Crystal structure of N′-[2-(benzo[d]thia­zol-2-yl)acet­yl]benzohydrazide, an achiral compound crystallizing in space group P1 with Z = 1

Azzam, R.A.; Elgemeie, G.H.; Seif, M.M.; Jones, P.G.

doi:10.1107/S2056989021007672

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Volume 77| Part 9| September 2021| Pages 891-894

https://doi.org/10.1107/S2056989021007672

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Crystal structure of N′-[2-(benzo[d]thiazol-2-yl)acetyl]benzohydrazide, an achiral compound crystallizing in space group P1 with Z = 1

Rasha A. Azzam,^a Galal H. Elgemeie,^a Mona M. Seif ^a and Peter G. Jones ^b ^*

^aChemistry Department, Faculty of Science, Helwan University, Cairo, Egypt, and ^bInstitut für Anorganische und Analytische Chemie, Technische Universität Braunschweig, Hagenring 30, D-38106 Braunschweig, Germany
^*Correspondence e-mail: p.jones@tu-bs.de

Edited by A. V. Yatsenko, Moscow State University, Russia (Received 19 July 2021; accepted 27 July 2021; online 3 August 2021)

In the molecule of the title compound, C₁₆H₁₃N₃O₂S, one hydrazinic nitrogen atom is essentially planar, but the other is slightly pyramidalized. The torsion angle about the hydrazinic bond is 66.44 (15)°. Both hydrazinic hydrogen atoms lie antiperiplanar to the oxygen of the adjacent carbonyl group. The molecular packing is a layer structure determined by two classical hydrogen bonds, N—H⋯O=C and N—H⋯N_thiazole. The space group is P1 with Z = 1, which is unusual for an achiral organic compound.

Keywords: thiazole; hydrazide; hydrogen bond; space group P1; crystal structure.

CCDC reference: 2099652

1. Chemical context

Heterocycles represent a link between organic synthesis and pharmaceutical chemistry, thereby encouraging researchers to discover new hetereocyclic drug candidates. One of the most prominent heterocycles is benzothiazole, a privileged scaffold in the field of synthetic and medicinal chemistry (Elgemeie et al., 2000a ,b ). Its derivatives and metal complexes possess a wide range of pharmacological properties and a high degree of structural diversity that have proved vital for the investigation for novel therapeutics (Elgemeie et al., 2020 ; Gill et al., 2015 ). The carbon atom C2 (standard numbering; the carbon atom between nitrogen and sulfur) is the most attractive site both from a synthetic and medicinal point of view (Azzam et al., 2020a ,b ). As structure–activity relationships have shown, changes in the substituent at C2 can induce marked changes in the biological activity (Azzam et al., 2017a ,b ). Numerous biologically potent molecules containing 2-substituted benzothiazole scaffolds have extensive biological applications (Keri et al., 2015 ), such as anti-microbial (König et al., 2011 ), anti-malarial (Bowyer et al., 2007 ) and anti-inflammatory (Wang et al., 2009 ). Among the 2-substituted benzothiazoles, 2-aryl benzothiazoles are versatile scaffolds that have major biological and industrial applications (Kamal et al., 2011 ). Part of our research has therefore concentrated on the synthetic pathways of 2-arylbenzothiazoles (Azzam et al., 2019 ; Elgemeie & Elghandour, 1990 ). Recently, we contributed to current progress in the manufacturing and biological estimation of 2-aryl, 2-pyridyl and 2-pyrimidylbenzothiazoles and other antimetabolites as potent chemotherapeutic agents (Azzam et al., 2020c ; Metwally et al., 2021 ). Here we deal with synthetic approaches to the new compound N′-(2-(benzo[d]thiazol-2-yl)acetyl)benzohydrazide (3). Compound 3 was prepared by the reaction of 2-(benzo[d]thiazol-2-yl)acetohydrazide (2) with benzoyl chloride in the presence of pyridine at room temperature. The structure of 3 was initially determined on the basis of spectroscopic data and elemental analysis. In order to establish the structure of the product unambiguously, its crystal structure was determined and is presented here.

2. Structural commentary

The structure determination confirms the formation of compound 3 (Fig. 1). Bond lengths and angles may be regarded as normal (Allen et al., 1987 ); a selection is presented in Table 1. The geometry at the hydrazinic nitrogen atom N1 is essentially planar, but N2 is slightly pyramidalized [angle sum 355 (2)°; the nitrogen atom lies 0.15 (1) Å out of the plane of its substituents]. The general shape of the molecule is defined by the torsion angles along the atom chain S1—C2—C8—C9—N1—N2—C10—C11—C12, which are also given in Table 1; in particular, the torsion angle about the hydrazine N1—N2 bond is 66.44 (15)° [cf. H01—N1—N2—H02 101 (3)°]. Each hydrazinic hydrogen atom lies antiperiplanar to a carbonyl oxygen atom across the respective N—C bond. The interplanar angle between the benzothiazol group and the phenyl ring is 75.65 (3)°.

Table 1
Selected geometric parameters (Å, °)

S1—C7A	1.7310 (13)	N1—N2	1.3901 (14)
S1—C2	1.7422 (12)	N3—C3A	1.3939 (16)
C2—N3	1.2993 (16)

C7A—S1—C2	89.49 (6)	C10—N2—N1	117.28 (10)
N3—C2—S1	115.83 (9)	C2—N3—C3A	110.61 (10)
C9—N1—N2	119.00 (10)

C9—N1—N2—C10	66.44 (15)	N2—C10—C11—C12	−18.46 (17)
S1—C2—C8—C9	80.26 (12)	O1—C9—N1—H01	175 (2)
N2—N1—C9—C8	−173.21 (10)	O2—C10—N2—H02	166 (2)
C2—C8—C9—N1	−152.41 (11)	H01—N1—N2—H02	101 (3)
N1—N2—C10—C11	−167.79 (10)

Figure 1
The molecule of compound 3 in the crystal. Ellipsoids represent 50% probability levels.

3. Supramolecular features

Two classical hydrogen bonds, from the hydrazinic hydrogen atoms to the carbonyl oxygen O1 and the heterocyclic nitrogen N3 (Table 2), link the molecules to form layers parallel to the ab plane (Fig. 2).

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H01⋯O1ⁱ	0.88 (3)	2.02 (3)	2.8438 (14)	157 (3)
N2—H02⋯N3ⁱⁱ	0.85 (3)	2.15 (3)	2.9736 (15)	162 (3)
Symmetry codes: (i) x+1, y, z; (ii) .

Figure 2
Packing diagram of compound 3 viewed perpendicular to the ab plane. Dashed lines represent classical hydrogen bonds. Hydrogen atoms not involved in hydrogen bonding are omitted for clarity. Selected atoms of the asymmetric unit are labelled.

4. Database survey

A database search (CSD Version 5.41) for other structures containing the same benzothiazol-acetylhydrazide moiety gave only one hit, refcode JEBQOZ, with a p-tosylate group replacing the benzoyl group of 3; this was our previous publication (Azzam et al., 2017b). There are major conformational differences between the two structures, e.g. the C—C—C(=O)—N torsion angle of JEBQOZ is −109.79 (19)° in contrast to −152.41 (11)° in the title structure. The average database bond lengths C2—S and C2—N for the benzo[d]thiazole ring system were calculated; for 444 hits (600 different molecules) the values were 1.750 (16) and 1.300 (29) Å, respectively, virtually unchanged from the values we obtained previously (Azzam et al., 2017b); however, we regret having mistyped the latter value as 1.200.

Anecdotal evidence, combined with previous experience, would suggest that it is unusual for an achiral compound to crystallize in space group P1, which may be considered as a moderately rare space group; of the over 1.1 million structures in the Cambridge database, only 9843 are in P1 (8832 with coordinates available, 6730 of these without disorder).

We therefore wished to see how many of the P1 structures in the CSD, particularly those with Z = 1, were achiral. Unfortunately, there is at present no means of identifying, labelling and searching for chirality or chiral (`asymmetric') atoms using the standard ConQuest search routines, and it is clearly unfeasible to check all the P1 structures by hand. We therefore began by simply considering the small and possibly non-representative subset of 20 P1 structures (13 with Z > 1) that were determined by PGJ. Of these, 14 were pure enantiomers; for 12 of these, the absolute configuration was determined. Of the remaining six, five were not organic compounds [two metal complexes with Z = 1 (Jones et al., 1996 ; Filimon et al., 2014 ), two organotellurium compounds (Jones et al., 2015 , Z = 1; du Mont et al., 2010 , Z = 4), and one phosphane sulfide (Taouss & Jones, 2013 , Z = 2)], and the remaining structure (Focken et al., 2001 , Z = 4) displayed planar chirality, but contained no `asymmetric' atom. On this limited basis, we would therefore postulate that is very rare for achiral organic compounds to crystallize in P1, especially with Z = 1. An extension of this survey to all P1 structures in the CCDC is being planned.

5. Synthesis and crystallization

A mixture of 2-(benzo[d]thiazol-2-yl)acetohydrazide 2 (0.08 mol) and pyridine (10 mL) was stirred for 15 min at room temperature. Benzoyl chloride (0.16 mol) was then added gradually to the reaction mixture, which was stirred for 15 min at 273 K. The reaction mixture was left to stand at room temperature for another 3 h, then poured onto ice water and neutralized with HCl. The precipitate thus formed was filtered off and dried to produce a white solid product 3. This was washed with ethyl acetate and recrystallized from ethanol; yield 85%, m.p. 487 K.

IR (KBr, cm⁻¹): υ 3429–3284 (NH), 2974 (CH aromatic), 1696, 1662 (2CO); ¹H NMR (400 MHz, DMSO-d₆): δ 4.23 (s, 2H, CH₂), 7.43 (t, J = 7.2 Hz, 1H, benzothiazole H), 7.49–7.53 (m, 3H, C₆H₅), 7.58 (t, J = 7.2 Hz, 1H, benzothiazole H), 7.91 (d, J = 7.2 Hz, 2H, C₆H₅), 7.99 (d, J = 9.6 Hz, 1H, benzothiazole H), 8.09 (d, J = 9.2 Hz, 1H, benzothiazole H), 10.48 (s, 1H, NH), 10.55 (s, 1H, NH); ¹³C NMR (100 MHz, DMSO-d₆): δ 39.4 (CH₂), 122.5, 122.8, 125.5, 126.5, 127.9, 128.9, 132.4, 132.8, 136.9, 152.7, 165.0 (Ar-C), 166.0, 167.1 (2CO). Analysis: calculated for C₁₆H₁₃N₃O₂S (311.36): C 61.72; H 4.21; N 13.50%; found: C 61.70; H 4.22; N 13.55%.

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 3. The hydrogen atoms of the NH groups were refined freely. Other hydrogens were included using a riding model starting from calculated positions (C—H_aromatic = 0.95, C—H_methylene = 0.99 Å). The U(H) values were fixed at 1.2 times the equivalent U_iso value of the parent carbon atoms.

Table 3
Experimental details

Crystal data
Chemical formula	C₁₆H₁₃N₃O₂S
M_r	311.35
Crystal system, space group	Triclinic, P1
Temperature (K)	100
a, b, c (Å)	4.71248 (9), 6.96463 (14), 11.5455 (3)
α, β, γ (°)	105.6168 (18), 95.7876 (16), 95.9993 (16)
V (Å³)	359.64 (1)
Z	1
Radiation type	Mo Kα
μ (mm⁻¹)	0.24
Crystal size (mm)	0.20 × 0.16 × 0.05

Data collection
Diffractometer	XtaLAB Synergy, HyPix
Absorption correction	Multi-scan (CrysAlis PRO; Rigaku OD, 2020 $[Rigaku OD (2020). CrysAlis PRO. Rigaku Oxford Diffraction, Yarnton, England.]$ )
T_min, T_max	0.844, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	60895, 6522, 6312
R_int	0.034
(sin θ/λ)_max (Å⁻¹)	0.843

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.030, 0.078, 1.06
No. of reflections	6522
No. of parameters	207
No. of restraints	3
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.41, −0.27
Absolute structure	Flack x determined using 2959 quotients [(I⁺)−(I⁻)]/[(I⁺)+(I⁻)] (Parsons et al., 2013 )
Absolute structure parameter	−0.016 (12)
Computer programs: CrysAlis PRO (Rigaku OD, 2020 $[Rigaku OD (2020). CrysAlis PRO. Rigaku Oxford Diffraction, Yarnton, England.]$ ), SHELXT (Sheldrick, 2015a ), SHELXL2018/3 (Sheldrick, 2015b ) and XP (Siemens, 1994 ).

The compound contains no chiral centres and crystallizes only by chance in a chiral (Sohncke) space group.

Supporting information

CCDC reference: 2099652

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S2056989021007672/yk2155sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989021007672/yk2155Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2056989021007672/yk2155Isup3.cml

checkCIF report

Computing details top

Data collection: CrysAlis PRO (Rigaku OD, 2020); cell refinement: CrysAlis PRO (Rigaku OD, 2020); data reduction: CrysAlis PRO (Rigaku OD, 2020); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2018/3 (Sheldrick, 2015b); molecular graphics: XP (Siemens, 1994); software used to prepare material for publication: SHELXL2018/3 (Sheldrick, 2015b).

N'-[2-(Benzo[d]thiazol-2-yl)acetyl]benzohydrazide top

Crystal data top

C₁₆H₁₃N₃O₂S	Z = 1
M_r = 311.35	F(000) = 162
Triclinic, P1	D_x = 1.438 Mg m⁻³
a = 4.71248 (9) Å	Mo Kα radiation, λ = 0.71073 Å
b = 6.96463 (14) Å	Cell parameters from 40070 reflections
c = 11.5455 (3) Å	θ = 3.0–37.0°
α = 105.6168 (18)°	µ = 0.24 mm⁻¹
β = 95.7876 (16)°	T = 100 K
γ = 95.9993 (16)°	Plate, colourless
V = 359.64 (1) Å³	0.20 × 0.16 × 0.05 mm

Data collection top

XtaLAB Synergy, HyPix diffractometer	6522 independent reflections
Radiation source: micro-focus sealed X-ray tube, PhotonJet (Mo) X-ray Source	6312 reflections with I > 2σ(I)
Mirror monochromator	R_int = 0.034
Detector resolution: 10.0000 pixels mm^-1	θ_max = 36.8°, θ_min = 3.1°
ω scans	h = −7→7
Absorption correction: multi-scan (CrysAlisPro; Rigaku OD, 2020)	k = −11→11
T_min = 0.844, T_max = 1.000	l = −18→19
60895 measured reflections

Refinement top

Refinement on F²	Hydrogen site location: mixed
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F² > 2σ(F²)] = 0.030	w = 1/[σ²(F_o²) + (0.0486P)² + 0.0499P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.078	(Δ/σ)_max < 0.001
S = 1.06	Δρ_max = 0.41 e Å⁻³
6522 reflections	Δρ_min = −0.27 e Å⁻³
207 parameters	Absolute structure: Flack x determined using 2959 quotients [(I⁺)-(I^-)]/[(I⁺)+(I^-)] (Parsons et al., 2013)
3 restraints	Absolute structure parameter: −0.016 (12)
Primary atom site location: structure-invariant direct methods

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.

Least-squares planes (x,y,z in crystal coordinates) and deviations from them (* indicates atom used to define plane)

3.5462 (0.0009) x + 3.6978 (0.0019) y - 0.2128 (0.0045) z = 6.1650 (0.0025)

* -0.0069 (0.0007) S1 * 0.0023 (0.0009) C2 * 0.0044 (0.0009) N3 * -0.0011 (0.0011) C4 * -0.0046 (0.0012) C5 * 0.0007 (0.0012) C6 * 0.0082 (0.0011) C7 * -0.0004 (0.0011) C3A * -0.0026 (0.0011) C7A -0.0318 (0.0015) C8

Rms deviation of fitted atoms = 0.0043

- 3.3343 (0.0019) x + 1.8849 (0.0037) y + 7.6563 (0.0052) z = 0.2749 (0.0019)

Angle to previous plane (with approximate esd) = 75.652 ( 0.033 )

* 0.0041 (0.0009) C11 * 0.0008 (0.0009) C12 * -0.0051 (0.0009) C13 * 0.0044 (0.0010) C14 * 0.0006 (0.0010) C15 * -0.0049 (0.0009) C16 -0.0026 (0.0020) C10

Rms deviation of fitted atoms = 0.0038

=============================================================================

- 0.0418 (0.0830) x - 3.0734 (0.0043) y + 11.3227 (0.0146) z = 3.7743 (0.0598)

* 0.0000 (0.0000) N2 * 0.0000 (0.0001) C9 * 0.0000 (0.0000) H01 0.0634 (0.0123) N1

Rms deviation of fitted atoms = 0.0000

4.0751 (0.0123) x - 3.1432 (0.0992) y - 3.6530 (0.1475) z = 1.0965 (0.0176)

* 0.0000 (0.0001) N1 * 0.0000 (0.0001) C10 * 0.0000 (0.0000) H02 0.1480 (0.0122) N2

Rms deviation of fitted atoms = 0.0000

=============================================================================

Further torsion angles:

97.53 ( 0.11) O2 - C10 ··· C9 - O1 175.44 ( 2.18) H01 - N1 - C9 - O1 165.89 ( 2.18) H02 - N2 - C10 - O2 101.08 ( 2.76) H01 - N1 - N2 - H02

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

	x	y	z	U_iso*/U_eq
S1	0.88408 (5)	0.86164 (4)	0.76703 (3)	0.01738 (7)
C2	0.8642 (3)	0.87459 (17)	0.61788 (11)	0.01314 (18)
N1	0.9484 (2)	0.36700 (15)	0.44206 (10)	0.01379 (17)
H01	1.135 (6)	0.377 (4)	0.440 (3)	0.031 (6)*
N2	0.7891 (2)	0.17967 (15)	0.38503 (10)	0.01379 (17)
H02	0.743 (6)	0.111 (4)	0.433 (2)	0.025 (6)*
N3	0.7208 (2)	1.01131 (16)	0.59308 (10)	0.01420 (17)
C3A	0.6136 (3)	1.11873 (18)	0.69578 (11)	0.01407 (18)
C4	0.4492 (3)	1.2765 (2)	0.70032 (13)	0.0202 (2)
H4	0.401227	1.318921	0.630063	0.024*
C5	0.3581 (3)	1.3691 (2)	0.80960 (15)	0.0232 (3)
H5	0.245566	1.475698	0.813913	0.028*
C6	0.4294 (3)	1.3082 (2)	0.91385 (13)	0.0214 (2)
H6	0.364372	1.374379	0.987636	0.026*
C7	0.5928 (3)	1.1534 (2)	0.91122 (12)	0.0191 (2)
H7	0.642508	1.113038	0.982118	0.023*
C7A	0.6821 (3)	1.05845 (18)	0.80085 (11)	0.01465 (19)
C8	1.0007 (3)	0.72931 (17)	0.52744 (11)	0.01505 (19)
H8A	1.188694	0.709803	0.566030	0.018*
H8B	1.035889	0.785089	0.459045	0.018*
C9	0.8084 (3)	0.52723 (17)	0.47944 (11)	0.01345 (18)
O1	0.5458 (2)	0.51401 (15)	0.47552 (10)	0.01766 (17)
C10	0.6341 (3)	0.15543 (17)	0.27343 (11)	0.01340 (18)
O2	0.6698 (2)	0.27818 (15)	0.21612 (10)	0.01878 (17)
C11	0.4201 (3)	−0.03063 (17)	0.22693 (11)	0.01309 (18)
C12	0.4296 (3)	−0.19751 (18)	0.27175 (12)	0.01574 (19)
H12	0.576152	−0.195084	0.335201	0.019*
C13	0.2252 (3)	−0.36724 (18)	0.22370 (12)	0.0172 (2)
H13	0.233253	−0.481009	0.253846	0.021*
C14	0.0089 (3)	−0.37052 (19)	0.13160 (12)	0.0180 (2)
H14	−0.132276	−0.485758	0.099661	0.022*
C15	−0.0006 (3)	−0.2051 (2)	0.08620 (13)	0.0191 (2)
H15	−0.147919	−0.208041	0.022925	0.023*
C16	0.2046 (3)	−0.03535 (19)	0.13308 (12)	0.0164 (2)
H16	0.198429	0.076976	0.101456	0.020*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.01905 (14)	0.01772 (12)	0.01655 (12)	0.00614 (9)	0.00163 (9)	0.00577 (9)
C2	0.0104 (5)	0.0131 (4)	0.0151 (4)	0.0011 (3)	0.0022 (3)	0.0026 (3)
N1	0.0089 (4)	0.0117 (4)	0.0194 (4)	0.0008 (3)	0.0019 (3)	0.0024 (3)
N2	0.0133 (4)	0.0114 (4)	0.0158 (4)	−0.0007 (3)	0.0011 (3)	0.0038 (3)
N3	0.0136 (4)	0.0139 (4)	0.0150 (4)	0.0025 (3)	0.0025 (3)	0.0034 (3)
C3A	0.0126 (5)	0.0129 (4)	0.0161 (4)	0.0021 (3)	0.0019 (3)	0.0030 (3)
C4	0.0209 (6)	0.0178 (5)	0.0229 (6)	0.0084 (4)	0.0036 (4)	0.0054 (4)
C5	0.0203 (6)	0.0198 (5)	0.0274 (6)	0.0077 (4)	0.0049 (5)	0.0008 (5)
C6	0.0173 (6)	0.0214 (6)	0.0212 (6)	0.0023 (4)	0.0051 (4)	−0.0023 (4)
C7	0.0182 (6)	0.0214 (5)	0.0156 (5)	0.0017 (4)	0.0032 (4)	0.0015 (4)
C7A	0.0132 (5)	0.0146 (4)	0.0152 (4)	0.0019 (3)	0.0023 (3)	0.0025 (3)
C8	0.0104 (5)	0.0126 (4)	0.0200 (5)	0.0006 (3)	0.0042 (4)	0.0006 (4)
C9	0.0106 (5)	0.0128 (4)	0.0160 (4)	0.0009 (3)	0.0026 (3)	0.0025 (3)
O1	0.0094 (4)	0.0163 (4)	0.0253 (4)	0.0008 (3)	0.0032 (3)	0.0026 (3)
C10	0.0128 (5)	0.0120 (4)	0.0158 (4)	0.0013 (3)	0.0032 (3)	0.0043 (3)
O2	0.0217 (5)	0.0158 (4)	0.0194 (4)	−0.0020 (3)	0.0015 (3)	0.0081 (3)
C11	0.0133 (5)	0.0113 (4)	0.0148 (4)	0.0006 (3)	0.0029 (3)	0.0039 (3)
C12	0.0158 (5)	0.0130 (4)	0.0182 (5)	0.0005 (4)	0.0007 (4)	0.0051 (4)
C13	0.0192 (6)	0.0121 (4)	0.0198 (5)	−0.0009 (4)	0.0029 (4)	0.0047 (4)
C14	0.0170 (5)	0.0156 (5)	0.0190 (5)	−0.0022 (4)	0.0028 (4)	0.0025 (4)
C15	0.0167 (6)	0.0193 (5)	0.0198 (5)	−0.0015 (4)	−0.0015 (4)	0.0058 (4)
C16	0.0158 (5)	0.0156 (5)	0.0179 (5)	0.0003 (4)	0.0005 (4)	0.0065 (4)

Geometric parameters (Å, º) top

S1—C7A	1.7310 (13)	C11—C16	1.3994 (17)
S1—C2	1.7422 (12)	C12—C13	1.3909 (17)
C2—N3	1.2993 (16)	C13—C14	1.390 (2)
C2—C8	1.4933 (17)	C14—C15	1.3911 (19)
N1—C9	1.3488 (16)	C15—C16	1.3919 (18)
N1—N2	1.3901 (14)	N1—H01	0.88 (3)
N2—C10	1.3747 (16)	N2—H02	0.85 (3)
N3—C3A	1.3939 (16)	C4—H4	0.9500
C3A—C4	1.4018 (18)	C5—H5	0.9500
C3A—C7A	1.4056 (17)	C6—H6	0.9500
C4—C5	1.386 (2)	C7—H7	0.9500
C5—C6	1.401 (2)	C8—H8A	0.9900
C6—C7	1.385 (2)	C8—H8B	0.9900
C7—C7A	1.3967 (19)	C12—H12	0.9500
C8—C9	1.5237 (16)	C13—H13	0.9500
C9—O1	1.2266 (15)	C14—H14	0.9500
C10—O2	1.2222 (14)	C15—H15	0.9500
C10—C11	1.4925 (16)	C16—H16	0.9500
C11—C12	1.3967 (17)

C7A—S1—C2	89.49 (6)	C14—C15—C16	120.28 (12)
N3—C2—C8	124.45 (11)	C15—C16—C11	119.80 (11)
N3—C2—S1	115.83 (9)	C9—N1—H01	123.3 (19)
C8—C2—S1	119.70 (9)	N2—N1—H01	116.8 (19)
C9—N1—N2	119.00 (10)	C10—N2—H02	123.3 (18)
C10—N2—N1	117.28 (10)	N1—N2—H02	114.4 (18)
C2—N3—C3A	110.61 (10)	C5—C4—H4	120.7
N3—C3A—C4	125.26 (11)	C3A—C4—H4	120.7
N3—C3A—C7A	114.95 (11)	C4—C5—H5	119.4
C4—C3A—C7A	119.79 (12)	C6—C5—H5	119.4
C5—C4—C3A	118.52 (13)	C7—C6—H6	119.4
C4—C5—C6	121.11 (13)	C5—C6—H6	119.4
C7—C6—C5	121.18 (13)	C6—C7—H7	121.1
C6—C7—C7A	117.77 (13)	C7A—C7—H7	121.1
C7—C7A—C3A	121.63 (12)	C2—C8—H8A	109.5
C7—C7A—S1	129.24 (10)	C9—C8—H8A	109.5
C3A—C7A—S1	109.13 (9)	C2—C8—H8B	109.5
C2—C8—C9	110.93 (10)	C9—C8—H8B	109.5
O1—C9—N1	123.27 (11)	H8A—C8—H8B	108.0
O1—C9—C8	121.67 (11)	C13—C12—H12	119.9
N1—C9—C8	115.06 (10)	C11—C12—H12	119.9
O2—C10—N2	122.11 (11)	C14—C13—H13	120.0
O2—C10—C11	122.31 (11)	C12—C13—H13	120.0
N2—C10—C11	115.59 (10)	C13—C14—H14	120.0
C12—C11—C16	119.69 (11)	C15—C14—H14	120.0
C12—C11—C10	122.96 (11)	C14—C15—H15	119.9
C16—C11—C10	117.35 (10)	C16—C15—H15	119.9
C13—C12—C11	120.15 (11)	C15—C16—H16	120.1
C14—C13—C12	120.05 (11)	C11—C16—H16	120.1
C13—C14—C15	120.02 (11)

C7A—S1—C2—N3	−0.19 (10)	N2—N1—C9—O1	6.66 (18)
C7A—S1—C2—C8	−178.46 (10)	N2—N1—C9—C8	−173.21 (10)
C9—N1—N2—C10	66.44 (15)	C2—C8—C9—O1	27.72 (16)
C8—C2—N3—C3A	178.23 (11)	C2—C8—C9—N1	−152.41 (11)
S1—C2—N3—C3A	0.05 (14)	N1—N2—C10—O2	12.34 (18)
C2—N3—C3A—C4	−179.93 (12)	N1—N2—C10—C11	−167.79 (10)
C2—N3—C3A—C7A	0.16 (15)	O2—C10—C11—C12	161.41 (13)
N3—C3A—C4—C5	−179.93 (13)	N2—C10—C11—C12	−18.46 (17)
C7A—C3A—C4—C5	0.0 (2)	O2—C10—C11—C16	−17.71 (18)
C3A—C4—C5—C6	0.4 (2)	N2—C10—C11—C16	162.42 (11)
C4—C5—C6—C7	−0.1 (2)	C16—C11—C12—C13	−0.29 (19)
C5—C6—C7—C7A	−0.6 (2)	C10—C11—C12—C13	−179.40 (12)
C6—C7—C7A—C3A	0.96 (19)	C11—C12—C13—C14	−0.6 (2)
C6—C7—C7A—S1	−179.59 (11)	C12—C13—C14—C15	0.9 (2)
N3—C3A—C7A—C7	179.25 (12)	C13—C14—C15—C16	−0.4 (2)
C4—C3A—C7A—C7	−0.65 (19)	C14—C15—C16—C11	−0.5 (2)
N3—C3A—C7A—S1	−0.30 (13)	C12—C11—C16—C15	0.84 (19)
C4—C3A—C7A—S1	179.80 (10)	C10—C11—C16—C15	179.99 (12)
C2—S1—C7A—C7	−179.25 (13)	O1—C9—N1—H01	175 (2)
C2—S1—C7A—C3A	0.26 (9)	O2—C10—N2—H02	166 (2)
N3—C2—C8—C9	−97.86 (14)	H01—N1—N2—H02	101 (3)
S1—C2—C8—C9	80.26 (12)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H01···O1ⁱ	0.88 (3)	2.02 (3)	2.8438 (14)	157 (3)
N2—H02···N3ⁱⁱ	0.85 (3)	2.15 (3)	2.9736 (15)	162 (3)

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

Acknowledgements

We are grateful to various colleagues at the CCDC for helpful advice and assistance. We acknowledge support by the Open Access Publication Funds of the Technical University of Braunschweig

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