An unusual acid: (±)-3-benzoyl-1,2-dimethyl-8a-phenyl-2-benzo­thieno­[2,3-b]pyrrole-1,2-dicarboxylic anhydride

The title compound, C₂₇H₂₁NO₄S, is a 2-benzothieno[2,3-b]pyrrole derivative with several substituents, present in the crystal as a racemate. The tetra­cyclic fused-ring system shows a `U-shaped' mol­ecular architecture, since the two rings flanking the central pyrrolidine ring both point in the same direction.

S1. Comment

Several syntheses of shape-specific molecules through heteroaromatic annulations in a cis–syn–cis mode have been achieved (Mehta et al., 1992). Often, U-shaped structures are obtained and are driven by stereospecific syntheses (Albrecht et al., 1992), and they are considered to be a new class of potential molecular hosts (Marchand et al., 1990; Mehta et al., 1989, 1998). Benzo[4,5]thieno[2,3-b]pyrrole derivatives have been produced in a domino cascade reaction starting from mesoionic 1,3-oxazolin-5-olates and thiocoumarins having an electron-withdrawing group at the 3-position (Grassi et al., 2005).

The crystal structure of the title compound contains molecules of (±)-3-benzoyl-1,2-dimethyl-8a-phenyl-2-benzothieno[2,3-b]pyrrole-1,2-dicarboxylic anhydride, (I), as a racemate. The main body of (I) consists of four consecutive ringsfused to each other by edge-sharing. The core pyrrolidine ring is flanked by a succinic anhydride on one side and a benzothiophene group on the other. These condensed rings confer on the structure a 'U-shaped' configuration (endo-form), with angles between the mean benzothiophene and pyrrolidine planes of 68.5 (1)°, and between pyrrolidine and succinic anhydride of 68.9 (1)° (Fig. 1). The succinic anhydride ring is close to planar [maximum deviation from the mean plane for C23 is 0.037 (3) Å], but the other five-membered rings show significant deviations from planarity.

Puckering analysis (Cremer & Pople, 1975) of the thiophene ring S1/C2/C3/C4/C9 shows an E (envelope) conformation, with Q = 0.316 (2) and ϕ = 4.3 (4)%. The same analysis of the pyrrolidine ring C18/C3/C2/N16/C17 shows a ³T₂ (twist) conformation [Q = 0.281 (2) and ϕ = −95.1 (5)], where the pseudo twofold symmetry axis passes through C18. The four atoms on the contact edges of this ring are chiral [C2(R), C3(R), C17(S), C18(R)] and, since the space group is centrosymmetric, the molecule exists in the solid state as a racemic pair.

The phenyl and methyl substituents on C2 and C17 favour a flattening of the pyramid-like geometry around atom N16, resulting in the sum of the bond angles around N16 being 345.8 (6)°, compared with 335.31° measured for an analogous unsubstituted pyrrolidine moiety (Pedrosa et al., 2002). Atom C8 bears a benzoyl group which, because of steric hindrance, cannot maintain a stable planar conformation. The dihedral angle around O1—C24—C25—C26, and the short C24—O1 and long C24—C25 bond distances (Table 1), compared with the corresponding geometric parameters of a similar structural moiety [O—C—C—C = 0.32°, C═O = 1.223 Å and C—C = 1.501 Å; Nagendrappa & Begum, 1999], indicate a hampered conjugation among the pure p orbitals belonging to each atom of this fragment. The peripheral rings flanking the pyrrolidine occur on the same side and almost parallel to each other, thus causing a noteworthy steric hindrance; this is reflected in the C18—C3 bond distance, which is longer than expected (Table 2), as already shown in another `boat-like' structure in which the equivalent bond length is 1.573 Å (Huang et al., 2001).

The crystal packing of (I) features two weak cyclic hydrogen-bonding interactions both lying across crystallographic inversion centres (Table 2). The first interaction, C30—H30···O3ⁱ [C···O = 3.272 (3) Å; symmetry code: (i) −x, 2 − y, −z], involves one of the two anhydride O atoms as acceptor and an aromatic C—H as donor, leading to a R₂²(16) graph-set pattern (Bernstein et al., 1995). The second interaction, C26—H26···O1ⁱⁱ [C···O = 3.484 (3) Å; symmetry code: (ii) 1 − x, 2 − y, 1 − z], involves, uniquely, the benzoyl group of two enantiomeric units joined in an R₂²(10) graph-set pattern. These intermolecular connections combine to give a `chain of rings' ribbon polymer N₂ = C₂² [R₂²(16)R₂²(10)] (Bernstein et al., 1995) extending along the [101] crystallographic direction (Fig. 2). Other weak dipolar and hydrophobic interactions support the overall lattice.

S2. Experimental

Thiocoumarin (1.0 eq) and N-benzoyl-N-methyl-alanine (1.2 eq) were reacted in dioxane (200 ml) after addition of acetic anhydride (5.0 eq), yielding (I), as described by Grassi et al. (2005). After purification, colourless crystals of (I) (m. p. 416–417 K) were obtained by slow evaporation from dioxane.

S3. Refinement

All H atoms were positioned geometrically and refined using a riding model, with C—H distances in the range 0.93–0.98 Å [Please check amended upper limit] and U_iso(H) values of 1.2U_eq(C) or 1.5U_eq(C_methyl).

Computing details

Data collection: X8 APEX software (Bruker, 2000); cell refinement: X8 APEX software (Bruker, 2000); data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XPW (Bruker, 2000); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures

	Fig. 1. A view of (I), with the atom-numbering scheme and 30% probability displacement ellipsoids. H atoms are shown as small spheres of arbitrary radii.
	Fig. 2. A view of the crystal packing of (I), showing a one-dimensional chain developing along the [101] direction. Atoms marked with an asterisk (*) or a hash (#) are at the symmetry positions (−x, 2 − y, −z) and (1 − x, 2 − y, 1 − z), respectively.

(±)-3-benzoyl-1,2-dimethyl-8a-phenyl-2-benzothieno[2,3-b]pyrrole- 1,2-dicarboxylic anhydride

Crystal data

C27H21NO4S	Z = 2
Mr = 455.51	F(000) = 476
Triclinic, P1	Dx = 1.300 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.6245 (7) Å	Cell parameters from 4015 reflections
b = 11.6423 (10) Å	θ = 2.6–25°
c = 13.1778 (11) Å	µ = 0.17 mm^−1
α = 97.658 (3)°	T = 298 K
β = 104.134 (3)°	Irregular, colourless
γ = 110.821 (3)°	0.58 × 0.4 × 0.32 mm
V = 1163.44 (17) Å^3

Data collection

X8 CCD area detector diffractometer	3329 reflections with I > 2σ(I)
ϕ and ω scans	Rint = 0.040
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	θmax = 25°, θmin = 2.6°
Tmin = 0.789, Tmax = 0.95	h = −10→10
17961 measured reflections	k = −13→13
4015 independent reflections	l = −15→15

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.051	w = 1/[σ^2(Fo^2) + (0.0886P)^2 + 0.5138P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.162	(Δ/σ)max < 0.001
S = 1.10	Δρmax = 0.50 e Å^−3
4015 reflections	Δρmin = −0.33 e Å^−3
300 parameters

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
O1	0.3141 (2)	1.01106 (18)	0.40812 (14)	0.0580 (5)
O2	0.3207 (2)	0.81060 (18)	0.12190 (14)	0.0538 (5)
O3	−0.1635 (2)	0.8682 (2)	−0.00333 (15)	0.0626 (5)
S1	−0.18367 (8)	0.59086 (6)	0.12573 (5)	0.0511 (2)
C2	−0.1025 (3)	0.7239 (2)	0.25133 (18)	0.0408 (5)
C3	0.0980 (3)	0.7678 (2)	0.28576 (18)	0.0373 (5)
H3	0.1463	0.7995	0.3643	0.045*
C4	0.1399 (3)	0.6572 (2)	0.25229 (18)	0.0409 (5)
C5	0.2961 (3)	0.6451 (3)	0.2947 (2)	0.0499 (6)
H5	0.3848	0.7072	0.3526	0.06*
C6	0.3183 (4)	0.5401 (3)	0.2502 (3)	0.0601 (7)
H6	0.4226	0.5317	0.2782	0.072*
C7	0.1868 (4)	0.4474 (3)	0.1643 (2)	0.0636 (8)
H7	0.2043	0.3778	0.1343	0.076*
C8	0.0293 (4)	0.4569 (3)	0.1223 (2)	0.0556 (7)
H8	−0.0598	0.3937	0.0653	0.067*
C9	0.0072 (3)	0.5622 (2)	0.16688 (19)	0.0442 (5)
C10	−0.1743 (3)	0.6773 (2)	0.34018 (19)	0.0441 (5)
C11	−0.1997 (4)	0.5576 (3)	0.3555 (2)	0.0603 (7)
H11	−0.182	0.5012	0.3073	0.072*
C12	−0.2514 (4)	0.5206 (3)	0.4422 (3)	0.0715 (9)
H12	−0.265	0.4406	0.4527	0.086*
C13	−0.2823 (4)	0.6011 (3)	0.5119 (2)	0.0680 (8)
H13	−0.318	0.5755	0.5693	0.082*
C14	−0.2608 (4)	0.7190 (3)	0.4975 (2)	0.0613 (7)
H14	−0.2848	0.7729	0.5441	0.074*
C15	−0.2031 (3)	0.7591 (3)	0.4133 (2)	0.0517 (6)
H15	−0.1838	0.8409	0.406	0.062*
N16	−0.1325 (2)	0.8329 (2)	0.22964 (16)	0.0447 (5)
C17	0.0002 (3)	0.9113 (2)	0.18809 (18)	0.0406 (5)
C18	0.1634 (3)	0.8811 (2)	0.23085 (17)	0.0373 (5)
C19	−0.3141 (3)	0.8140 (3)	0.1793 (3)	0.0620 (8)
H19A	−0.3574	0.7607	0.1077	0.093*
H19B	−0.3193	0.8944	0.1759	0.093*
H19C	−0.3844	0.7744	0.2214	0.093*
C20	0.0251 (3)	1.0489 (3)	0.2171 (2)	0.0546 (6)
H20A	−0.079	1.0572	0.1791	0.082*
H20B	0.1218	1.1008	0.1971	0.082*
H20C	0.0483	1.0757	0.2933	0.082*
C21	0.2046 (3)	0.8390 (2)	0.13019 (18)	0.0412 (5)
O22	0.0807 (2)	0.83481 (17)	0.03821 (12)	0.0481 (4)
C23	−0.0440 (3)	0.8698 (2)	0.06548 (19)	0.0457 (6)
C24	0.3196 (3)	0.9927 (2)	0.31661 (19)	0.0428 (5)
C25	0.4745 (3)	1.0749 (2)	0.2905 (2)	0.0461 (6)
C26	0.6335 (3)	1.1253 (3)	0.3730 (2)	0.0597 (7)
H26	0.6392	1.1055	0.4395	0.072*
C27	0.7833 (4)	1.2050 (3)	0.3563 (3)	0.0742 (9)
H27	0.8898	1.2379	0.4112	0.089*
C28	0.7744 (4)	1.2352 (3)	0.2588 (3)	0.0749 (9)
H28	0.8752	1.2885	0.2477	0.09*
C29	0.6182 (4)	1.1878 (3)	0.1770 (3)	0.0735 (9)
H29	0.6134	1.2102	0.1115	0.088*
C30	0.4676 (4)	1.1065 (3)	0.1920 (2)	0.0589 (7)
H30	0.3621	1.0732	0.1362	0.071*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0573 (11)	0.0605 (11)	0.0448 (10)	0.0123 (9)	0.0134 (8)	0.0139 (8)
O2	0.0478 (10)	0.0709 (12)	0.0598 (11)	0.0329 (9)	0.0254 (8)	0.0295 (9)
O3	0.0476 (10)	0.0881 (14)	0.0542 (11)	0.0294 (10)	0.0068 (8)	0.0361 (10)
S1	0.0407 (4)	0.0575 (4)	0.0474 (4)	0.0153 (3)	0.0070 (3)	0.0137 (3)
C2	0.0292 (11)	0.0508 (13)	0.0462 (12)	0.0156 (10)	0.0144 (9)	0.0208 (10)
C3	0.0302 (11)	0.0435 (12)	0.0401 (11)	0.0137 (10)	0.0111 (9)	0.0196 (9)
C4	0.0392 (12)	0.0450 (13)	0.0455 (12)	0.0169 (11)	0.0181 (10)	0.0250 (10)
C5	0.0425 (13)	0.0550 (15)	0.0623 (15)	0.0227 (12)	0.0195 (11)	0.0323 (12)
C6	0.0603 (17)	0.0699 (19)	0.080 (2)	0.0419 (16)	0.0365 (15)	0.0437 (16)
C7	0.088 (2)	0.0638 (18)	0.0697 (18)	0.0471 (18)	0.0433 (17)	0.0333 (15)
C8	0.0707 (18)	0.0521 (15)	0.0507 (14)	0.0242 (14)	0.0277 (13)	0.0197 (12)
C9	0.0455 (13)	0.0473 (13)	0.0437 (12)	0.0157 (11)	0.0197 (10)	0.0219 (10)
C10	0.0323 (12)	0.0537 (14)	0.0496 (13)	0.0158 (11)	0.0155 (10)	0.0230 (11)
C11	0.0642 (17)	0.0620 (17)	0.0738 (18)	0.0297 (15)	0.0392 (15)	0.0333 (14)
C12	0.076 (2)	0.072 (2)	0.088 (2)	0.0306 (17)	0.0462 (18)	0.0493 (17)
C13	0.0550 (17)	0.092 (2)	0.0594 (17)	0.0205 (16)	0.0275 (14)	0.0363 (16)
C14	0.0496 (15)	0.080 (2)	0.0474 (14)	0.0175 (14)	0.0183 (12)	0.0126 (13)
C15	0.0425 (14)	0.0572 (15)	0.0531 (14)	0.0157 (12)	0.0160 (11)	0.0172 (12)
N16	0.0322 (10)	0.0567 (12)	0.0570 (12)	0.0234 (9)	0.0178 (9)	0.0288 (10)
C17	0.0341 (12)	0.0486 (13)	0.0441 (12)	0.0198 (10)	0.0114 (9)	0.0198 (10)
C18	0.0312 (11)	0.0428 (12)	0.0406 (11)	0.0155 (10)	0.0103 (9)	0.0190 (9)
C19	0.0362 (13)	0.084 (2)	0.0808 (19)	0.0311 (14)	0.0205 (13)	0.0431 (16)
C20	0.0507 (15)	0.0538 (15)	0.0670 (16)	0.0286 (13)	0.0165 (12)	0.0225 (12)
C21	0.0371 (12)	0.0447 (13)	0.0441 (12)	0.0151 (11)	0.0137 (10)	0.0209 (10)
O22	0.0441 (9)	0.0626 (11)	0.0401 (9)	0.0227 (8)	0.0112 (7)	0.0205 (7)
C23	0.0381 (13)	0.0530 (14)	0.0485 (13)	0.0175 (11)	0.0121 (10)	0.0260 (11)
C24	0.0377 (12)	0.0439 (13)	0.0457 (13)	0.0161 (11)	0.0078 (10)	0.0184 (10)
C25	0.0376 (12)	0.0446 (13)	0.0537 (14)	0.0137 (11)	0.0095 (10)	0.0215 (11)
C26	0.0428 (15)	0.0609 (16)	0.0636 (17)	0.0139 (13)	0.0049 (12)	0.0187 (13)
C27	0.0374 (15)	0.0683 (19)	0.098 (2)	0.0072 (14)	0.0104 (15)	0.0197 (17)
C28	0.0510 (18)	0.0559 (18)	0.120 (3)	0.0129 (15)	0.0377 (18)	0.0325 (18)
C29	0.073 (2)	0.0675 (19)	0.096 (2)	0.0266 (17)	0.0408 (19)	0.0509 (18)
C30	0.0480 (15)	0.0614 (16)	0.0684 (17)	0.0179 (13)	0.0152 (13)	0.0372 (14)

Geometric parameters (Å, º)

O1—C24	1.212 (3)	C14—H14	0.93
O2—C21	1.185 (3)	C15—H15	0.93
O3—C23	1.188 (3)	N16—C17	1.463 (3)
S1—C9	1.765 (2)	N16—C19	1.466 (3)
S1—C2	1.900 (2)	C17—C20	1.521 (3)
C2—N16	1.432 (3)	C17—C23	1.533 (3)
C2—C10	1.528 (3)	C17—C18	1.562 (3)
C2—C3	1.544 (3)	C18—C21	1.518 (3)
C3—C4	1.497 (3)	C18—C24	1.550 (3)
C3—C18	1.583 (3)	C19—H19A	0.96
C3—H3	0.98	C19—H19B	0.96
C4—C5	1.391 (3)	C19—H19C	0.96
C4—C9	1.393 (3)	C20—H20A	0.96
C5—C6	1.380 (4)	C20—H20B	0.96
C5—H5	0.93	C20—H20C	0.96
C6—C7	1.382 (5)	C21—O22	1.389 (3)
C6—H6	0.93	O22—C23	1.383 (3)
C7—C8	1.386 (4)	C24—C25	1.491 (3)
C7—H7	0.93	C25—C30	1.389 (4)
C8—C9	1.384 (4)	C25—C26	1.392 (4)
C8—H8	0.93	C26—C27	1.386 (4)
C10—C11	1.382 (4)	C26—H26	0.93
C10—C15	1.392 (4)	C27—C28	1.368 (5)
C11—C12	1.390 (4)	C27—H27	0.93
C11—H11	0.93	C28—C29	1.372 (5)
C12—C13	1.364 (5)	C28—H28	0.93
C12—H12	0.93	C29—C30	1.387 (4)
C13—C14	1.364 (5)	C29—H29	0.93
C13—H13	0.93	C30—H30	0.93
C14—C15	1.391 (4)
C9—S1—C2	91.48 (10)	N16—C17—C20	110.25 (19)
N16—C2—C10	112.05 (19)	N16—C17—C23	113.37 (19)
N16—C2—C3	104.92 (18)	C20—C17—C23	108.22 (19)
C10—C2—C3	110.96 (17)	N16—C17—C18	105.35 (16)
N16—C2—S1	113.17 (15)	C20—C17—C18	117.16 (19)
C10—C2—S1	111.59 (16)	C23—C17—C18	102.43 (17)
C3—C2—S1	103.63 (15)	C21—C18—C24	113.68 (18)
C4—C3—C2	108.84 (18)	C21—C18—C17	104.54 (17)
C4—C3—C18	115.16 (17)	C24—C18—C17	113.78 (18)
C2—C3—C18	104.73 (16)	C21—C18—C3	111.42 (18)
C4—C3—H3	109.3	C24—C18—C3	108.37 (17)
C2—C3—H3	109.3	C17—C18—C3	104.70 (16)
C18—C3—H3	109.3	N16—C19—H19A	109.5
C5—C4—C9	119.5 (2)	N16—C19—H19B	109.5
C5—C4—C3	126.6 (2)	H19A—C19—H19B	109.5
C9—C4—C3	113.9 (2)	N16—C19—H19C	109.5
C6—C5—C4	119.5 (3)	H19A—C19—H19C	109.5
C6—C5—H5	120.3	H19B—C19—H19C	109.5
C4—C5—H5	120.3	C17—C20—H20A	109.5
C5—C6—C7	120.5 (3)	C17—C20—H20B	109.5
C5—C6—H6	119.7	H20A—C20—H20B	109.5
C7—C6—H6	119.7	C17—C20—H20C	109.5
C6—C7—C8	120.7 (3)	H20A—C20—H20C	109.5
C6—C7—H7	119.6	H20B—C20—H20C	109.5
C8—C7—H7	119.6	O2—C21—O22	119.7 (2)
C9—C8—C7	118.7 (3)	O2—C21—C18	129.6 (2)
C9—C8—H8	120.7	O22—C21—C18	110.65 (18)
C7—C8—H8	120.7	C23—O22—C21	110.53 (18)
C8—C9—C4	121.0 (2)	O3—C23—O22	119.9 (2)
C8—C9—S1	125.5 (2)	O3—C23—C17	128.5 (2)
C4—C9—S1	113.49 (18)	O22—C23—C17	111.48 (18)
C11—C10—C15	118.2 (2)	O1—C24—C25	119.9 (2)
C11—C10—C2	121.5 (2)	O1—C24—C18	117.7 (2)
C15—C10—C2	120.1 (2)	C25—C24—C18	122.4 (2)
C10—C11—C12	120.7 (3)	C30—C25—C26	119.3 (2)
C10—C11—H11	119.6	C30—C25—C24	124.3 (2)
C12—C11—H11	119.6	C26—C25—C24	116.4 (2)
C13—C12—C11	120.3 (3)	C27—C26—C25	120.2 (3)
C13—C12—H12	119.9	C27—C26—H26	119.9
C11—C12—H12	119.9	C25—C26—H26	119.9
C12—C13—C14	120.1 (3)	C28—C27—C26	119.8 (3)
C12—C13—H13	120	C28—C27—H27	120.1
C14—C13—H13	120	C26—C27—H27	120.1
C13—C14—C15	120.3 (3)	C27—C28—C29	120.8 (3)
C13—C14—H14	119.8	C27—C28—H28	119.6
C15—C14—H14	119.8	C29—C28—H28	119.6
C14—C15—C10	120.4 (3)	C28—C29—C30	120.1 (3)
C14—C15—H15	119.8	C28—C29—H29	120
C10—C15—H15	119.8	C30—C29—H29	120
C2—N16—C17	111.22 (17)	C29—C30—C25	119.9 (3)
C2—N16—C19	117.0 (2)	C29—C30—H30	120.1
C17—N16—C19	117.56 (18)	C25—C30—H30	120.1
C9—S1—C2—N16	137.23 (16)	C19—N16—C17—C18	−163.5 (2)
C9—S1—C2—C10	−95.29 (16)	N16—C17—C18—C21	124.21 (19)
C9—S1—C2—C3	24.17 (15)	C20—C17—C18—C21	−112.8 (2)
N16—C2—C3—C4	−149.03 (18)	C23—C17—C18—C21	5.4 (2)
C10—C2—C3—C4	89.8 (2)	N16—C17—C18—C24	−111.2 (2)
S1—C2—C3—C4	−30.11 (19)	C20—C17—C18—C24	11.8 (3)
N16—C2—C3—C18	−25.4 (2)	C23—C17—C18—C24	130.00 (19)
C10—C2—C3—C18	−146.57 (19)	N16—C17—C18—C3	6.9 (2)
S1—C2—C3—C18	93.55 (17)	C20—C17—C18—C3	129.9 (2)
C2—C3—C4—C5	−159.0 (2)	C23—C17—C18—C3	−111.85 (19)
C18—C3—C4—C5	83.8 (3)	C4—C3—C18—C21	18.0 (2)
C2—C3—C4—C9	23.8 (2)	C2—C3—C18—C21	−101.5 (2)
C18—C3—C4—C9	−93.4 (2)	C4—C3—C18—C24	−107.8 (2)
C9—C4—C5—C6	1.2 (3)	C2—C3—C18—C24	132.71 (19)
C3—C4—C5—C6	−175.9 (2)	C4—C3—C18—C17	130.45 (19)
C4—C5—C6—C7	−0.1 (4)	C2—C3—C18—C17	10.9 (2)
C5—C6—C7—C8	−1.0 (4)	C24—C18—C21—O2	52.4 (3)
C6—C7—C8—C9	1.1 (4)	C17—C18—C21—O2	177.0 (2)
C7—C8—C9—C4	0.0 (4)	C3—C18—C21—O2	−70.4 (3)
C7—C8—C9—S1	−179.37 (19)	C24—C18—C21—O22	−128.18 (19)
C5—C4—C9—C8	−1.1 (3)	C17—C18—C21—O22	−3.5 (2)
C3—C4—C9—C8	176.3 (2)	C3—C18—C21—O22	109.0 (2)
C5—C4—C9—S1	178.33 (17)	O2—C21—O22—C23	179.3 (2)
C3—C4—C9—S1	−4.3 (2)	C18—C21—O22—C23	−0.2 (3)
C2—S1—C9—C8	166.9 (2)	C21—O22—C23—O3	−177.8 (2)
C2—S1—C9—C4	−12.49 (18)	C21—O22—C23—C17	4.1 (3)
N16—C2—C10—C11	163.5 (2)	N16—C17—C23—O3	63.2 (3)
C3—C2—C10—C11	−79.6 (3)	C20—C17—C23—O3	−59.4 (3)
S1—C2—C10—C11	35.4 (3)	C18—C17—C23—O3	176.2 (3)
N16—C2—C10—C15	−21.5 (3)	N16—C17—C23—O22	−119.0 (2)
C3—C2—C10—C15	95.4 (2)	C20—C17—C23—O22	118.4 (2)
S1—C2—C10—C15	−149.59 (19)	C18—C17—C23—O22	−6.0 (2)
C15—C10—C11—C12	−0.5 (4)	C21—C18—C24—O1	−161.6 (2)
C2—C10—C11—C12	174.6 (3)	C17—C18—C24—O1	78.8 (3)
C10—C11—C12—C13	1.7 (5)	C3—C18—C24—O1	−37.2 (3)
C11—C12—C13—C14	−0.7 (5)	C21—C18—C24—C25	17.3 (3)
C12—C13—C14—C15	−1.6 (4)	C17—C18—C24—C25	−102.2 (2)
C13—C14—C15—C10	2.9 (4)	C3—C18—C24—C25	141.8 (2)
C11—C10—C15—C14	−1.8 (4)	O1—C24—C25—C30	−147.8 (3)
C2—C10—C15—C14	−177.0 (2)	C18—C24—C25—C30	33.2 (4)
C10—C2—N16—C17	152.47 (19)	O1—C24—C25—C26	30.0 (3)
C3—C2—N16—C17	32.0 (2)	C18—C24—C25—C26	−149.0 (2)
S1—C2—N16—C17	−80.3 (2)	C30—C25—C26—C27	−0.7 (4)
C10—C2—N16—C19	−68.5 (3)	C24—C25—C26—C27	−178.6 (3)
C3—C2—N16—C19	171.0 (2)	C25—C26—C27—C28	0.7 (5)
S1—C2—N16—C19	58.8 (2)	C26—C27—C28—C29	0.2 (5)
C2—N16—C17—C20	−152.0 (2)	C27—C28—C29—C30	−1.2 (5)
C19—N16—C17—C20	69.2 (3)	C28—C29—C30—C25	1.1 (5)
C2—N16—C17—C23	86.5 (2)	C26—C25—C30—C29	−0.2 (4)
C19—N16—C17—C23	−52.3 (3)	C24—C25—C30—C29	177.5 (3)
C2—N16—C17—C18	−24.7 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C30—H30···O3^i	0.93	2.48	3.272 (3)	143
C26—H26···O1^ii	0.93	2.60	3.484 (3)	159

Symmetry codes: (i) −x, −y+2, −z; (ii) −x+1, −y+2, −z+1.