Chlorometallate-Pyridinium Boronic Acid Salts for Crystal Engineering: Synthesis of One-, Two-, and Three-Dimensional Hydrogen Bond Networks

2015 ◽  
Vol 15 (6) ◽  
pp. 2652-2660 ◽  
Author(s):  
Yasemin Yahsi ◽  
Elif Gungor ◽  
Hulya Kara
Keyword(s):  
Hydrogen Bond ◽  
Crystal Engineering ◽  
Boronic Acid ◽  
Three Dimensional ◽  
Hydrogen Bond Networks ◽  
Acid Salts

Polysulfonylamine, CLXVII [1]. Wasserstoffbrücken in kristallinen Onium-dimesylamiden: Ein robustes Dreipunktmuster als Bestandteil eines 2D-, eines zweifach verwobenen 2D- und eines 3D-Wasserstoffbrücken-Netzwerks / Polysulfonylamines, CLXVII [1]. Hydrogen Bonding in Crystalline Onium Dimesylamides: A Robust Three-Point Pattern Integrated into a 2D, a Twofold Interwoven 2D, or a 3D Hydrogen-Bond Network

2004 ◽  
Vol 59 (1) ◽  
pp. 17-26 ◽  
Author(s):  
Karna Wijaya ◽  
Oliver Moers ◽  
Armand Blaschette ◽  
Peter G. Jones
Keyword(s):  
Hydrogen Bond ◽  
Hydrogen Bonding ◽  
Crystal Engineering ◽  
Three Dimensional ◽  
Double Layers ◽  
Point Pattern ◽  
Hydrogen Bond Donor ◽  
Layer Structures ◽  
Ionic Solids ◽  
Hydrogen Bond Networks

Abstract As an exercise in crystal engineering, preparations and low-temperature X-ray structures are reported for three ionic solids of general formula BH+(MeSO2)2N−, where BH+ is 2,4,6- triaminopyrimidinium (compound 1, triclinic, space group P1, Z = 2), 2,6-diaminopyridinium (2, monoclinic, C2/c, Z = 8), or 2,4-diaminopyrimidin-6(1H)-on-3-ium (3, monoclinic, P21/c, Z = 4). As a common feature, the onium cations in question exhibit a trifunctional hydrogen-bond donor sequence H-N-C-N(H)-C-N-H that is complementary to a W-shaped O-S-N-S-O fragment of the anion. Consequently, each structure displays a [DDD:AAA] three-point hydrogen-bond pattern formed by two lateral N-H···O bonds and a central N-H···N interaction. This grouping is integrated as a robust supramolecular synthon into two-dimensional (1, 2) or three-dimensional (3) hydrogen-bond networks, in which all good donors and all good acceptors are involved (excepting one S=O group in 2). In structure 1, the approximately planar cation-anion layers are perfect mosaics composed of 6-membered pyrimidine heterocycles and seven crystallographically independent types of 8-, 10-, 12- or 24-membered rings based upon hydrogen bonding. In contrast, the corresponding layers in structure 2 are marred by large 40-membered voids; in order to achieve dense packing, the imperfect layers adopt a strongly corrugated shape and interpenetrate to form twofold interwoven and nearly planar double-layers. Each structure features close C-H···O contacts consistent with weak hydrogen bonding; in the layer structures 1 and 2, some of these interactions serve as links between adjacent or interwoven layers.

Polysulfonylamine, CXXVI [1] Wasserstoffbrücken in kristallinen Onium-dimesylamiden: Ein robustes Achtring-Synthon in Koexistenz mit einem dritten Wasserstoffbrückenmotiv - Cyclodimere, Ketten, supramolekulare Bindungsisomere und ein fünffach verwobenes dreidimensionales (C-H ∙∙∙ O - Netzwerk / Polysulfonylamines, CXXVI [1] Hydrogen Bonding in Crystalline Onium Dimesylamides: A Robust Eight- Membered Ring Synthon in Coexistence with a Third Hydrogen Bonding Motif - Cyclodimers, Chains, Supramolecular Linkage Isomers, and a Quintuply Interwoven Three-Dimensional C - H ∙∙∙ O Network

2000 ◽  
Vol 55 (8) ◽  
pp. 738-752 ◽  
Author(s):  
Oliver Moers ◽  
Karna Wijaya ◽  
Ilona Lange ◽  
Armand Blaschette ◽  
Peter G. Jones
Keyword(s):  
Hydrogen Bond ◽  
Hydrogen Bonding ◽  
Crystal Engineering ◽  
Ion Pairs ◽  
Three Dimensional ◽  
Membered Ring ◽  
Monoclinic Space Group ◽  
Hydrogen Bond Donor ◽  
Linkage Isomers ◽  
Ionic Solids

As an exercise in crystal engineering, low-temperature X-ray structures were determined for six rationally designed ionic solids of general formula BH+(MeSO2)2N−, where BH+ is 2-aminopyridinium (2, monoclinic, space group P21/c, Z = 4), 2-aminopyrimidinium (3, orthorhombic, Pbca, Z = 8), 2-aminothiazolium (4, orthorhombic, Pbcn, Z = 8), 2-amino-6-methylpyridinium (5, solvated with 0.5 H20, monoclinic, C2/c, Z = 8), 2-amino-1,3,4-thiadiazolium (6, triclinic, P1̄, Z = 2), or 2-amino-4,6-dimethylpyrimidinium (7, orthorhombic. Fdd2, Z = 16). The onium cations in question exhibit a trifunctional hydrogen-bond donor sequence H − N (H*)-C (sp2) − N − H , which is complementary to an O − S (sp3)−N fragment of the anion and simultaneously expected to form a third hydrogen bond via the exocyclic N − H* donor. Consequently, all the crystal packings contain cation-anion pairs assembled by an N − H ∙∙∙ N and an N −H ∙∙∙ O hydrogen bond, these substructures being mutually associated through an N − H* ∙∙∙ O bond. For the robust eight-membered ring synthon within the ion pairs [graph set N2 = R22(8), antidromic], two supramolecular isomers were observed: In 2 and 3, N − H ∙∙∙ N originates from the ring NH donor and N − H ∙∙∙ O from the exocyclic amino group, whereas in 4-7 these connectivities are reversed. The third hydrogen bond, N − H*∙∙∙ O , leads either to chains of ion pairs (generated by a 21 transformation in 2-4 or by a glide plane in 5) or to cyclic dimers of ion pairs (Ci symmetric in 6, C2-symmetric in 7). The overall variety of motifs observed in a small number of structures reflects the limits imposed on the prediction of hydrogen bonding patterns. Owing to the excess of potential acceptors over traditional hydrogen-bond donors, several of the structures display prominent non-classical secondary bonding. Thus, the cyclodimeric units of 6 are associated into strands through short antiparallel O ∙∙∙ S(cation) interactions. In the hemihydrate 5, two independent C-H(cation) ∙∙∙ O bonds generate a second antidromic R22(8) pattern, leading to sheets composed of N − H ∙∙∙ N/O connected catemers; the water molecules are alternately sandwiched between and O - H ∙∙∙ O bonded to the sheets to form bilayers, which are cross-linked by a third C − H (cation ) ∙∙∙ O contact. The roof-shaped cyclodimers occurring in 7 occupy the polar C2 axes parallel to z and build up hollow Car− H ∙∙∙ O bonded tetrahedral lattices; in order to fill their large empty cavities, five translationally equivalent lattices mutually interpenetrate.

scholarly journals Crystal structures of 2-aminopyridine citric acid salts: C5H7N2 +·C6H7O7 − and 3C5H7N2 +·C6H5O7 3−

2018 ◽  
Vol 74 (8) ◽  
pp. 1111-1116 ◽  
Author(s):  
Shet M. Prakash ◽  
S. Naveen ◽  
N. K. Lokanath ◽  
P. A. Suchetan ◽  
Ismail Warad
Keyword(s):  
Hydrogen Bond ◽  
Citric Acid ◽  
Hydrogen Bonds ◽  
Crystal Structures ◽  
Crystal Engineering ◽  
Molecular Conformation ◽  
Crystal Packing ◽  
Three Dimensional ◽  
Dimensional Structure ◽  
Almost All

2-Aminopyridine and citric acid mixed in 1:1 and 3:1 ratios in ethanol yielded crystals of two 2-aminopyridinium citrate salts, viz. C5H7N2 +·C6H7O7 − (I) (systematic name: 2-aminopyridin-1-ium 3-carboxy-2-carboxymethyl-2-hydroxypropanoate), and 3C5H7N2 +·C6H5O7 3− (II) [systematic name: tris(2-aminopyridin-1-ium) 2-hydroxypropane-1,2,3-tricarboxylate]. The supramolecular synthons present are analysed and their effect upon the crystal packing is presented in the context of crystal engineering. Salt I is formed by the protonation of the pyridine N atom and deprotonation of the central carboxylic group of citric acid, while in II all three carboxylic groups of the acid are deprotonated and the charges are compensated for by three 2-aminopyridinium cations. In both structures, a complex supramolecular three-dimensional architecture is formed. In I, the supramolecular aggregation results from Namino—H...Oacid, Oacid...H—Oacid, Oalcohol—H...Oacid, Namino—H...Oalcohol, Npy—H...Oalcohol and Car—H...Oacid interactions. The molecular conformation of the citrate ion (CA3−) in II is stabilized by an intramolecular Oalcohol—H...Oacid hydrogen bond that encloses an S(6) ring motif. The complex three-dimensional structure of II features Namino—H...Oacid, Npy—H...Oacid and several Car—H...Oacid hydrogen bonds. In the crystal of I, the common charge-assisted 2-aminopyridinium–carboxylate heterosynthon exhibited in many 2-aminopyridinium carboxylates is not observed, instead chains of N—H...O hydrogen bonds and hetero O—H...O dimers are formed. In the crystal of II, the 2-aminopyridinium–carboxylate heterosynthon is sustained, while hetero O—H...O dimers are not observed. The crystal structures of both salts display a variety of hydrogen bonds as almost all of the hydrogen-bond donors and acceptors present are involved in hydrogen bonding.

Sulfur as hydrogen-bond acceptor in cocrystals of 2-thio-modified thymine

2018 ◽  
Vol 74 (1) ◽  
pp. 21-30 ◽  
Author(s):  
Wilhelm Maximilian Hützler ◽  
Michael Bolte
Keyword(s):  
Hydrogen Bond ◽  
Hydrogen Bonding ◽  
Crystal Engineering ◽  
Rational Design ◽  
Three Dimensional ◽  
Good Reliability ◽  
Hydrogen Bond Acceptor ◽  
Hydrogen Bonding Interactions ◽  
Hydrogen Bonding Site ◽  
Hydrogen Bonded

Doubly and triply hydrogen-bonded supramolecular synthons are of particular interest for the rational design of crystal and cocrystal structures in crystal engineering since they show a high robustness due to their high stability and good reliability. The compound 5-methyl-2-thiouracil (2-thiothymine) contains an ADA hydrogen-bonding site (A = acceptor and D = donor) if the S atom is considered as an acceptor. We report herein the results of cocrystallization experiments with the coformers 2,4-diaminopyrimidine, 2,4-diamino-6-phenyl-1,3,5-triazine, 6-amino-3H-isocytosine and melamine, which contain complementary DAD hydrogen-bonding sites and, therefore, should be capable of forming a mixed ADA–DAD N—H...S/N—H...N/N—H...O synthon (denoted synthon 3s N·S;N·N;N·O), consisting of three different hydrogen bonds with 5-methyl-2-thiouracil. The experiments yielded one cocrystal and five solvated cocrystals, namely 5-methyl-2-thiouracil–2,4-diaminopyrimidine (1/2), C5H6N2OS·2C4H6N4, (I), 5-methyl-2-thiouracil–2,4-diaminopyrimidine–N,N-dimethylformamide (2/2/1), 2C5H6N2OS·2C4H6N4·C3H7NO, (II), 5-methyl-2-thiouracil–2,4-diamino-6-phenyl-1,3,5-triazine–N,N-dimethylformamide (2/2/1), 2C5H6N2OS·2C9H9N5·C3H7NO, (III), 5-methyl-2-thiouracil–6-amino-3H-isocytosine–N,N-dimethylformamide (2/2/1), (IV), 2C5H6N2OS·2C4H6N4O·C3H7NO, (IV), 5-methyl-2-thiouracil–6-amino-3H-isocytosine–N,N-dimethylacetamide (2/2/1), 2C5H6N2OS·2C4H6N4O·C4H9NO, (V), and 5-methyl-2-thiouracil–melamine (3/2), 3C5H6N2OS·2C3H6N6, (VI). Synthon 3s N·S;N·N;N·O was formed in three structures in which two-dimensional hydrogen-bonded networks are observed, while doubly hydrogen-bonded interactions were formed instead in the remaining three cocrystals whereby three-dimensional networks are preferred. As desired, the S atoms are involved in hydrogen-bonding interactions in all six structures, thus illustrating the ability of sulfur to act as a hydrogen-bond acceptor and, therefore, its value for application in crystal engineering.

Crystal engineering of two-dimensional polar layer structures: hydrogen bond networks in some N-meta-phenylpyrimidinones

2003 ◽  
Vol 27 (3) ◽  
pp. 568-576 ◽  
Author(s):  
Sumod George ◽  
Ashwini Nangia ◽  
Muriel Bagieu-Beucher ◽  
René Masse ◽  
Jean-François Nicoud
Keyword(s):  
Hydrogen Bond ◽  
Crystal Engineering ◽  
Two Dimensional ◽  
Layer Structures ◽  
Hydrogen Bond Networks

Symmetry constraints, molecular recognition and crystal engineering. Comparative structural studies of urea–butanedioic and urea–E-butanedioic acid (2:1) cocrystals

1996 ◽  
Vol 52 (6) ◽  
pp. 1048-1056 ◽  
Author(s):  
V. Videnova-Adrabińska
Keyword(s):  
Hydrogen Bond ◽  
Crystal Engineering ◽  
Three Dimensional ◽  
Structural Studies ◽  
Hydrogen Bond Interaction ◽  
Space Group ◽  
One Dimensional ◽  
Hydrogen Bond Interactions ◽  
Symmetry Constraints ◽  
Butanedioic Acid

The crystal structures of two urea–dicarboxylic acid (2:1) cocrystals have been determined. Urea–butanedioic acid forms monoclinic crystals, space group P21/c (No. 14), with a = 5.637 (4), b = 8.243 (3), c = 12.258 (3) Å, β = 96.80 (5)°, V = 565.6 (8) Å3, Z = 2. Urea–E-butenedioic acid also forms monoclinic crystals, space group P21/c (No. 14), with a = 5.540 (1), b = 8.227 (1), c = 12.426 (3) Å, β = 97.22 (3)°, V = 561.9 (2) Å3, Z = 2. The geometry and the conformation of both molecular aggregates and the three-dimensional networks formed are very similar. The two strongest hydrogen-bond interactions are constrained in the formation of the heteroaggregates, the third hydrogen-bond interaction is used to self-associate the heteroaggregates in one-dimensional chains, whereas the next three weaker hydrogen bonds interconnect the chains into well organized three-dimensional networks.

Kinetic behaviour investigations and crystal structure of nitric acid dihydrate

2001 ◽  
Vol 57 (1) ◽  
pp. 27-35 ◽  
Author(s):  
N. Lebrun ◽  
F. Mahe ◽  
J. Lamiot ◽  
M. Foulon ◽  
J. C. Petit ◽  
...  
Keyword(s):  
Crystal Structure ◽  
Hydrogen Bond ◽  
Nitric Acid ◽  
Hydrogen Bonds ◽  
Single Crystal ◽  
Three Dimensional ◽  
Thermal Conditions ◽  
Kinetic Behaviour ◽  
Hydrogen Bond Networks ◽  
Atomic Distance

X-ray powder diffraction experiments are performed to prove the possible crystallization of nitric acid dihydrate (HNO3·2H2O, further denoted NAD) and to determine the best thermal conditions for growing a single crystal. It is shown that the kinetic behaviour of NAD strongly depends on the preliminary thermal treatment. One good single crystal obtained by an in situ adapted Bridgman method procedure enabled determination of the crystal structure. The intensities of diffracted lines with h odd are all very weak. The H atom of nitric acid is delocalized to one water molecule leading to an association of equimolar nitrate (NO3 −) and an H5O2 + ionic group. The asymmetric unit contains two such molecules. These two molecules are related by a pseudo a/2 translation (with a 0.3 Å mean atomic distance difference), except for one H atom of the water molecules (0.86 Å) because of their different orientations in the two molecules. The two molecules, linked by very strong hydrogen bonds, are arranged in layers. Two layers which are linked by weaker hydrogen bonds are approximately oriented along the c axis. The structure may be described by translations of this set of two layers along the c axis without hydrogen bonds leading to a two-dimensional hydrogen-bond network. The structures of the monohydrate (NAM) and trihydrate (NAT) are re-determined for comparisons. These structures may be described by one- and three-dimensional hydrogen-bond networks, respectively.

Crystal Engineering Using Bis- and Tris-phenols. Adducts with 1,4,8,11-Tetraazacyclotetradecane (Cyclam): Isolated Ladders in the Adduct with 4,4'-Thiodiphenol, Tethered Ladders in the Adduct with 4,4'-Sulfonyldiphenol and Two Interwoven Three-Dimensional Networks in the Adduct with 1,1,1-Tris(4-hydroxyphenyl)ethane

1998 ◽  
Vol 54 (2) ◽  
pp. 139-150 ◽  
Author(s):  
G. Ferguson ◽  
C. Glidewell ◽  
R. M. Gregson ◽  
P. R. Meehan
Keyword(s):  
Hydrogen Bond ◽  
Hydrogen Bonds ◽  
Crystal Engineering ◽  
Three Dimensional ◽  
Dimensional Array ◽  
Different Types ◽  
Molecular Components

The structure of 4,4′-thiodiphenol–1,4,8,11-tetraazacyclotetradecane (2/1), (C12H10O2S)2.C10H24N4 (1), monoclinic, P21/c, a = 11.1602 (12), b = 10.8084 (12), c = 14.001 (2) Å, β = 103.127 (10)°, with Z = 2, contains phenolate anions [HOC6H4SC6H4O]− and diprotonated cyclam cations [C10H26N4]2+: these cations have the centrosymmetric trans-III conformation and the two additional protons are contained within the N4 cavity of the macrocycle, held by three-centre hydrogen bonds. The phenolate anions form chains, held together by O—H...O hydrogen bonds, and pairs of these chains are cross-linked into ladders by the [cyclamH2]2+ cations by means of N—H...O hydrogen bonds. The structure of 4,4′-sulfonyldiphenol–1,4,8,11-tetraazacyclotetradecane (2/1), (C12H10O4S)2.C10H24N4 (2), triclinic, P1¯, a = 10.9345 (10), b = 11.0060 (10), c = 14.350 (2) Å, α = 79.532 (10), β = 86.739 (10), γ = 87.471 (10)°, with Z = 2, contains phenolate anions [HOC6H4SO2C6H4O]− and cyclam dications [C10H26N4]2+: the phenolate anions are linked into antiparallel chains, cross-linked by the cyclam cations. There are two distinct types of ladder in the structure running along (0, y, 0) and (1\over2, y, 1\over2), respectively, and these bundled ladders are tied together by C—H...O hydrogen bonds to form a continuous three-dimensional array. In 1,1,1-tris(4-hydroxyphenyl)ethane–1,4,8,11-tetraazacyclotetradecane–methanol (2/1/1), (C20H18O3)2.C10H24N4.CH4O (3), triclinic, P1¯, a = 8.2208 (11), b = 16.245 (2), c = 17.337 (2) Å, α = 81.694 (13), β = 89.656 (14), γ = 86.468 (12)°, with Z = 2, the structure contains centrosymmetric diprotonated cyclam cations of precisely the same type as found in (1), phenolate anions [(HOC6H4)2C(CH3)C6H4O]− and neutral methanol molecules. The molecular components are linked together by nine different types of hydrogen bond, five of O—H...O type and four of N—H...O type, to form chains running in the [001], [010] (two sets), [211] and [211¯] directions. The combination of these chain motifs generates two independent three-dimensional networks which are fully interwoven, but not bonded to one another.

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