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Title: Synthesis, structure, and magnetic properties of Co{sub 2}{l_brace}[N(CN){sub 2}]{sub 4}bpym{r_brace}{center_dot}H{sub 2}O and M{l_brace}[N(CN){sub 2}]{sub 2}bpym{r_brace}{center_dot}H{sub 2}O (M = Mn, Fe, Co; bpym = 2,2{prime}-bipyrimidine)

Abstract

Co{sub 2}{l_brace}[N(CN){sub 2}]{sub 4}bpym{r_brace}{center_dot}H{sub 2}O (1) and M{l_brace}[N(CN){sub 2}]{sub 2}bpym{r_brace}{center_dot}H{sub 2}O [M = Mn (2a), Fe (2b), Co (2c); bpym = 2,2{prime}-bipyrimidine] have been synthesized and characterized structurally and magnetically. All of the compounds crystallize in the orthorhombic space group Pnma. The unit cell parameters for 1 are a = 16.1684(5) {angstrom}, b = 12.9860(3) {angstrom}, c = 10.4207(3) {angstrom}, and Z = 4. Compound 1 is a 2-D layered structure with water intercalated between sheets. The sheets are composed of {hor_ellipsis}M-[NCNCN]{sub 2}-M-bpym-M-[NCNCN]{sub 2}-M{hor_ellipsis} chains, which are linked together by dicyanamides. 21--c are isomorphic with the unit cell parameters a = 17.5112(4) {angstrom}, b = 11.9955(4) {angstrom}, c = 7.4684(2) {angstrom} for 2a, a = 17.5814(7) {angstrom}, b = 11.9453(5) {angstrom}, c - 7.3292(3) {angstrom} for 2b, a = 17.8642(2) {angstrom}, b = 11.9216(2) {angstrom}, c = 7.2860(2) {angstrom} for 2c, and Z = 4 for all. They crystallize as chains containing metal centers coordinated to two bridging dicyanamides, one terminal dicyanamide, one terminal chelating bpym, and one water molecule. 2a--c are the first examples of compounds containing terminal and {mu}-bound dicyanamides in the same structure. The broad maximum in the magnetic susceptibility of 1 could not be fit tomore » any known dimer models. However, the high-temperature data were fit to the Curie-Weiss expression with g = 2.86 and {theta} = {minus}42 K. 2a--c could best be modeled as uniform 1-D chains with g = 2.04, {theta} = {minus}0.76, and J/{kappa}{sub B} = {minus}0.15 K for 2a, g = 2.34, {theta} = {minus}7.6, and J/{kappa}{sub B} = {minus}0.42 K for 2b, and g = 2.58, {theta} = {minus}5.4, and J/{kappa}{sub B} = {minus}1.42 K for 2c. Because of small exchange coupling throughout the extended networks, no long-range magnetic ordering was observed.« less

Authors:
; ; ; ;
Publication Date:
Research Org.:
Univ. of Utah, Salt Lake City, UT (US)
Sponsoring Org.:
American Chemical Society; USDOE
OSTI Identifier:
20075880
DOE Contract Number:  
FG03-93ER45504
Resource Type:
Journal Article
Journal Name:
Inorganic Chemistry
Additional Journal Information:
Journal Volume: 39; Journal Issue: 9; Other Information: PBD: 1 May 2000; Journal ID: ISSN 0020-1669
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; SYNTHESIS; CRYSTAL STRUCTURE; MAGNETIC PROPERTIES; COBALT COMPLEXES; MANGANESE COMPLEXES; IRON COMPLEXES; PYRIMIDINE DIMERS; CYANIDES

Citation Formats

Marshall, S.R., Incarvito, C.D., Manson, J.L., Rheingold, A.L., and Miller, J.S. Synthesis, structure, and magnetic properties of Co{sub 2}{l_brace}[N(CN){sub 2}]{sub 4}bpym{r_brace}{center_dot}H{sub 2}O and M{l_brace}[N(CN){sub 2}]{sub 2}bpym{r_brace}{center_dot}H{sub 2}O (M = Mn, Fe, Co; bpym = 2,2{prime}-bipyrimidine). United States: N. p., 2000. Web. doi:10.1021/ic991244r.
Marshall, S.R., Incarvito, C.D., Manson, J.L., Rheingold, A.L., & Miller, J.S. Synthesis, structure, and magnetic properties of Co{sub 2}{l_brace}[N(CN){sub 2}]{sub 4}bpym{r_brace}{center_dot}H{sub 2}O and M{l_brace}[N(CN){sub 2}]{sub 2}bpym{r_brace}{center_dot}H{sub 2}O (M = Mn, Fe, Co; bpym = 2,2{prime}-bipyrimidine). United States. doi:10.1021/ic991244r.
Marshall, S.R., Incarvito, C.D., Manson, J.L., Rheingold, A.L., and Miller, J.S. Mon . "Synthesis, structure, and magnetic properties of Co{sub 2}{l_brace}[N(CN){sub 2}]{sub 4}bpym{r_brace}{center_dot}H{sub 2}O and M{l_brace}[N(CN){sub 2}]{sub 2}bpym{r_brace}{center_dot}H{sub 2}O (M = Mn, Fe, Co; bpym = 2,2{prime}-bipyrimidine)". United States. doi:10.1021/ic991244r.
@article{osti_20075880,
title = {Synthesis, structure, and magnetic properties of Co{sub 2}{l_brace}[N(CN){sub 2}]{sub 4}bpym{r_brace}{center_dot}H{sub 2}O and M{l_brace}[N(CN){sub 2}]{sub 2}bpym{r_brace}{center_dot}H{sub 2}O (M = Mn, Fe, Co; bpym = 2,2{prime}-bipyrimidine)},
author = {Marshall, S.R. and Incarvito, C.D. and Manson, J.L. and Rheingold, A.L. and Miller, J.S.},
abstractNote = {Co{sub 2}{l_brace}[N(CN){sub 2}]{sub 4}bpym{r_brace}{center_dot}H{sub 2}O (1) and M{l_brace}[N(CN){sub 2}]{sub 2}bpym{r_brace}{center_dot}H{sub 2}O [M = Mn (2a), Fe (2b), Co (2c); bpym = 2,2{prime}-bipyrimidine] have been synthesized and characterized structurally and magnetically. All of the compounds crystallize in the orthorhombic space group Pnma. The unit cell parameters for 1 are a = 16.1684(5) {angstrom}, b = 12.9860(3) {angstrom}, c = 10.4207(3) {angstrom}, and Z = 4. Compound 1 is a 2-D layered structure with water intercalated between sheets. The sheets are composed of {hor_ellipsis}M-[NCNCN]{sub 2}-M-bpym-M-[NCNCN]{sub 2}-M{hor_ellipsis} chains, which are linked together by dicyanamides. 21--c are isomorphic with the unit cell parameters a = 17.5112(4) {angstrom}, b = 11.9955(4) {angstrom}, c = 7.4684(2) {angstrom} for 2a, a = 17.5814(7) {angstrom}, b = 11.9453(5) {angstrom}, c - 7.3292(3) {angstrom} for 2b, a = 17.8642(2) {angstrom}, b = 11.9216(2) {angstrom}, c = 7.2860(2) {angstrom} for 2c, and Z = 4 for all. They crystallize as chains containing metal centers coordinated to two bridging dicyanamides, one terminal dicyanamide, one terminal chelating bpym, and one water molecule. 2a--c are the first examples of compounds containing terminal and {mu}-bound dicyanamides in the same structure. The broad maximum in the magnetic susceptibility of 1 could not be fit to any known dimer models. However, the high-temperature data were fit to the Curie-Weiss expression with g = 2.86 and {theta} = {minus}42 K. 2a--c could best be modeled as uniform 1-D chains with g = 2.04, {theta} = {minus}0.76, and J/{kappa}{sub B} = {minus}0.15 K for 2a, g = 2.34, {theta} = {minus}7.6, and J/{kappa}{sub B} = {minus}0.42 K for 2b, and g = 2.58, {theta} = {minus}5.4, and J/{kappa}{sub B} = {minus}1.42 K for 2c. Because of small exchange coupling throughout the extended networks, no long-range magnetic ordering was observed.},
doi = {10.1021/ic991244r},
journal = {Inorganic Chemistry},
issn = {0020-1669},
number = 9,
volume = 39,
place = {United States},
year = {2000},
month = {5}
}