Poly[[hexa-μ-cyanido-manganese(II)iron(III)] penta-hydrate].

The structure of the title compound, Mn(II)[Fe(III)(CN)(6)](2/3)·5H(2)O, features a face-centered cubic -Mn-NC-Fe- framework with both Mn and Fe having site symmetry mm. 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 mol-ecules. In addition to ligand water mol-ecules, two types of non-coordinated water mol-ecules, so-called zeolitic water mol-ecules, exist in the inter-stitial sites of the -Mn-NC-Fe- framework. The positions of the O atoms of the zeolitic water mol-ecules are fixed by the linkage via hydrogen bonds between ligand water and zeolitic water mol-ecules. The structure is related to a recently reported rubidium manganese hexa-cyano-ferrate. 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.

Related literature

For structure and properties of the related rubidium manganese hexa­cyano­ferrate, see: Kato et al. (2003 ▶); Tokoro et al. (2007 ▶). For general background on Prussian blue compounds, see: Ludi & Güdel (1973 ▶). For related literature, see: Egan et al. (2006 ▶); Ferlay et al. (1995 ▶); Güdel et al. (1973 ▶); Gadet et al. (1992 ▶); Hatlevik et al. (1999 ▶); Holmes & Girolami (1999 ▶); Ludi et al. (1970 ▶); Margadonna et al. (2004 ▶); Ohkoshi & Hashimoto (2001 ▶); Ohkoshi et al. (1997 ▶, 2000 ▶, 2004 ▶, 2005 ▶); Sato et al. (1996 ▶); Tokoro et al. (2003 ▶, 2004 ▶); Zeigler et al. (1999 ▶).

Experimental

Crystal data

Mn[Fe(CN)6]2/3·5H2O

M = 286.50

Cubic,

a = 10.3859 (13) Å

V = 1120.3 (2) Å3

Z = 4

Mo Kα radiation

μ = 2.02 mm−1

T = 90 (1) K

0.25 × 0.20 × 0.15 mm

Data collection

Rigaku R-AXIS RAPID diffractometer

Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ▶) T min = 0.655, T max = 0.739

15777 measured reflections

278 independent reflections

268 reflections with F 2 > 2σ(F 2)

R int = 0.032

Refinement

R[F 2 > 2σ(F 2)] = 0.047

wR(F 2) = 0.136

S = 1.37

278 reflections

21 parameters

H-atom parameters not defined

Δρmax = 0.59 e Å−3

Δρmin = −1.41 e Å−3

Data collection: PROCESS-AUTO (Rigaku, 1998 ▶); cell refinement: PROCESS-AUTO; data reduction: CrystalStructure (Rigaku, 2007 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: VESTA (Momma & Izumi, 2006 ▶); software used to prepare material for publication: CrystalStructure.

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536807068869/sq2003sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536807068869/sq2003Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Mn[Fe(CN)6]0.6667·5H2O	Z = 4
Mr = 286.50	F000 = 577.68
Cubic, Fm3m	Dx = 1.699 Mg m−3Dm = 1.64 (1) Mg m−3Dm 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

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

Fe1—C1	1.918 (8)
Mn1—N1	2.105 (13)
N1—C1	1.169 (15)
Mn1—O1	2.247 (12)

O1—Mn1—O1i	87.8 (4)
O1—Mn1—O1ii	157.4 (3)
O1—Mn1—O1iii	180
O1—Mn1—N1iv	78.69 (14)
O1—Mn1—N1v	163.90 (14)

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) .