Diethyl-nicotinamide Ligands Research Articles

Crystal structure and Hirshfeld surface analysis of di-aqua-bis-(N,N-di-ethyl-nicotinamide-κN1)bis-(2,4,6-tri-methyl-benzoato-κO)manganese(II).

In the title centrosymmetric complex, [Mn(C10H11O2)2(C10H14N2O)2(H2O)2], the MnII cation is located on an inversion centre. The four O atoms form a slightly distorted square-planar arrangement around the MnII cation, and the distorted octa-hedral coordination is completed by two pyridine N atoms at distances of 2.3289 (15) Å. The dihedral angle between the planar carboxyl-ate group and the adjacent benzene ring is 87.73 (16)°, while the benzene and pyridine rings are oriented at a dihedral angle of 43.03 (8)°. In the crystal, the water mol-ecules are involved in both intra-molecular (to the non-coordinating carboxyl-ate O atom) and inter-molecular (to the amide carbonyl O atom) O-H⋯O hydrogen bonds. The latter lead to the formation of layers parallel to (100). These layers are further linked via weak C-H⋯O hydrogen bonds, resulting in a three-dimensional supra-molecular network. The Hirshfeld surface analysis of the crystal structure indicates that the most important contributions for the crystal packing are from H⋯H (70.0%), H⋯O/O⋯H (15.5%) and H⋯C/C⋯H (14.0%) inter-actions. One of the ethyl groups of the di-ethyl-nicotinamide ligand is disordered over two sets of sites, with an occupancy ratio of 0.282 (10):0.718 (10).

Novel mixed-ligand complexes of coumarilate/N,N′-diethylnicotinamide with some transition metals

Coordination complexes of transition metal cations (CoII, NiII, CuII and ZnII) containing coumarilate and N,N′-diethylnicotinamide were synthesized. The structural characterization and thermal behaviour analysis of novel samples synthesized were conducted through elemental analysis, magnetic susceptibility, solid-state UV–Vis, direct and injection probe mass spectra, FTIR spectra, thermoanalytic TG-DTG/DTA and single crystal X-ray diffraction methods. The structural details of single crystals of [Co(dena)2(H2O)4](coum)2 (I) and [Cu(coum)2(dena)2(H2O)2] (III) complexes were resolved completely. Moreover, the results of analysis obtained for [Ni(coum)2(dena)2(H2O)2] (II) and [Zn(dena)2(H2O)4](coum)2 (IV) complexes were interpreted considering the samples with crystal structures defined and made assumptions about the structural details. It was determined that the complex of CoII metal cation has salt-type structure and the coordination number of metal is accomplished to six as the sum of 4 mol of water and also 2 mol of N,N′-diethylnicotinamide ligands in trans position located within the coordination sphere. It was observed that 2 mol of coumarilate anions are located outside the coordination sphere and have stabilized to the charge (2+) of metal. The CuII complex has totally molecular structure, and the coordination sphere of metal cation was 6 as the sum of 2 mol of water, 2 mol of N,N′-diethylnicotinamide and 2 mol of monoanionic monodentate coumarilate ligands. All ligands have been located in –trans position. The geometry of both complex structures is distorted octahedral. It is assumed that the NiII complex structure is isostructural with CuII complex structure and also does ZnII complex with CoII structure. It was determined that the decomposition products obtained from thermal analysis are the oxides of related metal cations.

Crystal structure of trans-di-aqua-bis-(4-cyano-benzoato-κO)bis-(N,N-di-ethyl-nicotinamide-κN)cadmium.

The mononuclear title cadmium complex, [Cd(C10H14N2O)2(C8H4NO2)2(H2O)2], is centrosymmetric and contains two water mol-ecules, two 4-cyanobenzoate (CB) ligands and two di-ethyl-nicotinamide (DENA) ligands. All the ligands are coordinated to the CdII atom in a monodentate mode. The four nearest O atoms around the CdII atom form a slightly distorted square-planar arrangement, with the distorted octa-hedral coordination sphere being completed by the two pyridine N atoms of the DENA ligands at distances of 2.3336 (13) Å. The dihedral angle between the carboxyl-ate group and the adjacent benzene ring is 8.75 (16)°, while the benzene and pyridine rings are oriented at a dihedral angle of 57.83 (5)°. The water mol-ecules exhibit both intra-molecular [to the non-coordinating carboxyl-ate O atom, enclosing an S(6) hydrogen-bonding motif, where O⋯O = 2.670 (2) Å] and inter-molecular [to the amide carbonyl O atom, enclosing an R22(16) ring motif, where O⋯O = 2.781 (2) Å] O-H⋯O hydrogen bonds. The latter lead to the formation of supra-molecular chains propagating along [110].

Crystal structure of diaquabis(N,N-diethylnicotinamide-κN1)bis(2,4,6-trimethylbenzoato-κO1)cobalt(II)

The centrosymmetric mol-ecule in the monomeric title cobalt complex, [Co(C10H11O2)2(C10H14N2O)2(H2O)2], contains two water mol-ecules, two 2,4,6-tri-methyl-benzoate (TMB) ligands and two di-ethyl-nicotinamide (DENA) ligands. All ligands coordinate to the Co(II) atom in a monodentate fashion. The four O atoms around the Co(II) atom form a slightly distorted square-planar arrangement, with the distorted octa-hedral coordination sphere completed by two pyridine N atoms of the DENA ligands. The dihedral angle between the planar carboxyl-ate group and the adjacent benzene ring is 84.2 (4)°, while the benzene and pyridine rings are oriented at a dihedral angle of 38.87 (10)°. The water mol-ecules exhibit both intra-molecular (to the non-coordinating carboxyl-ate O atom) and inter-molecular (to the amide carbonyl O atom) O-H⋯O hydrogen bonds. The latter lead to the formation of layers parallel to (100), enclosing R 4 (4)(32) ring motifs. These layers are further linked via weak C-H⋯O hydrogen bonds, resulting in a three-dimensional network. One of the two ethyl groups of the DENA ligand is disordered over two sets of sites with an occupancy ratio of 0.490 (13):0.510 (13).

Diaquabis(4-bromobenzoato-κO)bis(N,N-diethylnicotinamide-κN1)copper(II)

The title CuII complex, [Cu(C7H4BrO2)2(C10H14N2O)2(H2O)2], contains two 4-bromo­benzoate (PBB), two diethyl­nicotinamide (DENA) monodentate ligands and two water mol­ecules. The four O atoms in the equatorial plane around the CuII ion form a slightly distorted square-planar arrangement, while the slightly distorted octa­hedral coordination is completed by two N atoms of the DENA ligands in the axial positions. Intra­molecular O—H⋯O hydrogen bonds link the water mol­ecules to the carboxyl­ate groups. The dihedral angles between the carboxyl­ate groups and the adjacent benzene rings are 3.1 (3) and 3.74 (17)°, while the pyridine rings and the benzene rings are oriented at dihedral angles of 6.81 (10) and 3.38 (12)°. In the crystal, inter­molecular O—H⋯O hydrogen bonds link the mol­ecules into double chains along the b axis. C—H⋯O inter­actions are also observed. π–π contacts between pyridine rings [centroid–centroid distance = 3.485 (2) Å] may further stabilize the crystal structure.

Diaquabis(N,N′-diethylnicotinamide-κN1)bis(4-fluorobenzoato-κO)copper(II)

The asymmetric unit of the title mononuclear CuII complex, [Cu(C7H4FO2)2(C10H14N2O)2(H2O)2], contains one-half of the mol­ecule. The CuII ion is located on an inversion centre, and is coordinated by two N atoms from two diethyl­nicotinamide ligands, two O atoms from two 4-fluoro­benzoate (PFB) ligands and two water mol­ecules in a distorted octa­hedral geometry. In the PFB ligand, the carboxyl­ate group is twisted at an angle of 2.10 (14)° from the attached benzene ring. In the crystal structure, inter­molecular O—H⋯O hydrogen bonds link mol­ecules related by translation along the a axis into chains. Weak inter­molecular C—H⋯O hydrogen bonds and π–π inter­actions between the pyridine rings of neighbouring mol­ecules [centroid-to-centroid distance = 3.571 (2) Å] further consolidate the crystal packing.

Diaquabis(N,N′-diethylnicotinamide-κN1)bis(4-ethylbenzoato-κO)copper(II)

The title CuII complex, [Cu(C9H9O2)2(C10H14N2O)2(H2O)2], contains two 4-ethyl­benzoate (PEB) ligands, two monodentate diethyl­nicotinamide (DENA) ligands and two water mol­ecules. The four O atoms in the equatorial plane around the CuII ion form a slightly distorted square-planar arrangement, while the distorted octa­hedral coordination is completed by the two N atoms of the DENA ligands in the axial positions. Intra­molecular O—H⋯O hydrogen bonds link the water mol­ecules to the carboxyl­ate groups. The dihedral angles between the carboxyl­ate groups and the adjacent benzene rings are 4.6 (3) and 3.7 (2)°, while the pyridine rings and the benzene rings are oriented at dihedral angles of 6.82 (11) and 3.63 (14)°. In the crystal, inter­molecular O—H⋯O hydrogen bonds link the mol­ecules into chains propagating along [010]. C—H⋯O inter­actions and a π–π contact between the pyridine rings [centroid–centroid distance = 3.469 (2) Å] are also observed.

Diaquabis(N,N-diethylnicotinamide-κN1)bis(4-ethylbenzoato-κO)cobalt(II)

The title CoII complex, [Co(C9H9O2)2(C10H14N2O)2(H2O)2], contains two 4-ethyl­benzoate (PEB), two monodentate diethyl­nicotinamide (DENA) ligands and two water mol­ecules. The four O atoms in the equatorial plane around the CoII ion form a slightly distorted square-planar arrangement, while the slightly distorted octa­hedral coordination is completed by the two N atoms of the DENA ligands in the axial positions. Intra­molecular O—H⋯O hydrogen bonds link the water mol­ecules to the carboxyl­ate groups. The dihedral angles between the carboxyl­ate groups and the adjacent benzene rings are 4.52 (18) and 4.56 (18)°, while the pyridine rings and the benzene rings are oriented at dihedral angles of 7.76 (10) and 5.67 (13)°. In the crystal, inter­molecular O—H⋯O hydrogen bonds link the mol­ecules into chains propagating along [010]. C—H⋯O inter­actions and a π–π contact between the pyridine rings [centroid–centroid distance = 3.476 (2) Å] are also observed.

Hydrogen‐Bond‐Based Magnetic Exchange Between μ‐Diethylnicotinamide(aqua)bis(X‐salicylato)copper(II) Polymeric Chains

AbstractPolymeric salicylatocopper(II) complexes of unusual composition [Cu(X‐sal)2(μ‐denia)(H2O)]n [denia = diethylnicotinamide, and X‐sal = 5‐methylsalicylate (1), 3‐methylsalicylate (2), 4‐methoxysalicylate (3), 3,5‐dichlorosalicylate (4) and 3,5‐dibromosalicylate (5)] were synthesized and characterized. Magnetic measurements were performed in the temperature range 1.8–300 K. The structural unit of all complexes consists of a CuII atom, which is monodentately coordinated by the pair of X‐salicylate anions in trans positions. Water and the diethylnicotinamide ligand occupy the other two basal plane positions of the tetragonal pyramid. The axial positions are occupied by a diethylnicotinamide oxygen atom of neighboring structural units, thus forming a spiral polymeric structure parallel to b axis. Magnetic measurements showed that all complexes 1–5 exhibit a susceptibility maximum at about 6–8 K. The obtained data fit to Bleaney–Bowers equation gave singlet‐triplet energy gaps 2J = –8.60 cm–1 for 1, 2J = –6.57 cm–1 for 2, 2J = –8.57 cm–1 for 3, 2J = –6.82 cm–1 for 4, and 2J = –6.45 cm–1 for 5. The supramolecular structure based on hydrogen bonds [described by supramolecular synthons R22(10) and R22(12)] is the pathway for antiferromagnetic interactions of the magnetically coupled pairs of copper atoms of neighboring chains within the 2D supramolecular layers. The results of the magnetic measurements suggest involvement of the COO groups in the magnetic interaction pathway for all five complexes.

Diaquabis(2-bromobenzoato-κO)bis(N,N-diethylnicotinamide-κN1)cobalt(II)

In the mononuclear title compound, [Co(C7H4BrO2)2(C10H14N2O)2(H2O)2], the CoII ion is located on a crystallographic inversion center. The asymmetric unit is completed by one 2-bromo­benzoate anion, one diethyl­nicotinamide (DENA) ligand and one coordinated water mol­ecule; all ligands are monodentate. The four O atoms in the equatorial plane around CoII form a slightly distorted square-planar arrangement, while the slightly distorted octa­hedral coordination is completed by the two pyridine N atoms of the DENA ligands in axial positions. The dihedral angle between the carboxyl­ate group and the attached benzene ring is 84.7 (1)°; the pyridine and benzene rings are oriented at a dihedral angle of 43.64 (6)°. In the crystal structure, inter­molecular O—H⋯O and C—H⋯O hydrogen bonds link the mol­ecules into a three-dimensional network.

Diaquabis(N,N-diethylnicotinamide-κN1)bis[4-(dimethylamino)benzoato-κO]cobalt(II)

The title CoII complex, [Co(C9H10NO2)2(C10H14N2O)2(H2O)2], is centrosymmetric. It contains two dimethyl­amino­benzoate (DMAB) and two diethyl­nicotinamide (DENA) ligands and two water mol­ecules, all of them being monodentate. The four O atoms in the equatorial plane around the Co atom form a slightly distorted square-planar arrangement, while the slightly distorted octa­hedral coordination is completed by the two pyridine N atoms of DENA ligands with the Co—N distance of 2.1519 (11) Å in the axial positions. The Co atom is displaced out of the least-squares plane of the carboxyl­ate group by −0.781 (1) Å. The dihedral angle between the carboxyl­ate group and the adjacent benzene ring is 5.05 (7)°, while the pyridine and benzene rings are oriented at a dihedral angle of 71.48 (5)°. In the crystal structure, inter­molecular O—H⋯O and C—H⋯O hydrogen bonds link the mol­ecules into a three-dimensional network. Two weak C—H⋯π inter­actions are also present.

Diaquabis(N,N-diethylnicotinamide-κN1)bis[4-(dimethylamino)benzoato-κO]nickel(II)

The centrosymmetric title NiII complex, [Ni(C9H10NO2)2(C10H14N2O)2(H2O)2], contains two dimethyl­amino­benzoate (DMAB), two diethyl­nicotinamide (DENA) ligands and two water mol­ecules, all of them monodentate. The four O atoms in the equatorial plane around the NiII atom form a slightly distorted square-planar arrangement, while the slightly distorted octa­hedral coordination is completed by the two pyridine N atoms of the DENA ligands in axial positions. The NiII atom is displaced by 0.681 (1) Å out of the least-squares plane of the carboxyl­ate group. The dihedral angle between the carboxyl­ate group and the adjacent benzene ring is 5.61 (7)°, while the pyridine and benzene rings are oriented at a dihedral angle of 73.20 (4)°. An intra­molecular O—H⋯O hydrogen bond results in the formation of a six-membered ring with a twisted conformation. In the crystal structure, inter­molecular O—H⋯O and C—H⋯O hydrogen bonds link mol­ecules into a three-dimensional network. Two weak C—H⋯π inter­actions are also present.

Diaquabis(2-bromobenzoato-κO)bis(N,N-diethylnicotinamide-κN1)nickel(II)

In the monomeric centrosymmetric title NiII complex, [Ni(C7H4BrO2)2(C10H14N2O)2(H2O)2], the NiII ion is located on an inversion center. The asymmetric unit contains one 2-bromo­benzoate ligand, one diethyl­nicotinamide (DENA) ligand and one coordinated water mol­ecule. The four O atoms in the equatorial plane around the NiII ion form a slightly distorted square-planar arrangement, while the slightly distorted octa­hedral coordination is completed by two N atoms of two DENA ligands in the axial positions. The dihedral angle between the benzene ring and the attached carboxyl­ate group is 87.73 (15)°, while the pyridine and benzene rings are oriented at a dihedral angle of 42.48 (7)°. In the crystal structure, O—H⋯O hydrogen bonds link the mol­ecules into a two-dimensional network parallel to (10). In addition, C—H⋯O hydrogen bonds are observed.

Diaquabis(2-chlorobenzoato-κO)bis(N,N-diethylnicotinamide-κN1)nickel(II)

In the monomeric and centrosymmetric title NiII complex, [Ni(C7H4ClO2)2(C10H14N2O)2(H2O)2], the NiII ion is located on an inversion center. The asymmetric unit contains one 2-chloro­benzoate ligand, one diethyl­nicotinamide (DENA) ligand and one coordinating water mol­ecule, the ligands being monodentate. The four O atoms in the equatorial plane around the NiII ion form a slightly distorted square-planar arrangement, while the slightly distorted octa­hedral coordination is completed by two N atoms of the DENA ligands in axial positions. The dihedral angle between the benzene ring and the attached carboxyl­ate group is 87.36 (10)°, while the pyridine and benzene rings are oriented at an angle of 41.90 (5)°. In the crystal structure, inter­molecular O—H⋯O hydrogen bonds link the mol­ecules into a two-dimensional network parallel to (10).

Diaquabis(2-bromobenzoato-κO)bis(N,N-diethylnicotinamide-κN1)manganese(II)

The title MnII complex, [Mn(C7H4BrO2)2(C10H14N2O)2(H2O)2], is centrosymmetric. The mol­ecule contains two 2-bromo­benzoate (BB) and two diethyl­nicotinamide (DENA) ligands and two water mol­ecules, all ligands being monodentate. The four O atoms in the equatorial plane around the Mn atom form a slightly distorted square-planar arrangement, while the distorted octa­hedral coordination is completed by the two N atoms of the DENA ligands in the axial positions. The dihedral angle between the carboxyl group and the adjacent benzene ring is 79.95 (11)°, while the pyridine and benzene rings are oriented at a dihedral angle of 45.66 (6)°. In the crystal structure, inter­molecular O—H⋯O hydrogen bonds link the mol­ecules into infinite chains.

Diaquabis(2-bromobenzoato-κO)bis(N,N-diethylnicotinamide-κN1)zinc(II)

In the centrosymmetric title complex, [Zn(C7H4BrO2)2(C10H14N2O)2(H2O)2], the ZnII atom is located on an inversion center. The asymmetric unit contains one 2-bromo­benzoate (BB), one diethyl­nicotinamide (DENA) ligand and one coordinating water molecule. The four O atoms in the equatorial plane around the Zn atom form a slightly distorted square-planar arrangement, while the slightly distorted octa­hedral coordination is completed by the two N atoms of the DENA ligands in the axial positions. The dihedral angle between the carboxyl group and the adjacent benzene ring is 85.51 (12)°, while the pyridine and benzene rings are oriented at a dihedral angle of 44.07 (6)°. In the crystal structure, O—H⋯O hydrogen bonds link the mol­ecules into infinite chains.

Diaquabis(N,N-diethylnicotinamide-κN1)bis(4-formylbenzoato-κO)cobalt(II)

In the crystal structure of the title CoII complex, [Co(C8H5O3)2(C10H14N2O)2(H2O)2], the metal centre is located on an inversion center and is coordinated by two 4-formyl­benzoate (FOB), two diethyl­nicotinamide (DENA) ligands and two water mol­ecules in a slightly distorted CoO4N2 octa­hedral geometry. In the crystal structure, O—H⋯O hydrogen bonds link the mol­ecules into infinite chains. π–π contacts between the parallel pyridine rings of neighboring DENA ligands [centroid–centroid distance = 3.652 (3) Å] further stabilize the crystal structure.

Diaquabis(N,N-diethylnicotinamide-κN1)bis(4-formylbenzoato-κO1)manganese(II)

The title compound, [Mn(C8H5O3)2(C10H14N2O)2(H2O)2], contains one MnII atom lying on an inversion centre, two 4-formyl­benzoate and two diethyl­nicotinamide ligands and two coordinated water mol­ecules. All ligands are monodentate. The four O atoms around the Mn atom form a slightly distorted equatorial plane, while the distorted octa­hedral coordination is completed by the two N atoms in the axial positions. An intra­molecular O—H⋯O hydrogen bond occurs in the complex. In the crystal structure, O—H⋯O hydrogen bonds link the mol­ecules through an R 2 2(16) ring motif, forming a one-dimensional chain along the a axis. The π–π contact between the pyridyl rings [centroid–centroid distance = 3.629 (2) Å] may further stabilize the structure.

Diaquabis(4-bromobenzoato-κO)bis(N,N′-diethylnicotinamide-κN 1)zinc(II)

The title compound, [Zn(C7H4BrO2)2(C10H14N2O)2(H2O)2], is a monomeric complex with the ZnII atom lying on an inversion center. It contains two 4-bromo­benzoate, two diethyl­nicotinamide ligands and two water mol­ecules, all of which are monodentate. The four O atoms in the equatorial plane around the Zn atom form a slightly distorted square-planar arrangement, while the distorted octa­hedral geometry is completed by two N atoms in the axial positions. The methyl group of one of the ethyl groups is disordered over two positions, with occupancies of ca 0.65 and 0.35. The two aromatic rings are oriented at an angle of 77.22 (14)°. In the crystal structure, O—H⋯O hydrogen bonds link the mol­ecules into chains along the a axis.

The Interaction of Sheep Genomic DNA with a Cobalt(II) Complex Containing p-Nitrobenzoate and N,N`-Diethylnicotinamide Ligands

The synthesized cobalt(II) complex, CoPNBDENA and the binding of thiscomplex with sheep genomic DNA were investigated by UV–Visible absorption andviscosity techniques. Also the interaction of sheep genomic DNA with the complex wasstudied using the agarose gel electrophoresis method. The results indicated that thecomplex interacted with DNA. The nature of the binding seemed to be mainly anelectrostatic interaction between DNA and the cobalt(II) complex. Other binding modessuch as hydrogen bonds may also exist in this system. In this study, after the interaction ofDNA– CoPNBDENA, it was observed that the migration of the DNA band became slow asthe amount of cobalt(II) complex was increased. This clearly demonstrates that theCoPNBDENA complex neutralizes the negative charges of DNA.