A thio­phene-based aza­cryptand Mannich base: 15,35-dipropyl-2,5,8,22,25,28-hexa­oxa-12,18,32,38-tetra­thia-15,35-diaza­penta­cyclo­[29.5.5.5.0.0]tetra­conta-1(37),9(13),10,17(21),19,29(33),30,39-octa­ene

Labat, G.; Halfpenny, J.

doi:10.1107/S1600536806026250

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 62| Part 8| August 2006| Pages o3310-o3312

https://doi.org/10.1107/S1600536806026250

A thiophene-based azacryptand Mannich base: 15,35-dipropyl-2,5,8,22,25,28-hexaoxa-12,18,32,38-tetrathia-15,35-diazapentacyclo[29.5.5.5.0.0]tetraconta-1(37),9(13),10,17(21),19,29(33),30,39-octaene

Gaël Labat ^a ^* and Joan Halfpenny ^b

^aUniversity of Liverpool, Department of Chemistry, Crown Street, L69 7ZD, England, and ^bDepartment of Chemistry and Physics, Nottingham Trent University, Clifton Lane, Nottingham, NG11 8NS, England
^*Correspondence e-mail: gael.labat@liv.ac.uk

(Received 7 June 2006; accepted 6 July 2006; online 12 July 2006)

The molecule of the title compound, C₃₄H₄₆N₂O₆S₄ is composed of four thiophene rings bridged by two –O(CH₂)₂O– and two –CH₂(NC₂H₅)CH₂– chains. The macrocyclic molecule possesses a center of symmetry. In the crystal structure, the molecules are bridged by C—H⋯O interactions, forming chains along the a axis.

Comment

The preparation of cryptand-like structures, incorporating four thiophene rings, was previously described by Chaffin et al. (2001 , 2002 ). The title compound is the first of a range of four thiophene-based azacryptand Mannich bases. The macrocycle incorporates six O and two N donor atoms. The coordination chemistry of aza and mixed oxa-aza macrocycles containing different pendant arms attached to the aza centers has attracted the attention of many researchers over the past twenty years (Tei et al., 2000 ; Wainwright, 1997 ; Bernhardt & Lawrance, 1990 ; Gokel, 1992 ; Hancock et al., 1996 ; Hambley et al., 2001 ; Buschmann & Schollmeyer, 2000 ; Dietrich et al., 1969 ). These ligands can exhibit remarkable metal-ion selectivity and show specific complexation behavior, forming metal complexes with unusual structures (references as above, together with Laufer, 1987 ; Parker & Williams, 1996 ). Macrocyclic crown ethers and other ionophores can bind cations (Gokel & Durst, 1976 ), anions and small neutral organic molecules (Kellogg, 1984 ).

The centrosymmetric molecule is non-planar. Selected bond distances and angles are given in Table 1. Each of the four thiophene rings is planar, and opposite rings are parallel by symmetry. The S1 and S2 rings form a dihedral angle of 82.50 (3)°. The cross-molecule distances between the thiophene rings are S1⋯S1ⁱ = 11.323 (2) Å and S2⋯S2ⁱ = 14.735 (4) Å [symmetry code: (i) −x, −y, 1 − z.] The large separation of the S1 and S2 thiophene rings [S1⋯S2 = 12.567 (3) Å], and the relative proximity of the S1 and S2ⁱ rings [S1⋯S2ⁱ = 3.8412 (12) Å], means that the O and N atoms do not lie in the same plane. The largest cross-cavity distances are N1⋯N1ⁱ = 10.223 (3) Å, and O3⋯O3ⁱ = 10.052 (4) Å. The macrocyclic cavity can be divided into three small cavities defined respectively by least-squares planes through the N1, O2, O3 and O1ⁱ donor atoms for the first, through N1ⁱ, O2ⁱ, O3ⁱ and O1 for the second, and through O1, O2, O1ⁱ and O2ⁱ for the third. The two NO₃ planes are parallel and form a dihedral angle of 47.61 (5)° with the third plane. The largest cross-cavity distances for these three smaller cavities are N1⋯O2 = N1ⁱ⋯O2ⁱ = 5.422 (2) Å, O1⋯O3ⁱ = O1ⁱ⋯O3 = 5.656 (2) Å, O1⋯O1ⁱ = 4.806 (3) Å, and O2⋯O2ⁱ = 6.425 (3) Å. The N1⋯S1ⁱ and N1⋯S2 distances are 3.0851 (18) Å and 3.4439 (17) Å, respectively. The N1⋯S2 distance is equal to the sum of the van der Waals radii (3.45 Å), whereas the N1⋯S1ⁱ distance is much shorter, and also considerably shorter than the non-bonded N⋯S interaction reported by Halfpenny & Sloman (2000 ) and Koziol et al. (1988 ). Consistent with this are the smaller S1—C1—C17 and S2—C10—C13 angles, compared with C2—C1—C17 and C9—C10—C13, and the smaller torsion angle S2—C10—C13—N1, compared with C9—C10—C13—N1. Some distortion in the thiophene ring bond lengths and angles is observed in many substituted thiophene compounds, the most obvious effect being the asymmetric nature of the S—C bonds (Koziol et al., 1988). In the present compound the rings associated with the S⋯N interactions have nearly symmetrical bond lengths, but the bond angles are clearly asymmetric. This is possibly due to the movement of some electron density towards N1. In many examples (Koziol et al., 1988), the nitrogen is sp² hybridized rather than sp³ as in the present compound, and therefore the C—N distance is shorter, facilitating the S⋯N interaction. As in the macrocycle described by Halfpenny & Sloman (2000), the steric restrictions imposed by the C and N atoms being part of the large macrocyclic ring makes such short S⋯N contacts quite remarkable. They confirm that the electron pairs of the N atoms are directed outside the cavity, which is not favorable for complexation with a metal ion. However, this macrocycle, compared with one having two thiophene groups (Halfpenny & Sloman, 2000), shows greater flexibility in solution, allowing the cavity to accommodate small as well as large metal cations.

The molecules are linked by hydrogen bonds (Table 2). Fig. 2 shows the packing arrangement, giving a chain along the a axis.

Figure 1
The molecular structure of (I)

, showing the atom-labeling scheme. Displacement ellipsoids are drawn at the 50% probability level. [Symmetry code: (a) −x, −y, 1 − z.]

Figure 2
The molecular packing of compound (I)

, with hydrogen bonds shown as dashed lines. H atoms not involved in hydrogen bonding have been omitted.

Experimental

Compound (I) was synthesized using method A described by Chaffin et al. (2001). It was dissolved with stirring in a minimum of a 1:1:1 mixture of methanol/diethyl ether/dichloromethane. Slow evaporation at 277 K gave yellow blocks suitable for X-ray crystallographic analysis.

Crystal data

C₃₄H₄₆N₂O₆S₄
M_r = 706.97
Triclinic, $[P \overline 1]$
a = 6.8178 (9) Å
b = 9.4311 (18) Å
c = 13.833 (2) Å
α = 105.69 (2)°
β = 92.453 (18)°
γ = 98.79 (2)°
V = 842.9 (2) Å³
Z = 1
D_x = 1.393 Mg m⁻³
Mo Kα radiation
μ = 0.33 mm⁻¹
T = 153 (2) K
Block, yellow
0.30 × 0.30 × 0.30 mm

Data collection

STOE IPDS diffractometer
φ scans
Absorption correction: none
6702 measured reflections
3075 independent reflections
2468 reflections with I > 2σ(I)
R_int = 0.026
θ_max = 25.9°

Refinement

Refinement on F²
R[F² > 2σ(F²)] = 0.028
wR(F²) = 0.071
S = 0.97
3075 reflections
209 parameters
H-atom parameters constrained
w = 1/[σ²(F_o²) + (0.0468P)²] where P = (F_o² + 2F_c²)/3
(Δ/σ)_max < 0.001
Δρ_max = 0.34 e Å⁻³
Δρ_min = −0.18 e Å⁻³

Table 1
Selected geometric parameters (Å, °)

C1—C2	1.374 (2)
C1—C17ⁱ	1.494 (2)
C1—S1	1.7245 (14)
C2—O1	1.3744 (18)
C2—C3	1.416 (2)
C3—C4	1.357 (2)
C4—S1	1.7147 (18)
C5—O1	1.4349 (18)
C5—C6	1.499 (2)
C6—O2	1.426 (2)
C7—O2	1.4231 (19)
C7—C8	1.506 (2)
C8—O3	1.4329 (17)
C9—C10	1.367 (2)
C9—O3	1.3727 (18)
C9—C12	1.424 (2)
C10—C13	1.494 (2)
C10—S2	1.7251 (15)
C11—C12	1.358 (2)
C11—S2	1.7065 (16)
C13—N1	1.4758 (18)
C14—N1	1.4710 (19)
C14—C15	1.521 (2)
C15—C16	1.518 (2)
C17—N1	1.4739 (18)
C17—C1ⁱ	1.494 (2)

C2—C1—C17ⁱ	128.46 (13)
C2—C1—S1	109.63 (12)
C17ⁱ—C1—S1	121.44 (10)
C1—C2—O1	119.10 (15)
C1—C2—C3	114.16 (13)
O1—C2—C3	126.72 (14)
C4—C3—C2	111.80 (14)
C3—C4—S1	112.00 (13)
O1—C5—C6	107.24 (14)
O2—C6—C5	111.60 (12)
O2—C7—C8	111.30 (13)
O3—C8—C7	107.47 (12)
C10—C9—O3	119.54 (13)
C10—C9—C12	114.17 (13)
O3—C9—C12	126.29 (13)
C9—C10—C13	127.96 (13)
C9—C10—S2	109.68 (11)
C13—C10—S2	122.34 (10)
C12—C11—S2	112.27 (12)
C11—C12—C9	111.38 (13)
N1—C13—C10	113.45 (13)
N1—C14—C15	114.07 (14)
C16—C15—C14	113.43 (13)
N1—C17—C1ⁱ	113.40 (12)
C14—N1—C17	111.82 (11)
C14—N1—C13	107.99 (12)
C17—N1—C13	110.93 (10)
C2—O1—C5	116.08 (13)
C7—O2—C6	115.95 (13)
C9—O3—C8	116.48 (12)
C4—S1—C1	92.39 (8)
C11—S2—C10	92.48 (7)

C9—C10—C13—N1	−108.44 (17)
S2—C10—C13—N1	73.47 (15)
C1—C2—O1—C5	168.99 (13)
C3—C2—O1—C5	−12.3 (2)
C10—C9—O3—C8	171.75 (13)
C12—C9—O3—C8	−8.3 (2)
Symmetry code: (i) -x, -y, -z+1.

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C3—H3A⋯O2ⁱⁱ	0.95	2.50	3.142 (2)	125
C13—H13A⋯O3	0.99	2.58	2.9636 (18)	103
Symmetry code: (ii) x+1, y, z.

H atoms were positioned geometrically and treated as riding atoms, with C—H = 0.95–0.99 Å and U_iso(H) = 1.2U_eq(C) [1.5U_eq(C) for methyl groups].

Data collection: EXPOSE (Stoe & Cie, 2000 ); cell refinement: CELL (Stoe & Cie, 2000); data reduction: INTEGRATE (Stoe & Cie, 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997 ); molecular graphics: PLATON (Spek, 2003 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536806026250/cf2037sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536806026250/cf2037Isup2.hkl

Computing details top

Data collection: EXPOSE (Stoe & Cie, 2000); cell refinement: CELL (Stoe & Cie, 2000); data reduction: INTEGRATE (Stoe & Cie, 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97.

(I) top

Crystal data top

C₃₄H₄₆N₂O₆S₄	Z = 1
M_r = 706.97	F(000) = 376
Triclinic, P1	D_x = 1.393 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.8178 (9) Å	Cell parameters from 8000 reflections
b = 9.4311 (18) Å	θ = 1.7–26.1°
c = 13.833 (2) Å	µ = 0.33 mm⁻¹
α = 105.69 (2)°	T = 153 K
β = 92.453 (18)°	Block, yellow
γ = 98.79 (2)°	0.30 × 0.30 × 0.30 mm
V = 842.9 (2) Å³

Data collection top

STOE IPDS diffractometer	2468 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.026
Graphite monochromator	θ_max = 25.9°, θ_min = 2.3°
φ scans	h = −8→8
6702 measured reflections	k = −11→11
3075 independent reflections	l = −17→16

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.028	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.071	H-atom parameters constrained
S = 0.97	w = 1/[σ²(F_o²) + (0.0468P)²] where P = (F_o² + 2F_c²)/3
3075 reflections	(Δ/σ)_max < 0.001
209 parameters	Δρ_max = 0.34 e Å⁻³
0 restraints	Δρ_min = −0.18 e Å⁻³

Special details top

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 (Å²) top

	x	y	z	U_iso*/U_eq
C1	0.4451 (2)	−0.01853 (16)	0.69307 (11)	0.0144 (3)
C2	0.4154 (2)	−0.11678 (16)	0.59807 (11)	0.0157 (3)
C3	0.5838 (2)	−0.18181 (17)	0.56586 (12)	0.0200 (3)
H3A	0.5870	−0.2509	0.5019	0.024*
C4	0.7401 (2)	−0.13354 (18)	0.63748 (12)	0.0226 (4)
H4A	0.8658	−0.1649	0.6296	0.027*
C5	0.2208 (2)	−0.22591 (17)	0.44070 (11)	0.0196 (3)
H5B	0.2688	−0.3219	0.4332	0.024*
H5A	0.3047	−0.1671	0.4036	0.024*
C6	0.0068 (2)	−0.25369 (18)	0.40002 (11)	0.0222 (4)
H6A	−0.0447	−0.1581	0.4171	0.027*
H6B	−0.0026	−0.2925	0.3256	0.027*
C7	−0.1501 (2)	−0.50898 (17)	0.37889 (12)	0.0203 (3)
H7B	−0.1424	−0.5767	0.4220	0.024*
H7A	−0.0465	−0.5245	0.3309	0.024*
C8	−0.3525 (2)	−0.54710 (16)	0.32111 (11)	0.0182 (3)
H8A	−0.3875	−0.6564	0.2900	0.022*
H8B	−0.4550	−0.5150	0.3669	0.022*
C9	−0.5217 (2)	−0.46729 (15)	0.19600 (11)	0.0154 (3)
C10	−0.5267 (2)	−0.38039 (15)	0.13156 (11)	0.0143 (3)
C11	−0.8579 (2)	−0.51720 (17)	0.14872 (12)	0.0202 (3)
H11A	−0.9946	−0.5595	0.1455	0.024*
C12	−0.7110 (2)	−0.54805 (17)	0.20517 (11)	0.0193 (3)
H12A	−0.7318	−0.6150	0.2456	0.023*
C13	−0.3552 (2)	−0.28857 (15)	0.10070 (11)	0.0148 (3)
H13A	−0.2298	−0.3171	0.1218	0.018*
H13B	−0.3660	−0.3117	0.0263	0.018*
C14	−0.1845 (2)	−0.04886 (16)	0.09950 (11)	0.0183 (3)
H14B	−0.2062	−0.0881	0.0252	0.022*
H14A	−0.0558	−0.0725	0.1208	0.022*
C15	−0.1706 (2)	0.12006 (17)	0.12842 (12)	0.0219 (4)
H15B	−0.1613	0.1585	0.2028	0.026*
H15A	−0.0468	0.1645	0.1051	0.026*
C16	−0.3466 (3)	0.17036 (17)	0.08441 (12)	0.0241 (4)
H16A	−0.4689	0.1324	0.1107	0.036*
H16B	−0.3584	0.1314	0.0108	0.036*
H16C	−0.3262	0.2798	0.1034	0.036*
C17	−0.3116 (2)	−0.08422 (16)	0.25501 (11)	0.0155 (3)
H17A	−0.1713	−0.0352	0.2755	0.019*
H17B	−0.3330	−0.1761	0.2775	0.019*
N1	−0.34467 (18)	−0.12615 (13)	0.14419 (9)	0.0131 (3)
O1	0.23168 (16)	−0.14461 (12)	0.54526 (8)	0.0204 (3)
O2	−0.11268 (17)	−0.35816 (13)	0.44016 (8)	0.0251 (3)
O3	−0.34329 (16)	−0.47027 (11)	0.24466 (8)	0.0189 (2)
S1	0.68377 (6)	−0.00920 (4)	0.74384 (3)	0.02039 (11)
S2	−0.76908 (6)	−0.39373 (4)	0.08420 (3)	0.01816 (11)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0129 (7)	0.0144 (7)	0.0158 (7)	−0.0007 (6)	0.0000 (6)	0.0056 (6)
C2	0.0132 (7)	0.0168 (7)	0.0164 (7)	0.0002 (6)	0.0009 (6)	0.0049 (6)
C3	0.0179 (8)	0.0200 (8)	0.0189 (7)	0.0021 (6)	0.0047 (7)	0.0002 (6)
C4	0.0157 (8)	0.0248 (8)	0.0280 (8)	0.0057 (7)	0.0056 (7)	0.0070 (7)
C5	0.0214 (9)	0.0214 (8)	0.0129 (7)	0.0000 (6)	0.0014 (6)	0.0014 (6)
C6	0.0252 (9)	0.0230 (8)	0.0158 (7)	0.0026 (7)	−0.0042 (7)	0.0030 (6)
C7	0.0208 (8)	0.0227 (8)	0.0182 (7)	0.0047 (6)	−0.0007 (7)	0.0067 (6)
C8	0.0206 (8)	0.0169 (7)	0.0179 (7)	0.0003 (6)	0.0000 (6)	0.0080 (6)
C9	0.0157 (8)	0.0134 (7)	0.0152 (7)	0.0018 (6)	−0.0015 (6)	0.0017 (6)
C10	0.0141 (8)	0.0111 (7)	0.0156 (7)	0.0011 (6)	−0.0007 (6)	0.0008 (5)
C11	0.0165 (8)	0.0186 (8)	0.0226 (8)	−0.0029 (6)	0.0011 (7)	0.0045 (6)
C12	0.0198 (8)	0.0174 (7)	0.0201 (7)	−0.0019 (6)	−0.0002 (7)	0.0070 (6)
C13	0.0164 (8)	0.0123 (7)	0.0148 (7)	0.0024 (6)	0.0009 (6)	0.0026 (6)
C14	0.0159 (8)	0.0174 (7)	0.0206 (7)	−0.0007 (6)	0.0026 (7)	0.0053 (6)
C15	0.0214 (9)	0.0175 (8)	0.0249 (8)	−0.0034 (6)	0.0023 (7)	0.0065 (6)
C16	0.0316 (10)	0.0171 (7)	0.0230 (8)	0.0002 (7)	0.0010 (7)	0.0068 (6)
C17	0.0159 (8)	0.0153 (7)	0.0142 (7)	0.0028 (6)	−0.0025 (6)	0.0030 (6)
N1	0.0146 (6)	0.0112 (6)	0.0131 (6)	0.0008 (5)	0.0014 (5)	0.0033 (5)
O1	0.0151 (6)	0.0248 (6)	0.0155 (5)	0.0034 (5)	−0.0022 (5)	−0.0034 (4)
O2	0.0201 (6)	0.0299 (6)	0.0181 (5)	−0.0030 (5)	0.0023 (5)	−0.0016 (5)
O3	0.0154 (5)	0.0209 (5)	0.0219 (5)	−0.0011 (4)	−0.0033 (5)	0.0117 (4)
S1	0.0147 (2)	0.0250 (2)	0.0195 (2)	0.00264 (15)	−0.00250 (16)	0.00388 (15)
S2	0.0155 (2)	0.01807 (19)	0.02069 (19)	0.00139 (14)	−0.00219 (16)	0.00645 (15)

Geometric parameters (Å, º) top

C1—C2	1.374 (2)	C9—C12	1.424 (2)
C1—C17ⁱ	1.494 (2)	C10—C13	1.494 (2)
C1—S1	1.7245 (14)	C10—S2	1.7251 (15)
C2—O1	1.3744 (18)	C11—C12	1.358 (2)
C2—C3	1.416 (2)	C11—S2	1.7065 (16)
C3—C4	1.357 (2)	C11—H11A	0.950
C3—H3A	0.950	C12—H12A	0.950
C4—S1	1.7147 (18)	C13—N1	1.4758 (18)
C4—H4A	0.950	C13—H13A	0.990
C5—O1	1.4349 (18)	C13—H13B	0.990
C5—C6	1.499 (2)	C14—N1	1.4710 (19)
C5—H5B	0.990	C14—C15	1.521 (2)
C5—H5A	0.990	C14—H14B	0.990
C6—O2	1.426 (2)	C14—H14A	0.990
C6—H6A	0.990	C15—C16	1.518 (2)
C6—H6B	0.990	C15—H15B	0.990
C7—O2	1.4231 (19)	C15—H15A	0.990
C7—C8	1.506 (2)	C16—H16A	0.980
C7—H7B	0.990	C16—H16B	0.980
C7—H7A	0.990	C16—H16C	0.980
C8—O3	1.4329 (17)	C17—N1	1.4739 (18)
C8—H8A	0.990	C17—C1ⁱ	1.494 (2)
C8—H8B	0.990	C17—H17A	0.990
C9—C10	1.367 (2)	C17—H17B	0.990
C9—O3	1.3727 (18)

C2—C1—C17ⁱ	128.46 (13)	C12—C11—H11A	123.9
C2—C1—S1	109.63 (12)	S2—C11—H11A	123.9
C17ⁱ—C1—S1	121.44 (10)	C11—C12—C9	111.38 (13)
C1—C2—O1	119.10 (15)	C11—C12—H12A	124.3
C1—C2—C3	114.16 (13)	C9—C12—H12A	124.3
O1—C2—C3	126.72 (14)	N1—C13—C10	113.45 (13)
C4—C3—C2	111.80 (14)	N1—C13—H13A	108.9
C4—C3—H3A	124.1	C10—C13—H13A	108.9
C2—C3—H3A	124.1	N1—C13—H13B	108.9
C3—C4—S1	112.00 (13)	C10—C13—H13B	108.9
C3—C4—H4A	124.0	H13A—C13—H13B	107.7
S1—C4—H4A	124.0	N1—C14—C15	114.07 (14)
O1—C5—C6	107.24 (14)	N1—C14—H14B	108.7
O1—C5—H5B	110.3	C15—C14—H14B	108.7
C6—C5—H5B	110.3	N1—C14—H14A	108.7
O1—C5—H5A	110.3	C15—C14—H14A	108.7
C6—C5—H5A	110.3	H14B—C14—H14A	107.6
H5B—C5—H5A	108.5	C16—C15—C14	113.43 (13)
O2—C6—C5	111.60 (12)	C16—C15—H15B	108.9
O2—C6—H6A	109.3	C14—C15—H15B	108.9
C5—C6—H6A	109.3	C16—C15—H15A	108.9
O2—C6—H6B	109.3	C14—C15—H15A	108.9
C5—C6—H6B	109.3	H15B—C15—H15A	107.7
H6A—C6—H6B	108.0	C15—C16—H16A	109.5
O2—C7—C8	111.30 (13)	C15—C16—H16B	109.5
O2—C7—H7B	109.4	H16A—C16—H16B	109.5
C8—C7—H7B	109.4	C15—C16—H16C	109.5
O2—C7—H7A	109.4	H16A—C16—H16C	109.5
C8—C7—H7A	109.4	H16B—C16—H16C	109.5
H7B—C7—H7A	108.0	N1—C17—C1ⁱ	113.40 (12)
O3—C8—C7	107.47 (12)	N1—C17—H17A	108.9
O3—C8—H8A	110.2	C1ⁱ—C17—H17A	108.9
C7—C8—H8A	110.2	N1—C17—H17B	108.9
O3—C8—H8B	110.2	C1ⁱ—C17—H17B	108.9
C7—C8—H8B	110.2	H17A—C17—H17B	107.7
H8A—C8—H8B	108.5	C14—N1—C17	111.82 (11)
C10—C9—O3	119.54 (13)	C14—N1—C13	107.99 (12)
C10—C9—C12	114.17 (13)	C17—N1—C13	110.93 (10)
O3—C9—C12	126.29 (13)	C2—O1—C5	116.08 (13)
C9—C10—C13	127.96 (13)	C7—O2—C6	115.95 (13)
C9—C10—S2	109.68 (11)	C9—O3—C8	116.48 (12)
C13—C10—S2	122.34 (10)	C4—S1—C1	92.39 (8)
C12—C11—S2	112.27 (12)	C11—S2—C10	92.48 (7)

C17ⁱ—C1—C2—O1	−10.0 (2)	C15—C14—N1—C13	173.59 (11)
S1—C1—C2—O1	177.86 (10)	C1ⁱ—C17—N1—C14	105.63 (14)
C17ⁱ—C1—C2—C3	171.12 (14)	C1ⁱ—C17—N1—C13	−133.75 (13)
S1—C1—C2—C3	−1.02 (16)	C10—C13—N1—C14	−173.83 (11)
C1—C2—C3—C4	0.73 (19)	C10—C13—N1—C17	63.30 (15)
O1—C2—C3—C4	−178.04 (14)	C1—C2—O1—C5	168.99 (13)
C2—C3—C4—S1	−0.09 (17)	C3—C2—O1—C5	−12.3 (2)
O1—C5—C6—O2	−69.51 (16)	C6—C5—O1—C2	175.84 (12)
O2—C7—C8—O3	71.31 (16)	C8—C7—O2—C6	−99.17 (16)
O3—C9—C10—C13	3.4 (2)	C5—C6—O2—C7	−96.95 (15)
C12—C9—C10—C13	−176.49 (15)	C10—C9—O3—C8	171.75 (13)
O3—C9—C10—S2	−178.27 (11)	C12—C9—O3—C8	−8.3 (2)
C12—C9—C10—S2	1.80 (17)	C7—C8—O3—C9	−168.07 (13)
S2—C11—C12—C9	0.63 (18)	C3—C4—S1—C1	−0.42 (13)
C10—C9—C12—C11	−1.6 (2)	C2—C1—S1—C4	0.81 (12)
O3—C9—C12—C11	178.48 (14)	C17ⁱ—C1—S1—C4	−171.98 (12)
C9—C10—C13—N1	−108.44 (17)	C12—C11—S2—C10	0.32 (13)
S2—C10—C13—N1	73.47 (15)	C9—C10—S2—C11	−1.20 (12)
N1—C14—C15—C16	−68.03 (17)	C13—C10—S2—C11	177.20 (13)
C15—C14—N1—C17	−64.09 (16)

Symmetry code: (i) −x, −y, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3A···O2ⁱⁱ	0.95	2.50	3.142 (2)	125
C13—H13A···O3	0.99	2.58	2.9636 (18)	103

Symmetry code: (ii) x+1, y, z.

Acknowledgements

We thank Professor Helen Stoeckli-Evans (Neuchâtel) for making available the Stoe IPDS diffractometer for data collection.

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