Synthesis and crystal structure of 1,3,5-tris­[(1H-benzotriazol-1-yl)meth­yl]-2,4,6-tri­ethyl­benzene

Koch, N.; Förster, S.; Mazik, M.

doi:10.1107/S2056989024009988

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ISSN: 2056-9890

Volume 80| Part 11| November 2024| Pages 1240-1243

https://doi.org/10.1107/S2056989024009988

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Synthesis and crystal structure of 1,3,5-tris[(1H-benzotriazol-1-yl)methyl]-2,4,6-triethylbenzene

Niklas Koch,^a Sebastian Förster ^a and Monika Mazik ^a ^*

^aInstitut für Organische Chemie, Technische Universität Bergakademie, Freiberg, Leipziger Str. 29, 09599 Freiberg/Sachsen, Germany
^*Correspondence e-mail: monika.mazik@chemie.tu-freiberg.de

Edited by T. Akitsu, Tokyo University of Science, Japan (Received 14 August 2024; accepted 12 October 2024; online 31 October 2024)

In the crystal structure of the title compound, C₃₃H₃₃N₉, the tripodal molecule exists in a conformation in which the substituents attached to the central arene ring are arranged in an alternating order above and below the ring plane. The three benzotriazolyl moieties are inclined at angles of 88.3 (1), 85.7 (1) and 82.1 (1)° with respect to the mean plane of the benzene ring. In the crystal, only weak molecular cross-linking involving C—H⋯N hydrogen bonds is observed.

Keywords: crystal structure; tripodal molecule; hydrogen bonding; C—H⋯π interactions.

CCDC reference: 2391226

1. Chemical context

Benzotriazole and its derivatives have found applications as auxiliaries in a variety of synthetic strategies (Katritzky & Rachwal, 2010 , 2011 ). In addition, numerous benzotriazole derivatives have valuable biological properties, including antibacterial, antiviral, antifungal, anticancer and others (for reviews, see: Bajaj & Sakhuja, 2015 ; Briguglio et al., 2015 ). Benzotriazole has also been used as a building block in various supramolecular architectures. As an example, a water-soluble cavitand bearing a benzotriazole upper rim can be mentioned (Rahman et al., 2022 ). Moreover, anticorrosive low molecular weight gelators based on compounds with benzotriazolyl units have been developed (Cai et al., 2011 ). It should also be noted that many benzotriazole-based compounds have been considered in the development of coordination polymers and organometallic frameworks (Loukopoulos & Kostakis, 2019 ). These compounds include, for example, benzene derivatives with two 1H-benzotriazol-1-ylmethyl groups (Loukopoulos et al., 2018a ,b ).

In this article, we describe the synthesis and crystal structure of a compound belonging to the class of 1,3,5-substituted 2,4,6-triethylbenzenes and bearing 1H-benzotriazol-1-ylmethyl substituents. Representatives of this class of compounds have been used by us in the development of artificial receptors for various neutral and ionic substrates, such as carbohydrates (Mazik, 2009 , 2012 ; Mazik et al., 2004 , 2005 ; Lippe et al., 2015 ; Koch et al., 2016 ; Kaiser et al., 2019 ; Stapf et al., 2020 ; Köhler et al., 2020 , 2021 , 2024 ), ammonium ions (Schulze et al., 2018 ; Fuhrmann et al., 2022a ,b ) and hydronium/hydroxide ions (Stapf et al., 2015 ).

2. Structural commentary

The crystal structure of the title compound, C₃₃H₃₃N₉, was solved in the orthorhombic space group P2₁2₁2₁ with the asymmetric unit containing one molecule (Fig. 1). The molecule adopts a conformation in which the benzotriazolyl units are located on one side of the central arene ring, while the ethyl groups are oriented in the opposite direction (ababab arrangement, a = above, b = below; Das & Barbour, 2008a ,b , 2009 ; Arunachalam et al., 2010 ; Arunachalam & Ghosh, 2010 ; Koch et al., 2015 ). The dihedral angles between the planes of the benzotriazolyl moieties are 13.6 (1), 88.0 (1) and 76.8 (1)°. The central arene ring of the molecule is noticeably twisted, with the largest atomic distance from the least-squares plane of the ring being 0.048 (1) Å for atom C1 and 0.040 (1) Å for atom C4. The N atoms of two benzotriazolyl moieties (labeled B and D) are directed outwards, while those of the remaining benzotriazolyl unit are directed towards the central arene ring. The distances of 2.76 and 2.96 Å between the arene H atoms H15 and H29 to the center of the benzene ring and the bond geometries (C—H⋯Cg = 140°) indicate the presence of two intramolecular C—H⋯π contacts (Nishio et al., 2009 ; Nishio, 2011 ; Tiekink & Zukerman-Schpector, 2012 ). In addition, an intramolecular C—H⋯N bond involving the atoms H11A and N1 [d(H⋯N) 2.54 Å, 133°; Table 1] is likely to have an influence on the conformation of the molecule.

Table 1
Hydrogen-bond geometry (Å, °)

Cg1 represents the centroid of the C1–C6 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C20—H20A⋯N8ⁱ	0.99	2.59	3.341 (3)	133
C27—H27A⋯N3ⁱⁱ	0.99	2.65	3.217 (3)	117
C11—H11A⋯N1	0.99	2.54	3.296 (3)	133
C15—H15⋯Cg1	0.95	2.96	3.741 (3)	140
C29—H29⋯Cg1	0.95	2.77	3.546 (3)	140
Symmetry codes: (i) $[-x+1, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) $[-x+{\script{1\over 2}}, -y+2, z+{\script{1\over 2}}]$ .

Figure 1
Perspective view of the title molecule including atom labeling and ring specification (A–D). Anisotropic displacement ellipsoids are drawn at the 50% probability level.

3. Supramolecular features

The crystal structure of the title compound is characterized by a low degree of molecular cross-linking. Only the methylene H atoms H20A and H27A and the N atoms N8 and N3 of adjacent molecules are involved in C—H⋯N hydrogen bonding [d(H⋯N) 2.59, 2.64 Å; 140.2° (Table 1); for other examples of C—H⋯N bonds, see: Desiraju & Steiner, 1999 ; Thalladi et al., 2000a ,b ; Reddy et al., 1996 ; Mazik et al., 1999 , 2000a ,b , 2001 , 2005]. Consequently, van der Waals forces play an important role in the cohesion of the crystal structure. An excerpt of the packing structure is shown in Fig. 2.

Figure 2
Illustration of the packing structure of the title compound. The dashed lines represent C—H⋯N bonds.

4. Database survey

A search in the Cambridge Structural Database (CSD, Version 5.45, update June 2024; Groom et al., 2016 ) for 1,3,5-substituted 2,4,6-trialkylbenzene derivatives bearing three 1H-benzotriazol-1-ylmethyl units gave no hits. However, the crystal structures of related tripodal molecules, e.g. those equipped with indazolyl (benzopyrazolyl) moieties, allow a comparison with the crystal structure of the title compound 1. In the solvent-free crystal structure of 1,3,5-tris(1H-indazolyl-1-yl)-2,4,6-triethylbenzene (QIDVIL; Schulze et al., 2018), the molecules adopt a conformation in which two indazolyl units point to the same face of the central benzene ring, while the third points in the opposite direction (aab arrangement of the functionalized side arms, a = above, b = below). By taking the ethyl groups into account, the conformation of the molecule can be defined as ab′ab′ba′ (position of the ethyl groups are marked as a′ and b′, a′ = ethyl above, b′ = ethyl below; Schulze et al., 2017 ; Koch et al., 2017 ).

For benzene derivatives with 1H-benzotriazol-1-ylmethyl groups, only crystal structures of mono- and disubstituted derivatives are known, which, however, often contain further substituents on the benzene ring, such as Br, NO₂, CN or PhOCH₂. In addition, the crystal structures of their metal complexes rather than those of the free ligands are mostly reported. As an example of the latter, the crystal structure of 1,3-bis(1H-benzotriazol-1-ylmethyl)benzene should be mentioned (AMEZEZ; Macías et al., 2016 ). In this case, the benzotriazolyl units form dihedral angles of 88.74 (11) and 85.83 (10)° with the central aromatic ring, which are similar to those observed for two heterocyclic moieties of 1. The crystal structure is mainly governed by C—H⋯N and C—H⋯π interactions.

5. Synthesis and crystallization

To a suspension of sodium hydroxide (204 mg, 5.10 mmol) in 10 mL of N,N-dimethylformamide, 1H-benzotriazole (608 mg, 5.10 mmol) was added and the mixture was stirred for 20 minutes at room temperature. After addition of 1,3,5-tris(bromomethyl)-2,4,6-triethylbenzene (500 mg, 1.13 mmol), the solution was stirred for several hours at room temperature (the course of the reaction was analyzed using TLC). The mixture was then added to 30 mL of ice water, the resulting precipitate was filtered off, washed with small portions of ice water and dried. The crude product was purified by column chromatography [SiO₂, EtOAc/n-hexane v/v 2:1]. This procedure yielded the compound 1 (340 mg, 0.61 mmol, 54%) and the structure isomer 2 (218 mg, 0.39 mmol, 35%), bearing two 1H-benzotriazol-1-ylmethyl units and one 2H-benzotriazol-2-ylmethyl group (Fig. 3). Crystals of the title compound suitable for single crystal X-ray diffraction were grown by slow evaporation of the solvent at room temperature. M.p. 481 K. ¹H NMR (500 MHz, CDCl₃, ppm): δ = 0.96 (t, J = 7.5 Hz, 9H, CH₃), 2.86 (q, J = 7.5 Hz, 6H, CH₂), 5.94 (s, 6H, CH₂), 7.03–7.06 (m, 3H, H_Ar), 7.22–7.27 (m, 3H, H_Ar), 7.29–7.33 (m, 3H, H_Ar), 8.00–8.04 (m, 3H, H_Ar).¹³C NMR (125 MHz, DMSO-d₆, ppm) δ = 15.1, 23.9, 47.1, 109.9, 120.1, 123.9, 127.7, 129.3, 132.9, 146.3, 146.9. MS (ESI): m/z calculated for C₃₃H₃₃N₉Na [M + Na]⁺: 578.2; found 578.2.

Figure 3
Synthesis of the title compound 1 and the byproduct 2 by reaction of 1H-benzotriazole and 1,3,5-tris(bromomethyl)-2,4,6-triethylbenzene.

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. The non-hydrogen atoms were refined anisotropically. All hydrogen atoms were positioned geometrically and refined isotropically using the riding model with C—H = 0.98–0.99 Å (alkyl), 0.95 Å (aryl); U_iso(H)= 1.2–1.5U_eq(C).

Table 2
Experimental details

Crystal data
Chemical formula	C₃₃H₃₃N₉
M_r	555.68
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	100
a, b, c (Å)	11.0204 (4), 16.1387 (6), 16.2772 (6)
V (Å³)	2894.98 (18)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.08
Crystal size (mm)	0.42 × 0.18 × 0.17

Data collection
Diffractometer	Bruker Kappa APEXII CCD area detector
No. of measured, independent and observed [I > 2σ(I)] reflections	25748, 6002, 5387
R_int	0.033
(sin θ/λ)_max (Å⁻¹)	0.628

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.035, 0.081, 1.05
No. of reflections	6002
No. of parameters	382
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.15, −0.19
Absolute structure	Flack x determined using 2115 quotients [(I⁺)−(I⁻)]/[(I⁺)+(I⁻)] (Parsons et al., 2013 )
Computer programs: APEX2 and SAINT (Bruker, 2014 ), SHELXS97 (Sheldrick, 2008 ), SHELXL2018/3 (Sheldrick, 2015 ), XP (Sheldrick, 2008), WinGX (Farrugia, 2012 ), publCIF (Westrip, 2010 ) and ShelXle (Hübschle et al., 2011 ).

Supporting information

CCDC reference: 2391226

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989024009988/jp2011sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989024009988/jp2011Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2056989024009988/jp2011Isup3.cml

checkCIF report

Computing details top

1,3,5-Tris[(1H-benzotriazol-1-yl)methyl]-2,4,6-triethylbenzene top

Crystal data top

C₃₃H₃₃N₉	D_x = 1.275 Mg m⁻³
M_r = 555.68	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, P2₁2₁2₁	Cell parameters from 7118 reflections
a = 11.0204 (4) Å	θ = 2.2–27.4°
b = 16.1387 (6) Å	µ = 0.08 mm⁻¹
c = 16.2772 (6) Å	T = 100 K
V = 2894.98 (18) Å³	Irregular, colourless
Z = 4	0.42 × 0.18 × 0.17 mm
F(000) = 1176

Data collection top

Bruker Kappa APEXII CCD area detector diffractometer	R_int = 0.033
phi and ω scans	θ_max = 26.5°, θ_min = 2.5°
25748 measured reflections	h = −13→13
6002 independent reflections	k = −16→20
5387 reflections with I > 2σ(I)	l = −18→20

Refinement top

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.035	w = 1/[σ²(F_o²) + (0.0406P)² + 0.3656P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.081	(Δ/σ)_max < 0.001
S = 1.05	Δρ_max = 0.15 e Å⁻³
6002 reflections	Δρ_min = −0.19 e Å⁻³
382 parameters	Absolute structure: Flack x determined using 2115 quotients [(I⁺)-(I^-)]/[(I⁺)+(I^-)] (Parsons et al., 2013)
0 restraints

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
C1	0.38004 (19)	0.88951 (13)	0.05254 (11)	0.0177 (4)
C2	0.45997 (19)	0.83741 (12)	0.09532 (12)	0.0182 (4)
C3	0.51962 (18)	0.86757 (13)	0.16516 (12)	0.0169 (4)
C4	0.50175 (17)	0.94963 (12)	0.19122 (11)	0.0156 (4)
C5	0.43143 (19)	1.00303 (12)	0.14297 (12)	0.0165 (4)
C6	0.37006 (18)	0.97360 (13)	0.07315 (11)	0.0172 (4)
C7	0.4830 (2)	0.74986 (13)	0.06507 (13)	0.0266 (5)
H7A	0.568545	0.734934	0.076171	0.032*
H7B	0.470442	0.747975	0.004872	0.032*
C8	0.4002 (3)	0.68626 (14)	0.10584 (16)	0.0400 (6)
H8A	0.413298	0.687060	0.165383	0.060*
H8B	0.418765	0.630947	0.084406	0.060*
H8C	0.315353	0.699898	0.093920	0.060*
C9	0.55736 (19)	0.97958 (13)	0.27096 (12)	0.0192 (4)
H9A	0.582015	1.038265	0.265053	0.023*
H9B	0.630853	0.946576	0.283300	0.023*
C10	0.4670 (2)	0.97151 (14)	0.34195 (12)	0.0234 (5)
H10A	0.395038	1.005195	0.330317	0.035*
H10B	0.505048	0.990816	0.392891	0.035*
H10C	0.443087	0.913352	0.348085	0.035*
C11	0.2956 (2)	1.03225 (14)	0.02043 (12)	0.0222 (5)
H11A	0.290222	1.009402	−0.035894	0.027*
H11B	0.338169	1.086176	0.017049	0.027*
C12	0.1676 (2)	1.04660 (17)	0.05315 (14)	0.0329 (6)
H12A	0.121795	0.994575	0.050980	0.049*
H12B	0.126717	1.088410	0.019366	0.049*
H12C	0.171915	1.066014	0.110123	0.049*
C13	0.30133 (19)	0.85410 (14)	−0.01529 (12)	0.0222 (5)
H13A	0.295301	0.793391	−0.007575	0.027*
H13B	0.218588	0.877347	−0.009856	0.027*
C14	0.45504 (19)	0.89480 (13)	−0.12918 (12)	0.0196 (4)
C15	0.5667 (2)	0.91672 (15)	−0.09411 (13)	0.0312 (5)
H15	0.580267	0.914007	−0.036529	0.037*
C16	0.6553 (2)	0.94227 (18)	−0.14752 (14)	0.0353 (6)
H16	0.731425	0.959233	−0.125868	0.042*
C17	0.6380 (2)	0.94438 (18)	−0.23308 (14)	0.0360 (6)
H17	0.702488	0.962073	−0.267630	0.043*
C18	0.5300 (2)	0.92138 (18)	−0.26732 (14)	0.0369 (6)
H18	0.518521	0.921543	−0.325168	0.044*
C19	0.4370 (2)	0.89761 (14)	−0.21403 (13)	0.0244 (5)
C20	0.60859 (19)	0.81289 (13)	0.21107 (12)	0.0205 (4)
H20A	0.596595	0.820114	0.270914	0.025*
H20B	0.592264	0.754142	0.197499	0.025*
C21	0.8348 (2)	0.82938 (15)	0.23835 (13)	0.0282 (5)
C22	0.8514 (2)	0.8141 (2)	0.32251 (15)	0.0438 (7)
H22	0.785438	0.802500	0.358278	0.053*
C23	0.9692 (3)	0.8170 (3)	0.34969 (17)	0.0646 (10)
H23	0.985119	0.807849	0.406328	0.078*
C24	1.0675 (3)	0.8331 (3)	0.29639 (19)	0.0663 (10)
H24	1.147464	0.833767	0.318119	0.080*
C25	1.0509 (2)	0.8478 (2)	0.21464 (17)	0.0468 (7)
H25	1.117336	0.859029	0.179129	0.056*
C26	0.9309 (2)	0.84539 (15)	0.18542 (14)	0.0294 (5)
C27	0.42433 (19)	1.09430 (12)	0.16442 (12)	0.0180 (4)
H27A	0.342861	1.115597	0.149888	0.022*
H27B	0.435267	1.101133	0.224410	0.022*
C28	0.62740 (18)	1.12435 (12)	0.08657 (11)	0.0160 (4)
C29	0.69299 (18)	1.05078 (13)	0.07298 (12)	0.0196 (4)
H29	0.662367	0.998252	0.089214	0.023*
C30	0.80371 (19)	1.05899 (14)	0.03498 (13)	0.0221 (5)
H30	0.850655	1.010634	0.025116	0.027*
C31	0.85043 (19)	1.13649 (14)	0.01001 (12)	0.0222 (4)
H31	0.927340	1.139038	−0.016233	0.027*
C32	0.7865 (2)	1.20794 (14)	0.02310 (13)	0.0224 (5)
H32	0.817485	1.260185	0.006310	0.027*
C33	0.67341 (19)	1.20129 (12)	0.06221 (12)	0.0189 (4)
N1	0.34537 (15)	0.87056 (10)	−0.09864 (10)	0.0176 (4)
N2	0.26511 (16)	0.86005 (12)	−0.16098 (11)	0.0235 (4)
N3	0.31885 (17)	0.87568 (14)	−0.23032 (11)	0.0307 (5)
N4	0.73447 (16)	0.83275 (11)	0.19011 (10)	0.0204 (4)
N5	0.76712 (17)	0.84885 (11)	0.11110 (10)	0.0225 (4)
N6	0.88511 (17)	0.85727 (11)	0.10747 (11)	0.0263 (4)
N7	0.51729 (15)	1.14327 (10)	0.12093 (10)	0.0172 (3)
N8	0.49855 (17)	1.22634 (10)	0.11714 (11)	0.0212 (4)
N9	0.59115 (17)	1.26176 (11)	0.08186 (11)	0.0252 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0162 (10)	0.0218 (11)	0.0150 (9)	−0.0036 (8)	0.0016 (8)	0.0000 (8)
C2	0.0208 (11)	0.0169 (10)	0.0169 (9)	−0.0013 (8)	0.0036 (8)	0.0006 (8)
C3	0.0162 (10)	0.0181 (10)	0.0166 (9)	0.0004 (8)	0.0029 (8)	0.0026 (8)
C4	0.0114 (10)	0.0199 (10)	0.0155 (9)	−0.0014 (8)	0.0024 (8)	0.0002 (8)
C5	0.0137 (10)	0.0169 (10)	0.0190 (9)	0.0010 (8)	0.0051 (8)	0.0012 (7)
C6	0.0140 (10)	0.0216 (10)	0.0159 (9)	0.0002 (8)	0.0045 (8)	0.0027 (8)
C7	0.0359 (13)	0.0191 (11)	0.0247 (10)	0.0028 (9)	−0.0025 (10)	−0.0037 (9)
C8	0.0561 (18)	0.0189 (12)	0.0450 (14)	−0.0048 (11)	−0.0052 (13)	0.0033 (11)
C9	0.0185 (11)	0.0204 (11)	0.0187 (9)	0.0014 (9)	−0.0027 (8)	−0.0010 (8)
C10	0.0292 (13)	0.0230 (11)	0.0179 (9)	0.0006 (9)	0.0007 (9)	0.0001 (9)
C11	0.0227 (11)	0.0250 (11)	0.0190 (10)	0.0069 (9)	−0.0016 (9)	0.0008 (9)
C12	0.0222 (12)	0.0463 (15)	0.0301 (12)	0.0116 (11)	−0.0034 (10)	−0.0042 (11)
C13	0.0194 (11)	0.0269 (12)	0.0202 (10)	−0.0054 (9)	−0.0012 (8)	−0.0001 (9)
C14	0.0184 (11)	0.0208 (10)	0.0197 (9)	−0.0006 (8)	−0.0002 (8)	−0.0004 (8)
C15	0.0226 (12)	0.0513 (15)	0.0197 (10)	−0.0093 (11)	−0.0051 (9)	0.0026 (10)
C16	0.0201 (12)	0.0578 (17)	0.0281 (12)	−0.0109 (12)	−0.0051 (10)	0.0031 (12)
C17	0.0225 (12)	0.0604 (17)	0.0251 (11)	−0.0090 (12)	0.0013 (10)	0.0075 (11)
C18	0.0250 (13)	0.0663 (18)	0.0193 (11)	−0.0098 (12)	−0.0018 (10)	0.0076 (11)
C19	0.0191 (11)	0.0335 (13)	0.0206 (10)	−0.0011 (10)	−0.0034 (9)	0.0012 (9)
C20	0.0217 (11)	0.0216 (11)	0.0182 (9)	0.0027 (9)	0.0015 (9)	0.0023 (8)
C21	0.0221 (12)	0.0379 (13)	0.0247 (11)	0.0111 (10)	−0.0027 (9)	−0.0013 (10)
C22	0.0322 (15)	0.077 (2)	0.0224 (11)	0.0135 (14)	−0.0011 (11)	0.0038 (12)
C23	0.0370 (17)	0.130 (3)	0.0266 (13)	0.0156 (19)	−0.0108 (13)	0.0061 (17)
C24	0.0285 (16)	0.123 (3)	0.0472 (17)	0.0109 (19)	−0.0144 (14)	0.0026 (18)
C25	0.0229 (13)	0.074 (2)	0.0432 (15)	0.0060 (14)	0.0010 (12)	0.0021 (14)
C26	0.0248 (12)	0.0363 (13)	0.0270 (11)	0.0088 (10)	0.0009 (10)	−0.0006 (10)
C27	0.0163 (10)	0.0177 (10)	0.0202 (9)	0.0003 (8)	0.0038 (8)	0.0001 (8)
C28	0.0157 (10)	0.0187 (10)	0.0135 (8)	0.0008 (8)	−0.0022 (8)	−0.0008 (8)
C29	0.0209 (11)	0.0154 (10)	0.0224 (10)	0.0018 (8)	0.0024 (8)	0.0007 (8)
C30	0.0207 (11)	0.0219 (11)	0.0238 (10)	0.0042 (9)	0.0012 (9)	−0.0008 (9)
C31	0.0158 (10)	0.0278 (11)	0.0230 (10)	0.0004 (9)	0.0011 (8)	0.0021 (9)
C32	0.0217 (12)	0.0205 (11)	0.0251 (10)	−0.0045 (8)	0.0000 (9)	0.0027 (9)
C33	0.0213 (11)	0.0162 (10)	0.0191 (9)	0.0012 (8)	−0.0033 (9)	0.0000 (8)
N1	0.0168 (9)	0.0184 (8)	0.0176 (8)	−0.0012 (7)	−0.0031 (7)	−0.0015 (7)
N2	0.0208 (9)	0.0299 (10)	0.0199 (8)	−0.0023 (8)	−0.0058 (7)	−0.0010 (8)
N3	0.0219 (10)	0.0516 (13)	0.0186 (8)	−0.0084 (9)	−0.0037 (8)	0.0019 (9)
N4	0.0223 (9)	0.0232 (10)	0.0157 (8)	0.0067 (7)	0.0008 (7)	−0.0003 (7)
N5	0.0262 (10)	0.0228 (9)	0.0183 (8)	0.0049 (8)	0.0017 (7)	0.0014 (7)
N6	0.0239 (10)	0.0282 (10)	0.0267 (9)	0.0065 (8)	0.0039 (8)	−0.0003 (8)
N7	0.0177 (8)	0.0135 (8)	0.0204 (8)	0.0015 (7)	0.0008 (7)	−0.0010 (7)
N8	0.0229 (10)	0.0144 (8)	0.0264 (9)	0.0035 (7)	0.0023 (8)	0.0010 (7)
N9	0.0248 (10)	0.0176 (9)	0.0333 (10)	0.0011 (7)	0.0036 (8)	0.0020 (8)

Geometric parameters (Å, º) top

C1—C6	1.402 (3)	C17—H17	0.9500
C1—C2	1.403 (3)	C18—C19	1.396 (3)
C1—C13	1.516 (3)	C18—H18	0.9500
C2—C3	1.401 (3)	C19—N3	1.375 (3)
C2—C7	1.517 (3)	C20—N4	1.464 (3)
C3—C4	1.404 (3)	C20—H20A	0.9900
C3—C20	1.516 (3)	C20—H20B	0.9900
C4—C5	1.400 (3)	C21—N4	1.358 (3)
C4—C9	1.515 (3)	C21—C26	1.389 (3)
C5—C6	1.405 (3)	C21—C22	1.404 (3)
C5—C27	1.516 (3)	C22—C23	1.372 (4)
C6—C11	1.518 (3)	C22—H22	0.9500
C7—C8	1.525 (3)	C23—C24	1.412 (4)
C7—H7A	0.9900	C23—H23	0.9500
C7—H7B	0.9900	C24—C25	1.364 (4)
C8—H8A	0.9800	C24—H24	0.9500
C8—H8B	0.9800	C25—C26	1.406 (4)
C8—H8C	0.9800	C25—H25	0.9500
C9—C10	1.531 (3)	C26—N6	1.379 (3)
C9—H9A	0.9900	C27—N7	1.475 (3)
C9—H9B	0.9900	C27—H27A	0.9900
C10—H10A	0.9800	C27—H27B	0.9900
C10—H10B	0.9800	C28—N7	1.371 (3)
C10—H10C	0.9800	C28—C33	1.399 (3)
C11—C12	1.526 (3)	C28—C29	1.408 (3)
C11—H11A	0.9900	C29—C30	1.374 (3)
C11—H11B	0.9900	C29—H29	0.9500
C12—H12A	0.9800	C30—C31	1.412 (3)
C12—H12B	0.9800	C30—H30	0.9500
C12—H12C	0.9800	C31—C32	1.368 (3)
C13—N1	1.465 (3)	C31—H31	0.9500
C13—H13A	0.9900	C32—C33	1.403 (3)
C13—H13B	0.9900	C32—H32	0.9500
C14—N1	1.364 (3)	C33—N9	1.370 (3)
C14—C19	1.396 (3)	N1—N2	1.357 (2)
C14—C15	1.402 (3)	N2—N3	1.299 (3)
C15—C16	1.371 (3)	N4—N5	1.360 (2)
C15—H15	0.9500	N5—N6	1.309 (3)
C16—C17	1.406 (3)	N7—N8	1.358 (2)
C16—H16	0.9500	N8—N9	1.303 (2)
C17—C18	1.366 (3)

C6—C1—C2	120.70 (18)	C16—C17—H17	119.5
C6—C1—C13	119.62 (18)	C17—C18—C19	117.5 (2)
C2—C1—C13	119.66 (18)	C17—C18—H18	121.3
C3—C2—C1	119.30 (18)	C19—C18—H18	121.3
C3—C2—C7	120.57 (18)	N3—C19—C14	108.51 (19)
C1—C2—C7	120.13 (18)	N3—C19—C18	130.2 (2)
C2—C3—C4	120.47 (18)	C14—C19—C18	121.2 (2)
C2—C3—C20	120.08 (18)	N4—C20—C3	111.75 (16)
C4—C3—C20	119.39 (17)	N4—C20—H20A	109.3
C5—C4—C3	119.26 (17)	C3—C20—H20A	109.3
C5—C4—C9	120.54 (18)	N4—C20—H20B	109.3
C3—C4—C9	120.20 (17)	C3—C20—H20B	109.3
C4—C5—C6	120.80 (18)	H20A—C20—H20B	107.9
C4—C5—C27	119.84 (18)	N4—C21—C26	104.78 (18)
C6—C5—C27	119.33 (18)	N4—C21—C22	132.6 (2)
C1—C6—C5	118.87 (18)	C26—C21—C22	122.6 (2)
C1—C6—C11	120.70 (18)	C23—C22—C21	115.6 (3)
C5—C6—C11	120.42 (18)	C23—C22—H22	122.2
C2—C7—C8	112.68 (19)	C21—C22—H22	122.2
C2—C7—H7A	109.1	C22—C23—C24	122.3 (3)
C8—C7—H7A	109.1	C22—C23—H23	118.9
C2—C7—H7B	109.1	C24—C23—H23	118.9
C8—C7—H7B	109.1	C25—C24—C23	121.9 (3)
H7A—C7—H7B	107.8	C25—C24—H24	119.0
C7—C8—H8A	109.5	C23—C24—H24	119.0
C7—C8—H8B	109.5	C24—C25—C26	116.8 (3)
H8A—C8—H8B	109.5	C24—C25—H25	121.6
C7—C8—H8C	109.5	C26—C25—H25	121.6
H8A—C8—H8C	109.5	N6—C26—C21	108.5 (2)
H8B—C8—H8C	109.5	N6—C26—C25	130.7 (2)
C4—C9—C10	110.89 (17)	C21—C26—C25	120.8 (2)
C4—C9—H9A	109.5	N7—C27—C5	111.98 (16)
C10—C9—H9A	109.5	N7—C27—H27A	109.2
C4—C9—H9B	109.5	C5—C27—H27A	109.2
C10—C9—H9B	109.5	N7—C27—H27B	109.2
H9A—C9—H9B	108.0	C5—C27—H27B	109.2
C9—C10—H10A	109.5	H27A—C27—H27B	107.9
C9—C10—H10B	109.5	N7—C28—C33	103.82 (17)
H10A—C10—H10B	109.5	N7—C28—C29	134.97 (19)
C9—C10—H10C	109.5	C33—C28—C29	121.20 (18)
H10A—C10—H10C	109.5	C30—C29—C28	116.45 (19)
H10B—C10—H10C	109.5	C30—C29—H29	121.8
C6—C11—C12	113.39 (18)	C28—C29—H29	121.8
C6—C11—H11A	108.9	C29—C30—C31	122.6 (2)
C12—C11—H11A	108.9	C29—C30—H30	118.7
C6—C11—H11B	108.9	C31—C30—H30	118.7
C12—C11—H11B	108.9	C32—C31—C30	120.91 (19)
H11A—C11—H11B	107.7	C32—C31—H31	119.5
C11—C12—H12A	109.5	C30—C31—H31	119.5
C11—C12—H12B	109.5	C31—C32—C33	117.62 (19)
H12A—C12—H12B	109.5	C31—C32—H32	121.2
C11—C12—H12C	109.5	C33—C32—H32	121.2
H12A—C12—H12C	109.5	N9—C33—C28	109.05 (18)
H12B—C12—H12C	109.5	N9—C33—C32	129.72 (19)
N1—C13—C1	114.61 (17)	C28—C33—C32	121.23 (19)
N1—C13—H13A	108.6	N2—N1—C14	109.94 (16)
C1—C13—H13A	108.6	N2—N1—C13	116.99 (16)
N1—C13—H13B	108.6	C14—N1—C13	133.07 (17)
C1—C13—H13B	108.6	N3—N2—N1	109.16 (16)
H13A—C13—H13B	107.6	N2—N3—C19	108.30 (17)
N1—C14—C19	104.09 (18)	C21—N4—N5	109.81 (18)
N1—C14—C15	134.57 (19)	C21—N4—C20	128.95 (17)
C19—C14—C15	121.3 (2)	N5—N4—C20	120.83 (16)
C16—C15—C14	116.29 (19)	N6—N5—N4	108.99 (17)
C16—C15—H15	121.9	N5—N6—C26	107.93 (18)
C14—C15—H15	121.9	N8—N7—C28	109.64 (16)
C15—C16—C17	122.6 (2)	N8—N7—C27	116.44 (16)
C15—C16—H16	118.7	C28—N7—C27	133.74 (16)
C17—C16—H16	118.7	N9—N8—N7	109.52 (16)
C18—C17—C16	121.0 (2)	N8—N9—C33	107.97 (16)
C18—C17—H17	119.5

C6—C1—C2—C3	7.4 (3)	C22—C21—C26—N6	179.7 (2)
C13—C1—C2—C3	−171.07 (17)	N4—C21—C26—C25	179.3 (2)
C6—C1—C2—C7	−171.50 (19)	C22—C21—C26—C25	−0.6 (4)
C13—C1—C2—C7	10.0 (3)	C24—C25—C26—N6	−179.9 (3)
C1—C2—C3—C4	−1.4 (3)	C24—C25—C26—C21	0.4 (4)
C7—C2—C3—C4	177.55 (18)	C4—C5—C27—N7	92.0 (2)
C1—C2—C3—C20	−178.56 (18)	C6—C5—C27—N7	−86.0 (2)
C7—C2—C3—C20	0.3 (3)	N7—C28—C29—C30	179.7 (2)
C2—C3—C4—C5	−5.1 (3)	C33—C28—C29—C30	0.1 (3)
C20—C3—C4—C5	172.09 (17)	C28—C29—C30—C31	−0.4 (3)
C2—C3—C4—C9	174.44 (18)	C29—C30—C31—C32	0.2 (3)
C20—C3—C4—C9	−8.3 (3)	C30—C31—C32—C33	0.1 (3)
C3—C4—C5—C6	5.7 (3)	N7—C28—C33—N9	−0.4 (2)
C9—C4—C5—C6	−173.84 (18)	C29—C28—C33—N9	179.32 (18)
C3—C4—C5—C27	−172.29 (18)	N7—C28—C33—C32	−179.47 (18)
C9—C4—C5—C27	8.1 (3)	C29—C28—C33—C32	0.2 (3)
C2—C1—C6—C5	−6.8 (3)	C31—C32—C33—N9	−179.2 (2)
C13—C1—C6—C5	171.67 (17)	C31—C32—C33—C28	−0.3 (3)
C2—C1—C6—C11	172.39 (18)	C19—C14—N1—N2	−0.6 (2)
C13—C1—C6—C11	−9.1 (3)	C15—C14—N1—N2	177.4 (2)
C4—C5—C6—C1	0.2 (3)	C19—C14—N1—C13	178.9 (2)
C27—C5—C6—C1	178.21 (18)	C15—C14—N1—C13	−3.1 (4)
C4—C5—C6—C11	−179.02 (18)	C1—C13—N1—N2	−163.28 (18)
C27—C5—C6—C11	−1.0 (3)	C1—C13—N1—C14	17.3 (3)
C3—C2—C7—C8	87.5 (3)	C14—N1—N2—N3	0.6 (2)
C1—C2—C7—C8	−93.6 (2)	C13—N1—N2—N3	−178.91 (18)
C5—C4—C9—C10	85.3 (2)	N1—N2—N3—C19	−0.4 (3)
C3—C4—C9—C10	−94.2 (2)	C14—C19—N3—N2	0.1 (3)
C1—C6—C11—C12	97.3 (2)	C18—C19—N3—N2	−178.6 (3)
C5—C6—C11—C12	−83.5 (2)	C26—C21—N4—N5	0.8 (2)
C6—C1—C13—N1	80.3 (2)	C22—C21—N4—N5	−179.2 (3)
C2—C1—C13—N1	−101.3 (2)	C26—C21—N4—C20	173.4 (2)
N1—C14—C15—C16	−176.6 (2)	C22—C21—N4—C20	−6.6 (4)
C19—C14—C15—C16	1.2 (4)	C3—C20—N4—C21	146.5 (2)
C14—C15—C16—C17	−1.9 (4)	C3—C20—N4—N5	−41.7 (2)
C15—C16—C17—C18	0.6 (5)	C21—N4—N5—N6	−1.0 (2)
C16—C17—C18—C19	1.4 (4)	C20—N4—N5—N6	−174.31 (17)
N1—C14—C19—N3	0.3 (3)	N4—N5—N6—C26	0.8 (2)
C15—C14—C19—N3	−178.0 (2)	C21—C26—N6—N5	−0.3 (3)
N1—C14—C19—C18	179.2 (2)	C25—C26—N6—N5	−179.9 (3)
C15—C14—C19—C18	0.8 (4)	C33—C28—N7—N8	0.1 (2)
C17—C18—C19—N3	176.5 (3)	C29—C28—N7—N8	−179.5 (2)
C17—C18—C19—C14	−2.1 (4)	C33—C28—N7—C27	−174.7 (2)
C2—C3—C20—N4	100.5 (2)	C29—C28—N7—C27	5.7 (4)
C4—C3—C20—N4	−76.8 (2)	C5—C27—N7—N8	162.10 (17)
N4—C21—C22—C23	−179.1 (3)	C5—C27—N7—C28	−23.4 (3)
C26—C21—C22—C23	0.8 (4)	C28—N7—N8—N9	0.1 (2)
C21—C22—C23—C24	−0.9 (5)	C27—N7—N8—N9	175.93 (17)
C22—C23—C24—C25	0.8 (6)	N7—N8—N9—C33	−0.3 (2)
C23—C24—C25—C26	−0.5 (5)	C28—C33—N9—N8	0.4 (2)
N4—C21—C26—N6	−0.4 (3)	C32—C33—N9—N8	179.5 (2)

Hydrogen-bond geometry (Å, º) top

Cg1 represents the centroid of the C1–C6 ring.

D—H···A	D—H	H···A	D···A	D—H···A
C20—H20A···N8ⁱ	0.99	2.59	3.341 (3)	133
C27—H27A···N3ⁱⁱ	0.99	2.65	3.217 (3)	117
C11—H11A···N1	0.99	2.54	3.296 (3)	133
C15—H15···Cg1	0.95	2.96	3.741 (3)	140
C29—H29···Cg1	0.95	2.77	3.546 (3)	140

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

Acknowledgements

Open Access Funding by the Publication Fund of the Technische Universität Bergakademie Freiberg is gratefully acknowledged.

References

Arunachalam, M., Ahamed, B. N. & Ghosh, P. (2010). Org. Lett. 12, 2742–2745. Web of Science CSD CrossRef CAS PubMed Google Scholar
Arunachalam, M. & Ghosh, P. (2010). Org. Lett. 12, 328–331. CSD CrossRef CAS PubMed Google Scholar
Bajaj, K. & Sakhuja, R. (2015). In The Chemistry of Benzotriazole Derivatives. Topics in Heterocyclic Chemistry, vol 43, edited by J.- C. M. Monbaliu, pp. 235–283. Dordrecht: Springer. Google Scholar
Briguglio, I., Piras, S., Corona, P., Gavini, E., Nieddu, M., Boatto, G. & Carta, A. (2015). Eur. J. Med. Chem. 97, 612–648. CrossRef CAS PubMed Google Scholar
Bruker, (2014). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Cai, M., Liang, Y., Zhou, F. & Liu, W. (2011). J. Mater. Chem. 21, 13399–13405. CrossRef CAS Google Scholar
Das, D. & Barbour, L. J. (2008a). J. Am. Chem. Soc. 130, 14032–14033. Web of Science CSD CrossRef PubMed CAS Google Scholar
Das, D. & Barbour, L. J. (2008b). Chem. Commun. pp. 5110–5112. Web of Science CSD CrossRef Google Scholar
Das, D. & Barbour, L. J. (2009). Cryst. Growth Des. 9, 1599–1604. Web of Science CSD CrossRef CAS Google Scholar
Desiraju, G. R. & Steiner, T. (1999). The Weak Hydrogen Bond. Oxford University Press. Google Scholar
Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854. Web of Science CrossRef CAS IUCr Journals Google Scholar
Fuhrmann, F., Meier, E., Seichter, W. & Mazik, M. (2022a). Acta Cryst. E78, 785–788. CSD CrossRef IUCr Journals Google Scholar
Fuhrmann, F., Seichter, W. & Mazik, M. (2022b). Org. Mater. 4, 61–72. CAS Google Scholar
Groom, C. R., Bruno, I. J., Lightfoot, M. P. & Ward, S. C. (2016). Acta Cryst. B72, 171–179. Web of Science CrossRef IUCr Journals Google Scholar
Hübschle, C. B., Sheldrick, G. M. & Dittrich, B. (2011). J. Appl. Cryst. 44, 1281–1284. Web of Science CrossRef IUCr Journals Google Scholar
Kaiser, S., Geffert, C. & Mazik, M. (2019). Eur. J. Org. Chem. pp. 7555–7562. Web of Science CrossRef Google Scholar
Katritzky, A. R. & Rachwal, S. (2010). Chem. Rev. 110, 15641–1610. Google Scholar
Katritzky, A. R. & Rachwal, S. (2011). Chem. Rev. 111, 7063–7120. CrossRef CAS PubMed Google Scholar
Koch, N., Seichter, W. & Mazik, M. (2015). Tetrahedron, 71, 8965–8974. Web of Science CSD CrossRef CAS Google Scholar
Koch, N., Seichter, W. & Mazik, M. (2016). Synthesis, 48, 2757–2767. CAS Google Scholar
Koch, N., Seichter, W. & Mazik, M. (2017). CrystEngComm, 19, 3817–3833. Web of Science CSD CrossRef CAS Google Scholar
Köhler, L., Hübler, C., Seichter, W. & Mazik, M. (2021). RSC Adv. 11, 22221–22229. Web of Science PubMed Google Scholar
Köhler, L., Kaiser, S. & Mazik, M. (2024). Nat. Prod. Commun. 19. https://doi. org/10.1177/1934578X241258352. Google Scholar
Köhler, L., Seichter, W. & Mazik, M. (2020). Eur. J. Org. Chem. pp. 7023–7034. Google Scholar
Lippe, J., Seichter, W. & Mazik, M. (2015). Org. Biomol. Chem. 13, 11622–11632. Web of Science CSD CrossRef CAS PubMed Google Scholar
Loukopoulos, E., Abdul-Sada, A., Csire, G., Kállay, C., Tizzard, G. J., Coles, S. J., Lykakis, I. N. & Kostakis, G. E. (2018b). Cryst. Growth Des. 47, 10491–10508. CAS Google Scholar
Loukopoulos, E., Abdul-Sada, A., Viseux, E. M. E., Lykakis, I. N. & Kostakis, G. E. (2018a). Cryst. Growth Des. 18, 5638–5651. CSD CrossRef CAS Google Scholar
Loukopoulos, E. & Kostakis, G. E. (2019). Coord. Chem. Rev. 395, 193–229. Web of Science CrossRef CAS Google Scholar
Macías, M. A., Nuñez-Dallos, N., Hurtado, J. & Suescun, L. (2016). Acta Cryst. E72, 815–818. CSD CrossRef IUCr Journals Google Scholar
Mazik, M. (2009). Chem. Soc. Rev. 38, 935–956. Web of Science CrossRef PubMed CAS Google Scholar
Mazik, M. (2012). RSC Adv. 2, 2630–2642. Web of Science CrossRef CAS Google Scholar
Mazik, M., Bläser, D. & Boese, R. (1999). Tetrahedron, 55, 7835–7840. CSD CrossRef CAS Google Scholar
Mazik, M., Bläser, D. & Boese, R. (2000a). Tetrahedron Lett. 41, 5827–5831. CSD CrossRef CAS Google Scholar
Mazik, M., Bläser, D. & Boese, R. (2000b). Chem. Eur. J. 6, 2865–2873. CrossRef PubMed CAS Google Scholar
Mazik, M., Bläser, D. & Boese, R. (2001). Tetrahedron, 57, 5791–5797. Web of Science CSD CrossRef CAS Google Scholar
Mazik, M., Bläser, D. & Boese, R. (2005). J. Org. Chem. 70, 9115–9122. CSD CrossRef PubMed CAS Google Scholar
Mazik, M., Radunz, W. & Boese, R. (2004). J. Org. Chem. 69, 7448–7462. Web of Science CSD CrossRef PubMed CAS Google Scholar
Nishio, M. (2011). Phys. Chem. Chem. Phys. 13, 13873–13900. Web of Science CrossRef CAS PubMed Google Scholar
Nishio, M., Umezawa, Y., Honda, K., Tsuboyama, S. & Suezawa, H. (2009). CrystEngComm, 11, 1757–1788. Web of Science CrossRef CAS Google Scholar
Parsons, S., Flack, H. D. & Wagner, T. (2013). Acta Cryst. B69, 249–259. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Rahman, F.-U., Wang, R., Zhang, H.-B., Brea, O., Himo, F., Rebek, J. & Yu, Y. (2022). Angew. Chem. Int. Ed. 61, e202205534. CrossRef Google Scholar
Reddy, D. S., Craig, D. C. & Desiraju, G. R. (1996). J. Am. Chem. Soc. 118, 4090–4093. CSD CrossRef CAS Web of Science Google Scholar
Schulze, M., Koch, N., Seichter, W. & Mazik, M. (2018). Eur. J. Org. Chem. 2018, 4317–4330. CSD CrossRef CAS Google Scholar
Schulze, M., Schwarzer, A. & Mazik, M. (2017). CrystEngComm, 19, 4003–4016. Web of Science CSD CrossRef CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sheldrick, G. M. (2015). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Stapf, M., Seichter, W. & Mazik, M. (2015). Chem. A Eur. J. 21, 6350–6354. CSD CrossRef CAS Google Scholar
Stapf, M., Seichter, W. & Mazik, M. (2020). Eur. J. Org. Chem. pp. 4900–4915. Web of Science CSD CrossRef Google Scholar
Thalladi, V. R., Gehrke, A. & Boese, R. (2000a). New J. Chem. 24, 463–470. CSD CrossRef CAS Google Scholar
Thalladi, V. R., Smolka, T., Gehrke, A., Boese, R. & Sustmann, R. (2000b). New J. Chem. 24, 143–147. CSD CrossRef CAS Google Scholar
Tiekink, E. R. T. & Zukerman-Schpector, J. (2012). In The Importance of Pi-Interactions in Crystal Engineering. Frontiers in Crystal Engineering. Chichester: Wiley. Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar

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