Conselho Nacional de Desenvolvimento Científico e Tecnológico / In this work six aqua complexes of the transition metals Fe2+, Co2+, Ni2+, Cu2+, Zn2+ and Cd2+ containing the dithionate ion were synthesized and characterized through metathesis reactions in aqueous solution between BaS2O6·2H2O and the sulfate of the metal. Single crystals suitable for X-ray diffraction were obtained from the filtrates of the reactions and the structures of four complex salts, hexaaquairon(2+) dithionate hydrate, [Fe(H2O)6](S2O6)·H2O 1, hexaaquacobalt(2+) dithionate, [Co(H2O)6](S2O6) 2, hexaaquanickel(2+) dithionate, [Ni(H2O)6](S2O6) 3 and hexaaquazinc(2+) dithionate [Zn(H2O)6](S2O6) 5, and of two coordination polymers, catena-poli-[trans-tetraaquacopper-μ-dithionato-κ2O,O ] ([Cu(H2O)4(S2O6)]) 4 and catena-poli-[trans-tetraaquacadmium-μ-dithionato-κ2O,O ] ([Cd(H2O)4(S2O6)]) 6, all in triclinic system, space group P1 ‾ . The products were characterized by infrared spectroscopic, thermogravimetric, single crystal X-ray diffraction and powder Xray diffraction analyses. The Hirshfeld surface and the electron density were mapped with a cutoff 0.002 e− au−3 and basis 6-31G** for 1 to 5 and basis 3-21G* to 6, both basis in the Hartree-Fock method, revealing 79% and 75% of the contacts O···H, 19% and 11% of contacts H···H and 2% and 9% of the contacts O···O, for salts and complex coordination polymers, respectively. With the Hirshfeld surface, it was also possible to determine the volume of the molecules, determining the distorted cubic packing, according to the rules of Pauling. / Neste trabalho foram sintetizados e caracterizados seis aquacomplexos dos metais de transição Fe2+, Co2+, Ni2+, Cu2+, Zn2+ e Cd2+, contendo o íon ditionato, através de reações de metátese em solução aquosa entre BaS2O6·2H2O e o sulfato do metal. Monocristais apropriados para a difração de raios X foram obtidos a partir dos filtrados das reações, sendo as estruturas de quatro sais complexos, ditionato de hexaaquaferro(2+) hidrato, [Fe(H2O)6](S2O6)·H2O 1, ditionato de hexaaquacobalto(2+), [Co(H2O)6](S2O6) 2, ditionato de hexaaquaníquel(2+), [Ni(H2O)6](S2O6) 3 e ditionato de hexaaquazinco(2+), [Zn(H2O)6](S2O6) 5 e de dois polímeros de coordenação, catena-poli-[trans-tetraaquacobre-μ-ditionato-κ2O,O ] ([Cu(H2O)4(S2O6)]) 4 e catena-poli-[trans-tetraaquacádmio-μ-ditionato-κ2O,O ] ([Cd(H2O)4(S2O6)]) 6, todos resolvidos em sistema triclínico, grupo espacial P1 ‾ . Os produtos foram caracterizados por espectroscopia de infravermelho, análise termogravimétrica, difração de raios X de monocristal e difração de raios X em pó. A superfície de Hirshfeld e a densidade eletrônica foram mapeadas com ponto de corte 0,002 e− au−3 e bases 6-31G** para 1 a 5 e bases 3-21G* para 6, ambas as bases em nível Hartree-Fock, revelando 79% e 75% de contatos O···H, 19% e 11% de contatos H···H e 2% e 9% de contatos O···O, para os sais complexos e polímeros de coordenação, respectivamente. Com a superfície de Hirshfeld também foi possível determinar o volume das moléculas, determinando o empacotamento cúbico distorcido, segundo as regras de Pauling.

Submitted by Renata Lopes (renatasil82@gmail.com) on 2017-05-25T14:19:15Z No. of bitstreams: 1 marianadasilvacunha.pdf: 6235170 bytes, checksum: e49cfdcb2f78bafd1146dd684a809c87 (MD5) / Approved for entry into archive by Adriana Oliveira (adriana.oliveira@ufjf.edu.br) on 2017-05-25T14:48:17Z (GMT) No. of bitstreams: 1 marianadasilvacunha.pdf: 6235170 bytes, checksum: e49cfdcb2f78bafd1146dd684a809c87 (MD5) / Made available in DSpace on 2017-05-25T14:48:17Z (GMT). No. of bitstreams: 1 marianadasilvacunha.pdf: 6235170 bytes, checksum: e49cfdcb2f78bafd1146dd684a809c87 (MD5) Previous issue date: 2017-02-21 / Neste trabalho foi investigada a influência da modificação dos ligantes Hidrogeno psulfobenzoato de potássio (PSB), Ácido 1,2,4,5-benzenotetracarboxílico (BTC) e Ácido 1,5-naftalenodissulfônico tetrahidratado (1,5NDS) nas interações com a molécula de Isoniazida (INH) em três novos compostos, PSB-INH, BTC-INH e 1,5NDS-INH, e também foi realizado um estudo sobre o composto 1,5NDS-INO no qual o ligante Isoniazida sofreu uma termodecomposição, levando à formação do Ácido isonicotínico (INO). Foi realizado um estudo das ligações de hidrogênio formadas entre os ligantes através da análise de superfície de Hirshfeld e gráficos de impressão digital. Estas análises são extremamente sensíveis ao ambiente químico da molécula e são únicas para cada molécula e, dessa forma, permitem a identificação das diferenças entre os empacotamentos cristalinos no estado sólido. Foi observado que, embora a conformação da molécula de Isoniazida seja praticamente idêntica nos compostos PSB-INH, BTC-INH e 1,5NDS-INH e as principais ligações de hidrogênio presentes envolvem interações do tipo N – H···O e O – H···N, os gráficos de impressão digital são diferentes e exibem a influência da modificação dos ligantes. Nos gráficos de impressão digital obtidos as contribuições mais importantes das interações estão relacionadas aos contatos O···H e N···H, que possuem valores de 31,3% e 6,0% para o composto PSB-INH, 49,9% e 6,9% para o composto BTC-INH e 44,8% e 5,0% para o composto 1,5NDS-INH. No composto 1,5NDS-INO as principais ligações de hidrogênio são do tipo O – H···O e O – H···N e a contribuição mais importante para o gráfico de impressão digital está relacionada ao contato O···H, que contribui com 41,9% para a superfície e também ao contato H···H, que contribui com 30,5%. Este trabalho demonstrou como as análises de superfície de Hirshfeld e dos gráficos de impressão digital conseguem identificar diferenças entre as moléculas no estado sólido e permitiu a análise das interações intermoleculares formadas nos diferentes compostos, comprovando a importância dessas novas ferramentas para a análise estrutural. / In this work was investigated the influence of the modification of the ligands Hydrogen p-sulfobenzoate of potassium (PSB), 1,2,4,5-benzenetetracarboxylic acid (BTC) and 1,5-naphthalenedisulfonic acid tetrahydrate (1,5NDS) in interactions with the molecule of Isoniazid (INH) in three new compounds, PSB-INH, BTC-INH and 1,5NDS-INH, and also a study on the compound 1,5NDS-INO in which the Isoniazid ligand underwent a thermodecomposition, leading to the formation of isonicotinic acid (INO). A study of the hydrogen bonds formed between the ligands was carried out through Hirshfeld surface analysis and fingerprint plots. These analysis are extremely sensitive to the chemical environment of the molecule and are unique to each molecule and thus allow identification of the differences between the crystalline packages in the solid state. It was observed that, although the conformation of the Isoniazide molecule is practically identical in the compounds PSB-INH, BTC-INH and 1,5NDS-INH and the main hydrogen bonds present involve N – H ··· O and O – H ··· N, the fingerprint plots are different and exhibit the influence of the modification of the ligands. In the fingerprint plots obtained, the most important contributions of the interactions are related to the contacts O···H and N···H, which have values of 31.3% and 6.0% for the compound PSB-INH, 49.9% and 6.9% for compound BTC-INH and 44.8% and 5.0% for the compound 1.5NDS-INH. In the compound 1,5NDS-INO the main hydrogen bonds are of the O – H ··· O and O – H ··· N type and the most important contribution to the fingerprint plot is related to the contact O···H, which contributes with 41.9% to the surface and also to the H···H contact, which contributes with 30.5%. This work demonstrated how Hirshfeld surface analysis and fingerprint plots can identify differences between molecules in the solid state and allowed the analysis of the intermolecular interactions formed in the different compounds, proving the importance of these new tools for structural analysis.

Le fullerène C60 est une molécule sphérique composée exclusivement d'atomes de carbone. Ce composé possède une surface aromatique convexe homogène et peut s'associer, entre autres, avec des molécules possédant des surfaces aromatiques par des interactions non-covalentes. Le triptycène est une molécule en forme de "Y" qui possède des surfaces aromatiques convexes. Cette molécule possède l'habileté de s'associer avec le C60 par des interactions de type π qui sont amplifiées par la complémentarité des surfaces concaves et convexes impliquées dans les arrangements cristallins. Nous avons synthétisé des dérivés triptycényles portant des groupements fonctionnels aux extrémités des bras de ce noyau de façon à étendre les cavités disponibles pour interagir avec le C60. En effet, nous avons découvert que les atomes de chlore, de brome et d'iode ainsi que les groupements méthyle permettent d'étendre les surfaces disponibles pour interagir avec les fullerènes C60 et C70. Nous avons étudié les associations entre les dérivés triptycényles et les fullerènes par l'analyse des structures cristallographiques résolues par diffraction des rayons-X. De plus, nous avons étudié les associations entre les molécules considérées par l'analyse des surfaces d'Hirshfeld entourant les fullerènes. Découlant de ces études, l'effet d'amplification des atomes de chlore, de brome et d'iode ainsi que les groupements méthyle a été employé pour identifier de nouveaux solvants aptes à solubiliser efficacement le C60. / The fullerene C60 is a spherical molecule made up exclusively of carbon atoms. The surface of this compound is homogenous, convex and aromatic. As a result, C60 can associate with other aromatic molecules via non-covalent π-stacking interactions to form supramolecular assemblies. The triptycene is a "Y"-shaped molecule with concave aromatic surfaces. This molecule can thereby interact with C60 and form crystals through amplified π-stacking interactions resulting from the concave/convex complementary arrangement. In the course of our work, we made a series of new triptycene derivatives with functional groups added to the periphery of the aromatic core. In particular, we found that methyl groups, as well as atoms of chlorine, bromine and iodine, can be placed on the extremities of the triptycene core to expand the concave cavities available to interact with C60 and C70. We studied the non-covalent interactions between fullerenes and triptycene derivatives using X-ray crystallography. Furthermore, Hirshfeld surfaces have been used to map the interaction patterns around fullerene surfaces. In addition, we have found that aromatic solvents that are properly functionalized with halogen atoms and methyl groups have a special ability to solubilize C60.

Le fullerène C60 est une molécule sphérique composée exclusivement d'atomes de carbone. Ce composé possède une surface aromatique convexe homogène et peut s'associer, entre autres, avec des molécules possédant des surfaces aromatiques par des interactions non-covalentes. Le triptycène est une molécule en forme de "Y" qui possède des surfaces aromatiques convexes. Cette molécule possède l'habileté de s'associer avec le C60 par des interactions de type π qui sont amplifiées par la complémentarité des surfaces concaves et convexes impliquées dans les arrangements cristallins. Nous avons synthétisé des dérivés triptycényles portant des groupements fonctionnels aux extrémités des bras de ce noyau de façon à étendre les cavités disponibles pour interagir avec le C60. En effet, nous avons découvert que les atomes de chlore, de brome et d'iode ainsi que les groupements méthyle permettent d'étendre les surfaces disponibles pour interagir avec les fullerènes C60 et C70. Nous avons étudié les associations entre les dérivés triptycényles et les fullerènes par l'analyse des structures cristallographiques résolues par diffraction des rayons-X. De plus, nous avons étudié les associations entre les molécules considérées par l'analyse des surfaces d'Hirshfeld entourant les fullerènes. Découlant de ces études, l'effet d'amplification des atomes de chlore, de brome et d'iode ainsi que les groupements méthyle a été employé pour identifier de nouveaux solvants aptes à solubiliser efficacement le C60. / The fullerene C60 is a spherical molecule made up exclusively of carbon atoms. The surface of this compound is homogenous, convex and aromatic. As a result, C60 can associate with other aromatic molecules via non-covalent π-stacking interactions to form supramolecular assemblies. The triptycene is a "Y"-shaped molecule with concave aromatic surfaces. This molecule can thereby interact with C60 and form crystals through amplified π-stacking interactions resulting from the concave/convex complementary arrangement. In the course of our work, we made a series of new triptycene derivatives with functional groups added to the periphery of the aromatic core. In particular, we found that methyl groups, as well as atoms of chlorine, bromine and iodine, can be placed on the extremities of the triptycene core to expand the concave cavities available to interact with C60 and C70. We studied the non-covalent interactions between fullerenes and triptycene derivatives using X-ray crystallography. Furthermore, Hirshfeld surfaces have been used to map the interaction patterns around fullerene surfaces. In addition, we have found that aromatic solvents that are properly functionalized with halogen atoms and methyl groups have a special ability to solubilize C60.

The title compound, C20H18O3, crystallizes in the space group P21/c with one mol­ecule in the asymmetric unit of the cell. The fluorene skeleton is nearly planar and the crystal structure is composed of mol­ecular layers extending parallel to the (302) plane. Within a layer, one formyl oxygen atom participates in the formation of a Carene—H...O bond, which is responsible for the formation of an inversion symmetric supra­molecular motif of graph set R22(10). A second oxygen atom is involved in an intra­molecular Carene—H...O hydrogen bond and is further connected with a formyl hydrogen atom of an adjacent mol­ecule. A Hirshfeld surface analysis indicated that the most important contributions to the overall surface are from H...H (46.9%), O...H (27.9%) and C...H (17.8%) inter­actions.

Conselho Nacional de Desenvolvimento Científico e Tecnológico / This study shows the influence of the molecular topology of the crystal of a series of 14 pyrazolo[1,5-a]pyrimidines. The topological data were obtained from X-ray diffraction data and energy stabilization were determined by thermal analysis and chemical computations. Topological analysis carried out was Molecular Coordination Number (NCM) using the Voronoi-Dirichlet polyhedra and Hirshfeld surface. The NCM found for the majority of compounds was 14. Furthermore, it was determined contact area and the solid angle between molecules of the first coordination sphere of the cluster. Several correlations between data were performed, where it is possible highlight the correlation between the area of contact of the cluster molecules and the interaction energy and the solid angle and interaction energy were established. These correlations showed that there is a proportionality between the data, showing that the greater the contact area, the greater the interaction energy for a series of pyrazolo[1,5-a]pyrimidine studied in this thesis. As the contact area, solid angle also presents proportionality with the calculated interaction energy. Among the atom-atom contacts present on the surface of the test compounds was observed that contacts C∙∙∙H and C∙∙∙C are key to stabilize the crystals. This result corroborates the hypothesis that the contact surface between the molecules would be the driving force for the crystalline arrangement. / Este trabalho apresenta o estudo da influência da topologia molecular na organização cristalina de uma série de 14 pirazolo[1,5-a]pirimidinas. Os dados topológicos foram obtidos por difratometria de raios-X e os dados de energia de estabilização foram determinados por análises térmicas e cálculos computacionais. Dentre as análises topológicas realizadas destaca-se a determinação do Número de Coordenação Molecular (NCM) usando o Poliedro de Voronoi-Dirichlet e a Superfície de Hirshfeld. O NMC encontrado para a maioria dos compostos foi de 14. Além disso, foi determinada a área de contato, bem como o ângulo sólido entre as moléculas da primeira esfera de coordenação do cluster. Estabeleceu-se uma serie de correlações entre os dados obtidos, entre elas, destaca-se a correlação entre esta área de contato entre as moléculas do cluster e a energia de interação, bem como a correlação ângulo sólido e energia de interação. Ambas correlações mostraram que há uma proporcionalidade entre os dados, mostrando que quanto maior a área de contato, maior a energia de interação para a série de pirazolo[1,5-a]pirimidinas estudadas nesta dissertação. Assim como a área de contato, o ângulo sólido também apresenta uma proporcionalidade com a energia de interação calculada. Dentre os contatos átomo-átomo presentes na superfície dos compostos em estudo, observou-se que os contatos C∙∙∙H e C∙∙∙C são os principais para a estabilização dos cristais estudados. Este resultado corrobora com a hipótese de que a superfície de contato entre as moléculas seria a força motriz para o arranjo cristalino.