Structures and magnetic properties of novel 1-D coordination polymers containing both dicyanamide and pyridine-type ligands
- Univ. of Utah, Salt Lake City, UT (United States). Dept. of Chemistry
- Univ. of Delaware, Newark, DE (United States). Dept. of Chemistry
Three novel 1-D coordination polymers consisting of {l_brace}Mn[N(CN){sub 2}]{sub 2}{r_brace}{sub {infinity}} structural units and L = 2 pyridines (i.e., 2), 2,2{prime}-bipyridine (i.e., 3), and 4,4{prime}-bipyridine (i.e., 4) have been synthesized and characterized by single crystal X-ray crystallography and magnetic susceptibility studies. Compound 2 crystallizes in the monoclinic space group P2{sub 1}/n with a = 7.5401 (7) {angstrom}, b = 13.2643 (4) {angstrom}, c = 8.6973 (9) {angstrom}, {beta} = 114.954 (2){degree}, V = 788.65 (11) {angstrom}{sup 3}, and Z = 2 with R(R{sub w}) = 0.0451 (0.1067). In 2, linear 1-D chains containing trans-{mu}-[N(CN){sub 2}]{sup {minus}} ligands and two pyridine ligands are formed while cis-{mu}-[N(CN){sub 2}]{sup {minus}} coordination gives rise to zigzag chains with chelated 2,2{prime}-bipyridine ligands in 3 which crystallizes in the monoclinic space group C2/c with a = 6.6769 /(3) {angstrom}, b = 17.2008 (2) {angstrom}, c - 13.0142 (4) {angstrom}, b =- 90.110 (4){degree}, V = 1494.65 (8) {angstrom}{sup 3}, and Z = 4 with R(R{sub w}) = 0.0514 (0.1218). Interestingly, incorporation of 4,4{prime}-bipyridine into the structure of 4 produces a unique cylindrical 1-D chain consisting of four trans-{mu}-[N(CN){sub 2}]{sup {minus},}s, one coordinated water, and an unusual monodentate 4,4{prime}-bipyridine ligand. X-ray crystallography established the orthorhombic space group Iba2 with a = 22.378 (6) {angstrom}, b = 22.517 (5) {angstrom}, c = 13.519 (5) {angstrom}, V = 6812 (3) {angstrom}{sup 3}, and Z = 8 with R(R{sub w}) = 0.0384 (0.0861). The magnetic susceptibilities of each compound were studied in the 2--300 K temperature range and the data fitted to the 1-D Fisher chain model for S = 5/2 with g-values of 2.00 and intrachain exchange constants, J/k{sub B} = {minus}0.10, {minus}0.17, and {minus}0.24 K for 2, 3, and 4, respectively.
- Sponsoring Organization:
- USDOE, Washington, DC (United States)
- DOE Contract Number:
- FG02-86ER45271; FG03-93ER45504; FG02-96ER12198
- OSTI ID:
- 679239
- Journal Information:
- Journal of Solid State Chemistry, Journal Name: Journal of Solid State Chemistry Journal Issue: 2 Vol. 145; ISSN 0022-4596; ISSN JSSCBI
- Country of Publication:
- United States
- Language:
- English
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