Poly[[diaqua-hexa-μ-cyanido-cerium(III)ferrate(III)] dihydrate].

In the structure of the title complex, {[CeFe(CN)(6)(H(2)O)(2)]·2H(2)O}(n), the Ce(III) and Fe(III) atoms exhibit square anti-prismatic [CeN(6)(H(2)O)(2)] (site symmetry m2m) and octahedral [FeC(6)] (site symmetry 2/m) coordination geometries, respectively. The metal atoms are linked alternately through the cyanide groups, forming a three-dimensional framework in which the {Ce(2)Fe(2)(CN)(4)} puckered square unit is the basic building block. The crystal packing is enforced by O-H⋯O and O-H⋯N hydrogen bonds, including the uncoordinated water molecule which is located on a mirror plane.

Related literature

For general background to hexa­cyanido­metalate(III)-based lanthanide complexes, see: Andruh et al. (2009 ▶). For related structures, see: Gramlich et al. (1990 ▶); Petter et al. (1989 ▶).

Experimental

Crystal data

[CeFe(CN)6(H2O)2]·2H2O

M = 424.15

Orthorhombic,

a = 7.3806 (11) Å

b = 12.7836 (19) Å

c = 13.619 (2) Å

V = 1285.0 (3) Å3

Z = 4

Mo Kα radiation

μ = 4.64 mm−1

T = 173 K

0.22 × 0.20 × 0.17 mm

Data collection

Bruker APEXII diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2004 ▶) T min = 0.428, T max = 0.506

5578 measured reflections

831 independent reflections

785 reflections with I > 2σ(I)

R int = 0.088

Refinement

R[F 2 > 2σ(F 2)] = 0.037

wR(F 2) = 0.098

S = 1.06

831 reflections

51 parameters

H-atom parameters constrained

Δρmax = 1.08 e Å−3

Δρmin = −2.69 e Å−3

Data collection: APEX2 (Bruker, 2004 ▶); cell refinement: SAINT (Bruker, 2004 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: DIAMOND (Brandenburg, 2006 ▶); software used to prepare material for publication: SHELXTL (Sheldrick, 2008 ▶).

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812016911/rz2741sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812016911/rz2741Isup2.hkl

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

[CeFe(CN)6(H2O)2]·2H2O	F(000) = 808
Mr = 424.15	Dx = 2.193 Mg m−3
Orthorhombic, Cmcm	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2c 2	Cell parameters from 3234 reflections
a = 7.3806 (11) Å	θ = 3.0–27.4°
b = 12.7836 (19) Å	µ = 4.64 mm−1
c = 13.619 (2) Å	T = 173 K
V = 1285.0 (3) Å3	Block, red
Z = 4	0.22 × 0.20 × 0.17 mm

Bruker APEXII diffractometer	831 independent reflections
Radiation source: fine-focus sealed tube	785 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.088
phi and ω scans	θmax = 27.4°, θmin = 3.0°
Absorption correction: multi-scan (SADABS; Bruker, 2004)	h = −9→9
Tmin = 0.428, Tmax = 0.506	k = −16→16
5578 measured reflections	l = −17→17

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.037	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.098	H-atom parameters constrained
S = 1.06	w = 1/[σ2(Fo2) + (0.0233P)2 + 48.4374P] where P = (Fo2 + 2Fc2)/3
831 reflections	(Δ/σ)max < 0.001
51 parameters	Δρmax = 1.08 e Å−3
0 restraints	Δρmin = −2.69 e Å−3

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

	x	y	z	Uiso*/Ueq
C1	1.0000	0.1368 (7)	0.0590 (7)	0.0204 (18)
C2	1.3141 (9)	0.4530 (5)	0.4106 (5)	0.0208 (13)
Ce1	1.0000	0.32343 (4)	0.2500	0.0064 (2)
Fe1	1.0000	0.0000	0.0000	0.0164 (4)
N1	1.0000	0.2186 (6)	0.0965 (6)	0.0254 (17)
N2	1.2003 (9)	0.4229 (4)	0.3582 (5)	0.0285 (13)
O1	0.7401 (11)	0.2171 (6)	0.2500	0.0347 (17)
H1A	0.7129	0.1879	0.3042	0.052*
O2	0.5000	0.1562 (6)	0.3993 (6)	0.0342 (17)
H2A	0.5000	0.0914	0.4131	0.051*
H2B	0.5000	0.1922	0.4518	0.051*

	U11	U22	U33	U12	U13	U23
C1	0.022 (5)	0.022 (4)	0.017 (4)	0.000	0.000	−0.001 (4)
C2	0.021 (3)	0.021 (3)	0.021 (3)	−0.002 (2)	0.000 (3)	−0.003 (2)
Ce1	0.0053 (3)	0.0080 (3)	0.0058 (3)	0.000	0.000	0.000
Fe1	0.0150 (8)	0.0176 (8)	0.0164 (9)	0.000	0.000	0.0002 (6)
N1	0.025 (4)	0.026 (4)	0.025 (4)	0.000	0.000	−0.002 (3)
N2	0.026 (3)	0.033 (3)	0.026 (3)	−0.005 (2)	−0.001 (3)	−0.002 (2)
O1	0.029 (4)	0.049 (4)	0.026 (4)	−0.015 (4)	0.000	0.000
O2	0.035 (4)	0.036 (4)	0.032 (4)	0.000	0.000	0.002 (3)

C1—N1	1.163 (12)	Ce1—N1	2.483 (8)
C1—Fe1	1.925 (9)	Ce1—N1iv	2.483 (8)
C2—N2	1.167 (9)	Fe1—C1v	1.925 (9)
C2—Fe1i	1.930 (7)	Fe1—C2vi	1.930 (7)
Ce1—O1	2.351 (7)	Fe1—C2vii	1.930 (7)
Ce1—O1ii	2.351 (7)	Fe1—C2viii	1.930 (7)
Ce1—N2	2.444 (6)	Fe1—C2ix	1.930 (7)
Ce1—N2iii	2.444 (6)	O1—H1A	0.8503
Ce1—N2ii	2.444 (6)	O2—H2A	0.8500
Ce1—N2iv	2.444 (6)	O2—H2B	0.8500
N1—C1—Fe1	178.7 (8)	N2—Ce1—N1iv	76.9 (2)
N2—C2—Fe1i	178.3 (6)	N2iii—Ce1—N1iv	142.05 (16)
O1—Ce1—O1ii	109.4 (4)	N2ii—Ce1—N1iv	76.9 (2)
O1—Ce1—N2	142.58 (15)	N2iv—Ce1—N1iv	142.05 (16)
O1ii—Ce1—N2	78.9 (2)	N1—Ce1—N1iv	114.7 (4)
O1—Ce1—N2iii	78.9 (2)	C1v—Fe1—C1	180.0 (5)
O1ii—Ce1—N2iii	142.58 (15)	C1v—Fe1—C2vi	91.1 (3)
N2—Ce1—N2iii	117.3 (3)	C1—Fe1—C2vi	88.9 (3)
O1—Ce1—N2ii	78.9 (2)	C1v—Fe1—C2vii	88.9 (3)
O1ii—Ce1—N2ii	142.58 (15)	C1—Fe1—C2vii	91.1 (3)
N2—Ce1—N2ii	74.4 (3)	C2vi—Fe1—C2vii	180.0 (4)
N2iii—Ce1—N2ii	74.2 (3)	C1v—Fe1—C2viii	88.9 (3)
O1—Ce1—N2iv	142.58 (15)	C1—Fe1—C2viii	91.1 (3)
O1ii—Ce1—N2iv	78.9 (2)	C2vi—Fe1—C2viii	89.4 (4)
N2—Ce1—N2iv	74.2 (3)	C2vii—Fe1—C2viii	90.6 (4)
N2iii—Ce1—N2iv	74.4 (3)	C1v—Fe1—C2ix	91.1 (3)
N2ii—Ce1—N2iv	117.3 (3)	C1—Fe1—C2ix	88.9 (3)
O1—Ce1—N1	71.82 (14)	C2vi—Fe1—C2ix	90.6 (4)
O1ii—Ce1—N1	71.82 (14)	C2vii—Fe1—C2ix	89.4 (4)
N2—Ce1—N1	142.05 (16)	C2viii—Fe1—C2ix	180.0 (4)
N2iii—Ce1—N1	76.9 (2)	C1—N1—Ce1	148.7 (8)
N2ii—Ce1—N1	142.05 (16)	C2—N2—Ce1	167.2 (5)
N2iv—Ce1—N1	76.9 (2)	Ce1—O1—H1A	116.5
O1—Ce1—N1iv	71.82 (14)	H2A—O2—H2B	110.0
O1ii—Ce1—N1iv	71.82 (14)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···O2	0.85	2.08	2.807 (8)	144
O2—H2B···N1x	0.85	2.28	3.126 (11)	177

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1A⋯O2	0.85	2.08	2.807 (8)	144
O2—H2B⋯N1i	0.85	2.28	3.126 (11)	177

Symmetry code: (i) .