Structural analysis and magnetic properties of the 1D [Fe(dca)2bipy(H2O)]·1/2H2O and the 3D [Ni(dca)2bipy] (dca = dicyanamide; bipy = 4,4′-bipyridine)

Martín, Susana; Barandika, Gotzone; Ezpeleta, Jose Marı́a; Cortés, Roberto; Larramendi, J.I. Ruiz de; Lezama, Luís; Rojo, Teófilo

doi:10.1039/b206069h

Cited by 33 publications

(13 citation statements)

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“…In general, the fit without the employment of the D parameter for Fe(II) ions has been used in several studies of the magnetic coupling of polynuclear iron complexes. The results are relatively good when the J coupling parameter is appreciable . Whereas in the scarce previously reported azido-bridged Fe(II) systems, either no study of the coupling was made, ,2b or the coupling was derived through the isotropic Hamiltonian.…”

Section: Resultsmentioning

confidence: 89%

Syntheses, Structural Analyses, and Magneto-Structural Correlations of Three Polymeric Fe(II) Complexes with Azide Ligand

et al. 2003

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Three new metal-organic polymeric complexes, [Fe(N(3))(2)(bpp)(2)] (1), [Fe(N(3))(2)(bpe)] (2), and [Fe(N(3))(2)(phen)] (3) [bpp = (1,3-bis(4-pyridyl)-propane), bpe = (1,2-bis(4-pyridyl)-ethane), phen = 1,10-phenanthroline], have been synthesized and characterized by single-crystal X-ray diffraction studies and low-temperature magnetic measurements in the range 300-2 K. Complexes 1 and 2 crystallize in the monoclinic system, space group C2/c, with the following cell parameters: a = 19.355(4) A, b = 7.076(2) A, c = 22.549(4) A, beta = 119.50(3) degrees, Z = 4, and a = 10.007(14) A, b = 13.789(18) A, c = 10.377(14) A, beta = 103.50(1) degrees, Z = 4, respectively. Complex 3 crystallizes in the triclinic system, space group P(-)1, with a = 7.155(12) A, b = 10.066(14) A, c = 10.508(14) A, alpha = 109.57(1) degrees, beta = 104.57(1) degrees, gamma = 105.10(1) degrees, and Z = 2. All coordination polymers exhibit octahedral Fe(II) nodes. The structural determination of 1 reveals a parallel interpenetrated structure of 2D layers of (4,4) topology, formed by Fe(II) nodes linked through bpp ligands, while mono-coordinated azide anions are pendant from the corrugated sheet. Complex 2 has a 2D arrangement constructed through 1D double end-to-end azide bridged iron(II) chains interconnected through bpe ligands. Complex 3 shows a polymeric arrangement where the metal ions are interlinked through pairs of end-on and end-to-end azide ligands exhibiting a zigzag arrangement of metals (Fe-Fe-Fe angle of 111.18 degrees) and an intermetallic separation of 3.347 A (through the EO azide) and of 5.229 A (EE azide). Variable-temperature magnetic susceptibility data suggest that there is no magnetic interaction between the metal centers in 1, whereas in 2 there is an antiferromagnetic interaction through the end-to-end azide bridge. Complex 3 shows ferro- as well as anti-ferromagnetic interactions between the metal centers generated through the alternating end-on and end-to-end azide bridges. Complex 1 has been modeled using the D parameter (considering distorted octahedral Fe(II) geometry and with any possible J value equal to zero) and complex 2 has been modeled as a one-dimensional system with classical and/or quantum spin where we have used two possible full diagonalization processes: without and with the D parameter, considering the important distortions of the Fe(II) ions. For complex 3, the alternating coupling model impedes a mathematical solution for the modeling as classical spins. With quantum spin, the modeling has been made as in 2.

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Section: Resultsmentioning

confidence: 89%

Syntheses, Structural Analyses, and Magneto-Structural Correlations of Three Polymeric Fe(II) Complexes with Azide Ligand

et al. 2003

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“…The values of the magnetic coupling through the double dca bridge in 2 , 6 , and 10 are small, antiferromagnetic, and very close to each other. Weak antiferromagnetic interactions between high-spin iron(II) ions through single and double μ 1,5 -dca bridges were observed in the few reports concerning this type of compound. 29c,− It deserves to be outlined that a value of J = −0.8 cm -1 was determined for the high-spin iron(II) dinuclear complex of formula [(dca)(tpm)Fe(μ 1,5 -dca) 2 Fe(tpm)(dca)] [tpm = tris(pyrazolyl)methane] in good agreement with the J values for 2 , 6 , and 10 , and a weaker antiferromagnetic interaction ( J = −0.3 cm -1 ) was reported for the high-spin iron(II) complex [Fe(dca) 2 (bipy)(H 2 O)] where the iron atoms are connected through single μ 1,5 -dca bridges …”

Section: Resultsmentioning

confidence: 99%

Ligand Effects on the Structures of Extended Networks of Dicyanamide-Containing Transition-Metal Ions

et al. 2006

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The structural characterization of a series of complexes of formula [M(dca)2L]n, where dca = dicyanamide, L = 1,10-phenanthroline (phen) [1-4] and 2,9-dimethylphenanthroline (2,9-dmphen) [9-12], and M = Mn (1 and 9), Fe (2 and 10), Co (3 and 11), and Ni (4 and 12), has revealed the effect of the presence of the methyl substituents of L on the resulting network. The structure of [Mn(dca)2(phen)]n (1), which is identical to those of 2-4, together with the investigation of its magnetic properties in the temperature range of 77-300 K were reported elsewhere. The use of the 4,7-dimethylphenanthroline (4,7-dmphen) as the co-ligand yielded a series of compounds of formula [M(dca)2(4,7-dmphen)]n [M = Mn (5), Fe (6), Co (7), and Ni (8)], which are isostructural with 1-4. Compounds containing phen (1-4) and 4,7-dmphen (5-8) are made of two-dimensional grids of metal atoms, each metal atom being linked to three other metal centers through single (three metal atoms involved) and double (two metal atoms involved) dca bridges exhibiting the mu-1,5 coordination mode. The isostructural complexes [M(dca)2(2,9-dmphen)]n (9-12) also have a sheetlike structure, the metal atoms in each layer being linked by two single and one double mu-1,5-dca units, as in 1-8. However, the topology of the network in 9-12 is different from that in 1-8 because of the different arrangement of the two single mu-1,5 dca bridges: cis in 1-8 versus trans in 9-12. The magnetic study of compounds 1-12 in the temperature range of 1.9-290 K has revealed the occurrence of weak ferromagnetic (M = Ni) and antiferromagnetic interactions (M = Mn, Fe, and Co). The different magnetic behavior in 1-12 was analyzed in the light of their structures, and the values of the magnetic interactions were compared to those of related systems.

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“…The bim ligand acts as an additional intra-chain bridge connecting neighboring Cd II atoms, without increasing the dimensionality. This behavior of bim is different from that of the rigid ligand 4,4 0 -bipyridine, which would act as inter-chain bridges to increase the dimensionality (Jensen et al, 2002;Martin et al, 2002). The r.m.s.…”

Section: Commentmentioning

confidence: 89%

A novel triple-stranded cadmium(II) polymer chain:catena-poly[cadmium(II)-μ-1,2-bis(imidazol-1-yl)ethane-κ²N³:N^3′-di-μ-1,5-dicyanamido-κ⁴N¹:N⁵]

Zhang¹,

Wang²,

Zhang³

et al. 2005

Acta Cryst E

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In the crystal structure of the title complex, [Cd(C2N3)2(C8H10N4)]n or [Cd(dca)2(bim)]n, where dca is dicyanamide and bim is 1,2‐bis(imidazol‐1‐yl)ethane, each CdII atom is in a distorted octahedral environment. Four N atoms from four dca ligands occupy the equatorial positions, and two N atoms from two bim ligands occupy the axial positions. Each CdII atom is situated at a center of symmetry, and a twofold axis runs through the mid‐points of the bim exocyclic C—C bond and the Cd⋯Cd vector. The structure consists of chains in which neighboring CdII atoms are connected through one bim and two end‐to‐end dca bridges.

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Structural analysis and magnetic properties of the 1D [Fe(dca)₂bipy(H₂O)]·1/2H₂O and the 3D [Ni(dca)₂bipy] (dca = dicyanamide; bipy = 4,4′-bipyridine)

Cited by 33 publications

References 50 publications

Syntheses, Structural Analyses, and Magneto-Structural Correlations of Three Polymeric Fe(II) Complexes with Azide Ligand

Syntheses, Structural Analyses, and Magneto-Structural Correlations of Three Polymeric Fe(II) Complexes with Azide Ligand

Ligand Effects on the Structures of Extended Networks of Dicyanamide-Containing Transition-Metal Ions

A novel triple-stranded cadmium(II) polymer chain:catena-poly[cadmium(II)-μ-1,2-bis(imidazol-1-yl)ethane-κ²N³:N^3′-di-μ-1,5-dicyanamido-κ⁴N¹:N⁵]

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Structural analysis and magnetic properties of the 1D [Fe(dca)2bipy(H2O)]·1/2H2O and the 3D [Ni(dca)2bipy] (dca = dicyanamide; bipy = 4,4′-bipyridine)

Cited by 33 publications

References 50 publications

Syntheses, Structural Analyses, and Magneto-Structural Correlations of Three Polymeric Fe(II) Complexes with Azide Ligand

Syntheses, Structural Analyses, and Magneto-Structural Correlations of Three Polymeric Fe(II) Complexes with Azide Ligand

Ligand Effects on the Structures of Extended Networks of Dicyanamide-Containing Transition-Metal Ions

A novel triple-stranded cadmium(II) polymer chain:catena-poly[cadmium(II)-μ-1,2-bis(imidazol-1-yl)ethane-κ2N3:N3′-di-μ-1,5-dicyanamido-κ4N1:N5]

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Structural analysis and magnetic properties of the 1D [Fe(dca)₂bipy(H₂O)]·1/2H₂O and the 3D [Ni(dca)₂bipy] (dca = dicyanamide; bipy = 4,4′-bipyridine)

A novel triple-stranded cadmium(II) polymer chain:catena-poly[cadmium(II)-μ-1,2-bis(imidazol-1-yl)ethane-κ²N³:N^3′-di-μ-1,5-dicyanamido-κ⁴N¹:N⁵]