Crystal structure of 1-amino-3-(4-chloro­phen­yl)-2-cyano-3H-benzo[4,5]thia­zolo[3,2-a]pyridine-4-carboxamide

Metwally, N.H.; Elgemeie, G.H.; Abd Al-latif, E.S.M.; Jones, P.G.

doi:10.1107/S2056989025001562

research communications

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ISSN: 2056-9890

Volume 81| Part 4| April 2025| Pages 279-283

https://doi.org/10.1107/S2056989025001562

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Crystal structure of 1-amino-3-(4-chlorophenyl)-2-cyano-3H-benzo[4,5]thiazolo[3,2-a]pyridine-4-carboxamide

Nadia H. Metwally,^a Galal H. Elgemeie,^b El-shimaa S. M. Abd Al-latif ^a and Peter G. Jones ^c ^*

^aChemistry Department, Faculty of Science, Cairo University, Giza, 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: p.jones@tu-braunschweig.de

Edited by C. Schulzke, Universität Greifswald, Germany (Received 27 January 2025; accepted 20 February 2025; online 4 March 2025)

In the structure of the title compound, C₁₉H₁₃ClN₄OS, the four atoms of the pyridinic ring that are not fused with the thiazole, including the sp³ C atom, lie significantly outside the benzothiazole plane. A short intramolecular S⋯O contact of 2.5992 (4) Å is observed. The amide NH₂ group is planar, whereas the amine NH₂ group is pyramidalized. The three-dimensional packing involves two interconnected layer structures. The first, parallel to the bc plane, involves three classical hydrogen bonds N—H_amine⋯O (one of two), N—H_amine⋯Cl and one N—H_amide ⋯N_cyano; the second, parallel to the ab plane, involves two hydrogen bonds, N—H_amide⋯O and the second N—H_amine⋯O, together with the short and linear contact N_cyano⋯Cl—C, which may be regarded as a halogen bond.

Keywords: benzothiazole; hydrogen bonds; halogen bonds; crystal structure.

CCDC reference: 2425470

1. Chemical context

Benzothiazole and its fused-ring derivatives are among the most important heterocyclic compounds used in medicinal chemistry and are essential constituents of many medicines and natural heterocyclic compounds (Ammazzalorso et al., 2020 ). Fused benzothiazoles have a variety of established pharmacological qualities that are useful in the search for new and important therapeutic medications (Wang et al., 2009 ). Benzothiazoles display noteworthy biological actions, including antibacterial (Kashyap et al., 2023 ), antiviral (Ke et al., 2013 ) and anticancer (Irfan et al., 2020 ) effects, and are thus significant compounds for drug development (Rana et al., 2008 ); for some ongoing studies and associated discoveries, see Abdallah et al., 2023a ,b . The use of medications derived from benzothiazole derivatives has been extensively developed in clinical practice to treat a range of illnesses with great therapeutic efficacy (Huang et al., 2009 ).

We are interested in developing syntheses for the production of heterocycles based on benzothiazoles (and other heterocycles) that may find application in medicine (Mohamed-Ezzat et al. 2024 ); in this respect, we have reported the biological activity of a range of 2-pyrimidyl- and 2-pyridyl benzothiazole compounds with promising cytotoxic action (Azzam et al., 2020a ,b , 2022a ,b ).

As an extension of these results and our earlier studies (Metwally et al., 2022a ,b ), the goal of the current study was to design and produce benzothiazopyridines. The title compound 2, a substituted benzo[4,5]thiazolo[3,2-a]pyridine-4-carboxamide, was synthesized in good yield by reacting 2-(1,3-benzothiazol-2-yl)-3-(4-chlorophenyl)prop-2-enamide 1 with malononitrile in refluxing ethanol containing catalytic amounts of piperidine for 5 h (Fig. 1). We postulate that the reaction proceeds via the formation of Michael intermediate adducts. Compound 2 was previously synthesized by us using the reaction of 1,3-benzothiazole-2-acetamide with 4-chlorobenzylidenemalononitrile (Fathy & Elgemeie, 1988 ). The crystal structure of 2 was determined to establish its structure unambiguously.

Figure 1
The synthesis of compound 2 (Pip. = piperidine).

2. Structural commentary

The structure of compound 2 is shown in Fig. 2, with selected molecular dimensions in Table 1. Bond lengths and angles may be considered normal, e.g. the wide formally sp² external angles of ca. 125° at the junctions of five- and six-membered rings, and the bond lengths and angles around the sp³ atom C3. In the tricyclic ring system, the nine atoms C5–N13 are approximately coplanar (r.m.s. deviation = 0.04 Å); atoms C1, C2, C3 and C4 lie outside this plane by −0.474 (1), −0.234 (1), 0.492 (1) and 0.188 (1) Å, respectively. In the pyridinic ring, the atoms N13, C1, C2 and C3 are coplanar (r.m.s. deviation = 0.004 Å), with C4 and C5 lying outside this plane by 0.711 (1) and 0.556 (1) Å, respectively. The torsion angle C4—C5—N13—C1 differs markedly from zero, which may be associated with steric pressure imposed by the substituents at C1 and C4; however, N13, with its three at least formally single N—C bonds (cf. bond lengths in Table 1), may not be extensively involved in the aromatic system and thus would not necessarily impose planarity on the sequence C4—C5—N13—C1. The chlorophenyl ring is approximately perpendicular to the grouping C5–N13 [interplanar angle = 81.60 (1)°]; this is made clear by the side-on view of the molecule in Fig. 3. The geometry of the nitrogen atom N3 of the amide NH₂ group is essentially planar (angle sum = 359.5°), whereas that at the amine nitrogen N1 is pyramidalized (angle sum = 342.9°) and at N13 slightly pyramidalized (358.1°). There is a short intramolecular contact S6⋯O1 of 2.5992 (4) Å that determines the orientation of the amide group, being associated with a synperiplanar geometry in the atom sequence S6—C5—C4—C14—O1.

Table 1
Selected geometric parameters (Å, °)

C1—N1	1.3663 (6)	C5—N13	1.3998 (6)
C1—C2	1.3684 (6)	C5—S6	1.7464 (4)
C1—N13	1.3970 (6)	S6—C7	1.7523 (5)
C2—C15	1.4125 (6)	C12—N13	1.4168 (6)
C2—C3	1.5184 (6)	C14—O1	1.2567 (6)
C3—C4	1.5105 (6)	C14—N3	1.3422 (6)
C4—C5	1.3597 (6)	C15—N2	1.1627 (6)

C4—C5—S6	126.72 (3)	C1—N13—C5	117.93 (4)
C5—S6—C7	90.51 (2)	C1—N13—C12	126.47 (4)
C8—C7—S6	125.87 (4)	C5—N13—C12	113.70 (4)
C11—C12—N13	128.37 (4)

N13—C1—C2—C3	1.19 (6)	C14—C4—C5—S6	−7.60 (6)
C1—C2—C3—C4	−30.53 (6)	C2—C1—N13—C5	25.76 (6)
C2—C3—C4—C5	35.97 (5)	C4—C5—N13—C1	−19.82 (6)
C3—C4—C5—N13	−13.42 (6)	C5—C4—C14—O1	6.00 (7)

Figure 2
The molecule of compound 2 in the crystal. Ellipsoids represent 50% probability levels.

Figure 3
Side-on view of molecule 2.

3. Supramolecular features

The molecular packing is dominated by four classical hydrogen bonds from the hydrogen atoms of the NH₂ groups (Table 2), together with the short contact N2⋯Cl1(1 + x, −1 + y, z) of 3.1296 (5) Å. The angle C24—Cl1⋯N2′ is 177.86 (2)°, and the linearity indicates that the interaction is probably to be regarded as a halogen bond (see e.g. Metrangelo et al., 2008 ).

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H01⋯O1ⁱ	0.845 (11)	2.391 (11)	3.1341 (6)	147.2 (10)
N1—H02⋯Cl1ⁱⁱ	0.906 (13)	2.755 (13)	3.4516 (5)	134.6 (10)
N3—H03⋯O1ⁱⁱⁱ	0.837 (13)	2.016 (13)	2.8336 (6)	165.3 (12)
N3—H04⋯N2^iv	0.834 (12)	2.287 (13)	3.1109 (6)	169.9 (12)
C23—H23⋯S6^v	0.95	2.90	3.7631 (6)	152
Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) .

The packing is three-dimensional, but can be analysed as two interconnected layer structures. The first, parallel to the bc plane, involves the hydrogen bonds from H01, H02 and H04 (Fig. 4). Ribbons parallel to the c axis are prominent, and these are crosslinked parallel to the b axis by the interactions H02⋯Cl1. The second and more complex (thicker) layer is parallel to the ab plane and involves the hydrogen bonds from H01 and H03 together with the N⋯Cl halogen bonds (Fig. 5). Ribbons of molecules parallel to [1 $[\overline{1}]$ 0] (horizontal in Fig. 5) are prominent; these are linked by the contacts H03⋯O1, which are however difficult to recognize in Fig. 5 because the inversion-symmetric hydrogen-bond systems are viewed approximately edge-on (they are clearer on the right-hand edge of Fig. 5).

Figure 4
Packing diagram of compound 2 viewed perpendicular to the bc plane. Hydrogen bonds are indicated by thick dashed lines. Hydrogen atoms not involved in hydrogen bonds are omitted for clarity.

Figure 5
Packing diagram of compound 2 viewed perpendicular to the ab plane. Hydrogen bonds are indicated by thick and halogen bonds by thin dashed lines. Hydrogen atoms not involved in hydrogen bonds are omitted for clarity.

We incorporated three different contacts in both Figs. 4 and 5. A referee has correctly pointed out that this comes at the cost of some loss of clarity, and that a much more striking motif comes from the two hydrogen bonds H04⋯N2 and H03⋯O1. The ribbon thus generated is shown in Fig. 6; it runs parallel to [10 $[\overline{1}]$ ]. Neighbouring ribbons are related by the vector [111] (amongst others) and the ribbons thus lie in planes parallel to (1 $[\overline{2}]$ 1).

Figure 6
Packing diagram of compound 2 showing a ribbon generated by the hydrogen bonds H04⋯N2 and H03⋯N1 (indicated by dashed lines). The view direction is perpendicular to (1 $[\overline{2}]$ 1).

4. Database survey

The search employed the routine ConQuest (Bruno et al., 2002 ), part of Version 5.46 of the Cambridge Database (Groom et al., 2016 ). Only one structure containing the same tricyclic ring system as that in 2 was found, namely benzyl 4-benzoyl-1-methyl-3-phenyl-3H-benzo[4,5]thiazolo-[3,2-a]pyridine-2-carboxylate 3 (Chauhan & Kumara Swamy, 2024 ; refcode GOYRAR). This structure involves two independent molecules, which are however closely similar to each other except for ring orientations of the substituents (Fig. 7; r.m.s. deviation of fitted atoms = 0.029 Å). A similar fit of one molecule of 3 to the molecule of 2 (Fig. 8) gave an r.m.s deviation of 0.118 Å. There are significant differences between the pyridinic rings C1/C2/C3/C4/C5/N13, e.g. the bond length C1—N13, which is 1.3970 (6) / 1.420 (3) / 1.420 (3) Å for 2 and the two molecules in the structure of 3, in that order, and the ring torsion angles (starting with the bond C5—N13 and moving clockwise, these are −20/−28/−26, 26/28/29, 1/9/5, −30/−43/−37, 36/43/39 and −23/−11/−11, rounded to the nearest degree, for 2 and the two molecules of 3, in that order).

Figure 7
Least-squares fit of the two molecules of 3 (Chauhan & Kumara Swamy, 2024

), renumbered to be consistent with the numbering of 2. The fitted atoms are labelled.

Figure 8
Least-squares fit of 2 (full bonds, purple) to one molecule of 3 (dashed bonds, green). The fitted atoms are labelled.

Similar, but not identical, ring systems were reported in the structures of 2-(1-amino-2-cyano-3-oxo-3H-pyrido[2,1-b][1,3]benzothiazol-4-yl)-2,3,3-trimethylcyclopropane-1,1-dicarbonitrile methanol solvate (ROPSOH, Rémond et al., 2019 ) and 1-amino-2-(1,3-benzothiazol-2-yl)-3H-pyrido[2,1-b][1,3]benzothiazol-3-iminium chloride methanol solvate (REZVUQ; Chen et al., 2018 ), both of which have exocyclic double bonds at the atom corresponding to C3 of 2; and also tetramethyl 4aH-pyrido[2,1-b][1,3]benzothiazole-2,3,4,4a-tetracarboxylate and tetramethyl 1H-pyrido[2,1-b][1,3]benzothiazole-1,2,3,4-tetracarboxylate (VIZPIH and VIZPON; Li et al., 2023 ) and 5-imino-2,2-dimethyl-1-methylidene-1,2-dihydro-5H-furo[3′,2′:3,4]pyrido[2,1-b][1,3]benzothiazole-4-carbonitrile (ROPQAR; Rémond et al., 2019), in which the atoms corresponding to C5 in 2 bear an additional substituent and the double bond positions correspond to C1—C2 and C3—C4 of 2.

5. Synthesis and crystallization

Equimolar amounts of 2-(1,3-benzothiazol-2-yl)-3-(4-chlorophenyl) prop-2-enamide (1) (3.15 g, 1 mmol) and malononitrile (0.66 g, 1 mmol) were placed in a reaction flask and dissolved in 50 mL dry EtOH. A few drops of piperidine were added and the reaction mixture was heated to reflux for 5 h with stirring. After completing the reaction, the mixture was cooled to room temperature; the solid thus formed was filtered off and dried under vacuum. The product (2) was recrystallized from DMF and dried at room temperature.

Pale-yellow crystals, yield 80%, m.p. 578–580 K. IR (KBr): ν (cm⁻¹) 3423, 3394 (NH₂), 3156 (CH aromatic), 2184 (CN), 1644 (C=O); ¹H-NMR (400 MHz, DMSO-d₆): δ = 4.85 (s, 1H, pyridine-H), 6.43 (s, 2H, NH₂), 7.16–7.29 (m, 6H, Ar-H, NH₂), 7.36 (d, 2H, J = 8.4 Hz, Ar-H), 7.63 (d, 1H, J = 7.52 Hz, Ar-H), 7.74 (d, 1H, J = 8.24 Hz, Ar-H) ppm. ¹³C-NMR (100 MHz, DMSO-d₆): δ = 19.02, 56.53, 56.19, 99.53, 116.84, 120.91, 122.77, 124.61, 126.17, 127.88, 129.45, 136.29, 146.93, 148.43, 152.01, 152.03, 167.47 ppm. Analysis calculated for C₁₉H₁₃ClN₄OS (380.05): C 59.92, H 3.44, N 14.71, S 8.42. Found: C 60.09, H 2.92, N 14.90, S 8.24%.

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 3. The hydrogen atoms of the NH₂ groups were refined freely. Other hydrogen atoms were included using a riding model starting from calculated positions (C—H_methine = 1.00, C—H_arom = 0.95 Å). The U(H) values were fixed at 1.2 × U_eq of the parent carbon atoms.

Table 3
Experimental details

Crystal data
Chemical formula	C₁₉H₁₃ClN₄OS
M_r	380.84
Crystal system, space group	Triclinic, P $[\overline{1}]$
Temperature (K)	100
a, b, c (Å)	9.12784 (17), 9.29662 (17), 10.85172 (19)
α, β, γ (°)	83.0139 (14), 73.4998 (16), 71.4982 (16)
V (Å³)	836.80 (3)
Z	2
Radiation type	Mo Kα
μ (mm⁻¹)	0.37
Crystal size (mm)	0.15 × 0.15 × 0.12

Data collection
Diffractometer	XtaLAB Synergy
Absorption correction	Multi-scan (CrysAlis PRO; Rigaku OD, 2023 $[Rigaku OD (2023). CrysAlis PRO, Version 1.171.42.79a. Rigaku Oxford Diffraction, Yarnton, England.]$ )
T_min, T_max	0.953, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	138480, 13768, 11364
R_int	0.041
θ values (°)	θ_max = 45.0, θ_min = 2.3
(sin θ/λ)_max (Å⁻¹)	0.996

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.029, 0.092, 1.05
No. of reflections	13768
No. of parameters	251
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.79, −0.43
Computer programs: CrysAlis PRO (Rigaku OD, 2023 $[Rigaku OD (2023). CrysAlis PRO, Version 1.171.42.79a. Rigaku Oxford Diffraction, Yarnton, England.]$ ), SHELXT (Sheldrick, 2015a ), SHELXL2019/3 (Sheldrick, 2015b ) and XP (Bruker, 1998 ), publCIF (Westrip, 2010 ).

The program checkCIF reported a problem with badly-fitting reflections at the level ALERT B: ‘Number of (Iobs-Icalc)/Sigma(W) > 10 Outliers. . 2’. In our experience, this is not unusual for organic structures measured to high diffraction angles. Omitting the five worst reflections in fact led (after an appropriate change of the weighting scheme) to a slight increase in wR2, so they were retained.

Supporting information

CCDC reference: 2425470

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S2056989025001562/yz2064sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989025001562/yz2064Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2056989025001562/yz2064Isup3.cml

checkCIF report

Computing details top

1-Amino-3-(4-chlorophenyl)-2-cyano-3H-benzo[4,5]thiazolo[3,2-a]pyridine-4-carboxamide top

Crystal data top

C₁₉H₁₃ClN₄OS	Z = 2
M_r = 380.84	F(000) = 392
Triclinic, P1	D_x = 1.511 Mg m⁻³
a = 9.12784 (17) Å	Mo Kα radiation, λ = 0.71073 Å
b = 9.29662 (17) Å	Cell parameters from 73214 reflections
c = 10.85172 (19) Å	θ = 2.3–45.1°
α = 83.0139 (14)°	µ = 0.37 mm⁻¹
β = 73.4998 (16)°	T = 100 K
γ = 71.4982 (16)°	Block, pale yellow
V = 836.80 (3) Å³	0.15 × 0.15 × 0.12 mm

Data collection top

XtaLAB Synergy diffractometer	13768 independent reflections
Radiation source: micro-focus sealed X-ray tube, PhotonJet (Mo) X-ray Source	11364 reflections with I > 2σ(I)
Mirror monochromator	R_int = 0.041
Detector resolution: 10.0000 pixels mm^-1	θ_max = 45.0°, θ_min = 2.3°
ω scans	h = −18→18
Absorption correction: multi-scan (CrysAlisPro; Rigaku OD, 2023)	k = −18→18
T_min = 0.953, T_max = 1.000	l = −21→21
138480 measured reflections

Refinement top

Refinement on F²	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.029	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.092	w = 1/[σ²(F_o²) + (0.0528P)² + 0.0873P] where P = (F_o² + 2F_c²)/3
S = 1.05	(Δ/σ)_max = 0.002
13768 reflections	Δρ_max = 0.79 e Å⁻³
251 parameters	Δρ_min = −0.43 e Å⁻³
0 restraints

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

	x	y	z	U_iso*/U_eq
C1	0.62863 (5)	0.18304 (5)	0.26384 (4)	0.00979 (6)
C2	0.55764 (5)	0.15435 (5)	0.17797 (4)	0.00975 (6)
C3	0.38005 (5)	0.17027 (5)	0.21294 (4)	0.00936 (6)
H3	0.366407	0.090592	0.166731	0.011*
C4	0.32786 (5)	0.13443 (5)	0.35529 (4)	0.00979 (6)
C5	0.39633 (5)	0.17806 (5)	0.43467 (4)	0.00967 (6)
S6	0.33319 (2)	0.18032 (2)	0.60235 (2)	0.01162 (2)
C7	0.48320 (6)	0.25861 (5)	0.60550 (4)	0.01302 (7)
C8	0.50543 (8)	0.30447 (7)	0.71456 (5)	0.01844 (9)
H8	0.440305	0.289424	0.797584	0.022*
C9	0.62517 (9)	0.37289 (7)	0.69938 (6)	0.02188 (10)
H9	0.643736	0.403125	0.772723	0.026*
C10	0.71786 (8)	0.39714 (7)	0.57686 (6)	0.02012 (9)
H10	0.797670	0.445775	0.567855	0.024*
C11	0.69604 (7)	0.35157 (6)	0.46715 (5)	0.01556 (8)
H11	0.758821	0.369660	0.383928	0.019*
C12	0.57950 (6)	0.27875 (5)	0.48314 (4)	0.01175 (6)
N13	0.53378 (5)	0.22529 (5)	0.38728 (4)	0.01024 (5)
C14	0.19973 (5)	0.06575 (5)	0.41360 (4)	0.01091 (6)
C15	0.65300 (5)	0.10088 (5)	0.05570 (4)	0.01129 (6)
C21	0.27580 (5)	0.32411 (5)	0.17334 (4)	0.01002 (6)
C22	0.12148 (6)	0.38940 (6)	0.24858 (5)	0.01569 (8)
H22	0.082993	0.340524	0.327728	0.019*
C23	0.02267 (6)	0.52478 (6)	0.21005 (5)	0.01809 (9)
H23	−0.082033	0.568194	0.262528	0.022*
C24	0.07886 (6)	0.59555 (6)	0.09417 (5)	0.01406 (7)
C25	0.23230 (6)	0.53403 (6)	0.01705 (5)	0.01415 (7)
H25	0.270135	0.583256	−0.062092	0.017*
C26	0.32980 (6)	0.39891 (5)	0.05771 (4)	0.01231 (7)
H26	0.435145	0.356780	0.005776	0.015*
N1	0.78675 (5)	0.17302 (5)	0.23985 (4)	0.01353 (6)
H01	0.8258 (14)	0.1355 (13)	0.3026 (11)	0.023 (3)*
H02	0.8437 (16)	0.1369 (14)	0.1610 (12)	0.034 (3)*
N2	0.72660 (6)	0.05978 (6)	−0.04687 (4)	0.01580 (7)
N3	0.13807 (5)	0.01158 (6)	0.33732 (4)	0.01399 (6)
H03	0.0645 (15)	−0.0260 (14)	0.3758 (12)	0.031 (3)*
H04	0.1759 (15)	0.0036 (14)	0.2581 (12)	0.029 (3)*
Cl1	−0.04686 (2)	0.76356 (2)	0.04690 (2)	0.01904 (3)
O1	0.14777 (5)	0.06089 (5)	0.53392 (3)	0.01460 (6)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.00992 (14)	0.01110 (14)	0.00817 (13)	−0.00344 (11)	−0.00189 (11)	0.00008 (11)
C2	0.00965 (13)	0.01188 (14)	0.00725 (13)	−0.00326 (11)	−0.00126 (10)	−0.00066 (11)
C3	0.00985 (13)	0.01111 (14)	0.00723 (13)	−0.00380 (11)	−0.00155 (10)	−0.00048 (10)
C4	0.01045 (14)	0.01187 (14)	0.00733 (13)	−0.00455 (11)	−0.00160 (11)	0.00026 (11)
C5	0.01058 (14)	0.01073 (14)	0.00727 (13)	−0.00326 (11)	−0.00151 (10)	−0.00036 (10)
S6	0.01369 (5)	0.01322 (4)	0.00677 (4)	−0.00345 (3)	−0.00127 (3)	−0.00071 (3)
C7	0.01710 (18)	0.01301 (15)	0.00945 (14)	−0.00394 (13)	−0.00428 (13)	−0.00177 (12)
C8	0.0267 (2)	0.0196 (2)	0.01145 (17)	−0.00738 (18)	−0.00704 (16)	−0.00321 (15)
C9	0.0317 (3)	0.0220 (2)	0.0178 (2)	−0.0100 (2)	−0.0117 (2)	−0.00437 (17)
C10	0.0265 (3)	0.0193 (2)	0.0211 (2)	−0.01052 (19)	−0.01112 (19)	−0.00304 (17)
C11	0.01864 (19)	0.01591 (18)	0.01571 (18)	−0.00815 (15)	−0.00618 (15)	−0.00159 (14)
C12	0.01476 (16)	0.01154 (14)	0.01035 (14)	−0.00424 (12)	−0.00459 (12)	−0.00149 (11)
N13	0.01129 (13)	0.01244 (13)	0.00781 (12)	−0.00481 (10)	−0.00186 (10)	−0.00145 (10)
C14	0.01048 (14)	0.01328 (15)	0.00875 (14)	−0.00461 (12)	−0.00140 (11)	0.00065 (11)
C15	0.01112 (15)	0.01340 (15)	0.00857 (14)	−0.00324 (12)	−0.00156 (11)	−0.00097 (11)
C21	0.01000 (14)	0.01172 (14)	0.00826 (13)	−0.00336 (11)	−0.00222 (11)	−0.00002 (11)
C22	0.01240 (16)	0.01564 (17)	0.01317 (17)	−0.00125 (13)	0.00101 (13)	0.00295 (14)
C23	0.01289 (17)	0.01701 (19)	0.01685 (19)	0.00025 (14)	0.00087 (14)	0.00324 (15)
C24	0.01290 (16)	0.01323 (16)	0.01366 (17)	−0.00141 (13)	−0.00331 (13)	0.00137 (13)
C25	0.01363 (16)	0.01496 (17)	0.01114 (15)	−0.00240 (13)	−0.00235 (13)	0.00258 (13)
C26	0.01138 (15)	0.01422 (16)	0.00922 (14)	−0.00260 (12)	−0.00144 (12)	0.00120 (12)
N1	0.00978 (13)	0.01948 (17)	0.01153 (14)	−0.00498 (12)	−0.00243 (11)	−0.00033 (12)
N2	0.01548 (16)	0.02044 (18)	0.00983 (14)	−0.00432 (13)	−0.00068 (12)	−0.00344 (12)
N3	0.01429 (15)	0.02009 (17)	0.01006 (13)	−0.01010 (13)	−0.00136 (11)	−0.00046 (12)
Cl1	0.01564 (5)	0.01623 (5)	0.01936 (5)	0.00067 (4)	−0.00360 (4)	0.00431 (4)
O1	0.01479 (14)	0.02202 (16)	0.00799 (12)	−0.00936 (12)	−0.00088 (10)	0.00136 (11)

Geometric parameters (Å, º) top

C1—N1	1.3663 (6)	C11—C12	1.3941 (7)
C1—C2	1.3684 (6)	C11—H11	0.9500
C1—N13	1.3970 (6)	C12—N13	1.4168 (6)
C2—C15	1.4125 (6)	C14—O1	1.2567 (6)
C2—C3	1.5184 (6)	C14—N3	1.3422 (6)
C3—C4	1.5105 (6)	C15—N2	1.1627 (6)
C3—C21	1.5345 (6)	C21—C22	1.3942 (7)
C3—H3	1.0000	C21—C26	1.3982 (6)
C4—C5	1.3597 (6)	C22—C23	1.3922 (7)
C4—C14	1.4599 (6)	C22—H22	0.9500
C5—N13	1.3998 (6)	C23—C24	1.3870 (7)
C5—S6	1.7464 (4)	C23—H23	0.9500
S6—C7	1.7523 (5)	C24—C25	1.3897 (7)
C7—C8	1.3921 (7)	C24—Cl1	1.7382 (5)
C7—C12	1.3971 (7)	C25—C26	1.3940 (7)
C8—C9	1.3928 (9)	C25—H25	0.9500
C8—H8	0.9500	C26—H26	0.9500
C9—C10	1.3941 (10)	N1—H01	0.845 (11)
C9—H9	0.9500	N1—H02	0.906 (13)
C10—C11	1.3955 (7)	N3—H03	0.837 (13)
C10—H10	0.9500	N3—H04	0.834 (12)

N1—C1—C2	125.51 (4)	C11—C12—C7	120.44 (4)
N1—C1—N13	116.24 (4)	C11—C12—N13	128.37 (4)
C2—C1—N13	118.25 (4)	C7—C12—N13	111.08 (4)
C1—C2—C15	119.32 (4)	C1—N13—C5	117.93 (4)
C1—C2—C3	121.78 (4)	C1—N13—C12	126.47 (4)
C15—C2—C3	118.82 (4)	C5—N13—C12	113.70 (4)
C4—C3—C2	107.98 (3)	O1—C14—N3	121.44 (4)
C4—C3—C21	112.20 (3)	O1—C14—C4	119.33 (4)
C2—C3—C21	114.45 (4)	N3—C14—C4	119.22 (4)
C4—C3—H3	107.3	N2—C15—C2	177.40 (5)
C2—C3—H3	107.3	C22—C21—C26	118.16 (4)
C21—C3—H3	107.3	C22—C21—C3	120.83 (4)
C5—C4—C14	117.99 (4)	C26—C21—C3	120.93 (4)
C5—C4—C3	118.16 (4)	C23—C22—C21	121.32 (5)
C14—C4—C3	123.69 (4)	C23—C22—H22	119.3
C4—C5—N13	121.84 (4)	C21—C22—H22	119.3
C4—C5—S6	126.72 (3)	C24—C23—C22	119.23 (5)
N13—C5—S6	111.43 (3)	C24—C23—H23	120.4
C5—S6—C7	90.51 (2)	C22—C23—H23	120.4
C8—C7—C12	121.12 (5)	C23—C24—C25	120.98 (5)
C8—C7—S6	125.87 (4)	C23—C24—Cl1	118.59 (4)
C12—C7—S6	112.95 (3)	C25—C24—Cl1	120.43 (4)
C7—C8—C9	118.59 (5)	C24—C25—C26	118.92 (4)
C7—C8—H8	120.7	C24—C25—H25	120.5
C9—C8—H8	120.7	C26—C25—H25	120.5
C8—C9—C10	120.19 (5)	C25—C26—C21	121.38 (4)
C8—C9—H9	119.9	C25—C26—H26	119.3
C10—C9—H9	119.9	C21—C26—H26	119.3
C9—C10—C11	121.48 (5)	C1—N1—H01	113.3 (8)
C9—C10—H10	119.3	C1—N1—H02	112.1 (8)
C11—C10—H10	119.3	H01—N1—H02	117.5 (11)
C12—C11—C10	118.12 (5)	C14—N3—H03	115.2 (9)
C12—C11—H11	120.9	C14—N3—H04	124.2 (9)
C10—C11—H11	120.9	H03—N3—H04	120.1 (12)

N1—C1—C2—C15	4.07 (7)	N1—C1—N13—C5	−153.81 (4)
N13—C1—C2—C15	−175.46 (4)	C2—C1—N13—C5	25.76 (6)
N1—C1—C2—C3	−179.29 (4)	N1—C1—N13—C12	9.45 (7)
N13—C1—C2—C3	1.19 (6)	C2—C1—N13—C12	−170.98 (4)
C1—C2—C3—C4	−30.53 (6)	C4—C5—N13—C1	−19.82 (6)
C15—C2—C3—C4	146.13 (4)	S6—C5—N13—C1	159.01 (3)
C1—C2—C3—C21	95.20 (5)	C4—C5—N13—C12	174.83 (4)
C15—C2—C3—C21	−88.14 (5)	S6—C5—N13—C12	−6.34 (5)
C2—C3—C4—C5	35.97 (5)	C11—C12—N13—C1	25.29 (8)
C21—C3—C4—C5	−91.07 (5)	C7—C12—N13—C1	−158.51 (4)
C2—C3—C4—C14	−148.76 (4)	C11—C12—N13—C5	−170.85 (5)
C21—C3—C4—C14	84.19 (5)	C7—C12—N13—C5	5.35 (6)
C14—C4—C5—N13	171.04 (4)	C5—C4—C14—O1	6.00 (7)
C3—C4—C5—N13	−13.42 (6)	C3—C4—C14—O1	−169.28 (4)
C14—C4—C5—S6	−7.60 (6)	C5—C4—C14—N3	−175.18 (4)
C3—C4—C5—S6	167.94 (3)	C3—C4—C14—N3	9.55 (7)
C4—C5—S6—C7	−176.96 (4)	C4—C3—C21—C22	−22.43 (6)
N13—C5—S6—C7	4.28 (4)	C2—C3—C21—C22	−145.92 (5)
C5—S6—C7—C8	175.90 (5)	C4—C3—C21—C26	160.82 (4)
C5—S6—C7—C12	−1.30 (4)	C2—C3—C21—C26	37.33 (6)
C12—C7—C8—C9	0.71 (8)	C26—C21—C22—C23	0.40 (8)
S6—C7—C8—C9	−176.28 (5)	C3—C21—C22—C23	−176.43 (5)
C7—C8—C9—C10	1.29 (10)	C21—C22—C23—C24	0.31 (9)
C8—C9—C10—C11	−1.26 (10)	C22—C23—C24—C25	−0.61 (9)
C9—C10—C11—C12	−0.79 (9)	C22—C23—C24—Cl1	179.40 (5)
C10—C11—C12—C7	2.78 (8)	C23—C24—C25—C26	0.19 (8)
C10—C11—C12—N13	178.66 (5)	Cl1—C24—C25—C26	−179.82 (4)
C8—C7—C12—C11	−2.79 (8)	C24—C25—C26—C21	0.55 (8)
S6—C7—C12—C11	174.56 (4)	C22—C21—C26—C25	−0.84 (7)
C8—C7—C12—N13	−179.33 (5)	C3—C21—C26—C25	176.00 (4)
S6—C7—C12—N13	−1.99 (5)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H01···O1ⁱ	0.845 (11)	2.391 (11)	3.1341 (6)	147.2 (10)
N1—H02···Cl1ⁱⁱ	0.906 (13)	2.755 (13)	3.4516 (5)	134.6 (10)
N3—H03···O1ⁱⁱⁱ	0.837 (13)	2.016 (13)	2.8336 (6)	165.3 (12)
N3—H04···N2^iv	0.834 (12)	2.287 (13)	3.1109 (6)	169.9 (12)
C23—H23···S6^v	0.95	2.90	3.7631 (6)	152

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

Acknowledgements

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

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