2,3,4,6-Tetra-O-acetyl-1-[(dimethylcarbamothioyl)sulfanyl]-β-d-galacto­pyran­ose

Mohamed-Ezzat, R.A.; Elgemeie, G.H.; Jones, P.G.

doi:10.1107/S2414314625005449

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 10| Part 6| June 2025| x250544

https://doi.org/10.1107/S2414314625005449

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2,3,4,6-Tetra-O-acetyl-1-[(dimethylcarbamothioyl)sulfanyl]-β-D-galactopyranose

Reham A. Mohamed-Ezzat,^a Galal H. Elgemeie ^b and Peter G. Jones ^c ^*

^aChemistry of Natural and Microbial Products Department, Pharmaceutical and Drug Industries Research Institute, National Research Centre, Cairo, Egypt, ^bChemistry Department, Faculty of Science, Helwan University, Cairo, Egypt, and ^cInstitut für Anorganische und Analytische Chemie, Technische Universität Braunschweig, Hagenring 30, D-38106 Braunschweig, Germany
^*Correspondence e-mail: [email protected]

Edited by M. Bolte, Goethe-Universität Frankfurt, Germany (Received 9 June 2025; accepted 18 June 2025; online 24 June 2025)

In the structure of the title compound, C₁₇H₂₅NO₉S₂, the bond lengths in the C—S—C moiety are almost equal at 1.7959 (8) and 1.7877 (9) Å, with a shorter formally double C—S bond of 1.6698 (9) Å at the other sulfur atom. The eight-atom sequence O3—C3—C2—C1—S—C—N—C (using standard sugar numbering) shows an extended conformation. The packing involves ‘weak’ hydrogen bonds, whereby the three shortest C—H⋯O contacts combine to form layers of molecules parallel to the ab plane.

Keywords: thiocarbamate; galactose; weak hydrogen bonds; crystal structure.

CCDC reference: 2465327

Structure description

Thioglycosides have been the focus of much attention because of their role as glycosyl donors in a variety of chemical processes. They can be subjected to most common manipulations of carbohydrate-protecting groups (Toshima et al., 2007 ), and can be activated for glycosidation under a variety of conditions. An associated advantage is their stability in such processes (Lian et al., 2015 ). Oligosaccharides and glycoconjugates have a wide range of biological roles because of the extensive variety of their molecular structures. They are particularly desirable synthetic targets in terms both of their biological significance and of the synthetic challenges they offer, and synthetic carbohydrate chemistry has long been a major area of interest in organic chemistry (Codée et al., 2005 ). Additionally, some thioglycoside derivatives have been reported to be inhibitors of protein glycosylation (Scala et al., 1997 ).

We have reported the structures of several thioglycosides, the most recent being four structures involving carbamimidothioate groups (Abu-Zaied et al., 2024 ; see also references therein). Here, we report the structure of N,N-dimethylcarbamodithio(2,3,4,6-tetra-O-acetyl-β-D-galactopyranose), made by reacting potassium cyanocarbonimidodithioate with the protected α-D-galactopyranosyl bromide in dimethyl formamide in the presence of sodium ethoxide at room temperature for 24 h. The compound has been previously reported by Li et al. (2016 ), Pluigers et al. (1969 ), Ferrier & Furneaux (1977 ) and Tejima & Ishiguro (1967 ).

The molecule of the title compound is shown in Fig. 1, with selected molecular dimensions in Table 1. Bond lengths and angles may be considered normal, e.g. the two almost equal C—S1 bond lengths and the shorter S2—C15, corresponding to its formal double bond nature. The atom sequence O3—C3—C2—C1—S1—C15—N1—C17 shows an extended conformation, with absolute torsion angles 155.53 (6)° for C2—C1—S1—C15 (confirming the β position of the substituent at C1) and > 170° for all others. The geometry at the nitrogen atom is planar (angle sum 359.9°).

Table 1
Selected geometric parameters (Å, °)

C1—S1	1.7959 (8)	S2—C15	1.6698 (9)
S1—C15	1.7877 (9)	C15—N1	1.3327 (12)

C15—S1—C1	101.77 (4)	C15—N1—C17	119.92 (9)
N1—C15—S2	124.18 (7)	C15—N1—C16	123.38 (8)
N1—C15—S1	112.09 (7)	C17—N1—C16	116.62 (8)
S2—C15—S1	123.71 (5)

S1—C1—C2—C3	−179.78 (5)	C1—S1—C15—N1	170.41 (7)
C1—C2—C3—O3	−173.98 (6)	C1—S1—C15—S2	−11.04 (7)
C2—C1—S1—C15	155.53 (6)	S1—C15—N1—C17	175.46 (10)

Figure 1
The molecule of the title compound in the crystal. Ellipsoids indicate 50% probability levels.

In the absence of classical hydrogen bond donors, the packing involves ‘weak’ hydrogen bonds. The three shortest C—H⋯O contacts (Table 2) combine to form layers of molecules parallel to the ab plane at z = 1/4, 1/2, 3/4, etc. (Fig. 2). Layers are linked by the other two C—H⋯O contacts (Fig. 3).

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C4—H4⋯O7ⁱ	1.00	2.45	3.2096 (11)	132
C8—H8B⋯O8ⁱⁱ	0.98	2.41	3.3157 (15)	154
C16—H16C⋯O10ⁱⁱⁱ	0.98	2.44	3.1795 (18)	132
C17—H17B⋯O1^iv	0.98	2.55	3.3558 (13)	139
C1—H1⋯S2	1.00	2.56	3.1175 (8)	115
C8—H8A⋯O8^v	0.98	2.66	3.3384 (15)	127
Symmetry codes: (i) ; (ii) ; (iii) ; (iv) $[-x, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (v) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, -z]$ .

Figure 2
Packing diagram of the title compound, viewed parallel to the c axis, showing the layer at z ≃ 0.25. Dashed lines indicate C—H⋯O hydrogen bonds. Hydrogen atoms not involved in the hydrogen bonds are omitted for clarity. Atoms labels correspond to the asymmetric unit.

Figure 3
Packing diagram of the title compound, projected parallel to the a axis, showing the links between the layers of Fig. 2

. Dashed lines indicate C—H⋯O hydrogen bonds. Hydrogen atoms not involved in the hydrogen bonds are omitted for clarity.

A search employing the routine CONQUEST (Bruno et al., 2002 ), part of Version 2024.3.0 of the Cambridge Database (Groom et al., 2016 ), found only one other pyranose sugar with a dithiocarbamate substituent at the 1-position, namely 1-(N,N-diethyldithiocarbamato)-2,3,4,6-tetra-O-benzyl-β-D-glucopyranose (refcode YIYKEY; Padungros et al., 2014 ). A least-squares fit of 13 selected atoms in or near the sugar rings of both molecules (Fig. 4) was performed. In view of the markedly different protecting groups of the sugar rings, together with the opposite configurations of glucose and galactose at C4, no great similarity should be expected, but the the r.m.s. deviation of the fitted atoms is still quite low at 0.08 Å. The deviation for S2, the terminal sulfur atom of the dithiocarbamate, is appreciably higher at 0.69 Å, reflecting the slightly larger torsion angles C2—C1—S1—C15 and C1—S1—C15—S2 (162.1 and 3.0°, respectively) for YIYKEY.

Figure 4
Least-squares fit of the title compound (purple) to YIYKEY (Padungros et al., 2014

) (green; coordinates taken from the CCDC). Fitted atoms are labelled.

Synthesis and crystallization

A mixture of potassium cyanocarbonimidodithioate (0.01 mol, 1.94 g m) and 2,3,4,6-tetra-O-acetyl-β-D-galactopyranosyl bromide (0.01 mol, 4.11 g m) was reacted in dimethyl formamide (10 ml) in the presence of sodium ethoxide (0.01 mole, 0.68 g m) at room temperature for 24 h. Ice–water (10 ml) was then added and the solid product thus furnished was filtered off and recrystallized from dimethyl sulfoxide.

The title compound was obtained as a pale-yellow crystalline solid; m.p. 458–459 K; ¹H NMR (500 MHz, DMSO-d₆): δ 1.90, 1.94, 1.98, 2.09 (4 s, 12H, 4OAc), 3.29 (s, 3H, CH₃), 3.42 (s, 3H, CH₃), 3.93–3.96 (m, 2H, H-6), 4.25 (t, 1H, H-5), 5.22 (t, 1H, H-4), 5.28 (t, 1H, H-3), 5.36 (t, 1H, H-2), 5.79 (d, J = 10 Hz, 1H, H-1). Analysis calculated for C₁₇H₂₅NO₉S₂ (451.51): C 45.22, H 5.58, N 3.10; S 14.20. Found: C 45.20, H 5.56, N 3.10, S 14.18%. One large prism was cut to an irregular block for intensity measurements.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 3. Methyl groups were refined as idealized rigid groups allowed to rotate but not tip (AFIX 137), with C—H 0.98, H—C—H 109.5°. Other hydrogen atoms were included using a riding model starting from calculated positions (C—H_methine 1.00, C—H_methylene 0.99 Å). The U(H) values were fixed for methyl groups at 1.5 × U_eq, and for other H atoms at 1.2 × U_eq of the parent carbon atoms. Three badly-fitting reflections (deviations > 8σ) were omitted from the refinement. The absolute configuration was confirmed by the Flack x value of 0.001 (8).

Table 3
Experimental details

Crystal data
Chemical formula	C₁₇H₂₅NO₉S₂
M_r	451.50
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	100
a, b, c (Å)	7.28265 (10), 8.64720 (15), 34.8789 (3)
V (Å³)	2196.48 (5)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.29
Crystal size (mm)	0.22 × 0.20 × 0.15

Data collection
Diffractometer	XtaLAB Synergy
Absorption correction	Multi-scan (CrysAlis PRO; Rigaku OD, 2022 $[Rigaku OD (2022). CrysAlis PRO. Rigaku Oxford Diffraction, Yarnton, England.]$ )
T_min, T_max	0.818, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	225004, 14433, 13593
R_int	0.045
θ values (°)	θ_max = 41.4, θ_min = 2.3
(sin θ/λ)_max (Å⁻¹)	0.930

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.031, 0.083, 1.12
No. of reflections	14433
No. of parameters	268
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.56, −0.27
Absolute structure	Flack x determined using 5769 quotients [(I⁺)−(I⁻)]/[(I⁺)+(I⁻)] (Parsons et al., 2013 )
Absolute structure parameter	0.001 (8)
Computer programs: CrysAlis PRO (Rigaku OD, 2022 $[Rigaku OD (2022). CrysAlis PRO. Rigaku Oxford Diffraction, Yarnton, England.]$ ), SHELXT (Sheldrick, 2015a ), SHELXL2019/3 (Sheldrick, 2015b ), XP (Bruker, 1998 ) and publCIF (Westrip, 2010 ).

Structural data

CCDC reference: 2465327

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S2414314625005449/bt4175sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314625005449/bt4175Isup2.hkl

checkCIF report

Computing details top

2,3,4,6-Tetra-O-acetyl-1-[(dimethylcarbamothioyl)sulfanyl]-β-D-galactopyranose top

Crystal data top

C₁₇H₂₅NO₉S₂	D_x = 1.365 Mg m⁻³
M_r = 451.50	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, P2₁2₁2₁	Cell parameters from 126110 reflections
a = 7.28265 (10) Å	θ = 2.3–41.3°
b = 8.64720 (15) Å	µ = 0.29 mm⁻¹
c = 34.8789 (3) Å	T = 100 K
V = 2196.48 (5) Å³	Block, colourless
Z = 4	0.22 × 0.20 × 0.15 mm
F(000) = 952

Data collection top

XtaLAB Synergy diffractometer	14433 independent reflections
Radiation source: micro-focus sealed X-ray tube, PhotonJet (Mo) X-ray Source	13593 reflections with I > 2σ(I)
Mirror monochromator	R_int = 0.045
Detector resolution: 10.0000 pixels mm^-1	θ_max = 41.4°, θ_min = 2.3°
ω scans	h = −13→13
Absorption correction: multi-scan (CrysAlisPro; Rigaku OD, 2022)	k = −15→15
T_min = 0.818, T_max = 1.000	l = −63→63
225004 measured reflections

Refinement top

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.031	w = 1/[σ²(F_o²) + (0.0464P)² + 0.1937P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.083	(Δ/σ)_max = 0.010
S = 1.12	Δρ_max = 0.56 e Å⁻³
14433 reflections	Δρ_min = −0.27 e Å⁻³
268 parameters	Absolute structure: Flack x determined using 5769 quotients [(I⁺)-(I^-)]/[(I⁺)+(I^-)] (Parsons et al., 2013)
0 restraints	Absolute structure parameter: 0.001 (8)
Primary atom site location: dual

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
C1	0.22016 (11)	0.52540 (10)	0.14258 (2)	0.01348 (11)
H1	0.301124	0.432274	0.144357	0.016*
C2	0.20058 (11)	0.57372 (9)	0.10035 (2)	0.01244 (11)
H2	0.119080	0.666256	0.097869	0.015*
C3	0.39260 (11)	0.60872 (9)	0.08518 (2)	0.01229 (11)
H3	0.466514	0.511270	0.084781	0.015*
C4	0.48993 (11)	0.72864 (9)	0.10985 (2)	0.01316 (10)
H4	0.620302	0.739994	0.101305	0.016*
C5	0.48404 (12)	0.67805 (10)	0.15167 (2)	0.01507 (12)
H5	0.557771	0.581254	0.154690	0.018*
C6	0.55721 (13)	0.80002 (13)	0.17912 (3)	0.02065 (15)
H6A	0.482407	0.895388	0.177473	0.025*
H6B	0.553206	0.761446	0.205830	0.025*
C7	−0.05084 (12)	0.44818 (10)	0.06923 (3)	0.01588 (12)
C8	−0.10298 (17)	0.30603 (14)	0.04748 (4)	0.0290 (2)
H8A	−0.004042	0.278698	0.029677	0.044*
H8B	−0.216034	0.325520	0.033023	0.044*
H8C	−0.123073	0.220596	0.065454	0.044*
C9	0.44387 (13)	0.57971 (13)	0.01780 (3)	0.02005 (15)
C10	0.4443 (2)	0.6688 (2)	−0.01898 (3)	0.0349 (3)
H10A	0.318449	0.699657	−0.025372	0.052*
H10B	0.493721	0.603806	−0.039557	0.052*
H10C	0.520872	0.761240	−0.016113	0.052*
C11	0.48662 (15)	0.99031 (11)	0.08844 (4)	0.02412 (18)
C12	0.3713 (2)	1.13341 (14)	0.08674 (6)	0.0395 (4)
H12A	0.250639	1.108055	0.075993	0.059*
H12B	0.431714	1.210509	0.070465	0.059*
H12C	0.355954	1.175358	0.112643	0.059*
C13	0.79252 (16)	0.97920 (15)	0.16185 (5)	0.0314 (2)
C14	0.98327 (19)	0.9884 (2)	0.14586 (6)	0.0408 (3)
H14A	1.061908	0.913046	0.158930	0.061*
H14B	1.032239	1.092733	0.149860	0.061*
H14C	0.980359	0.965477	0.118356	0.061*
O1	0.29972 (9)	0.64895 (8)	0.16373 (2)	0.01595 (10)
O2	0.13054 (9)	0.44673 (7)	0.07833 (2)	0.01412 (9)
O3	0.38060 (11)	0.67005 (8)	0.04701 (2)	0.01719 (11)
O4	0.39544 (9)	0.87439 (7)	0.10612 (2)	0.01611 (10)
O6	0.74333 (11)	0.83094 (10)	0.16784 (3)	0.02342 (14)
O7	−0.15325 (10)	0.55175 (9)	0.07833 (3)	0.02197 (13)
O8	0.49188 (14)	0.44747 (11)	0.02195 (2)	0.02792 (16)
O9	0.64113 (15)	0.97836 (12)	0.07640 (4)	0.0420 (3)
O10	0.69249 (18)	1.08682 (14)	0.16806 (6)	0.0599 (5)
S1	−0.00073 (3)	0.48124 (3)	0.16268 (2)	0.01509 (4)
S2	0.26816 (3)	0.27711 (4)	0.20661 (2)	0.02352 (5)
C15	0.05929 (12)	0.35345 (11)	0.20097 (2)	0.01559 (12)
N1	−0.08300 (11)	0.32376 (11)	0.22384 (2)	0.01961 (13)
C16	−0.26558 (14)	0.39147 (15)	0.21834 (3)	0.02370 (18)
H16A	−0.254152	0.503647	0.215141	0.036*
H16B	−0.342140	0.369253	0.240783	0.036*
H16C	−0.322539	0.346774	0.195424	0.036*
C17	−0.06368 (18)	0.2123 (2)	0.25515 (4)	0.0335 (3)
H17A	−0.028969	0.111306	0.244663	0.050*
H17B	−0.180709	0.203067	0.268826	0.050*
H17C	0.031589	0.247892	0.272924	0.050*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0139 (3)	0.0139 (3)	0.0126 (2)	−0.0006 (2)	0.0018 (2)	0.0012 (2)
C2	0.0134 (3)	0.0111 (3)	0.0128 (3)	0.0005 (2)	0.0010 (2)	0.0000 (2)
C3	0.0142 (3)	0.0114 (3)	0.0112 (2)	0.0007 (2)	0.0021 (2)	0.00144 (19)
C4	0.0124 (2)	0.0112 (2)	0.0159 (3)	0.0009 (2)	0.0020 (2)	−0.0005 (2)
C5	0.0137 (3)	0.0170 (3)	0.0146 (3)	0.0001 (2)	0.0002 (2)	−0.0010 (2)
C6	0.0169 (3)	0.0255 (4)	0.0195 (3)	−0.0028 (3)	−0.0002 (3)	−0.0068 (3)
C7	0.0145 (3)	0.0150 (3)	0.0181 (3)	0.0008 (2)	−0.0015 (2)	−0.0009 (2)
C8	0.0228 (4)	0.0222 (4)	0.0421 (6)	0.0004 (3)	−0.0091 (4)	−0.0124 (4)
C9	0.0173 (3)	0.0306 (4)	0.0123 (3)	−0.0039 (3)	0.0002 (2)	−0.0016 (3)
C10	0.0389 (6)	0.0525 (8)	0.0134 (3)	−0.0133 (6)	−0.0001 (4)	0.0069 (4)
C11	0.0218 (4)	0.0125 (3)	0.0380 (5)	0.0005 (3)	0.0094 (4)	0.0044 (3)
C12	0.0348 (6)	0.0154 (4)	0.0684 (10)	0.0063 (4)	0.0162 (7)	0.0115 (5)
C13	0.0208 (4)	0.0259 (5)	0.0474 (7)	−0.0059 (3)	0.0048 (4)	−0.0147 (5)
C14	0.0215 (5)	0.0388 (7)	0.0620 (10)	−0.0095 (5)	0.0094 (5)	−0.0147 (6)
O1	0.0155 (2)	0.0186 (3)	0.0138 (2)	−0.00277 (19)	0.00266 (18)	−0.0023 (2)
O2	0.0133 (2)	0.0123 (2)	0.0167 (2)	0.00077 (17)	−0.00018 (18)	−0.00223 (18)
O3	0.0224 (3)	0.0169 (2)	0.0123 (2)	−0.0007 (2)	0.00171 (19)	0.00366 (19)
O4	0.0152 (2)	0.0107 (2)	0.0225 (3)	0.00143 (18)	0.0041 (2)	0.00108 (19)
O6	0.0152 (3)	0.0243 (3)	0.0308 (4)	−0.0012 (2)	−0.0009 (2)	−0.0068 (3)
O7	0.0162 (3)	0.0204 (3)	0.0294 (3)	0.0049 (2)	−0.0024 (2)	−0.0041 (3)
O8	0.0306 (4)	0.0338 (4)	0.0194 (3)	0.0082 (3)	−0.0021 (3)	−0.0102 (3)
O9	0.0289 (4)	0.0214 (3)	0.0756 (8)	0.0018 (3)	0.0261 (5)	0.0143 (5)
O10	0.0344 (5)	0.0249 (5)	0.1202 (15)	−0.0055 (4)	0.0250 (7)	−0.0233 (7)
S1	0.01293 (7)	0.01785 (8)	0.01451 (7)	0.00059 (6)	0.00218 (6)	0.00388 (6)
S2	0.01376 (8)	0.03284 (13)	0.02396 (10)	0.00211 (8)	−0.00070 (7)	0.01238 (9)
C15	0.0137 (3)	0.0196 (3)	0.0136 (3)	−0.0015 (2)	−0.0003 (2)	0.0036 (2)
N1	0.0150 (3)	0.0284 (4)	0.0154 (3)	−0.0016 (3)	0.0019 (2)	0.0076 (3)
C16	0.0145 (3)	0.0331 (5)	0.0235 (4)	0.0011 (3)	0.0047 (3)	0.0061 (3)
C17	0.0257 (5)	0.0479 (7)	0.0270 (5)	−0.0008 (5)	0.0029 (4)	0.0226 (5)

Geometric parameters (Å, º) top

C1—O1	1.4216 (11)	N1—C17	1.4631 (14)
C1—C2	1.5378 (11)	N1—C16	1.4655 (13)
C1—S1	1.7959 (8)	C1—H1	1.0000
C2—O2	1.4339 (10)	C2—H2	1.0000
C2—C3	1.5255 (11)	C3—H3	1.0000
C3—O3	1.4358 (10)	C4—H4	1.0000
C3—C4	1.5226 (11)	C5—H5	1.0000
C4—O4	1.4419 (10)	C6—H6A	0.9900
C4—C5	1.5234 (11)	C6—H6B	0.9900
C5—O1	1.4290 (11)	C8—H8A	0.9800
C5—C6	1.5209 (12)	C8—H8B	0.9800
C6—O6	1.4365 (13)	C8—H8C	0.9800
C7—O7	1.2079 (11)	C10—H10A	0.9800
C7—O2	1.3585 (11)	C10—H10B	0.9800
C7—C8	1.4936 (14)	C10—H10C	0.9800
C9—O8	1.2045 (15)	C12—H12A	0.9800
C9—O3	1.3639 (12)	C12—H12B	0.9800
C9—C10	1.4966 (15)	C12—H12C	0.9800
C11—O9	1.2055 (14)	C14—H14A	0.9800
C11—O4	1.3513 (12)	C14—H14B	0.9800
C11—C12	1.4968 (16)	C14—H14C	0.9800
C13—O10	1.2015 (18)	C16—H16A	0.9800
C13—O6	1.3475 (16)	C16—H16B	0.9800
C13—C14	1.4989 (18)	C16—H16C	0.9800
S1—C15	1.7877 (9)	C17—H17A	0.9800
S2—C15	1.6698 (9)	C17—H17B	0.9800
C15—N1	1.3327 (12)	C17—H17C	0.9800

O1—C1—C2	109.30 (7)	C2—C3—H3	109.3
O1—C1—S1	108.81 (5)	O4—C4—H4	109.9
C2—C1—S1	110.40 (6)	C3—C4—H4	109.9
O2—C2—C3	106.99 (6)	C5—C4—H4	109.9
O2—C2—C1	109.76 (6)	O1—C5—H5	109.0
C3—C2—C1	107.53 (6)	C6—C5—H5	109.0
O3—C3—C4	107.51 (6)	C4—C5—H5	109.0
O3—C3—C2	109.82 (7)	O6—C6—H6A	110.4
C4—C3—C2	111.46 (6)	C5—C6—H6A	110.4
O4—C4—C3	108.79 (7)	O6—C6—H6B	110.4
O4—C4—C5	108.90 (6)	C5—C6—H6B	110.4
C3—C4—C5	109.42 (6)	H6A—C6—H6B	108.6
O1—C5—C6	105.43 (7)	C7—C8—H8A	109.5
O1—C5—C4	111.03 (7)	C7—C8—H8B	109.5
C6—C5—C4	113.18 (7)	H8A—C8—H8B	109.5
O6—C6—C5	106.69 (8)	C7—C8—H8C	109.5
O7—C7—O2	123.08 (8)	H8A—C8—H8C	109.5
O7—C7—C8	125.92 (9)	H8B—C8—H8C	109.5
O2—C7—C8	110.99 (8)	C9—C10—H10A	109.5
O8—C9—O3	123.52 (9)	C9—C10—H10B	109.5
O8—C9—C10	126.22 (11)	H10A—C10—H10B	109.5
O3—C9—C10	110.25 (11)	C9—C10—H10C	109.5
O9—C11—O4	123.65 (10)	H10A—C10—H10C	109.5
O9—C11—C12	125.51 (10)	H10B—C10—H10C	109.5
O4—C11—C12	110.83 (9)	C11—C12—H12A	109.5
O10—C13—O6	123.22 (12)	C11—C12—H12B	109.5
O10—C13—C14	126.00 (14)	H12A—C12—H12B	109.5
O6—C13—C14	110.77 (11)	C11—C12—H12C	109.5
C1—O1—C5	111.25 (6)	H12A—C12—H12C	109.5
C7—O2—C2	117.64 (7)	H12B—C12—H12C	109.5
C9—O3—C3	117.41 (7)	C13—C14—H14A	109.5
C11—O4—C4	117.07 (7)	C13—C14—H14B	109.5
C13—O6—C6	118.06 (9)	H14A—C14—H14B	109.5
C15—S1—C1	101.77 (4)	C13—C14—H14C	109.5
N1—C15—S2	124.18 (7)	H14A—C14—H14C	109.5
N1—C15—S1	112.09 (7)	H14B—C14—H14C	109.5
S2—C15—S1	123.71 (5)	N1—C16—H16A	109.5
C15—N1—C17	119.92 (9)	N1—C16—H16B	109.5
C15—N1—C16	123.38 (8)	H16A—C16—H16B	109.5
C17—N1—C16	116.62 (8)	N1—C16—H16C	109.5
O1—C1—H1	109.4	H16A—C16—H16C	109.5
C2—C1—H1	109.4	H16B—C16—H16C	109.5
S1—C1—H1	109.4	N1—C17—H17A	109.5
O2—C2—H2	110.8	N1—C17—H17B	109.5
C3—C2—H2	110.8	H17A—C17—H17B	109.5
C1—C2—H2	110.8	N1—C17—H17C	109.5
O3—C3—H3	109.3	H17A—C17—H17C	109.5
C4—C3—H3	109.3	H17B—C17—H17C	109.5

O1—C1—C2—O2	176.61 (6)	C8—C7—O2—C2	−178.12 (9)
S1—C1—C2—O2	−63.74 (7)	C3—C2—O2—C7	−142.58 (7)
O1—C1—C2—C3	60.57 (8)	C1—C2—O2—C7	101.04 (8)
S1—C1—C2—C3	−179.78 (5)	O8—C9—O3—C3	7.42 (14)
O2—C2—C3—O3	68.17 (8)	C10—C9—O3—C3	−172.48 (9)
C1—C2—C3—O3	−173.98 (6)	C4—C3—O3—C9	127.59 (8)
O2—C2—C3—C4	−172.80 (6)	C2—C3—O3—C9	−110.98 (8)
C1—C2—C3—C4	−54.95 (8)	O9—C11—O4—C4	−1.10 (18)
O3—C3—C4—O4	53.85 (8)	C12—C11—O4—C4	179.96 (11)
C2—C3—C4—O4	−66.55 (8)	C3—C4—O4—C11	−113.01 (9)
O3—C3—C4—C5	172.72 (7)	C5—C4—O4—C11	127.80 (9)
C2—C3—C4—C5	52.32 (8)	O10—C13—O6—C6	5.4 (2)
O4—C4—C5—O1	64.22 (9)	C14—C13—O6—C6	−173.27 (11)
C3—C4—C5—O1	−54.58 (9)	C5—C6—O6—C13	127.99 (11)
O4—C4—C5—C6	−54.12 (9)	O1—C1—S1—C15	−84.52 (6)
C3—C4—C5—C6	−172.92 (7)	C2—C1—S1—C15	155.53 (6)
O1—C5—C6—O6	179.61 (8)	C1—S1—C15—N1	170.41 (7)
C4—C5—C6—O6	−58.86 (10)	C1—S1—C15—S2	−11.04 (7)
C2—C1—O1—C5	−65.67 (8)	S2—C15—N1—C17	−3.08 (15)
S1—C1—O1—C5	173.70 (6)	S1—C15—N1—C17	175.46 (10)
C6—C5—O1—C1	−174.41 (7)	S2—C15—N1—C16	−179.75 (9)
C4—C5—O1—C1	62.66 (9)	S1—C15—N1—C16	−1.21 (13)
O7—C7—O2—C2	1.12 (13)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4···O7ⁱ	1.00	2.45	3.2096 (11)	132
C8—H8B···O8ⁱⁱ	0.98	2.41	3.3157 (15)	154
C16—H16C···O10ⁱⁱⁱ	0.98	2.44	3.1795 (18)	132
C17—H17B···O1^iv	0.98	2.55	3.3558 (13)	139
C1—H1···S2	1.00	2.56	3.1175 (8)	115
C8—H8A···O8^v	0.98	2.66	3.3384 (15)	127

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

Acknowledgements

The authors acknowledge support by the Open Access Publication Funds of the Technical University of Braunschweig.

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