Syntheses, crystal structures and Hirshfeld surface analyses of N-aryl­sulfonyl derivatives of cytisine

Okmanov, R.Y.; Olimova, M.I.; Karabaeva, S.B.; Sapaev, F.A.; Abdireymov, K.B.

doi:10.1107/S2056989023001950

research communications

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 79| Part 4| April 2023| Pages 313-318

https://doi.org/10.1107/S2056989023001950

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Syntheses, crystal structures and Hirshfeld surface analyses of N-arylsulfonyl derivatives of cytisine

Rasul Ya. Okmanov,^a,^b ^* Manzura I. Olimova,^a Surayyo B. Karabaeva,^b Frunza A. Sapaev ^b and Kudaybergen B. Abdireymov ^c

^aS. Yunusov Institute of the Chemistry of Plant Substances, Academy of Sciences of Uzbekistan, Mirzo Ulugbek Str. 77, Tashkent, 100170, Uzbekistan, ^bNational University of Uzbekistan named after Mirzo Ulugbek, massif Universitet shakharchasi 4, Tashkent, 100174, Uzbekistan, and ^cKara-Kalpak State University, acad. Abdirov Str., 1, Nukus, 742000, Uzbekistan
^*Correspondence e-mail: raxul@mail.ru

Edited by M. Weil, Vienna University of Technology, Austria (Received 8 February 2023; accepted 2 March 2023; online 10 March 2023)

By arylsulfonylation of cytisine in the presence of triethylamine, three new compounds have been obtained in good yields: (7R,9R)-N-[(4-ethylphenyl)sulfonyl]cytisine, C₁₉H₂₂N₂O₃S (I) {systematic name: (1R,5R)-3-[(4-ethylphenyl)sulfonyl]-1,2,3,4,5,6-hexahydro-8H-1,5-methanopyrido[1,2-a][1,5]diazocin-8-one}, (7R,9R)-N-[(4-chlorophenyl)sulfonyl]cytisine, C₁₇H₁₇ClN₂O₃S (II) {systematic name: (1R,5R)-3-[(4-chlorophenyl)sulfonyl]-1,2,3,4,5,6-hexahydro-8H-1,5-methanopyrido[1,2-a][1,5]diazocin-8-one} and (7R,9R)-N-[(3-nitrophenyl)sulfonyl]cytisine, C₁₇H₁₇N₃O₅S (III) {systematic name: (1R,5R)-3-[(3-nitrophenyl)sulfonyl]-1,2,3,4,5,6-hexahydro-8H-1,5-methanopyrido[1,2-a][1,5]diazocin-8-one}. The crystal structures of the compounds were determined on the basis of single-crystal X-ray diffraction data. The crystal structures of (I)–(III) are distinguished by the arrangement of two fragments of the molecule around the sulfonyl site. For all structures, weak C—H⋯O hydrogen bonds are developed. Hirshfeld surface analysis shows that H⋯H (for I and II) and H⋯O/O⋯H (for III) interactions make the most important contribution to the crystal packing.

Keywords: alkaloid; cytisine; arylsulfonylation; synthesis; crystal structure; Hirshfeld surface analysis.

CCDC references: 2245793; 2245792; 2245791

1. Chemical context

Cytisine was first isolated by Huzeman and Marme from the seeds of Cytisus Laburnum Med. in 1865. To this day, other sources of cytisine have been found (Azimova & Yunusov, 2013 ), mainly isolated from plants of the legume family (especially the seeds of Laburnum anagyroides). Cytisine is a quinolizidine alkaloid, which is found in different sources by different names: 1,2,3,4,5,6-hexahydro-1,5-methano-8H-pyrido(1,2-a)(1,5)-diazocin-8-one (Freer et al., 1987 ), 7,11-diazatricyclo[7.3.1.0^2,7]trideca-2,4-dien-6-one (Kulakov et al., 2010 ), (1R,5S)-cytisine (Rouden et al., 2014 ) or (7R,9S)-cytisine.

Various studies report modern methods for the synthesis of cytisine (Barát et al., 2018 ; Hirschhäuser et al., 2011 ; O'Neill et al., 2000 ; Pérez et al., 2012 ) or cytisine modification (Brel, 2016 ; Kulakov et al., 2010; Kulakov & Nurkenov, 2012 ; Shishkin et al., 2010 ; Marrière et al., 2000 ; Frasinyuk et al., 2007 ). From the large number of cytisine derivatives, substances with biological activity (Tutka et al., 2019 ; Gotti & Clementi, 2021 ; Liu et al., 2020 ) and agents used in medicine (Tabex) have been found. From a chemical point of view, derivation studies of cytisine as well as the development of new methods for the synthesis of various cytisine derivatives are of interest.

This communication describes the synthesis and crystal structures of three N-arylsulfonyl derivatives of cytisine. To obtain these N-arylsulfonyl derivatives, 4-ethylbenzenesulfonyl chloride, 4-chlorobenzenesulfonyl chloride and 3-nitrobenzenesulfonyl chloride were used, resulting in (7R,9R)-N-[(4-ethylphenyl)sulfonyl]cytisine (I), (7R,9R)-N-[(4-chlorophenyl)sulfonyl]cytisine (II) and (7R,9R)-N-[(3-nitrophenyl)sulfonyl]cytisine (III).

2. Structural commentary

The conformations of the cytisine cores in structures (I)–(III) are virtually identical and also do not differ from that of the cytisine molecule itself (Freer et al., 1987), or its various N-derivatives. The configurations of the chiral C atoms in cytisine are 7R, 9S, whereas in the case of (I)–(III) obtained by arylsulfonation of cytisine, the configurations are 7R, 9R in each case.

The asymmetric unit of (I) consists of one molecule of (7R,9R)-N-[(4-ethylphenyl)sulfonyl]cytisine (Fig. 1). The methyl fragment (C8′A, C8′B) of the ethyl group bound to the phenyl ring is disordered over two sets of sites. In the crystal structures of (II) and (III), both asymmetric units likewise comprise one molecule of (7R,9R)-N-[(4-chlorophenyl)sulfonyl]cytisine and (7R,9R)-N-[(3-nitrophenyl)sulfonyl]cytisine, respectively (Figs. 2, 3). The cytisine moieties in (I)–(III) are almost superimposable in the three molecules (Fig. 4). Basically, the difference in the molecular structures pertains to the arrangement of two fragments around the sulfonyl site, i.e. the arrangement of fragments along the S1—N12 and S1—C1′ bonds). Corresponding torsion angles C1′—S1—N12—C11 and N12—S1—C1′—C2′ are listed in Tables 1, 2 and 3.

Table 1
Selected torsion angles (°) for (I)

C1′—S1—N12—C11	76.6 (2)	N12—S1—C1′—C2′	−79.4 (2)

Table 2
Selected torsion angles (°) for (II)

C1′—S1—N12—C11	72.1 (2)	N12—S1—C1′—C2′	−79.4 (2)

Table 3
Selected torsion angles (°) for (III)

C1′—S1—N12—C11	57.3 (3)	N12—S1—C1′—C2′	−87.9 (3)

Figure 1
The asymmetric unit of (I) with atom labelling. Displacement ellipsoids represent 30% probability levels.

Figure 2
The asymmetric unit of (II) with atom labelling. Displacement ellipsoids represent 30% probability levels.

Figure 3
The asymmetric unit of (III) with atom labelling. Displacement ellipsoids represent 30% probability levels.

Figure 4
Overlay plot of the molecules in the crystal structures of (I)–(III).

3. Supramolecular features

In the crystal packing of (I)–(III), weak intermolecular hydrogen bonds of the type C—H⋯O(C) are developed. In the crystal structures of (I) and (II), C—H⋯O1 hydrogen bonds link molecules into chains directed parallel to [100] (Figs. 5, 6), besides other C—H⋯O or C—H⋯Cl (in the case of II) interactions (Tables 4, 5). In the crystal structure of (III), the C—H⋯O1 interactions link the molecules into a chain running along [1 $[\overline{1}]$ 0] (Fig. 7, Table 6).

Table 4
Hydrogen-bond geometry (Å, °) for (I)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C5—H5A⋯O1ⁱ	0.93	2.34	3.116 (3)	141
C7—H7A⋯O2ⁱⁱ	0.98	2.44	3.254 (3)	140
Symmetry codes: (i) x+1, y, z; (ii) $[-x+2, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Table 5
Hydrogen-bond geometry (Å, °) for (II)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C5—H5A⋯O1ⁱ	0.93	2.61	3.375 (4)	140
C13—H13B⋯O1ⁱ	0.97	2.69	3.475 (3)	139
C5′—H5′A⋯O3ⁱ	0.93	2.42	3.198 (3)	142
C8—H8A⋯O3ⁱⁱ	0.97	2.56	3.424 (3)	149
C4—H4A⋯Cl1ⁱⁱⁱ	0.93	2.94	3.764 (3)	148
Symmetry codes: (i) ; (ii) $[-x+1, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iii) $[-x, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Table 6
Hydrogen-bond geometry (Å, °) for (III)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C4′—H4′A⋯O1ⁱ	0.93	2.61	3.257 (5)	127
C10—H10A⋯O5ⁱⁱ	0.97	2.58	3.460 (6)	151
C11—H11A⋯O5ⁱⁱⁱ	0.97	2.55	3.428 (7)	150
C13—H13A⋯O3^iv	0.97	2.46	3.330 (4)	150
Symmetry codes: (i) ; (ii) x+1, y, z; (iii) $[-x, y-{\script{1\over 2}}, -z+2]$ ; (iv) x, y+1, z.

Figure 5
The observed C5—H⋯O1 hydrogen bond in the crystal structure of (I). For clarity, the disordered methyl fragment is not shown.

Figure 6
The observed hydrogen bonds (C5—H⋯O1, C13—H⋯O1, C5′—H⋯O3) in the crystal structure of (II).

Figure 7
The observed hydrogen bonds (C4′—H⋯O1) in the crystal structure of (III).

In order to visualize and quantify intermolecular interactions in (I)–(III), a Hirshfeld surface analysis (Spackman & Jayatilaka, 2009 ) was performed with Crystal Explorer 21 (Spackman et al., 2021 ), and the associated two-dimensional fingerprint plots (McKinnon et al., 2007 ) generated.

The Hirshfeld surfaces for the molecules in (I)–(III) are shown in Figs. 8–10 in which the two-dimensional fingerprint plots of the most dominant contacts are also presented.

Figure 8
Three-dimensional Hirshfeld surfaces of the compound (I) plotted over d_norm in the range −0.2931 to 1.5624 a.u., and Hirshfeld fingerprint plots for all contacts and decomposed into H⋯H, H⋯O/O⋯H and H⋯C/C⋯H contacts. d_i and d_e denote the closest internal and external distances (in Å) from a point on the surface.

Figure 9
Three-dimensional Hirshfeld surfaces of the compound (II) plotted over d_norm in the range −0.2332 to 1.6350 a.u., and Hirshfeld fingerprint plots for all contacts and decomposed into H⋯H, H⋯O/O⋯H, H⋯C/C⋯H and H⋯Cl/Cl⋯H contacts. d_i and d_e denote the closest internal and external distances (in Å) from a point on the surface.

Figure 10
Three-dimensional Hirshfeld surfaces of the compound (III) plotted over d_norm in the range −0.1815 to 1.3331 a.u., and Hirshfeld fingerprint plots for all contacts and decomposed into H⋯O/O⋯H, H⋯H and H⋯C/C⋯H contacts. d_i and d_e denote the closest internal and external distances (in Å) from a point on the surface.

For structure (I), H⋯H contacts are responsible for the largest contribution (54.9%) to the Hirshfeld surface. Besides these contacts, H⋯O/O⋯H (26.2%) and H⋯C/C⋯H (16.7%) interactions contribute significantly to the total Hirshfeld surface (Fig. 8). The contributions of further contacts are only minor and amount to H⋯N/N⋯H (1.8%), C⋯C (0.2%) and H⋯S/S⋯H (0.1%).

In structure (II), the contribution percentages of the most significant contacts change because of the presence of H⋯Cl/Cl⋯H interactions and amount to H⋯H (38.9%), H⋯O/O⋯H (25.4%), H⋯C/C⋯H (16.7%) and H⋯Cl/Cl⋯H (10.9%) (Fig. 9). The contributions of further contacts are only minor and are Cl⋯O/O⋯Cl (2.4%), Cl⋯C/C⋯Cl (1.8%), C⋯O/O⋯C (1.7%), H⋯N/N⋯H (1.6%), C⋯C (0.3%) and Cl⋯S/S⋯Cl (0.1%).

In structure (III), the existence of a nitro group likewise changes the contributions of the significant interactions: H⋯O/O⋯H (44.3%), H⋯H (33.3%) and H⋯C/C⋯H (10.2%) (Fig. 10). Other minor contributions amount to C⋯C (3.8%), C⋯O/O⋯C (3.2%), H⋯N/N⋯H (2.5%), O⋯N/N⋯O (1.3%), O⋯O (1.2%) and C⋯N/N⋯C (0.2%).

4. Database survey

A Cambridge Structural Database search (version 2022.3.0; Groom et al., 2016 ) revealed 99 N-derivatives of cytisine, of which twelve are N-benzyl derivatives of cytisine. N-arylsulfonylcytisine derivatives are not found. The most similar structure with respect to (I)–(III) is 3-[(4-bromophenyl)methyl]-8-oxo-1,3,4,5,6,8-hexahydro-2H-1,5-methanopyrido[1,2-a][1,5]diazocin-3-ium perchlorate (KINBOB; Przybył et al., 2019 ).

5. Synthesis and crystallization

General method

Arylsulfonyl chloride (0.01 mol) and 10 ml of acetone were placed in a two-necked flask with a volume of 50 ml. After cooling, a previously prepared solution (1.9 g (0.01 mol) of cytisine and 0.01 mol of triethylamine in 15 ml of acetone) was added under stirring through a separatory funnel. The reaction mixture was stirred at room temperature for 10 h. The reaction mixture was then left in the open air overnight to produce a dry mass. The mass was treated with 15 ml of distilled water and the remaining solid filtered off and dried in air. The reaction scheme is shown in Fig. 11.

Figure 11
General reaction scheme for the synthesis of N-arylsulfonyl derivatives of cytisine.

(7R,9R)-N-[(4-ethylphenyl)sulfonyl]cytisine (I)

Yield 64% (2.29 g), m.p. 456–458 K, R_f = 0.59 [5:1 (v/v) benzene–ethanol].

(7R,9R)-N-[(4-chlorophenyl)sulfonyl]cytisine (II)

Yield 76% (2.77 g), m.p. 488–490 K, R_f = 0.71 [5:1 (v/v) benzene–ethanol].

(7R,9R)-N-[(3-nitrophenyl)sulfonyl]cytisine (III)

Yield 72% (2.71 g), m.p. 524–526 K, R_f = 0.50 [5:1 (v/v) benzene–ethanol].

Colourless crystals of (I)–(III) suitable for X-ray analysis were obtained by slow evaporation of an ethanol solution.

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 7. In (I), the methyl C8′ atom is disordered over two positions (C8′A, C8′B). The site occupancy factors of the disordered fragment were refined with a free variable to a ratio of 0.55 (2):0.45 (2). Hydrogen atoms bonded to C atoms were placed geometrically (with C—H distances of 0.98 Å for CH, 0.97 Å for CH₂, 0.96 Å for CH₃ and 0.93 Å for C_ar) and included in the refinement in a riding motion approximation with U_iso(H) = 1.2U_eq(C) or U_iso = 1.5U_eq(C) for methyl H atoms.

Table 7
Experimental details

	(I)	(II)	(III)
Crystal data
Chemical formula	C₁₉H₂₂N₂O₃S	C₁₇H₁₇ClN₂O₃S	C₁₇H₁₇N₃O₅S
M_r	358.44	364.83	375.39
Crystal system, space group	Orthorhombic, P2₁2₁2₁	Orthorhombic, P2₁2₁2₁	Monoclinic, P2₁
Temperature (K)	299	299	296
a, b, c (Å)	6.9503 (14), 10.585 (2), 24.975 (5)	7.1374 (14), 11.448 (2), 20.844 (4)	11.040 (2), 6.2621 (13), 12.424 (3)
α, β, γ (°)	90, 90, 90	90, 90, 90	90, 94.03 (3), 90
V (Å³)	1837.5 (6)	1703.2 (6)	856.8 (3)
Z	4	4	2
Radiation type	Cu Kα	Cu Kα	Cu Kα
μ (mm⁻¹)	1.73	3.29	2.00
Crystal size (mm)	0.25 × 0.20 × 0.10	0.30 × 0.20 × 0.15	0.20 × 0.15 × 0.10

Data collection
Diffractometer	XtaLAB Synergy, Single source at home/near, HyPix3000	XtaLAB Synergy, Single source at home/near, HyPix3000	XtaLAB Synergy, Single source at home/near, HyPix3000
Absorption correction	Multi-scan (SADABS; Krause et al., 2015 )	Multi-scan (SADABS; Krause et al., 2015)	Multi-scan (SADABS; Krause et al., 2015)
T_min, T_max	0.032, 1.000	0.795, 1.000	0.639, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	17786, 3553, 3348	16028, 3289, 3203	7776, 2446, 2363
R_int	0.054	0.027	0.023
(sin θ/λ)_max (Å⁻¹)	0.615	0.615	0.615

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.038, 0.094, 1.11	0.030, 0.078, 1.05	0.039, 0.114, 1.04
No. of reflections	3553	3289	2446
No. of parameters	238	217	235
No. of restraints	0	0	1
H-atom treatment	H-atom parameters constrained	H-atom parameters constrained	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.22, −0.44	0.42, −0.33	0.47, −0.22
Absolute structure	Flack x determined using 1319 quotients [(I⁺)−(I⁻)]/[(I⁺)+(I⁻)] (Parsons et al., 2013 )	Flack x determined using 1318 quotients [(I⁺)−(I⁻)]/[(I⁺)+(I⁻)] (Parsons et al., 2013)	Flack x determined using 579 quotients [(I⁺)−(I⁻)]/[(I⁺)+(I⁻)] (Parsons et al., 2013)
Absolute structure parameter	0.012 (9)	−0.004 (5)	0.017 (16)
Computer programs: CrysAlis PRO (Rigaku OD, 2021 $[Rigaku OD (2021). CrysAlis PRO. Rigaku Oxford Diffraction, Yarnton, England.]$ ), SHELXS7 (Sheldrick, 2008 ), SHELXL2018/3 (Sheldrick, 2015 ), XP in SHELXTL (Sheldrick, 2008), Mercury (Macrae et al., 2020 ), PLATON (Spek, 2020 ) and publCIF (Westrip, 2010 ).

Supporting information

CCDC references: 2245793; 2245792; 2245791

Crystal structure: contains datablocks I, II, III, Global. DOI: https://doi.org/10.1107/S2056989023001950/wm5674sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989023001950/wm5674Isup2.hkl

Structure factors: contains datablock II. DOI: https://doi.org/10.1107/S2056989023001950/wm5674IIsup3.hkl

Structure factors: contains datablock III. DOI: https://doi.org/10.1107/S2056989023001950/wm5674IIIsup4.hkl

checkCIF report

Computing details top

For all structures, data collection: CrysAlis PRO (Rigaku OD, 2021); cell refinement: CrysAlis PRO (Rigaku OD, 2021); data reduction: CrysAlis PRO (Rigaku OD, 2021); program(s) used to solve structure: SHELXS7 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2018/3 (Sheldrick, 2015); molecular graphics: XP in SHELXTL (Sheldrick, 2008) and Mercury (Macrae et al., 2020); software used to prepare material for publication: SHELXTL (Sheldrick, 2015), PLATON (Spek, 2020) and publCIF (Westrip, 2010).

(1R,5R)-3-[(4-Ethylphenyl)sulfonyl]-1,2,3,4,5,6-hexahydro-8H-1,5-methanopyrido[1,2-a][1,5]diazocin-8-one (I) top

Crystal data top

C₁₉H₂₂N₂O₃S	D_x = 1.296 Mg m⁻³
M_r = 358.44	Cu Kα radiation, λ = 1.54184 Å
Orthorhombic, P2₁2₁2₁	Cell parameters from 10591 reflections
a = 6.9503 (14) Å	θ = 3.5–70.9°
b = 10.585 (2) Å	µ = 1.73 mm⁻¹
c = 24.975 (5) Å	T = 299 K
V = 1837.5 (6) Å³	Prizmatic, colorless
Z = 4	0.25 × 0.20 × 0.10 mm
F(000) = 760

Data collection top

XtaLAB Synergy, Single source at home/near, HyPix3000 diffractometer	3553 independent reflections
Radiation source: micro-focus sealed X-ray tube, PhotonJet (Cu) X-ray Source	3348 reflections with I > 2σ(I)
Detector resolution: 10.0000 pixels mm^-1	R_int = 0.054
ω scans	θ_max = 71.4°, θ_min = 3.5°
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	h = −8→8
T_min = 0.032, T_max = 1.000	k = −12→13
17786 measured reflections	l = −23→30

Refinement top

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.038	w = 1/[σ²(F_o²) + (0.0523P)² + 0.0534P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.094	(Δ/σ)_max < 0.001
S = 1.11	Δρ_max = 0.22 e Å⁻³
3553 reflections	Δρ_min = −0.44 e Å⁻³
238 parameters	Absolute structure: Flack x determined using 1319 quotients [(I⁺)-(I^-)]/[(I⁺)+(I^-)] (Parsons et al., 2013)
0 restraints	Absolute structure parameter: 0.012 (9)

Special details top

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.

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
S1	0.72079 (9)	0.74770 (5)	0.14537 (2)	0.05691 (18)
O1	0.3969 (2)	0.73366 (18)	0.35879 (6)	0.0609 (4)
O2	0.8449 (3)	0.64623 (16)	0.16065 (7)	0.0707 (5)
O3	0.5240 (3)	0.7222 (2)	0.13301 (8)	0.0766 (6)
N1	0.6396 (3)	0.83845 (17)	0.31683 (7)	0.0442 (4)
N12	0.7204 (3)	0.84820 (18)	0.19511 (7)	0.0525 (4)
C2	0.5717 (3)	0.7474 (2)	0.35284 (8)	0.0489 (5)
C3	0.7162 (4)	0.6760 (3)	0.38004 (10)	0.0620 (6)
H3A	0.679416	0.612285	0.403557	0.074*
C4	0.9054 (4)	0.6993 (3)	0.37223 (11)	0.0660 (7)
H4A	0.996719	0.652682	0.390946	0.079*
C5	0.9646 (4)	0.7917 (3)	0.33673 (10)	0.0605 (6)
H5A	1.095137	0.807418	0.331995	0.073*
C6	0.8326 (3)	0.8596 (2)	0.30875 (9)	0.0492 (5)
C7	0.8915 (4)	0.9562 (3)	0.26785 (10)	0.0585 (6)
H7A	1.017190	0.990569	0.278075	0.070*
C8	0.7474 (5)	1.0639 (2)	0.26561 (11)	0.0692 (7)
H8A	0.736511	1.104049	0.300400	0.083*
H8B	0.788228	1.126854	0.239766	0.083*
C9	0.5559 (4)	1.0075 (3)	0.24915 (11)	0.0612 (7)
H9A	0.461650	1.076197	0.247158	0.073*
C10	0.4861 (3)	0.9134 (2)	0.29083 (10)	0.0524 (5)
H10A	0.416201	0.959033	0.318316	0.063*
H10B	0.396456	0.855705	0.273849	0.063*
C11	0.5739 (4)	0.9493 (3)	0.19342 (10)	0.0641 (7)
H11A	0.451036	0.914628	0.182325	0.077*
H11B	0.611563	1.013563	0.167793	0.077*
C13	0.9099 (4)	0.8943 (3)	0.21250 (10)	0.0592 (6)
H13A	0.958528	0.955410	0.186892	0.071*
H13B	1.000046	0.824482	0.214244	0.071*
C1'	0.8285 (4)	0.8251 (2)	0.09016 (9)	0.0585 (6)
C2'	0.7190 (5)	0.9095 (3)	0.06041 (11)	0.0780 (8)
H2'A	0.590106	0.923114	0.068566	0.094*
C3'	0.8057 (7)	0.9728 (3)	0.01842 (12)	0.0894 (11)
H3'A	0.732521	1.029034	−0.001706	0.107*
C4'	0.9946 (6)	0.9558 (3)	0.00544 (11)	0.0819 (10)
C5'	1.1005 (6)	0.8709 (3)	0.03537 (12)	0.0849 (9)
H5'A	1.229082	0.857186	0.026912	0.102*
C6'	1.0180 (5)	0.8052 (3)	0.07808 (11)	0.0712 (7)
H6'A	1.091003	0.748680	0.098065	0.085*
C7'	1.0838 (8)	1.0285 (4)	−0.04059 (14)	0.1161 (17)
H7'A	1.164041	0.971279	−0.061123	0.139*	0.55 (2)
H7'B	0.981596	1.057716	−0.063967	0.139*	0.55 (2)
H7'C	1.053155	0.983559	−0.073354	0.139*	0.45 (2)
H7'D	1.019922	1.109830	−0.042531	0.139*	0.45 (2)
C8'A	1.199 (3)	1.1360 (16)	−0.0246 (4)	0.136 (7)	0.55 (2)
H8'A	1.233872	1.184056	−0.055681	0.205*	0.55 (2)
H8'B	1.312957	1.107082	−0.006780	0.205*	0.55 (2)
H8'C	1.125652	1.188309	−0.000638	0.205*	0.55 (2)
C8'B	1.280 (2)	1.050 (2)	−0.0404 (4)	0.111 (5)	0.45 (2)
H8'D	1.312947	1.105567	−0.069535	0.166*	0.45 (2)
H8'E	1.347397	0.971814	−0.044349	0.166*	0.45 (2)
H8'F	1.316353	1.089349	−0.007150	0.166*	0.45 (2)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0714 (4)	0.0452 (3)	0.0542 (3)	−0.0046 (3)	0.0012 (2)	0.0040 (2)
O1	0.0488 (9)	0.0641 (10)	0.0699 (10)	−0.0067 (8)	0.0057 (7)	0.0023 (9)
O2	0.0982 (14)	0.0453 (9)	0.0687 (10)	0.0091 (9)	0.0036 (10)	0.0092 (8)
O3	0.0790 (13)	0.0775 (13)	0.0733 (11)	−0.0218 (11)	−0.0037 (9)	−0.0046 (10)
N1	0.0400 (9)	0.0428 (9)	0.0498 (9)	0.0003 (7)	−0.0009 (7)	−0.0053 (7)
N12	0.0558 (11)	0.0508 (10)	0.0510 (9)	0.0010 (9)	0.0009 (9)	0.0024 (8)
C2	0.0483 (11)	0.0486 (11)	0.0499 (10)	−0.0027 (10)	−0.0015 (8)	−0.0064 (11)
C3	0.0698 (16)	0.0617 (14)	0.0546 (12)	0.0022 (13)	−0.0104 (12)	0.0050 (11)
C4	0.0597 (15)	0.0767 (17)	0.0614 (13)	0.0145 (13)	−0.0193 (11)	−0.0041 (13)
C5	0.0406 (11)	0.0813 (18)	0.0595 (12)	0.0023 (11)	−0.0057 (10)	−0.0113 (12)
C6	0.0419 (11)	0.0543 (12)	0.0514 (11)	−0.0040 (10)	0.0013 (9)	−0.0133 (10)
C7	0.0522 (13)	0.0583 (14)	0.0649 (14)	−0.0145 (11)	0.0065 (11)	−0.0104 (11)
C8	0.088 (2)	0.0459 (12)	0.0741 (15)	−0.0106 (14)	0.0117 (15)	−0.0046 (11)
C9	0.0679 (17)	0.0469 (13)	0.0689 (15)	0.0121 (12)	0.0039 (14)	0.0033 (11)
C10	0.0443 (11)	0.0503 (12)	0.0625 (13)	0.0082 (10)	−0.0002 (10)	−0.0019 (10)
C11	0.0740 (17)	0.0561 (14)	0.0623 (14)	0.0117 (13)	−0.0004 (13)	0.0086 (12)
C13	0.0566 (13)	0.0607 (14)	0.0603 (13)	−0.0092 (11)	0.0106 (11)	0.0014 (11)
C1'	0.0768 (17)	0.0495 (12)	0.0492 (11)	−0.0015 (12)	0.0001 (11)	0.0000 (10)
C2'	0.087 (2)	0.0819 (19)	0.0648 (15)	0.0054 (18)	−0.0035 (15)	0.0168 (14)
C3'	0.126 (3)	0.079 (2)	0.0635 (17)	0.003 (2)	−0.0097 (19)	0.0196 (15)
C4'	0.125 (3)	0.0704 (19)	0.0503 (14)	−0.0161 (19)	0.0094 (17)	0.0020 (13)
C5'	0.094 (2)	0.093 (2)	0.0684 (17)	−0.0076 (19)	0.0210 (16)	−0.0031 (16)
C6'	0.0838 (19)	0.0683 (16)	0.0615 (14)	0.0077 (15)	0.0101 (14)	0.0040 (13)
C7'	0.182 (5)	0.106 (3)	0.0603 (18)	−0.035 (3)	0.018 (2)	0.0090 (19)
C8'A	0.219 (15)	0.128 (10)	0.062 (4)	−0.069 (11)	0.000 (6)	0.020 (5)
C8'B	0.130 (9)	0.134 (12)	0.069 (5)	−0.043 (8)	0.023 (5)	0.010 (7)

Geometric parameters (Å, º) top

S1—O3	1.428 (2)	C10—H10B	0.9700
S1—O2	1.429 (2)	C11—H11A	0.9700
S1—N12	1.635 (2)	C11—H11B	0.9700
S1—C1'	1.770 (3)	C13—H13A	0.9700
O1—C2	1.233 (3)	C13—H13B	0.9700
N1—C6	1.375 (3)	C1'—C6'	1.368 (4)
N1—C2	1.400 (3)	C1'—C2'	1.389 (4)
N1—C10	1.479 (3)	C2'—C3'	1.383 (5)
N12—C13	1.471 (3)	C2'—H2'A	0.9300
N12—C11	1.478 (3)	C3'—C4'	1.365 (6)
C2—C3	1.429 (3)	C3'—H3'A	0.9300
C3—C4	1.352 (4)	C4'—C5'	1.381 (5)
C3—H3A	0.9300	C4'—C7'	1.515 (4)
C4—C5	1.383 (4)	C5'—C6'	1.396 (4)
C4—H4A	0.9300	C5'—H5'A	0.9300
C5—C6	1.359 (3)	C6'—H6'A	0.9300
C5—H5A	0.9300	C7'—C8'B	1.385 (12)
C6—C7	1.502 (4)	C7'—C8'A	1.447 (11)
C7—C8	1.519 (4)	C7'—H7'A	0.9700
C7—C13	1.535 (3)	C7'—H7'B	0.9700
C7—H7A	0.9800	C7'—H7'C	0.9700
C8—C9	1.516 (4)	C7'—H7'D	0.9700
C8—H8A	0.9700	C8'A—H8'A	0.9600
C8—H8B	0.9700	C8'A—H8'B	0.9600
C9—C10	1.520 (4)	C8'A—H8'C	0.9600
C9—C11	1.527 (4)	C8'B—H8'D	0.9600
C9—H9A	0.9800	C8'B—H8'E	0.9600
C10—H10A	0.9700	C8'B—H8'F	0.9600

O3—S1—O2	119.57 (13)	C9—C11—H11A	109.9
O3—S1—N12	106.61 (11)	N12—C11—H11B	109.9
O2—S1—N12	106.68 (10)	C9—C11—H11B	109.9
O3—S1—C1'	108.91 (13)	H11A—C11—H11B	108.3
O2—S1—C1'	107.49 (13)	N12—C13—C7	109.45 (19)
N12—S1—C1'	106.94 (11)	N12—C13—H13A	109.8
C6—N1—C2	122.35 (18)	C7—C13—H13A	109.8
C6—N1—C10	123.50 (19)	N12—C13—H13B	109.8
C2—N1—C10	114.07 (17)	C7—C13—H13B	109.8
C13—N12—C11	112.7 (2)	H13A—C13—H13B	108.2
C13—N12—S1	116.04 (16)	C6'—C1'—C2'	120.6 (3)
C11—N12—S1	116.78 (16)	C6'—C1'—S1	120.5 (2)
O1—C2—N1	119.4 (2)	C2'—C1'—S1	118.9 (2)
O1—C2—C3	125.0 (2)	C3'—C2'—C1'	118.6 (3)
N1—C2—C3	115.6 (2)	C3'—C2'—H2'A	120.7
C4—C3—C2	121.2 (3)	C1'—C2'—H2'A	120.7
C4—C3—H3A	119.4	C4'—C3'—C2'	122.4 (3)
C2—C3—H3A	119.4	C4'—C3'—H3'A	118.8
C3—C4—C5	120.7 (2)	C2'—C3'—H3'A	118.8
C3—C4—H4A	119.6	C3'—C4'—C5'	118.0 (3)
C5—C4—H4A	119.6	C3'—C4'—C7'	120.4 (4)
C6—C5—C4	120.2 (2)	C5'—C4'—C7'	121.6 (4)
C6—C5—H5A	119.9	C4'—C5'—C6'	121.3 (3)
C4—C5—H5A	119.9	C4'—C5'—H5'A	119.4
C5—C6—N1	119.8 (2)	C6'—C5'—H5'A	119.4
C5—C6—C7	121.7 (2)	C1'—C6'—C5'	119.2 (3)
N1—C6—C7	118.5 (2)	C1'—C6'—H6'A	120.4
C6—C7—C8	110.9 (2)	C5'—C6'—H6'A	120.4
C6—C7—C13	110.2 (2)	C8'B—C7'—C4'	119.0 (6)
C8—C7—C13	110.0 (2)	C8'A—C7'—C4'	114.5 (5)
C6—C7—H7A	108.6	C8'A—C7'—H7'A	108.6
C8—C7—H7A	108.6	C4'—C7'—H7'A	108.6
C13—C7—H7A	108.6	C8'A—C7'—H7'B	108.6
C9—C8—C7	107.0 (2)	C4'—C7'—H7'B	108.6
C9—C8—H8A	110.3	H7'A—C7'—H7'B	107.6
C7—C8—H8A	110.3	C8'B—C7'—H7'C	107.6
C9—C8—H8B	110.3	C4'—C7'—H7'C	107.6
C7—C8—H8B	110.3	C8'B—C7'—H7'D	107.6
H8A—C8—H8B	108.6	C4'—C7'—H7'D	107.6
C8—C9—C10	110.6 (2)	H7'C—C7'—H7'D	107.0
C8—C9—C11	109.5 (2)	C7'—C8'A—H8'A	109.5
C10—C9—C11	112.7 (2)	C7'—C8'A—H8'B	109.5
C8—C9—H9A	107.9	H8'A—C8'A—H8'B	109.5
C10—C9—H9A	107.9	C7'—C8'A—H8'C	109.5
C11—C9—H9A	107.9	H8'A—C8'A—H8'C	109.5
N1—C10—C9	115.0 (2)	H8'B—C8'A—H8'C	109.5
N1—C10—H10A	108.5	C7'—C8'B—H8'D	109.5
C9—C10—H10A	108.5	C7'—C8'B—H8'E	109.5
N1—C10—H10B	108.5	H8'D—C8'B—H8'E	109.5
C9—C10—H10B	108.5	C7'—C8'B—H8'F	109.5
H10A—C10—H10B	107.5	H8'D—C8'B—H8'F	109.5
N12—C11—C9	108.8 (2)	H8'E—C8'B—H8'F	109.5
N12—C11—H11A	109.9

O3—S1—N12—C13	−176.35 (18)	C8—C9—C10—N1	−35.6 (3)
O2—S1—N12—C13	54.8 (2)	C11—C9—C10—N1	87.4 (3)
C1'—S1—N12—C13	−60.0 (2)	C13—N12—C11—C9	−58.7 (3)
O3—S1—N12—C11	−39.7 (2)	S1—N12—C11—C9	163.28 (18)
O2—S1—N12—C11	−168.57 (19)	C8—C9—C11—N12	60.8 (3)
C1'—S1—N12—C11	76.6 (2)	C10—C9—C11—N12	−62.8 (3)
C6—N1—C2—O1	179.2 (2)	C11—N12—C13—C7	57.4 (3)
C10—N1—C2—O1	2.3 (3)	S1—N12—C13—C7	−164.26 (18)
C6—N1—C2—C3	−1.1 (3)	C6—C7—C13—N12	64.3 (3)
C10—N1—C2—C3	−178.03 (19)	C8—C7—C13—N12	−58.3 (3)
O1—C2—C3—C4	−178.3 (2)	O3—S1—C1'—C6'	−146.7 (2)
N1—C2—C3—C4	2.1 (3)	O2—S1—C1'—C6'	−15.8 (3)
C2—C3—C4—C5	−1.3 (4)	N12—S1—C1'—C6'	98.4 (2)
C3—C4—C5—C6	−0.7 (4)	O3—S1—C1'—C2'	35.4 (3)
C4—C5—C6—N1	1.7 (4)	O2—S1—C1'—C2'	166.3 (2)
C4—C5—C6—C7	−176.9 (2)	N12—S1—C1'—C2'	−79.4 (2)
C2—N1—C6—C5	−0.7 (3)	C6'—C1'—C2'—C3'	0.0 (5)
C10—N1—C6—C5	175.9 (2)	S1—C1'—C2'—C3'	177.9 (3)
C2—N1—C6—C7	177.89 (18)	C1'—C2'—C3'—C4'	−0.4 (5)
C10—N1—C6—C7	−5.5 (3)	C2'—C3'—C4'—C5'	0.7 (6)
C5—C6—C7—C8	−148.0 (2)	C2'—C3'—C4'—C7'	−179.3 (3)
N1—C6—C7—C8	33.4 (3)	C3'—C4'—C5'—C6'	−0.7 (5)
C5—C6—C7—C13	90.0 (3)	C7'—C4'—C5'—C6'	179.3 (3)
N1—C6—C7—C13	−88.6 (3)	C2'—C1'—C6'—C5'	0.0 (4)
C6—C7—C8—C9	−61.4 (3)	S1—C1'—C6'—C5'	−177.9 (2)
C13—C7—C8—C9	60.7 (3)	C4'—C5'—C6'—C1'	0.4 (5)
C7—C8—C9—C10	62.7 (3)	C3'—C4'—C7'—C8'B	154.4 (12)
C7—C8—C9—C11	−62.1 (3)	C5'—C4'—C7'—C8'B	−25.7 (12)
C6—N1—C10—C9	6.6 (3)	C3'—C4'—C7'—C8'A	101.1 (12)
C2—N1—C10—C9	−176.56 (19)	C5'—C4'—C7'—C8'A	−78.9 (12)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C5—H5A···O1ⁱ	0.93	2.34	3.116 (3)	141
C7—H7A···O2ⁱⁱ	0.98	2.44	3.254 (3)	140

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

(1R,5R)-3-[(4-chlorophenyl)sulfonyl]-1,2,3,4,5,6-hexahydro-8H-1,5-methanopyrido[1,2-a][1,5]diazocin-8-one (II) top

Crystal data top

C₁₇H₁₇ClN₂O₃S	D_x = 1.423 Mg m⁻³
M_r = 364.83	Cu Kα radiation, λ = 1.54184 Å
Orthorhombic, P2₁2₁2₁	Cell parameters from 12750 reflections
a = 7.1374 (14) Å	θ = 3.9–71.2°
b = 11.448 (2) Å	µ = 3.29 mm⁻¹
c = 20.844 (4) Å	T = 299 K
V = 1703.2 (6) Å³	Prizmatic, colorless
Z = 4	0.30 × 0.20 × 0.15 mm
F(000) = 760

Data collection top

XtaLAB Synergy, Single source at home/near, HyPix3000 diffractometer	3289 independent reflections
Radiation source: micro-focus sealed X-ray tube, PhotonJet (Cu) X-ray Source	3203 reflections with I > 2σ(I)
Detector resolution: 10.0000 pixels mm^-1	R_int = 0.027
ω scans	θ_max = 71.4°, θ_min = 4.2°
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	h = −8→8
T_min = 0.795, T_max = 1.000	k = −14→13
16028 measured reflections	l = −25→25

Refinement top

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.030	w = 1/[σ²(F_o²) + (0.0503P)² + 0.1799P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.078	(Δ/σ)_max < 0.001
S = 1.05	Δρ_max = 0.42 e Å⁻³
3289 reflections	Δρ_min = −0.33 e Å⁻³
217 parameters	Absolute structure: Flack x determined using 1318 quotients [(I⁺)-(I^-)]/[(I⁺)+(I^-)] (Parsons et al., 2013)
0 restraints	Absolute structure parameter: −0.004 (5)

Special details top

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

	x	y	z	U_iso*/U_eq
S1	0.22478 (8)	0.27207 (5)	0.34739 (3)	0.03902 (15)
Cl1	−0.32153 (13)	0.49086 (7)	0.54785 (3)	0.0699 (2)
O1	0.7771 (3)	0.28000 (19)	0.15317 (11)	0.0647 (5)
O2	0.1269 (3)	0.18068 (15)	0.31475 (8)	0.0502 (4)
O3	0.3999 (3)	0.24823 (16)	0.37824 (9)	0.0524 (4)
N1	0.4944 (3)	0.36786 (17)	0.16841 (9)	0.0409 (4)
N12	0.2648 (3)	0.37419 (16)	0.29491 (8)	0.0401 (4)
C2	0.6102 (4)	0.2880 (2)	0.13668 (12)	0.0488 (6)
C3	0.5244 (5)	0.2229 (3)	0.08706 (15)	0.0627 (7)
H3A	0.596685	0.171265	0.063104	0.075*
C4	0.3400 (5)	0.2340 (3)	0.07356 (14)	0.0655 (8)
H4A	0.287153	0.189194	0.041014	0.079*
C5	0.2283 (4)	0.3117 (3)	0.10791 (13)	0.0562 (6)
H5A	0.100971	0.317377	0.098975	0.067*
C6	0.3060 (3)	0.3793 (2)	0.15466 (11)	0.0423 (5)
C7	0.1922 (3)	0.4659 (2)	0.19194 (12)	0.0451 (5)
H7A	0.088762	0.492844	0.164794	0.054*
C8	0.3121 (4)	0.5714 (2)	0.21021 (14)	0.0529 (6)
H8A	0.363572	0.607885	0.172078	0.064*
H8B	0.237218	0.628713	0.232979	0.064*
C9	0.4687 (4)	0.5263 (2)	0.25296 (13)	0.0476 (5)
H9A	0.546300	0.592999	0.265695	0.057*
C10	0.5921 (3)	0.4407 (2)	0.21691 (13)	0.0471 (6)
H10A	0.690567	0.484286	0.195534	0.057*
H10B	0.651477	0.389329	0.247811	0.057*
C11	0.3847 (4)	0.4731 (2)	0.31352 (12)	0.0480 (6)
H11A	0.483789	0.446415	0.341787	0.058*
H11B	0.311175	0.531235	0.336171	0.058*
C13	0.1095 (3)	0.4089 (2)	0.25235 (12)	0.0451 (5)
H13A	0.027946	0.463659	0.274269	0.054*
H13B	0.036134	0.340816	0.240581	0.054*
C1'	0.0721 (3)	0.3307 (2)	0.40561 (11)	0.0395 (5)
C2'	0.1424 (4)	0.4029 (3)	0.45401 (13)	0.0536 (6)
H2'A	0.270287	0.417502	0.456776	0.064*
C3'	0.0214 (5)	0.4522 (3)	0.49743 (13)	0.0607 (7)
H3'A	0.066574	0.501348	0.529405	0.073*
C4'	−0.1678 (4)	0.4284 (2)	0.49336 (11)	0.0472 (6)
C5'	−0.2378 (4)	0.3554 (3)	0.44671 (12)	0.0549 (6)
H5'A	−0.365241	0.338706	0.445122	0.066*
C6'	−0.1173 (4)	0.3073 (2)	0.40242 (12)	0.0496 (6)
H6'A	−0.163668	0.259030	0.370264	0.060*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0399 (3)	0.0367 (3)	0.0404 (3)	−0.0018 (2)	0.0007 (2)	−0.0021 (2)
Cl1	0.0922 (6)	0.0660 (4)	0.0514 (4)	0.0183 (4)	0.0234 (4)	−0.0014 (3)
O1	0.0432 (9)	0.0705 (12)	0.0805 (13)	0.0155 (9)	0.0077 (9)	0.0098 (11)
O2	0.0568 (10)	0.0399 (8)	0.0539 (9)	−0.0081 (7)	0.0038 (8)	−0.0110 (8)
O3	0.0469 (9)	0.0530 (10)	0.0572 (10)	0.0070 (8)	−0.0037 (8)	0.0050 (8)
N1	0.0363 (9)	0.0433 (10)	0.0432 (10)	0.0015 (8)	0.0017 (7)	0.0079 (8)
N12	0.0380 (9)	0.0428 (9)	0.0395 (9)	−0.0068 (8)	−0.0036 (8)	0.0006 (8)
C2	0.0471 (13)	0.0464 (13)	0.0530 (14)	0.0065 (10)	0.0087 (11)	0.0103 (10)
C3	0.0742 (19)	0.0554 (15)	0.0586 (15)	0.0143 (15)	0.0122 (14)	−0.0012 (14)
C4	0.077 (2)	0.0630 (17)	0.0562 (15)	0.0023 (16)	−0.0086 (14)	−0.0106 (14)
C5	0.0486 (14)	0.0666 (16)	0.0533 (14)	0.0015 (12)	−0.0082 (12)	−0.0014 (12)
C6	0.0393 (11)	0.0476 (12)	0.0398 (11)	0.0024 (9)	−0.0019 (9)	0.0099 (10)
C7	0.0398 (12)	0.0509 (13)	0.0446 (12)	0.0077 (10)	−0.0028 (9)	0.0080 (10)
C8	0.0580 (15)	0.0406 (12)	0.0602 (15)	0.0069 (11)	0.0042 (12)	0.0103 (11)
C9	0.0495 (13)	0.0387 (12)	0.0547 (13)	−0.0094 (10)	−0.0014 (12)	0.0027 (10)
C10	0.0369 (12)	0.0502 (13)	0.0543 (14)	−0.0047 (10)	−0.0028 (10)	0.0054 (11)
C11	0.0506 (13)	0.0461 (12)	0.0472 (12)	−0.0113 (11)	−0.0041 (11)	−0.0037 (10)
C13	0.0335 (10)	0.0559 (14)	0.0458 (12)	0.0017 (10)	−0.0003 (9)	0.0004 (10)
C1'	0.0424 (11)	0.0396 (11)	0.0365 (10)	−0.0049 (9)	0.0009 (9)	−0.0017 (9)
C2'	0.0494 (14)	0.0638 (15)	0.0477 (13)	−0.0126 (12)	−0.0036 (12)	−0.0117 (12)
C3'	0.0720 (18)	0.0653 (17)	0.0447 (14)	−0.0100 (15)	−0.0002 (13)	−0.0196 (13)
C4'	0.0609 (15)	0.0447 (12)	0.0360 (11)	0.0056 (11)	0.0060 (10)	0.0023 (10)
C5'	0.0441 (13)	0.0681 (16)	0.0527 (13)	−0.0021 (12)	0.0034 (11)	−0.0091 (12)
C6'	0.0454 (13)	0.0590 (15)	0.0444 (12)	−0.0114 (11)	−0.0008 (11)	−0.0125 (11)

Geometric parameters (Å, º) top

S1—O2	1.4304 (17)	C8—C9	1.520 (4)
S1—O3	1.4319 (18)	C8—H8A	0.9700
S1—N12	1.6262 (19)	C8—H8B	0.9700
S1—C1'	1.764 (2)	C9—C10	1.517 (4)
Cl1—C4'	1.733 (3)	C9—C11	1.524 (4)
O1—C2	1.243 (3)	C9—H9A	0.9800
N1—C6	1.381 (3)	C10—H10A	0.9700
N1—C2	1.399 (3)	C10—H10B	0.9700
N1—C10	1.485 (3)	C11—H11A	0.9700
N12—C11	1.471 (3)	C11—H11B	0.9700
N12—C13	1.474 (3)	C13—H13A	0.9700
C2—C3	1.414 (4)	C13—H13B	0.9700
C3—C4	1.352 (5)	C1'—C6'	1.379 (3)
C3—H3A	0.9300	C1'—C2'	1.398 (3)
C4—C5	1.393 (4)	C2'—C3'	1.372 (4)
C4—H4A	0.9300	C2'—H2'A	0.9300
C5—C6	1.363 (4)	C3'—C4'	1.380 (4)
C5—H5A	0.9300	C3'—H3'A	0.9300
C6—C7	1.499 (3)	C4'—C5'	1.376 (4)
C7—C8	1.528 (4)	C5'—C6'	1.377 (4)
C7—C13	1.537 (3)	C5'—H5'A	0.9300
C7—H7A	0.9800	C6'—H6'A	0.9300

O2—S1—O3	120.05 (11)	C8—C9—C11	109.4 (2)
O2—S1—N12	106.96 (10)	C10—C9—H9A	108.0
O3—S1—N12	106.62 (11)	C8—C9—H9A	108.0
O2—S1—C1'	107.67 (11)	C11—C9—H9A	108.0
O3—S1—C1'	107.63 (11)	N1—C10—C9	115.3 (2)
N12—S1—C1'	107.33 (11)	N1—C10—H10A	108.4
C6—N1—C2	122.6 (2)	C9—C10—H10A	108.4
C6—N1—C10	123.0 (2)	N1—C10—H10B	108.4
C2—N1—C10	114.32 (19)	C9—C10—H10B	108.4
C11—N12—C13	112.9 (2)	H10A—C10—H10B	107.5
C11—N12—S1	118.55 (15)	N12—C11—C9	108.5 (2)
C13—N12—S1	117.80 (16)	N12—C11—H11A	110.0
O1—C2—N1	118.9 (3)	C9—C11—H11A	110.0
O1—C2—C3	125.4 (3)	N12—C11—H11B	110.0
N1—C2—C3	115.7 (2)	C9—C11—H11B	110.0
C4—C3—C2	121.6 (3)	H11A—C11—H11B	108.4
C4—C3—H3A	119.2	N12—C13—C7	108.57 (19)
C2—C3—H3A	119.2	N12—C13—H13A	110.0
C3—C4—C5	120.7 (3)	C7—C13—H13A	110.0
C3—C4—H4A	119.7	N12—C13—H13B	110.0
C5—C4—H4A	119.7	C7—C13—H13B	110.0
C6—C5—C4	119.9 (3)	H13A—C13—H13B	108.4
C6—C5—H5A	120.1	C6'—C1'—C2'	120.1 (2)
C4—C5—H5A	120.1	C6'—C1'—S1	119.92 (18)
C5—C6—N1	119.4 (2)	C2'—C1'—S1	120.00 (19)
C5—C6—C7	121.7 (2)	C3'—C2'—C1'	119.6 (2)
N1—C6—C7	118.9 (2)	C3'—C2'—H2'A	120.2
C6—C7—C8	110.4 (2)	C1'—C2'—H2'A	120.2
C6—C7—C13	110.61 (19)	C2'—C3'—C4'	119.6 (2)
C8—C7—C13	110.3 (2)	C2'—C3'—H3'A	120.2
C6—C7—H7A	108.5	C4'—C3'—H3'A	120.2
C8—C7—H7A	108.5	C5'—C4'—C3'	121.2 (2)
C13—C7—H7A	108.5	C5'—C4'—Cl1	118.9 (2)
C9—C8—C7	106.80 (19)	C3'—C4'—Cl1	119.8 (2)
C9—C8—H8A	110.4	C4'—C5'—C6'	119.3 (2)
C7—C8—H8A	110.4	C4'—C5'—H5'A	120.3
C9—C8—H8B	110.4	C6'—C5'—H5'A	120.3
C7—C8—H8B	110.4	C5'—C6'—C1'	120.2 (2)
H8A—C8—H8B	108.6	C5'—C6'—H6'A	119.9
C10—C9—C8	110.9 (2)	C1'—C6'—H6'A	119.9
C10—C9—C11	112.4 (2)

O2—S1—N12—C11	−172.55 (18)	C6—N1—C10—C9	2.5 (3)
O3—S1—N12—C11	−43.0 (2)	C2—N1—C10—C9	−178.8 (2)
C1'—S1—N12—C11	72.1 (2)	C8—C9—C10—N1	−33.3 (3)
O2—S1—N12—C13	45.5 (2)	C11—C9—C10—N1	89.4 (3)
O3—S1—N12—C13	175.12 (17)	C13—N12—C11—C9	−60.2 (3)
C1'—S1—N12—C13	−69.78 (19)	S1—N12—C11—C9	156.07 (18)
C6—N1—C2—O1	−177.7 (2)	C10—C9—C11—N12	−62.0 (3)
C10—N1—C2—O1	3.6 (3)	C8—C9—C11—N12	61.6 (3)
C6—N1—C2—C3	3.0 (3)	C11—N12—C13—C7	58.3 (3)
C10—N1—C2—C3	−175.7 (2)	S1—N12—C13—C7	−157.68 (17)
O1—C2—C3—C4	177.7 (3)	C6—C7—C13—N12	64.2 (3)
N1—C2—C3—C4	−3.0 (4)	C8—C7—C13—N12	−58.2 (3)
C2—C3—C4—C5	0.9 (5)	O2—S1—C1'—C6'	−15.8 (3)
C3—C4—C5—C6	1.5 (5)	O3—S1—C1'—C6'	−146.5 (2)
C4—C5—C6—N1	−1.5 (4)	N12—S1—C1'—C6'	99.0 (2)
C4—C5—C6—C7	178.7 (3)	O2—S1—C1'—C2'	165.7 (2)
C2—N1—C6—C5	−0.8 (3)	O3—S1—C1'—C2'	35.0 (2)
C10—N1—C6—C5	177.8 (2)	N12—S1—C1'—C2'	−79.4 (2)
C2—N1—C6—C7	179.0 (2)	C6'—C1'—C2'—C3'	−1.3 (4)
C10—N1—C6—C7	−2.4 (3)	S1—C1'—C2'—C3'	177.2 (2)
C5—C6—C7—C8	−147.4 (2)	C1'—C2'—C3'—C4'	1.0 (4)
N1—C6—C7—C8	32.8 (3)	C2'—C3'—C4'—C5'	0.4 (5)
C5—C6—C7—C13	90.2 (3)	C2'—C3'—C4'—Cl1	−179.7 (2)
N1—C6—C7—C13	−89.6 (3)	C3'—C4'—C5'—C6'	−1.5 (4)
C6—C7—C8—C9	−62.1 (3)	Cl1—C4'—C5'—C6'	178.7 (2)
C13—C7—C8—C9	60.5 (3)	C4'—C5'—C6'—C1'	1.2 (4)
C7—C8—C9—C10	62.6 (3)	C2'—C1'—C6'—C5'	0.2 (4)
C7—C8—C9—C11	−61.9 (3)	S1—C1'—C6'—C5'	−178.2 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C5—H5A···O1ⁱ	0.93	2.61	3.375 (4)	140
C13—H13B···O1ⁱ	0.97	2.69	3.475 (3)	139
C5′—H5′A···O3ⁱ	0.93	2.42	3.198 (3)	142
C8—H8A···O3ⁱⁱ	0.97	2.56	3.424 (3)	149
C4—H4A···Cl1ⁱⁱⁱ	0.93	2.94	3.764 (3)	148

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

(1R,5R)-3-((3-nitrophenyl)sulfonyl)-1,2,3,4,5,6-hexahydro-8H-1,5-methanopyrido[1,2-a][1,5]diazocin-8-one (III) top

Crystal data top

C₁₇H₁₇N₃O₅S	F(000) = 392
M_r = 375.39	D_x = 1.455 Mg m⁻³
Monoclinic, P2₁	Cu Kα radiation, λ = 1.54184 Å
a = 11.040 (2) Å	Cell parameters from 5501 reflections
b = 6.2621 (13) Å	θ = 4.0–71.4°
c = 12.424 (3) Å	µ = 2.00 mm⁻¹
β = 94.03 (3)°	T = 296 K
V = 856.8 (3) Å³	Prizmatic, colorless
Z = 2	0.20 × 0.15 × 0.10 mm

Data collection top

XtaLAB Synergy, Single source at home/near, HyPix3000 diffractometer	2446 independent reflections
Radiation source: micro-focus sealed X-ray tube, PhotonJet (Cu) X-ray Source	2363 reflections with I > 2σ(I)
Detector resolution: 10.0000 pixels mm^-1	R_int = 0.023
ω scans	θ_max = 71.5°, θ_min = 3.6°
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	h = −13→13
T_min = 0.639, T_max = 1.000	k = −6→7
7776 measured reflections	l = −15→15

Refinement top

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.039	w = 1/[σ²(F_o²) + (0.0754P)² + 0.1248P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.114	(Δ/σ)_max < 0.001
S = 1.04	Δρ_max = 0.47 e Å⁻³
2446 reflections	Δρ_min = −0.22 e Å⁻³
235 parameters	Absolute structure: Flack x determined using 579 quotients [(I⁺)-(I^-)]/[(I⁺)+(I^-)] (Parsons et al., 2013)
1 restraint	Absolute structure parameter: 0.017 (16)

Special details top

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

	x	y	z	U_iso*/U_eq
S1	0.15419 (6)	0.10657 (14)	0.65911 (6)	0.0503 (2)
O1	0.6728 (3)	−0.1378 (5)	0.7756 (3)	0.0777 (8)
O2	0.1535 (2)	0.1620 (5)	0.54790 (18)	0.0696 (9)
O3	0.1536 (3)	−0.1126 (4)	0.6914 (3)	0.0761 (8)
O4	−0.1062 (4)	0.0114 (12)	0.9888 (4)	0.143 (2)
O5	−0.2278 (4)	0.2805 (12)	0.9936 (3)	0.140 (2)
N1	0.5589 (2)	0.1629 (4)	0.7462 (2)	0.0446 (6)
N12	0.2750 (2)	0.2153 (4)	0.71985 (18)	0.0421 (5)
N3	−0.1493 (3)	0.1778 (10)	0.9537 (3)	0.0916 (16)
C2	0.6474 (3)	0.0176 (6)	0.7157 (3)	0.0557 (8)
C3	0.7019 (3)	0.0648 (7)	0.6191 (3)	0.0639 (11)
H3A	0.759057	−0.028879	0.594281	0.077*
C4	0.6726 (3)	0.2440 (8)	0.5615 (3)	0.0638 (10)
H4A	0.710971	0.272896	0.498892	0.077*
C5	0.5843 (3)	0.3867 (6)	0.5960 (3)	0.0553 (8)
H5A	0.564335	0.509117	0.556234	0.066*
C6	0.5290 (3)	0.3440 (5)	0.6875 (2)	0.0436 (6)
C7	0.4346 (3)	0.4905 (5)	0.7275 (3)	0.0492 (7)
H7A	0.451784	0.635774	0.703421	0.059*
C8	0.4401 (3)	0.4899 (7)	0.8499 (3)	0.0580 (9)
H8A	0.520190	0.532007	0.879470	0.070*
H8B	0.380876	0.588526	0.875750	0.070*
C9	0.4120 (3)	0.2638 (7)	0.8834 (2)	0.0526 (8)
H9A	0.413307	0.261073	0.962380	0.063*
C10	0.5094 (3)	0.1127 (8)	0.8501 (2)	0.0539 (7)
H10A	0.575597	0.113061	0.905801	0.065*
H10B	0.476096	−0.030658	0.846320	0.065*
C11	0.2850 (3)	0.1977 (6)	0.8394 (2)	0.0514 (8)
H11A	0.269259	0.051691	0.860401	0.062*
H11B	0.225028	0.289081	0.869484	0.062*
C13	0.3064 (3)	0.4300 (6)	0.6827 (3)	0.0495 (7)
H13A	0.248524	0.533033	0.706739	0.059*
H13B	0.302369	0.432878	0.604459	0.059*
C1'	0.0293 (3)	0.2314 (5)	0.7149 (2)	0.0449 (6)
C2'	−0.0143 (3)	0.1467 (6)	0.8071 (2)	0.0517 (8)
H2'A	0.014481	0.017681	0.835735	0.062*
C3'	−0.1031 (3)	0.2624 (8)	0.8550 (3)	0.0606 (10)
C4'	−0.1479 (3)	0.4520 (8)	0.8136 (4)	0.0693 (11)
H4'A	−0.207272	0.525883	0.847895	0.083*
C5'	−0.1040 (3)	0.5310 (7)	0.7212 (4)	0.0696 (10)
H5'A	−0.135141	0.657808	0.691690	0.084*
C6'	−0.0138 (3)	0.4237 (6)	0.6715 (3)	0.0558 (8)
H6'A	0.017549	0.479393	0.609888	0.067*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0495 (4)	0.0415 (4)	0.0608 (4)	0.0046 (3)	0.0094 (3)	−0.0112 (4)
O1	0.0648 (16)	0.0635 (19)	0.105 (2)	0.0234 (14)	0.0084 (14)	0.0117 (17)
O2	0.0688 (14)	0.090 (3)	0.0508 (11)	−0.0015 (14)	0.0079 (10)	−0.0178 (13)
O3	0.0725 (17)	0.0361 (14)	0.121 (2)	0.0036 (12)	0.0151 (16)	−0.0143 (15)
O4	0.109 (3)	0.205 (6)	0.120 (3)	0.006 (4)	0.038 (2)	0.085 (4)
O5	0.123 (3)	0.186 (6)	0.120 (3)	−0.016 (4)	0.071 (3)	−0.029 (4)
N1	0.0405 (11)	0.0402 (15)	0.0533 (12)	0.0025 (10)	0.0038 (9)	−0.0029 (11)
N12	0.0437 (12)	0.0376 (14)	0.0458 (11)	0.0058 (11)	0.0079 (9)	0.0014 (10)
N3	0.060 (2)	0.148 (5)	0.069 (2)	−0.013 (2)	0.0244 (16)	0.009 (3)
C2	0.0444 (15)	0.0499 (19)	0.072 (2)	0.0058 (15)	0.0022 (14)	−0.0110 (18)
C3	0.0494 (16)	0.069 (3)	0.074 (2)	0.0040 (17)	0.0143 (15)	−0.022 (2)
C4	0.060 (2)	0.072 (3)	0.0609 (18)	−0.0118 (19)	0.0194 (16)	−0.0169 (19)
C5	0.0612 (19)	0.056 (2)	0.0495 (16)	−0.0082 (16)	0.0095 (13)	−0.0003 (15)
C6	0.0436 (14)	0.0395 (16)	0.0477 (14)	−0.0042 (12)	0.0023 (11)	−0.0048 (13)
C7	0.0570 (16)	0.0318 (16)	0.0595 (17)	0.0019 (13)	0.0089 (13)	−0.0002 (13)
C8	0.0631 (18)	0.054 (2)	0.0570 (17)	0.0011 (17)	0.0084 (14)	−0.0178 (16)
C9	0.0546 (17)	0.062 (2)	0.0415 (13)	0.0025 (16)	0.0069 (12)	−0.0016 (15)
C10	0.0491 (14)	0.0588 (19)	0.0539 (15)	0.0031 (18)	0.0039 (12)	0.0138 (18)
C11	0.0500 (15)	0.058 (2)	0.0474 (14)	0.0080 (15)	0.0120 (12)	0.0053 (15)
C13	0.0505 (16)	0.0400 (17)	0.0578 (16)	0.0086 (14)	0.0039 (13)	0.0096 (15)
C1'	0.0380 (13)	0.0422 (17)	0.0542 (15)	0.0021 (12)	0.0018 (11)	−0.0016 (14)
C2'	0.0394 (13)	0.055 (2)	0.0613 (16)	−0.0045 (14)	0.0056 (12)	0.0088 (16)
C3'	0.0426 (15)	0.083 (3)	0.0572 (17)	−0.0108 (17)	0.0072 (13)	−0.0053 (19)
C4'	0.0446 (16)	0.076 (3)	0.089 (3)	0.0053 (18)	0.0116 (16)	−0.024 (2)
C5'	0.0525 (17)	0.056 (2)	0.100 (3)	0.0152 (17)	0.0041 (18)	0.004 (2)
C6'	0.0490 (16)	0.051 (2)	0.0682 (19)	0.0059 (15)	0.0058 (14)	0.0066 (17)

Geometric parameters (Å, º) top

S1—O2	1.424 (3)	C7—H7A	0.9800
S1—O3	1.430 (3)	C8—C9	1.514 (6)
S1—N12	1.634 (3)	C8—H8A	0.9700
S1—C1'	1.768 (3)	C8—H8B	0.9700
O1—C2	1.245 (5)	C9—C10	1.512 (5)
O4—N3	1.214 (8)	C9—C11	1.526 (5)
O5—N3	1.212 (7)	C9—H9A	0.9800
N1—C6	1.376 (4)	C10—H10A	0.9700
N1—C2	1.407 (4)	C10—H10B	0.9700
N1—C10	1.471 (4)	C11—H11A	0.9700
N12—C13	1.471 (4)	C11—H11B	0.9700
N12—C11	1.485 (4)	C13—H13A	0.9700
N3—C3'	1.460 (5)	C13—H13B	0.9700
C2—C3	1.411 (5)	C1'—C2'	1.379 (4)
C3—C4	1.357 (6)	C1'—C6'	1.390 (5)
C3—H3A	0.9300	C2'—C3'	1.386 (5)
C4—C5	1.411 (6)	C2'—H2'A	0.9300
C4—H4A	0.9300	C3'—C4'	1.372 (7)
C5—C6	1.354 (4)	C4'—C5'	1.370 (6)
C5—H5A	0.9300	C4'—H4'A	0.9300
C6—C7	1.499 (4)	C5'—C6'	1.383 (5)
C7—C8	1.519 (4)	C5'—H5'A	0.9300
C7—C13	1.531 (5)	C6'—H6'A	0.9300

O2—S1—O3	120.4 (2)	C10—C9—C8	110.3 (3)
O2—S1—N12	107.14 (14)	C10—C9—C11	112.7 (3)
O3—S1—N12	106.87 (16)	C8—C9—C11	110.8 (3)
O2—S1—C1'	108.78 (16)	C10—C9—H9A	107.6
O3—S1—C1'	107.17 (17)	C8—C9—H9A	107.6
N12—S1—C1'	105.56 (13)	C11—C9—H9A	107.6
C6—N1—C2	122.4 (3)	N1—C10—C9	114.9 (3)
C6—N1—C10	123.5 (3)	N1—C10—H10A	108.5
C2—N1—C10	114.0 (3)	C9—C10—H10A	108.5
C13—N12—C11	112.2 (3)	N1—C10—H10B	108.5
C13—N12—S1	116.0 (2)	C9—C10—H10B	108.5
C11—N12—S1	115.6 (2)	H10A—C10—H10B	107.5
O5—N3—O4	125.6 (5)	N12—C11—C9	109.9 (2)
O5—N3—C3'	116.9 (6)	N12—C11—H11A	109.7
O4—N3—C3'	117.5 (4)	C9—C11—H11A	109.7
O1—C2—N1	118.4 (3)	N12—C11—H11B	109.7
O1—C2—C3	125.5 (3)	C9—C11—H11B	109.7
N1—C2—C3	116.1 (3)	H11A—C11—H11B	108.2
C4—C3—C2	121.4 (3)	N12—C13—C7	110.2 (2)
C4—C3—H3A	119.3	N12—C13—H13A	109.6
C2—C3—H3A	119.3	C7—C13—H13A	109.6
C3—C4—C5	120.5 (3)	N12—C13—H13B	109.6
C3—C4—H4A	119.7	C7—C13—H13B	109.6
C5—C4—H4A	119.7	H13A—C13—H13B	108.1
C6—C5—C4	119.4 (4)	C2'—C1'—C6'	121.7 (3)
C6—C5—H5A	120.3	C2'—C1'—S1	118.9 (3)
C4—C5—H5A	120.3	C6'—C1'—S1	119.1 (2)
C5—C6—N1	120.1 (3)	C1'—C2'—C3'	117.0 (3)
C5—C6—C7	121.5 (3)	C1'—C2'—H2'A	121.5
N1—C6—C7	118.4 (3)	C3'—C2'—H2'A	121.5
C6—C7—C8	110.5 (3)	C4'—C3'—C2'	122.5 (3)
C6—C7—C13	112.0 (3)	C4'—C3'—N3	119.4 (4)
C8—C7—C13	109.5 (3)	C2'—C3'—N3	118.1 (4)
C6—C7—H7A	108.2	C5'—C4'—C3'	119.2 (3)
C8—C7—H7A	108.2	C5'—C4'—H4'A	120.4
C13—C7—H7A	108.2	C3'—C4'—H4'A	120.4
C9—C8—C7	106.5 (3)	C4'—C5'—C6'	120.5 (4)
C9—C8—H8A	110.4	C4'—C5'—H5'A	119.8
C7—C8—H8A	110.4	C6'—C5'—H5'A	119.8
C9—C8—H8B	110.4	C5'—C6'—C1'	119.1 (3)
C7—C8—H8B	110.4	C5'—C6'—H6'A	120.5
H8A—C8—H8B	108.6	C1'—C6'—H6'A	120.5

O2—S1—N12—C13	38.6 (2)	C8—C9—C10—N1	−36.5 (4)
O3—S1—N12—C13	168.9 (2)	C11—C9—C10—N1	87.9 (4)
C1'—S1—N12—C13	−77.3 (2)	C13—N12—C11—C9	−55.3 (4)
O2—S1—N12—C11	173.1 (2)	S1—N12—C11—C9	168.5 (2)
O3—S1—N12—C11	−56.6 (3)	C10—C9—C11—N12	−65.9 (4)
C1'—S1—N12—C11	57.3 (3)	C8—C9—C11—N12	58.2 (4)
C6—N1—C2—O1	177.1 (3)	C11—N12—C13—C7	56.7 (3)
C10—N1—C2—O1	1.8 (5)	S1—N12—C13—C7	−167.3 (2)
C6—N1—C2—C3	−1.8 (4)	C6—C7—C13—N12	62.7 (3)
C10—N1—C2—C3	−177.0 (3)	C8—C7—C13—N12	−60.3 (4)
O1—C2—C3—C4	−176.7 (4)	O2—S1—C1'—C2'	157.4 (3)
N1—C2—C3—C4	2.0 (5)	O3—S1—C1'—C2'	25.8 (3)
C2—C3—C4—C5	−1.3 (6)	N12—S1—C1'—C2'	−87.9 (3)
C3—C4—C5—C6	0.2 (5)	O2—S1—C1'—C6'	−29.2 (3)
C4—C5—C6—N1	0.1 (5)	O3—S1—C1'—C6'	−160.8 (3)
C4—C5—C6—C7	−180.0 (3)	N12—S1—C1'—C6'	85.5 (3)
C2—N1—C6—C5	0.8 (4)	C6'—C1'—C2'—C3'	−0.3 (5)
C10—N1—C6—C5	175.6 (3)	S1—C1'—C2'—C3'	173.0 (2)
C2—N1—C6—C7	−179.2 (3)	C1'—C2'—C3'—C4'	0.7 (5)
C10—N1—C6—C7	−4.4 (4)	C1'—C2'—C3'—N3	−179.0 (3)
C5—C6—C7—C8	−147.0 (3)	O5—N3—C3'—C4'	1.1 (6)
N1—C6—C7—C8	33.0 (4)	O4—N3—C3'—C4'	−178.9 (5)
C5—C6—C7—C13	90.6 (4)	O5—N3—C3'—C2'	−179.3 (4)
N1—C6—C7—C13	−89.4 (3)	O4—N3—C3'—C2'	0.8 (6)
C6—C7—C8—C9	−62.1 (3)	C2'—C3'—C4'—C5'	0.2 (6)
C13—C7—C8—C9	61.7 (4)	N3—C3'—C4'—C5'	179.8 (4)
C7—C8—C9—C10	64.2 (3)	C3'—C4'—C5'—C6'	−1.4 (6)
C7—C8—C9—C11	−61.3 (3)	C4'—C5'—C6'—C1'	1.8 (6)
C6—N1—C10—C9	6.1 (5)	C2'—C1'—C6'—C5'	−0.9 (5)
C2—N1—C10—C9	−178.7 (3)	S1—C1'—C6'—C5'	−174.1 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C4′—H4′A···O1ⁱ	0.93	2.61	3.257 (5)	127
C10—H10A···O5ⁱⁱ	0.97	2.58	3.460 (6)	151
C11—H11A···O5ⁱⁱⁱ	0.97	2.55	3.428 (7)	150
C13—H13A···O3^iv	0.97	2.46	3.330 (4)	150

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

Acknowledgements

We are especially grateful to Professor B. Tashkhodzhaev for help in discussing the results.

References

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Volume 79| Part 4| April 2023| Pages 313-318

https://doi.org/10.1107/S2056989023001950

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research communications\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Syntheses, crystal structures and Hirshfeld surface analyses of N-aryl­sulfonyl derivatives of cytisine

1. Chemical context

2. Structural commentary

3. Supra­molecular features

4. Database survey

5. Synthesis and crystallization

6. Refinement

Supporting information

Acknowledgements

References

research communications

Syntheses, crystal structures and Hirshfeld surface analyses of N-arylsulfonyl derivatives of cytisine

3. Supramolecular features