More Like this

1. π-Complexation and C—H hydrogen bonding in the formation of colored cocrystals

   https://doi.org/10.1107/S2053229623002231  

   Bosch, Eric ; Moreno, Bryce S. ; Bowling, Nathan P. ( April 2023 , Acta Crystallographica Section C Structural Chemistry)

   The present study evaluates the potential combination of charge-transfer electron-donor–acceptor π–π complexation and C—H hydrogen bonding to form colored cocrystals. The crystal structures of the red 1:1 cocrystals formed from the isomeric pyridines 4- and 3-{2-[4-(dimethylamino)phenyl]ethynyl}pyridine with 1-[2-(3,5-dinitrophenyl)ethynyl]-2,3,5,6-tetrafluorobenzene, both C 14 H 4 F 4 N 2 O 4 ·C 15 H 14 N 2 , are reported. Intermolecular interaction energy calculations confirm that π-stacking interactions dominate the intermolecular interactions within each crystal structure. The close contacts revealed by Hirshfeld surface calculations are predominantly C—H interactions with N, O, and F atoms. 

   more » « less
2. Structural diversity in copper(I) iodide complexes with 6-thioxopiperidin-2-one, piperidine-2,6-dithione and isoindoline-1,3-dithione ligands

   https://doi.org/10.1107/S2056989020009676  

   Wheaton, Amelia M. ; Guzei, Ilia A. ; Berry, John F. ( August 2020 , Acta Crystallographica Section E Crystallographic Communications)

   null (Ed.)

   Copper(I) iodide complexes are well known for displaying a diverse array of structural features even when only small changes in ligand design are made. This structural diversity is well displayed by five copper(I) iodide compounds reported here with closely related piperidine-2,6-dithione (SNS), isoindoline-1,3-dithione (SNS6), and 6-thioxopiperidin-2-one (SNO) ligands: di-μ-iodido-bis[(acetonitrile-κ N )(6-sulfanylidenepiperidin-2-one-κ S )copper(I)], [Cu 2 I 2 (CH 3 CN) 2 (C 5 H 7 NOS) 2 ] ( I ), bis(acetonitrile-κ N )tetra-μ 3 -iodido-bis(6-sulfanylidenepiperidin-2-one-κ S )- tetrahedro -tetracopper(I), [Cu 4 I 4 (CH 3 CN) 4 (C 5 H 7 NOS) 4 ] ( II ), catena -poly[[(μ-6-sulfanylidenepiperidin-2-one-κ 2 O : S )copper(I)]-μ 3 -iodido], [CuI(C 5 H 7 NOS)] n ( III ), poly[[(piperidine-2,6-dithione-κ S )copper(I)]-μ 3 -iodido], [CuI(C 5 H 7 NS 2 )] n ( IV ), and poly[[(μ-isoindoline-1,3-dithione-κ 2 S : S )copper(I)]-μ 3 -iodido], [CuI(C 8 H 5 NS 2 )] n ( V ). Compounds I and II crystallize as discrete dimeric and tetrameric complexes, whereas III , IV , and V crystallize as polymeric two-dimensional sheets. To the best of our knowledge, compound III is the first instance of an extended hexagonal [Cu 3 I 3 ] structure that is not supported by bridging ligands. Structures I , II , and IV display weak to moderately strong Cu...Cu cuprophilic interactions [Cu...Cu internuclear distances range between 2.5803 (10) and 2.8485 (14) Å]. All structures except III display weak hydrogen-bonding interactions between the N—H of the ligand and the μ 2 and μ 3 -I − atoms. Structure III contains classical N–H...O interactions between the SNO ligands that connect the molecules in a three-dimensional framework. Complex V features π–π stacking interactions between the aryl rings of the SNS6 ligands within the same polymeric sheet. In structure IV , there were three partially occupied solvent molecules of dichloromethane and one partially occupied molecule of acetonitrile present in the asymmetric unit. The SQUEEZE routine [Spek (2015). Acta Cryst . C 71 , 9–18] was used to correct the diffraction data for diffuse scattering effects and to identify the solvent molecules. The given chemical formula and other crystal data do not take into account the solvent molecules. 

   more » « less
3. Syntheses and crystal structures of the anhydride 4-oxatetracyclo[5.3.2.0 2,6 .0 8,10 ]dodec-11-ene-3,5-dione and the related imide 4-(4-bromophenyl)-4-azatetracyclo[5.3.2.0 2,6 .0 8,10 ]dodec-11-ene-3,5-dione

   https://doi.org/10.1107/S2056989020009512  

   Hulsman, Andrew ; Lorenzana, Isabel ; Schultz, Theodore ; Squires, Breezy ; Stenfors, Brock A. ; Tolonen, Mason ; Staples, Richard J. ; Biros, Shannon M. ; Winchester, William R. ( August 2020 , Acta Crystallographica Section E Crystallographic Communications)

   null (Ed.)

   The syntheses and crystal structures of the two title compounds, C 11 H 10 O 3 ( I ) and C 17 H 14 BrNO 2 ( II ), both containing the bicyclo[2.2.2]octene ring system, are reported here [the structure of I has been reported previously: White & Goh (2014). Private Communication (refcode HOKRIK). CCDC, Cambridge, England]. The bond lengths and angles of the bicyclo[2.2.2]octene ring system are similar for both structures. The imide functional group of II features carbonyl C=O bond lengths of 1.209 (2) and 1.210 (2) Å, with C—N bond lengths of 1.393 (2) and 1.397 (2) Å. The five-membered imide ring is nearly planar, and it is positioned exo relative to the alkene bridgehead carbon atoms of the bicyclo[2.2.2]octene ring system. Non-covalent interactions present in the crystal structure of II include a number of C—H...O interactions. The extended structure of II also features C—H...O hydrogen bonds as well as C—H...π and lone pair–π interactions, which combine together to create supramolecular sheets. 

   more » « less
4. The reaction of thiourea and 1,3-dimethylthiourea towards organoiodines: oxidative bond formation and halogen bonding

   https://doi.org/10.1107/S205322962100869X  

   Peloquin, Andrew J. ; Ragusa, Arianna C. ; McMillen, Colin D. ; Pennington, William T. ( October 2021 , Acta Crystallographica Section C Structural Chemistry)

   By varying the halogen-bond-donor molecule, 11 new halogen-bonding cocrystals involving thiourea or 1,3-dimethylthiourea were obtained, namely, 1,3-dimethylthiourea–1,2-diiodo-3,4,5,6-tetrafluorobenzene (1/1), C 6 F 4 I 2 ·C 3 H 8 N 2 S, 1 , thiourea–1,3-diiodo-2,4,5,6-tetrafluorobenzene (1/1), C 6 F 4 I 2 ·CH 4 N 2 S, 2 , 1,3-dimethylthiourea–1,3-diiodo-2,4,5,6-tetrafluorobenzene (1/1), C 6 F 4 I 2 ·C 3 H 8 N 2 S, 3 , 1,3-dimethylthiourea–1,3-diiodo-2,4,5,6-tetrafluorobenzene–methanol (1/1/1), C 6 F 4 I 2 ·C 3 H 8 N 2 S·CH 4 O, 4 , 1,3-dimethylthiourea–1,3-diiodo-2,4,5,6-tetrafluorobenzene–ethanol (1/1/1), C 6 F 4 I 2 ·C 3 H 8 N 2 S·C 2 H 6 O, 5 , 1,3-dimethylthiourea–1,4-diiodo-2,3,5,6-tetrafluorobenzene (1/1), C 6 F 4 I 2 ·C 3 H 8 N 2 S, 6 , 1,3-dimethylthiourea–1,3,5-trifluoro-2,4,6-triiodobenzene (1/1), C 6 F 3 I 3 ·C 3 H 8 N 2 S, 7 , 1,3-dimethylthiourea–1,1,2,2-tetraiodoethene (1/1), C 6 H 16 N 4 S 2 ·C 2 I 4 , 8 , [(dimethylamino)methylidene](1,2,2-triiodoethenyl)sulfonium iodide–1,1,2,2-tetraiodoethene–acetone (1/1/1), C 5 H 8 I 3 N 2 S + ·I − ·C 3 H 6 O·C 2 I 4 , 9 , 2-amino-4-methyl-1,3-thiazol-3-ium iodide–1,1,2,2-tetraiodoethene (2/3), 2C 4 H 7 N 2 S + ·2I − ·3C 2 I 4 , 10 , and 4,4-dimethyl-4 H -1,3,5-thiadiazine-3,5-diium diiodide–1,1,2,2-tetraiodoethene (2/3), 2C 5 H 12 N 4 S 2+ ·4I − ·3C 2 I 4 , 11 . When utilizing the common halogen-bond-donor molecules 1,2-, 1,3-, and 1,4-diiodotetrafluorobenzene, as well as 1,3,5-trifluoro-2,4,6-triiodobenzene, bifurcated I...S...I interactions were observed, resulting in the formation of isolated rings, chains, and sheets. Tetraiodoethylene (TIE) provided I...S...I cocrystals as well, but further yielded a sulfonium-containing product through the reaction of the S atom with TIE. This particular sulfonium motif is the first of its kind to be structurally characterized, and is stabilized in the solid state through a three-dimensional I...I halogen-bonding network. Thiourea reacted with acetone in the presence of TIE to provide two novel heterocyclic products, again stabilized in the solid state through I...I halogen bonding. 

   more » « less
5. Crystal structures of three copper(II)–2,2′-bipyridine (bpy) compounds, [Cu(bpy) 2 (H 2 O)][SiF 6 ]·4H 2 O, [Cu(bpy) 2 (TaF 6 ) 2 ] and [Cu(bpy) 3 ][TaF 6 ] 2 and a related coordination polymer, [Cu(bpy)(H 2 O) 2 SnF 6 ] n

   https://doi.org/10.1107/S2056989021000633  

   Nisbet, Matthew L. ; Hiralal, Emily ; Poeppelmeier, Kenneth R. ( February 2021 , Acta Crystallographica Section E Crystallographic Communications)

   null (Ed.)

   We report the hydrothermal syntheses and crystal structures of aquabis(2,2′-bipyridine-κ 2 N , N ′)copper(II) hexafluoridosilicate tetrahydrate, [Cu(bpy) 2 (H 2 O)][SiF 6 ]·4H 2 O (bpy is 2,2′-bipyridine, C 10 H 8 N 2 ), (I), bis(2,2′-bipyridine-3κ 2 N , N ′)-di-μ-fluorido-1:3κ 2 F : F ;2:3κ 2 F : F -decafluorido-1κ 5 F ,2κ 5 F -ditantalum(V)copper(II), [Cu(bpy) 2 (TaF 6 ) 2 ], (II), tris(2,2′-bipyridine-κ 2 N , N ′)copper(II) bis[hexafluoridotantalate(V)], [Cu(bpy) 3 ][TaF 6 ] 2 , (III), and catena -poly[[diaqua(2,2′-bipyridine-κ 2 N , N ′)copper(II)]-μ-fluorido-tetrafluoridotin-μ-fluorido], [Cu(bpy)(H 2 O) 2 SnF 6 ] n , (IV). Compounds (I), (II) and (III) contain locally chiral copper coordination complexes with C 2 , D 2 , and D 3 symmetry, respectively. The extended structures of (I) and (IV) are consolidated by O—H...F and O—H...O hydrogen bonds. The structure of (III) was found to be a merohedral (racemic) twin. 

   more » « less