	C22—C23—H23	120.5
C6—C7—C2	121.5 (3)	C23—C24—C19	120.9 (2)
C6—C7—H7	119.3	C23—C24—H24	119.6
C2—C7—H7	119.3	C19—C24—H24	119.6
C9—C8—C15	123.5 (3)	C26—C25—C32	122.8 (3)
C9—C8—O3	118.4 (3)	C26—C25—O6	120.3 (3)
C15—C8—O3	117.9 (2)	C32—C25—O6	116.9 (2)
C8—C9—C16	118.6 (3)	C25—C26—C33	119.4 (3)
C8—C9—H9	120.7	C25—C26—H26	120.3
C16—C9—H9	120.7	C33—C26—H26	120.3
C11—C10—C16	120.2 (3)	C28—C27—C33	119.5 (3)
C11—C10—H10	119.9	C28—C27—H27	120.2
C16—C10—H10	119.9	C33—C27—H27	120.2
C10—C11—C12	120.8 (3)	C27—C28—C29	121.1 (3)
C10—C11—H11	119.6	C27—C28—H28	119.4
C12—C11—H11	119.6	C29—C28—H28	119.4
C13—C12—C11	120.2 (3)	C30—C29—C28	120.6 (3)
C13—C12—H12	119.9	C30—C29—H29	119.7
C11—C12—H12	119.9	C28—C29—H29	119.7
C12—C13—C17	120.3 (3)	C29—C30—C34	120.3 (3)
C12—C13—H13	119.8	C29—C30—H30	119.8
C17—C13—H13	119.8	C34—C30—H30	119.8
C15—C14—C17	121.1 (3)	C32—C31—C34	120.7 (3)
C15—C14—H14	119.5	C32—C31—H31	119.7
C17—C14—H14	119.5	C34—C31—H31	119.7
C14—C15—C8	118.3 (3)	C31—C32—C25	118.9 (3)
C14—C15—H15	120.9	C31—C32—H32	120.5
C8—C15—H15	120.9	C25—C32—H32	120.5
C10—C16—C17	120.1 (3)	C27—C33—C34	120.8 (3)
C10—C16—C9	121.4 (3)	C27—C33—C26	121.3 (3)
C17—C16—C9	118.5 (3)	C34—C33—C26	117.9 (3)
C14—C17—C16	120.1 (3)	C31—C34—C33	120.3 (3)
C14—C17—C13	121.6 (3)	C31—C34—C30	122.0 (3)
C16—C17—C13	118.3 (3)	C33—C34—C30	117.6 (3)
O1—S1—O3—C8	−163.2 (2)	O4—S2—O6—C25	−179.4 (2)
O2—S1—O3—C8	−33.9 (2)	O5—S2—O6—C25	−50.6 (2)
C5—S1—O3—C8	82.6 (2)	C22—S2—O6—C25	65.6 (2)
C7—C2—C3—C4	2.3 (4)	C24—C19—C20—C21	−1.3 (4)
C1—C2—C3—C4	−178.1 (3)	C18—C19—C20—C21	179.5 (3)
C2—C3—C4—C5	−1.1 (4)	C19—C20—C21—C22	0.5 (4)
C3—C4—C5—C6	−1.2 (4)	C20—C21—C22—C23	0.6 (4)
C3—C4—C5—S1	−178.8 (2)	C20—C21—C22—S2	−178.1 (2)
O1—S1—C5—C6	−42.8 (3)	O4—S2—C22—C21	−39.0 (2)
O2—S1—C5—C6	−177.4 (2)	O5—S2—C22—C21	−173.9 (2)
O3—S1—C5—C6	66.5 (2)	O6—S2—C22—C21	70.3 (2)
O1—S1—C5—C4	134.8 (2)	O4—S2—C22—C23	142.2 (2)
O2—S1—C5—C4	0.2 (3)	O5—S2—C22—C23	7.3 (2)
O3—S1—C5—C4	−115.9 (2)	O6—S2—C22—C23	−108.5 (2)
C4—C5—C6—C7	2.1 (4)	C21—C22—C23—C24	−0.9 (4)
S1—C5—C6—C7	179.7 (2)	S2—C22—C23—C24	177.8 (2)
C5—C6—C7—C2	−0.8 (4)	C22—C23—C24—C19	0.1 (4)
C3—C2—C7—C6	−1.4 (4)	C20—C19—C24—C23	1.0 (4)
C1—C2—C7—C6	179.1 (3)	C18—C19—C24—C23	−179.8 (3)
S1—O3—C8—C9	−105.7 (3)	S2—O6—C25—C26	81.7 (3)
S1—O3—C8—C15	79.5 (3)	S2—O6—C25—C32	−102.1 (2)
C15—C8—C9—C16	0.5 (4)	C32—C25—C26—C33	0.0 (4)
O3—C8—C9—C16	−174.0 (2)	O6—C25—C26—C33	176.0 (2)
C16—C10—C11—C12	−0.9 (5)	C33—C27—C28—C29	0.2 (5)
C10—C11—C12—C13	0.2 (5)	C27—C28—C29—C30	−1.2 (5)
C11—C12—C13—C17	0.4 (5)	C28—C29—C30—C34	1.0 (5)
C17—C14—C15—C8	−0.8 (4)	C34—C31—C32—C25	0.6 (4)
C9—C8—C15—C14	0.1 (4)	C26—C25—C32—C31	−0.1 (4)
O3—C8—C15—C14	174.6 (3)	O6—C25—C32—C31	−176.2 (2)
C11—C10—C16—C17	0.9 (5)	C28—C27—C33—C34	0.9 (4)
C11—C10—C16—C9	−178.0 (3)	C28—C27—C33—C26	179.6 (3)
C8—C9—C16—C10	178.7 (3)	C25—C26—C33—C27	−179.2 (3)
C8—C9—C16—C17	−0.3 (4)	C25—C26—C33—C34	−0.4 (4)
C15—C14—C17—C16	1.0 (4)	C32—C31—C34—C33	−1.0 (4)
C15—C14—C17—C13	−178.0 (3)	C32—C31—C34—C30	179.7 (3)
C10—C16—C17—C14	−179.4 (3)	C27—C33—C34—C31	179.7 (3)
C9—C16—C17—C14	−0.4 (4)	C26—C33—C34—C31	0.9 (4)
C10—C16—C17—C13	−0.3 (4)	C27—C33—C34—C30	−1.0 (4)
C9—C16—C17—C13	178.6 (3)	C26—C33—C34—C30	−179.8 (2)
C12—C13—C17—C14	178.7 (3)	C29—C30—C34—C31	179.4 (3)
C12—C13—C17—C16	−0.3 (5)	C29—C30—C34—C33	0.0 (4)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C24—H24···O6^i	0.95	2.77	3.663 (3)	157
C24—H24···O4^i	0.95	2.70	3.458 (4)	138
C18—H18A···O4^ii	0.98	2.86	3.495 (4)	124
C18—H18C···O4^iii	0.98	2.38	3.298 (4)	156
C32—H32···O5^iv	0.95	2.63	3.549 (4)	163
C21—H21···O5^iv	0.95	2.90	3.273 (3)	105
C6—H6···O2^iv	0.95	2.88	3.138 (3)	97
C6—H6···O1^v	0.95	2.82	3.555 (4)	135
C1—H1B···O1^vi	0.98	2.66	3.386 (4)	131
C1—H1A···O3^vii	0.98	2.85	3.753 (4)	153
C3—H3···O3^vii	0.95	2.69	3.554 (3)	152
C3—H3···O1^vii	0.95	2.73	3.521 (4)	142
C26—H26···O5	0.95	2.80	3.111 (3)	100
C23—H23···O5	0.95	2.51	2.900 (3)	104
C21—H21···O4	0.95	2.77	3.054 (4)	98
C15—H15···O2	0.95	2.78	3.012 (4)	95
C6—H6···O1	0.95	2.81	3.061 (4)	96
C4—H4···O2	0.95	2.51	2.895 (4)	104
C7—H7···Cg1^viii	0.95	2.84	3.578	133
C10—H10···Cg6	0.95	2.74	3.383	121
C11—H11···Cg5	0.95	3.14	3.835	121
C14—H14···Cg5^ix	0.95	2.74	3.430	128
C15—H15···Cg6^ix	0.95	3.05	3.744	123
C20—H20···Cg4^x	0.95	2.82	3.574	138
C26—H26···Cg3^vii	0.95	3.15	3.806	128
C27—H27···Cg2^vii	0.95	2.63	3.415	132
C30—H30···Cg2^iv	0.95	3.23	3.956	138
C31—H31···Cg3^iv	0.95	2.84	3.582	132

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