Crystal structure of (E)-3-(iodomethylene)-2,3-dihydro-[1,4]oxazino- [2,3,4-ij]quinolin-4-ium triodide —iodine (2:1), [C12H9INO]I3·0.5I2, C12H9I5NO

Abstract

Source of material 8-(propargyloxy)quinoline was obtained by the reaction of 8-quinolinol with propargylbromide in acetone/K 2 CO 3 with reflux. Asolutionof8-(propargyloxy)quinoline (0.145g,1mmol) in 5 mL of dichloromethane wasm ixed with 0.762 go fi odine( 3 mmol) in 15 mL of dichloromethane. Dark purplesingle crystals for the X-ray diffraction study were obtained after keeping the mixture at room temperatureinclosed flask for 48 hours, yield: 0.447 g(55 %). Experimental detailsPosition of theHatoms were calculated based on geometric criteria(C-H=0.97 Å, 0.93 Åand 0.85 Åfor methylene, aromatic and methine atoms,respectively)than have been placed in their calculatedposition andrefined isotropicallyusing arider modelwith U iso (H)=1.2U eq (C). The resulting six-membered ring is partially planar, where the C10 atom of the methylene group is slightly out of plane. The crystal structure confirms the closure of the ring between O1 and N1 atoms, where formed C11-N1 bond is covalent (1.451(5) Å).T he C11-C12 bond, that is associated with sixmember ring, has double bond character with abond distance of 1.324(6) Å. TheC12-I1 bond (2.082(4) Å) significantly deviated from mean plane of quinolinium moiety, the C11-C12-I1 angle is 123.6(3)°. Crystal packing is formedbymultiple interactions of [C 12 H 9 INO] + cations, triiodide and iodine molecules. Theorganic cationspackcould be represented as the dimeric association establishedbyap-p interaction.The fusedrings aresituated in opposite directions and lie nearly parallel to oneanother;the closest centroid-centroidd istance is 3.51(6)Å .T he dimers ares urroundedbytriiodide anions and iodine molecules. The geometry of triiodide is almost linear, I2-I3 and I3-I4 distancesa re Z. Kristallogr. Discussion

Raman spectroscopy study of new thia- and oxazinoquinolinium triodides

“…68 Crystal structures were proven by X-ray diffraction experiments and described earlier. 13,[69][70][71] Herein, we can see various types of polyiodide organization: isolated slightly asymmetric triiodide 1 and asymmetric triiodide 2, which interact with the organic cation, and symmetric triiodide 3 and triiodide 4 as a part of the polyiodide formed as a result of Z-shaped I 3 À Á Á ÁI 2 interactions. These types of triiodide anions demonstrate the different crystal packing due to specific non-covalent interactions, thus we can presume their different spectral properties.…”

Halogen Bonding and Other Iodine Interactions in Crystals of Dihydrothiazolo(oxazino)quinolinium Oligoiodides from the Electron-Density Viewpoint

“…They can be divided into four main groups: influence) function for the electron density, 18−20 one-electron potential, 21,22 the electrostatic potential (ESP) mapped onto the molecular electron-density surfaces, 23−25 and superposition of the gradient fields of electron density and electrostatic potential. Crystalline 1-iodomethyl-1,2-dihydro [1,3]thiazolo[3,2-a]quinolinium 15 and (iodomethylene)-2,3-dihydro- [1,4]oxazino-[2,3,4-ij]quinolin-4-ium 16 salts can be obtained as oligoiodides with various iodine ratios in an anion. In crystallographic database CSD v 5.35 (2014) 26,27 there are few analogs for such co-crystals, in which a C-, N-, S-, H-containing heterocyclic cation forms crystalline salts with two or more oligoiodide anions of different structures (without taking into account any other molecules: water, solvents, etc.)…”

“…The recent work dealing with noncovalent interactions of halogens in crystals − shows that the characterization of halogen bonds is based on the extensive experience and modern methods of charge density analysis. − Understanding the halogen bonds as essential features of significant supramolecular synthons appears to be the important problem of crystal design technology, which is now being solved from crystallographic, spectroscopic, and computational positions. In this work we focus on the electronic structure features of quinolinium oligoiodides − C 12 H 11 INS + I 3 – ( 1 ), 2(C 12 H 11 INS + I 3 – )·I 2 ( 2 ), and C 12 H 9 INO + I 3 – ·I 2 ( 3 ). The ability of these compounds to form the different crystalline structures of oligoiodides with varying composition makes them interesting objects in solid state design.…”

Testing the tools for revealing and characterizing the iodine–iodine halogen bond in crystals

“…The following example illustrates the unambiguity of the r 2 (r bcp ) versus d(I, I) relationship. For both the weak noncovalent interaction IÁ Á ÁI with d(I, I) = 4.020 Å in DOWMEJ (Bartashevich, Yushina, Vershinina et al, 2014) and the covalent bond with d(I, I) = 2.830 Å in ZOJPAR (Batalov et al, 2014), the same values of r 2 (r bcp ) = 0.022 a.u. have been found.…”

“…The series of organic polyiodides: NUTSOL (Abate et al, 2010), NUTSUR (Abate et al, 2010), DULZOZ01 (Filgueiras et al, 2001), YUSYUH (Nelyubina et al, 2010), the crystalline I 2 (Bertolotti et al, 2014) and the electrically neutral crystalline complexes with I 2 : HAFLAC (Antoniadis et al, 2003), NULBUR (Bailey et al, 1997), TIJLUU (Skabara et al, 2007) from the Cambridge Structural Database (Groom et al, 2016) have been examined and are listed in Table S1 of the supporting information. We have also taken advantage of our observations of chalcogenazolo(ino)quinolinium polyiodides with IÁ Á ÁI halogen bonds, which have been synthesized and analysed in our group: QIRZEY (Batalov et al, 2013), ZOJPAR (Batalov et al, 2014), DOWMAF (Bartashevich, Yushina, Vershinina et al, 2014), DOWMEJ (Bartashevich, Yushina, Vershinina et al, 2014), SUFLUC (Bartashevich, Nasibullina et al, 2016;Slepukhin, 2015), EJUPOQ (Bartashevich, and IVOVOG .…”