Midway between Energetic Molecular Crystals and High-Density Energetic Salts: Crystal Engineering with Hydrogen Bonded Chains of Polynitro Bipyrazoles

2020 ◽  
Vol 20 (2) ◽  
pp. 755-764 ◽  
Author(s):  
Ivan Gospodinov ◽  
Kostiantyn V. Domasevitch ◽  
Cornelia C. Unger ◽  
Thomas M. Klapötke ◽  
Jörg Stierstorfer
Keyword(s):  
Crystal Engineering ◽  
Molecular Crystals ◽  
High Density ◽  
Energetic Salts ◽  
Hydrogen Bonded

Hydrogen-bonded assemblies in the molecular crystals of 2,2′-thiodiacetic acid with ethylenediamine ando-phenylenediamine

2017 ◽  
Vol 73 (2) ◽  
pp. 97-103 ◽  
Author(s):  
V. Gomathi ◽  
C. Theivarasu
Keyword(s):  
Crystal Engineering ◽  
Mechanical Stability ◽  
Three Dimensional ◽  
Molecular Crystals ◽  
Charge Transfer Complexes ◽  
Supramolecular Network ◽  
One Dimensional ◽  
Supramolecular Networks ◽  
Supramolecular Chains ◽  
Hydrogen Bonded

Carboxylate molecular crystals have been of interest due to the presence of hydrogen bonding, which plays a significant role in chemical and crystal engineering, as well as in supramolecular chemistry. Acid–base adducts possess hydrogen bonds which increase the thermal and mechanical stability of the crystal. 2,2′-Thiodiacetic acid (Tda) is a versatile ligand that has been widely explored, employing its multidendate and chelating coordination abilities with many metals; however, charge-transfer complexes of thiodiacetic acid have not been reported. Two salts, namely ethylenediaminium 2,2′-thiodiacetate, C2H10N22+·C4H4O4S22−, denoted Tdaen, and 2-aminoanilinium 2-(carboxymethylsulfanyl)acetate, C6H9N2+·C4H5O4S−, denoted Tdaophen, were synthesized and characterized by IR,1H and13C NMR spectroscopies, and single-crystal X-ray diffraction. In these salts, Tda reacts with the aliphatic (ethylenediamine) and aromatic (o-phenylenediamine) diamines, and deprotonates them to form anions with different valencies and different supramolecular networks. In Tdaen, the divalent Tda2−anions form one-dimensional linear supramolecular chains and these are extended into a three-dimensional sandwich-type supramolecular network by interaction with the ethylenediaminium cations. However, in Tdaophen, the monovalent Tda−anions form one-dimensional zigzag supramolecular chains, which are extended into a three-dimensional supramolecular network by interaction with the 2-aminoanilinium cations. Thus, both three-dimensional structures display different ring motifs. The structures of these diamines, which are influenced by hydrogen-bonded assemblies in the molecular crystals, are discussed in detail.

Concomitant polymorphs of 1,3-bis(3-fluorophenyl)urea

2016 ◽  
Vol 72 (9) ◽  
pp. 692-696 ◽  
Author(s):  
Christina A. Capacci-Daniel ◽  
Jeffery A. Bertke ◽  
Shoaleh Dehghan ◽  
Rupa Hiremath-Darji ◽  
Jennifer A. Swift
Keyword(s):  
Hydrogen Bonding ◽  
Crystal Engineering ◽  
Structural Motif ◽  
Parallel Orientation ◽  
One Dimensional ◽  
Monoclinic Form ◽  
Engineering Studies ◽  
Hydrogen Bonded

Hydrogen bonding between urea functionalities is a common structural motif employed in crystal-engineering studies. Crystallization of 1,3-bis(3-fluorophenyl)urea, C13H10F2N2O, from many solvents yielded concomitant mixtures of at least two polymorphs. In the monoclinic form, one-dimensional chains of hydrogen-bonded urea molecules align in an antiparallel orientation, as is typical of many diphenylureas. In the orthorhombic form, one-dimensional chains of hydrogen-bonded urea molecules have a parallel orientation rarely observed in symmetrically substituted diphenylureas.

scholarly journals Unusual co-crystal of isonicotinamide: the structural landscape in crystal engineering

2012 ◽  
Vol 370 (1969) ◽  
pp. 2900-2915 ◽  
Author(s):  
Srinu Tothadi ◽  
Gautam R. Desiraju
Keyword(s):  
Crystal Structure ◽  
Crystal Structures ◽  
Crystal Engineering ◽  
Organic Molecule ◽  
Reference Molecule ◽  
Hydrogen Bonded

The idea of a structural landscape is based on the fact that a large number of crystal structures can be associated with a particular organic molecule. Taken together, all these structures constitute the landscape. The landscape includes polymorphs, pseudopolymorphs and solvates. Under certain circumstances, it may also include multi-component crystals (or co-crystals) that contain the reference molecule as one of the components. Under still other circumstances, the landscape may include the crystal structures of molecules that are closely related to the reference molecule. The idea of a landscape is to facilitate the understanding of the process of crystallization. It includes all minima that can, in principle, be accessed by the molecule in question as it traverses the path from solution to the crystal. Isonicotinamide is a molecule that is known to form many co-crystals. We report here a 2:1 co-crystal of this amide with 3,5-dinitrobenzoic acid, wherein an unusual N−H⋯N hydrogen-bonded pattern is observed. This crystal structure offers some hints about the recognition processes between molecules that might be implicated during crystallization. Also included is a review of other recent results that illustrate the concept of the structural landscape.

The Oxamate Anion:  A Flexible Building Block of Hydrogen-Bonded Architectures for Crystal Engineering

1996 ◽  
Vol 118 (42) ◽  
pp. 10134-10140 ◽  
Author(s):  
Christer B. Aakeröy ◽  
Deirdre P. Hughes ◽  
Mark Nieuwenhuyzen
Keyword(s):  
Crystal Engineering ◽  
Building Block ◽  
Hydrogen Bonded

Crystal Engineering Using Bisphenols. Chains, Ladders and Sheets Formed by the Adducts of 1,4-Diazabicyclo[2.2.2]octane with Bisphenols: Structures of Adducts with 4,4'-Isopropylidenediphenol (1/1), 4,4'-Oxodiphenol (1/1) and 4,4'-Thiodiphenol (1/1 and 2/1)

1997 ◽  
Vol 53 (3) ◽  
pp. 513-520 ◽  
Author(s):  
G. Ferguson ◽  
P. I. Coupar ◽  
C. Glidewell
Keyword(s):  
Hydrogen Bonds ◽  
Crystal Engineering ◽  
Cross Links ◽  
Graph Set ◽  
N Vector ◽  
Hydrogen Bonded

4,4′-Isopropylidenediphenol-1,4-diazabicyclo[2.2.2]octane (1/1), (1), C15H16O2.C6H12N2, monoclinic, P2/a, a = 11.385 (2), b = 6.5565 (12), c = 13.076 (2) Å, \beta = 96.240 (11)°, with Z = 2; the two components of the adduct, which each lie across twofold axes, are joined into simple chains via O—H...N hydrogen bonds in a motif with graph set C_{2}^2(17). 4,4′-Oxodiphenol-1,4-diazabicyclo[2.2.2]octane (1/1), (2), C12H10O3.C6H12N2, orthorhombic, P212121, a = 9.4222 (11), b = 11.1886 (15), c = 15.694 (2), with Z = 4; the diamine component is disordered by rotation about the N...N vector, having two orientations [populations 0.76 (1) and 0.24 (1)] rotated by 48 (3)° from coincidence: the components are joined into chains via O—H...N hydrogen bonds in a motif with graph set C_{2}^2(17); pairs of these chains are joined into ladders by C—H...O hydrogen bonds in a motif of graph set R_{2}^2(22). 4,4′-Thiodiphenol-l,4-diazabicyclo[2.2.2]octane (1/1), (3), C12H10O2S.C6H12N2, isomorphous, a = 9.5785 (11), b = 11.4525 (13), c = 15.759 (2) Å (and ipso facto isostructural), with (2); the diamine disorder is characterized by two equally populated orientations related by a rotation about the N...N vector of 37.1 (2)° and pairs of chains are now joined into ladders by C—H...S hydrogen bonds. 4,4′-Thiodiphenol-1,4-diazabicyclo[2.2.2]octane (2/1), (5), (C12H10O2S)2.C6H12N2, monoclinic, P21/n, a = 8.3198 (9), b = 11.4006 (13), c = 15.056 (2) Å, \beta = 104.955 (8)°, with Z = 2; the diamine component of the adduct is disordered across a centre of inversion, and the bisphenol components are linked into chains by O—H...O hydrogen bonds in a motif with graph set C(12). These chains form cross-links via the diamine component by means of O—H...N hydrogen bonds in a C_{3}^3(19) motif to yield sheets within which are large hydrogen-bonded rings described by the unusual graph set R_{8}^8(62).

Sign in / Sign up

Export Citation Format

Share Document