Rage Against Conformity: Ruthenium(ɪɪ) Bisterpyridine Complexes Respond to Crystal Engineering Instructions with Whelming Results

2017 ◽  
Vol 70 (5) ◽  
pp. 529 ◽  
Author(s):  
Hasti Iranmanesh ◽  
Kasun S. A. Arachchige ◽  
William A. Donald ◽  
Niamh Kyriacou ◽  
Chao Shen ◽  
...  
Keyword(s):  
Hydrogen Bond ◽  
Hydrogen Bonding ◽  
Solid State ◽  
Single Crystal ◽  
Crystal Engineering ◽  
Intermolecular Hydrogen Bonding ◽  
Hydrogen Bond Donor ◽  
One Dimensional ◽  
X Ray ◽  
Hydrogen Bonded

Four heteroleptic ruthenium(ii) complexes of 4′-functionalised 2,2′:6′,2′′-terpyridine are reported, along with their solid-state single-crystal X-ray structures. The complexes feature complementary hydrogen-bond donor (phenol) and acceptor (pyridyl) groups designed to assemble into one-dimensional polymers. In one example, the system obeys the programmed instructions to form a one-dimensional, self-complementary hydrogen-bonded polymer. In one other example, a water-bridged hydrogen-bonded polymer is formed. In the remaining two structures, aryl–aryl interactions dominate the intermolecular interactions, and outweigh the contribution of intermolecular hydrogen bonding.

The structures of several modified isoindolines, the building blocks of phthalocyanines

2013 ◽  
Vol 17 (08n09) ◽  
pp. 712-721 ◽  
Author(s):  
James T. Engle ◽  
Ashley N. Allison ◽  
Joshua M. Standard ◽  
Ingrid-Suzy Tamgho ◽  
Christopher J. Ziegler
Keyword(s):  
Hydrogen Bonding ◽  
Solid State ◽  
Low Temperature ◽  
Single Crystal ◽  
Building Blocks ◽  
Double Bonds ◽  
Crystal Forms ◽  
X Ray ◽  
Hydrogen Bonded

This report presents the single crystal X-ray structures of several substituted isoindolines that have been frequently used as starting materials for phthalocyanines, phthalocyanine analogs and related chelates. The structures of 1,3-diiminoisoindoline (1), 1,3-bis(hydroxyimino)isoindoline (2), 1,4-diaminophthalazine (3), 1,1,3-trichloroisoindoline (4) and 3-imino-1-oxoisoindoline (5) are reported; compounds 2 and 3 are synthesized from diiminoisoindoline (1) and 4 and 5 are produced from phthalimide. All five compounds are planar macrocycles, and localization of double bonds can be readily determined. We elucidated one of the known structures of 1 at low temperature, and observed two additional new structures of 1. For the crystal forms of 1 and compounds 2, 3, and 5, hydrogen bonding in the solid state was observed. Compounds 1, 2 and 3 form extended hydrogen bonded arrays in the solid state, whereas 5 forms discrete hydrogen bonded dimers.

scholarly journals Main Chain Noncentrosymmetric Hydrogen Bonded Macromolecules Incorporating Aniline, Alkanol, and Alkanoic Acid Hydrogen Bond Donors

2014 ◽  
Vol 2014 ◽  
pp. 1-7 ◽  
Author(s):  
Jeremy R. Wolf
Keyword(s):  
Hydrogen Bond ◽  
Hydrogen Bonding ◽  
Main Chain ◽  
Attenuated Total Reflectance ◽  
Intermolecular Hydrogen Bonding ◽  
Hydrogen Bond Donor ◽  
Alkanoic Acid ◽  
Total Reflectance ◽  
Hydrogen Bonded

The syntheses and characterization of three noncentrosymmetric main chain hydrogen bonded macromolecules which incorporate aniline, alkanoic acid, and alkanol hydrogen bond donor units are reported. These macromolecules participate in weak intermolecular hydrogen bonding as demonstrated using attenuated total reflectance (ATR) FTIR. The phase transitions of these macromolecules depend on the identity of the hydrogen bond donor.

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 1-[N-Methyl-N-(Phenyl)amino]-3- (4-Methylphenyl)Thiourea

Molbank ◽  
10.3390/m1052 ◽  
2019 ◽  
Vol 2019 (1) ◽  
pp. M1052 ◽  
Author(s):  
Chien Yeo ◽  
Edward Tiekink
Keyword(s):  
Hydrogen Bond ◽  
Solid State ◽  
Hydrogen Bonds ◽  
Single Crystal ◽  
Elemental Analysis ◽  
Title Compound ◽  
Molecular Conformation ◽  
Phenyl Hydrazine ◽  
X Ray ◽  
X Ray Crystallography

The title compound, 1-[N-methyl-N-(phenyl)amino]-3-(4-methylphenyl)thiourea (1), was synthesized by the reaction of 1-methyl-1-phenyl hydrazine and 4-tolyl isothiocyanate, and was characterized by spectroscopy (1H and 13C{1H} NMR, IR, and UV), elemental analysis as well as by single crystal X-ray crystallography. In the solid state, the molecule exists as the thioamide tautomer and features an anti-disposition of the thioamide–N–H atoms; an intramolecular N–H⋯N hydrogen bond is noted. The molecular conformation resembles that of the letter L. In the molecular packing, thioamide-N1–H⋯S1(thione) hydrogen bonds lead to centrosymmetric eight-membered {⋯HNCS}2 synthons. The dimers are assembled into a supramolecular layer in the bc-plane by phenyl- and methyl-C–H⋯π(phenyl) interactions.

Synthese, Struktur und thermisches Verhalten von Thiophosphorsäuretriamid SP(NH2)3 [1] / Synthesis, Structure, and Thermal Behaviour of Phosphorothionic Triamide SP(ΝΗ2)3 [1]

1989 ◽  
Vol 44 (8) ◽  
pp. 942-945 ◽  
Author(s):  
Wolfgang Schnick
Keyword(s):  
Crystal Structure ◽  
Hydrogen Bonding ◽  
Thermal Properties ◽  
Single Crystal ◽  
Melting Temperature ◽  
Intermolecular Hydrogen Bonding ◽  
X Ray ◽  
Hydrogen Bonding Interactions ◽  
Ray Methods ◽  
Single Bonds

Phosphorothionic triamide SP(NH2)3 is obtained by slow addition of SPCl3 dissolved in dry CH2Cl2 to a satured solution of NH3 in CH2Cl2 at —50°C. Ammonium chloride is removed from the resulting precipitate by treatment with HNEt2 followed by extraction with CH2Cl2. Coarse crystalline SP(NH2)3 is obtained after recrystallization from dry methanol. The crystal structure of SP(NH2)3 has been determined by single crystal X-ray methods (Pbca; a = 922.3(1), b = 953.8(1), c = 1058.4(2) pm, Z = 8). In the crystals the molecules show non-crystallographic point symmetry C8. The P—S bond (195.4(1) pm) is slightly longer than in SPCl3. From P—N bond lengths of about 166 pm a significant electrostatic strengthening of the P—N single bonds is assumed. Weak intermolecular hydrogen bonding interactions (N —H · · · N ≥ 329.5 pm; N — H · · · S ≥ 348.3 pm) are observed.Investigation of thermal properties shows a melting temperature of 115°C for SP(NH2)3. According to combined DTA/TG and MS investigations above this temperature the compound decomposes by evolution of H2S and NH3 to yield amorphous phosphorus(V)nitride.

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.

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.

Molecular tectonics — Use of urethanes and ureas derived from tetraphenylmethane and tetraphenylsilane to build porous chiral hydrogen-bonded networks

2004 ◽  
Vol 82 (2) ◽  
pp. 386-398 ◽  
Author(s):  
Dominic Laliberté ◽  
Thierry Maris ◽  
James D Wuest
Keyword(s):  
Hydrogen Bonding ◽  
Asymmetric Catalysis ◽  
Crystal Engineering ◽  
Three Dimensional ◽  
Enantiomerically Pure ◽  
X Ray ◽  
Molecular Tectonics ◽  
X Ray Crystallography ◽  
Open Networks ◽  
Hydrogen Bonded

Tetraphenylmethane, tetraphenylsilane, and simple derivatives with substituents that do not engage in hydrogen bonding typically crystallize as close-packed structures with essentially no space available for the inclusion of guests. In contrast, derivatives with hydrogen-bonding groups are known to favor the formation of open networks that include significant amounts of guests. To explore this phenomenon, we synthesized six new derivatives 5a–5e and 6a of tetraphenylmethane and tetraphenylsilane with urethane and urea groups at the para positions, crystallized the compounds, and determined their structures by X-ray crystallography. As expected, all six compounds crystallize to form porous three-dimensional hydrogen-bonded networks. In the case of tetraurea 5e, 66% of the volume of the crystals is accessible to guests, and guests can be exchanged in single crystals without loss of crystallinity. Of special note are: (i) the use of tetrakis(4-isocyanatophenyl)methane (1f) as a precursor for making enantiomerically pure tetraurethanes and tetraureas, including compounds 5b, 5c; and (ii) their subsequent crystallization to give porous chiral hydrogen-bonded networks. Such materials promise to include chiral guests enantioselectively and to be useful in the separation of racemates, asymmetric catalysis, and other applications.Key words: crystal engineering, molecular tectonics, hydrogen bonding, networks, porosity, urethanes, ureas, tetraphenylmethane, tetraphenylsilane.

Eindimensionale Kupfer(II)-Koordinationspolymere: Kristall-Engineering durch variable Verknüpfungsmuster [1] / One Dimensional Copper(II) Coordination Polymers: Crystal Engineering through Variable Types of Linkage [1]

1997 ◽  
Vol 52 (1) ◽  
pp. 125-134 ◽  
Author(s):  
Rolf W. Saalfrank ◽  
Roland Harbig ◽  
Oliver Struck ◽  
Frank Hampel ◽  
Eva Maria Peters ◽  
...  
Keyword(s):  
Coordination Polymer ◽  
Single Crystal ◽  
Coordination Polymers ◽  
Crystal Engineering ◽  
Coordination Compounds ◽  
Acetate Solution ◽  
X Ray Diffraction ◽  
One Dimensional ◽  
X Ray ◽  
1D Coordination Polymer

Reaction of a methanolic copper(II) acetate solution with tetrazolyl enol derivatives 2a or 2b leads to the formation of the corresponding lD-coordination polymer 1∞[CuL2] 3a and pseudo 1D-coordination polymer [CuL2]2 3b, respectively. On the contrary, reaction of 2c with methanolic copper(II) acetate solution yields OH-bridged 1D-coordination polymer 1∞[CuL2(MeOH)2 3c. Single-crystal X-ray diffraction of the supramolecular species 3 established unequivocally the structures of the stairlike coordination compounds. Reaction of a methanolic copper(II) acetate solution with amidotetrazole derivative 6 leads to the formation of the lD-coordination polymer 1∞ [CuL2] 7. The structure of 7 has been established by X-ray structure analysis

Single Crystal Formation by Solid-State Reaction Between p-Benzoquinone and 2,4,5-Trichlorophenol

2002 ◽  
Vol 55 (4) ◽  
pp. 271 ◽  
Author(s):  
N. B. Singh ◽  
A. Pathak ◽  
R. Fröhlich
Keyword(s):  
Hydrogen Bond ◽  
Solid State ◽  
Single Crystal ◽  
Single Crystals ◽  
Solid State Reaction ◽  
Carbonyl Oxygen ◽  
Crystal Formation ◽  
X Ray Diffraction ◽  
X Ray

Vapours of p-benzoquinone (BQ) have been found to react with solid 2,4,5-trichlorophenol (TCP). The reaction product (BQ-TCP) separated in the form of monoclinic single crystals, the structure of which was determined by X-ray diffraction to reveal that the two molecules are linked by a single hydrogen bond between the carbonyl oxygen of BQ and the phenolic hydrogen of TCP.

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