Two cyanide-bridged Mn II -Nb IV coordination chain ferrimagnets promoted by interchain ferromagnetic interactions
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1 Supporting information Two cyanide-bridged Mn II -Nb IV coordination chain ferrimagnets promoted by interchain ferromagnetic interactions Michał Magott, Hanna Tomkowiak, Andrzej Katrusiak, Wojciech Nitek, Barbara Sieklucka and Dawid Pinkowicz*, Faculty of Chemistry, Jagiellonian University, Ingardena 3, Kraków, Poland Faculty of Chemistry, Adam Mickiewicz University, Umultowska 89b, Poznań, Poland Table of contents: Figure S1. IR spectra for 1 (black line) and 2 (red line) in the cm -1 (a) and cm -1 (b) range. Table S1. Comparison of the selected crystallographic parameters for 2 collected at 100 and 200 K using MoKα and CuKα, respectively. Table S2. Details of the Continuous Shape Measure (CShM) analysis a for the coordination spheres of Nb IV centres in 1 and 2, and for W IV centre in the tungsten(iv)-analogue of 1 {[Mn II (bpy)(h2o)2]2[w IV (CN)8] 6H2O}n (ref. 19). Figure S2. Fragments of structure of 1, showing interchain hydrogen bonding. 2,2 -bipyridine molecules and hydrogen atoms were omitted for clarity. Mn pink, Nb cyan, C gray, N blue, O red. Figure S3. Fragments of structure of 1, showing intrachain hydrogen bonds. 2,2 -bipyridine molecules and hydrogen atoms were omitted for clarity. Mn pink, Nb cyan, C gray, N blue, O red. Figure S4. Layers of crystallization water molecules between chains in 1. Only skeletons of the chains were pictured. Ellipsoids at 50% probability level. Mn pink, Nb cyan, C gray, N blue, O red. Figure S5. Fragments of structure of 1, showing π-π stacking between the neighboring chains. Crystallization water molecules and hydrogen atoms omitted for clarity. Mn pink, Nb cyan, C gray, N blue, O red. 1
2 Figure S6. Autostereographic projection (A. Katrusiak, J. Mol. Graphics Modell., 2001, 19, ) of the crystal structure of compound 2. Hydrogen bonds are marked by cyan dotted lines. Figure S7. Fragments of structure of 2, showing H-shaped hydrogen bonding patterns. Mn pink, Nb cyan, C gray, N blue, O red. Figure S8. Fragments of structure of 2, showing intrachain hydrogen bonding interactions. Mn pink, Nb cyan, C gray, N blue, O red. Figure S9. Fragments of structure of 2, showing π-π interactions between chains. Crystallization water molecules and hydrogen atoms were omitted for clarity. Mn pink, Nb cyan, C gray, N blue, O red. Figure S10. Results of the AC magnetic susceptibility measurements for compound 1 (HAC = 1.5 Oe, HDC = 0 Oe). Figure S11. Results of the AC magnetic susceptibility measurements for compound 2 (HAC = 1.5 Oe, HDC = 0 Oe). Figure S12. (a) χ -1 (T) dependence for 1 (black) and 2 (red) with Curie-Weiss fits in K range (dotted lines) and the best fits to the model described in the text in the K range (solid lines); (b) the scheme showing how the Mn2 Nb Mn2 Nb molecule has been closed into a loop in order to roughly approximate the magnetic behaviour of an infinite Mn2 Nb chain at temperatures above 50 K. 2
3 Figure S1. IR spectra for 1 (black line) and 2 (red line) in the cm -1 (a) and cm -1 (b) range. 3
4 Table S1. Comparison of the selected crystallographic parameters for 2 collected at 100 and 200 K using MoKα and CuKα, respectively. Temperature 100 K 200 K Instrument Bruker D8 Quest Eco SuperNova Detector Photon50 CMOS CCD X-ray source Mo Kα Cu Kα Formula C152H96Mn8N56Nb4O28 C152H126Mn8N56Nb4O23 FW / g mol Crystal system monoclinic monoclinic Space group P21/n P21/n a / Å (2) (1) b / Å (7) (3) c / Å (3) (1) β / º (2) (8) V / Å (4) 17368(2) Z 4 4 ρ / g cm Abs. coeff. / mm F(000) Crystal / mm θ range / º Refl. collected Rint Indep. refl Refl. I > 2σ(I) Parameters GOF on F R1 (refl. I > 2σ(I)) wr2 (all refl.) Completness Largest diff. peak/hole / e Å / /
5 Table S2. Details of the Continuous Shape Measure (CShM) Analysis a for the coordination spheres of Nb IV centres in 1 and 2, and for W IV centre in the tungsten(iv)-analogue of 1 {[Mn II (bpy)(h2o)2]2[w IV (CN)8] 6H2O}n (ref. 19). 1 2(Nb1) 2(Nb2) 2(Nb3) 2(Nb4) ref. 19 SDD SSAPR SBTPR a SDD, SSAPR, SBTPR - shape measure relatives to the triangular dodecahedron (DD), square antiprism (SAPR) and biaugmented trigonal prism (BTPR). When the respective shape measure parameter equals zero, the real geometry coincides with the idealized one. Figure S2. Fragments of structure of 1, showing interchain hydrogen bonding. 2,2 -bipyridine molecules and hydrogen atoms were omitted for clarity. Mn pink, Nb cyan, C gray, N blue, O red. 5
6 Figure S3. Fragments of structure of 1, showing intrachain hydrogen bonds. 2,2 -bipyridine molecules and hydrogen atoms were omitted for clarity. Mn pink, Nb cyan, C gray, N blue, O red. 6
7 Figure S4. Layers of crystallization water molecules between chains in 1. Only skeletons of the chains were pictured. Ellipsoids at 50% probability level. Mn pink, Nb cyan, C gray, N blue, O red. 7
8 Figure S5. Fragments of structure of 1, showing π-π stacking between the neighboring chains. Crystallization water molecules and hydrogen atoms omitted for clarity. Mn pink, Nb cyan, C gray, N blue, O red. 8
9 Figure S6. Autostereographic projection (A. Katrusiak, J. Mol. Graphics Modell., 2001, 19, ) of the crystal structure of compound 2. Hydrogen bonds are marked by cyan dotted lines. 9
10 Figure S7. Fragments of structure of 2, showing H-shaped hydrogen bonding patterns. Mn pink, Nb cyan, C gray, N blue, O red. 10
11 Figure S8. Fragments of structure of 2, showing intrachain hydrogen bonding interactions. Mn pink, Nb cyan, C gray, N blue, O red. 11
12 Figure S9. Fragments of structure of 2, showing π-π interactions between chains. Crystallization water molecules and hydrogen atoms were omitted for clarity. Mn pink, Nb cyan, C gray, N blue, O red. 12
13 Figure S10. Results of the AC magnetic susceptibility measurements for compound 1 (HAC = 1.5 Oe, HDC = 0 Oe). Figure S11. Results of the AC magnetic susceptibility measurements for compound 2 (HAC = 1.5 Oe, HDC = 0 Oe). 13
14 Figure S12. (a) χ -1 (T) dependence for 1 (black) and 2 (red) with Curie-Weiss fits in K range (dotted lines) and the best fits to the model described in the text in the K range (solid lines); (b) the scheme showing how the Mn2 Nb Mn2 Nb molecule has been closed into a loop in order to approximate the magnetic behaviour of an infinite Mn2 Nb chain at temperatures above 50 K. 14
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