Crystal structure of ethyl 2'',3-dioxo-7',7a'-di-hydro-1'H,3H,3'H-di-spiro[benzo[b]thio-phene-2,6'-pyrrolo-[1,2-c]thia-zole-5',3''-indoline]-7'-carboxyl-ate.

In the title compound, C23H20N2O4S2, the central pyrrolidine ring adopts an envelope conformation with the spiro C atom, shared with the benzo-thio-phene ring system, as the flap. The thia-zole ring has a twisted conformation on the S-C bond, where the C atom is that closest to methine C atom. The mean planes of the benzo-thio-phene and indoline ring systems are inclined to the mean plane of the central pyrrolidine ring by 82.75 (8) and 80.03 (8)°, respectively, and to each other by 61.49 (6)°. In the crystal, mol-ecules are linked via pairs of N-H⋯O hydrogen bonds, forming inversion dimers with an R 2 (2)(8) ring motif. The dimers are linked via C-H⋯O and C-H⋯N hydrogen bonds, forming a three-dimensional structure. The eth-oxy-carbonyl group is disordered over two orientations, with an occupancy ratio of 0.717 (12):0.283 (12).

Related literature

For the biological activity of spiro-pyrrolidine derivatives, see: Obniska et al. (2003 ▸); Peddi et al. (2004 ▸); Zapf et al. (2011 ▸); Stylianakis et al. (2003 ▸); Waldmann (1995 ▸); Suzuki et al. (1994 ▸); Huryn et al. (1991 ▸). For a related structure, see: Narayanan et al. (2013 ▸).

Experimental

Crystal data

C23H20N2O4S2

M = 452.53

Monoclinic,

a = 11.8894 (5) Å

b = 10.2181 (4) Å

c = 17.5044 (8) Å

β = 97.991 (2)°

V = 2105.91 (15) Å3

Z = 4

Mo Kα radiation

μ = 0.29 mm−1

T = 293 K

0.35 × 0.30 × 0.30 mm

Data collection

Bruker Kappa APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2004 ▸) T min = 0.906, T max = 0.919

19635 measured reflections

3706 independent reflections

3169 reflections with I > 2σ(I)

R int = 0.027

Refinement

R[F 2 > 2σ(F 2)] = 0.032

wR(F 2) = 0.088

S = 0.98

3705 reflections

312 parameters

65 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.26 e Å−3

Δρmin = −0.27 e Å−3

Data collection: APEX2 (Bruker, 2004 ▸); cell refinement: APEX2 and SAINT (Bruker, 2004 ▸); data reduction: SAINT and XPREP (Bruker, 2004 ▸); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▸); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▸, 2015 ▸); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ▸); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009 ▸).

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989015002030/su5067sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015002030/su5067Isup2.hkl

Click here for additional data file.

. DOI: 10.1107/S2056989015002030/su5067fig1.tif

The mol­ecular structure of the title compound with the atom numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. The dashed lines represent the bonds involving the minor component of the disordered ethyl carboxyl­ate unit.

Click here for additional data file.

b . DOI: 10.1107/S2056989015002030/su5067fig2.tif

The mol­ecular packing of the title compound viewed along the b axis. Dashed lines show the C—H⋯N, C—H⋯O and C—H⋯N hydrogen bonds (Table 1).

CCDC reference: 1046458

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

C23H20N2O4S2	F(000) = 944
Mr = 452.53	Dx = 1.427 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3706 reflections
a = 11.8894 (5) Å	θ = 2.3–25.0°
b = 10.2181 (4) Å	µ = 0.29 mm−1
c = 17.5044 (8) Å	T = 293 K
β = 97.991 (2)°	Block, colourless
V = 2105.91 (15) Å3	0.35 × 0.30 × 0.30 mm
Z = 4

Bruker Kappa APEXII CCD diffractometer	3706 independent reflections
Radiation source: fine-focus sealed tube	3169 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.027
ω and φ scans	θmax = 25.0°, θmin = 2.3°
Absorption correction: multi-scan (SADABS; Bruker, 2004)	h = −14→14
Tmin = 0.906, Tmax = 0.919	k = −12→11
19635 measured reflections	l = −20→20

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)] = 0.032	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.088	H atoms treated by a mixture of independent and constrained refinement
S = 0.98	w = 1/[σ2(Fo2) + (0.0443P)2 + 1.0594P] where P = (Fo2 + 2Fc2)/3
3705 reflections	(Δ/σ)max < 0.001
312 parameters	Δρmax = 0.26 e Å−3
65 restraints	Δρmin = −0.27 e Å−3

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.

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 > 2sigma(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.

	x	y	z	Uiso*/Ueq	Occ. (<1)
C3	0.22511 (16)	−0.15734 (19)	0.81332 (11)	0.0408 (4)
C4	0.22481 (14)	−0.12481 (18)	0.72929 (10)	0.0342 (4)
H4	0.1500	−0.1486	0.7019	0.041*
C5	0.31386 (14)	−0.19721 (18)	0.69063 (10)	0.0354 (4)
H5	0.3821	−0.2098	0.7283	0.042*
C6	0.26623 (13)	0.00729 (17)	0.62479 (9)	0.0298 (4)
C7	0.24619 (13)	0.02012 (17)	0.71114 (9)	0.0314 (4)
C8	0.15041 (14)	0.11732 (18)	0.72277 (10)	0.0343 (4)
C9	0.19513 (13)	0.23396 (18)	0.76473 (10)	0.0336 (4)
C10	0.13286 (15)	0.3444 (2)	0.77968 (11)	0.0437 (5)
H10	0.0549	0.3473	0.7640	0.052*
C11	0.18760 (17)	0.4486 (2)	0.81770 (13)	0.0501 (5)
H11	0.1467	0.5223	0.8285	0.060*
C12	0.30442 (17)	0.4440 (2)	0.84011 (12)	0.0475 (5)
H12	0.3411	0.5158	0.8650	0.057*
C13	0.36685 (15)	0.33556 (19)	0.82629 (11)	0.0393 (4)
H13	0.4450	0.3338	0.8414	0.047*
C14	0.31142 (13)	0.22884 (17)	0.78951 (9)	0.0319 (4)
C15	0.14879 (13)	−0.01360 (18)	0.57169 (9)	0.0334 (4)
C16	0.22851 (14)	0.17108 (17)	0.52915 (10)	0.0331 (4)
C17	0.24522 (16)	0.27754 (19)	0.48425 (11)	0.0415 (4)
H17	0.1892	0.3057	0.4453	0.050*
C18	0.34843 (18)	0.34133 (19)	0.49905 (12)	0.0461 (5)
H18	0.3620	0.4140	0.4697	0.055*
C19	0.43177 (17)	0.29921 (19)	0.55657 (12)	0.0451 (5)
H19	0.5004	0.3441	0.5658	0.054*
C20	0.41404 (15)	0.19029 (18)	0.60081 (11)	0.0381 (4)
H20	0.4710	0.1606	0.6386	0.046*
C21	0.31061 (13)	0.12661 (17)	0.58786 (10)	0.0309 (4)
C22	0.35408 (17)	−0.17203 (19)	0.55696 (11)	0.0422 (4)
H22A	0.4206	−0.1392	0.5368	0.051*
H22B	0.2879	−0.1571	0.5189	0.051*
N1	0.34078 (11)	−0.10643 (14)	0.62958 (8)	0.0313 (3)
N2	0.13369 (12)	0.08759 (15)	0.52250 (9)	0.0373 (4)
O1	0.28776 (14)	−0.23233 (15)	0.84987 (8)	0.0601 (4)
O3	0.05293 (10)	0.09693 (14)	0.69704 (9)	0.0510 (4)
O4	0.08550 (10)	−0.10764 (13)	0.57322 (7)	0.0430 (3)
S1	0.37513 (3)	0.07922 (4)	0.77110 (3)	0.03457 (13)
S2	0.36970 (5)	−0.34399 (5)	0.57908 (3)	0.05123 (16)
C23	0.27897 (18)	−0.3280 (2)	0.65305 (13)	0.0504 (5)
H23A	0.1995	−0.3274	0.6308	0.061*
H23B	0.2917	−0.3989	0.6901	0.061*
C1	−0.0015 (4)	−0.0975 (10)	0.9230 (3)	0.100 (2)	0.717 (12)
H1A	−0.0235	−0.1289	0.9704	0.149*	0.717 (12)
H1B	−0.0522	−0.1320	0.8803	0.149*	0.717 (12)
H1C	−0.0050	−0.0036	0.9220	0.149*	0.717 (12)
C2	0.1165 (5)	−0.1407 (8)	0.9171 (3)	0.0663 (17)	0.717 (12)
H2A	0.1212	−0.2354	0.9163	0.080*	0.717 (12)
H2B	0.1689	−0.1080	0.9603	0.080*	0.717 (12)
O2	0.1435 (9)	−0.0828 (9)	0.8414 (5)	0.059 (2)	0.717 (12)
C1A	0.0427 (18)	−0.1791 (17)	0.9270 (6)	0.085 (5)	0.283 (12)
H1A1	0.0230	−0.1767	0.9784	0.128*	0.283 (12)
H1A2	0.0661	−0.2661	0.9157	0.128*	0.283 (12)
H1A3	−0.0221	−0.1546	0.8908	0.128*	0.283 (12)
C2A	0.1380 (12)	−0.0854 (14)	0.9211 (8)	0.053 (3)	0.283 (12)
H2A1	0.1182	0.0052	0.9290	0.063*	0.283 (12)
H2A2	0.2080	−0.1085	0.9537	0.063*	0.283 (12)
O2A	0.1378 (19)	−0.120 (2)	0.8381 (10)	0.043 (3)	0.283 (12)
H2	0.0730 (15)	0.098 (2)	0.4891 (11)	0.051 (6)*

	U11	U22	U33	U12	U13	U23
C3	0.0357 (10)	0.0462 (11)	0.0390 (10)	−0.0027 (9)	−0.0008 (8)	0.0047 (9)
C4	0.0275 (8)	0.0386 (10)	0.0346 (9)	−0.0026 (7)	−0.0020 (7)	0.0035 (8)
C5	0.0308 (9)	0.0369 (10)	0.0369 (9)	−0.0002 (7)	−0.0010 (7)	0.0034 (8)
C6	0.0220 (8)	0.0339 (9)	0.0318 (9)	−0.0008 (7)	−0.0020 (6)	0.0000 (7)
C7	0.0209 (8)	0.0383 (10)	0.0330 (9)	−0.0002 (7)	−0.0032 (6)	−0.0002 (7)
C8	0.0235 (8)	0.0453 (10)	0.0335 (9)	0.0022 (7)	0.0016 (7)	0.0056 (8)
C9	0.0252 (8)	0.0411 (10)	0.0342 (9)	0.0037 (7)	0.0031 (7)	0.0033 (8)
C10	0.0270 (9)	0.0511 (12)	0.0526 (12)	0.0096 (8)	0.0035 (8)	0.0030 (9)
C11	0.0440 (11)	0.0426 (12)	0.0634 (13)	0.0125 (9)	0.0062 (10)	−0.0036 (10)
C12	0.0441 (11)	0.0392 (11)	0.0577 (12)	−0.0006 (9)	0.0015 (9)	−0.0070 (9)
C13	0.0291 (9)	0.0442 (11)	0.0432 (10)	0.0019 (8)	−0.0003 (8)	−0.0012 (9)
C14	0.0261 (8)	0.0375 (10)	0.0317 (8)	0.0034 (7)	0.0029 (7)	0.0027 (7)
C15	0.0257 (8)	0.0401 (10)	0.0325 (9)	0.0000 (7)	−0.0026 (7)	0.0007 (8)
C16	0.0326 (9)	0.0353 (10)	0.0314 (9)	0.0011 (7)	0.0041 (7)	−0.0025 (7)
C17	0.0473 (11)	0.0392 (11)	0.0377 (10)	0.0032 (8)	0.0049 (8)	0.0039 (8)
C18	0.0599 (12)	0.0340 (10)	0.0472 (11)	−0.0048 (9)	0.0168 (10)	0.0008 (9)
C19	0.0435 (11)	0.0407 (11)	0.0533 (12)	−0.0121 (9)	0.0148 (9)	−0.0078 (9)
C20	0.0298 (9)	0.0409 (10)	0.0433 (10)	−0.0028 (8)	0.0044 (7)	−0.0043 (8)
C21	0.0273 (8)	0.0317 (9)	0.0336 (9)	0.0007 (7)	0.0041 (7)	−0.0029 (7)
C22	0.0456 (11)	0.0405 (11)	0.0394 (10)	0.0036 (8)	0.0019 (8)	−0.0043 (8)
N1	0.0280 (7)	0.0332 (8)	0.0317 (7)	0.0019 (6)	0.0004 (6)	−0.0010 (6)
N2	0.0284 (8)	0.0437 (9)	0.0362 (8)	−0.0021 (6)	−0.0078 (6)	0.0061 (7)
O1	0.0696 (10)	0.0639 (10)	0.0447 (8)	0.0189 (8)	0.0010 (7)	0.0148 (7)
O3	0.0220 (6)	0.0628 (9)	0.0652 (9)	0.0014 (6)	−0.0046 (6)	−0.0071 (7)
O4	0.0315 (6)	0.0463 (8)	0.0463 (8)	−0.0113 (6)	−0.0115 (5)	0.0067 (6)
S1	0.0218 (2)	0.0417 (3)	0.0377 (2)	0.00479 (17)	−0.00465 (17)	−0.00587 (19)
S2	0.0606 (3)	0.0380 (3)	0.0542 (3)	0.0045 (2)	0.0047 (2)	−0.0082 (2)
C23	0.0546 (12)	0.0383 (11)	0.0580 (13)	−0.0051 (9)	0.0065 (10)	0.0005 (10)
C1	0.090 (3)	0.137 (6)	0.082 (3)	−0.018 (4)	0.047 (3)	−0.029 (4)
C2	0.068 (3)	0.093 (5)	0.041 (2)	−0.007 (3)	0.020 (2)	0.013 (3)
O2	0.060 (3)	0.076 (5)	0.0464 (19)	0.021 (3)	0.0200 (16)	0.014 (2)
C1A	0.123 (13)	0.102 (10)	0.039 (5)	−0.060 (9)	0.036 (6)	−0.012 (6)
C2A	0.062 (6)	0.050 (6)	0.046 (5)	−0.012 (5)	0.012 (4)	0.008 (5)
O2A	0.036 (4)	0.060 (8)	0.033 (4)	0.015 (5)	0.006 (3)	0.017 (4)

C3—O1	1.191 (2)	C16—C21	1.392 (2)
C3—O2A	1.24 (2)	C16—N2	1.406 (2)
C3—O2	1.376 (10)	C17—C18	1.382 (3)
C3—C4	1.508 (2)	C17—H17	0.9300
C4—C5	1.525 (2)	C18—C19	1.380 (3)
C4—C7	1.543 (2)	C18—H18	0.9300
C4—H4	0.9800	C19—C20	1.389 (3)
C5—N1	1.483 (2)	C19—H19	0.9300
C5—C23	1.522 (3)	C20—C21	1.382 (2)
C5—H5	0.9800	C20—H20	0.9300
C6—N1	1.457 (2)	C22—N1	1.465 (2)
C6—C21	1.509 (2)	C22—S2	1.803 (2)
C6—C7	1.568 (2)	C22—H22A	0.9700
C6—C15	1.581 (2)	C22—H22B	0.9700
C7—C8	1.546 (2)	N2—H2	0.869 (15)
C7—S1	1.8355 (16)	S2—C23	1.804 (2)
C8—O3	1.202 (2)	C23—H23A	0.9700
C8—C9	1.461 (3)	C23—H23B	0.9700
C9—C14	1.391 (2)	C1—C2	1.488 (6)
C9—C10	1.394 (3)	C1—H1A	0.9600
C10—C11	1.372 (3)	C1—H1B	0.9600
C10—H10	0.9300	C1—H1C	0.9600
C11—C12	1.391 (3)	C2—O2	1.526 (9)
C11—H11	0.9300	C2—H2A	0.9700
C12—C13	1.373 (3)	C2—H2B	0.9700
C12—H12	0.9300	C1A—C2A	1.499 (9)
C13—C14	1.386 (3)	C1A—H1A1	0.9600
C13—H13	0.9300	C1A—H1A2	0.9600
C14—S1	1.7558 (17)	C1A—H1A3	0.9600
C15—O4	1.223 (2)	C2A—O2A	1.497 (17)
C15—N2	1.342 (2)	C2A—H2A1	0.9700
C16—C17	1.373 (3)	C2A—H2A2	0.9700
O1—C3—O2A	120.0 (9)	C18—C17—H17	121.2
O1—C3—O2	125.7 (4)	C19—C18—C17	121.24 (18)
O2A—C3—O2	16.2 (13)	C19—C18—H18	119.4
O1—C3—C4	125.62 (18)	C17—C18—H18	119.4
O2A—C3—C4	112.7 (8)	C18—C19—C20	120.51 (17)
O2—C3—C4	108.7 (4)	C18—C19—H19	119.7
C3—C4—C5	114.74 (15)	C20—C19—H19	119.7
C3—C4—C7	115.75 (15)	C21—C20—C19	119.12 (17)
C5—C4—C7	103.29 (13)	C21—C20—H20	120.4
C3—C4—H4	107.5	C19—C20—H20	120.4
C5—C4—H4	107.5	C20—C21—C16	118.96 (17)
C7—C4—H4	107.5	C20—C21—C6	131.79 (16)
N1—C5—C23	108.13 (15)	C16—C21—C6	109.21 (14)
N1—C5—C4	104.42 (14)	N1—C22—S2	106.25 (13)
C23—C5—C4	116.98 (15)	N1—C22—H22A	110.5
N1—C5—H5	109.0	S2—C22—H22A	110.5
C23—C5—H5	109.0	N1—C22—H22B	110.5
C4—C5—H5	109.0	S2—C22—H22B	110.5
N1—C6—C21	115.02 (13)	H22A—C22—H22B	108.7
N1—C6—C7	100.60 (12)	C6—N1—C22	116.95 (13)
C21—C6—C7	117.02 (14)	C6—N1—C5	110.48 (13)
N1—C6—C15	114.01 (13)	C22—N1—C5	113.52 (14)
C21—C6—C15	100.96 (13)	C15—N2—C16	112.36 (14)
C7—C6—C15	109.75 (12)	C15—N2—H2	123.3 (14)
C4—C7—C8	116.36 (14)	C16—N2—H2	124.3 (14)
C4—C7—C6	99.77 (13)	C14—S1—C7	92.53 (8)
C8—C7—C6	113.21 (13)	C22—S2—C23	90.69 (9)
C4—C7—S1	110.27 (11)	C5—C23—S2	103.62 (13)
C8—C7—S1	106.58 (12)	C5—C23—H23A	111.0
C6—C7—S1	110.61 (11)	S2—C23—H23A	111.0
O3—C8—C9	126.48 (17)	C5—C23—H23B	111.0
O3—C8—C7	121.94 (17)	S2—C23—H23B	111.0
C9—C8—C7	111.54 (13)	H23A—C23—H23B	109.0
C14—C9—C10	120.18 (17)	C2—C1—H1A	109.5
C14—C9—C8	113.73 (15)	C2—C1—H1B	109.6
C10—C9—C8	126.09 (15)	H1A—C1—H1B	109.5
C11—C10—C9	119.42 (17)	C2—C1—H1C	109.3
C11—C10—H10	120.3	H1A—C1—H1C	109.5
C9—C10—H10	120.3	H1B—C1—H1C	109.5
C10—C11—C12	119.88 (18)	C1—C2—O2	105.0 (7)
C10—C11—H11	120.1	C1—C2—H2A	110.6
C12—C11—H11	120.1	O2—C2—H2A	110.7
C13—C12—C11	121.40 (19)	C1—C2—H2B	110.8
C13—C12—H12	119.3	O2—C2—H2B	110.8
C11—C12—H12	119.3	H2A—C2—H2B	108.8
C12—C13—C14	118.87 (16)	C3—O2—C2	109.9 (7)
C12—C13—H13	120.6	C2A—C1A—H1A1	109.5
C14—C13—H13	120.6	C2A—C1A—H1A2	109.8
C13—C14—C9	120.21 (16)	H1A1—C1A—H1A2	109.5
C13—C14—S1	125.52 (13)	C2A—C1A—H1A3	109.1
C9—C14—S1	114.26 (13)	H1A1—C1A—H1A3	109.5
O4—C15—N2	126.28 (15)	H1A2—C1A—H1A3	109.5
O4—C15—C6	126.10 (15)	O2A—C2A—C1A	90.8 (14)
N2—C15—C6	107.56 (14)	O2A—C2A—H2A1	113.6
C17—C16—C21	122.63 (16)	C1A—C2A—H2A1	113.9
C17—C16—N2	127.72 (16)	O2A—C2A—H2A2	113.4
C21—C16—N2	109.58 (15)	C1A—C2A—H2A2	113.1
C16—C17—C18	117.51 (17)	H2A1—C2A—H2A2	110.8
C16—C17—H17	121.2	C3—O2A—C2A	121.6 (16)
O1—C3—C4—C5	0.2 (3)	C7—C6—C15—N2	118.46 (16)
O2A—C3—C4—C5	−165.0 (11)	C21—C16—C17—C18	0.1 (3)
O2—C3—C4—C5	178.2 (5)	N2—C16—C17—C18	−176.61 (17)
O1—C3—C4—C7	−120.0 (2)	C16—C17—C18—C19	0.3 (3)
O2A—C3—C4—C7	74.8 (11)	C17—C18—C19—C20	0.5 (3)
O2—C3—C4—C7	58.0 (5)	C18—C19—C20—C21	−1.7 (3)
C3—C4—C5—N1	−150.45 (14)	C19—C20—C21—C16	2.0 (3)
C7—C4—C5—N1	−23.56 (16)	C19—C20—C21—C6	179.27 (17)
C3—C4—C5—C23	90.12 (19)	C17—C16—C21—C20	−1.2 (3)
C7—C4—C5—C23	−142.99 (16)	N2—C16—C21—C20	175.96 (15)
C3—C4—C7—C8	−69.85 (19)	C17—C16—C21—C6	−179.05 (16)
C5—C4—C7—C8	163.90 (14)	N2—C16—C21—C6	−1.86 (19)
C3—C4—C7—C6	168.03 (14)	N1—C6—C21—C20	−49.8 (2)
C5—C4—C7—C6	41.78 (14)	C7—C6—C21—C20	68.0 (2)
C3—C4—C7—S1	51.64 (17)	C15—C6—C21—C20	−173.01 (18)
C5—C4—C7—S1	−74.60 (14)	N1—C6—C21—C16	127.64 (15)
N1—C6—C7—C4	−44.39 (14)	C7—C6—C21—C16	−114.60 (15)
C21—C6—C7—C4	−169.73 (13)	C15—C6—C21—C16	4.43 (17)
C15—C6—C7—C4	76.07 (15)	C21—C6—N1—C22	−69.72 (19)
N1—C6—C7—C8	−168.73 (13)	C7—C6—N1—C22	163.60 (14)
C21—C6—C7—C8	65.93 (18)	C15—C6—N1—C22	46.2 (2)
C15—C6—C7—C8	−48.27 (18)	C21—C6—N1—C5	158.38 (13)
N1—C6—C7—S1	71.74 (13)	C7—C6—N1—C5	31.70 (15)
C21—C6—C7—S1	−53.60 (16)	C15—C6—N1—C5	−85.67 (16)
C15—C6—C7—S1	−167.80 (11)	S2—C22—N1—C6	−145.63 (12)
C4—C7—C8—O3	−48.7 (2)	S2—C22—N1—C5	−15.15 (17)
C6—C7—C8—O3	66.1 (2)	C23—C5—N1—C6	119.60 (16)
S1—C7—C8—O3	−172.12 (15)	C4—C5—N1—C6	−5.64 (17)
C4—C7—C8—C9	133.65 (15)	C23—C5—N1—C22	−14.04 (19)
C6—C7—C8—C9	−111.60 (16)	C4—C5—N1—C22	−139.28 (14)
S1—C7—C8—C9	10.22 (17)	O4—C15—N2—C16	−172.24 (17)
O3—C8—C9—C14	178.35 (18)	C6—C15—N2—C16	5.08 (19)
C7—C8—C9—C14	−4.1 (2)	C17—C16—N2—C15	174.80 (18)
O3—C8—C9—C10	−2.6 (3)	C21—C16—N2—C15	−2.2 (2)
C7—C8—C9—C10	174.91 (17)	C13—C14—S1—C7	−171.66 (16)
C14—C9—C10—C11	1.2 (3)	C9—C14—S1—C7	9.31 (14)
C8—C9—C10—C11	−177.76 (18)	C4—C7—S1—C14	−137.86 (12)
C9—C10—C11—C12	0.7 (3)	C8—C7—S1—C14	−10.72 (12)
C10—C11—C12—C13	−1.2 (3)	C6—C7—S1—C14	112.74 (12)
C11—C12—C13—C14	−0.3 (3)	N1—C22—S2—C23	31.91 (14)
C12—C13—C14—C9	2.3 (3)	N1—C5—C23—S2	36.32 (17)
C12—C13—C14—S1	−176.71 (15)	C4—C5—C23—S2	153.75 (13)
C10—C9—C14—C13	−2.7 (3)	C22—S2—C23—C5	−39.29 (14)
C8—C9—C14—C13	176.35 (16)	O1—C3—O2—C2	−19.0 (10)
C10—C9—C14—S1	176.34 (14)	O2A—C3—O2—C2	56 (4)
C8—C9—C14—S1	−4.56 (19)	C4—C3—O2—C2	163.0 (6)
N1—C6—C15—O4	47.7 (2)	C1—C2—O2—C3	−154.3 (7)
C21—C6—C15—O4	171.64 (17)	O1—C3—O2A—C2A	42 (2)
C7—C6—C15—O4	−64.2 (2)	O2—C3—O2A—C2A	−73 (4)
N1—C6—C15—N2	−129.59 (15)	C4—C3—O2A—C2A	−151.8 (15)
C21—C6—C15—N2	−5.69 (17)	C1A—C2A—O2A—C3	−126.0 (17)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O4i	0.87 (2)	2.05 (2)	2.9029 (18)	169 (2)
C11—H11···O3ii	0.93	2.47	3.215 (2)	137
C13—H13···N1iii	0.93	2.60	3.505 (2)	165

Table 1

Hydrogen-bond geometry (, )

DHA	DH	HA	D A	DHA
N2H2O4i	0.87(2)	2.05(2)	2.9029(18)	169(2)
C11H11O3ii	0.93	2.47	3.215(2)	137
C13H13N1iii	0.93	2.60	3.505(2)	165

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