Two oxo complexes with tetra­nuclear [Fe₄(μ₃-O)₂]⁸⁺ and trinuclear [Fe₃(μ₃-O)]⁷⁺ units

Two new oxo complexes, namely hexa-μ₂-acetato-acetato­aquabis­(di-3-pyridylamine)di-μ₃-oxo-tetra­iron(III) chloride mono­hydrate ethanol 1.25-solvate, [Fe₄(C₂H₃O₂)₇O₂(C₁₀H₉N₃)₂(H₂O)]Cl·1.25C₂H₆O·H₂O, (I), containing a tetra­nuclear [Fe₄(μ₃-O)₂]⁸⁺ unit, and 2-methyl­imidazolium hexa-μ₂-acetato-acetatodiaqua-μ₃-oxo-triiron(III) chloride dihydrate, (C₄H₇N₂)[Fe₃(C₂H₃O₂)₇O(H₂O)₂]Cl·2H₂O, (II), with a trinuclear [Fe₃(μ₃-O)]⁷⁺ unit, are presented. Both structures are formed by two well differentiated entities, viz. a compact isolated cluster composed of Fe^III ions coordinated to O²⁻ and CH₃CO₂⁻ anions, and an external group formed by a central Cl⁻ ion surrounded by different solvent groups to which the anion is bound through hydrogen bonding. In the case of (I), charge balance cannot be achieved within the groups, so the structure is macroscopically ionic; in the case of (II), in contrast, each group is locally neutral owing to the inter­nal compensation of charges. The trinuclear complex crystallizes with the metal cluster, chloride anion and 2-methyl­imidazolium cation bisected by a crystallographic mirror plane.

S1. Comment

Molecules containing one or more oxo-bridged Fe atoms have been the subject of extensive investigation in a variety of contexts, viz. biological [due to the fact that polynuclear oxo-bridged Fe^III units are frequently found in active sites of different proteins (Gilles et al., 2002)], technological [as in the design of new molecule-based magnets (Podgajny et al., 2002; Marchivie et al., 2002; Sokol et al., 2002; Larrionava et al., 2000)], physico-chemical {valence trapping problems in mixed valence [Fe^IIFe^III₂O]⁺⁶ trinuclear carboxylate complexes (Oh et al., 1984; Woehler et al., 1987)], etc.

As a contribution to the general understanding of oxo-bridged polynuclear iron complexes, we present here the crystal structures of two oxo-bridged Fe^III ionic complexes, viz. [Fe₄O₂(CH₃COO)₇(BPA)₂(H₂O)]⁺·Cl⁻·1.25CH₃CH₂OH·H₂O (BPA is bipyridylamine), (I), and [Fe₃O(CH₃COO)₇(H₂O)]·Cl⁻·(MeImid)⁺·H₂O, (II) (MeImid⁺ is 2-methylimidazolinium).

In a general overview, the two structures can be defined as similar in their gross features, being formed by isolated clusters composed of Fe^III ions coordinated to oxo²⁻ and acetate⁻ anions, stabilized by an external group of different solvates having a central Cl⁻ to which they attach through a variety of hydrogen-bonding interactions (see below).

A charge-balance analysis, however, shows the structures to be rather different in that the metal cluster in (I) does not balance the twelve positive charges furnished by the metals with the eleven negative ones provided by the anions (two oxo and seven acetate units). The result is a singly charged cationic cluster externally balanced by a Cl⁻ anion. The cluster in (II), however, is neutral owing to the presence of three Fe³⁺ ion on one hand and one oxo²⁻ and seven acetate⁻ ions on the other; the external part, in turn, also presents electrostatic balance with the Cl⁻ hydrogen bonded to an MeImid⁺ group.

In addition to the coulomb forces present, both group types interact with each other via hydrogen bonding through a definite number of hydrogen bonding `active sites'. Figs. 1 and 4 present complete views of both structures in terms of this latter description, while Figs. 2 and 5 show schematic sketchs of the corresponding metal clusters. It can be readily seen that each one of the general organizational features mentioned so far is achieved in each structure in a different way, according to the number and nature of their ligands/solvates. We shall now describe this fact in detail.

In compound (I), the isolated cationic clusters are composed of four Fe^III cations, coordinated to two oxo²⁻ groups, seven CH₃CO₂⁻ anions, two BPA bases and one water molecule. The internal charge balance gives a net cationic charge of +1.

The cation comprises an innermost core of two Fe atoms (Fe1 and Fe4) doubly bridged by atoms O1 and O2, the oxo units, which in turn connect outwards to the remaining Fe atoms (one each), Fe2 and Fe3, to fulfill their µ₃ coordination. To these outermost Fe atoms, the trinitrogenated BPA bases chelate via the pyridyl atoms N11, N12 and N21, N22, respectively. Adjacent Fe atoms are in turn connected by a different number of acetate bridges: The pairs Fe1,Fe2 and Fe3,Fe4 are doubly bridged by acetates 6, 8 and 4, 5, respectively, while the pairs Fe1, Fe3 and Fe4, Fe2 are singly bridged by acetates 3 and 7, respectively. The central pair Fe1, Fe4 is the only exception to this rather symmetric coordination, their bridging being achieved through a larger, hydrogen-bonded loop involving acetate 9 (singly bound to Fe1) and aqua atom O1W, bound to Fe4. As a consequence of the tight binding resulting from this latter bridge and the double oxo bridges, there is a rather short Fe1···Fe4 distance in the innermost Fe₂O₂ loop [2.924 (1) Å], a value in the lower 7 t h percentile of homologous distances reported for similar loops in the November 2005 version of the Cambridge Structural Database (CSD; Allen, 2002).

All four iron environments are slightly distorted octahedral; as a measure of this distortion, the maximum deviations from the ideal 180° angles are 14.7 (2), 12.95 (19), 12.65 (19) and 9.5 (2)°, respectively, for the sequence Fe1–Fe4.

The Fe—O bond distances also present differences, but with similarly coordinated cations showing analogous trends; thus, the environments for the iron pair Fe1/Fe4 are alike, as are those for Fe2/Fe3.

The first group (Fe1/Fe4) is characterized by three sets of rather similar bond lengths [short, medium and long, with mean values 1.95 (3), 1.99 (2) and 2.06 (2) Å; Table 1], the first corresponding to the oxo bonds, and the other two showing no obvious characteristic telling them apart. The second group also has three sets of distances, the oxo distances being by far the shortest [mean 1.825 (5) Å], the remaning acetate O atoms filling the second [mean 2.027 (9) Å] and finally the BPA N atoms the third [mean 2.17 (2) Å].

The six chelating acetate groups exhibit rather erratic behaviour regarding delocalization of the double bond, as inferred from the differences in their C—O distances, which range from some 0.3% of their mean value (almost complete delocalization) climbing to 9.5% (almost a pure single/double bond situation). Even though this is a rather extreme case for a chelating acetate, it is by no means unique: we could trace in the CSD (Allen, 2002) chelating acetates with asymmetries as large as 10.2% (CSD code ACENOL). The singly coordinated Ac9 seems to lie somewhere in between the two extreme cases, with a 3.7% difference.

The stabilizing `anionic group' in (1) consists of a chloride anion and three solvent molecules [one water and two depleted ethanol sites, with occupation factors 0.52 (2) and 0.73 (2), these latter four molecules strongly linked to each other through hydrogen bonding into a unique, rather `linear' entity as shown in Fig. 1].

In spite of the fact that H atoms attached to O atoms could not be confidently found in the difference Fourier map, a plausible interaction scheme can be envisaged from the short D···A distances between the two clusters.

The cationic group presents three different active sites (Fig. 1), represented by both amino N atoms N31 and N32 (acting as donors) and the set composed of aqua O1W (acting as a donor), and the uncoordinated carboxylate atom O29, a double acceptor of both an intermolecular hydrogen bond from O2W in the anionic group and the only intramolecular hydrogen bond in the cation, from O1W (entries 1–5 in Table 2).

The anionic group, in turn, presents three weak internal interactions attributable to hydrogen bonding and contributing to its internal coherence (entries 6–8 in Table 2).

The final result is a packing structure composed of cationic and anionic sheets parallel to (101), as shown in Fig. 3.

In the case of (II), the isolated metal clusters are composed of three Fe^III cations, centrally coordinated by a single oxo²⁻ group, seven CH₃CO₂⁻ anions, and two water molecules, rendering a neutral environment around the metals.

The group is, however, much more symmetric than its counterpart in (I), being bisected by a mirror plane that passes though one of the Fe atoms (Fe2) and the central oxo O1 atom, and which bisects acetate ions Ac3, Ac4 and Ac5 [symmetry code (i) x, 3/2 − y, z].

The innermost core consists of the Fe₃O group. In addition to this oxo bridging, all pairs of Fe atoms are doubly bridged by acetate anions, as follows: Fe1 and Fe2 by acetate ions Ac1 and Ac2; Fe1 and Fe1ⁱ by acetate ions Ac3 and Ac4. Finally, atom Fe1 (Fe1ⁱ) coordinates to aqua ligand O1W (O1Wⁱ), while atom Fe2 binds to the monocoordinated acetate Ac5. This completes the distorted octahedral environment for each Fe atom (Table 3, and Figs. 4 and 5).

Though to a lesser degree than in (I), the six chelating acetate groups also display a variety of double-bond behaviours, from perfect 100% delocalization in the symmetric Ac3 and Ac4 ions, up to larger differences as in Ac2 (4.2%). The singly coordinated Ac5 ion has an asymmetry of 3.4%.

The `solvate part' in (II) lies, as the iron cluster does, on a symmetry plane passing through Cl1⁻ and the MeImid⁺ cation. The ensemble is completed by two hydration water molecules (atoms O2W and O2Wⁱⁱ in Fig 4), one on each side of the plane.

As with (I), we were unable to find the H atoms involved in hydrogen-bonding interactions in (II), but here again the interaction scheme could be ascertained from the short D···A distances between the clusters. In this case, the cationic group has five active sites (see Fig. 4), represented by O1W as a double donor, O13 as an acceptor, and lastly O15 and O25 as joint acceptors of a single bifurcated interaction with the N1/H1 group (entries 3–7 in Table 4). The anionic group, in turn, is stabilized by two internal hydrogen bonds to Cl1 (entries 1 and 2 in Table 4).

The resulting packing scheme is a three-dimensional structure composed of anionic cages where the cations lodge (Fig. 6).

S2. Experimental

The syntheses were performed according to the procedure reported by McCuster et al. (1991). However, only in the case of (I) did the corresponding amine (BPA) appear, as expected, in a coordinated mode. In the case of (II), the MeImid group did not bind to the cation, ending up as a solvate. For the preparation of (I) and (II), to an orange solution of FeCl₃·6H₂O (2.67 mmol) in ethanol (50 ml) were added sodium acetate (6.63 mmol) and 1.43 mmol of the respective amine, BPA in the case of (1), MeImid in that of (2). The resultant solutions were stirred at room temperature for 10 min. Following the literature method, an excess of KClO₄ was added to the reaction mixture, and the resulting solutions were stirred overnight at room temperature. In both cases, a fine red–brown solid was collected by filtration. Recrystallization from an EtOH/Et₂O mixture provided the poorly diffracting crystals used for data collection.

S3. Refinement

H atoms attached to C and N atoms were placed at calculated positions (N—H = 0.86 Å, C—H_aromatic = 0.93 Å and C—H_methyl = 0.96 Å) and allowed to ride. Even though located in a poorly defined, rather shallow, electron density plateau, H atoms from the methyl groups were also included [AFIX 137 in SHELXL97 (Sheldrick, 1997)] because of their incidence in the refinement. Those attached to O, however, were excluded, because they could not be confidently located from the difference Fourier syntheses. It was therefore preferred to derive a hydrogen-bonding description mainly in terms of short O···O/O···N contacts. All H atoms included were assigned a U_iso(H) value of xU_eq(host), with x = 1.2 for aromatic H atoms and x = 1.5 for methyl H atoms. The quality of the crystals obtained was extremely poor and only with rather long measurement times (20 and 25 s per frame, respectively) was it possible to account for an observed/unique ratio larger than 0.5 (about 0.55 in both cases).

Computing details

For both compounds, data collection: SMART-NT (Bruker, 2001); cell refinement: SAINT-NT (Bruker, 2000); data reduction: SAINT-NT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP in SHELXTL-NT (Bruker, 2000); software used to prepare material for publication: SHELXL97.

Figures

	Fig. 1. : A molecular ellipsoid plot of (I) (30% probability level), showing the complete tetrameric cation and the three symmetry-related `anionic groups' hydrogen bonded to it. Independent atoms are drawn in principal axis displacement ellipsoids, while their symmetry-related counterparts are shown as open ones. Heavy broken lines denote interactions internal to the `anionic groups'; light broken lines denote those involving the cation. C atoms are not labelled for clarity. Symmetry codes are as in Table 2.
	Fig. 2. : A schematic view of the tetrameric core in (I), with H and some C atoms omitted, for clarity. Double dashed lines denote the intramolecular hydrogen bond connecting atom O1W and acetate ion 9.
	Fig. 3. : A packing plot of (I), viewed along b and showing the way in which both cationic and anionic groups form sheets parallel to (101), the anions (in bold lines) passing through the cell center, and the cations (in light lines) lying immediately above/below the cell center.
	Fig. 4. : A molecular ellipsoid plot of (II) (30% probability level), showing the complete trimeric cation and the four symmetry-related `anionic groups' hydrogen bonded to it. Independent atoms drawn in principal axis displacement ellipsoids, while their symmetry-related counterparts are shown as open ones. Heavy broken lines denote interactions internal to the `anionic groups'; light broken lines those involving the cation. C atoms are not labelled for clarity. Symmetry codes are as in Table 4.
	Fig. 5. : A schematic view of the trimeric core in (II), with H and some C atoms omitted, for clarity.
	Fig. 6. : A packing plot of (II), viewed along c and showing the anionic cages (in bolder lines) in which the cationic groups (in lighter lines) lodge.

(I) hexa-µ₂-acetato-acetatoaqua(di-3-pyridylamine)di-µ₃-oxo-tetrairon(III) chloride monohydrate ethanol 1.25-solvate

Crystal data

[Fe4(C2H3O2)7O2(C10H9N3)2(H2O)]Cl·1.25C2H6O·H2O	F(000) = 2346
Mr = 1140.18	Dx = 1.494 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 3678 reflections
a = 16.044 (4) Å	θ = 2.3–23.7°
b = 17.619 (4) Å	µ = 1.25 mm^−1
c = 17.942 (5) Å	T = 295 K
β = 91.571 (5)°	Plates, red
V = 5070 (2) Å^3	0.23 × 0.15 × 0.08 mm
Z = 4

Data collection

Bruker SMART CCD area-detector diffractometer	8964 independent reflections
Radiation source: fine-focus sealed tube	4931 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.072
ϕ and ω scans	θmax = 25.2°, θmin = 1.6°
Absorption correction: multi-scan (SADABS; Sheldrick, 2001)	h = −19→19
Tmin = 0.79, Tmax = 0.90	k = −20→21
8964 measured reflections	l = −21→21

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.068	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.160	H-atom parameters constrained
S = 1.01	w = 1/[σ^2(Fo^2) + (0.0623P)^2] where P = (Fo^2 + 2Fc^2)/3
8964 reflections	(Δ/σ)max = 0.007
635 parameters	Δρmax = 0.48 e Å^−3
0 restraints	Δρmin = −0.50 e Å^−3

Special details

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
Fe1	0.66459 (6)	0.68617 (5)	0.14334 (5)	0.0350 (3)
Fe2	0.61716 (6)	0.68213 (6)	−0.03867 (5)	0.0376 (3)
Fe3	0.60828 (6)	0.83537 (6)	0.25238 (5)	0.0367 (3)
Fe4	0.65251 (6)	0.83606 (6)	0.07391 (5)	0.0377 (3)
O1	0.6626 (3)	0.7281 (3)	0.0438 (2)	0.0373 (12)
O2	0.6581 (3)	0.7931 (3)	0.1719 (2)	0.0377 (12)
N11	0.5681 (3)	0.6267 (3)	−0.1389 (3)	0.0422 (15)
N21	0.7188 (4)	0.7056 (3)	−0.1103 (3)	0.0427 (15)
N31	0.6378 (3)	0.7040 (3)	−0.2217 (3)	0.0422 (15)
H31N	0.6283	0.7332	−0.2594	0.051*
C11	0.5104 (4)	0.5703 (4)	−0.1296 (4)	0.0454 (19)
H11	0.5033	0.5515	−0.0817	0.054*
C21	0.4637 (5)	0.5409 (5)	−0.1851 (5)	0.069 (3)
H21	0.4268	0.5012	−0.1774	0.083*
C31	0.4733 (6)	0.5730 (5)	−0.2555 (5)	0.078 (3)
H31	0.4391	0.5564	−0.2948	0.094*
C41	0.5315 (5)	0.6285 (5)	−0.2688 (4)	0.063 (2)
H41	0.5392	0.6487	−0.3160	0.075*
C51	0.5767 (3)	0.6513 (3)	−0.2080 (3)	0.0334 (16)
C61	0.7123 (3)	0.7164 (3)	−0.1830 (3)	0.0328 (16)
C71	0.7792 (5)	0.7411 (4)	−0.2229 (4)	0.051 (2)
H71	0.7725	0.7492	−0.2739	0.061*
C81	0.8554 (5)	0.7539 (5)	−0.1889 (4)	0.063 (2)
H81	0.9006	0.7704	−0.2159	0.076*
C91	0.8626 (4)	0.7413 (4)	−0.1129 (4)	0.054 (2)
H91	0.9127	0.7500	−0.0869	0.065*
C101	0.7940 (4)	0.7158 (4)	−0.0769 (4)	0.047 (2)
H101	0.7997	0.7048	−0.0263	0.056*
N12	0.5555 (4)	0.8822 (3)	0.3530 (3)	0.0469 (16)
N22	0.7162 (3)	0.8153 (3)	0.3279 (3)	0.0398 (14)
N32	0.6349 (3)	0.8076 (3)	0.4342 (3)	0.0584 (19)
H32N	0.6308	0.7812	0.4743	0.070*
C12	0.4927 (4)	0.9325 (4)	0.3444 (4)	0.0452 (19)
H12	0.4829	0.9537	0.2975	0.054*
C22	0.4437 (6)	0.9533 (5)	0.3998 (5)	0.074 (3)
H22	0.4011	0.9885	0.3922	0.089*
C32	0.4589 (6)	0.9205 (6)	0.4692 (5)	0.081 (3)
H32	0.4251	0.9331	0.5086	0.097*
C42	0.5194 (4)	0.8725 (5)	0.4801 (5)	0.056 (2)
H42	0.5308	0.8521	0.5271	0.068*
C52	0.5655 (3)	0.8531 (4)	0.4205 (4)	0.0358 (17)
C62	0.7092 (4)	0.7946 (4)	0.3988 (3)	0.0386 (18)
C72	0.7754 (5)	0.7619 (4)	0.4381 (4)	0.052 (2)
H72	0.7686	0.7462	0.4871	0.063*
C82	0.8478 (5)	0.7531 (4)	0.4068 (4)	0.051 (2)
H82	0.8925	0.7313	0.4332	0.061*
C92	0.8565 (4)	0.7765 (4)	0.3345 (5)	0.055 (2)
H92	0.9077	0.7720	0.3117	0.066*
C102	0.7891 (4)	0.8064 (5)	0.2958 (4)	0.058 (2)
H102	0.7946	0.8207	0.2463	0.070*
O13	0.5599 (3)	0.7384 (3)	0.2923 (2)	0.0420 (12)
O23	0.6437 (3)	0.6502 (3)	0.2467 (2)	0.0411 (12)
C13	0.5928 (4)	0.6743 (4)	0.2919 (4)	0.0292 (15)
C23	0.5564 (6)	0.6202 (5)	0.3479 (5)	0.088 (3)
H23A	0.5899	0.5751	0.3510	0.132*
H23B	0.5005	0.6070	0.3324	0.132*
H23C	0.5557	0.6441	0.3960	0.132*
O14	0.4984 (3)	0.8581 (3)	0.1968 (3)	0.0467 (13)
O24	0.5247 (3)	0.8410 (3)	0.0769 (3)	0.0441 (12)
C14	0.4778 (4)	0.8545 (4)	0.1287 (4)	0.0377 (17)
C24	0.3843 (5)	0.8663 (5)	0.1087 (5)	0.083 (3)
H24A	0.3784	0.8858	0.0588	0.124*
H24B	0.3608	0.9018	0.1429	0.124*
H24C	0.3555	0.8187	0.1119	0.124*
O15	0.6495 (3)	0.9420 (3)	0.2342 (3)	0.0532 (14)
O25	0.6537 (3)	0.9438 (3)	0.1102 (3)	0.0508 (14)
C15	0.6682 (4)	0.9719 (4)	0.1736 (4)	0.0425 (19)
C25	0.7044 (6)	1.0485 (5)	0.1773 (5)	0.091 (3)
H25A	0.7453	1.0507	0.2172	0.137*
H25B	0.6611	1.0848	0.1860	0.137*
H25C	0.7303	1.0599	0.1310	0.137*
O16	0.6716 (3)	0.5804 (3)	−0.0182 (3)	0.0484 (13)
O26	0.6747 (3)	0.5770 (3)	0.1060 (3)	0.0514 (14)
C16	0.6895 (4)	0.5501 (4)	0.0451 (4)	0.0345 (17)
C26	0.7319 (5)	0.4761 (5)	0.0465 (5)	0.072 (3)
H26A	0.7680	0.4730	0.0899	0.107*
H26B	0.7642	0.4708	0.0025	0.107*
H26C	0.6911	0.4363	0.0479	0.107*
O17	0.5614 (3)	0.7756 (3)	−0.0833 (2)	0.0419 (12)
O27	0.6338 (3)	0.8703 (3)	−0.0315 (3)	0.0433 (13)
C17	0.5875 (6)	0.8450 (5)	−0.0773 (5)	0.059 (2)
C27	0.5389 (7)	0.8980 (5)	−0.1295 (6)	0.105 (4)
H27A	0.5603	0.9487	−0.1242	0.157*
H27B	0.4811	0.8973	−0.1172	0.157*
H27C	0.5448	0.8814	−0.1801	0.157*
O18	0.5103 (3)	0.6509 (3)	0.0116 (3)	0.0426 (13)
O28	0.5361 (3)	0.6708 (3)	0.1331 (3)	0.0426 (12)
C18	0.4935 (4)	0.6544 (4)	0.0785 (4)	0.0426 (19)
C28	0.4003 (5)	0.6371 (5)	0.0950 (5)	0.073 (3)
H28A	0.3965	0.6164	0.1443	0.110*
H28B	0.3786	0.6011	0.0593	0.110*
H28C	0.3684	0.6831	0.0915	0.110*
O19	0.7851 (3)	0.6747 (3)	0.1648 (3)	0.0618 (15)
O29	0.8769 (4)	0.7410 (4)	0.1001 (4)	0.102 (2)
C19	0.8620 (5)	0.6903 (6)	0.1468 (5)	0.064 (2)
C29	0.9240 (5)	0.6392 (5)	0.1775 (5)	0.084 (3)
H29A	0.9778	0.6529	0.1597	0.127*
H29B	0.9109	0.5882	0.1624	0.127*
H29C	0.9246	0.6424	0.2310	0.127*
O1A	0.1618 (10)	0.5819 (9)	0.1995 (10)	0.144 (6)	0.52 (2)
C1A	0.2417 (11)	0.5563 (10)	0.2101 (14)	0.114 (8)	0.52 (2)
H1AA	0.2676	0.5871	0.2490	0.137*	0.52 (2)
H1AB	0.2711	0.5667	0.1647	0.137*	0.52 (2)
C2A	0.2570 (10)	0.4789 (10)	0.2290 (11)	0.097 (7)	0.52 (2)
H2AA	0.3102	0.4746	0.2543	0.145*	0.52 (2)
H2AB	0.2568	0.4488	0.1843	0.145*	0.52 (2)
H2AC	0.2141	0.4612	0.2610	0.145*	0.52 (2)
O1B	0.8904 (5)	0.9528 (5)	0.0365 (6)	0.085 (3)	0.73 (2)
C1B	0.8796 (11)	0.9820 (10)	−0.0352 (7)	0.141 (7)	0.73 (2)
H1BA	0.8628	0.9411	−0.0685	0.169*	0.73 (2)
H1BB	0.9327	1.0012	−0.0516	0.169*	0.73 (2)
C2B	0.8183 (11)	1.0424 (10)	−0.0416 (10)	0.170 (9)	0.73 (2)
H2BA	0.8192	1.0638	−0.0907	0.255*	0.73 (2)
H2BB	0.8312	1.0810	−0.0054	0.255*	0.73 (2)
H2BC	0.7638	1.0222	−0.0328	0.255*	0.73 (2)
Cl1	0.15592 (15)	0.74444 (16)	0.10728 (12)	0.0861 (8)
O1W	0.7793 (3)	0.8503 (3)	0.0692 (3)	0.0618 (15)
O2W	0.9975 (5)	0.8290 (4)	0.0347 (4)	0.113 (2)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Fe1	0.0299 (5)	0.0343 (6)	0.0406 (6)	0.0005 (5)	−0.0013 (4)	0.0018 (5)
Fe2	0.0360 (6)	0.0397 (7)	0.0373 (6)	−0.0015 (5)	0.0028 (5)	0.0002 (5)
Fe3	0.0297 (5)	0.0385 (7)	0.0419 (6)	−0.0030 (5)	−0.0014 (5)	−0.0041 (5)
Fe4	0.0402 (6)	0.0362 (6)	0.0367 (6)	−0.0042 (5)	−0.0005 (5)	0.0016 (5)
O1	0.026 (3)	0.049 (3)	0.037 (3)	−0.014 (2)	0.001 (2)	−0.006 (2)
O2	0.027 (2)	0.049 (3)	0.037 (3)	−0.002 (2)	−0.014 (2)	−0.010 (2)
N11	0.044 (4)	0.036 (4)	0.046 (4)	−0.014 (3)	−0.013 (3)	0.000 (3)
N21	0.056 (4)	0.041 (4)	0.031 (3)	−0.003 (3)	0.012 (3)	−0.002 (3)
N31	0.043 (4)	0.048 (4)	0.036 (3)	−0.004 (3)	−0.004 (3)	0.011 (3)
C11	0.043 (4)	0.046 (5)	0.046 (5)	−0.007 (4)	−0.013 (4)	−0.014 (4)
C21	0.062 (6)	0.070 (6)	0.077 (7)	−0.029 (5)	0.021 (5)	−0.010 (5)
C31	0.086 (7)	0.075 (7)	0.072 (7)	−0.026 (6)	−0.007 (6)	−0.029 (5)
C41	0.079 (6)	0.080 (7)	0.031 (5)	−0.017 (5)	0.014 (4)	−0.008 (4)
C51	0.021 (3)	0.037 (4)	0.042 (4)	−0.012 (3)	0.006 (3)	0.003 (3)
C61	0.031 (4)	0.042 (4)	0.026 (4)	−0.012 (3)	0.000 (3)	0.002 (3)
C71	0.054 (5)	0.057 (5)	0.040 (4)	−0.009 (4)	0.003 (4)	0.001 (4)
C81	0.028 (4)	0.103 (7)	0.059 (6)	−0.002 (4)	0.005 (4)	0.003 (5)
C91	0.028 (4)	0.070 (5)	0.064 (5)	−0.010 (4)	−0.004 (4)	0.004 (4)
C101	0.022 (4)	0.048 (5)	0.068 (5)	0.007 (3)	−0.012 (4)	0.009 (4)
N12	0.061 (4)	0.047 (4)	0.033 (4)	0.009 (3)	−0.004 (3)	−0.005 (3)
N22	0.048 (4)	0.038 (4)	0.033 (3)	0.001 (3)	−0.010 (3)	−0.006 (3)
N32	0.066 (5)	0.071 (5)	0.039 (4)	−0.008 (4)	0.012 (3)	−0.008 (3)
C12	0.023 (4)	0.057 (5)	0.056 (5)	0.006 (4)	0.009 (3)	−0.009 (4)
C22	0.090 (7)	0.070 (7)	0.062 (6)	0.009 (5)	0.010 (5)	−0.005 (5)
C32	0.089 (8)	0.101 (8)	0.053 (6)	−0.004 (6)	0.023 (5)	−0.011 (6)
C42	0.030 (4)	0.068 (6)	0.071 (6)	0.011 (4)	0.003 (4)	0.009 (5)
C52	0.012 (3)	0.044 (5)	0.052 (5)	0.002 (3)	0.006 (3)	−0.006 (4)
C62	0.025 (4)	0.042 (5)	0.049 (5)	−0.018 (3)	−0.005 (3)	0.003 (4)
C72	0.052 (5)	0.061 (6)	0.043 (5)	0.007 (4)	−0.002 (4)	−0.006 (4)
C82	0.032 (4)	0.053 (5)	0.068 (6)	0.017 (4)	0.004 (4)	−0.002 (4)
C92	0.019 (4)	0.068 (6)	0.079 (6)	0.010 (4)	0.007 (4)	−0.007 (5)
C102	0.032 (4)	0.088 (7)	0.055 (5)	−0.008 (4)	0.022 (4)	−0.019 (4)
O13	0.055 (3)	0.038 (3)	0.034 (3)	−0.014 (3)	0.007 (2)	−0.004 (2)
O23	0.022 (2)	0.057 (3)	0.044 (3)	0.017 (2)	−0.009 (2)	−0.003 (2)
C13	0.026 (3)	0.015 (4)	0.047 (4)	0.003 (3)	0.000 (3)	0.004 (3)
C23	0.099 (8)	0.088 (8)	0.079 (7)	0.018 (6)	0.042 (6)	0.031 (6)
O14	0.032 (3)	0.058 (4)	0.050 (3)	0.019 (2)	0.002 (2)	−0.005 (3)
O24	0.051 (3)	0.041 (3)	0.041 (3)	0.000 (2)	0.007 (2)	−0.003 (2)
C14	0.026 (4)	0.044 (5)	0.043 (5)	0.005 (3)	−0.005 (3)	−0.004 (4)
C24	0.047 (5)	0.119 (8)	0.083 (7)	0.021 (5)	−0.004 (5)	−0.014 (6)
O15	0.074 (4)	0.039 (3)	0.047 (3)	−0.010 (3)	0.003 (3)	0.001 (3)
O25	0.064 (4)	0.042 (3)	0.046 (3)	−0.001 (3)	−0.006 (3)	0.001 (3)
C15	0.045 (4)	0.037 (5)	0.045 (5)	−0.024 (4)	−0.005 (4)	−0.009 (4)
C25	0.109 (8)	0.079 (8)	0.087 (7)	−0.021 (6)	0.019 (6)	−0.013 (6)
O16	0.058 (3)	0.038 (3)	0.050 (3)	0.013 (3)	0.005 (3)	0.006 (3)
O26	0.076 (4)	0.043 (3)	0.036 (3)	0.011 (3)	0.009 (3)	0.003 (2)
C16	0.038 (4)	0.022 (4)	0.044 (5)	−0.017 (3)	0.012 (4)	−0.010 (3)
C26	0.076 (6)	0.057 (6)	0.081 (6)	0.027 (5)	−0.009 (5)	0.005 (5)
O17	0.043 (3)	0.038 (3)	0.044 (3)	−0.001 (2)	−0.006 (2)	−0.001 (2)
O27	0.027 (3)	0.059 (4)	0.044 (3)	−0.013 (2)	−0.011 (2)	0.000 (3)
C17	0.081 (7)	0.045 (6)	0.053 (6)	0.004 (5)	0.010 (5)	0.021 (4)
C27	0.113 (9)	0.078 (8)	0.120 (9)	−0.012 (6)	−0.051 (7)	0.026 (6)
O18	0.028 (3)	0.060 (4)	0.040 (3)	−0.023 (2)	0.006 (2)	0.005 (2)
O28	0.016 (2)	0.060 (4)	0.052 (3)	−0.013 (2)	−0.001 (2)	−0.005 (3)
C18	0.033 (4)	0.046 (5)	0.049 (5)	−0.027 (4)	0.003 (4)	0.005 (4)
C28	0.045 (5)	0.101 (8)	0.074 (6)	−0.017 (5)	−0.001 (5)	−0.007 (5)
O19	0.041 (3)	0.070 (4)	0.075 (4)	0.024 (3)	0.003 (3)	0.014 (3)
O29	0.052 (4)	0.148 (7)	0.106 (5)	0.012 (4)	0.007 (4)	0.060 (5)
C19	0.051 (5)	0.086 (7)	0.056 (6)	0.011 (5)	0.015 (4)	−0.004 (5)
C29	0.041 (5)	0.127 (9)	0.085 (7)	0.032 (5)	−0.017 (5)	0.017 (6)
O1A	0.120 (13)	0.109 (12)	0.200 (16)	−0.027 (11)	−0.028 (13)	−0.027 (11)
C1A	0.096 (16)	0.091 (17)	0.157 (19)	−0.046 (14)	0.022 (15)	−0.023 (14)
C2A	0.072 (13)	0.113 (16)	0.105 (15)	−0.043 (12)	0.001 (11)	0.002 (13)
O1B	0.052 (5)	0.089 (7)	0.113 (8)	−0.018 (5)	0.011 (5)	0.029 (6)
C1B	0.122 (15)	0.121 (15)	0.181 (18)	0.034 (12)	0.030 (14)	−0.021 (13)
C2B	0.139 (16)	0.193 (19)	0.177 (18)	0.018 (15)	−0.012 (14)	0.035 (15)
Cl1	0.0620 (15)	0.145 (2)	0.0512 (14)	0.0106 (15)	0.0009 (11)	−0.0209 (14)
O1W	0.026 (3)	0.075 (4)	0.084 (4)	−0.016 (3)	−0.002 (3)	0.007 (3)
O2W	0.119 (6)	0.109 (6)	0.112 (6)	−0.008 (5)	0.002 (5)	0.013 (4)

Geometric parameters (Å, º)

Fe1—O1	1.933 (4)	C82—H82	0.9300
Fe1—O2	1.956 (5)	C92—C102	1.374 (10)
Fe1—O19	1.971 (5)	C92—H92	0.9300
Fe1—O23	1.996 (5)	C102—H102	0.9300
Fe1—O26	2.044 (5)	O13—C13	1.246 (7)
Fe1—O28	2.082 (4)	O23—C13	1.242 (7)
Fe2—O1	1.820 (4)	C13—C23	1.514 (10)
Fe2—O16	2.024 (5)	C23—H23A	0.9600
Fe2—O17	2.028 (5)	C23—H23B	0.9600
Fe2—O18	2.035 (4)	C23—H23C	0.9600
Fe2—N21	2.145 (5)	O14—C14	1.258 (7)
Fe2—N11	2.175 (5)	O24—C14	1.235 (8)
Fe3—O2	1.828 (4)	C14—C24	1.547 (9)
Fe3—O13	2.016 (5)	C24—H24A	0.9600
Fe3—O15	2.021 (5)	C24—H24B	0.9600
Fe3—O14	2.041 (5)	C24—H24C	0.9600
Fe3—N12	2.176 (6)	O15—C15	1.253 (8)
Fe3—N22	2.198 (5)	O25—C15	1.257 (8)
Fe4—O2	1.915 (4)	C15—C25	1.469 (10)
Fe4—O1	1.986 (5)	C25—H25A	0.9600
Fe4—O27	2.000 (5)	C25—H25B	0.9600
Fe4—O25	2.006 (5)	C25—H25C	0.9600
Fe4—O1W	2.054 (5)	O16—C16	1.279 (8)
Fe4—O24	2.055 (5)	O26—C16	1.221 (7)
N11—C51	1.325 (6)	C16—C26	1.471 (9)
N11—C11	1.371 (6)	C26—H26A	0.9600
N21—C61	1.318 (6)	C26—H26B	0.9600
N21—C101	1.344 (6)	C26—H26C	0.9600
N31—C51	1.376 (4)	O17—C17	1.297 (9)
N31—C61	1.384 (4)	O27—C17	1.179 (9)
N31—H31N	0.8600	C17—C27	1.522 (11)
C11—C21	1.335 (10)	C27—H27A	0.9600
C11—H11	0.9300	C27—H27B	0.9600
C21—C31	1.395 (11)	C27—H27C	0.9600
C21—H21	0.9300	O18—C18	1.239 (8)
C31—C41	1.377 (11)	O28—C18	1.213 (8)
C31—H31	0.9300	C18—C28	1.564 (9)
C41—C51	1.355 (9)	C28—H28A	0.9600
C41—H41	0.9300	C28—H28B	0.9600
C61—C71	1.378 (9)	C28—H28C	0.9600
C71—C81	1.370 (10)	O19—C19	1.313 (9)
C71—H71	0.9300	O29—C19	1.251 (10)
C81—C91	1.384 (10)	C19—C29	1.441 (11)
C81—H81	0.9300	C29—H29A	0.9600
C91—C101	1.368 (9)	C29—H29B	0.9600
C91—H91	0.9300	C29—H29C	0.9600
C101—H101	0.9300	O1A—C1A	1.367 (9)
N12—C52	1.322 (6)	C1A—C2A	1.424 (9)
N12—C12	1.348 (6)	C1A—H1AA	0.9700
N22—C102	1.327 (6)	C1A—H1AB	0.9700
N22—C62	1.331 (6)	C2A—H2AA	0.9600
N32—C62	1.384 (4)	C2A—H2AB	0.9600
N32—C52	1.388 (4)	C2A—H2AC	0.9600
N32—H32N	0.8600	O1B—C1B	1.392 (9)
C12—C22	1.336 (10)	C1B—C2B	1.450 (9)
C12—H12	0.9300	C1B—H1BA	0.9700
C22—C32	1.388 (11)	C1B—H1BB	0.9700
C22—H22	0.9300	C2B—H2BA	0.9600
C32—C42	1.298 (11)	C2B—H2BB	0.9600
C32—H32	0.9300	C2B—H2BC	0.9600
C42—C52	1.361 (9)	Fe1—Fe2	3.3335 (16)
C42—H42	0.9300	Fe1—Fe3	3.4134 (16)
C62—C72	1.384 (9)	Fe1—Fe4	2.9243 (16)
C72—C82	1.314 (10)	Fe2—Fe4	3.4199 (17)
C72—H72	0.9300	Fe3—Fe4	3.2990 (16)
C82—C92	1.373 (10)	Fe2—Fe3	5.8840 (16)
O1—Fe1—O2	82.83 (18)	C22—C32—H32	119.3
O1—Fe1—O19	102.2 (2)	C32—C42—C52	117.7 (8)
O2—Fe1—O19	96.1 (2)	C32—C42—H42	121.1
O1—Fe1—O23	168.76 (18)	C52—C42—H42	121.1
O2—Fe1—O23	92.89 (19)	N12—C52—C42	124.6 (6)
O19—Fe1—O23	88.57 (19)	N12—C52—N32	117.6 (6)
O1—Fe1—O26	93.20 (18)	C42—C52—N32	117.2 (6)
O2—Fe1—O26	175.74 (19)	N22—C62—N32	119.3 (6)
O19—Fe1—O26	83.2 (2)	N22—C62—C72	121.2 (6)
O23—Fe1—O26	91.30 (19)	N32—C62—C72	119.5 (6)
O1—Fe1—O28	88.64 (18)	C82—C72—C62	120.4 (7)
O2—Fe1—O28	95.12 (18)	C82—C72—H72	119.8
O19—Fe1—O28	165.3 (2)	C62—C72—H72	119.8
O23—Fe1—O28	81.37 (18)	C72—C82—C92	118.9 (7)
O26—Fe1—O28	86.3 (2)	C72—C82—H82	120.6
O1—Fe2—O16	94.9 (2)	C92—C82—H82	120.6
O1—Fe2—O17	97.01 (19)	C82—C92—C102	119.6 (7)
O16—Fe2—O17	167.05 (19)	C82—C92—H92	120.2
O1—Fe2—O18	94.78 (18)	C102—C92—H92	120.2
O16—Fe2—O18	92.6 (2)	N22—C102—C92	121.2 (7)
O17—Fe2—O18	91.5 (2)	N22—C102—H102	119.4
O1—Fe2—N21	96.2 (2)	C92—C102—H102	119.4
O16—Fe2—N21	87.0 (2)	C13—O13—Fe3	126.8 (4)
O17—Fe2—N21	86.6 (2)	C13—O23—Fe1	129.0 (4)
O18—Fe2—N21	169.0 (2)	O23—C13—O13	126.8 (6)
O1—Fe2—N11	177.6 (2)	O23—C13—C23	119.4 (6)
O16—Fe2—N11	84.1 (2)	O13—C13—C23	113.3 (6)
O17—Fe2—N11	83.86 (19)	C13—C23—H23A	109.5
O18—Fe2—N11	87.4 (2)	C13—C23—H23B	109.5
N21—Fe2—N11	81.7 (2)	H23A—C23—H23B	109.5
O2—Fe3—O13	96.69 (19)	C13—C23—H23C	109.5
O2—Fe3—O15	95.7 (2)	H23A—C23—H23C	109.5
O13—Fe3—O15	167.35 (19)	H23B—C23—H23C	109.5
O2—Fe3—O14	94.85 (18)	C14—O14—Fe3	131.7 (4)
O13—Fe3—O14	90.3 (2)	C14—O24—Fe4	131.0 (5)
O15—Fe3—O14	91.2 (2)	O24—C14—O14	126.2 (6)
O2—Fe3—N12	176.1 (2)	O24—C14—C24	117.3 (7)
O13—Fe3—N12	82.2 (2)	O14—C14—C24	116.5 (6)
O15—Fe3—N12	85.3 (2)	C14—C24—H24A	109.5
O14—Fe3—N12	88.9 (2)	C14—C24—H24B	109.5
O2—Fe3—N22	93.85 (19)	H24A—C24—H24B	109.5
O13—Fe3—N22	87.1 (2)	C14—C24—H24C	109.5
O15—Fe3—N22	89.6 (2)	H24A—C24—H24C	109.5
O14—Fe3—N22	171.1 (2)	H24B—C24—H24C	109.5
N12—Fe3—N22	82.4 (2)	C15—O15—Fe3	128.1 (5)
O2—Fe4—O1	82.50 (18)	C15—O25—Fe4	131.8 (5)
O2—Fe4—O27	171.92 (18)	O15—C15—O25	125.3 (7)
O1—Fe4—O27	92.45 (19)	O15—C15—C25	116.7 (7)
O2—Fe4—O25	94.38 (19)	O25—C15—C25	117.8 (7)
O1—Fe4—O25	174.03 (19)	C15—C25—H25A	109.5
O27—Fe4—O25	91.2 (2)	C15—C25—H25B	109.5
O2—Fe4—O1W	93.68 (19)	H25A—C25—H25B	109.5
O1—Fe4—O1W	91.0 (2)	C15—C25—H25C	109.5
O27—Fe4—O1W	92.71 (19)	H25A—C25—H25C	109.5
O25—Fe4—O1W	84.1 (2)	H25B—C25—H25C	109.5
O2—Fe4—O24	90.85 (18)	C16—O16—Fe2	128.0 (4)
O1—Fe4—O24	97.82 (18)	C16—O26—Fe1	132.7 (5)
O27—Fe4—O24	83.57 (18)	O26—C16—O16	126.1 (7)
O25—Fe4—O24	87.3 (2)	O26—C16—C26	115.5 (7)
O1W—Fe4—O24	170.5 (2)	O16—C16—C26	118.5 (6)
Fe2—O1—Fe1	125.3 (2)	C16—C26—H26A	109.5
Fe2—O1—Fe4	127.8 (2)	C16—C26—H26B	109.5
Fe1—O1—Fe4	96.51 (18)	H26A—C26—H26B	109.5
Fe3—O2—Fe4	123.6 (2)	C16—C26—H26C	109.5
Fe3—O2—Fe1	128.8 (3)	H26A—C26—H26C	109.5
Fe4—O2—Fe1	98.12 (19)	H26B—C26—H26C	109.5
C51—N11—C11	116.1 (5)	C17—O17—Fe2	126.5 (5)
C51—N11—Fe2	125.6 (4)	C17—O27—Fe4	128.3 (5)
C11—N11—Fe2	117.1 (4)	O27—C17—O17	127.6 (7)
C61—N21—C101	117.9 (6)	O27—C17—C27	120.0 (8)
C61—N21—Fe2	125.4 (4)	O17—C17—C27	111.6 (8)
C101—N21—Fe2	116.5 (5)	C17—C27—H27A	109.5
C51—N31—C61	128.7 (6)	C17—C27—H27B	109.5
C51—N31—H31N	115.6	H27A—C27—H27B	109.5
C61—N31—H31N	115.6	C17—C27—H27C	109.5
C21—C11—N11	123.8 (7)	H27A—C27—H27C	109.5
C21—C11—H11	118.1	H27B—C27—H27C	109.5
N11—C11—H11	118.1	C18—O18—Fe2	128.6 (4)
C11—C21—C31	116.4 (8)	C18—O28—Fe1	129.6 (5)
C11—C21—H21	121.8	O28—C18—O18	131.4 (6)
C31—C21—H21	121.8	O28—C18—C28	114.5 (7)
C41—C31—C21	122.5 (8)	O18—C18—C28	114.0 (6)
C41—C31—H31	118.7	C18—C28—H28A	109.5
C21—C31—H31	118.7	C18—C28—H28B	109.5
C51—C41—C31	114.9 (7)	H28A—C28—H28B	109.5
C51—C41—H41	122.5	C18—C28—H28C	109.5
C31—C41—H41	122.6	H28A—C28—H28C	109.5
N11—C51—C41	126.1 (6)	H28B—C28—H28C	109.5
N11—C51—N31	118.8 (5)	C19—O19—Fe1	148.6 (6)
C41—C51—N31	115.1 (6)	O29—C19—O19	120.9 (8)
N21—C61—C71	121.1 (6)	O29—C19—C29	124.0 (8)
N21—C61—N31	121.2 (5)	O19—C19—C29	114.7 (9)
C71—C61—N31	117.6 (6)	C19—C29—H29A	109.5
C81—C71—C61	121.3 (7)	C19—C29—H29B	109.5
C81—C71—H71	119.3	H29A—C29—H29B	109.5
C61—C71—H71	119.3	C19—C29—H29C	109.5
C71—C81—C91	117.5 (7)	H29A—C29—H29C	109.5
C71—C81—H81	121.2	H29B—C29—H29C	109.5
C91—C81—H81	121.2	O1A—C1A—C2A	120.2 (14)
C101—C91—C81	118.1 (7)	O1A—C1A—H1AA	107.3
C101—C91—H91	121.0	C2A—C1A—H1AA	107.3
C81—C91—H91	121.0	O1A—C1A—H1AB	107.3
N21—C101—C91	123.9 (7)	C2A—C1A—H1AB	107.3
N21—C101—H101	118.1	H1AA—C1A—H1AB	106.9
C91—C101—H101	118.1	C1A—C2A—H2AA	109.5
C52—N12—C12	115.5 (6)	C1A—C2A—H2AB	109.5
C52—N12—Fe3	125.0 (4)	H2AA—C2A—H2AB	109.5
C12—N12—Fe3	117.5 (5)	C1A—C2A—H2AC	109.5
C102—N22—C62	118.7 (6)	H2AA—C2A—H2AC	109.5
C102—N22—Fe3	116.1 (5)	H2AB—C2A—H2AC	109.5
C62—N22—Fe3	123.2 (4)	O1B—C1B—C2B	114.3 (11)
C62—N32—C52	135.3 (6)	O1B—C1B—H1BA	108.7
C62—N32—H32N	112.4	C2B—C1B—H1BA	108.7
C52—N32—H32N	112.4	O1B—C1B—H1BB	108.7
C22—C12—N12	123.3 (8)	C2B—C1B—H1BB	108.7
C22—C12—H12	118.3	H1BA—C1B—H1BB	107.6
N12—C12—H12	118.3	C1B—C2B—H2BA	109.5
C12—C22—C32	117.4 (9)	C1B—C2B—H2BB	109.5
C12—C22—H22	121.3	H2BA—C2B—H2BB	109.5
C32—C22—H22	121.3	C1B—C2B—H2BC	109.5
C42—C32—C22	121.3 (9)	H2BA—C2B—H2BC	109.5
C42—C32—H32	119.3	H2BB—C2B—H2BC	109.5

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N31—H31N···Cl1^i	0.86	2.48	3.221 (6)	145
N32—H32N···Cl1^ii	0.86	2.45	3.246 (6)	154
O1W···O29	?	?	2.534 (9)	?
O1W···O1B	?	?	2.618 (10)	?
O2W···O29	?	?	2.765 (10)	?
O2W···Cl1	?	?	3.196 (8)	?
O1A···Cl1	?	?	3.313 (15)	?
O1B···O2W	?	?	2.774 (11)	?

Symmetry codes: (i) x+1/2, −y+3/2, z−1/2; (ii) x+1/2, −y+3/2, z+1/2.

(II) 2-methylimidazolium hexa-µ₂-acetato-acetatodiaqua-µ₃-oxo-triiron(III) chloride dihydrate

Crystal data

(C4H7N2)[Fe3(C2H3O2)7O(H2O)2]Cl·2H2O	F(000) = 1620
Mr = 787.49	Dx = 1.675 Mg m^−3
Orthorhombic, Pnma	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2n	Cell parameters from 1322 reflections
a = 32.147 (6) Å	θ = 2.9–23.9°
b = 12.048 (2) Å	µ = 1.54 mm^−1
c = 8.0652 (16) Å	T = 295 K
V = 3123.6 (11) Å^3	Block, red
Z = 4	0.26 × 0.25 × 0.20 mm

Data collection

Bruker SMART CCD area-detector diffractometer	2877 independent reflections
Radiation source: fine-focus sealed tube	1584 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.079
ϕ and ω scans	θmax = 25.0°, θmin = 2.1°
Absorption correction: multi-scan (SADABS; Sheldrick, 2001)	h = −37→38
Tmin = 0.68, Tmax = 0.73	k = −14→14
5673 measured reflections	l = −9→9

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.069	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.223	H-atom parameters constrained
S = 1.01	w = 1/[σ^2(Fo^2) + (0.0993P)^2 + 17.3868P] where P = (Fo^2 + 2Fc^2)/3
2877 reflections	(Δ/σ)max = 0.013
225 parameters	Δρmax = 0.89 e Å^−3
0 restraints	Δρmin = −0.79 e Å^−3

Special details

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
Fe1	0.15105 (3)	0.61315 (8)	1.08730 (11)	0.0245 (2)
Fe2	0.07772 (4)	0.7500	0.88154 (16)	0.0244 (3)
O1	0.12758 (17)	0.7500	1.0192 (8)	0.0263 (16)
O1W	0.18246 (13)	0.4661 (4)	1.1581 (6)	0.0343 (13)
O11	0.10002 (14)	0.6286 (4)	0.7317 (6)	0.0381 (13)
O21	0.14458 (15)	0.5287 (4)	0.8741 (6)	0.0401 (13)
C11	0.1241 (2)	0.5475 (5)	0.7467 (7)	0.0290 (17)
C21	0.1296 (3)	0.4716 (6)	0.6037 (8)	0.052 (2)
H21A	0.1412	0.5120	0.5120	0.079*
H21B	0.1032	0.4413	0.5724	0.079*
H21C	0.1481	0.4124	0.6341	0.079*
O12	0.04943 (13)	0.6332 (4)	1.0263 (6)	0.0353 (13)
O22	0.09833 (14)	0.5462 (4)	1.1763 (6)	0.0422 (14)
C12	0.06033 (17)	0.5677 (5)	1.1361 (8)	0.0268 (16)
C22	0.02711 (18)	0.5105 (6)	1.2318 (8)	0.0381 (19)
H22A	0.0116	0.5642	1.2945	0.057*
H22B	0.0395	0.4576	1.3060	0.057*
H22C	0.0088	0.4727	1.1567	0.057*
O13	0.20923 (13)	0.6585 (4)	1.0038 (6)	0.0427 (14)
C13	0.2271 (2)	0.7500	0.9800 (13)	0.036 (3)
C23	0.2717 (2)	0.7500	0.9331 (14)	0.043 (3)
H23A	0.2872	0.7936	1.0114	0.064*	0.50
H23B	0.2748	0.7812	0.8243	0.064*	0.50
H23C	0.2820	0.6752	0.9334	0.064*	0.50
O14	0.16757 (15)	0.6574 (4)	1.3165 (6)	0.0393 (13)
C14	0.1737 (3)	0.7500	1.3862 (10)	0.036 (3)
C24	0.1906 (3)	0.7500	1.5580 (9)	0.053 (4)
H24A	0.2173	0.7856	1.5588	0.080*	0.50
H24B	0.1934	0.6749	1.5962	0.080*	0.50
H24C	0.1719	0.7895	1.6298	0.080*	0.50
O15	0.02623 (17)	0.7500	0.7451 (8)	0.0250 (16)
O25	−0.0213 (2)	0.7500	0.5473 (10)	0.054 (2)
C15	0.0166 (3)	0.7500	0.5887 (11)	0.040 (3)
C25	0.0501 (3)	0.7500	0.4605 (11)	0.040 (3)
H25A	0.0744	0.7861	0.5039	0.061*	0.50
H25B	0.0406	0.7890	0.3639	0.061*	0.50
H25C	0.0568	0.6749	0.4312	0.061*	0.50
C1	0.0911 (2)	0.2500	1.1040 (11)	0.043 (3)
C2	0.0771 (3)	0.2500	0.8327 (14)	0.064 (4)
H2	0.0808	0.2500	0.7183	0.076*
C3	0.0407 (3)	0.2500	0.9196 (15)	0.091 (6)
H3	0.0140	0.2500	0.8745	0.109*
C4	0.1144 (4)	0.2500	1.2666 (14)	0.068 (4)
H4A	0.1382	0.2022	1.2581	0.101*	0.50
H4B	0.0964	0.2237	1.3532	0.101*	0.50
H4C	0.1234	0.3241	1.2918	0.101*	0.50
N1	0.0502 (3)	0.2500	1.0820 (14)	0.081 (4)
H1N	0.0322	0.2500	1.1610	0.097*
N2	0.1077 (2)	0.2500	0.9558 (10)	0.047 (3)
H2N	0.1340	0.2500	0.9368	0.057*
Cl1	0.20342 (8)	0.2500	0.9160 (4)	0.0503 (8)
O2W	0.24374 (17)	0.4883 (5)	0.7884 (9)	0.076 (2)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Fe1	0.0196 (4)	0.0252 (5)	0.0289 (4)	0.0000 (4)	−0.0008 (4)	0.0016 (5)
Fe2	0.0219 (6)	0.0251 (7)	0.0261 (7)	0.000	0.0007 (6)	0.000
O1	0.018 (3)	0.030 (3)	0.031 (3)	0.000	−0.002 (3)	0.000
O1W	0.026 (2)	0.030 (3)	0.047 (3)	0.008 (2)	−0.005 (2)	0.008 (2)
O11	0.036 (2)	0.048 (3)	0.031 (2)	0.004 (3)	−0.004 (2)	0.001 (3)
O21	0.051 (3)	0.027 (3)	0.042 (3)	0.007 (2)	−0.010 (2)	−0.002 (2)
C11	0.038 (4)	0.024 (3)	0.025 (3)	0.003 (3)	0.002 (3)	0.005 (3)
C21	0.091 (6)	0.036 (4)	0.030 (4)	0.019 (4)	0.009 (4)	−0.018 (4)
O12	0.025 (2)	0.037 (3)	0.045 (3)	−0.007 (2)	0.001 (2)	0.009 (2)
O22	0.033 (2)	0.043 (3)	0.050 (3)	−0.005 (2)	0.009 (2)	0.016 (3)
C12	0.027 (3)	0.020 (3)	0.034 (4)	−0.002 (3)	0.000 (3)	0.008 (3)
C22	0.032 (3)	0.047 (4)	0.035 (4)	−0.012 (3)	0.009 (3)	0.024 (4)
O13	0.025 (2)	0.044 (3)	0.059 (3)	0.008 (2)	0.018 (2)	0.008 (3)
C13	0.023 (5)	0.049 (6)	0.037 (6)	0.000	0.002 (5)	0.000
C23	0.034 (5)	0.040 (6)	0.054 (7)	0.000	0.017 (5)	0.000
O14	0.053 (3)	0.035 (3)	0.029 (2)	0.004 (3)	−0.003 (2)	0.005 (2)
C14	0.021 (4)	0.049 (6)	0.039 (6)	0.000	−0.002 (5)	0.000
C24	0.040 (6)	0.106 (11)	0.013 (5)	0.000	0.003 (5)	0.000
O15	0.016 (3)	0.029 (3)	0.030 (3)	0.000	0.001 (3)	0.000
O25	0.046 (4)	0.063 (5)	0.053 (5)	0.000	−0.010 (4)	0.000
C15	0.029 (5)	0.066 (7)	0.024 (5)	0.000	0.007 (5)	0.000
C25	0.045 (6)	0.051 (7)	0.025 (5)	0.000	−0.002 (5)	0.000
C1	0.030 (5)	0.027 (5)	0.071 (8)	0.000	0.024 (5)	0.000
C2	0.034 (6)	0.069 (9)	0.087 (10)	0.000	0.026 (7)	0.000
C3	0.020 (5)	0.092 (11)	0.161 (16)	0.000	0.013 (9)	0.000
C4	0.094 (10)	0.048 (8)	0.061 (8)	0.000	0.016 (8)	0.000
N1	0.054 (6)	0.060 (7)	0.128 (10)	0.000	0.052 (7)	0.000
N2	0.019 (4)	0.050 (6)	0.073 (7)	0.000	0.004 (5)	0.000
Cl1	0.0360 (13)	0.0395 (15)	0.075 (2)	0.000	−0.0005 (15)	0.000
O2W	0.058 (3)	0.046 (4)	0.125 (5)	−0.010 (3)	0.050 (4)	−0.004 (4)

Geometric parameters (Å, º)

Fe1—O1	1.894 (3)	O14—C14	1.264 (6)
Fe1—O14	1.996 (5)	C14—O14^i	1.264 (6)
Fe1—O21	2.009 (5)	C14—C24	1.489 (9)
Fe1—O22	2.009 (5)	C24—H24A	0.9600
Fe1—O13	2.062 (5)	C24—H24B	0.9600
Fe1—O1W	2.118 (5)	C24—H24C	0.9600
Fe2—O1	1.950 (6)	O15—C15	1.298 (10)
Fe2—O15	1.988 (6)	O25—C15	1.264 (11)
Fe2—O11	2.029 (5)	C15—C25	1.492 (9)
Fe2—O12	2.042 (5)	C25—H25A	0.9600
O11—C11	1.253 (8)	C25—H25B	0.9600
O21—C11	1.241 (7)	C25—H25C	0.9600
C11—C21	1.482 (7)	C1—N2	1.308 (11)
C21—H21A	0.9600	C1—N1	1.325 (11)
C21—H21B	0.9600	C1—C4	1.510 (12)
C21—H21C	0.9600	C2—C3	1.366 (12)
O12—C12	1.237 (7)	C2—N2	1.397 (11)
O22—C12	1.290 (7)	C2—H2	0.9300
C12—C22	1.487 (7)	C3—N1	1.346 (13)
C22—H22A	0.9600	C3—H3	0.9300
C22—H22B	0.9600	C4—H4A	0.9600
C22—H22C	0.9600	C4—H4B	0.9600
O13—C13	1.258 (6)	C4—H4C	0.9600
C13—O13^i	1.258 (6)	N1—H1N	0.8600
C13—C23	1.484 (9)	N2—H2N	0.8600
C23—H23A	0.9600	Fe1—Fe1^i	3.298 (2)
C23—H23B	0.9600	Fe1—Fe2	3.321 (2)
C23—H23C	0.9600
O1—Fe1—O14	98.2 (2)	H22A—C22—H22C	109.5
O1—Fe1—O21	98.7 (2)	H22B—C22—H22C	109.5
O14—Fe1—O21	162.9 (2)	C13—O13—Fe1	134.2 (4)
O1—Fe1—O22	96.7 (2)	O13^i—C13—O13	122.4 (7)
O14—Fe1—O22	90.0 (2)	O13^i—C13—C23	118.7 (3)
O21—Fe1—O22	90.9 (2)	O13—C13—C23	118.7 (3)
O1—Fe1—O13	92.1 (2)	C13—C23—H23A	109.5
O14—Fe1—O13	89.4 (2)	C13—C23—H23B	109.5
O21—Fe1—O13	87.1 (2)	H23A—C23—H23B	109.5
O22—Fe1—O13	171.2 (2)	C13—C23—H23C	109.5
O1—Fe1—O1W	175.0 (2)	H23A—C23—H23C	109.5
O14—Fe1—O1W	81.2 (2)	H23B—C23—H23C	109.5
O21—Fe1—O1W	81.75 (19)	C14—O14—Fe1	133.5 (5)
O22—Fe1—O1W	88.29 (19)	O14—C14—O14^i	123.8 (7)
O13—Fe1—O1W	82.94 (19)	O14—C14—C24	118.1 (4)
O1—Fe2—O15	178.9 (3)	O14^i—C14—C24	118.1 (4)
O1—Fe2—O11	92.80 (18)	C14—C24—H24A	109.5
O15—Fe2—O11	87.96 (18)	C14—C24—H24B	109.5
O1—Fe2—O11^i	92.80 (18)	H24A—C24—H24B	109.5
O15—Fe2—O11^i	87.96 (18)	C14—C24—H24C	109.5
O11—Fe2—O11^i	92.3 (3)	H24A—C24—H24C	109.5
O1—Fe2—O12^i	92.32 (18)	H24B—C24—H24C	109.5
O15—Fe2—O12^i	86.89 (18)	C15—O15—Fe2	137.3 (5)
O11—Fe2—O12^i	174.24 (19)	O25—C15—O15	119.1 (7)
O11^i—Fe2—O12^i	90.08 (19)	O25—C15—C25	120.8 (8)
O1—Fe2—O12	92.32 (18)	O15—C15—C25	120.2 (8)
O15—Fe2—O12	86.89 (18)	C15—C25—H25A	109.5
O11—Fe2—O12	90.08 (19)	C15—C25—H25B	109.5
O11^i—Fe2—O12	174.24 (19)	H25A—C25—H25B	109.5
O12^i—Fe2—O12	87.1 (3)	C15—C25—H25C	109.5
Fe1—O1—Fe1^i	121.0 (3)	H25A—C25—H25C	109.5
Fe1—O1—Fe2	119.50 (15)	H25B—C25—H25C	109.5
Fe1^i—O1—Fe2	119.50 (15)	N2—C1—N1	106.4 (8)
C11—O11—Fe2	136.3 (4)	N2—C1—C4	126.2 (8)
C11—O21—Fe1	132.2 (4)	N1—C1—C4	127.4 (9)
O21—C11—O11	123.4 (6)	C3—C2—N2	103.8 (9)
O21—C11—C21	118.0 (6)	C3—C2—H2	128.1
O11—C11—C21	118.6 (6)	N2—C2—H2	128.1
C11—C21—H21A	109.5	N1—C3—C2	107.6 (10)
C11—C21—H21B	109.5	N1—C3—H3	126.2
H21A—C21—H21B	109.5	C2—C3—H3	126.2
C11—C21—H21C	109.5	C1—C4—H4A	109.5
H21A—C21—H21C	109.5	C1—C4—H4B	109.5
H21B—C21—H21C	109.5	H4A—C4—H4B	109.5
C12—O12—Fe2	136.3 (4)	C1—C4—H4C	109.5
C12—O22—Fe1	128.9 (4)	H4A—C4—H4C	109.5
O12—C12—O22	125.2 (5)	H4B—C4—H4C	109.5
O12—C12—C22	117.6 (5)	C1—N1—C3	110.9 (9)
O22—C12—C22	117.2 (5)	C1—N1—H1N	124.6
C12—C22—H22A	109.5	C3—N1—H1N	124.6
C12—C22—H22B	109.5	C1—N2—C2	111.3 (8)
H22A—C22—H22B	109.5	C1—N2—H2N	124.4
C12—C22—H22C	109.5	C2—N2—H2N	124.4

Symmetry code: (i) x, −y+3/2, z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
REMOVE—*···*	The following lines beginning with REMOVE are dummy	?	?	?
REMOVE—*···*	lines included so as to systematize the symmetry codes	?	?	?
REMOVE—*···*	in Table 4 and Figure 4	?	?	?
REMOVE—*···*	They are expected to be removed by the Editor at the	?	?	?
REMOVE—*···*	final edition stage. Thanks. RB.	?	?	?
REMOVE—X···X^i	Dummy line to be removed!!!!	?	?	?
REMOVE—X···X^ii	Dummy line to be removed!!!!	?	?	?
REMOVE—*···*	******************************************************	?	?	?
N2—H2N···Cl1	0.86	2.24	3.094 (13)	174
O2W···Cl1	?	?	3.315 (9)	?
O1W···Cl1	?	?	3.323 (8)	?
O1W···O2W^iii	?	?	2.651 (11)	?
O2W···O13	?	?	2.910 (13)	?
N1—H1N···O15^iv	0.86	2.03	2.826 (12)	154
N1—H1N···O25^iv	0.86	2.38	3.132 (12)	146

Symmetry codes: (i) x, −y+3/2, z; (ii) x, −y+1/2, z; (iii) −x+1/2, −y+1, z+1/2; (iv) −x, −y+1, −z+2.