10 research outputs found
CCDC 1479096: Experimental Crystal Structure Determination
An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.,Related Article: N. P. Godman, D. B. Barbee, F. B. Carty, C. D. McMillen, C. A. Corley, E. Shurdha, S. T. Iacono|2016|Polym.Chem.|7|5799|doi:10.1039/C6PY00966
Extended Network Thiocyanate- and Tetracyanoethanide-Based First-Row Transition Metal Complexes
Linear chain thiocyanate complexes of M(NCS)<sub>2</sub>(OCMe<sub>2</sub>)<sub>2</sub> (M = Fe, Mn, Cr) composition have
been prepared and structurally, chemically, and magnetically characterized.
Fe(NCS)<sub>2</sub>(OCMe<sub>2</sub>)<sub>2</sub> exhibits metamagnetic-like
behavior, and orders as an antiferromagnet at 6 K. The Mn and Cr compounds
are antiferromagnets with <i>T</i><sub>c</sub> of 30 and
50 K, respectively, with <i>J</i>/<i>k</i><sub>B</sub> = −3.5 (−2.4 cm<sup>–1</sup>) and −9.9
K (−6.9 cm<sup>–1</sup>), respectively, when fit to
one-dimensional (1-D) Fisher chain model (<i>H</i> = −2<i>J</i>S<sub><i>i</i></sub>·S<sub><i>j</i></sub>). Co(NCS)<sub>2</sub> was prepared by a new synthetic route,
and powder diffraction was used to determine its structure to be
a two-dimensional (2-D) layer with μ<sub>N,S,S</sub>-NCS motif,
and it is an antiferromagnet (<i>T</i><sub>c</sub> = 22
K; θ = −33 K for <i>T</i> > 25 K). M(NCS)<sub>2</sub>(OCMe<sub>2</sub>)<sub>2</sub> (M = Fe, Mn) and Co(NCS)<sub>2</sub> react with (NBu<sub>4</sub>)(TCNE) in dichloromethane to
form M(TCNE)[C<sub>4</sub>(CN)<sub>8</sub>]<sub>1/2</sub>, and in
acetone to form M[C<sub>4</sub>(CN)<sub>8</sub>](OCMe<sub>2</sub>)<sub>2</sub> (M = Fe, Mn, Co). These materials possess μ<sub>4</sub>-[C<sub>4</sub>(CN)<sub>8</sub>]<sup>2–</sup> that form 2-D
layered structural motifs, which exhibit weak antiferromagnetic coupling.
Co(TCNE)[C<sub>4</sub>(CN)<sub>8</sub>]<sub>1/2</sub> behaves as a
paramagnet with strong antiferromagnetic coupling (θ = −50
K)
Extended Network Thiocyanate- and Tetracyanoethanide-Based First-Row Transition Metal Complexes
Linear chain thiocyanate complexes of M(NCS)<sub>2</sub>(OCMe<sub>2</sub>)<sub>2</sub> (M = Fe, Mn, Cr) composition have
been prepared and structurally, chemically, and magnetically characterized.
Fe(NCS)<sub>2</sub>(OCMe<sub>2</sub>)<sub>2</sub> exhibits metamagnetic-like
behavior, and orders as an antiferromagnet at 6 K. The Mn and Cr compounds
are antiferromagnets with <i>T</i><sub>c</sub> of 30 and
50 K, respectively, with <i>J</i>/<i>k</i><sub>B</sub> = −3.5 (−2.4 cm<sup>–1</sup>) and −9.9
K (−6.9 cm<sup>–1</sup>), respectively, when fit to
one-dimensional (1-D) Fisher chain model (<i>H</i> = −2<i>J</i>S<sub><i>i</i></sub>·S<sub><i>j</i></sub>). Co(NCS)<sub>2</sub> was prepared by a new synthetic route,
and powder diffraction was used to determine its structure to be
a two-dimensional (2-D) layer with μ<sub>N,S,S</sub>-NCS motif,
and it is an antiferromagnet (<i>T</i><sub>c</sub> = 22
K; θ = −33 K for <i>T</i> > 25 K). M(NCS)<sub>2</sub>(OCMe<sub>2</sub>)<sub>2</sub> (M = Fe, Mn) and Co(NCS)<sub>2</sub> react with (NBu<sub>4</sub>)(TCNE) in dichloromethane to
form M(TCNE)[C<sub>4</sub>(CN)<sub>8</sub>]<sub>1/2</sub>, and in
acetone to form M[C<sub>4</sub>(CN)<sub>8</sub>](OCMe<sub>2</sub>)<sub>2</sub> (M = Fe, Mn, Co). These materials possess μ<sub>4</sub>-[C<sub>4</sub>(CN)<sub>8</sub>]<sup>2–</sup> that form 2-D
layered structural motifs, which exhibit weak antiferromagnetic coupling.
Co(TCNE)[C<sub>4</sub>(CN)<sub>8</sub>]<sub>1/2</sub> behaves as a
paramagnet with strong antiferromagnetic coupling (θ = −50
K)
First Row Transition Metal(II) Thiocyanate Complexes, and Formation of 1‑, 2‑, and 3‑Dimensional Extended Network Structures of M(NCS)<sub>2</sub>(Solvent)<sub>2</sub> (M = Cr, Mn, Co) Composition
The
reaction of first row transition M<sup>II</sup> ions with KSCN in
various solvents form tetrahedral (NMe<sub>4</sub>)<sub>2</sub>[M<sup>II</sup>(NCS)<sub>4</sub>] (M = Fe, Co), octahedral <i>trans</i>-M<sup>II</sup>(NCS)<sub>2</sub>(Sol)<sub>4</sub> (M = Fe, V, Ni;
Sol = MeCN, THF), and K<sub>4</sub>[M<sup>II</sup>(NCS)<sub>6</sub>] (M = V, Ni). The reaction of M(NCS)<sub>2</sub>(OCMe<sub>2</sub>)<sub>2</sub> (M = Cr, Mn) in MeCN and [Co(NCMe)<sub>6</sub>](BF<sub>4</sub>)<sub>2</sub> and KSCN in acetone and after diffusion of diethyl
ether form M(NCS)<sub>2</sub>(Sol)<sub>2</sub> that structurally differ
as they form one-dimensional (1-D) (M = Co; Sol = THF), two-dimensional
(2-D) (M = Mn; Sol = MeCN), and three-dimensional (3-D) (M = Cr; Sol
= MeCN) extended structures. 1-D Co(NCS)<sub>2</sub>(THF)<sub>2</sub> has <i>trans</i>-THFs, while the acetonitriles have a <i>cis</i> geometry for 2- and 3-D M(NCS)<sub>2</sub>(NCMe)<sub>2</sub> (M = Cr, Mn). 2-D Mn(NCS)<sub>2</sub>(NCMe)<sub>2</sub> is
best described as Mn<sup>II</sup>(μ<sub>N,N</sub>-NCS)(μ<sub>N,S</sub>-NCS)(NCMe)<sub>2</sub> [= Mn<sub>2</sub>(μ<sub>N,N</sub>-NCS)<sub>2</sub>(μ<sub>N,S</sub>-NCS)<sub>2</sub>(NCMe)<sub>4</sub>] with the latter μ<sub>N,S</sub>-NCS providing the
2-D connectivity. In addition, the reaction of Fe(NCS)<sub>2</sub>(OCMe<sub>2</sub>)<sub>2</sub> and 7,7,8,8-tetracyanoquino-<i>p</i>-dimethane (TCNQ) forms 2-D structured Fe<sup>II</sup>(NCS)<sub>2</sub>TCNQ. The magnetic behavior of 1-D Co(NCS)<sub>2</sub>(THF)<sub>2</sub> can be modeled by a 1-D Fisher expression (<i>H</i> = −2<i>J</i>S<sub><i>i</i></sub>·S<sub><i>j</i></sub>) with <i>g</i> = 2.4 and <i>J</i>/<i>k</i><sub>B</sub> = 0.68 K (0.47 cm<sup>–1</sup>) and exhibit weak ferromagnetic coupling. Cr(NCS)<sub>2</sub>(NCMe)<sub>2</sub> and Fe<sup>II</sup>(NCS)<sub>2</sub>TCNQ magnetically order
as antiferromagnets with <i>T</i><sub>c</sub>’s of
37 and 29 K, respectively, while Mn(NCS)<sub>2</sub>(NCMe)<sub>2</sub> exhibits strong antiferromagnetic coupling. M(NCS)<sub>2</sub>(THF)<sub>4</sub> and K<sub>4</sub>[M(NCS)<sub>6</sub>] (M = V, Ni) are paramagnets
with weak coupling between the octahedral metal centers
First Row Transition Metal(II) Thiocyanate Complexes, and Formation of 1‑, 2‑, and 3‑Dimensional Extended Network Structures of M(NCS)<sub>2</sub>(Solvent)<sub>2</sub> (M = Cr, Mn, Co) Composition
The
reaction of first row transition M<sup>II</sup> ions with KSCN in
various solvents form tetrahedral (NMe<sub>4</sub>)<sub>2</sub>[M<sup>II</sup>(NCS)<sub>4</sub>] (M = Fe, Co), octahedral <i>trans</i>-M<sup>II</sup>(NCS)<sub>2</sub>(Sol)<sub>4</sub> (M = Fe, V, Ni;
Sol = MeCN, THF), and K<sub>4</sub>[M<sup>II</sup>(NCS)<sub>6</sub>] (M = V, Ni). The reaction of M(NCS)<sub>2</sub>(OCMe<sub>2</sub>)<sub>2</sub> (M = Cr, Mn) in MeCN and [Co(NCMe)<sub>6</sub>](BF<sub>4</sub>)<sub>2</sub> and KSCN in acetone and after diffusion of diethyl
ether form M(NCS)<sub>2</sub>(Sol)<sub>2</sub> that structurally differ
as they form one-dimensional (1-D) (M = Co; Sol = THF), two-dimensional
(2-D) (M = Mn; Sol = MeCN), and three-dimensional (3-D) (M = Cr; Sol
= MeCN) extended structures. 1-D Co(NCS)<sub>2</sub>(THF)<sub>2</sub> has <i>trans</i>-THFs, while the acetonitriles have a <i>cis</i> geometry for 2- and 3-D M(NCS)<sub>2</sub>(NCMe)<sub>2</sub> (M = Cr, Mn). 2-D Mn(NCS)<sub>2</sub>(NCMe)<sub>2</sub> is
best described as Mn<sup>II</sup>(μ<sub>N,N</sub>-NCS)(μ<sub>N,S</sub>-NCS)(NCMe)<sub>2</sub> [= Mn<sub>2</sub>(μ<sub>N,N</sub>-NCS)<sub>2</sub>(μ<sub>N,S</sub>-NCS)<sub>2</sub>(NCMe)<sub>4</sub>] with the latter μ<sub>N,S</sub>-NCS providing the
2-D connectivity. In addition, the reaction of Fe(NCS)<sub>2</sub>(OCMe<sub>2</sub>)<sub>2</sub> and 7,7,8,8-tetracyanoquino-<i>p</i>-dimethane (TCNQ) forms 2-D structured Fe<sup>II</sup>(NCS)<sub>2</sub>TCNQ. The magnetic behavior of 1-D Co(NCS)<sub>2</sub>(THF)<sub>2</sub> can be modeled by a 1-D Fisher expression (<i>H</i> = −2<i>J</i>S<sub><i>i</i></sub>·S<sub><i>j</i></sub>) with <i>g</i> = 2.4 and <i>J</i>/<i>k</i><sub>B</sub> = 0.68 K (0.47 cm<sup>–1</sup>) and exhibit weak ferromagnetic coupling. Cr(NCS)<sub>2</sub>(NCMe)<sub>2</sub> and Fe<sup>II</sup>(NCS)<sub>2</sub>TCNQ magnetically order
as antiferromagnets with <i>T</i><sub>c</sub>’s of
37 and 29 K, respectively, while Mn(NCS)<sub>2</sub>(NCMe)<sub>2</sub> exhibits strong antiferromagnetic coupling. M(NCS)<sub>2</sub>(THF)<sub>4</sub> and K<sub>4</sub>[M(NCS)<sub>6</sub>] (M = V, Ni) are paramagnets
with weak coupling between the octahedral metal centers