Crystal structure of tetrakis­(acetyl­acetonato)di­chloridodi-μ3-methano­lato-tetra-μ2-methano­lato-tetra­iron(III)

Richers, C.P.; Bertke, J.A.; Gray, D.L.; Rauchfuss, T.B.

doi:10.1107/S2056989015013535

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ISSN: 2056-9890

Volume 71| Part 8| August 2015| Pages 976-979

https://doi.org/10.1107/S2056989015013535

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Crystal structure of tetrakis(acetylacetonato)dichloridodi-μ₃-methanolato-tetra-μ₂-methanolato-tetrairon(III)

Casseday P. Richers,^a Jeffery A. Bertke,^a Danielle L. Gray ^a ^* and Thomas B. Rauchfuss ^a

^aSchool of Chemical Sciences, University of Illinois at Urbana-Champaign, Urbana, Illinois 61801, USA
^*Correspondence e-mail: dgray@illinois.edu

Edited by V. V. Chernyshev, Moscow State University, Russia (Received 26 June 2015; accepted 14 July 2015; online 29 July 2015)

The title complex, [Fe₄(C₅H₇O₂)₄(CH₃O)₆Cl₂] or [Fe₄(acac)₄(μ₂-OMe)₄(μ₃-OMe)₂Cl₂] (acac = acetylacetonate), crystallizes in the orthorhombic Pbca space group with one half of the molecule per asymmetric unit, the other half being completed by inversion symmetry. The core structure consists of a face-sharing double pseudo-cubane entity with two opposite corners missing. Weak C—H⋯Cl intermolecular interactions result in a two-dimensional layered structure parallel to the ac plane.

Keywords: crystal structure; cluster; iron(III); acetylacetonate; ouble cubane.

CCDC reference: 1412851

1. Chemical context

Metal silanolate complexes bearing methoxy and ethoxy groups on silicon are relatively rare (Dupuy et al., 2012 ) in comparison to tert-butoxysilanolate complexes (McMullen et al., 1989 , 1990 ; Nozaki et al., 2002 ; Terry et al., 1993 , 1996 ; Truscott et al., 2013 ). Nevertheless, such compounds may play a pivotal role in sol-gel reactions and in metal-catalysed curing reactions, such as room-temperature vulcanization (Cervantes et al., 2012 ; Levitsky et al., 2007 ; van Der Weij, 1980 ).

We have investigated the syntheses of metal methoxysilanolates via the additions of NaOSi(OMe)₂Me to metal halides and discovered that, in certain cases, the addition of NaOSi(OMe)₂Me to a metal halide results in the formation of a methanolate complex instead of silanolate complex. In line with this observation, we now report that the addition of NaOSi(OMe)₂Me to Fe(acac)₂Cl results in the formation of a tetranuclear iron(III) methanolate compound, Fe₄(acac)₄(μ₂-OMe)₄(μ₃-OMe)₂Cl₂, (I).

2. Structural commentary

The structure of (I) contains two crystallographically independent Fe^III metal atoms. Both cations are in approximately octahedral coordination environments. The coordination sphere of Fe1 is filled by the O atoms of one κ²-acac ligand [Fe1—O1 = 1.9971 (13) Å and Fe1—O2 = 1.9934 (13) Å], two μ₂-methanolate groups [Fe1—O3 = 1.9861 (12) Å and Fe1—O5ⁱ = 1.9885 (12) Å; symmetry code: (i) −x + 1, −y + 1, −z + 1], one μ₃-methanolate group [Fe1—O4 = 2.2135 (12) Å], and one terminal chloride ligand [Fe1—Cl1 = 2.2776 (5) Å]. The coordination sphere of Fe2 is filled by the O atoms of one κ²-acac ligand [Fe2—O6 = 1.9717 (13) Å and Fe2—O7 = 1.9692 (12) Å], two μ₂-methanolate groups [Fe2—O3 = 1.9755 (12) Å and Fe2—O5 = 1.9823 (12) Å], and two μ₃-methanolate groups [Fe2—O4 = 2.0815 (12) Å and Fe2—O4ⁱ = 2.0809 (12) Å]. The angles around both Fe1 and Fe2 distort significantly from the ideal values of 90 and 180° of a perfect octahedron. For Fe1, the cis angles range from 75.69 (5) to 98.40 (4)°, while the trans angles range from 164.47 (5) to 170.40 (3)°. The angles around Fe2 have narrower ranges, with cis being 78.95 (5)–96.48 (5)° and trans being 170.08 (5)–170.16 (5)°.

The molecular structure of (I) (Fig. 1) can be described as an [Fe₄(OMe)₆] face-sharing double pseudo-cubane entity with two opposite corners missing. The outside of the cluster is decorated by one acac ligand per metal and the Fe atoms at either end of the cluster are coordinated by one chloride ion. Neighboring Fe⋯Fe distances range from 3.1997 (4) to 3.2175 (6) Å, while the Fe1⋯Fe1ⁱ distance is 5.5702 (6) Å.

Figure 1
View of the molecular structure of (I)

, showing the atomic numbering and 35% probability displacement ellipsoids for the non-H atoms. The unlabeled atoms are related to the labeled ones by the symmetry operator (−x + 1, −y + 1, −z + 1). H atoms have been removed for clarity.

3. Supramolecular features

There are no significant supramolecular features to discuss with the extended structure of (I). There are weak interactions between the Cl⁻ ion and an acac ligand on neighboring molecules (Table 1). Taking into account these weak interactions, the extended structure becomes layers of two-dimensional 4⁴-nets normal to the b axis (Fig. 2).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C3—H3⋯Cl1ⁱ	0.95	2.91	3.797 (2)	155
C5—H5B⋯Cl1ⁱ	0.98	2.91	3.800 (2)	152
Symmetry code: (i) $[x+{\script{1\over 2}}, y, -z+{\script{1\over 2}}]$ .

Figure 2
A view along the b axis of the extended two-dimensional network of (I)

with an overlay of the unit cell. The intermolecular Cl—H interations are shown as dashed red lines. All C atoms except those in the hydrogen-bonded acac ligand and all H atoms except those of the hydrogen-bonded methyl group have been removed for clarity. Color key: blue = Fe, light-green = Cl, red = O, gray = C, and green = H.

4. Database survey

One closely related complex, [Fe₄(acac)₄(OMe)₆(N₃)₂], has previously been reported (Li et al., 1997 ) in which N₃⁻ takes the position of Cl⁻ in (I). The molecular structure of the azide complex is very similar to that of (I), and can be described as the same [Fe₄(OMe)₆] face-sharing double cubane cluster with two opposite corners missing. The average Fe—O_acac distance of 1.978 Å is quite close to the average Fe—O_acac distance of 1.982 Å in (I). The average Fe—OMe distances in the azide complex (μ₂-OMe: 1.977 Å; μ₃-OMe: 2.124 Å) are also comparable to those in (I) (μ₂-OMe: 1.983 Å; μ₃-OMe: 2.125 Å).

A search of the Cambridge Structural Database (Groom & Allen, 2014 ) returned 14 complexes with an [Fe₄(OR)₆] cluster core similar to (I) (Abu-Nawwas et al., 2009 ; Mulyana et al., 2009 ). All of these materials, except the azide compound described above, use more complex, multidentate ligands to form the polynuclear entity. The [Fe₄(OR)₆] motif is present is 63 additional materials as part of a higher-order cluster complex (Ferguson et al., 2013 ; Murugesu et al., 2004 ).

5. Synthesis and crystallization

A solution of NaOSi(OMe)₂Me (57 mg, 3.96 × 10 ⁻⁴ mol, 1 equivalent) in THF (3 ml) was added to a solution of Fe(acac)₂Cl (200 mg, 3.96 × 10 ⁻⁴ mol, 1 equivalent) in THF (see Scheme). The mixture was stirred rapidly at room temperature, and a slight color change from a dark-red to a lighter red was observed. Removal of the solvent under vacuum resulted in the precipitation of an orange solid, which upon washing with dry Et₂O (2 × 10 ml) left a yellow solid. The yellow solid was extracted into dry CH₂Cl₂ and filtered through Celite. The CH₂Cl₂ was then removed under vacuum, leaving a yellow solid (54 mg, 6.16 × 10 ⁻⁵ mol, 62% yield). Crystals suitable for X-ray diffraction were grown by slow diffusion of pentane into a CH₂Cl₂ solution of the yellow solid.

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. Methyl-H atom positions, RCH₃, were optimized by rotation about R—C bonds, with idealized C—H, R—H and H⋯H distances (C—H = 0.98 Å). The remaining H atoms were included as riding idealized contributors (C—H = 0.95 Å). H atoms were assigned U_iso(H) = 1.5U_eq(C) for methyl H atoms and U_iso(H) = 1.2U_eq(C) otherwise. The 102 reflection was omitted from the final refinement because it was partially obscured by the shadow of the beam stop.

Table 2
Experimental details

Crystal data
Chemical formula	[Fe₄(C₅H₇O₂)₄(CH₃O)₆Cl₂]
M_r	876.93
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	102
a, b, c (Å)	14.0714 (6), 12.1888 (4), 21.3543 (7)
V (Å³)	3662.6 (2)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	1.76
Crystal size (mm)	0.38 × 0.37 × 0.23

Data collection
Diffractometer	Bruker D8 Venture/Photon 100
Absorption correction	Integration (SADABS; Bruker, 2012 )
T_min, T_max	0.568, 0.718
No. of measured, independent and observed [I > 2σ(I)] reflections	46682, 4559, 3837
R_int	0.060
(sin θ/λ)_max (Å⁻¹)	0.668

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.028, 0.070, 1.04
No. of reflections	4559
No. of parameters	215
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.39, −0.34
Computer programs: APEX2, SAINT, XPREP and XCIF (Bruker, 2013 ), SHELXT (Sheldrick, 2015a ), SHELXL2013 (Sheldrick, 2015b ), SHELXTL (Sheldrick, 2008 ), CrystalMaker (CrystalMaker, 2014 ) and publCIF (Westrip, 2010 ).

Supporting information

CCDC reference: 1412851

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989015013535/cv5491sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989015013535/cv5491Isup2.hkl

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2013); cell refinement: SAINT (Bruker, 2013); data reduction: SAINT (Bruker, 2013), XPREP (Bruker, 2013), SADABS (Bruker, 2012) and TWINABS (Bruker, 2012); program(s) used to solve structure: SHELXTL (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2015b); molecular graphics: SHELXTL (Bruker, 2013) and CrystalMaker (CrystalMaker, 2014); software used to prepare material for publication: XCIF (Bruker, 2013) and publCIF (Westrip, 2010).

Tetrakis(acetylacetonato)dichloridodi-µ₃-methanolato-tetra-µ₂-methanolato-tetrairon(III) top

Crystal data top

[Fe₄(C₅H₇O₂)₄(CH₃O)₆Cl₂]	D_x = 1.590 Mg m⁻³
M_r = 876.93	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pbca	Cell parameters from 9882 reflections
a = 14.0714 (6) Å	θ = 2.4–28.3°
b = 12.1888 (4) Å	µ = 1.76 mm⁻¹
c = 21.3543 (7) Å	T = 102 K
V = 3662.6 (2) Å³	Prism, orange
Z = 4	0.38 × 0.37 × 0.23 mm
F(000) = 1808

Data collection top

Bruker D8 Venture/Photon 100 diffractometer	4559 independent reflections
Radiation source: microfocus sealed tube	3837 reflections with I > 2σ(I)
Multilayer mirrors monochromator	R_int = 0.060
profile data from φ and ω scans	θ_max = 28.3°, θ_min = 2.9°
Absorption correction: integration (SADABS; Bruker, 2012)	h = −18→18
T_min = 0.568, T_max = 0.718	k = −15→16
46682 measured reflections	l = −28→28

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.028	H-atom parameters constrained
wR(F²) = 0.070	w = 1/[σ²(F_o²) + (0.0352P)² + 1.8648P] where P = (F_o² + 2F_c²)/3
S = 1.04	(Δ/σ)_max = 0.001
4559 reflections	Δρ_max = 0.39 e Å⁻³
215 parameters	Δρ_min = −0.34 e Å⁻³

Special details top

Experimental. One distinct cell was identified using APEX2 (Bruker, 2013). Four frame series were integrated and filtered for statistical outliers using SAINT (Bruker, 2013) then corrected for absorption by integration using SADABS v2012/1 (Bruker, 2012). No decay correction was applied.

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. Structure was phased by intrinsic phasing methods (XT, Sheldrick, 2013). Systematic conditions suggested the unambiguous space group. The space group choice was confirmed by successful convergence of the full-matrix least-squares refinement on F². The final difference Fourier had no significant features. A final analysis of variance between observed and calculated structure factors showed little dependence on amplitude or resolution.

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

	x	y	z	U_iso*/U_eq
Fe1	0.44600 (2)	0.60052 (2)	0.38841 (2)	0.01161 (7)
Fe2	0.49483 (2)	0.38287 (2)	0.46636 (2)	0.01051 (7)
Cl1	0.31634 (3)	0.65927 (4)	0.33408 (2)	0.01952 (11)
O1	0.52694 (10)	0.73202 (11)	0.37204 (6)	0.0177 (3)
O2	0.51458 (9)	0.52865 (11)	0.31778 (6)	0.0170 (3)
O3	0.39890 (9)	0.45244 (10)	0.41172 (5)	0.0126 (2)
O4	0.55491 (8)	0.53740 (10)	0.45395 (5)	0.0106 (2)
O5	0.59118 (9)	0.33767 (10)	0.52897 (5)	0.0130 (3)
O6	0.41693 (9)	0.25001 (10)	0.47819 (6)	0.0158 (3)
O7	0.56371 (9)	0.31011 (10)	0.39767 (6)	0.0153 (3)
C1	0.63600 (17)	0.85947 (17)	0.33019 (11)	0.0306 (5)
H1A	0.5958	0.9116	0.3530	0.046*
H1B	0.6452	0.8854	0.2872	0.046*
H1C	0.6978	0.8535	0.3511	0.046*
C2	0.58856 (14)	0.74858 (16)	0.32912 (9)	0.0190 (4)
C3	0.61526 (14)	0.67189 (17)	0.28427 (9)	0.0204 (4)
H3	0.6604	0.6933	0.2535	0.024*
C4	0.57959 (13)	0.56530 (16)	0.28188 (8)	0.0169 (4)
C5	0.61965 (15)	0.48447 (18)	0.23600 (9)	0.0246 (4)
H5A	0.6607	0.4323	0.2581	0.037*
H5B	0.6568	0.5236	0.2042	0.037*
H5C	0.5676	0.4447	0.2157	0.037*
C6	0.34499 (14)	0.38938 (16)	0.36761 (9)	0.0201 (4)
H6A	0.3847	0.3723	0.3312	0.030*
H6B	0.2894	0.4317	0.3541	0.030*
H6C	0.3240	0.3210	0.3874	0.030*
C7	0.65434 (12)	0.54563 (16)	0.43948 (8)	0.0151 (4)
H7A	0.6918	0.5215	0.4756	0.023*
H7B	0.6701	0.6220	0.4296	0.023*
H7C	0.6690	0.4990	0.4034	0.023*
C8	0.63734 (16)	0.23375 (17)	0.52457 (10)	0.0242 (5)
H8A	0.5895	0.1754	0.5233	0.036*
H8B	0.6785	0.2232	0.5611	0.036*
H8C	0.6757	0.2313	0.4863	0.036*
C9	0.35287 (16)	0.07273 (17)	0.46844 (10)	0.0258 (5)
H9A	0.3624	0.0571	0.5130	0.039*
H9B	0.3634	0.0057	0.4440	0.039*
H9C	0.2878	0.0987	0.4617	0.039*
C10	0.42174 (14)	0.15947 (15)	0.44786 (9)	0.0171 (4)
C11	0.48468 (15)	0.13917 (15)	0.39877 (9)	0.0198 (4)
H11	0.4823	0.0689	0.3796	0.024*
C12	0.55074 (14)	0.21388 (16)	0.37582 (9)	0.0175 (4)
C13	0.61370 (17)	0.18240 (18)	0.32192 (10)	0.0286 (5)
H13A	0.6064	0.2360	0.2881	0.043*
H13B	0.5957	0.1095	0.3067	0.043*
H13C	0.6801	0.1812	0.3358	0.043*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Fe1	0.01076 (13)	0.01374 (13)	0.01034 (12)	−0.00004 (9)	0.00102 (9)	0.00161 (9)
Fe2	0.01094 (13)	0.01008 (12)	0.01050 (13)	−0.00020 (9)	0.00027 (9)	−0.00061 (9)
Cl1	0.0182 (2)	0.0259 (2)	0.0145 (2)	0.00438 (18)	−0.00364 (17)	0.00256 (17)
O1	0.0174 (7)	0.0180 (7)	0.0179 (7)	−0.0018 (5)	0.0040 (5)	0.0027 (5)
O2	0.0156 (7)	0.0208 (7)	0.0146 (6)	0.0001 (5)	0.0040 (5)	0.0015 (5)
O3	0.0119 (6)	0.0147 (6)	0.0112 (6)	−0.0025 (5)	−0.0017 (5)	−0.0005 (5)
O4	0.0074 (6)	0.0125 (6)	0.0121 (6)	−0.0004 (5)	0.0015 (4)	0.0004 (5)
O5	0.0127 (6)	0.0126 (6)	0.0138 (6)	0.0031 (5)	−0.0001 (5)	−0.0005 (5)
O6	0.0164 (7)	0.0139 (6)	0.0171 (6)	−0.0030 (5)	0.0016 (5)	0.0001 (5)
O7	0.0166 (7)	0.0144 (6)	0.0149 (6)	−0.0002 (5)	0.0029 (5)	−0.0029 (5)
C1	0.0292 (12)	0.0239 (11)	0.0388 (13)	−0.0074 (9)	0.0114 (10)	0.0021 (9)
C2	0.0147 (9)	0.0205 (10)	0.0216 (10)	−0.0003 (8)	−0.0005 (8)	0.0080 (8)
C3	0.0154 (10)	0.0280 (10)	0.0177 (9)	−0.0016 (8)	0.0047 (7)	0.0064 (8)
C4	0.0134 (9)	0.0268 (10)	0.0105 (8)	0.0042 (8)	−0.0008 (7)	0.0044 (7)
C5	0.0230 (11)	0.0302 (11)	0.0205 (10)	0.0037 (9)	0.0077 (8)	−0.0007 (8)
C6	0.0198 (10)	0.0216 (10)	0.0191 (9)	−0.0059 (8)	−0.0080 (8)	−0.0011 (7)
C7	0.0076 (8)	0.0205 (9)	0.0172 (9)	−0.0002 (7)	0.0020 (7)	0.0018 (7)
C8	0.0272 (11)	0.0190 (10)	0.0263 (11)	0.0127 (8)	−0.0064 (9)	−0.0051 (8)
C9	0.0244 (11)	0.0176 (10)	0.0353 (12)	−0.0064 (8)	0.0005 (9)	0.0005 (8)
C10	0.0164 (9)	0.0131 (9)	0.0217 (9)	−0.0005 (7)	−0.0053 (7)	0.0014 (7)
C11	0.0236 (11)	0.0129 (9)	0.0229 (10)	−0.0008 (7)	−0.0019 (8)	−0.0056 (7)
C12	0.0193 (10)	0.0182 (9)	0.0151 (9)	0.0044 (8)	−0.0013 (7)	−0.0035 (7)
C13	0.0334 (13)	0.0252 (11)	0.0274 (11)	0.0016 (9)	0.0113 (9)	−0.0107 (9)

Geometric parameters (Å, º) top

Fe1—O3	1.9861 (12)	C3—C4	1.394 (3)
Fe1—O5ⁱ	1.9885 (12)	C3—H3	0.9500
Fe1—O2	1.9934 (13)	C4—C5	1.499 (3)
Fe1—O1	1.9971 (13)	C5—H5A	0.9800
Fe1—O4	2.2135 (12)	C5—H5B	0.9800
Fe1—Cl1	2.2776 (5)	C5—H5C	0.9800
Fe2—O7	1.9692 (12)	C6—H6A	0.9800
Fe2—O6	1.9717 (13)	C6—H6B	0.9800
Fe2—O3	1.9755 (12)	C6—H6C	0.9800
Fe2—O5	1.9823 (12)	C7—H7A	0.9800
Fe2—O4ⁱ	2.0809 (12)	C7—H7B	0.9800
Fe2—O4	2.0815 (12)	C7—H7C	0.9800
O1—C2	1.278 (2)	C8—H8A	0.9800
O2—C4	1.274 (2)	C8—H8B	0.9800
O3—C6	1.433 (2)	C8—H8C	0.9800
O4—C7	1.436 (2)	C9—C10	1.500 (3)
O4—Fe2ⁱ	2.0808 (12)	C9—H9A	0.9800
O5—C8	1.426 (2)	C9—H9B	0.9800
O5—Fe1ⁱ	1.9885 (12)	C9—H9C	0.9800
O6—C10	1.281 (2)	C10—C11	1.394 (3)
O7—C12	1.275 (2)	C11—C12	1.391 (3)
C1—C2	1.508 (3)	C11—H11	0.9500
C1—H1A	0.9800	C12—C13	1.502 (3)
C1—H1B	0.9800	C13—H13A	0.9800
C1—H1C	0.9800	C13—H13B	0.9800
C2—C3	1.390 (3)	C13—H13C	0.9800

O3—Fe1—O5ⁱ	91.96 (5)	O1—C2—C1	115.54 (18)
O3—Fe1—O2	87.24 (5)	C3—C2—C1	119.58 (18)
O5ⁱ—Fe1—O2	164.84 (5)	C2—C3—C4	123.69 (17)
O3—Fe1—O1	164.47 (5)	C2—C3—H3	118.2
O5ⁱ—Fe1—O1	90.08 (5)	C4—C3—H3	118.2
O2—Fe1—O1	86.80 (5)	O2—C4—C3	124.28 (18)
O3—Fe1—O4	75.92 (5)	O2—C4—C5	115.63 (18)
O5ⁱ—Fe1—O4	75.69 (5)	C3—C4—C5	120.07 (17)
O2—Fe1—O4	89.45 (5)	C4—C5—H5A	109.5
O1—Fe1—O4	89.70 (5)	C4—C5—H5B	109.5
O3—Fe1—Cl1	98.40 (4)	H5A—C5—H5B	109.5
O5ⁱ—Fe1—Cl1	97.01 (4)	C4—C5—H5C	109.5
O2—Fe1—Cl1	98.08 (4)	H5A—C5—H5C	109.5
O1—Fe1—Cl1	96.63 (4)	H5B—C5—H5C	109.5
O4—Fe1—Cl1	170.40 (3)	O3—C6—H6A	109.5
O7—Fe2—O6	89.95 (5)	O3—C6—H6B	109.5
O7—Fe2—O3	95.14 (5)	H6A—C6—H6B	109.5
O6—Fe2—O3	92.77 (5)	O3—C6—H6C	109.5
O7—Fe2—O5	92.33 (5)	H6A—C6—H6C	109.5
O6—Fe2—O5	93.76 (5)	H6B—C6—H6C	109.5
O3—Fe2—O5	170.08 (5)	O4—C7—H7A	109.5
O7—Fe2—O4ⁱ	170.08 (5)	O4—C7—H7B	109.5
O6—Fe2—O4ⁱ	95.27 (5)	H7A—C7—H7B	109.5
O3—Fe2—O4ⁱ	93.02 (5)	O4—C7—H7C	109.5
O5—Fe2—O4ⁱ	78.95 (5)	H7A—C7—H7C	109.5
O7—Fe2—O4	96.48 (5)	H7B—C7—H7C	109.5
O6—Fe2—O4	170.16 (5)	O5—C8—H8A	109.5
O3—Fe2—O4	79.28 (5)	O5—C8—H8B	109.5
O5—Fe2—O4	93.41 (5)	H8A—C8—H8B	109.5
O4ⁱ—Fe2—O4	79.52 (5)	O5—C8—H8C	109.5
C2—O1—Fe1	129.75 (13)	H8A—C8—H8C	109.5
C4—O2—Fe1	130.44 (13)	H8B—C8—H8C	109.5
C6—O3—Fe2	121.31 (11)	C10—C9—H9A	109.5
C6—O3—Fe1	119.96 (11)	C10—C9—H9B	109.5
Fe2—O3—Fe1	108.06 (6)	H9A—C9—H9B	109.5
C7—O4—Fe2ⁱ	118.09 (10)	C10—C9—H9C	109.5
C7—O4—Fe2	119.09 (10)	H9A—C9—H9C	109.5
Fe2ⁱ—O4—Fe2	100.48 (5)	H9B—C9—H9C	109.5
C7—O4—Fe1	120.95 (10)	O6—C10—C11	124.49 (18)
Fe2ⁱ—O4—Fe1	97.00 (5)	O6—C10—C9	115.14 (17)
Fe2—O4—Fe1	96.53 (5)	C11—C10—C9	120.37 (18)
C8—O5—Fe2	120.92 (11)	C12—C11—C10	124.99 (17)
C8—O5—Fe1ⁱ	120.97 (11)	C12—C11—H11	117.5
Fe2—O5—Fe1ⁱ	108.25 (6)	C10—C11—H11	117.5
C10—O6—Fe2	127.83 (12)	O7—C12—C11	124.67 (17)
C12—O7—Fe2	128.04 (12)	O7—C12—C13	115.52 (18)
C2—C1—H1A	109.5	C11—C12—C13	119.81 (17)
C2—C1—H1B	109.5	C12—C13—H13A	109.5
H1A—C1—H1B	109.5	C12—C13—H13B	109.5
C2—C1—H1C	109.5	H13A—C13—H13B	109.5
H1A—C1—H1C	109.5	C12—C13—H13C	109.5
H1B—C1—H1C	109.5	H13A—C13—H13C	109.5
O1—C2—C3	124.85 (18)	H13B—C13—H13C	109.5

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···Cl1ⁱⁱ	0.95	2.91	3.797 (2)	155
C5—H5B···Cl1ⁱⁱ	0.98	2.91	3.800 (2)	152

Symmetry code: (ii) x+1/2, y, −z+1/2.

Acknowledgements

This research was conducted under contract DEFG02-90ER14146 with the US Department of Energy by its Division of Chemical Sciences, Office of Basic Energy Sciences.

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