Syntheses, Structure, and Magnetic Properties of New Types of Cu(II), Co(II), and Mn(II) Organophosphonate Materials:  Three-Dimensional Frameworks and a One-Dimensional Chain Motif

Abstract

The hydrothermal syntheses, structures, and magnetic properties of the Cu(II), Co(II), and Mn(II) complexes with organophosphonic acid 1) crystallizes in the orthorhombic space group Pbca, with unit cell parameters a ) 9.4430(10) Å, b ) 9.3681(10) Å, c ) 16.0755(17) Å, V ) 1422.1(3) Å 3 , and Z ) 4. The X-ray crystallographic determination reveals copper ions in two different coordination environments that are bridged by one terminal oxygen atom to form a threedimensional framework of corner-sharing layers. Antiferromagnetic coupling between the two types of Cu units in 1 was observed at 15 K, followed by ferromagnetic ordering at 9 K. Compound Co 3 [NH 2 (CH 2 PO 3 ) 2 ] 2 (2) crystallizes in the orthorhombic space group P2 1 2 1 2 with unit cell parameters a ) 10.7346(8) Å, b ) 13.3704(10) Å, c ) 5.3699(4) Å, V ) 770.72(10) Å 3 , and Z ) 2. All Co(II) ions are in a tetrahedral environment with both ends of the ligand bound via O atoms to adjacent Co(II) ions, thus creating tetranuclear 16-membered rings. Compound Mn{[NH 2 (CH 2 PO 3 H) 2 ] 2 (H 2 O) 2 } (3) crystallizes in the monoclinic space group P2 1 / n, with unit cell parameters a ) 7.3668(11) Å, b ) 8.1540(12) Å, c ) 14.090(2) Å, β ) 103.935-(2)°, V ) 821.4(2) Å 3 , and Z ) 2. Four phosphate oxygen atoms and two water molecules are coordinated to the mononuclear octahedral Mn(II) ions. The amino groups are protonated and therefore do not coordinate to Mn(II). Compound 3 features a one-dimensional chain architecture stitched together by hydrogen bonds.

Complexes of N-(thio)phosphorylthioureas AdNHC(S)NHP(X)(OiPr)2 (X = O, S) with cobalt(II), zinc(II), and cadmium(II). Crystal structure of Co[AdNHC(S)NP(S)(OiPr)2]2

“…The values are considerably higher than the reported spin-only value of 3.87 l B for non-interaction of one S = 3/2 spin of Co(II). Effective magnetic moments between 4.4 and 5.2 for Co(II) compounds around room temperature are characteristic for mononuclear, high-spin, tetrahedral Co(II) complexes [22][23][24][25][26][27]. This is consistent with the experimental values observed for other systems at room temperature, and is attributed to the spin-orbit coupling of the cobalt(II) ion.…”

High-spin Co(II) in monomeric and exchange coupled oligomeric structures: Magnetic and magnetic circular dichroism investigations

“…[29] the magnetic properties of a linear tetrahedral Co trimer Co 3 [NH 2 (CH 2 PO 3 ) 2 ] 2 were analyzed. The T/3 value obtained at 300 K was 2.57 emu K/mol, higher than expected for the spin-only value.…”

Synthesis, crystal structure and characterizations of a new 3D porous zinc phosphonate: Zn6[(O3PCH2)2NHC6H11]4·6H2O

“…The integration of the inorganic phosphonate (CPO 3 ) group and numerous rigid or flexible organic functional groups within the same composite would, therefore, be expected to result in new inorganic-organic hybrid materials with interesting structures and properties. Along this line, the use of bifunctional or multifunctional anionic units, such as diphosphonates, aminophosphonates or phosphonocarboxylates has led to a number of new materials with microporous or openframework structures [5][6][7][8].Based on 2-hydroxyphosphonoacetic acid, proline-Nmethyl-phosphonic acid and DL-(a-aminoethyl)phosphonic acid, a series of metal phosphonates with two-dimensional (2D) layer and three-dimensional (3D) open-framework have been isolated in our laboratory [9]. In the point of view of structural construction of inorganic-organic hybrid compounds, the substituted aminodiphosphonic acid, RN(CH 2 PO 3 H 2 ) 2 , is very useful ligands in the synthesis of metal phosphonates with new structure types [10][11][12][13][14].…”

“…The integration of the inorganic phosphonate (CPO 3 ) group and numerous rigid or flexible organic functional groups within the same composite would, therefore, be expected to result in new inorganic-organic hybrid materials with interesting structures and properties. Along this line, the use of bifunctional or multifunctional anionic units, such as diphosphonates, aminophosphonates or phosphonocarboxylates has led to a number of new materials with microporous or openframework structures [5][6][7][8].…”