Startseite The crystal structure of trichlorido[N-[(2-oxyphenyl)methylidene]phenylglycinemethylester-κ3O,N,O′]-tin(IV) – methylene chloride (1/1), C16H14Cl3NO3Sn·CH2Cl2
Artikel Open Access

The crystal structure of trichlorido[N-[(2-oxyphenyl)methylidene]phenylglycinemethylester-κ3O,N,O′]-tin(IV) – methylene chloride (1/1), C16H14Cl3NO3Sn·CH2Cl2

  • Uwe Böhme ORCID logo EMAIL logo und Gisela Weling
Veröffentlicht/Copyright: 16. Februar 2023

Abstract

C16H14Cl3NO3Sn·CH2Cl2, monoclinic, P21/n (no. 14), a = 11.1341(4) Å, b = 10.5867(2) Å, c = 18.6979(6) Å, β = 93.126(3)°, V = 2200.7(1) Å3, Z = 4, Rgt(F) = 0.0405, wR ref (F2) = 0.0847, T = 213 K.

CCDC no.: 2239240

The molecular structure is shown in the figure. Table 1 contains crystallographic data and Table 2 contains the list of the atoms including atomic coordinates and displacement parameters.

Table 1:

Data collection and handling.

Crystal: Yellow prism
Size: 0.35 × 0.35 × 0.11 mm
Wavelength: Mo Kα radiation (0.71073 Å)
μ: 1.79 mm−1
Diffractometer, scan mode: STOE IPDS 2, rotation method
θmax, completeness: 27.5°, >99%
N(hkl)measured, N(hkl)unique, Rint: 42,096, 5039, 0.073
Criterion for Iobs, N(hkl)gt: Iobs > 2σ(Iobs), 4344
N(param)refined: 274
Programs: X-RED/X-AREA [1], SHELX [2, 3], ORTEP-3 [4]
Table 2:

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

Atom x y z Uiso*/Ueq
Sn1 0.91778 (2) 0.56903 (2) 0.20402 (2) 0.02073 (9)
Cl1 0.82415 (9) 0.63209 (11) 0.31046 (5) 0.0346 (2)
Cl2 0.98323 (11) 0.38128 (11) 0.26073 (7) 0.0480 (3)
Cl3 0.98527 (11) 0.49880 (11) 0.09299 (6) 0.0450 (3)
O1 0.7401 (2) 0.4982 (3) 0.16225 (15) 0.0297 (6)
O2 0.5794 (2) 0.5432 (3) 0.09052 (15) 0.0339 (7)
O3 1.0644 (2) 0.6768 (2) 0.22129 (16) 0.0289 (6)
N1 0.8292 (3) 0.7313 (3) 0.15465 (15) 0.0207 (6)
C1 0.6790 (3) 0.5740 (4) 0.12546 (18) 0.0250 (7)
C2 0.7097 (3) 0.7125 (4) 0.11888 (19) 0.0232 (7)
H2 0.6515 0.7603 0.1465 0.028*
C3 0.6991 (3) 0.7615 (4) 0.0429 (2) 0.0273 (8)
C4 0.7867 (4) 0.7356 (5) −0.0046 (2) 0.0450 (12)
H4 0.8530 0.6850 0.0099 0.054*
C5 0.7770 (5) 0.7844 (7) −0.0737 (3) 0.0605 (16)
H5 0.8379 0.7689 −0.1054 0.073*
C6 0.6794 (5) 0.8545 (5) −0.0955 (3) 0.0523 (13)
H6 0.6731 0.8870 −0.1424 0.063*
C7 0.5898 (5) 0.8782 (5) −0.0497 (3) 0.0501 (13)
H7 0.5219 0.9254 −0.0654 0.060*
C8 0.5999 (4) 0.8322 (4) 0.0201 (2) 0.0381 (10)
H8 0.5392 0.8493 0.0518 0.046*
C9 0.8658 (3) 0.8459 (4) 0.1645 (2) 0.0246 (7)
H9 0.8144 0.9102 0.1466 0.030*
C10 0.9778 (3) 0.8855 (3) 0.2004 (2) 0.0231 (7)
C11 1.0697 (3) 0.8026 (3) 0.22616 (19) 0.0219 (7)
C12 1.1747 (3) 0.8544 (4) 0.2575 (2) 0.0307 (9)
H12 1.2379 0.8005 0.2731 0.037*
C13 1.1880 (4) 0.9826 (4) 0.2661 (3) 0.0380 (10)
H13 1.2595 1.0153 0.2878 0.046*
C14 1.0963 (4) 1.0639 (4) 0.2429 (3) 0.0405 (10)
H14 1.1046 1.1514 0.2502 0.049*
C15 0.9938 (4) 1.0163 (4) 0.2095 (2) 0.0319 (9)
H15 0.9331 1.0720 0.1923 0.038*
C16 0.5384 (4) 0.4117 (4) 0.0948 (2) 0.0403 (11)
H16A 0.5962 0.3565 0.0736 0.060*
H16B 0.4608 0.4031 0.0690 0.060*
H16C 0.5310 0.3887 0.1446 0.060*
Cl4Aa 0.2922 (8) 0.6754 (9) 0.0655 (5) 0.129 (3)
C17Aa 0.1794 (17) 0.7960 (18) 0.0565 (8) 0.099 (6)
H17Aa 0.0999 0.7625 0.0661 0.119*
H17Ba 0.1983 0.8667 0.0890 0.119*
Cl5Aa 0.1856 (6) 0.8423 (6) −0.0330 (3) 0.119 (3)
Cl4Bb 0.2952 (6) 0.7371 (8) 0.0794 (4) 0.118 (2)
C17Bb 0.1650 (15) 0.7438 (15) 0.0209 (11) 0.123 (7)
H17Cb 0.1818 0.7008 −0.0239 0.148*
H17Db 0.1001 0.6975 0.0427 0.148*
Cl5Bb 0.1154 (9) 0.8980 (8) 0.0010 (5) 0.184 (4)
  1. aOccupancy: 0.463 (9), bOccupancy: 0.537 (9).

Source of materials

The O,N,O′-ligand was prepared from salicylaldehyde and D-phenylglycine methylester hydrochloride according to a literature procedure [10].

In a representative experiment 1.0 g (3.7 mmol) N-[(2-hydroxyphenyl)methylidene]phenylglycinemethylester was placed in a Schlenk flask under argon and solved in 40 ml dry dichloromethane. To this solution was added 0.2 mL (0.5 g, 1.9 mmol) SnCl4. A thin white precipitate formed after several minutes. The mixture was stirred overnight at room temperature. Filtration and storage of the filtered solution at 5 °C for 6 month yielded yellow crystals of the title compound. Yield: 0.76 g (68% based on SnCl4). M.pt: 428 K.

Experimental details

The carbon-bound H atoms were geometrically placed (C–H = 0.94–0.99 Å) and refined as riding atoms with Uiso(H) = 1.2–1.5 Ueq(C). The disordered molecule methylene chloride was refined with a split atom model. Site occupation factors for parts A and B were refined to 0.46/0.54, respectively. Restraints were applied in order to keep both parts of the disordered methylene chloride to sensible values regarding bond lengths and anisotropic displacement parameters.

Comment

Organotin complexes of Schiff bases are a fast developing field of research which is due to their various possible applications. These complexes can exhibit antitumor, antimicrobial, antinematicidal, antiinsecticidal, and antiinflammatory properties [5]. We are interested in chiral complexes of group 14 elements. For that purpose we explored several chiral ligand types [6], [7], [8], [9].

The molecular structure is shown in the figure (50% displacement ellipsoids) with a tin complex and a disordered molecule methylene chloride in the asymmetric unit. The centrosymmetric space group P21/n indicates that both enantiomers of the amino acid derivative are present in the crystal under investigation. The batch product shows no rotation of polarized light ([α]D20 = 0°). D-phenylglycine methylester has been used for the synthesis of the Schiff-base ligand. The ligand was checked to be chiral ([α]D20 = +59.3°). That means racemization of the ligand system must have occurred during complex formation. This was already observed in other cases [10, 11].

The tin complex features a hexacoordinate tin(IV) centre within a NO2Cl3 donor set defined by the O,N,O′ atoms of the negative tridentate Schiff base ligand and three chlorido ligands. The Schiff-base ligand is coordinated meridional to the central atom. The chlorido ligands Cl1 and Cl3 are in trans position to each other. The chlorido ligand Cl2 is in trans position to the Schiff-base nitrogen atom N1. The angle O1–Sn1–O3 with a value of 162.3(1)° deviates strongly from 180°. The angle Cl1–Sn1–Cl3 is 172.59(4)° and N(1)–Sn(1)–Cl(2) 170.94(8)°. The bond Sn1–O1 [2.218(3) Å] is longer than the bond Sn1–O3 [2.003(3) Å]. This can be explained with the carbonyl type oxygen atom O1 and the (formal) anionic character of O3. The bond length Sn1–N1 is similar as in comparable hexacoordinated tin complexes [12, 13]. The distances Sn–Cl1, Sn–Cl2 and Sn–Cl3 are 2.392(1), 2.35(1), and 2.366(1) Å, respectively. This corresponds well with Sn–Cl bonds in directly related structures. These consist of octahedral tin-complexes with tridentate O,N,O-Schiff-base ligands coordinated to a SnCl3-unit [1418].

Two closely related tin complexes with the N-[(2-oxyphenyl)methylidene]phenylglycinato ligand have been reported [10, 19]. Therein, the Schiff-base ligand coordinates as tridentate dianion to a SnR2-unit with R=Me, Ph, resulting in pentacoordinated tin complexes.


Corresponding author: Uwe Böhme, Institut für Anorganische Chemie, Technische Universität Bergakademie Freiberg, Leipziger Str. 29, 09599 Freiberg, Germany, E-mail:

Funding source: TU Bergakademie Freiberg (Freiberg, Germany)

  1. Author contribution: All the authors have accepted responsibility for the entire content of this submitted manuscript and approved submission.

  2. Research funding: TU Bergakademie Freiberg (Freiberg, Germany), Open Access Funding by the Publication Fund of the TU Bergakademie Freiberg.

  3. Conflict of interest statement: The authors declare no conflicts of interest regarding this article.

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Received: 2023-01-03
Accepted: 2023-02-01
Published Online: 2023-02-16
Published in Print: 2023-04-25

© 2023 the author(s), published by De Gruyter, Berlin/Boston

This work is licensed under the Creative Commons Attribution 4.0 International License.

Artikel in diesem Heft

  1. Frontmatter
  2. New Crystal Structures
  3. The crystal structure of methyl 2-((4-chloro-2-fluoro-6-((2,2,2-trifluoroethyl) thio)phenoxy)methyl)benzoate, C17H13ClF4O3S
  4. The crystal structure of 3-hydroxy-5-oxo-4-propanoylcyclohex-3-ene-1-carboxylic monohydrate, C10H14O6
  5. Crystal structure of 2-({[5-(adamantan-2-yl)-2-sulfanylidene-1,3,4-oxadiazolidin-3-yl]methyl}amino)benzonitrile, C20H22N4OS
  6. Crystal structure of 1-(3-bromopropyl)-2-((4-chlorophenoxy)methyl)-4-methyl-1H-benzo[d]imidazole, C18H18BrClN2O
  7. Crystal structure of 2-methoxy-6-[(2-morpholin-4-yl-phenylamino)-methylene]-4-nitro-cyclohexa-2,4-dienone, C18H19N3O5
  8. The crystal structure of 2-(7-(2,3-dimethoxyphenyl)-[1,2,4]triazolo[1,5-a]-pyrimidin-5-yl)-3-methoxyphenol, C20H18N4O4
  9. The crystal structure of 3-(1-(2-(4-hydroxy-3,5-dimethoxybenzylidene)hydrazinyl)ethylidene)chroman-2,4-dione dihydrate, C20H22N2O8
  10. Crystal structure of 3,5,7-trimethoxy-3′,4′-methylenedioxy-flavone, C19H16O7
  11. The crystal structure of strictic acid, C20H26O3
  12. Crystal structure of 1,1′-(pyrazine-1,4-diyl)-bis(propan-2-one), C10H14N2O2
  13. The crystal structure of 1-(adamantan-1-yl)-3-(4-chlorophenyl)urea, C17H21ClN2O
  14. The crystal structure of (2R,6′R)-2′,7-dichloro-4,6-dimethoxy-6′-methyl-3H-spiro[benzofuran-2,1′-cyclohexan]-2′-ene-3,4′-dione, C16H14Cl2O5
  15. Synthesis and crystal structure of 1-((3R,10S,13R,17S)-3-((4-methoxyphenyl)amino)-10,13-dimethylhexadecahydro-1H-cyclopenta[α]-phenanthren-17-yl)ethan-1-one, C28H41NO2
  16. Crystal structure of N-2,6-difluorobenzoyl-N′-[1-(3-chloro-4-methyl-phenyl)-4-cyano-1H-pyrazol-5-carbamoyl]urea, C19H12ClF2N5O2
  17. Crystal structure of (−)-β-D-19-glucopiranosyl-9,15-dihydroxy kaurenoate, C26H40O9
  18. Crystal structure of 7-hydroxy-6-(2-hydroxyethyl)-2H-chromen-2-one, C11H10O4
  19. Crystal structure of S-(benzo[d]thiazol-2-yl)-N-(tert-butyl)thiohydroxylamine, C11H14N2S2
  20. Crystal structure of poly[di-µ2-aqua-aqua-nitrato-κ2O,O′-(µ3-2-nitroisophthalato-κ4O,O′:O″:O′″)barium(II)natrium(II)] monohydrate, C8H11BaN2NaO13
  21. The crystal structure of diaqua-bis(pyrazolo[1,5-a]pyrimidine-3-carboxylato-κ2 N,O)-cobalt(II) dihydrate, C14H16N6O8Co
  22. Crystal structure of (S,E)-3-((pyridin-2-ylmethylene)amino)-2-(pyridin-4-yl)-2,3- dihydroquinazolin-4(1H)-one monohydrate, C19H15N5O⋅H2O
  23. Synthesis and crystal structure of 5-(8-(((5-carboxypentyl)ammonio)methyl)-7-hydroxy-4-oxo-4H-chromen-3-yl)-2-hydroxy-3-nitrobenzenesulfonate monohydrate, C22H24N2O12S
  24. Synthesis and crystal structure of 8-bromo-3-(1H-pyrazole-1-carbonyl)-2H-chromen-2-one, C13H7BrN2O3
  25. Crystal structure of E-7-fluoro-2-(4-methoxy-3-(trifluoromethyl)benzylidene)-3,4-dihydronaphthalen-1(2H)-one, C19H14F4O2
  26. Hydrogen bonded dimers in the crystal structure of 2-chloro-N-((3,5-dimethylphenyl)carbamoyl)-nicotinamide, C30H28Cl2N6O4
  27. Crystal structure of 3,3′-(1,4-phenylenebis(methylene))bis(1-allyl-1H-imidazol-3-ium) bis(hexafluoro phosphate)(V), C10H12F6N2P
  28. Crystal structure of (E)-7-bromo-2-(4-(4-methylpiperazin-1-yl)benzylidene)-3,4-dihydronaphthalen-1(2H)-one, C22H23BrN2O
  29. Crystal structure of pentacarbonyl-(μ2-ethane-1,2-dithiolato-κ4S:S,S′:S′)-(diphenyl(o-tolyl)phosphine-κ1P)diiron (Fe–Fe), C26H21Fe2O5PS2
  30. Crystal structure of 9-(2-chloroethoxy)-4-(4-methoxy-3-(trifluoromethyl)phenyl)- 5,6-dihydrobenzo[h]quinazolin-2-amine, C22H19ClF3N3O2
  31. Crystal structure of triaqua-[5-bromo-2-(carboxylatomethoxy)benzoate-κ3 O,O′,O″]nickel(II), C9H11BrNiO8
  32. The crystal structure of 4,4′-dichloro-3,5′-diphenyl-1′H-1,3′- bipyrazole, C18H12Cl2N4
  33. The crystal structure of bis(1H-pyrazole-carboxamidine-κN,N′)bis(nitrato-κO)-copper(II), C8H12CuN10O6
  34. Synthesis and crystal structure of 3-bromo-4-phenyl-2H-chromene, C15H11BrO
  35. Crystal structure of (E)-5-(diethylamino)-2-((morpholinoimino)methyl)phenol, C15H23N3O2
  36. Crystal structure of niobium trigallide, NbGa3
  37. Crystal structure of dimethyl 4,4′-(((1R, 2R)-cyclohexane-1,2-diyl)bis(azanediyl))dibenzoate, C22H26N2O4
  38. Crystal structure of dimethyl 4,4′-((4R, 5R)-4,5-diphenylimidazolidine-1,3-diyl)dibenzoate, C31H28N2O4
  39. The crystal structure of 2-(2-bromophenyl)-4-phenylbenzo[b][1,4]oxaphosphinine 4-oxide, C20H14BrO2P
  40. The crystal structure of 3-hydroxy-2-nitroestra-1,3,5(10)-trien-17-one, C18H21NO4
  41. Crystal structure of catena-poly[[μ2-1,3-bis[(1H-imidazol-1- yl)methyl]benzene-N:N′]-(μ2–D–camphorato-O, O′: O″, O‴)cadmium(II)], C48H56Cd2N8O8
  42. Crystal structure of N-(4-bromophenyl)-4-[3-(trifluoromethyl)phenyl]-piperazine-1-carbothioamide, C18H17BrF3N3S
  43. The crystal structure of cis-Dicyano-bis(2,2′-bipyridine)k2N,N′-chromium(III) hexafluorophosphate, C22H16N6F6PCr
  44. Crystal structure of 4-((6-bromohexyl)oxy)-2-hydroxybenzaldehyde, C13H17BrO3
  45. Crystal structure of hydrazinium methanesulfonate, CH8N2O3S
  46. Crystal structure of 1-(2-iodobenzoyl)-6-methoxy-1H-indole-3-carbaldehyde, C17H12INO3
  47. Crystal structure of bis(acridinium) tetrabromidomanganate(II), C26H20Br4MnN2
  48. The crystal structure of 6,6′-((1E,1′E)-hydrazine-1,2-diylidenebis(methanylylidene)) bis(2-(tert-butyl)phenol), C22H28N2O2
  49. The crystal structure of the cocrystal di-μ2-chlorido-tetramethyl-tetraphenyl-di-μ3-oxido-dichloridotetratin(IV) – diphenyl-methyl-chloridotin(IV)(1/2), C54H58Cl6O2Sn6
  50. Crystal structure of (3a7R,13bR)-3-((1R)-1-hydroxy-1-(5-methyl-6-oxo-3,6-dihydro-2H-pyran-2-yl)ethyl)-3a,11,11,13b-tetramethyl-2,3,3a,4,5,11,11a,12,13,13b-decahydroindeno[5′,4′:4,5] cyclohepta[1,2-c]oxepin-9(1H)-one, C30H40O5
  51. Crystal structure of 1-(4-methoxyphenyl)-2-phenoxyethan-1-one, C15H14O3
  52. Crystal structure of trans-tetrakis(3-phenylpyridine-κN)bis(thiocyanato-κN)nickel(II), C46H36N6NiS2
  53. Crystal structure of sodium catena-poly[bis(thiourea-κ1S)-tetrakis(μ2-thiourea-κ2S,S)tricopper(I)] difumarate, C14H29Cu3N12NaO8S6
  54. Crystal structure of bis(benzylamine-κ1N)-bis((E)-2-methyl-3-phenylacrylato-κ1O)copper(II), C34H36CuN2O4
  55. The crystal structure of 3,4-dihydroxybenzoic acid – 3-[7-{[2-(3,4-difluorophenyl)cyclopropyl]amino}-5-(propylsulfanyl)-3H-[1,2,3] triazolo[4,5-d]pyrimidin-3-yl]-5-(2-hydroxyethoxy)cyclopentane-1,2-diol – water (1/1/1), C30H36F2N6O9S
  56. Crystal structure of catena-poly[dipyridine-bis(pyridine-2-carboxylato-κ 2 N,O)-bis(μ 2-pyridine-2-carboxylato-κ 2 N,O)-dinickel(II)], C34H26N6Ni2O8
  57. The crystal structure of 1-((1-methyl-1H-1,2,4-triazol-3-yl) methyl)-3-(2,4,5-trifluorobenzyl)-1,3,5-triazinane-2,4,6-trione, C14H11F3N6O3
  58. Crystal structure of (E)-2-((Z)-2-((1S,4R)-3,3-dimethylbicyclo[2.2.1] heptan-2-ylidene)ethylidene)hydrazine-1-carbothioamide, C24H38N6S2
  59. Crystal structure of photochromic 3-(5-(2,5-dimethylthiophen-3-yl)-2,2,3,3,4,4-hexafluorocyclopentyl)-2-methylbenzo[b]-thiophene, C20H14F6S2
  60. Crystal structure of bis(2,5,5,7-tetramethyl-1,4-diazepane-1,4-diium) diaqua-bis(1,2-diaminopropane)copper(II) bis(μ6-oxido)tetrakis(μ3-oxido)-tetradecakis(μ2-oxido)-octaoxido-decavanadium(V) – water (1/4), C24H76CuN8V10O34
  61. Crystal structure of 1,2,3,5,13-pentamethoxy-6,7-dimethyl-1,2,3,4,4a,5,6,7,8,13b-decahydrobenzo[3′,4′]cycloocta[1′,2′:4,5]benzo[1,2-d][1,3]dioxole, C24H30O7
  62. Crystal structure of bis(6-carboxyhexyl)-4,4′-bipyridinium dibromide – 2,6-dihydroxynaphthalene (1/2), C42H46Br2N2O8
  63. Crystal structure of methyl 2-(2-chloroacetyl)-1-(4-(methoxycarbonyl)phenyl)-2,3,4,9-tetrahydro-1H-pyrido[3,4-b] indole-3-carboxylate, C23H21ClN2O5
  64. Crystal structure of bis(dimethylammonium) poly[{μ4-1,1ʹ-(1,4-phenylenebis(methylene))bis(1H-pyrazole-3,5-dicarboxylato)-κ6N4O2}zinc(II)], C22H26N6O8Zn
  65. Crystal structure of 2-(2-(4-methoxyphenyl)-2H-indazol-3-yl)acetonitrile, C16H13N3O
  66. Crystal structure of (E)-7-methoxy-2-(4-morpholinobenzylidene)-3,4-dihydronaphthalen-1(2H)-one, C22H23NO3
  67. The crystal structure of N′1,N′2-bis((E)-3-(tert-butyl)-2-hydroxybenzylidene)oxalohydrazide, C24H30N4O4
  68. The crystal structure of trimethyl 2,2′,2′′-(benzene-1,3,5-triyltris(oxy))triacetate, C15H18O9
  69. Crystal structure of bis(N,N-dimethylformamide-κO)-bis(pyridine-2-carboxylato-κ2N,O)-bis(μ2-pyridine-2-carboxylato-κ2N,O)-dinickel(II), C30H30N6Ni2O10
  70. Crystal structure of bis(μ2-1-pyrenecarboxylato-κ3O,O′:O′)-bis(1-pyrenecarboxylato-κ2O,O′)-(benzimidazole-κ1N)dicadmium(II), C82H48Cd2N4O8
  71. One-pot synthesis and crystal structure of diethyl 2,6-dimethyl-4-(1-(2-nitrophenyl)-1H-1,2,3-triazol-4-yl)-1,4-dihydropyridine-3,5-dicarboxylate, C21H23N5O6
  72. The crystal structure of 1-(2-fluorobenzoyl)-5-methoxy-2-methyl-1H-indole-3-carbonitrile, C18H13FN2O2
  73. Crystal structure of bis(trimethylphenylammonium) aqua-oxido-octathiotritungstate, (Me3PhN)2[W3OS8(H2O)]
  74. The crystal structure of trichlorido[N-[(2-oxyphenyl)methylidene]phenylglycinemethylester-κ3O,N,O′]-tin(IV) – methylene chloride (1/1), C16H14Cl3NO3Sn·CH2Cl2
  75. The crystal structure of furan-2,5-diylbis((4-chlorophenyl)methanol), C18H14Cl2O3
  76. The crystal structure of hexalithium decavanadate hexadecahydrate, H32Li6O44V10
  77. Crystal structure of ethyl 4-{[5-(adamantan-1-yl)-2-sulfanylidene-2,3-dihydro-1,3,4-oxadiazol-3-yl]methyl}piperazine-1-carboxylate, C20H30N4O3S
  78. Crystal structure of aqua(μ2-2,2′,2″-((nitrilo)tris(ethane-2,1-diyl(nitrilo)methylylidene))tris (6-ethoxyphenolato))(pentane-2,4-dionato-κ2O,O′)-dinickel(II), C38H48N4Ni2O9
Heruntergeladen am 10.9.2025 von https://www.degruyterbrill.com/document/doi/10.1515/ncrs-2023-0004/html
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