catena-poly[[[(2,2′-bipyridine-2κ2N,N′)-μ-cyanido-1:2κ2N:C-cyanido-2κC-tris­(methanol-1κO)(nitrato-1κ2O,O′)iron(II)yttrium(III)]-di-μ-cyanido-1:2′κ2N:C;2:1′κ2C:N] methanol solvate hemihydrate]

Xu, Y.; Shu, H.-Q.; Shen, X.-P.

doi:10.1107/S1600536810029843

metal-organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 66| Part 8| August 2010| Pages m1034-m1035

https://doi.org/10.1107/S1600536810029843

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catena-poly[[[(2,2′-bipyridine-2κ²N,N′)-μ-cyanido-1:2κ²N:C-cyanido-2κC-tris(methanol-1κO)(nitrato-1κ²O,O′)iron(II)yttrium(III)]-di-μ-cyanido-1:2′κ²N:C;2:1′κ²C:N] methanol solvate hemihydrate]

Yan Xu,^a He-Qing Shu ^b and Xiao-Ping Shen ^b ^*

^aSuqian College, Suqian 223800, People's Republic of China, and ^bSchool of Chemistry and Chemical Engineering, Jiangsu University, Zhenjiang 212013, People's Republic of China
^*Correspondence e-mail: xiaopingshen@163.com

(Received 1 July 2010; accepted 27 July 2010; online 31 July 2010)

The title complex, {[Fe^IIY^III(CN)₄(NO₃)(C₁₀H₈N₂)(CH₃OH)₃]·CH₃OH·0.5H₂O}_n, is built up of ladder-like chains oriented along the c axis. Each ladder consists of two strands based on alternating Fe^II and Y^III ions connected by cyanide bridges. Two such parallel chains are connected by additional cyanide anions (the `rungs' of the ladder), which likewise connect Fe^II and Y^III ions, such that each [Fe(bipy)(CN)₄]²⁻ (bipy is 2,2′-bipyridine) unit coordinates with three Y^III ions and each Y^III ion connects with three different [Fe(bipy)(CN)₄]²⁻ units. The Fe^II atom is six-coordinated in a distorted octahedral geometry and the Y^III atom cation is eight-coordinated in a distorted dodecahedral environment. The uncoordinated methanol solvent molecules are involved in hydrogen-bonding interactions with the one terminal cyanide group and a coordinated methanol molecule from another [Y^III(NO₃)(CH₃OH)₃]²⁺ unit. Adjacent ladder-like chains are also held together by hydrogen bonds between the terminal cyanide ligands of the [Fe(CN)₄(bipy)]²⁻ units in one chain and the OH donors of CH₃OH ligands from [Y^III(NO₃)(CH₃OH)³] units in neighboring chains. The water molecule exhibits half-occupation.

Related literature

For background to the design, synthesis and properties of mixed rare earth–transition metal complexes, see: Wilson et al. (2009 ); Zhou et al. (2002 ); Li et al. (2008 ); Karan et al. (2002 ); Sokol et al. (2002 ); Toma et al. (2003 ); Xu et al. (2009 ). For related structures, see: Baca et al. (2007 ); Liu et al. (2008 ); Yuan et al. (2004 ).

Experimental

Crystal data

[FeY(CN)₄(NO₃)(C₁₀H₈N₂)(CH₄O)₃]·CH₄O·0.5H₂O
M_r = 604.21
Monoclinic, P 2₁ /c
a = 12.803 (3) Å
b = 18.132 (4) Å
c = 10.728 (2) Å
β = 103.439 (3)°
V = 2422.2 (9) Å³
Z = 4
Mo Kα radiation
μ = 3.04 mm⁻¹
T = 173 K
0.26 × 0.22 × 0.20 mm

Data collection

Bruker SMART APEX CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2002 ) T_min = 0.46, T_max = 0.55
18891 measured reflections
4760 independent reflections
3490 reflections with I > 2σ(I)
R_int = 0.067

Refinement

R[F² > 2σ(F²)] = 0.052
wR(F²) = 0.107
S = 1.07
4760 reflections
316 parameters
H-atom parameters constrained
Δρ_max = 0.49 e Å⁻³
Δρ_min = −0.57 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O5—H5A⋯N6ⁱ	0.99	1.78	2.762 (5)	172
O7—H7B⋯N6	0.85	2.03	2.823 (5)	154
Symmetry code: (i) $[x, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ .

Data collection: SMART (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: SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg, 2006 ); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536810029843/nc2192sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810029843/nc2192Isup2.hkl

checkCIF report

Comment top

Much attention is currently devoted to the design and synthesis of mixed rare earth–transition metal complexes because rare earth ions have a rich coordination chemistry with high coordination numbers and significant coordination flexibility, which often leads to unanticipated but remarkable structures (Karan et al., 2002; Li et al., 2008; Wilson et al., 2009; Zhou et al., 2002.) [M(CN)_x(L)_y]^n- [M = Cr, Fe, Ru and Mo; L = chelate ligand; and x = 2, 3, 4) can be used as the bricks to synthesize low-dimensional cyanide-bridged bimetallic compounds, which is a elaborate strategy as revealed by a few research groups (Sokol et al., 2002; Toma et al., 2003). However, the assemblies of [M(CN)_x(L)_y]^n- with rare earth ions have rarely been reported so far (Xu et al., 2009). In this paper, we report a new cyano-bridged Fe^IIY^III bimetallic ladder-like chain complex, based on the [Fe^II(bipy)(CN)₄]^2- [bipy = 2,2'-bipyridine] building block.

The asymmetric unit in the structure of the title complex comprises one [Fe^II(bipy)(CN)₄]^2- anion, one [Y^III(NO₃)(CH₃OH)₃]²⁺ cation, one solvent methanol molecule and half a water molecule (Fig. 1). The crystal structure consists of one-dimensional ladder-like bimetallic chains, {[Fe^II(bipy)(CN)₄][Y^III(NO₃)(CH₃OH)₃]}_n, built up from alternating Fe^II and Y^III metal centers linked through the cyano bridges (Fig. 2). The ladder-like bimetallic chains contain Fe₂Y₂ centrosymmetric motifs. The [Fe(bipy)(CN)₄]^2- fragment exhibits a distorted octahedral structure consisting of two N atoms from a planar bipy ligand and four C atoms from four CN^- groups. The small bite angle subtended by the chelating bipy group [79.90 (15)° for N1—Fe1—N2] is one of the main factors accounting for this distortion. Three of the four cyano groups of the [Fe(bipy)(CN)₄]^2- unit are bridging, while the fourth is terminal. The Fe—C—N angles for both terminal [178.6 (5)°] and bridging [178.7 (4), 179.4 (4) and 174.4 (4)°] CN^- groups deviate slightly from strict linearity. Each Y^III cation is eight-coordinated, connecting with two O atoms from the NO₃ group, three O atoms from three CH₃OH units and three N atoms from three CN^- ligands, building distorted YN₃O₅ dodecahedral surroundings (Fig. 1). The Y—O bond lengths fall in a very narrow range [2.385 (3)–2.448 (3)Å for Y—O(NO₃) and 2.372 (3)–2.392 (3)(3) Å for Y—O(CH₃OH)]. The Y—N(cyanide) bond distances [2.401 (4)–2.344 (4) Å] are somewhat smaller than those from {[Ru(phen)(CN)₄]₃[Ln(terpy)(H₂O)₃]₂.nH₂O}_∞ [2.530 (9)–2.548 (11) Å; Baca et al., 2007]. The angles of Y^III—N—C(cyano) are far from linear [165.9 (3)–169.9 (3)°]. The NO₃^- ion acts as a bidentate ligand toward Y^III through two of its three O atoms, which is different from previously reported cases (Yuan et al., 2004; Liu et al., 2008), in which an NO₃^- ion coordinated to a rare earth ion acts as a monodenate ligand in rare earth–transition metal complexes.

The Fe···Y separations across cyanide bridges are 5.410 (4), 5.357 (3) and 5.424 (4) Å. The uncoordinated methanol solvent molecules are involved in hydrogen-bonding interactions with the one terminal cyanide group and a coordinated methanol molecule from another [Y^III(NO₃)(CH₃OH)₃]^2- unit (Table 1). Adjacent ladder-like chains are also held together by hydrogen bonds between the terminal cyanide ligands of the [Fe(CN)₄(bipy)]^2- units in one chain and the OH donors of CH₃OH ligands from [Y^III(NO₃)(CH₃OH)³] units in neighboring chains. From this arrangement a two-dimensional structure is formed.

Related literature top

For background to the design, synthesis and properties of mixed rare earth–transition metal complexes, see: Wilson et al. (2009); Zhou et al. (2002); Li et al. (2008); Karan et al. (2002); Sokol et al. (2002); Toma et al. (2003); Xu et al. (2009). For related structures, see: Baca et al. (2007); Liu et al. (2008); Yuan et al. (2004).

Experimental top

Red brown prism crystals of the title complex were obtained by slow diffusion of a MeOH solution of K₂[Fe(bipy)(CN)₄].3H₂O(0.1 mmol) and an aqueous solution of Y(NO₃)₃.6H₂O (0.1 mmol) through an H-tube at room temperature. The resulting crystals were collected, washed with H₂O and MeOH, respectively, and dried in air.

Structure description top

For background to the design, synthesis and properties of mixed rare earth–transition metal complexes, see: Wilson et al. (2009); Zhou et al. (2002); Li et al. (2008); Karan et al. (2002); Sokol et al. (2002); Toma et al. (2003); Xu et al. (2009). For related structures, see: Baca et al. (2007); Liu et al. (2008); Yuan et al. (2004).

Computing details top

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

Figures top

	Fig. 1. The molecular structure of the title complex, showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. [Symmetry codes: (i) -x + 1, -y, -z + 1; (ii) x, -y, z - 1; (iii) x, y, z + 1.]
	Fig. 2. The one-dimensional chain of the title complex. [Symmetry code: (i) -x + 1, -y, -z + 1.]

catena-poly[[[(2,2'-bipyridine-2κ²N,N')-µ-cyanido- κ²1:2N:C-cyanido-2κC-tris(methanol- 1κO)(nitrato-1κ²O,O')iron(II)yttrium(III)]- di-µ-cyanido-1:2'κ²N:C;2:1'κ²C:N] methanol solvate hemihydrate] top

Crystal data top

[FeY(CN)₄(NO₃)(C₁₀H₈N₂)(CH₄O)₃]·CH₄O·0.5H₂O	F(000) = 1228
M_r = 604.21	D_x = 1.657 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 838 reflections
a = 12.803 (3) Å	θ = 3.0–23.5°
b = 18.132 (4) Å	µ = 3.04 mm⁻¹
c = 10.728 (2) Å	T = 173 K
β = 103.439 (3)°	Prism, red brown
V = 2422.2 (9) Å³	0.26 × 0.22 × 0.20 mm
Z = 4

Data collection top

Bruker SMART APEX CCD diffractometer	4760 independent reflections
Radiation source: sealed tube	3490 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.067
phi and ω scans	θ_max = 26.0°, θ_min = 1.6°
Absorption correction: multi-scan (SADABS; Bruker, 2002)	h = −14→15
T_min = 0.46, T_max = 0.55	k = −22→22
18891 measured reflections	l = −13→12

Refinement top

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)] = 0.052	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.107	H-atom parameters constrained
S = 1.07	w = 1/[σ²(F_o²) + (0.0481P)²] where P = (F_o² + 2F_c²)/3
4760 reflections	(Δ/σ)_max < 0.001
316 parameters	Δρ_max = 0.49 e Å⁻³
0 restraints	Δρ_min = −0.57 e Å⁻³

Crystal data top

[FeY(CN)₄(NO₃)(C₁₀H₈N₂)(CH₄O)₃]·CH₄O·0.5H₂O	V = 2422.2 (9) Å³
M_r = 604.21	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 12.803 (3) Å	µ = 3.04 mm⁻¹
b = 18.132 (4) Å	T = 173 K
c = 10.728 (2) Å	0.26 × 0.22 × 0.20 mm
β = 103.439 (3)°

Data collection top

Bruker SMART APEX CCD diffractometer	4760 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2002)	3490 reflections with I > 2σ(I)
T_min = 0.46, T_max = 0.55	R_int = 0.067
18891 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.052	0 restraints
wR(F²) = 0.107	H-atom parameters constrained
S = 1.07	Δρ_max = 0.49 e Å⁻³
4760 reflections	Δρ_min = −0.57 e Å⁻³
316 parameters

Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
C1	0.7345 (4)	−0.1231 (2)	0.3081 (4)	0.0385 (10)
H1	0.6595	−0.1259	0.3029	0.046*
C2	0.7916 (4)	−0.1886 (2)	0.3052 (4)	0.0347 (10)
H2	0.7570	−0.2353	0.2975	0.042*
C3	0.9033 (4)	−0.1825 (3)	0.3155 (4)	0.0394 (10)
H3	0.9455	−0.2258	0.3174	0.047*
C4	0.9530 (4)	−0.1133 (3)	0.3213 (4)	0.0419 (11)
H4	1.0277	−0.1089	0.3257	0.050*
C5	0.8893 (3)	−0.0504 (3)	0.3225 (5)	0.0391 (10)
C6	0.9318 (3)	0.0236 (3)	0.3317 (4)	0.0384 (10)
C7	1.0374 (4)	0.0395 (3)	0.3333 (5)	0.0452 (11)
H7	1.0858	0.0014	0.3238	0.054*
C8	1.0714 (3)	0.1123 (2)	0.3497 (4)	0.0348 (10)
H8	1.1439	0.1241	0.3504	0.042*
C9	1.0006 (3)	0.1689 (3)	0.3651 (4)	0.0354 (10)
H9	1.0240	0.2185	0.3790	0.042*
C10	0.8930 (3)	0.1483 (2)	0.3587 (4)	0.0281 (8)
H10	0.8423	0.1853	0.3663	0.034*
C11	0.7170 (3)	0.0426 (2)	0.4978 (4)	0.0363 (10)
C12	0.5697 (3)	0.0028 (2)	0.2858 (4)	0.0363 (10)
C13	0.6951 (3)	0.0482 (2)	0.1340 (4)	0.0298 (9)
C14	0.6443 (3)	0.1349 (3)	0.3103 (4)	0.0385 (10)
C15	0.8118 (4)	−0.0835 (3)	0.9317 (4)	0.0427 (11)
H15A	0.8576	−0.0470	0.9859	0.064*
H15B	0.8564	−0.1163	0.8933	0.064*
H15C	0.7734	−0.1124	0.9840	0.064*
C16	0.7459 (4)	0.2236 (3)	0.6177 (4)	0.0390 (10)
H16A	0.8181	0.2152	0.6712	0.059*
H16B	0.7319	0.2767	0.6094	0.059*
H16C	0.7408	0.2022	0.5326	0.059*
C17	0.4893 (4)	0.1450 (3)	0.9517 (5)	0.0429 (11)
H17A	0.4907	0.0916	0.9660	0.064*
H17B	0.4155	0.1608	0.9139	0.064*
H17C	0.5158	0.1704	1.0336	0.064*
C18	0.4471 (3)	0.1056 (3)	0.4540 (4)	0.0385 (10)
H18A	0.4135	0.1343	0.5089	0.058*
H18B	0.4307	0.0544	0.4617	0.058*
H18C	0.5235	0.1125	0.4785	0.058*
Fe1	0.70769 (5)	0.04235 (3)	0.31568 (6)	0.03166 (16)
N1	0.7825 (3)	−0.05414 (19)	0.3170 (4)	0.0338 (8)
N2	0.8605 (3)	0.07728 (19)	0.3405 (3)	0.0307 (7)
N3	0.7168 (3)	0.0475 (2)	0.6043 (4)	0.0364 (8)
N4	0.4832 (3)	−0.0227 (2)	0.2667 (4)	0.0394 (9)
N5	0.6896 (3)	0.05129 (18)	0.0266 (4)	0.0339 (8)
N6	0.6040 (3)	0.1931 (2)	0.3041 (4)	0.0385 (9)
N7	0.8853 (3)	0.1436 (2)	0.9291 (3)	0.0354 (8)
O1	0.8747 (2)	0.08407 (17)	0.8686 (3)	0.0398 (7)
O2	0.7993 (2)	0.17623 (15)	0.9284 (3)	0.0367 (7)
O3	0.9709 (2)	0.16875 (16)	0.9851 (3)	0.0399 (7)
O4	0.7341 (2)	−0.04552 (16)	0.8312 (3)	0.0361 (7)
H4A	0.6659	−0.0724	0.8253	0.054*
O5	0.6676 (2)	0.18859 (16)	0.6775 (3)	0.0379 (7)
H5A	0.6452	0.2280	0.7297	0.057*
O6	0.5579 (2)	0.16346 (17)	0.8642 (3)	0.0354 (7)
H6A	0.5993	0.2077	0.9002	0.053*
O7	0.4061 (2)	0.12975 (17)	0.3204 (3)	0.0408 (7)
H7B	0.4582	0.1451	0.2907	0.061*
O8	0.3088 (5)	0.2478 (4)	0.4772 (7)	0.0489 (17)	0.50
H8B	0.2447	0.2322	0.4670	0.073*	0.50
H8C	0.3318	0.2622	0.5540	0.073*	0.50
Y1	0.68339 (3)	0.08045 (2)	0.80828 (4)	0.03110 (12)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.040 (2)	0.028 (2)	0.045 (3)	−0.0085 (19)	0.005 (2)	0.0008 (19)
C2	0.044 (2)	0.033 (2)	0.028 (2)	−0.0147 (19)	0.0103 (18)	−0.0087 (17)
C3	0.039 (2)	0.037 (2)	0.042 (3)	−0.0070 (19)	0.0076 (19)	−0.003 (2)
C4	0.051 (3)	0.035 (2)	0.043 (3)	−0.009 (2)	0.017 (2)	−0.002 (2)
C5	0.030 (2)	0.043 (3)	0.046 (3)	0.0014 (19)	0.0119 (19)	0.001 (2)
C6	0.029 (2)	0.048 (3)	0.039 (3)	−0.0038 (19)	0.0103 (18)	−0.003 (2)
C7	0.041 (3)	0.050 (3)	0.044 (3)	−0.003 (2)	0.008 (2)	0.002 (2)
C8	0.036 (2)	0.038 (2)	0.036 (2)	−0.0024 (18)	0.0191 (18)	0.0030 (19)
C9	0.036 (2)	0.043 (3)	0.029 (2)	0.0085 (19)	0.0124 (17)	−0.0080 (19)
C10	0.034 (2)	0.027 (2)	0.0260 (19)	0.0081 (16)	0.0131 (16)	0.0043 (16)
C11	0.036 (2)	0.033 (2)	0.038 (3)	−0.0010 (19)	0.0049 (19)	0.001 (2)
C12	0.028 (2)	0.031 (2)	0.045 (3)	−0.0038 (18)	−0.0014 (19)	−0.0016 (19)
C13	0.027 (2)	0.029 (2)	0.032 (2)	−0.0095 (16)	0.0043 (17)	0.0037 (17)
C14	0.033 (2)	0.042 (3)	0.046 (3)	0.0122 (19)	0.0193 (19)	−0.002 (2)
C15	0.034 (2)	0.044 (3)	0.040 (3)	−0.013 (2)	−0.0127 (19)	−0.001 (2)
C16	0.037 (2)	0.041 (3)	0.042 (3)	0.003 (2)	0.015 (2)	−0.010 (2)
C17	0.041 (3)	0.038 (3)	0.054 (3)	0.011 (2)	0.018 (2)	0.019 (2)
C18	0.034 (2)	0.037 (2)	0.044 (3)	−0.0078 (18)	0.009 (2)	0.008 (2)
Fe1	0.0315 (3)	0.0311 (3)	0.0327 (3)	−0.0019 (2)	0.0080 (2)	−0.0011 (2)
N1	0.0317 (19)	0.0258 (18)	0.045 (2)	−0.0048 (14)	0.0115 (16)	−0.0053 (15)
N2	0.0281 (17)	0.0279 (18)	0.0366 (19)	−0.0061 (14)	0.0088 (14)	0.0024 (15)
N3	0.0317 (19)	0.041 (2)	0.040 (2)	−0.0017 (15)	0.0149 (16)	0.0024 (17)
N4	0.037 (2)	0.035 (2)	0.045 (2)	0.0037 (16)	0.0059 (17)	−0.0022 (17)
N5	0.0308 (19)	0.0293 (19)	0.043 (2)	−0.0113 (15)	0.0113 (16)	0.0014 (16)
N6	0.036 (2)	0.034 (2)	0.047 (2)	0.0065 (16)	0.0133 (17)	−0.0072 (17)
N7	0.0316 (19)	0.044 (2)	0.0310 (19)	0.0007 (16)	0.0075 (15)	−0.0157 (17)
O1	0.0346 (16)	0.0331 (17)	0.0493 (19)	0.0044 (13)	0.0050 (14)	−0.0012 (14)
O2	0.0293 (16)	0.0297 (16)	0.0476 (19)	−0.0013 (13)	0.0014 (13)	0.0034 (13)
O3	0.0343 (17)	0.0299 (16)	0.0509 (19)	−0.0084 (13)	0.0004 (14)	0.0013 (14)
O4	0.0432 (17)	0.0295 (15)	0.0309 (16)	−0.0158 (13)	−0.0010 (13)	−0.0060 (12)
O5	0.0487 (18)	0.0341 (17)	0.0327 (16)	−0.0156 (14)	0.0128 (13)	−0.0033 (13)
O6	0.0306 (16)	0.0370 (17)	0.0412 (17)	−0.0026 (12)	0.0137 (13)	0.0023 (13)
O7	0.0412 (18)	0.0439 (19)	0.0346 (17)	−0.0068 (14)	0.0034 (13)	0.0051 (14)
O8	0.041 (4)	0.045 (4)	0.058 (4)	0.012 (3)	0.006 (3)	−0.001 (3)
Y1	0.0295 (2)	0.0324 (2)	0.0303 (2)	−0.00059 (17)	0.00460 (15)	0.00014 (17)

Geometric parameters (Å, º) top

C1—N1	1.386 (5)	C16—H16A	0.9799
C1—C2	1.399 (6)	C16—H16B	0.9800
C1—H1	0.9500	C16—H16C	0.9800
C2—C3	1.413 (6)	C17—O6	1.465 (5)
C2—H2	0.9500	C17—H17A	0.9799
C3—C4	1.402 (6)	C17—H17B	0.9800
C3—H3	0.9500	C17—H17C	0.9799
C4—C5	1.404 (6)	C18—O7	1.474 (5)
C4—H4	0.9502	C18—H18A	0.9599
C5—N1	1.356 (6)	C18—H18B	0.9600
C5—C6	1.442 (6)	C18—H18C	0.9600
C6—N2	1.353 (6)	Fe1—N1	1.993 (4)
C6—C7	1.379 (6)	Fe1—N2	2.015 (3)
C7—C8	1.387 (7)	N3—Y1	2.401 (4)
C7—H7	0.9500	N4—Y1ⁱ	2.344 (4)
C8—C9	1.405 (6)	N5—Y1ⁱⁱ	2.384 (4)
C8—H8	0.9500	N7—O3	1.210 (4)
C9—C10	1.413 (6)	N7—O2	1.248 (4)
C9—H9	0.9500	N7—O1	1.251 (4)
C10—N2	1.353 (5)	N7—Y1	2.849 (4)
C10—H10	0.9500	O1—Y1	2.384 (3)
C11—N3	1.146 (6)	O2—Y1	2.448 (3)
C11—Fe1	1.930 (5)	O4—Y1	2.372 (3)
C12—N4	1.173 (5)	O4—H4A	0.9900
C12—Fe1	1.865 (4)	O5—Y1	2.392 (3)
C13—N5	1.140 (5)	O5—H5A	0.9900
C13—Fe1	1.921 (4)	O6—Y1	2.378 (3)
C14—N6	1.169 (5)	O6—H6A	0.9901
C14—Fe1	1.860 (4)	O7—H7B	0.8501
C15—O4	1.459 (5)	O8—H8B	0.8499
C15—H15A	0.9801	O8—H8C	0.8500
C15—H15B	0.9800	Y1—N4ⁱ	2.344 (4)
C15—H15C	0.9800	Y1—N5ⁱⁱⁱ	2.384 (4)
C16—O5	1.455 (5)

N1—C1—C2	122.8 (4)	C12—Fe1—N2	175.02 (17)
N1—C1—H1	118.7	C13—Fe1—N2	88.11 (15)
C2—C1—H1	118.5	C11—Fe1—N2	92.05 (16)
C1—C2—C3	117.2 (4)	N1—Fe1—N2	79.90 (14)
C1—C2—H2	121.6	C5—N1—C1	118.3 (4)
C3—C2—H2	121.2	C5—N1—Fe1	115.7 (3)
C4—C3—C2	120.9 (4)	C1—N1—Fe1	125.9 (3)
C4—C3—H3	119.3	C6—N2—C10	120.4 (3)
C2—C3—H3	119.9	C6—N2—Fe1	114.5 (3)
C3—C4—C5	118.0 (4)	C10—N2—Fe1	125.1 (3)
C3—C4—H4	121.3	C11—N3—Y1	165.9 (4)
C5—C4—H4	120.7	C12—N4—Y1ⁱ	169.3 (4)
N1—C5—C4	122.7 (4)	C13—N5—Y1ⁱⁱ	169.9 (3)
N1—C5—C6	114.2 (4)	O3—N7—O2	121.4 (4)
C4—C5—C6	123.1 (4)	O3—N7—O1	124.0 (4)
N2—C6—C7	121.6 (4)	O2—N7—O1	114.6 (3)
N2—C6—C5	115.1 (4)	O3—N7—Y1	177.2 (3)
C7—C6—C5	123.3 (4)	O2—N7—Y1	58.8 (2)
C6—C7—C8	118.6 (5)	O1—N7—Y1	55.87 (19)
C6—C7—H7	120.5	N7—O1—Y1	98.4 (2)
C8—C7—H7	120.9	N7—O2—Y1	95.3 (2)
C7—C8—C9	121.1 (4)	C15—O4—Y1	130.8 (2)
C7—C8—H8	119.5	C15—O4—H4A	104.8
C9—C8—H8	119.3	Y1—O4—H4A	104.6
C8—C9—C10	116.8 (4)	C16—O5—Y1	130.0 (3)
C8—C9—H9	121.5	C16—O5—H5A	104.7
C10—C9—H9	121.7	Y1—O5—H5A	104.8
N2—C10—C9	121.4 (4)	C17—O6—Y1	123.9 (2)
N2—C10—H10	119.5	C17—O6—H6A	106.4
C9—C10—H10	119.1	Y1—O6—H6A	106.2
N3—C11—Fe1	174.3 (4)	C18—O7—H7B	109.2
N4—C12—Fe1	179.4 (4)	H8B—O8—H8C	109.5
N5—C13—Fe1	178.7 (4)	N4ⁱ—Y1—O4	79.10 (11)
N6—C14—Fe1	178.6 (4)	N4ⁱ—Y1—O6	75.80 (12)
O4—C15—H15A	109.3	O4—Y1—O6	140.19 (10)
O4—C15—H15B	109.9	N4ⁱ—Y1—N5ⁱⁱⁱ	93.33 (12)
H15A—C15—H15B	109.5	O4—Y1—N5ⁱⁱⁱ	74.86 (11)
O4—C15—H15C	109.2	O6—Y1—N5ⁱⁱⁱ	76.29 (11)
H15A—C15—H15C	109.5	N4ⁱ—Y1—O1	154.27 (12)
H15B—C15—H15C	109.5	O4—Y1—O1	76.06 (10)
O5—C16—H16A	109.1	O6—Y1—O1	128.74 (11)
O5—C16—H16B	109.8	N5ⁱⁱⁱ—Y1—O1	86.64 (12)
H16A—C16—H16B	109.5	N4ⁱ—Y1—O5	102.62 (12)
O5—C16—H16C	109.5	O4—Y1—O5	146.51 (11)
H16A—C16—H16C	109.5	O6—Y1—O5	70.07 (10)
H16B—C16—H16C	109.5	N5ⁱⁱⁱ—Y1—O5	137.47 (11)
O6—C17—H17A	109.6	O1—Y1—O5	94.49 (11)
O6—C17—H17B	109.4	N4ⁱ—Y1—N3	85.22 (13)
H17A—C17—H17B	109.5	O4—Y1—N3	75.66 (12)
O6—C17—H17C	109.4	O6—Y1—N3	131.40 (11)
H17A—C17—H17C	109.5	N5ⁱⁱⁱ—Y1—N3	150.21 (13)
H17B—C17—H17C	109.5	O1—Y1—N3	82.26 (12)
O7—C18—H18A	109.0	O5—Y1—N3	71.22 (12)
O7—C18—H18B	109.6	N4ⁱ—Y1—O2	152.81 (12)
H18A—C18—H18B	109.5	O4—Y1—O2	120.72 (10)
O7—C18—H18C	109.8	O6—Y1—O2	77.33 (10)
H18A—C18—H18C	109.5	N5ⁱⁱⁱ—Y1—O2	76.24 (11)
H18B—C18—H18C	109.5	O1—Y1—O2	51.58 (10)
C14—Fe1—C12	87.3 (2)	O5—Y1—O2	71.68 (10)
C14—Fe1—C13	89.19 (19)	N3—Y1—O2	116.23 (11)
C12—Fe1—C13	89.64 (18)	N4ⁱ—Y1—N7	173.07 (12)
C14—Fe1—C11	87.33 (19)	O4—Y1—N7	98.20 (10)
C12—Fe1—C11	90.5 (2)	O6—Y1—N7	103.03 (10)
C13—Fe1—C11	176.51 (19)	N5ⁱⁱⁱ—Y1—N7	79.78 (11)
C14—Fe1—N1	176.55 (18)	O1—Y1—N7	25.75 (10)
C12—Fe1—N1	95.62 (17)	O5—Y1—N7	83.18 (11)
C13—Fe1—N1	88.99 (17)	N3—Y1—N7	100.36 (11)
C11—Fe1—N1	94.48 (17)	O2—Y1—N7	25.85 (9)
C14—Fe1—N2	97.11 (18)

Symmetry codes: (i) −x+1, −y, −z+1; (ii) x, y, z−1; (iii) x, y, z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O5—H5A···N6^iv	0.99	1.78	2.762 (5)	172
O7—H7B···N6	0.85	2.03	2.823 (5)	154

Symmetry code: (iv) x, −y+1/2, z+1/2.

Experimental details

Crystal data
Chemical formula	[FeY(CN)₄(NO₃)(C₁₀H₈N₂)(CH₄O)₃]·CH₄O·0.5H₂O
M_r	604.21
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	173
a, b, c (Å)	12.803 (3), 18.132 (4), 10.728 (2)
β (°)	103.439 (3)
V (Å³)	2422.2 (9)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	3.04
Crystal size (mm)	0.26 × 0.22 × 0.20

Data collection
Diffractometer	Bruker SMART APEX CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2002)
T_min, T_max	0.46, 0.55
No. of measured, independent and observed [I > 2σ(I)] reflections	18891, 4760, 3490
R_int	0.067
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.052, 0.107, 1.07
No. of reflections	4760
No. of parameters	316
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.49, −0.57

Computer programs: SMART (Bruker, 2004), SAINT (Bruker, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg, 2006), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O5—H5A···N6ⁱ	0.99	1.78	2.762 (5)	171.8
O7—H7B···N6	0.85	2.03	2.823 (5)	154.2

Symmetry code: (i) x, −y+1/2, z+1/2.

Acknowledgements

The authors thank the Natural Science Foundation of Jiangsu Province (No. BK2009196) for financial support.

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