Thailandepsin a.

THAILANDEPSIN A [SYSTEMATIC NAME: (E)-(1S,5S,6R,9S,20R)-6-[(2S)-butan-2-yl]-5-hy-droxy-20-[2-(meth-yl-sulfan-yl)eth-yl]-2-oxa-11,12-dithia-7,19,22-triaza-bicyclo-[7.7.6]docosa-15-ene-3,8,18,21-tetra-one], C(23)H(37)N(3)O(6)S(3), is a newly reported [Wang et al. (2011). J. Nat. Prod. doi:10.1021/np200324x] bicyclic depsipeptide that has potent histone deacetyl-ase inhibitory activity and broad-spectrum anti-proliferative activity. The absolute configuration of thailandepsin A has been determined from the anomalous dispersion and the stereochemistry of all chiral C atoms. Intra-molecular N-H⋯O and N-H⋯S hydrogen bonds occur. Inter-molecular N-H⋯O and O-H⋯O hydrogen bonds are observed in the crystal structure.

Related literature

For general background to histone deacetyl­ase (HDAC) inhibitors as a new class of anti­cancer agents, see: FDA (2010 ▶); Furumai et al. (2002 ▶); Grant et al. (2010 ▶); Khan & La Thangue (2008 ▶); Mann et al. (2007 ▶); Ueda et al. (1994 ▶). For related structures, see: Shigematsu et al. (1994 ▶). For geometric data, see: Chou & Blinn (1997 ▶). For the biological activity of the title compound, see: Wang et al. (2011 ▶).

Experimental

Crystal data

C23H37N3O6S3

M = 547.74

Orthorhombic,

a = 12.7747 (3) Å

b = 13.2926 (3) Å

c = 15.4218 (4) Å

V = 2618.76 (11) Å3

Z = 4

Cu Kα radiation

μ = 2.96 mm−1

T = 100 K

0.45 × 0.42 × 0.38 mm

Data collection

Bruker SMART APEXII area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2007 ▶) T min = 0.352, T max = 0.403

34598 measured reflections

4990 independent reflections

4981 reflections with I > 2σ(I)

R int = 0.025

Refinement

R[F 2 > 2σ(F 2)] = 0.027

wR(F 2) = 0.071

S = 1.05

4990 reflections

326 parameters

4 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.35 e Å−3

Δρmin = −0.36 e Å−3

Absolute structure: Flack (1983 ▶), 2102 Friedel pairs

Flack parameter: 0.000 (9)

Data collection: APEX2 (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL and OLEX2 (Dolomanov et al., 2009 ▶); software used to prepare material for publication: SHELXTL.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536811041390/zl2411sup1.cif

Supplementary material file. DOI: 10.1107/S1600536811041390/zl2411Isup2.cdx

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811041390/zl2411Isup3.hkl

Supplementary material file. DOI: 10.1107/S1600536811041390/zl2411Isup4.cml

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C23H37N3O6S3	F(000) = 1168
Mr = 547.74	Dx = 1.389 Mg m−3
Orthorhombic, P212121	Cu Kα radiation, λ = 1.54178 Å
Hall symbol: P 2ac 2ab	Cell parameters from 9793 reflections
a = 12.7747 (3) Å	θ = 3.5–71.2°
b = 13.2926 (3) Å	µ = 2.96 mm−1
c = 15.4218 (4) Å	T = 100 K
V = 2618.76 (11) Å3	Block, colourless
Z = 4	0.45 × 0.42 × 0.38 mm

Bruker SMART APEXII area-detector diffractometer	4990 independent reflections
Radiation source: fine-focus sealed tube	4981 reflections with I > 2σ(I)
graphite	Rint = 0.025
0.50° ω and 0.5 ° φ scans	θmax = 71.7°, θmin = 4.4°
Absorption correction: multi-scan (SADABS; Bruker, 2007)	h = −15→14
Tmin = 0.352, Tmax = 0.403	k = −15→16
34598 measured reflections	l = −18→17

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.027	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.071	w = 1/[σ2(Fo2) + (0.051P)2 + 0.7593P] where P = (Fo2 + 2Fc2)/3
S = 1.05	(Δ/σ)max = 0.001
4990 reflections	Δρmax = 0.35 e Å−3
326 parameters	Δρmin = −0.36 e Å−3
4 restraints	Absolute structure: Flack (1983), ???? Friedel pairs
Primary atom site location: structure-invariant direct methods	Flack parameter: 0.000 (9)

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.

	x	y	z	Uiso*/Ueq
S1	1.10290 (3)	−0.14637 (3)	0.38774 (2)	0.02184 (10)
S2	0.97356 (3)	−0.08216 (3)	0.33328 (2)	0.01709 (9)
S3	0.91337 (3)	0.40012 (3)	0.40152 (3)	0.02362 (10)
O1	1.08885 (10)	−0.18335 (9)	0.67591 (8)	0.0223 (3)
O2	0.77376 (8)	−0.09984 (8)	0.61157 (7)	0.0141 (2)
O3	0.69383 (9)	−0.08629 (9)	0.74184 (7)	0.0190 (2)
O4	0.85790 (9)	−0.16775 (8)	0.88174 (7)	0.0140 (2)
H4	0.8699 (17)	−0.2254 (7)	0.9016 (13)	0.021*
O5	1.11125 (9)	0.14154 (8)	0.55597 (7)	0.0179 (2)
O6	0.86120 (9)	0.12479 (8)	0.64747 (7)	0.0158 (2)
N1	0.99720 (10)	−0.04020 (10)	0.70173 (8)	0.0128 (3)
H1	0.9652 (14)	0.0126 (9)	0.6798 (12)	0.015*
N2	1.00458 (10)	0.00984 (9)	0.52676 (8)	0.0121 (2)
H2	0.9444 (8)	−0.0082 (14)	0.5038 (12)	0.014*
N3	0.83857 (10)	0.13784 (10)	0.50282 (8)	0.0138 (3)
H3	0.7955 (12)	0.1335 (15)	0.4584 (8)	0.017*
C1	1.05386 (12)	−0.10227 (12)	0.65205 (10)	0.0143 (3)
C2	1.07489 (12)	−0.06840 (11)	0.55727 (9)	0.0131 (3)
H2A	1.1482	−0.0423	0.5537	0.016*
C3	1.06714 (13)	−0.16258 (12)	0.50086 (10)	0.0174 (3)
H3A	0.9943	−0.1877	0.5034	0.021*
H3B	1.1128	−0.2151	0.5262	0.021*
C4	0.88346 (14)	−0.18723 (13)	0.31638 (11)	0.0202 (3)
H4A	0.8850	−0.2082	0.2548	0.024*
H4B	0.9052	−0.2453	0.3524	0.024*
C5	0.77251 (12)	−0.15466 (13)	0.34132 (11)	0.0190 (3)
H5A	0.7542	−0.0927	0.3091	0.023*
H5B	0.7225	−0.2079	0.3240	0.023*
C6	0.76184 (12)	−0.13526 (13)	0.43705 (10)	0.0173 (3)
H6	0.7980	−0.1793	0.4752	0.021*
C7	0.70632 (12)	−0.06202 (12)	0.47258 (10)	0.0162 (3)
H7	0.6720	−0.0170	0.4341	0.019*
C8	0.69224 (12)	−0.04303 (12)	0.56827 (10)	0.0154 (3)
H8	0.6227	−0.0704	0.5865	0.018*
C9	0.76158 (12)	−0.12126 (11)	0.69723 (10)	0.0136 (3)
C10	0.84280 (12)	−0.19799 (11)	0.72498 (10)	0.0138 (3)
H10A	0.8877	−0.2133	0.6743	0.017*
H10B	0.8059	−0.2608	0.7409	0.017*
C11	0.91409 (12)	−0.16801 (11)	0.80094 (9)	0.0127 (3)
H11	0.9724	−0.2180	0.8051	0.015*
C12	0.96190 (12)	−0.06200 (11)	0.79096 (9)	0.0125 (3)
H12	0.9029	−0.0143	0.8019	0.015*
C13	1.04416 (12)	−0.03790 (11)	0.86101 (10)	0.0146 (3)
H13	1.0124	−0.0559	0.9182	0.017*
C14	1.06664 (13)	0.07539 (12)	0.86315 (10)	0.0184 (3)
H14A	1.1138	0.0927	0.8144	0.022*
H14B	1.0002	0.1125	0.8548	0.022*
C15	1.11702 (14)	0.10927 (13)	0.94810 (11)	0.0222 (3)
H15A	1.0677	0.0988	0.9960	0.033*
H15B	1.1350	0.1808	0.9443	0.033*
H15C	1.1807	0.0700	0.9585	0.033*
C16	1.14602 (12)	−0.09806 (13)	0.85283 (10)	0.0184 (3)
H16A	1.1848	−0.0752	0.8017	0.028*
H16B	1.1296	−0.1697	0.8467	0.028*
H16C	1.1888	−0.0878	0.9048	0.028*
C17	1.02739 (12)	0.10824 (11)	0.52881 (9)	0.0134 (3)
C18	0.94399 (12)	0.17890 (11)	0.49209 (10)	0.0138 (3)
H18	0.9480	0.2442	0.5241	0.017*
C19	0.80478 (12)	0.11430 (11)	0.58346 (10)	0.0141 (3)
C20	0.69604 (12)	0.06994 (12)	0.59060 (10)	0.0160 (3)
H20A	0.6486	0.1068	0.5510	0.019*
H20B	0.6701	0.0797	0.6505	0.019*
C21	0.96752 (13)	0.19916 (11)	0.39575 (10)	0.0158 (3)
H21A	1.0409	0.2224	0.3904	0.019*
H21B	0.9613	0.1351	0.3634	0.019*
C22	0.89580 (13)	0.27705 (12)	0.35353 (10)	0.0168 (3)
H22A	0.8220	0.2558	0.3605	0.020*
H22B	0.9112	0.2807	0.2907	0.020*
C23	0.82077 (15)	0.46899 (14)	0.33643 (12)	0.0250 (4)
H23A	0.8190	0.5393	0.3554	0.037*
H23B	0.7510	0.4392	0.3431	0.037*
H23C	0.8419	0.4659	0.2754	0.037*

	U11	U22	U33	U12	U13	U23
S1	0.01829 (19)	0.0340 (2)	0.01321 (18)	0.00771 (17)	−0.00022 (14)	−0.00696 (15)
S2	0.01714 (18)	0.02111 (19)	0.01302 (16)	0.00009 (15)	−0.00063 (14)	−0.00078 (14)
S3	0.0279 (2)	0.0207 (2)	0.0222 (2)	0.00109 (16)	−0.00648 (16)	0.00032 (16)
O1	0.0286 (6)	0.0210 (6)	0.0172 (6)	0.0118 (5)	0.0048 (5)	0.0045 (5)
O2	0.0140 (5)	0.0171 (5)	0.0112 (5)	0.0017 (4)	0.0001 (4)	0.0034 (4)
O3	0.0199 (5)	0.0216 (6)	0.0156 (5)	0.0040 (5)	0.0037 (4)	0.0017 (5)
O4	0.0190 (5)	0.0131 (5)	0.0098 (5)	0.0019 (4)	0.0019 (4)	0.0018 (4)
O5	0.0167 (5)	0.0166 (5)	0.0205 (5)	−0.0020 (4)	−0.0032 (5)	−0.0018 (5)
O6	0.0197 (5)	0.0159 (5)	0.0119 (5)	0.0022 (4)	0.0004 (4)	−0.0001 (4)
N1	0.0161 (6)	0.0129 (6)	0.0093 (6)	0.0026 (5)	−0.0002 (5)	0.0029 (5)
N2	0.0122 (6)	0.0137 (6)	0.0103 (6)	−0.0004 (5)	−0.0003 (4)	−0.0003 (5)
N3	0.0139 (6)	0.0155 (6)	0.0121 (6)	0.0005 (5)	−0.0008 (5)	0.0010 (5)
C1	0.0145 (7)	0.0156 (7)	0.0129 (7)	0.0005 (6)	0.0002 (5)	0.0013 (6)
C2	0.0146 (7)	0.0142 (7)	0.0104 (6)	0.0017 (6)	0.0001 (5)	−0.0004 (6)
C3	0.0227 (7)	0.0153 (7)	0.0142 (7)	0.0037 (6)	−0.0015 (6)	−0.0014 (6)
C4	0.0243 (8)	0.0191 (7)	0.0170 (8)	−0.0014 (7)	−0.0020 (7)	−0.0043 (6)
C5	0.0184 (8)	0.0213 (8)	0.0172 (8)	−0.0030 (6)	−0.0031 (6)	−0.0015 (6)
C6	0.0167 (7)	0.0196 (7)	0.0156 (7)	−0.0045 (6)	−0.0035 (6)	0.0037 (6)
C7	0.0150 (7)	0.0194 (7)	0.0143 (7)	−0.0019 (6)	−0.0042 (6)	0.0040 (6)
C8	0.0126 (7)	0.0182 (7)	0.0154 (7)	0.0001 (6)	−0.0011 (6)	0.0038 (6)
C9	0.0165 (7)	0.0135 (7)	0.0107 (6)	−0.0032 (6)	−0.0007 (6)	0.0002 (5)
C10	0.0183 (7)	0.0118 (7)	0.0111 (7)	0.0006 (6)	−0.0002 (6)	−0.0001 (5)
C11	0.0157 (7)	0.0136 (7)	0.0087 (6)	0.0015 (6)	0.0001 (6)	0.0010 (5)
C12	0.0152 (7)	0.0133 (6)	0.0089 (6)	0.0014 (6)	0.0010 (6)	0.0009 (5)
C13	0.0176 (7)	0.0156 (7)	0.0106 (7)	0.0009 (6)	−0.0008 (6)	0.0000 (5)
C14	0.0249 (8)	0.0155 (7)	0.0148 (7)	−0.0014 (6)	−0.0034 (6)	0.0017 (6)
C15	0.0287 (9)	0.0189 (8)	0.0190 (8)	−0.0025 (7)	−0.0021 (7)	−0.0013 (6)
C16	0.0161 (7)	0.0208 (8)	0.0182 (8)	0.0011 (6)	−0.0020 (6)	0.0011 (6)
C17	0.0164 (7)	0.0158 (7)	0.0079 (6)	−0.0003 (6)	0.0022 (6)	−0.0004 (5)
C18	0.0153 (7)	0.0133 (7)	0.0127 (7)	−0.0014 (6)	0.0000 (6)	0.0000 (6)
C19	0.0160 (7)	0.0119 (7)	0.0144 (7)	0.0037 (6)	0.0017 (6)	0.0005 (6)
C20	0.0154 (7)	0.0184 (7)	0.0142 (7)	0.0036 (6)	0.0020 (6)	0.0026 (6)
C21	0.0192 (7)	0.0154 (7)	0.0128 (7)	−0.0013 (6)	0.0012 (6)	0.0013 (6)
C22	0.0210 (8)	0.0171 (7)	0.0122 (7)	−0.0029 (6)	−0.0026 (6)	0.0015 (5)
C23	0.0259 (8)	0.0281 (9)	0.0209 (8)	0.0081 (7)	0.0006 (7)	0.0028 (7)

S1—C3	1.8162 (17)	C8—C20	1.541 (2)
S1—S2	2.0406 (6)	C8—H8	1.0000
S2—C4	1.8285 (17)	C9—C10	1.517 (2)
S3—C23	1.8014 (18)	C10—C11	1.536 (2)
S3—C22	1.8095 (16)	C10—H10A	0.9900
O1—C1	1.223 (2)	C10—H10B	0.9900
O2—C9	1.3602 (18)	C11—C12	1.543 (2)
O2—C8	1.4494 (18)	C11—H11	1.0000
O3—C9	1.199 (2)	C12—C13	1.541 (2)
O4—C11	1.4380 (17)	C12—H12	1.0000
O4—H4	0.8399 (10)	C13—C16	1.533 (2)
O5—C17	1.233 (2)	C13—C14	1.533 (2)
O6—C19	1.230 (2)	C13—H13	1.0000
N1—C1	1.338 (2)	C14—C15	1.528 (2)
N1—C12	1.4769 (18)	C14—H14A	0.9900
N1—H1	0.8797 (10)	C14—H14B	0.9900
N2—C17	1.340 (2)	C15—H15A	0.9800
N2—C2	1.4524 (19)	C15—H15B	0.9800
N2—H2	0.8798 (10)	C15—H15C	0.9800
N3—C19	1.353 (2)	C16—H16A	0.9800
N3—C18	1.4624 (18)	C16—H16B	0.9800
N3—H3	0.8799 (10)	C16—H16C	0.9800
C1—C2	1.553 (2)	C17—C18	1.529 (2)
C2—C3	1.528 (2)	C18—C21	1.540 (2)
C2—H2A	1.0000	C18—H18	1.0000
C3—H3A	0.9900	C19—C20	1.513 (2)
C3—H3B	0.9900	C20—H20A	0.9900
C4—C5	1.531 (2)	C20—H20B	0.9900
C4—H4A	0.9900	C21—C22	1.528 (2)
C4—H4B	0.9900	C21—H21A	0.9900
C5—C6	1.505 (2)	C21—H21B	0.9900
C5—H5A	0.9900	C22—H22A	0.9900
C5—H5B	0.9900	C22—H22B	0.9900
C6—C7	1.323 (2)	C23—H23A	0.9800
C6—H6	0.9500	C23—H23B	0.9800
C7—C8	1.508 (2)	C23—H23C	0.9800
C7—H7	0.9500
C3—S1—S2	103.96 (6)	C12—C11—H11	108.5
C4—S2—S1	104.41 (6)	N1—C12—C13	113.84 (12)
C23—S3—C22	98.63 (8)	N1—C12—C11	113.14 (12)
C9—O2—C8	118.31 (12)	C13—C12—C11	112.95 (12)
C11—O4—H4	102.9 (15)	N1—C12—H12	105.3
C1—N1—C12	125.27 (13)	C13—C12—H12	105.3
C1—N1—H1	121.5 (13)	C11—C12—H12	105.3
C12—N1—H1	111.9 (13)	C16—C13—C14	110.81 (13)
C17—N2—C2	123.82 (13)	C16—C13—C12	114.39 (13)
C17—N2—H2	117.7 (13)	C14—C13—C12	110.31 (12)
C2—N2—H2	118.4 (13)	C16—C13—H13	107.0
C19—N3—C18	118.95 (13)	C14—C13—H13	107.0
C19—N3—H3	120.1 (13)	C12—C13—H13	107.0
C18—N3—H3	120.8 (13)	C15—C14—C13	112.76 (13)
O1—C1—N1	124.65 (14)	C15—C14—H14A	109.0
O1—C1—C2	118.38 (14)	C13—C14—H14A	109.0
N1—C1—C2	116.97 (13)	C15—C14—H14B	109.0
N2—C2—C3	111.24 (12)	C13—C14—H14B	109.0
N2—C2—C1	113.92 (12)	H14A—C14—H14B	107.8
C3—C2—C1	106.69 (12)	C14—C15—H15A	109.5
N2—C2—H2A	108.3	C14—C15—H15B	109.5
C3—C2—H2A	108.3	H15A—C15—H15B	109.5
C1—C2—H2A	108.3	C14—C15—H15C	109.5
C2—C3—S1	115.69 (11)	H15A—C15—H15C	109.5
C2—C3—H3A	108.4	H15B—C15—H15C	109.5
S1—C3—H3A	108.4	C13—C16—H16A	109.5
C2—C3—H3B	108.4	C13—C16—H16B	109.5
S1—C3—H3B	108.4	H16A—C16—H16B	109.5
H3A—C3—H3B	107.4	C13—C16—H16C	109.5
C5—C4—S2	109.33 (11)	H16A—C16—H16C	109.5
C5—C4—H4A	109.8	H16B—C16—H16C	109.5
S2—C4—H4A	109.8	O5—C17—N2	123.19 (14)
C5—C4—H4B	109.8	O5—C17—C18	120.72 (13)
S2—C4—H4B	109.8	N2—C17—C18	116.05 (13)
H4A—C4—H4B	108.3	N3—C18—C17	111.75 (12)
C6—C5—C4	112.26 (13)	N3—C18—C21	110.75 (12)
C6—C5—H5A	109.2	C17—C18—C21	109.20 (12)
C4—C5—H5A	109.2	N3—C18—H18	108.4
C6—C5—H5B	109.2	C17—C18—H18	108.4
C4—C5—H5B	109.2	C21—C18—H18	108.4
H5A—C5—H5B	107.9	O6—C19—N3	121.62 (14)
C7—C6—C5	125.51 (15)	O6—C19—C20	121.58 (14)
C7—C6—H6	117.2	N3—C19—C20	116.73 (14)
C5—C6—H6	117.2	C19—C20—C8	113.10 (13)
C6—C7—C8	126.32 (14)	C19—C20—H20A	109.0
C6—C7—H7	116.8	C8—C20—H20A	109.0
C8—C7—H7	116.8	C19—C20—H20B	109.0
O2—C8—C7	106.14 (12)	C8—C20—H20B	109.0
O2—C8—C20	112.45 (12)	H20A—C20—H20B	107.8
C7—C8—C20	112.21 (13)	C22—C21—C18	114.37 (13)
O2—C8—H8	108.6	C22—C21—H21A	108.7
C7—C8—H8	108.6	C18—C21—H21A	108.7
C20—C8—H8	108.6	C22—C21—H21B	108.7
O3—C9—O2	123.95 (14)	C18—C21—H21B	108.7
O3—C9—C10	126.34 (14)	H21A—C21—H21B	107.6
O2—C9—C10	109.66 (12)	C21—C22—S3	111.34 (11)
C9—C10—C11	116.50 (12)	C21—C22—H22A	109.4
C9—C10—H10A	108.2	S3—C22—H22A	109.4
C11—C10—H10A	108.2	C21—C22—H22B	109.4
C9—C10—H10B	108.2	S3—C22—H22B	109.4
C11—C10—H10B	108.2	H22A—C22—H22B	108.0
H10A—C10—H10B	107.3	S3—C23—H23A	109.5
O4—C11—C10	111.44 (12)	S3—C23—H23B	109.5
O4—C11—C12	106.37 (11)	H23A—C23—H23B	109.5
C10—C11—C12	113.29 (12)	S3—C23—H23C	109.5
O4—C11—H11	108.5	H23A—C23—H23C	109.5
C10—C11—H11	108.5	H23B—C23—H23C	109.5
C3—S1—S2—C4	−79.45 (8)	O4—C11—C12—N1	−164.12 (12)
C12—N1—C1—O1	−4.2 (2)	C10—C11—C12—N1	−41.37 (17)
C12—N1—C1—C2	175.04 (13)	O4—C11—C12—C13	64.71 (15)
C17—N2—C2—C3	−143.88 (14)	C10—C11—C12—C13	−172.53 (12)
C17—N2—C2—C1	95.49 (16)	N1—C12—C13—C16	−61.27 (17)
O1—C1—C2—N2	161.20 (14)	C11—C12—C13—C16	69.54 (16)
N1—C1—C2—N2	−18.11 (19)	N1—C12—C13—C14	64.44 (16)
O1—C1—C2—C3	38.06 (19)	C11—C12—C13—C14	−164.75 (12)
N1—C1—C2—C3	−141.25 (14)	C16—C13—C14—C15	−71.70 (17)
N2—C2—C3—S1	61.75 (15)	C12—C13—C14—C15	160.60 (13)
C1—C2—C3—S1	−173.45 (10)	C2—N2—C17—O5	0.9 (2)
S2—S1—C3—C2	−79.42 (12)	C2—N2—C17—C18	178.86 (12)
S1—S2—C4—C5	138.27 (10)	C19—N3—C18—C17	57.26 (17)
S2—C4—C5—C6	−67.15 (16)	C19—N3—C18—C21	179.24 (13)
C4—C5—C6—C7	141.33 (16)	O5—C17—C18—N3	−152.25 (13)
C5—C6—C7—C8	178.20 (15)	N2—C17—C18—N3	29.76 (18)
C9—O2—C8—C7	−160.50 (12)	O5—C17—C18—C21	84.87 (16)
C9—O2—C8—C20	76.45 (16)	N2—C17—C18—C21	−93.11 (15)
C6—C7—C8—O2	16.4 (2)	C18—N3—C19—O6	−1.4 (2)
C6—C7—C8—C20	139.65 (16)	C18—N3—C19—C20	−178.68 (12)
C8—O2—C9—O3	−9.1 (2)	O6—C19—C20—C8	−97.53 (17)
C8—O2—C9—C10	168.50 (12)	N3—C19—C20—C8	79.73 (16)
O3—C9—C10—C11	−58.7 (2)	O2—C8—C20—C19	47.62 (17)
O2—C9—C10—C11	123.75 (13)	C7—C8—C20—C19	−71.95 (17)
C9—C10—C11—O4	71.69 (16)	N3—C18—C21—C22	62.21 (16)
C9—C10—C11—C12	−48.21 (17)	C17—C18—C21—C22	−174.33 (13)
C1—N1—C12—C13	84.41 (18)	C18—C21—C22—S3	64.71 (15)
C1—N1—C12—C11	−46.31 (19)	C23—S3—C22—C21	179.27 (12)

D—H···A	D—H	H···A	D···A	D—H···A
O4—H4···O5i	0.84 (1)	1.90 (1)	2.7394 (15)	176 (2)
N1—H1···O6	0.88 (1)	2.06 (1)	2.9203 (17)	166.(2)
N2—H2···S2	0.88 (1)	2.83 (2)	3.2491 (13)	111.(2)
N3—H3···O4ii	0.88 (1)	2.33 (1)	3.1534 (16)	155.(2)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O4—H4⋯O5i	0.84 (1)	1.90 (1)	2.7394 (15)	176 (2)
N1—H1⋯O6	0.88 (1)	2.06 (1)	2.9203 (17)	166 (2)
N2—H2⋯S2	0.88 (1)	2.83 (2)	3.2491 (13)	111 (2)
N3—H3⋯O4ii	0.88 (1)	2.33 (1)	3.1534 (16)	155 (2)

Symmetry codes: (i) ; (ii) .