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Syntheses, Crystal Structures and Magnetic Properties of Two Cyano-Bridged Two-Dimensional Assemblies [Fe(Salpn)]2 [Fe(CN)5NO] and [Fe(Salpn)]2[Ni(CN)4]

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Syntheses, Crystal Structures and Magnetic Properties of Two Cyano-Bridged Two-Dimensional Assemblies [Fe(Salpn)]2 [Fe(CN)5NO] and [Fe(Salpn)]2[Ni(CN)4] Transition Metal Chemistry 29: 100–106, 2004. 100 Ó 2004 Kluwer Academic Publishers. Printed in the Netherlands. Syntheses, crystal structures and magnetic properties of two cyano-bridged two-dimensional assemblies [Fe(salpn)]2 [Fe(CN)5NO] and [Fe(salpn)]2[Ni(CN)4] Xiao-Ping Shen and Zheng Xu* Coordination Chemistry Institute, State Key Laboratory of Coordination Chemistry, Nanjing University, Nanjing 210093, PR China Ai-Hua Yuan Department of Material and Environmental Engineering, East China Shipbuilding Institute, Zhenjiang 212003, PR China Zi-Xiang Huang State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian 350002, PR China Received 13 May 2003; accepted 07 July 2003 Abstract III II III II Two cyano-bridged assemblies, [Fe (salpn)]2[Fe (CN)5NO] (1) and [Fe (salpn)]2[Ni (CN)4] (2) [salpn ¼ N, N¢- 1,2-propylenebis(salicylideneiminato)dianion], have been prepared and structurally and magnetically characterized. 2) 2) + In each complex, [Fe(CN)5NO] or [Ni(CN)4] coordinates with four [Fe(salpn)] cations using four co-planar ) + 2) 2) CN ligands, whereas each [Fe(salpn)] links two [Fe(CN)5NO] or [Ni(CN)4] ions in the trans form, which II III results in a two-dimensional (2D) network consisting of pillow-like octanuclear [AM ACNAFe ANCA]4 units 2) (M ¼ Fe or Ni). In complex (1), the NO group of [Fe(CN)5NO] remains monodentate and the bond angle of FeIIANAO is 180.0°. The variable temperature magnetic susceptibilities, measured in the 5–300 K range, show weak intralayer antiferromagnetic interactions in both complexes with the intramolecular iron(III)ÁÁÁiron(III) exchange integrals of )0.017 cm)1 for (1) and –0.020 cm-1 for (2), respectively. Introduction been studied structurally and magnetically [11–16]. These complexes exhibit fascinating structures ranging In recent years, an enormous amount of research work from discrete entities to 3D extended networks, and has been devoted to the study of cyano-bridged coor- interesting magnetic properties, such as magnetic order- dination polymers due to their potential use as func- ing and high spin ground states. For example, the tional solid materials, such as catalysts, optical devices reaction between [M¢(BS)]+ (M¢ ¼ Mn, Fe; BS ¼ Schiff 3) as well as molecular-based magnets [1–5]. It is known base ligand) and [M(CN)6] (M ¼ Fe, Cr) has already that the cyano-bridged 3D bimetallic assemblies of the led to a variety of lattice structures depending on the Prussian Blue type, derived from hexacyanometalate nature of the Schiff base, the metal ion and the n) ions [M(CN)6] and simple transition metal ions, countercation etc., e.g., the discrete heptanuclear exhibit spontaneous magnetization at TC as high as complex [Cr{(CN)Mn(salen Æ H2O)}6][Cr(CN)6] Æ 6H2O 376 K, and interesting optoelectronic and magnetoop- [salen ¼ N,N¢-ethylenebis(salicylideneiminato)dianion] tical properties [6–10]. However, magneto-structural [17], the 1D chain complex [NEt4]2{Mn(acacen)} correlation of these high TC or TN compounds remains [Fe(CN)6] [acacen ¼ N,N¢-ethylenebis(acetylacetony- unclear because of the difficulty in obtaining single lideneaminato)dianion] [18], 2D network complexes crystals. Furthermore, the face-centred cubic structures [{Mn(saltmen)}4{Fe(CN)6}]ClO4 Æ H2O [saltmen ¼ N, (based on powder XRD results) usually possess low or N¢-(1,1,2,2-tetramethylethylene)bis(salicylideneiminato) no magnetic anisotropy. To overcome these problems, a dianion] [19] and [{Fe(salen)}3 {Fe(CN)6}(MeOH)2] Æ wide variety of hybrid Prussian Blue complexes assem- 3H2O [20]. They exhibit the ferromagnetic or antiferro- m) bled from cyanometalate building blocks [M(CN)n] magnetic interaction between adjacent paramagnetic (M ¼ Fe, Cr, Co, Mn, Mo and W etc.) and coordin- centers through the cyanide bridge. Recently, we have atively unsaturated transition metal complexes have prepared two new cyano-bridged coordination III II III polymers, [Fe (salpn)]2[Fe (CN)5NO] (1) and [Fe - II * Author for correspondence (salpn)]2[Ni (CN)4] (2) [salpn ¼ N,N¢-1,2-propylenebis 101 (salicylideneiminato) dianion], using the Schiff base Table 1. Crystallographic data for (1) and (2) complex cation [Fe(salpn)]+ as a template. Here we (1) (2) report the syntheses, structures and magnetic properties of the two 2D assemblies with neutral layers. Formula C39H32Fe3N10O5 C38H32Fe2N8NiO4 Formula weight 888.30 835.13 Crystal system Tetragonal Tetragonal Space group P 4/ncc P 4/ncc Experimental a(A˚ ) 14.3982 (1) 14.250 (2) b (A˚ ) 14.3982 (1) 14.250 (2) Physical measurements c (A˚ ) 18.3434 (1) 18.322 (4) V (A˚ 3) 3802.74(4) 3720.8 (11) Z44 Elemental analyses for C, H and N were performed with )3 Dc (g cm ) 1.552 1.491 a Perkin-Elmer 240C analyzer. Fe and Ni analyses were l (mm)1) 1.188 1.322 made on a Jarrell-Ash 1100 + 2000 inductively coupled Crystal size (mm3) 0.40 · 0.375 · 0.20 0.40 · 0.375 · 0.20 plasma quantometer. I.r. spectra were recorded on a h range (°) 2.00–25.97 2.22–25.97 Nicolet FT-170SX spectrometer with KBr pellets in the Reflections measured 3568 1357 4000–400 cm)1 region. Magnetic susceptibilities on Independent reflections 1841(Rint = 0.0969) 1355 (Rint = 0.0227) Final R indices R = 0.0698 R = 0.0571 crystalline samples were measured with a Quantum 1 1 [I >2r(I)] wR2 = 0.1474 wR2 = 0.1543 Design MPMS-5 SQUID susceptometer under an ap- Goodness-of-fit 0.931 0.962 plied magnetic field of 10 kOe in the 5–300 K range. Diamagnetic corrections were made using Pascal’s constants. Effective magnetic moments were calculated X-ray crystallography 1/2 using the equation leff ¼ 2.828(vM · T) , where vM is the magnetic susceptibility per formula unit. Diffraction data were collected at 293(2) K on Enraf- Nonius CAD4 and Rigaku AFC5R diffractometers for Syntheses (1) and (2), respectively, using graphite-monochromat- ˚ ed MoKa radiation (k ¼ 0.71073 A)withthex)2h scan All chemicals and solvents used for the synthesis were mode. The unit cell parameters were obtained by a least- reagent grade. The quadridentate Schiff base ligand squares refinement of the setting angles of 25 reflections H2salpn was prepared by mixing salicylaldehyde and with 11.92° < h < 13.90° for (1), and of 20 reflections 1,2-diaminopropane in a 2:1 molar ratio in MeOH with 15.60° < h < 19.62° for (2). The structures were according to the literature [21, 22]. [Fe(salpn)NO3] was solved by direct methods and refined by full matrix 2 prepared by mixing Fe(NO3)3 Æ 9H2O, H2salpn and least-squares techniques based on F . All non-hydrogen LiOH Æ H2O in a 1:1:1.5 molar ratio in MeOH according atoms were refined anisotropically and the sites of to the method reported previously [23]. hydrogen atoms were placed by the geometry. The unweighted and weighted agreement factors of the ) 2 [Fe(salpn)]2 [Fe(CN)5NO] (1) forms R1 ¼ S||F0| |Fc||/S|F0| and wR2 ¼ [S[w(F0 À 2 2 2 2 1/2 Well-shaped black crystals of (1) were obtained by slow Fc ) ]/S[w(F0 ) ]] were used. The weighting schemes 3 2 2 2 diffusion of a dark brown MeOH solution (15 cm )of are w ¼ 1/[r (F0 ) + (0.0805P) + 0.0000P] (1) and 1/ 2 2 2 2 [Fe(salpn)NO3] (0.15 mmol) and an aqueous solution [r (F0 )+(0.0976P) + 0.0000P] (2), where P ¼ (F0 + 3 2 (15 cm )ofNa2[Fe(CN)5NO] Æ 2H2O (0.15 mmol) 2Fc )/3. All computations were carried out using the through a U-tube containing silica gel at room temper- SHELXTL programs. The crystallographic data are ature. The resulting crystals were collected, washed with summarized in Table 1. H2O and MeOH respectively, and dried in air. (Found: C, 52.2; H, 3.75; N, 16.1; Fe, 19. C39H32Fe3N10O5 calcd.: C, 52.7; H, 3.6; N, 15.8; Fe, 18.9%.) I.r. mmax Results and discussion (cm)1): 2161(s), 1925(vs), 1629(vs), 1596(m), 1548(m), 1468(w), 1446(m), 1395(w), 1322(w), 1293(vs), 1149(w), Spectroscopic studies 900(m), 800(m), 768(s), 615(m). Relevant i.r. spectral data for complexes (1) and (2) are [Fe(salpn)]2[Ni(CN)4] (2) given in the Experimental section. The formation of The complex was prepared as black single crystals in a cyanide bridges in both complexes is evidenced by the way similar to that of complex (1), except for the use of m(CBN) stretching bands in the 2000–2200 cm)1 region. )1 K2[Ni(CN)4] Æ H2O (0.15 mmol) instead of Na2[Fe(CN)5- Complex (1) shows a sharp band at 2161 cm , which NO] Æ 2H2O. (Found: C, 55.1; H, 3.6; N, 13.3; Fe, 13.5; can be attributed to the intermetallic bridging m(CB N), Ni, 7.1. C38H32Fe2N8NiO4 calcd.: C, 54.65; H, 3.9; N, as observed for other cyano-bridged complexes contain- )1 13.4; Fe, 13.4; Ni, 7.0%.) I.r. mmax (cm ): 2155(s), ing nitroprusside. The result also suggests that nearly all 2) 2133(s), 1628(vs), 1596(s), 1544(s), 1469(m), 1445(s), cyanide groups in [Fe(CN)5NO] are involved in 1394(m), 1326(m), 1298(s), 1199(m), 1148(m), 903(m), coordination. A very strong band at 1925 cm)1 for (1) 802(m), 761(s), 615(m), 449(m).
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