Synthesis, Characterization, Crystal Structures, Properties Studies Of Metal Complexes With Sulfanilamide Ligands

The researches on of metal sulfanilamide complexes have received much attention due to the fact that sulfanilamides were the effective chemotherapeutic agents to be employed for the prevention and cure of bacterial infections in humans.Although sulfamides present bacteriostatic activity related to the inhibition of the bacterial enzyme DHPS which catalysizes the incorporation of p-aminobenzoic acid into the precursor of folic acid, the pharmacological activity of these types of molecules is often enhanced by complexation with metal ions.Thus, rapid healing of skin disorders has been promoted by silver–sulfadiazine complex in human topical burn therapy, and zinc–sulfadiazine complex in the prevention of bacterial infection in burned animals, in which the effectiveness of burn treatment seems to depend not only on the presence of a metal ion [slow release of the Ag(I) or Zn(II)], but also crucially on the nature of the material to which the metal ion is bound in this dissert fifteen crystal structures have been obtained by hydrothermal synthesis of sulfanilamide with metal ions. Chapter One: The complex CoC₃₀H₃₄N₈O₆S₂ (1) is obtained by the reaction of sulfamethoxazole and Co(Ac)₂·4H₂O under the hydro(solv) thermal conditon. It belongs to triclinic crystal system, space group P-1, with cell parameters: a = 9.0045(13)A|°, b = 9.8632(14)A|°, c =10.4321(15)A|°, α=84.271(3)°, β=77.933(3)°, γ=86.125(3)°, V =900.5(2)(A|°)³, Z = 1, Dc =1.464Mg/m³. In complex 1, the geometry around the Co (II) ion can be described as a slightly compressed octahedron. Two pyridine N and two isoxazole N atoms are located in the equatorial plane and two oxygen atoms of two water molecules are placed in the apical positions. Two-dimensional network is formed via abundant intermolecular hydrogen bonds involving O-H…N ,O-H…O and N-H…O. The complex NiC₃₀H₃₄N₈O₆S₂ (2) is obtained by the reaction of sulfamethoxazole and Ni(Ac)₂·4H₂O under the hydro(solv) thermal conditon. The X-ray crystallographic analysia indicate that two complex 1 and 2 are isostructure. The complex Co(C14H11N4O2S)2(C5H5N)2 (3) is obtained by the reaction of sulfaquinoxaline and Co(Ac)2·4H2O under the hydro(solv) thermal conditon. It belongs to triclinic crystal system, space group P-1 ,with cell parameters: a =10.6910(6) ?, b =11.1039(5)?, c =18.1880(14)?, α=77.772(7)°, β=80.975(7)°, γ=63.957(5)°, V =1890.9(2)?3, Z =2, Dc =1.433Mg/m3. The center metal ion Co(II) adopts six-coordinated octahedral geometry , being coordinated to the sulfonamidic N and the heterocyclic N of two bidentate sulfadimidine ligands and generating two four-membered rings and two pyridine N atoms to complete the coordination sphere.Two-dimensional network is formed via abundant intermolecular hydrogen bonds involving O-H…N ,N-H…O and N-H…S. The complex Ni(C14H11N4O2S)2(C5H5N)2 (4) is obtained by the reaction of sulfaquinoxaline and Ni (Ac)2·4H2O under the hydro(solv) thermal conditon. It belongs to monoclinic crystal system, space group P21/c,with cell parameters: a =17.494(3)?, b =10.8595(14)?, c =20.125(3)?, β=106.464(5)°, V =3666.5(9)?3, Z =4, Dc =1.477 Mg/m3 . The center metal ion Ni(II) adopts six-coordinated octahedral geometry, being coordinated to the sulfonamidic N and the heterocyclic N of two bidentate sulfadimidine ligands generating two four-membered rings and two pyridine N atoms to complete the coordination sphere. One pyridine N and three sulfaquinoxaline N atoms are located in the equatorial plane and the other pyridine N and one sulfaquinoxaline N atoms are placed in the apical positions. Two-dimensional network is formed via abundant intermolecular hydrogen bonds involving N-H…N, N-H…O. Chapter Two: The binuclear Cu(I) complex Cu2C20H16N8O4S2Cl2 (5) is obtained by the reaction of sulfachloropyridazine and Cu(Ac)2 under the hydro(solv) thermal conditon. It belongs to Monoclinic crystal system, space group P21/c,with cell parameters: a =5.4877(7)?, b =20.191(3)?, c =11.2645(14)?,β=11.2645(14)°, V =1233.9(3)?3, Z =2, Dc =1.869Mg/m3. In complex 5, two copper(I) ions are linked by NCN and generate a eight-membered rings Cu2N4C2. Each copper center presents a nearly linear geometry.The molecules connect into two-dimensional network via abundant intermolecular hydrogen bonds involving N-H…O.The tetranuclear Cu(I) complex Cu2C22H22N8O4S2 (6) is obtained by the reaction of sulfamerizine and Cu(Ac)2 under the hydro(solv) thermal conditon. It belongs to monoclinic crystal system, space group P21/c,with cell parameters: a =21.251(6)?, b =12.331(3)?, c =12.331(3)?,β=98.118(5)°, V =2547.5(12)?3, Z =4, Dc =1.704Mg/m3. The complex 6 exists as a cage with Cu-Cu-O-S-N-Cu-Cu-O-S-N ten–membered ring in which Cu(I) atoms are bridged by NCN pertaining to the deprotonated sulfamerizine ligands.The molecules connect into two-dimensional network via abundant intermolecular hydrogen bonds involving N-H…S, N-H…O and O-H…S. The cleavage experiment involving of PBR322 DNA by complexes Cu2C20H16N8O4S2Cl2 (5) and Cu2C22H22N8O4S2 (6) were carried out. The results indicate that this two complexs are efficient cleavage agent for single strand of plasmid PBR322 DNA. Chapter Three: The complex Mn(C10H9N4O2S)2 (C10H8N2) (7) is obtained by the reaction of sulfadiazine, Mn(Ac2)·4H2O and 2,2-bipy under the hydro(solv)thermal conditon. It belongs to monoclinic crystal system, space group C2/c,with cell parameters: a =20.121(3)?, b =17.555(3)?, c =17.956(3)?,β=106.973(4)°, V =6066.4(17)?3, Z =8, Dc =1.554Mg/m3. The center metal ion Mn(II) adopts six-coordinated octahedral geometry, being coordinated to the sulfonamidic N and the heterocyclic N of two bidentate sulfadiazine ligands generating two four-membered rings and two 2,2-bipy N atoms generating a five-membered ring. The molecules connect into two-dimensional framework via abundant intermolecular hydrogen bonds involving N-H…O and N-H…N. Chapter Four: The complex(CoC22H26N8O6S2)n (8) is obtained by the reaction of sulfamerizine and Co(Ac)2·4H2O under the hydro(solv) thermal conditon. It belongs to monoclinic crystal system, space group I4(1)/a, with cell parameters: a =12.675(2)?, b =13.749(2)?, c =14.560(2)?, β=94.502(5)?, V =2529.4(7)?3, Z =4, Dc =1.632 Mg/m3. The center metal ion Co(II) adopts six-coordinated octahedral geometry and is surrounded by six N atoms from sulfamerizine. The polymeric cobalt(â…¡) complex exhibits a heavily distorted octahedral geometry, involving the sulfonamidic nitrogen andthe heterocyclic of two bidentate sulfamerizine ligands generating two four-membered rings., the two terminal amino of the other two sulfamerizine which is bonded to two adjacent cobalt(II).Two-dimentional infinite network of complex 8 is formed through sulfamerizine linking. The molecules connect to three-dimensional network via intermolecular hydrogen bonds involving N-H…O. The complex (ZnC33H36N9O7S2)n (9) is obtained by the reaction of sulfamerizine, Zn(Ac)2·4H2O and 4,4-bipy under the hydro(solv) thermal conditon. It belongs to monoclinic crystal system with space group P21/c , cell parameters:a =9.0027(3),b = 23.9229(8),c =18.7850(6),β=116.5590(10)°,Z = 4,V = 3618.8(2) ?3,Dc = 1.469 Mg/m3,The Zn(II) is five-coordinated and surrounded by two N atom from two 4,4-bipy, one N atom from sulfamerizine and two N atom of the other sulfamerizine chelating ligand generating a fourmembered ring , this ZnN5 coordination forms a distorted square-pyramidal geometry. The two sulfamerizine bound to the metal ion in two coordinated modes: the monodentate and bidentate. The complex is infinite one-dimesional chain formed by a repeating mononuclear structural unit bridged by 4,4-bipy . The complex [C25H36MnN8O7S2]n (10) is obtained by the reaction of sulfamethazine and Mn(Ac)2·4H2O under the hydro(solv) thermal conditon. It belongs to monoclinic crystal system, space group P2(1)/c, with cell parameters: a =15.7504(8)?, b =14.8680(8)?, c =13.1803(7)?, β=97.6750(10)?, V =3058.9(3)?3, Z =4, Dc =1.476Mg/m3. The center metal ion Mn(II) adopts six-coordinated octahedral geometry and is surrounded surrounded by five N atoms from sulfamethazine and one O atom. The polymeric Mn(II) complex exhibits a high distorted octahedral geometry, involving the sulfonamidic nitrogen and the heterocyclic of two bidentate sulfamethazine ligands generating two four-membered rings. One terminal amino group of the third sulfamerizine ligand which is bonded to two adjacent Mn (â…¡), and one O atom from a water molecule. One-dimentional infinite-chain of complex 10 is formed through sulfamethazine linking. The molecules connect into two-dimensional net work via intermolecular hydrogen bonds involving O-H…O. The complex (ZnC24H32N8O7S2 )n (11), (NiC25H32N8O6S2)n (12) is obtained bythe reaction of sulfamethazine, Zn(Ac)2·4H2O and Ni(Ac)2·4H2O under the hydro(solv) thermal conditon. The X-ray crystallographic analysis indicates that three complexes 10, 11 and 12 are isostructure . The complex (ZnClC19H16N6O2S)n (13) is obtained by the reaction of sulfaquinoxaline and ZnCl2 under the hydro(solv) thermal conditon. It belongs to triclinic crystal system with space group P-1,cell parameters: a =8.1711(12) ?, b = 8.6407(12) ?, c =14.775(2) ?, α=85.717(3)°, β=85.717(3)°, γ=85.717(3)°,Z = 2, V = 958.2(2) ?3, Dc = 1.661Mg/m3. The Zn(II) is five-coordinated by one Cl atom from ZnCl2, one N atom from pyridine, two N atom of the one sulfaquinoxaline chelating ligand generating a four-membered ring and the terminal amino of the other sulfaquinoxaline, which is bonded to two adjacent Zn(â…¡), this ZnN4Cl coordination forms a distorted square-pyramidal. One-dimentional infinite-chain of complex 13 formed through sulfaquinoxaline linking. The molecules connect into two-dimensional network via intermolecular hydrogen bonds involving N-H…O and N-H…Cl. Chapter Five: The complex Mn(C18H12N4O5S)2(H2O)2 (14) is obtained by the reaction of sulfasalazine and Mn(Ac)2·4H2O under the hydro(solv) thermal conditon. Compound 14 belongs to the tetragonal crystal system, space group I4(1)/a, cell parameters: a = 20.183(2) ?, b =20.183(2) ?, c =21.349(2) ?, V = 8696.3(16) ?3, Z =16, Dc =1.592 Mg/m3. Center metal ion Mn(II) for compound 14 adopts six-coordinated distorted octahedral geometry and is surrounded by two O atoms from two water molecule and four O atoms from two sulfasalazine ligands generating two six-membered rings. The complex Cu(C18H13N4O5S)(PPh3)2 (15) is obtained by the reaction of sulfasalazine and [Cu(MeCN)2(PPh3)2]ClO4 under the hydro(solv) thermal conditon. Compound 15 belongs to the triclinic crystal system, space group P-1, cell parameters: a = 14.0126(5) ?, b =14.2236(12) ?, c =14.2302(4)?, α=81.068(11)°,β=61.606(7)°, γ=75.011(10)°,V = 2408.4(2) ?3, Z =2, Dc = 1.359 Mg/m3. Center metal ion copper(I) adopts distorted tetrahedron geometry. The Cu(I) is four-coordinated and is surrounded by two oxygen from carboxylic acid and two phosphine atoms from triphenyl phosphine. The molecules connect into two-dimensional network via abundant hydrogen bondsinvolving O-H…O,N-H…O and C-H…O.