skip to main content
US FlagAn official website of the United States government
dot gov icon
Official websites use .gov
A .gov website belongs to an official government organization in the United States.
https lock icon
Secure .gov websites use HTTPS
A lock ( lock ) or https:// means you've safely connected to the .gov website. Share sensitive information only on official, secure websites.

Attention:

The NSF Public Access Repository (PAR) system and access will be unavailable from 8:00 PM ET on Friday, March 21 until 8:00 AM ET on Saturday, March 22 due to maintenance. We apologize for the inconvenience.

Explore Research Products in the PAR
It may take a few hours for recently added research products to appear in PAR search results.


  • NSF Public Access
  • Search Results
  • Role of secondary interactions in a series of 2:1 halogen-bonded cocrystals formed between 4-(dimethylamino)pyridine and ditopic halogen-bond donors

This content will become publicly available on September 1, 2025

Title: Role of secondary interactions in a series of 2:1 halogen-bonded cocrystals formed between 4-(dimethylamino)pyridine and ditopic halogen-bond donors
The structures of a series of 2:1 cocrystals formed between 4-(dimethylamino)pyridine and each of 1,2,4,5-tetrachloro-3,6-diiodobenzene, 2C7H10N2·C6Cl4I2, 1,2,4,5-tetrabromo-3,6-diiodobenzene, 2C7H10N2·C6Br4I2, 1-bromo-4-iodo-2,3,5,6-tetrafluorobenzene, 2C7H10N2·C6BrF4I, and 1,2-dibromo-4,5-difluoro-3,6-diiodobenzene, 2C7H10N2·C6Br2F2I2, are reported. In all five structures, the core halogen-bonded 2:1 trimolecular units have geometrically similar parameters, with the central halogen-bond donor flanked by two pyridine halogen-bond acceptors twisted with respect to the central halogen-bond donor at angles ranging from 76 to 86°. The I...N halogen-bond separations are all short, ranging from 73.3 to 76.7% of the sum of the van der Waals radii, while the C—I...N bond angles are essentially linear. The Br...N halogen-bond separation in the cocrystal formed with 1-bromo-4-iodo-2,3,5,6-tetrafluorobenzene is 80.4% of the sum of the van der Waals radii. Subtle differences in the crystal packings are attributed to the role of secondary C—H...π and weak π-type interactions with chloro and bromo substituents. The cocrystals 2C7H10N2·C6Cl4I2and 2C7H10N2·C6Br4I2are isomorphous.  more » « less
Award ID(s):
2117129 2303822
PAR ID:
10538038
Author(s) / Creator(s):
;
Publisher / Repository:
IUCr
Date Published:
Journal Name:
Acta Crystallographica Section C Structural Chemistry
Volume:
80
Issue:
9
ISSN:
2053-2296
Page Range / eLocation ID:
553-561
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. ; ; ; (, Acta Crystallographica Section C Structural Chemistry)
    The amino group of 2-amino-5-(4-halophenyl)-1,3,4-chalcogenadiazole has been replaced with bromo/iodo substituents to obtain a library of four compositionally related compounds. These are 2-iodo-5-(4-iodophenyl)-1,3,4-thiadiazole, C8H4I2N2S, 2-bromo-5-(4-bromophenyl)-1,3,4-selenadiazole, C8H4Br2N2Se, 2-bromo-5-(4-iodophenyl)-1,3,4-selenadiazole, C8H4BrIN2Se, and 2-bromo-5-(4-iodophenyl)-1,3,4-thiadiazole, C8H4BrIN2S. All were isostructural and contained bifurcated Ch...N (Ch is chalcogen) andX...X(Xis halogen) interactions forming a zigzag packing motif. The noncovalent Ch...N interaction between the chalcogen-bond donor and the best-acceptor N atom appeared preferentially instead of a possible halogen bond to the same N atom. Hirshfeld surface analysis and energy framework calculations showed that, collectively, a bifurcated chalcogen bond was stronger than halogen bonding and this is more structurally influential in this system. 
    more » « less
  2. ; ; ; (, 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
  3. ; (, Acta Crystallographica Section C Structural Chemistry)
    The rapid evaporation of 1:1 solutions of diethynylpyridines and N -halosuccinimides, that react together to form haloalkynes, led to the isolation of unreacted 1:1 cocrystals of the two components. The 1:1 cocrystal formed between 2,6-diethynylpyridine and N -iodosuccinimide (C 4 H 4 INO 2 ·C 9 H 5 N) contains an N -iodosuccinimide–pyridine I...N halogen bond and two terminal alkyne–succinimide carbonyl C—H...O hydrogen bonds. The three-dimensional extended structure features interwoven double-stranded supramolecular polymers that are interconnected through halogen bonds. The cocrystal formed between 3,5-diethynylpyridine and N -iodosuccinimide (C 4 H 4 INO 2 ·C 9 H 5 N) also features an I...N halogen bond and two C—H...O hydrogen bonds. However, the components form essentially planar double-stranded one-dimensional zigzag supramolecular polymers. The cocrystal formed between 3,5-diethynylpyridine and N -bromosuccinimide (C 4 H 4 BrNO 2 ·C 9 H 5 N) is isomorphous to the cocrystal formed between 3,5-diethynylpyridine and N -iodosuccinimide, with a Br...N halogen bond instead of an I...N halogen bond. 
    more » « less
  4. ; ; ; (, Acta Crystallographica Section C Structural Chemistry)
    The potential of pyrimidines to serve as ditopic halogen-bond acceptors is explored. The halogen-bonded cocrystals formed from solutions of either 5,5′-bipyrimidine (C 8 H 6 N 4 ) or 1,2-bis(pyrimidin-5-yl)ethyne (C 10 H 6 N 4 ) and 2 molar equivalents of 1,3-diiodotetrafluorobenzene (C 6 F 4 I 2 ) have a 1:1 composition. Each pyrimidine moiety acts as a single halogen-bond acceptor and the bipyrimidines act as ditopic halogen-bond acceptors. In contrast, the activated pyrimidines 2- and 5-{[4-(dimethylamino)phenyl]ethynyl}pyrimidine (C 14 H 13 N 3 ) are ditopic halogen-bond acceptors, and 1:1 halogen-bonded cocrystals are formed from 1:1 mixtures of each of the activated pyrimidines and either 1,2- or 1,3-diiodotetrafluorobenzene. A 1:1 cocrystal was also formed between 2-{[4-(dimethylamino)phenyl]ethynyl}pyrimidine and 1,4-diiodotetrafluorobenzene, while a 2:1 cocrystal was formed between 5-{[4-(dimethylamino)phenyl]ethynyl}pyrimidine and 1,4-diiodotetrafluorobenzene. 
    more » « less
  5. ; ; ; (, Molecules)
    This study expands and combines concepts from two of our earlier studies. One study reported the complementary halogen bonding and π-π charge transfer complexation observed between isomeric electron rich 4-N,N-dimethylaminophenylethynylpyridines and the electron poor halogen bond donor, 1-(3,5-dinitrophenylethynyl)-2,3,5,6-tetrafluoro-4-iodobenzene while the second study elaborated the ditopic halogen bonding of activated pyrimidines. Leveraging our understanding on the combination of these non-covalent interactions, we describe cocrystallization featuring ditopic halogen bonding and π-stacking. Specifically, red cocrystals are formed between the ditopic electron poor halogen bond donor 1-(3,5-dinitrophenylethynyl)-2,4,6-triflouro-3,5-diiodobenzene and each of electron rich pyrimidines 2- and 5-(4-N,N-dimethyl-aminophenylethynyl)pyrimidine. The X-ray single crystal structures of these cocrystals are described in terms of halogen bonding and electron donor-acceptor π-complexation. Computations confirm that the donor-acceptor π-stacking interactions are consistently stronger than the halogen bonding interactions and that there is cooperativity between π-stacking and halogen bonding in the crystals. 
    more » « less
  • Citation Formats
  • MLA
  • APA
  • Chicago
  • BibTeX
  • Save / Share this Record
  • Send to Email