Acta Cryst. (2008). E64, i11-i12 [ doi:10.1107/S1600536807068869 ]
![[mu]](/logos/entities/mu_rmgif.gif)
-cyanido-manganese(II)iron(III)] pentahydrate]The structure of the title compound, MnII[FeIII(CN)6]2/3·5H2O, features a face-centered cubic -Mn-NC-Fe- framework with both Mn and Fe having site symmetry m
m. Since one-third of the [Fe(CN)6]3- units are missing for a given formula in order to maintain charge neutrality, each Mn atom around such a vacancy is coordinated not only by the N atoms of the CN groups but also by the O atoms of the ligand water molecules. In addition to ligand water molecules, two types of non-coordinated water molecules, so-called zeolitic water molecules, exist in the interstitial sites of the -Mn-NC-Fe- framework. The positions of the O atoms of the zeolitic water molecules are fixed by the linkage via hydrogen bonds between ligand water and zeolitic water molecules. The structure is related to a recently reported rubidium manganese hexacyanoferrate. Site occupancy factors for Fe, C, N are 0.67; for two O atoms the value is 0.83 and for one O atom is 0.17.
Single crystals of Mn[Fe(CN)6]2/3.5H2O were prepared by slow diffusion of aqueous solutions of MnCl2.5H2O (0.1 mmol) and K3[Fe(CN)6] (0.07 mmol) at 40 °C. After one month, dark brown block-shaped crystals were obtained. Elemental analysis of Mn and Fe was performed using inductively coupled plasma mass spectrometry (ICP-MS). The observed ratio of metal ions was Mn:Fe = 0.67:1.00. The density measured by the flotation method in toluene and tetrabromoethane was 1.64 (1) g cm-3, which is consistent with the expected value of 1.63 g cm-3 calculated considering the lattice constant of 10.480 Å at 293 K. The CN stretching vibrations are observed at 2151 cm-1 in the IR spectrum.
The H atoms of the water molecules could not be located. The site occupancy factors for Fe, C, and N were constrained to 2/3. The O1 atoms of the coordinated water molecules were located in a difference Fourier map and the site occupancy factor for O1 was constrained to 1/12, according to the formula of the crystal. The obtained anisotropic displacement factor of the N atom is rather large, but this is understood by the rotational vibration of CN around Fe—Mn.
Data collection: PROCESS-AUTO (Rigaku, 1998); cell refinement: PROCESS-AUTO (Rigaku, 1998); data reduction: CrystalStructure (Rigaku, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: VESTA (Momma & Izumi, 2006); software used to prepare material for publication: CrystalStructure (Rigaku, 2007).
![[Figure 1]](./sq2003fig1thm.gif)
| Fig. 1. (a) Three dimensional crystal structure of Mn[Fe(CN)6]2/3.5H2O, showing the distribution of zeolitic water molecules (teal spheres). The –Mn–NC–Fe– framework is described in stick form for clarity. Blue, red, dark gray, light gray and teal represent Fe, Mn, C, N and O atoms, respectively. (b) Projection of the structure in the ab plane. The value g is the occupancy for each atom. [Symmetry codes: (i) 1/2 - z, 1/2 - x, 1 - y; (ii) z, -x, 1 - y; (iii) z, -y, x; (iv) z, 1/2 - x, 1/2 + y.] |
| Mn[Fe(CN)6]0.6667·5H2O | Z = 4 |
| Mr = 286.50 | F000 = 577.68 |
| Cubic, Fm3m | Dx = 1.699 Mg m−3 Dm = 1.64 (1) Mg m−3 Dm measured by flotation in toluene and tetrabromomethane |
| Hall symbol: -F 4 2 3 | Mo Kα radiation λ = 0.71075 Å |
| a = 10.3859 (13) Å | Cell parameters from 3216 reflections |
| b = 10.3859 (13) Å | θ = 5.6–45.1º |
| c = 10.3859 (13) Å | µ = 2.02 mm−1 |
| α = 90º | T = 90 (1) K |
| β = 90º | Block, brown |
| γ = 90º | 0.25 × 0.20 × 0.15 mm |
| V = 1120.3 (2) Å3 |
| Rigaku R-AXIS RAPID diffractometer | 268 reflections with F2 > 2σ(F2) |
| Detector resolution: 10.00 pixels mm-1 | Rint = 0.032 |
| ω scans | θmax = 45.1º |
| Absorption correction: multi-scan (ABSCOR; Higashi, 1995) | h = −20→20 |
| Tmin = 0.655, Tmax = 0.739 | k = −20→20 |
| 15777 measured reflections | l = −20→20 |
| 278 independent reflections |
| Refinement on F2 | w = 1/[σ2(Fo2) + (0.0526P)2 + 2.6431P] where P = (Fo2 + 2Fc2)/3 |
| R[F2 > 2σ(F2)] = 0.047 | (Δ/σ)max < 0.001 |
| wR(F2) = 0.136 | Δρmax = 0.59 e Å−3 |
| S = 1.37 | Δρmin = −1.41 e Å−3 |
| 278 reflections | Extinction correction: SHELXL97 (Sheldrick, 1997) |
| 21 parameters | Extinction coefficient: 0.002 (2) |
| H-atom parameters not defined |
| Mn[Fe(CN)6]0.6667·5H2O | γ = 90º |
| Mr = 286.50 | V = 1120.3 (2) Å3 |
| Cubic, Fm3m | Z = 4 |
| a = 10.3859 (13) Å | Mo Kα |
| b = 10.3859 (13) Å | µ = 2.02 mm−1 |
| c = 10.3859 (13) Å | T = 90 (1) K |
| α = 90º | 0.25 × 0.20 × 0.15 mm |
| β = 90º |
| Rigaku R-AXIS RAPID diffractometer | 278 independent reflections |
| Absorption correction: multi-scan (ABSCOR; Higashi, 1995) | 268 reflections with F2 > 2σ(F2) |
| Tmin = 0.655, Tmax = 0.739 | Rint = 0.032 |
| 15777 measured reflections |
| R[F2 > 2σ(F2)] = 0.047 | ? restraints |
| wR(F2) = 0.136 | H-atom parameters not defined |
| S = 1.37 | Δρmax = 0.59 e Å−3 |
| 278 reflections | Δρmin = −1.41 e Å−3 |
| 21 parameters |
Refinement. Refinement was performed using all reflections. The weighted R-factor (wR) and goodness of fit (S) are based on F2. R-factor (gt) are based on F. The threshold expression of F2 > 2.0 σ(F2) is used only for calculating R-factor (gt). |
| x | y | z | Uiso*/Ueq | Occ. (<1) | |
| Fe1 | 0.5000 | 0.5000 | 0.0000 | 0.0176 (2) | 0.6667 |
| Mn1 | 0.5000 | 0.5000 | 0.5000 | 0.0183 (2) | |
| O1 | 0.4576 (10) | 0.4576 (10) | 0.2922 (11) | 0.036 (3) | 0.0833 |
| O2 | 0.7500 | 0.2500 | 0.2500 | 0.096 (6) | 0.8333 |
| O3 | 0.6550 (16) | 0.3450 (16) | 0.1550 (16) | 0.054 (6) | 0.1667 |
| N1 | 0.5000 | 0.5000 | 0.2973 (12) | 0.086 (3) | 0.6667 |
| C1 | 0.5000 | 0.5000 | 0.1847 (8) | 0.064 (2) | 0.6667 |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Fe1 | 0.0176 (2) | 0.0176 (2) | 0.0176 (2) | 0.0000 | 0.0000 | 0.0000 |
| Mn1 | 0.0183 (2) | 0.0183 (2) | 0.0183 (2) | 0.0000 | 0.0000 | 0.0000 |
| O1 | 0.052 (5) | 0.052 (5) | 0.006 (3) | −0.026 (5) | −0.002 (2) | −0.002 (2) |
| O2 | 0.096 (6) | 0.096 (6) | 0.096 (6) | 0.0000 | 0.0000 | 0.0000 |
| O3 | 0.054 (6) | 0.054 (6) | 0.054 (6) | −0.018 (6) | 0.018 (6) | −0.018 (6) |
| N1 | 0.114 (5) | 0.114 (5) | 0.030 (3) | 0.0000 | 0.0000 | 0.0000 |
| C1 | 0.085 (4) | 0.085 (4) | 0.023 (2) | 0.0000 | 0.0000 | 0.0000 |
| Fe1—C1 | 1.918 (8) | Mn1—O1ix | 2.247 (12) |
| Fe1—C1i | 1.918 (8) | Mn1—O1xiii | 2.247 (12) |
| Fe1—C1ii | 1.918 (8) | Mn1—O1x | 2.247 (12) |
| Fe1—C1iii | 1.918 (8) | Mn1—O1xiv | 2.247 (12) |
| Fe1—C1iv | 1.918 (8) | Mn1—O1xv | 2.247 (12) |
| Fe1—C1v | 1.918 (8) | Mn1—O1xvi | 2.247 (12) |
| Mn1—N1 | 2.105 (13) | Mn1—O1xvii | 2.247 (12) |
| Mn1—N1vi | 2.105 (13) | Mn1—O1xviii | 2.247 (12) |
| Mn1—N1vii | 2.105 (13) | Mn1—O1xix | 2.247 (12) |
| Mn1—N1viii | 2.105 (13) | Mn1—O1xx | 2.247 (12) |
| Mn1—N1ix | 2.105 (13) | Mn1—O1xxi | 2.247 (12) |
| Mn1—N1x | 2.105 (13) | Mn1—O1xxii | 2.247 (12) |
| N1—C1 | 1.169 (15) | Mn1—O1xxiii | 2.247 (12) |
| Mn1—O1 | 2.247 (12) | Mn1—O1xxiv | 2.247 (12) |
| Mn1—O1vi | 2.247 (12) | Mn1—O1xxv | 2.247 (12) |
| Mn1—O1vii | 2.247 (12) | Mn1—O1xxvi | 2.247 (12) |
| Mn1—O1viii | 2.247 (12) | Mn1—O1xxvii | 2.247 (12) |
| Mn1—O1xi | 2.247 (12) | Mn1—O1xxviii | 2.247 (12) |
| Mn1—O1xii | 2.247 (12) | ||
| C1—Fe1—C1i | 180.0000 | N1ix—Mn1—N1x | 90.0000 |
| C1—Fe1—C1ii | 90.0000 | Mn1—N1—C1 | 180.0000 |
| C1—Fe1—C1iii | 90.0000 | Fe1—C1—N1 | 180.0000 |
| C1—Fe1—C1iv | 90.0000 | O1—Mn1—O1vi | 65.5 (4) |
| C1—Fe1—C1v | 90.0000 | O1—Mn1—O1vii | 65.5 (4) |
| C1i—Fe1—C1ii | 90.0000 | O1—Mn1—O1viii | 147.8 (3) |
| C1i—Fe1—C1iii | 90.0000 | O1—Mn1—O1xi | 87.8 (4) |
| C1i—Fe1—C1iv | 90.0000 | O1—Mn1—O1xii | 87.8 (4) |
| C1i—Fe1—C1v | 90.0000 | O1—Mn1—O1ix | 109.8 (4) |
| C1ii—Fe1—C1iii | 180.0000 | O1—Mn1—O1xiii | 92.2 (4) |
| C1ii—Fe1—C1iv | 90.0000 | O1—Mn1—O1x | 109.8 (4) |
| C1ii—Fe1—C1v | 90.0000 | O1—Mn1—O1xiv | 157.4 (3) |
| C1iii—Fe1—C1iv | 90.0000 | O1—Mn1—O1xv | 92.2 (4) |
| C1iii—Fe1—C1v | 90.0000 | O1—Mn1—O1xvi | 157.4 (3) |
| C1iv—Fe1—C1v | 180.0000 | O1—Mn1—O1xvii | 180.0 (5) |
| N1—Mn1—N1vi | 90.0000 | O1—Mn1—O1xviii | 114.5 (4) |
| N1—Mn1—N1vii | 90.0000 | O1—Mn1—O1xix | 114.5 (4) |
| N1—Mn1—N1viii | 180.0000 | O1—Mn1—O1xxi | 92.2 (4) |
| N1—Mn1—N1ix | 90.0000 | O1—Mn1—O1xxii | 92.2 (4) |
| N1—Mn1—N1x | 90.0000 | O1—Mn1—O1xxiii | 70.2 (4) |
| N1vi—Mn1—N1vii | 90.0000 | O1—Mn1—O1xxiv | 87.8 (4) |
| N1vi—Mn1—N1viii | 90.0000 | O1—Mn1—O1xxv | 70.2 (4) |
| N1vi—Mn1—N1ix | 180.0000 | O1—Mn1—O1xxvii | 87.8 (4) |
| N1vi—Mn1—N1x | 90.0000 | O1—Mn1—N1vi | 78.69 (14) |
| N1vii—Mn1—N1viii | 90.0000 | O1—Mn1—N1vii | 78.19 (14) |
| N1vii—Mn1—N1ix | 90.0000 | O1—Mn1—N1viii | 163.90 (14) |
| N1vii—Mn1—N1x | 180.0000 | O1—Mn1—N1ix | 101.31 (14) |
| N1viii—Mn1—N1ix | 90.0000 | O1—Mn1—N1x | 101.31 (14) |
| N1viii—Mn1—N1x | 90.0000 |
| Symmetry codes: (i) x, y, −z; (ii) y, z+1/2, x−1/2; (iii) y, −z+1/2, −x+1/2; (iv) z+1/2, x, y−1/2; (v) −z+1/2, x, −y+1/2; (vi) y, z, x; (vii) z, x, y; (viii) x, y, −z+1; (ix) y, −z+1, −x+1; (x) −z+1, x, −y+1; (xi) y, z, −x+1; (xii) z, x, −y+1; (xiii) z, −x+1, −y+1; (xiv) −x+1, y, −z+1; (xv) −y+1, z, −x+1; (xvi) x, −y+1, −z+1; (xvii) −x+1, −y+1, −z+1; (xviii) −y+1, −z+1, −x+1; (xix) −z+1, −x+1, −y+1; (xx) −x+1, −y+1, z; (xxi) −y+1, −z+1, x; (xxii) −z+1, −x+1, y; (xxiii) −y+1, z, x; (xxiv) −z+1, x, y; (xxv) z, −x+1, y; (xxvi) x, −y+1, z; (xxvii) y, −z+1, x; (xxviii) −x+1, y, z. |
| Fe1—C1 | 1.918 (8) | N1—C1 | 1.169 (15) |
| Mn1—N1 | 2.105 (13) | Mn1—O1 | 2.247 (12) |
| O1—Mn1—O1i | 87.8 (4) | O1—Mn1—N1iv | 78.69 (14) |
| O1—Mn1—O1ii | 157.4 (3) | O1—Mn1—N1v | 163.90 (14) |
| O1—Mn1—O1iii | 180.0 (5) |
| Symmetry codes: (i) y, z, −x+1; (ii) −x+1, y, −z+1; (iii) −x+1, −y+1, −z+1; (iv) y, z, x; (v) x, y, −z+1. |
This research was supported in part by a Grant for the Global COE Program for Chemistry Innovation, a Grant-in-Aid for Scientific Research in Priority Area `Chemistry of Coordination Space', a Grant-in-Aid for Scientific Research (B), and a Grant-in-Aid for Exploratory Research from the Ministry of Education, Culture, Sports, Science, and Technology of Japan, the Asahi Glass Foundation, Iketani Science and Technology Foundation, Inamori Foundation, the Kurata Memorial Hitachi Science and Technology Foundation, the Murata Science Foundation and the Yamada Science Foundation. [Could the text be clarified by giving the relevant funding body or bodies after each grant?]
Egan, L., Kamenev, K., Papanikolaou, D., Takabayashi, Y. & Margadonna, S. (2006). J. Am. Chem. Soc. 128, 6034–6035.
Ferlay, S., Mallah, T., Ouahès, R., Veillet, P. & Verdaguer, M. (1995). Nature (London), 378, 701–703.
Gadet, V., Mallah, T., Castro, I. & Verdaguer, M. (1992). J. Am. Chem. Soc. 114, 9213–9214.
Güdel, H. U., Stucki, H. & Ludi, A. (1973). Inorg. Chim. Acta, 7, 121–124.
Hatlevik, Ø., Buschmann, W. E., Zhang, J., Manson, J. L. & Miller, J. S. (1999). Adv. Mater. 11, 914–918.
Higashi, T. (1995). ABSCOR. Rigaku Corporation, Tokyo, Japan.
Holmes, S. M. & Girolami, G. S. (1999). J. Am. Chem. Soc. 121, 5593–5594.
Kato, K., Moritomo, Y., Takata, M., Sakata, M., Umekawa, M., Hamada, N., Ohkoshi, S., Tokoro, H. & Hashimoto, K. (2003). Phys. Rev. Lett. 91, 2555021–2555024.
Ludi, A. & Güdel, H. U. (1973). Struct. Bonding (Berlin), 14, 1–21.
Ludi, A., Güdel, H. U. & Rüegg, M. (1970). Inorg. Chem. 9, 2224–2227.
Margadonna, S., Prassides, K. & Fitch, A. N. (2004). J. Am. Chem. Soc. 126, 15390–15391.
Momma, K. & Izumi, F. (2006). IUCr Commission on Crystallographic Computing Newsletter, 130, 106-119.
Ohkoshi, S., Arai, K., Sato, Y. & Hashimoto, K. (2004). Nat. Mater. 3, 857–861.
Ohkoshi, S. & Hashimoto, K. (2001). J. Photochem. Photobiol. Photochem. Rev. C2, 71–88.
Ohkoshi, S., Matsuda, T., Tokoro, H. & Hashimoto, K. (2005). Chem. Mater. 17, 81–84.
Ohkoshi, S., Mizuno, M., Hung, G. J. & Hashimoto, K. (2000). J. Phys. Chem. B, 104, 9365–9367.
Ohkoshi, S., Yorozu, S., Sato, O., Iyoda, T., Fujishima, A. & Hashimoto, K. (1997). Appl. Phys. Lett. 70, 1040–1042.
Rigaku (1998). PROCESS-AUTO. Rigaku Corporation, Tokyo, Japan.
Rigaku (2007). CrystalStructure. Version 3.80. Rigaku Corporation, Tokyo, Japan, and Rigaku Americas, The Woodlands, Texas, USA.
Sato, O., Iyoda, T., Fujishima, A. & Hashimoto, K. (1996). Science, 272, 704–705.
Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany.
Tokoro, H., Ohkoshi, S. & Hashimoto, K. (2003). Appl. Phys. Lett. 82, 1245–1247.
Tokoro, H., Ohkoshi, S., Matsuda, T. & Hashimoto, K. (2004). Inorg. Chem. 43, 5231–5236.
Tokoro, H., Shiro, M., Hashimoto, K. & Ohkoshi, S. (2007). Z. Anorg. Allg. Chem. 633, 1134–1136.
Zeigler, B., Witzel, M., Schwarten, M. & Babel, D. (1999). Z. Naturforsch. Teil B, 54, 870–876.
In the last decade, various interesting magnetic functionalities have been reported with Prussian blue analogs, e.g., high Curie temperatures (TC) (Ferlay et al., 1995; Holmes & Girolami, 1999; Hatlevik et al., 1999; Ohkoshi et al., 2000), humidity-response (Ohkoshi et al., 2004), photomagnetism (Ohkoshi & Hashimoto, 2001; Sato et al., 1996; Ohkoshi et al.,1997), and zero thermal expansion (Margadonna et al., 2004). Prussian blue analogs have two types of crystal structures, MA[MB(CN)6]2/3.zH2O (Ludi et al., 1970; Ludi & Güdel, 1973; Güdel et al., 1973) and AMA[MB(CN)6] (Gadet et al., 1992; Zeigler et al., 1999; Kato et al., 2003), where MA and MB are transition metal ions and A is an alkali metal ion. Recently, rubidium manganese hexacyanoferrate, RbxMn[Fe(CN)6](x + 2)/3.zH2O, has received attention due to its various functionalities such as a charge-transfer phase transition (Tokoro et al., 2004; Ohkoshi et al., 2005), a pressure-induced magnetic pole inversion (Egan et al., 2006), and a photomagnetic effect (Tokoro et al., 2003). Although the crystal structure of rubidium manganese hexacyanoferrate was determined (Kato et al., 2003; Tokoro et al., 2007), the structure of manganese hexacyanoferrate of MA[MB(CN)6]2/3.zH2O has not been determined yet. In this work, we successfully synthesized a single-crystal of Mn[Fe(CN)6]2/3.5H2O and analyzed the crystal structure.
The crystal structure of the title compound consists of MnII and FeIII with cyanide bridges to form a three-dimensional face-centered cubic structure (space group; Fm3m), containing ligand water and zeolitic water molecules (Fig. 1). Fe, Mn, C, and N atoms occupy the positions 4a (0, 0, 0), 4 b (1/2, 1/2, 1/2), 24 e (0.1847 (8), 0,0), and 24 e (0.2973 (12), 0, 0), respectively. The Fe atoms are coordinated to six C atoms with octahedral geometries. On the other hand, the Mn atoms are coordinated to four N atoms and two O1 atoms of ligand water, since there are vacancies of 1/3 × [Fe(CN)6]3- to maintain charge neutrality. The O1 atoms occupy the 96k (0.4576 (10), 0.4576 (10), 0.2922 (11)) positions with occupancy of 1/12. The coordination geometry in the MnNxO6 - x (x = 0–5) moiety is octahedral with some potentially large distortions [O1—Mn—N bond angles of 78.19 (14)°, and 163.9 (2)°] due to the location of the disordered O1 water molecule. The oxygen atoms (O2 and O3) of zeolitic waters occupy 8c (1/4, 1/4, 1/4) positions with occupancy of 5/6 and 32f (0.1550 (16), 0.1550 (16), 0.1550 (16)) positions with occupancy of 1/6. The contact distances of 3.081 (11), 2.76 (2), 2.79 (2) Å between O1—O2i, O1—O3, and O3—O3ii [Symmetry codes: (i) 1 - x, y, z; (ii) 1 - z, 1 - x, y], respectively, suggest the existence of hydrogen bonds.
The structure of the title compound differs from that of the rubidium phase in the position of the O1 atom of the ligand water. This atom occupies the 96k position in Mn[Fe(CN)6]2/3.5H2O and the 24 e position in Rb0.61Mn[Fe(CN)6]0.87.1.7H2O (Tokoro et al., 2007). This difference may be explained by the hydrogen bonding between ligand water and zeolitic water in the title compound. The O2 atom of the zeolitic water exists on the 8c (1/4, 1/4, 1/4) position in Mn[Fe(CN)6]2/3.5H2O. The shortest length between the 8c and 24 e positions is 3.67 Å which is rather far to construct a hydrogen bond. In our refinement with the O1 atom in the 96k position, the distance of 3.081 (11) Å between O1 and O2i [Symmetry code: (i) 1 - x, y, z] is acceptable as a hydrogen bond. By contrast, in Rb0.61Mn[Fe(CN)6]0.87.1.7H2O, since the Rb cation is contained in the channels between the –Mn–NC–Fe– framework and the amount of vacant space is thus less than in Mn[Fe(CN)6]2/3.5H2O, the O2 atom of zeolitic water does not exist on the 8c position in the Rb compound, so no similar O1···O2 interaction occurs.