Tris(1,10-phenanthroline)iron(II) μ-oxido-bis­[trichloridoferrate(III)]

Ling, C.; Song, L.; Wang, X.

doi:10.1107/S1600536811031783

metal-organic compounds

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ISSN: 2056-9890

Volume 67| Part 9| September 2011| Pages m1232-m1233

doi:10.1107/S1600536811031783

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Tris(1,10-phenanthroline)iron(II) μ-oxido-bis[trichloridoferrate(III)]

Chun Ling,^a Li Song ^a ^* and Xinping Wang ^a

^aDepartment of Chemistry, Key Laboratory of Advanced Textile Materials and Manufacturing Technology of the Education Ministry, Zhejiang Sci-Tech University, Hangzhou 310018, People's Republic of China
^*Correspondence e-mail: songli_spring@yahoo.com.cn

(Received 26 July 2011; accepted 5 August 2011; online 11 August 2011)

In the title salt, [Fe(C₁₂H₈N₂)₃][Fe₂Cl₆O], the ionic components are linked into a two-dimensional supramolecular layer by two pairs of C—H⋯Cl hydrogen bonds and π–π stacking interactions [centroid–centroid distances = 3.655 (4) and 3.498 (3) Å]. The salt is characterized as a mixed-valent Fe^II–Fe^III compound, in which an Fe^II atom is coordinated by three phen ligands, forming a six-coordinated cationic entity and the anionic part is formed by two Fe^III atoms in tetrahedral coordination environments constructed by three chloride ions and one bridging oxide ligand. Intramolecular C—H⋯N hydrogen bonds are observed.

Related literature

For related compounds containing the [Cl₃FeOFeCl₃]²⁻ anion, see: Yan et al. (2000 ); Li et al. (2008 ); Haselhorst et al. (1993 ); Drew et al. (1978 ); Ondrejkovicová et al. (1998 ); James et al. (1997 ); Köhn et al. (1997 ); Bullen et al. (1986 ). For polynuclear iron(II/III) clusters, see: Pierre et al. (1996 ); Proul-Curry & Chasteen (1995 ). For the use of iron(III) complexes containing an Fe—O—Fe linkage as models for non-heme metalloproteins, see: Kurtz (1990 ); Gorun & Lippard (1991 ); Davydov et al. (1997 ); Ito et al. (1996 ); Mauerer et al. (1993 ); Menage et al. (1993 ); Okuno et al. (1997 ). For their use as models in studies of intramolecular antiferromagnetic spin exchange coupling between high-spin ferric ions in material science, see: Kurtz (1990); Gatteschi et al. (2000 ); Haselhorst et al. (1993). For π–π stacking interactions between two phen ligands, see: Chandrasekhar et al. (2006 ).

Experimental

Crystal data

[Fe(C₁₂H₈N₂)₃][Fe₂Cl₆O]
M_r = 936.86
Triclinic, $[P \overline 1]$
a = 11.422 (2) Å
b = 13.357 (3) Å
c = 14.045 (3) Å
α = 77.61 (3)°
β = 89.16 (3)°
γ = 65.99 (3)°
V = 1905.3 (7) Å³
Z = 2
Mo Kα radiation
μ = 1.59 mm⁻¹
T = 293 K
0.38 × 0.20 × 0.12 mm

Data collection

Rigaku R-AXIS RAPID diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ) T_min = 0.584, T_max = 0.832
18867 measured reflections
8629 independent reflections
5284 reflections with I > 2σ(I)
R_int = 0.038

Refinement

R[F² > 2σ(F²)] = 0.050
wR(F²) = 0.172
S = 1.14
8629 reflections
469 parameters
H-atom parameters constrained
Δρ_max = 1.02 e Å⁻³
Δρ_min = −1.14 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C1—H1⋯Cl6ⁱ	0.93	2.80	3.416 (7)	125
C11—H11⋯Cl2	0.93	2.82	3.740 (7)	172
C12—H12⋯N4	0.93	2.55	3.038 (7)	113
C25—H25⋯N3	0.93	2.62	3.098 (7)	113
C36—H36⋯N2	0.93	2.60	3.084 (8)	113
Symmetry code: (i) x, y-1, z.

Data collection: PROCESS-AUTO (Rigaku, 1998 ); cell refinement: PROCESS-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2004 ); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811031783/bg2417sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811031783/bg2417Isup2.hkl

checkCIF report

Comment top

Recently polynuclear iron(II/III) clusters have received considerable attention in inorganic chemistry and material science (Proul-Curry et al., 1995; Pierre et al., 1996). In particular, iron(III) complexes containing Fe—O—Fe linkage have been one of the more celebrated objects for research and exploiture. In bioioganic chemistry, they are simple and useful models for non-heme metalloproteins containing dinuclear iron units in their active site, such as the methane monooxygenase, hemerythrin, etc (Kurtz et al., 1990; Gorun et al., 1991; Davydov et al., 1997). In material science, they have also been considered as useful models in studies of intramolecular antiferromagnetic spin exchange coupling between high-spin ferric ions (Kurtz et al., 1990; Haselhorst et al., 1993; Gatteschi et al., 2000). Previously, many efforts have been contributed to these researches, especially to the models for non-heme metalloproteins (Davydov et al., 1997; Mauerer et al., 1993; Ito et al., 1996; Okuno et al., 1997; Menage et al., 1993). Here, we report a ionic compound, [Fe(phen)₃][Cl₃FeOFeCl₃] (I), composed of a dinuclear Fe^III cluster anion, [Cl₃FeOFeCl₃]^2-, and a coordinated cation containing Fe^II, [Fe(phen)₃]²⁺.

The Fe^II centre is coordinated in octahedral geometry by three phen ligands to form a coordination cation. In this FeN₆ octahedron, Fe—N bond lengths range from 1.972 (4) Å to 1.985 (4) Å and are similar to those reported in the literature (Yan et al., 2000; Li et al., 2008). In the anionic group two Fe^III cations locate in similar tetrahedral environments constructed by three Cl_- and one µ₂-bridged O^2- ligand. Fe—Cl bond lengths range from 2.206 (2) Å to 2.247 (2) Å and are similar to those in the literature (Haselhorst et al., 1993; Drew et al., 1978; Ondrejkovicová et al., 1998; James et al., 1997; Köhn et al., 1997; Bullen et al., 1986). These two FeOCl₃ tetrahedra are fused through the µ₂-bridged O^2- ligand (Fe1—O1 = 1.747 (4) Å, Fe2—O1 = 1.753 (4) Å ) to give out a dinuclear cluster.

In the crystal structure offset face-to face aromatic π-π stacking interactions and hydrogen bonds lead to the formation of a two-dimensional supramolecular layer. Firstly, along the [1 - 1 1] direction, all adjacent cation of [Fe(phen)₃]²⁺ are joined to each other by virtue of π–π stacking interactions between two phen ligands to form a one-dimensional supramolecular chain (Chandrasekhar et al., 2006). Two pairs of phen skeletons are arranged in a parallel fashion, ring 1 (C4—C9) of one cation stacks with ring 2 (C4—C9)ⁱ[(i): 2 - x, -y, 1 - z] of a neighbouring cation with an interplanar distance of 3.487 (9) Å, and ring 3 (N4/C20—C24) of one cation stacks with ring 4 (N4/C20—C24)ⁱⁱ [(ii) 1 - x, 1 - y, -z] of a neighbouring cation with an interplanar distance of 3.250 (6) Å. Adjacent chains, in turn, are fused together by the [Cl₃FeOFeCl₃]^2-inorganic anion through two pairs of (C—H···Cl) hydrogen bonding interactions between cations and anions (Table 1). As a result, the supramolecular chains interconnect to form a two-dimensional supramolecular layer.

Related literature top

For related compounds containing the [Cl₃FeOFeCl₃]^2- anion, see: Yan et al. (2000); Li et al. (2008); Haselhorst et al. (1993); Drew et al. (1978); Ondrejkovicová et al. (1998); James et al. (1997); Köhn et al. (1997); Bullen et al. (1986). For polynuclear iron(II/III) clusters, see: Pierre et al. (1996); Proul-Curry & Chasteen (1995). For the use in bioioganic chemistry of iron(III) complexes containing an Fe—O—Fe linkage as models for non-heme metalloproteins, see: Kurtz (1990); Gorun & Lippard (1991); Davydov et al. (1997); Ito et al. (1996); Mauerer et al. (1993); Menage et al. (1993); Okuno et al. (1997). For their use as models in studies of intramolecular antiferromagnetic spin exchange coupling between high-spin ferric ions in material science, see: Kurtz (1990); Gatteschi et al. (2000); Haselhorst et al. (1993). For π–π stacking interactions between two phen ligands, see: Chandrasekhar et al. (2006).

Experimental top

The title compound (I) was synthesized by solvothermal reaction of FeCl₂ tetrahydrate (20 mg, 0.1 mmol), Et₄NBr (21 mg, 0.1 mmol), α-Ketoglutaric acid (15 mg, 0.1 mmol) and 1,10-phenanthroline monohydrate (20 mg, 0.1 mmol) in 6 mL e thanol and 0.5 ml water containing NaOH (4 mg, 0.1 mmol). The mixture was heated to 373 K at a rate of 20 K/h, and kept at this temperature for 1 day and then cooled to room temperature at a rate of 2 K/h. Dark red crystals of (I) were obtained. Anal. Calc. for C36H24Cl6Fe3N6O (%): C, 46.15; H, 2.58; N, 8.97; O, 1.71. Found: C, 42.58; H, 2.73; N, 8.36;O, 1.97. Crystals of (I) suitable for single-crystal X-ray diffraction were selected directly from the sample as prepared.

Computing details top

Data collection: PROCESS-AUTO (Rigaku, 1998); cell refinement: PROCESS-AUTO (Rigaku, 1998); data reduction: CrystalStructure (Rigaku/MSC, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. Structure and labeling of the title compound, with displacement ellipsoids drawn at the 30% probability level and H atoms shown as small spheres of arbitrary radii.
	Fig. 2. The supramolecular organic-inorganic hybrid layer constructed by π-π stacking interactions and hydrogen bonds.
	Fig. 3. The packing diagram viewed along the a-direction.

Tris(1,10-phenanthroline)iron(II) µ-oxido-bis[trichloridoferrate(III)] top

Crystal data top

[Fe(C₁₂H₈N₂)₃][Fe₂Cl₆O]	V = 1905.3 (7) Å³
M_r = 936.86	Z = 2
Triclinic, P1	F(000) = 940
Hall symbol: -P 1	D_x = 1.633 Mg m⁻³
a = 11.422 (2) Å	Mo Kα radiation, λ = 0.71075 Å
b = 13.357 (3) Å	θ = 3.1–27.4°
c = 14.045 (3) Å	µ = 1.59 mm⁻¹
α = 77.61 (3)°	T = 293 K
β = 89.16 (3)°	Chunk, dark red
γ = 65.99 (3)°	0.38 × 0.20 × 0.12 mm

Data collection top

Rigaku R-AXIS RAPID diffractometer	8629 independent reflections
Radiation source: fine-focus sealed tube	5284 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.038
Detector resolution: 14.6306 pixels mm^-1	θ_max = 27.4°, θ_min = 3.1°
CCD_Profile_fitting scans	h = −14→14
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	k = −16→17
T_min = 0.584, T_max = 0.832	l = −18→18
18867 measured reflections

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)] = 0.050	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.172	H-atom parameters constrained
S = 1.14	w = 1/[σ²(F_o²) + (0.0663P)² + 2.5229P] where P = (F_o² + 2F_c²)/3
8629 reflections	(Δ/σ)_max < 0.001
469 parameters	Δρ_max = 1.02 e Å⁻³
0 restraints	Δρ_min = −1.14 e Å⁻³

Crystal data top

[Fe(C₁₂H₈N₂)₃][Fe₂Cl₆O]	γ = 65.99 (3)°
M_r = 936.86	V = 1905.3 (7) Å³
Triclinic, P1	Z = 2
a = 11.422 (2) Å	Mo Kα radiation
b = 13.357 (3) Å	µ = 1.59 mm⁻¹
c = 14.045 (3) Å	T = 293 K
α = 77.61 (3)°	0.38 × 0.20 × 0.12 mm
β = 89.16 (3)°

Data collection top

Rigaku R-AXIS RAPID diffractometer	8629 independent reflections
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	5284 reflections with I > 2σ(I)
T_min = 0.584, T_max = 0.832	R_int = 0.038
18867 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.050	0 restraints
wR(F²) = 0.172	H-atom parameters constrained
S = 1.14	Δρ_max = 1.02 e Å⁻³
8629 reflections	Δρ_min = −1.14 e Å⁻³
469 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
Fe1	0.77271 (7)	0.70380 (6)	0.21753 (6)	0.0453 (2)
Fe2	0.45222 (7)	0.78460 (8)	0.25534 (7)	0.0592 (2)
Fe3	0.63944 (6)	0.23329 (5)	0.26545 (5)	0.03354 (17)
Cl1	0.87079 (12)	0.57349 (12)	0.13308 (12)	0.0588 (4)
Cl2	0.88071 (16)	0.64218 (14)	0.36574 (11)	0.0678 (4)
Cl3	0.78594 (18)	0.86418 (12)	0.14353 (12)	0.0726 (5)
Cl4	0.4048 (2)	0.64893 (16)	0.34770 (13)	0.0815 (5)
Cl5	0.31464 (15)	0.86581 (16)	0.12050 (13)	0.0815 (5)
Cl6	0.4309 (2)	0.9143 (3)	0.3368 (2)	0.1410 (12)
O1	0.6116 (4)	0.7255 (4)	0.2250 (4)	0.0808 (14)
N1	0.6923 (4)	0.0922 (3)	0.3668 (3)	0.0388 (8)
N2	0.7466 (4)	0.2671 (3)	0.3528 (3)	0.0376 (8)
N3	0.7857 (3)	0.1709 (3)	0.1870 (3)	0.0350 (8)
N4	0.6082 (4)	0.3749 (3)	0.1681 (3)	0.0372 (8)
N5	0.5217 (4)	0.2003 (3)	0.1873 (3)	0.0388 (8)
N6	0.4822 (3)	0.3024 (3)	0.3321 (3)	0.0390 (9)
C1	0.6653 (5)	0.0032 (4)	0.3706 (4)	0.0504 (12)
H1	0.6160	0.0030	0.3186	0.060*
C2	0.7092 (6)	−0.0902 (5)	0.4507 (4)	0.0620 (15)
H2	0.6884	−0.1508	0.4513	0.074*
C3	0.7815 (6)	−0.0918 (5)	0.5265 (4)	0.0633 (15)
H3	0.8112	−0.1536	0.5793	0.076*
C4	0.8118 (5)	0.0006 (4)	0.5251 (4)	0.0497 (12)
C5	0.7658 (4)	0.0887 (4)	0.4445 (4)	0.0420 (11)
C6	0.8841 (6)	0.0092 (6)	0.6028 (4)	0.0688 (17)
H6	0.9149	−0.0494	0.6582	0.083*
C7	0.9084 (6)	0.1003 (6)	0.5973 (4)	0.0676 (17)
H7	0.9538	0.1042	0.6497	0.081*
C8	0.8658 (5)	0.1921 (5)	0.5122 (4)	0.0504 (12)
C9	0.7944 (4)	0.1850 (4)	0.4368 (4)	0.0416 (11)
C10	0.8893 (5)	0.2893 (5)	0.5004 (4)	0.0602 (15)
H10	0.9346	0.2985	0.5499	0.072*
C11	0.8450 (5)	0.3699 (5)	0.4156 (4)	0.0564 (14)
H11	0.8628	0.4333	0.4058	0.068*
C12	0.7732 (5)	0.3570 (5)	0.3440 (4)	0.0494 (12)
H12	0.7422	0.4136	0.2873	0.059*
C13	0.8717 (4)	0.0659 (4)	0.1962 (4)	0.0451 (11)
H13	0.8637	0.0097	0.2444	0.054*
C14	0.9742 (5)	0.0355 (5)	0.1367 (4)	0.0533 (13)
H14	1.0332	−0.0392	0.1462	0.064*
C15	0.9870 (5)	0.1160 (5)	0.0647 (4)	0.0562 (14)
H15	1.0552	0.0968	0.0252	0.067*
C16	0.8967 (5)	0.2280 (5)	0.0505 (4)	0.0488 (12)
C17	0.7975 (4)	0.2507 (4)	0.1139 (3)	0.0363 (10)
C18	0.8991 (6)	0.3197 (6)	−0.0222 (4)	0.0624 (16)
H18	0.9632	0.3063	−0.0655	0.075*
C19	0.8106 (6)	0.4249 (5)	−0.0291 (4)	0.0588 (15)
H19	0.8164	0.4832	−0.0759	0.071*
C20	0.7072 (5)	0.4504 (4)	0.0336 (4)	0.0463 (12)
C21	0.7017 (4)	0.3619 (4)	0.1050 (3)	0.0379 (10)
C22	0.6122 (6)	0.5585 (4)	0.0306 (4)	0.0522 (13)
H22	0.6130	0.6204	−0.0144	0.063*
C23	0.5188 (5)	0.5719 (4)	0.0942 (4)	0.0503 (12)
H23	0.4551	0.6432	0.0928	0.060*
C24	0.5192 (5)	0.4778 (4)	0.1619 (4)	0.0428 (11)
H24	0.4540	0.4882	0.2043	0.051*
C25	0.5450 (5)	0.1474 (4)	0.1150 (4)	0.0455 (11)
H25	0.6290	0.1156	0.0977	0.055*
C26	0.4467 (6)	0.1377 (5)	0.0631 (4)	0.0591 (14)
H26	0.4662	0.1009	0.0119	0.071*
C27	0.3247 (6)	0.1815 (5)	0.0876 (5)	0.0640 (16)
H27	0.2602	0.1735	0.0545	0.077*
C28	0.2949 (5)	0.2394 (4)	0.1632 (4)	0.0498 (12)
C29	0.3974 (4)	0.2457 (4)	0.2119 (4)	0.0397 (10)
C30	0.1686 (5)	0.2942 (6)	0.1940 (5)	0.0660 (17)
H30	0.0989	0.2925	0.1622	0.079*
C31	0.1479 (5)	0.3481 (5)	0.2676 (5)	0.0646 (17)
H31	0.0644	0.3830	0.2849	0.077*
C32	0.2513 (5)	0.3525 (4)	0.3196 (4)	0.0506 (13)
C33	0.3761 (4)	0.3017 (4)	0.2895 (4)	0.0408 (10)
C34	0.2381 (5)	0.4033 (5)	0.3984 (5)	0.0640 (16)
H34	0.1575	0.4389	0.4201	0.077*
C35	0.3444 (6)	0.4002 (5)	0.4429 (5)	0.0634 (16)
H35	0.3369	0.4314	0.4971	0.076*
C36	0.4660 (5)	0.3501 (5)	0.4081 (4)	0.0517 (13)
H36	0.5371	0.3505	0.4391	0.062*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Fe1	0.0378 (4)	0.0458 (4)	0.0546 (5)	−0.0166 (3)	0.0088 (3)	−0.0176 (3)
Fe2	0.0421 (4)	0.0729 (6)	0.0750 (6)	−0.0270 (4)	0.0207 (4)	−0.0364 (5)
Fe3	0.0321 (3)	0.0315 (3)	0.0363 (4)	−0.0117 (3)	0.0047 (3)	−0.0094 (3)
Cl1	0.0447 (7)	0.0568 (8)	0.0797 (10)	−0.0154 (6)	0.0089 (7)	−0.0369 (7)
Cl2	0.0802 (10)	0.0777 (10)	0.0498 (8)	−0.0375 (9)	−0.0072 (7)	−0.0122 (7)
Cl3	0.1030 (12)	0.0447 (8)	0.0744 (10)	−0.0344 (9)	0.0205 (9)	−0.0150 (7)
Cl4	0.1150 (14)	0.0870 (12)	0.0655 (10)	−0.0621 (12)	0.0340 (10)	−0.0241 (9)
Cl5	0.0482 (8)	0.0802 (11)	0.0802 (11)	0.0078 (8)	−0.0025 (8)	−0.0149 (9)
Cl6	0.1111 (16)	0.183 (3)	0.226 (3)	−0.1023 (18)	0.0912 (19)	−0.164 (3)
O1	0.041 (2)	0.104 (4)	0.107 (4)	−0.027 (2)	0.020 (2)	−0.049 (3)
N1	0.040 (2)	0.037 (2)	0.040 (2)	−0.0161 (18)	0.0058 (17)	−0.0100 (17)
N2	0.0375 (19)	0.038 (2)	0.038 (2)	−0.0161 (17)	0.0071 (17)	−0.0113 (17)
N3	0.0319 (18)	0.0342 (19)	0.038 (2)	−0.0109 (16)	0.0040 (16)	−0.0126 (16)
N4	0.0381 (19)	0.032 (2)	0.037 (2)	−0.0106 (17)	0.0030 (16)	−0.0069 (16)
N5	0.039 (2)	0.035 (2)	0.041 (2)	−0.0148 (18)	0.0003 (17)	−0.0065 (17)
N6	0.0362 (19)	0.034 (2)	0.046 (2)	−0.0123 (17)	0.0098 (17)	−0.0128 (17)
C1	0.059 (3)	0.037 (3)	0.056 (3)	−0.023 (3)	0.008 (3)	−0.007 (2)
C2	0.079 (4)	0.046 (3)	0.063 (4)	−0.033 (3)	0.004 (3)	−0.003 (3)
C3	0.075 (4)	0.042 (3)	0.054 (3)	−0.015 (3)	−0.002 (3)	0.008 (3)
C4	0.052 (3)	0.047 (3)	0.035 (3)	−0.012 (3)	−0.001 (2)	0.003 (2)
C5	0.035 (2)	0.044 (3)	0.044 (3)	−0.012 (2)	0.008 (2)	−0.011 (2)
C6	0.072 (4)	0.068 (4)	0.048 (3)	−0.021 (3)	−0.008 (3)	0.007 (3)
C7	0.059 (3)	0.086 (5)	0.047 (3)	−0.022 (3)	−0.018 (3)	−0.006 (3)
C8	0.039 (3)	0.067 (4)	0.044 (3)	−0.019 (3)	−0.004 (2)	−0.019 (3)
C9	0.034 (2)	0.049 (3)	0.042 (3)	−0.015 (2)	0.010 (2)	−0.015 (2)
C10	0.055 (3)	0.081 (4)	0.058 (4)	−0.033 (3)	−0.001 (3)	−0.032 (3)
C11	0.055 (3)	0.063 (4)	0.063 (4)	−0.033 (3)	0.003 (3)	−0.022 (3)
C12	0.056 (3)	0.051 (3)	0.053 (3)	−0.030 (3)	0.006 (2)	−0.019 (2)
C13	0.040 (2)	0.040 (3)	0.050 (3)	−0.011 (2)	0.006 (2)	−0.014 (2)
C14	0.040 (3)	0.052 (3)	0.062 (3)	−0.009 (2)	0.007 (2)	−0.023 (3)
C15	0.039 (3)	0.074 (4)	0.063 (4)	−0.022 (3)	0.021 (3)	−0.035 (3)
C16	0.043 (3)	0.060 (3)	0.050 (3)	−0.025 (3)	0.012 (2)	−0.019 (3)
C17	0.034 (2)	0.042 (3)	0.037 (2)	−0.018 (2)	0.0058 (19)	−0.014 (2)
C18	0.067 (4)	0.077 (4)	0.056 (4)	−0.042 (4)	0.025 (3)	−0.018 (3)
C19	0.075 (4)	0.065 (4)	0.047 (3)	−0.044 (3)	0.017 (3)	−0.007 (3)
C20	0.055 (3)	0.048 (3)	0.043 (3)	−0.031 (3)	−0.001 (2)	−0.004 (2)
C21	0.041 (2)	0.042 (3)	0.036 (2)	−0.022 (2)	0.002 (2)	−0.010 (2)
C22	0.072 (4)	0.045 (3)	0.047 (3)	−0.035 (3)	−0.006 (3)	−0.001 (2)
C23	0.060 (3)	0.030 (2)	0.058 (3)	−0.014 (2)	−0.007 (3)	−0.011 (2)
C24	0.043 (3)	0.035 (3)	0.044 (3)	−0.010 (2)	−0.002 (2)	−0.007 (2)
C25	0.050 (3)	0.041 (3)	0.048 (3)	−0.016 (2)	−0.002 (2)	−0.020 (2)
C26	0.067 (4)	0.057 (3)	0.060 (4)	−0.027 (3)	−0.008 (3)	−0.020 (3)
C27	0.065 (4)	0.064 (4)	0.073 (4)	−0.039 (3)	−0.008 (3)	−0.011 (3)
C28	0.039 (3)	0.050 (3)	0.055 (3)	−0.020 (2)	−0.009 (2)	0.005 (2)
C29	0.036 (2)	0.034 (2)	0.046 (3)	−0.016 (2)	0.003 (2)	0.000 (2)
C30	0.041 (3)	0.084 (4)	0.068 (4)	−0.032 (3)	−0.006 (3)	0.006 (3)
C31	0.031 (3)	0.078 (4)	0.064 (4)	−0.014 (3)	0.003 (3)	0.008 (3)
C32	0.037 (2)	0.049 (3)	0.052 (3)	−0.011 (2)	0.010 (2)	0.003 (2)
C33	0.037 (2)	0.035 (2)	0.046 (3)	−0.013 (2)	0.008 (2)	−0.003 (2)
C34	0.045 (3)	0.065 (4)	0.067 (4)	−0.007 (3)	0.024 (3)	−0.016 (3)
C35	0.063 (4)	0.066 (4)	0.059 (4)	−0.018 (3)	0.028 (3)	−0.028 (3)
C36	0.053 (3)	0.054 (3)	0.049 (3)	−0.019 (3)	0.013 (2)	−0.021 (3)

Geometric parameters (Å, º) top

Fe1—O1	1.747 (4)	C11—C12	1.388 (7)
Fe1—Cl1	2.2251 (16)	C11—H11	0.9300
Fe1—Cl3	2.2350 (17)	C12—H12	0.9300
Fe1—Cl2	2.2463 (19)	C13—C14	1.402 (7)
Fe2—O1	1.753 (4)	C13—H13	0.9300
Fe2—Cl6	2.206 (2)	C14—C15	1.363 (8)
Fe2—Cl4	2.2424 (19)	C14—H14	0.9300
Fe2—Cl5	2.247 (2)	C15—C16	1.401 (8)
Fe3—N1	1.972 (4)	C15—H15	0.9300
Fe3—N3	1.976 (4)	C16—C17	1.405 (6)
Fe3—N6	1.981 (4)	C16—C18	1.427 (8)
Fe3—N4	1.983 (4)	C17—C21	1.421 (6)
Fe3—N2	1.985 (4)	C18—C19	1.339 (8)
Fe3—N5	1.985 (4)	C18—H18	0.9300
N1—C1	1.335 (6)	C19—C20	1.434 (7)
N1—C5	1.367 (6)	C19—H19	0.9300
N2—C12	1.334 (6)	C20—C21	1.400 (6)
N2—C9	1.367 (6)	C20—C22	1.401 (8)
N3—C13	1.324 (6)	C22—C23	1.361 (7)
N3—C17	1.361 (6)	C22—H22	0.9300
N4—C24	1.320 (6)	C23—C24	1.403 (7)
N4—C21	1.357 (6)	C23—H23	0.9300
N5—C25	1.322 (6)	C24—H24	0.9300
N5—C29	1.370 (6)	C25—C26	1.412 (7)
N6—C36	1.331 (6)	C25—H25	0.9300
N6—C33	1.363 (6)	C26—C27	1.346 (8)
C1—C2	1.407 (8)	C26—H26	0.9300
C1—H1	0.9300	C27—C28	1.403 (8)
C2—C3	1.348 (8)	C27—H27	0.9300
C2—H2	0.9300	C28—C29	1.405 (7)
C3—C4	1.407 (8)	C28—C30	1.437 (8)
C3—H3	0.9300	C29—C33	1.414 (7)
C4—C5	1.373 (7)	C30—C31	1.347 (9)
C4—C6	1.430 (8)	C30—H30	0.9300
C5—C9	1.433 (7)	C31—C32	1.427 (8)
C6—C7	1.339 (9)	C31—H31	0.9300
C6—H6	0.9300	C32—C34	1.393 (8)
C7—C8	1.439 (8)	C32—C33	1.410 (6)
C7—H7	0.9300	C34—C35	1.354 (9)
C8—C9	1.389 (7)	C34—H34	0.9300
C8—C10	1.405 (8)	C35—C36	1.407 (7)
C10—C11	1.363 (8)	C35—H35	0.9300
C10—H10	0.9300	C36—H36	0.9300

O1—Fe1—Cl1	110.07 (16)	C10—C11—H11	120.2
O1—Fe1—Cl3	110.06 (18)	C12—C11—H11	120.2
Cl1—Fe1—Cl3	109.18 (7)	N2—C12—C11	123.1 (5)
O1—Fe1—Cl2	112.02 (18)	N2—C12—H12	118.5
Cl1—Fe1—Cl2	106.97 (7)	C11—C12—H12	118.5
Cl3—Fe1—Cl2	108.45 (7)	N3—C13—C14	123.0 (5)
O1—Fe2—Cl6	108.97 (16)	N3—C13—H13	118.5
O1—Fe2—Cl4	109.22 (18)	C14—C13—H13	118.5
Cl6—Fe2—Cl4	110.12 (10)	C15—C14—C13	119.6 (5)
O1—Fe2—Cl5	111.14 (18)	C15—C14—H14	120.2
Cl6—Fe2—Cl5	108.54 (12)	C13—C14—H14	120.2
Cl4—Fe2—Cl5	108.85 (8)	C14—C15—C16	119.5 (4)
N1—Fe3—N3	93.83 (16)	C14—C15—H15	120.2
N1—Fe3—N6	90.17 (16)	C16—C15—H15	120.2
N3—Fe3—N6	174.48 (16)	C15—C16—C17	116.9 (5)
N1—Fe3—N4	172.55 (16)	C15—C16—C18	124.9 (5)
N3—Fe3—N4	82.51 (15)	C17—C16—C18	118.1 (5)
N6—Fe3—N4	93.94 (16)	N3—C17—C16	123.7 (4)
N1—Fe3—N2	82.86 (16)	N3—C17—C21	115.4 (4)
N3—Fe3—N2	91.56 (15)	C16—C17—C21	120.8 (4)
N6—Fe3—N2	92.71 (15)	C19—C18—C16	121.0 (5)
N4—Fe3—N2	90.73 (16)	C19—C18—H18	119.5
N1—Fe3—N5	95.14 (16)	C16—C18—H18	119.5
N3—Fe3—N5	93.20 (15)	C18—C19—C20	122.1 (5)
N6—Fe3—N5	82.65 (16)	C18—C19—H19	119.0
N4—Fe3—N5	91.54 (16)	C20—C19—H19	119.0
N2—Fe3—N5	174.96 (15)	C21—C20—C22	116.9 (5)
Fe1—O1—Fe2	158.4 (3)	C21—C20—C19	118.1 (5)
C1—N1—C5	117.0 (4)	C22—C20—C19	124.9 (5)
C1—N1—Fe3	129.7 (4)	N4—C21—C20	123.8 (4)
C5—N1—Fe3	113.3 (3)	N4—C21—C17	116.5 (4)
C12—N2—C9	117.1 (4)	C20—C21—C17	119.8 (4)
C12—N2—Fe3	130.6 (4)	C23—C22—C20	119.4 (5)
C9—N2—Fe3	112.3 (3)	C23—C22—H22	120.3
C13—N3—C17	117.1 (4)	C20—C22—H22	120.3
C13—N3—Fe3	129.8 (3)	C22—C23—C24	119.7 (5)
C17—N3—Fe3	113.0 (3)	C22—C23—H23	120.2
C24—N4—C21	117.4 (4)	C24—C23—H23	120.2
C24—N4—Fe3	129.9 (3)	N4—C24—C23	122.7 (5)
C21—N4—Fe3	112.3 (3)	N4—C24—H24	118.6
C25—N5—C29	117.9 (4)	C23—C24—H24	118.6
C25—N5—Fe3	129.9 (3)	N5—C25—C26	122.2 (5)
C29—N5—Fe3	112.1 (3)	N5—C25—H25	118.9
C36—N6—C33	117.4 (4)	C26—C25—H25	118.9
C36—N6—Fe3	129.9 (3)	C27—C26—C25	120.1 (5)
C33—N6—Fe3	112.6 (3)	C27—C26—H26	119.9
N1—C1—C2	122.0 (5)	C25—C26—H26	119.9
N1—C1—H1	119.0	C26—C27—C28	119.8 (5)
C2—C1—H1	119.0	C26—C27—H27	120.1
C3—C2—C1	119.9 (5)	C28—C27—H27	120.1
C3—C2—H2	120.0	C27—C28—C29	117.1 (5)
C1—C2—H2	120.0	C27—C28—C30	125.6 (5)
C2—C3—C4	119.6 (5)	C29—C28—C30	117.3 (5)
C2—C3—H3	120.2	N5—C29—C28	122.9 (5)
C4—C3—H3	120.2	N5—C29—C33	116.3 (4)
C5—C4—C3	117.2 (5)	C28—C29—C33	120.8 (4)
C5—C4—C6	118.5 (5)	C31—C30—C28	122.1 (5)
C3—C4—C6	124.3 (5)	C31—C30—H30	118.9
N1—C5—C4	124.2 (5)	C28—C30—H30	118.9
N1—C5—C9	115.2 (4)	C30—C31—C32	121.3 (5)
C4—C5—C9	120.6 (5)	C30—C31—H31	119.3
C7—C6—C4	121.2 (5)	C32—C31—H31	119.3
C7—C6—H6	119.4	C34—C32—C33	117.5 (5)
C4—C6—H6	119.4	C34—C32—C31	124.7 (5)
C6—C7—C8	121.7 (5)	C33—C32—C31	117.8 (5)
C6—C7—H7	119.2	N6—C33—C32	123.3 (5)
C8—C7—H7	119.2	N6—C33—C29	116.0 (4)
C9—C8—C10	117.5 (5)	C32—C33—C29	120.6 (5)
C9—C8—C7	117.5 (5)	C35—C34—C32	119.1 (5)
C10—C8—C7	124.9 (5)	C35—C34—H34	120.5
N2—C9—C8	123.4 (5)	C32—C34—H34	120.5
N2—C9—C5	116.2 (4)	C34—C35—C36	120.7 (5)
C8—C9—C5	120.4 (5)	C34—C35—H35	119.7
C11—C10—C8	119.3 (5)	C36—C35—H35	119.7
C11—C10—H10	120.4	N6—C36—C35	122.0 (5)
C8—C10—H10	120.4	N6—C36—H36	119.0
C10—C11—C12	119.7 (5)	C35—C36—H36	119.0

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1···Cl6ⁱ	0.93	2.80	3.416 (7)	125
C11—H11···Cl2	0.93	2.82	3.740 (7)	172
C12—H12···N4	0.93	2.55	3.038 (7)	113
C25—H25···N3	0.93	2.62	3.098 (7)	113
C36—H36···N2	0.93	2.60	3.084 (8)	113

Symmetry code: (i) x, y−1, z.

Experimental details

Crystal data
Chemical formula	[Fe(C₁₂H₈N₂)₃][Fe₂Cl₆O]
M_r	936.86
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	11.422 (2), 13.357 (3), 14.045 (3)
α, β, γ (°)	77.61 (3), 89.16 (3), 65.99 (3)
V (Å³)	1905.3 (7)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	1.59
Crystal size (mm)	0.38 × 0.20 × 0.12

Data collection
Diffractometer	Rigaku R-AXIS RAPID diffractometer
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995)
T_min, T_max	0.584, 0.832
No. of measured, independent and observed [I > 2σ(I)] reflections	18867, 8629, 5284
R_int	0.038
(sin θ/λ)_max (Å⁻¹)	0.648

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.050, 0.172, 1.14
No. of reflections	8629
No. of parameters	469
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.02, −1.14

Computer programs: PROCESS-AUTO (Rigaku, 1998), CrystalStructure (Rigaku/MSC, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1···Cl6ⁱ	0.93	2.80	3.416 (7)	124.9
C11—H11···Cl2	0.93	2.82	3.740 (7)	172.1
C12—H12···N4	0.93	2.55	3.038 (7)	113.1
C25—H25···N3	0.93	2.62	3.098 (7)	112.6
C36—H36···N2	0.93	2.60	3.084 (8)	113.0

Symmetry code: (i) x, y−1, z.

Acknowledgements

We are grateful for financial support from the Natural Science Foundation of Zhejiang Province (project Y4100610).

References

Bullen, G. J., Howlin, B. J., Silver, J., Fitzsimmons, B. W., Sayer, I. & Larkworthy, L. F. (1986). J. Chem. Soc. Dalton Trans. pp. 1937–1940. CSD CrossRef Web of Science Google Scholar
Chandrasekhar, V., Thilagar, P., Steiner, A. & Bickley, J. F. (2006). Chem. Eur. J. 12, 8847–8861. Web of Science CSD CrossRef PubMed CAS Google Scholar
Davydov, R. M., Ménage, S., Fontecave, M., Gräslund, A. & Ehrenberg, A. (1997). J. Biol. Inorg. Chem. 2, 242–255. CAS Google Scholar
Drew, M. G. B., McKee, V. & Nelson, S. M. (1978). J. Chem. Soc. Dalton Trans. pp. 80–84. CSD CrossRef Web of Science Google Scholar
Gatteschi, D., Sessoli, R. & Cornia, A. (2000). Chem. Commun. pp. 725–732. Web of Science CrossRef Google Scholar
Gorun, S. M. & Lippard, S. J. (1991). Inorg. Chem. 30, 1625–1630. CrossRef CAS Web of Science Google Scholar
Haselhorst, G., Wieghardt, K., Keller, S. & Schrader, B. (1993). Inorg. Chem. 32, 520–525. CSD CrossRef CAS Web of Science Google Scholar
Higashi, T. (1995). ABSCOR. Rigaku Corporation, Tokyo, Japan. Google Scholar
Ito, S., Okuno, T., Matsushima, H., Tokii, T. & Nishida, T. (1996). J. Chem. Soc. Dalton Trans. pp. 4479–4484. CrossRef Google Scholar
James, M., Kawaguchi, H. & Tatsumi, K. (1997). Polyhedron, 16, 4279–4282. CrossRef CAS Google Scholar
Köhn, R. D., Seifert, G. & Kociok-Köhn, G. (1997). Angew. Chem. Int. Ed. Engl. 35, 2879–2881. Google Scholar
Kurtz, D. M. Jr (1990). Chem. Rev. 90, 585–606. CrossRef CAS Web of Science Google Scholar
Li, Z.-X., Yu, M.-M., Zhang, Y.-N. & Wei, L.-H. (2008). Acta Cryst. E64, m1514. Web of Science CrossRef IUCr Journals Google Scholar
Mauerer, B., Crane, J., Schuler, J., Wieghardt, K. & Nuber, B. (1993). Angew. Chem. Int. Ed. Engl. 32, 289–291. CrossRef Google Scholar
Menage, S., Vincent, J. M., Lambeaux, C., Chottard, G., Grand, A. & Foantecave, M. (1993). Inorg. Chem. 32, 4766–4773. CrossRef CAS Google Scholar
Okuno, T., Ito, S., Ohba, S. & Nishida, T. (1997). J. Chem. Soc. Dalton Trans. pp. 3547–3551. CrossRef Google Scholar
Ondrejkovicová, I., Lis, T., Mrozinski, J., Vancová, V. & Melník, M. (1998). Polyhedron, 17, 3181–3192. Google Scholar
Pierre T. G. St, Chain, P., Banchspiess, K. R., Webb, J., Belleridge, S., Walton, S. & Dickson, D. P. E. (1996). Coord. Chem. Rev. 151, 125–143. Google Scholar
Proul-Curry, P. M. & Chasteen, N. D. (1995). Coord. Chem. Rev. 144, 347–368. Google Scholar
Rigaku (1998). PROCESS-AUTO. Rigaku Corporation, Tokyo, Japan. Google Scholar
Rigaku/MSC (2004). CrystalStructure. Rigaku/MSC, The Woodlands, Texas, USA. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Yan, B., Chen, Z. D. & Wang, S. X. (2000). J. Chin. Chem. Soc. (Taipei), 47, 1211–1214. CAS Google Scholar