Tetrakis(5-tert-butylpyrazole-1κN²)tetrachloro-1κCl,2κ³Cl-μ-oxo-1:2κ²O-diiron(III)

The title compound, [Fe₂Cl₄O(C₇H₁₂N₂)₄], contains vertex-sharing distorted tetrahedral [FeOCl₃]⁻ and octahedral [FeOCl(Hpz^tBu)₄]⁺ moieties (Hpz^tBu is 5-tert-­butyl­pyrazole), linked by a bent oxo bridging ligand. The two Fe^III centres are also bridged by intramolecular hydrogen bonds between the pyrazole N—H groups and the O²⁻ and Cl⁻ ligands.

S1. Comment

We have recently reported that complexation of CuCl₂ by Hpz^tBu in basic MeOH affords a heptacopper aggregate with a double-cubane core structure, which is templated by N—H···Cl hydrogen bonding between the pyrazole ligands and non-coordinated Cl^- anions (Liu et al., 2002). As an extension of this work, we were keen to determine the products of similar reactions using other transition metal halide precursors. We report here the title compound, (I), which we isolated in moderate yield from an otherwise identical procedure using FeCl₃ as starting material. Our isolation of (I) contrasts with a report of a very similar reaction using unsubstituted pyrazole as ligand, which instead afforded a unique octanuclear aggregate containing bridging oxo and pyrazolide groups (Raptis et al., 1999). Unsymmetrical diiron complexes containing the [FeOX₃]^- moiety (X^- is Cl^- or Br^-) have been described previously (Gómez-Romero et al., 1989, 1990; Wang et al., 1996; James et al., 1997; Ondrejkovičová et al., 1998a,b), most relevantly in [Fe₂OCl₄tz₄] (tz is thiazole; James et al., 1997). \sch

The asymmetric unit of (I) contains one molecule of the complex lying on a general position, with the two Fe centres linked by a bent oxo bridge having an Fe1—O3—Fe2 angle that is within the usual range for compounds containing [FeOCl₃]^- centres (tabulated in Ondrejkovičová et al., 1998b). The failure of atom Fe1 to achieve perfect C_3v symmetry is seen in small variations in the Fe1—Cl bond lengths: the differences between individual Fe1—Cl distances are in the range 0.0042 (7)–0.0088 (7) Å. These differences may be related to the hydrogen bonds accepted by these three Cl^- donors (see below), since there is a perfect correlation between each Fe1—Cl bond length (Table 1) and the strength of the hydrogen bond accepted by that Cl atom, as expressed by its N—H···Cl angle (Table 2). However, this suggestion remains to be confirmed, since [Fe₂OCl₄tz₄] (James et al., 1997) and other compounds containing the [FeOCl₃]^- moiety that do not possess hydrogen bonding to the Cl^- ligands (Ondrejkovičová et al., 1998b) also show unequal Fe—Cl bond lengths.

The local geometry at Fe2 is approximately C_4v, but with a distribution of Fe2—N bond distances; while Fe2—N17 and Fe2—N35 are metrically equivalent, Fe2—N8 is shorter than the average of these two bonds by 0.012 (2) Å, and Fe2—N26 is longer by 0.019 (2) Å. A similar spread of Fe—N distances is also exhibited by [Fe₂OCl₄tz₄] (James et al., 1997). The Fe2—Cl7 bond is longer than the Fe1—Cl bonds by an average of 0.1755 (10) Å, which should reflect both the higher coordination number at Fe2 and the strong trans influence of the bridging oxo ligand.

While all the pyrazole rings are coordinated as the 5-substituted tautomer, the N35—C43 ligand is rotated by ca 180° about the Fe2—N35 bond relative to the other three Hpz^tBu ligands. This is related to the intramolecular hydrogen bonding within the compound (see below).

The four pyrazole ligands in (I) form intramolecular N—H···X (X is O or Cl) hydrogen bonds to different acceptors in the molecule. Three of these NH groups interact with atom O3, and/or a Cl^- ligand bound to Fe1. Both atoms H9 and H18 form bifurcated hydrogen bonds to atom O3 and atoms Cl4 and Cl5, respectively. While the N9—H9···Cl4 interaction is quite short and close to linear, the N18—H18···Cl5 contact is much longer and is substantially bent, to the extent that this should be considered a very weak interaction. In contrast, atom H27 forms a near-linear hydrogen bond to atom Cl6 only. The irregularity of the hydrogen bonds formed by these three pyrazole groups reflects the poor complementarity between hydrogen bond-donors bound to a near-C_4v-symmetric metal centre, with N—Fe2—N angles of ca 90°, and hydrogen-bond acceptors at a C_3v-symmetric centre, related by ca 109.5°. The fourth pyrazole N—H atom, H36, forms a hydrogen bond to Cl7. There are no noteworthy intermolecular contacts within the crystal lattice.

S2. Experimental

To a solution of FeCl₃ (0.32 g, 2.0 mmol) in MeOH (30 ml) was added an MeOH (30 ml) solution of 3{5}-tertbutylpyrazole (0.49 g, 4.0 mmol) and NaOH (0.080 g, 2.0 mmol). The mixture was stirred at room temperature for 2 h and then evaporated to dryness. The residue was dissolved in a minimum volume of CH₂Cl₂, and the filtered extracts were layered with pentane to give dark-brown crystals of (I) (yield 0.28 g, 37%). Analysis found: C 43.9, H 6.2, N 14.8%; calculated for C₂₈H₄₈Cl₄Fe₂N₈O: C 43.9, H 6.3, N 14.6%.

S3. Refinement

All H atoms were placed in calculated positions, and refined using a riding model. The constraints employed were as follows: Csp²—H = 0.95 Å and U_iso(H) = 1.2U_eq(C), C_methyl—H = 0.98 Å and U_iso(H) = 1.5U_eq(C), and N—H = 0.88 Å and U_iso(H) = 1.2U_eq(N).

Computing details

Data collection: COLLECT (Nonius, 1999); cell refinement: DENZO-SMN (Otwinowski & Minor, 1997); data reduction: DENZO-SMN; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEX (McArdle, 1995); software used to prepare material for publication: local program.

Figures

Fig. 1. A view of the molecular structure of (I) with 50% probability displacement ellipsoids, showing the atom-numbering scheme employed. All C-bound H atoms have been omitted for clarity.

Tetrakis(5-tert-butylpyrazole-1κN²)tetrachloro-1κCl,2κ³Cl-µ-oxo- 1:2κ²O-diiron(III)

Crystal data

[Fe2Cl4O(C7H12N2)4]	Z = 2
Mr = 766.24	F(000) = 800
Triclinic, P1	Dx = 1.304 Mg m^−3
a = 10.3075 (1) Å	Mo Kα radiation, λ = 0.71073 Å
b = 10.9284 (1) Å	Cell parameters from 44449 reflections
c = 17.3424 (2) Å	θ = 2.7–27.5°
α = 87.5556 (4)°	µ = 1.05 mm^−1
β = 88.8661 (4)°	T = 150 K
γ = 89.3366 (5)°	Prism, brown
V = 1951.25 (3) Å^3	0.43 × 0.30 × 0.20 mm

Data collection

Nonius KappaCCD area-detector diffractometer	8944 independent reflections
Radiation source: fine-focus sealed tube	8129 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.054
Detector resolution: 9.091 pixels mm^-1	θmax = 27.5°, θmin = 2.7°
ϕ or ω scans?	h = −13→13
Absorption correction: multi-scan (SORTAV; Blessing, 1995)	k = −14→14
Tmin = 0.661, Tmax = 0.818	l = −22→22
44449 measured reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.033	H-atom parameters constrained
wR(F^2) = 0.091	w = 1/[σ^2(Fo^2) + (0.042P)^2 + 1.185P] where P = (Fo^2 + 2Fc^2)/3
S = 1.03	(Δ/σ)max = 0.001
8944 reflections	Δρmax = 0.68 e Å^−3
401 parameters	Δρmin = −0.46 e Å^−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 1997), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0074 (11)

Special details

Experimental. Detector set at 30 mm from sample with different 2theta offsets 1 degree phi exposures for chi = 0 degree settings 1 degree omega exposures for chi = 90 degree settings

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.

No disorder was detected during refinement. All non-H atoms were refined anisotropically, while H atoms were placed in calculated positions and refined using a riding model.

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

	x	y	z	Uiso*/Ueq
Fe1	0.41378 (2)	0.27268 (2)	0.785051 (14)	0.02569 (8)
Fe2	0.18626 (2)	0.51040 (2)	0.733357 (13)	0.02143 (8)
O3	0.30286 (11)	0.38557 (10)	0.74966 (7)	0.0270 (2)
Cl4	0.48973 (5)	0.17574 (5)	0.68300 (3)	0.04227 (12)
Cl5	0.30469 (5)	0.14164 (4)	0.86208 (3)	0.04562 (13)
Cl6	0.56810 (5)	0.36669 (5)	0.84687 (3)	0.04381 (13)
Cl7	0.02717 (4)	0.66874 (4)	0.71027 (2)	0.02889 (10)
N8	0.21379 (14)	0.49550 (14)	0.61217 (8)	0.0279 (3)
N9	0.29234 (14)	0.40677 (14)	0.58331 (8)	0.0282 (3)
H9	0.3420	0.3579	0.6119	0.034*
C10	0.28539 (18)	0.40240 (19)	0.50580 (10)	0.0341 (4)
C11	0.1984 (2)	0.4930 (2)	0.48349 (11)	0.0447 (5)
H11	0.1720	0.5139	0.4324	0.054*
C12	0.15653 (19)	0.5482 (2)	0.55084 (11)	0.0383 (4)
H12	0.0958	0.6141	0.5527	0.046*
C13	0.36163 (19)	0.3101 (2)	0.46002 (11)	0.0404 (5)
C14	0.3394 (3)	0.3363 (3)	0.37413 (13)	0.0658 (8)
H14A	0.2468	0.3291	0.3635	0.099*
H14B	0.3890	0.2771	0.3441	0.099*
H14C	0.3681	0.4194	0.3596	0.099*
C15	0.5070 (2)	0.3187 (2)	0.47622 (13)	0.0434 (5)
H15A	0.5373	0.4013	0.4615	0.065*
H15B	0.5551	0.2587	0.4461	0.065*
H15C	0.5214	0.3017	0.5313	0.065*
C16	0.3149 (3)	0.1803 (2)	0.48311 (16)	0.0598 (7)
H16A	0.3332	0.1620	0.5376	0.090*
H16B	0.3605	0.1209	0.4513	0.090*
H16C	0.2213	0.1754	0.4751	0.090*
N17	0.03181 (13)	0.38172 (12)	0.73012 (8)	0.0251 (3)
N18	0.06060 (14)	0.26120 (13)	0.72268 (9)	0.0283 (3)
H18	0.1392	0.2298	0.7275	0.034*
C19	−0.04439 (17)	0.19512 (16)	0.70704 (10)	0.0295 (4)
C20	−0.14720 (18)	0.27707 (17)	0.70420 (11)	0.0330 (4)
H20	−0.2353	0.2596	0.6944	0.040*
C21	−0.09530 (17)	0.39078 (16)	0.71873 (11)	0.0301 (4)
H21	−0.1441	0.4649	0.7203	0.036*
C22	−0.0360 (2)	0.05790 (18)	0.69825 (13)	0.0389 (4)
C23	−0.0167 (3)	−0.0067 (2)	0.77871 (16)	0.0673 (8)
H23A	−0.0876	0.0167	0.8137	0.101*
H23B	0.0662	0.0181	0.7996	0.101*
H23C	−0.0164	−0.0957	0.7737	0.101*
C24	0.0785 (3)	0.0257 (2)	0.64687 (19)	0.0664 (8)
H24A	0.0788	−0.0625	0.6386	0.100*
H24B	0.1591	0.0476	0.6716	0.100*
H24C	0.0717	0.0710	0.5971	0.100*
C25	−0.1617 (3)	0.0123 (2)	0.6678 (2)	0.0736 (9)
H25A	−0.1780	0.0520	0.6171	0.110*
H25B	−0.2329	0.0317	0.7036	0.110*
H25C	−0.1559	−0.0766	0.6628	0.110*
N26	0.33073 (14)	0.65078 (13)	0.74043 (8)	0.0262 (3)
N27	0.42701 (13)	0.63822 (13)	0.79259 (8)	0.0262 (3)
H27	0.4517	0.5674	0.8139	0.031*
C28	0.48066 (16)	0.74608 (15)	0.80819 (10)	0.0276 (3)
C29	0.41610 (18)	0.83397 (16)	0.76322 (12)	0.0340 (4)
H29	0.4308	0.9197	0.7606	0.041*
C30	0.32477 (18)	0.77038 (16)	0.72253 (11)	0.0317 (4)
H30	0.2661	0.8076	0.6868	0.038*
C31	0.58927 (17)	0.75550 (17)	0.86476 (11)	0.0324 (4)
C32	0.6104 (2)	0.8911 (2)	0.88003 (15)	0.0524 (6)
H32A	0.6317	0.9358	0.8313	0.079*
H32B	0.6820	0.8983	0.9159	0.079*
H32C	0.5310	0.9259	0.9027	0.079*
C33	0.5529 (2)	0.6864 (2)	0.94078 (11)	0.0404 (4)
H33A	0.4700	0.7182	0.9606	0.061*
H33B	0.6206	0.6980	0.9786	0.061*
H33C	0.5449	0.5990	0.9317	0.061*
C34	0.71368 (19)	0.6991 (2)	0.83047 (13)	0.0434 (5)
H34A	0.6980	0.6136	0.8188	0.065*
H34B	0.7836	0.7025	0.8678	0.065*
H34C	0.7388	0.7453	0.7829	0.065*
N35	0.16108 (14)	0.53483 (13)	0.85458 (8)	0.0265 (3)
N36	0.11578 (14)	0.64142 (13)	0.88234 (8)	0.0275 (3)
H36	0.0775	0.6992	0.8538	0.033*
C37	0.13576 (16)	0.64931 (15)	0.95849 (10)	0.0264 (3)
C38	0.19761 (19)	0.54193 (17)	0.98154 (11)	0.0340 (4)
H38	0.2252	0.5187	1.0321	0.041*
C39	0.21147 (18)	0.47424 (16)	0.91543 (10)	0.0313 (4)
H39	0.2514	0.3956	0.9140	0.038*
C40	0.09855 (17)	0.76062 (17)	1.00299 (11)	0.0312 (4)
C41	−0.0331 (2)	0.81112 (19)	0.97703 (12)	0.0405 (4)
H41A	−0.0264	0.8411	0.9231	0.061*
H41B	−0.0598	0.8786	1.0095	0.061*
H41C	−0.0977	0.7460	0.9819	0.061*
C42	0.0885 (2)	0.7232 (2)	1.08944 (12)	0.0438 (5)
H42A	0.0243	0.6582	1.0974	0.066*
H42B	0.0617	0.7943	1.1187	0.066*
H42C	0.1732	0.6932	1.1073	0.066*
C43	0.2043 (2)	0.85660 (19)	0.99072 (16)	0.0505 (6)
H43A	0.2874	0.8220	1.0081	0.076*
H43B	0.1820	0.9284	1.0204	0.076*
H43C	0.2113	0.8809	0.9358	0.076*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Fe1	0.02496 (13)	0.02369 (13)	0.02849 (14)	0.00402 (9)	−0.00314 (9)	−0.00194 (9)
Fe2	0.02206 (12)	0.02076 (12)	0.02166 (13)	0.00110 (8)	−0.00237 (9)	−0.00254 (8)
O3	0.0281 (6)	0.0246 (6)	0.0284 (6)	0.0039 (5)	−0.0031 (5)	−0.0029 (5)
Cl4	0.0490 (3)	0.0405 (3)	0.0376 (3)	0.0117 (2)	0.0028 (2)	−0.0101 (2)
Cl5	0.0500 (3)	0.0337 (2)	0.0517 (3)	0.0015 (2)	0.0109 (2)	0.0092 (2)
Cl6	0.0369 (2)	0.0400 (3)	0.0558 (3)	0.00361 (19)	−0.0202 (2)	−0.0083 (2)
Cl7	0.0280 (2)	0.02482 (19)	0.0340 (2)	0.00477 (15)	−0.00568 (16)	−0.00191 (15)
N8	0.0270 (7)	0.0329 (7)	0.0241 (7)	0.0001 (6)	−0.0015 (6)	−0.0027 (6)
N9	0.0276 (7)	0.0343 (7)	0.0229 (7)	−0.0005 (6)	0.0000 (6)	−0.0037 (6)
C10	0.0286 (9)	0.0506 (11)	0.0236 (8)	−0.0056 (8)	−0.0006 (7)	−0.0069 (8)
C11	0.0406 (11)	0.0700 (15)	0.0233 (9)	0.0060 (10)	−0.0054 (8)	−0.0008 (9)
C12	0.0359 (10)	0.0513 (11)	0.0274 (9)	0.0064 (8)	−0.0043 (7)	0.0014 (8)
C13	0.0345 (10)	0.0594 (13)	0.0283 (9)	−0.0030 (9)	0.0030 (8)	−0.0140 (9)
C14	0.0582 (15)	0.111 (2)	0.0292 (11)	0.0204 (15)	0.0001 (10)	−0.0197 (13)
C15	0.0350 (10)	0.0552 (12)	0.0405 (11)	−0.0006 (9)	0.0045 (8)	−0.0079 (9)
C16	0.0563 (14)	0.0624 (15)	0.0631 (16)	−0.0161 (12)	0.0117 (12)	−0.0314 (13)
N17	0.0262 (7)	0.0222 (6)	0.0272 (7)	0.0007 (5)	−0.0010 (5)	−0.0032 (5)
N18	0.0242 (7)	0.0239 (7)	0.0372 (8)	0.0003 (5)	−0.0011 (6)	−0.0061 (6)
C19	0.0292 (8)	0.0294 (8)	0.0300 (9)	−0.0054 (7)	0.0013 (7)	−0.0039 (7)
C20	0.0270 (8)	0.0351 (9)	0.0373 (10)	−0.0042 (7)	−0.0043 (7)	−0.0031 (7)
C21	0.0257 (8)	0.0300 (8)	0.0345 (9)	0.0016 (6)	−0.0022 (7)	−0.0003 (7)
C22	0.0398 (10)	0.0299 (9)	0.0478 (12)	−0.0060 (8)	0.0018 (9)	−0.0108 (8)
C23	0.113 (2)	0.0330 (11)	0.0562 (15)	−0.0079 (13)	−0.0130 (15)	−0.0004 (10)
C24	0.0692 (17)	0.0361 (12)	0.094 (2)	0.0014 (11)	0.0262 (15)	−0.0133 (12)
C25	0.0610 (16)	0.0416 (13)	0.121 (3)	−0.0110 (12)	−0.0189 (17)	−0.0214 (15)
N26	0.0258 (7)	0.0259 (7)	0.0271 (7)	−0.0011 (5)	−0.0051 (5)	−0.0006 (5)
N27	0.0257 (7)	0.0256 (7)	0.0274 (7)	−0.0005 (5)	−0.0057 (5)	0.0002 (5)
C28	0.0255 (8)	0.0290 (8)	0.0285 (8)	−0.0035 (6)	0.0009 (6)	−0.0054 (7)
C29	0.0331 (9)	0.0243 (8)	0.0447 (11)	−0.0033 (7)	−0.0048 (8)	−0.0007 (7)
C30	0.0317 (9)	0.0267 (8)	0.0366 (10)	−0.0008 (7)	−0.0055 (7)	0.0033 (7)
C31	0.0283 (9)	0.0370 (9)	0.0327 (9)	−0.0031 (7)	−0.0045 (7)	−0.0091 (7)
C32	0.0530 (13)	0.0443 (12)	0.0619 (15)	−0.0104 (10)	−0.0190 (11)	−0.0157 (11)
C33	0.0359 (10)	0.0555 (12)	0.0304 (10)	0.0031 (9)	−0.0047 (8)	−0.0069 (9)
C34	0.0267 (9)	0.0639 (14)	0.0408 (11)	−0.0037 (9)	−0.0028 (8)	−0.0128 (10)
N35	0.0299 (7)	0.0242 (7)	0.0255 (7)	0.0019 (5)	0.0006 (6)	−0.0048 (5)
N36	0.0319 (7)	0.0241 (7)	0.0265 (7)	0.0047 (5)	−0.0004 (6)	−0.0043 (5)
C37	0.0264 (8)	0.0284 (8)	0.0248 (8)	−0.0012 (6)	0.0007 (6)	−0.0054 (6)
C38	0.0441 (10)	0.0334 (9)	0.0245 (8)	0.0057 (8)	−0.0014 (7)	−0.0018 (7)
C39	0.0410 (10)	0.0268 (8)	0.0259 (8)	0.0044 (7)	−0.0005 (7)	−0.0010 (7)
C40	0.0304 (9)	0.0321 (9)	0.0317 (9)	0.0033 (7)	−0.0009 (7)	−0.0110 (7)
C41	0.0424 (11)	0.0416 (10)	0.0378 (10)	0.0112 (8)	−0.0038 (8)	−0.0084 (8)
C42	0.0483 (12)	0.0536 (12)	0.0301 (10)	0.0109 (9)	−0.0015 (8)	−0.0100 (9)
C43	0.0473 (12)	0.0326 (10)	0.0726 (16)	−0.0064 (9)	0.0113 (11)	−0.0186 (10)

Geometric parameters (Å, º)

Fe1—O3	1.7710 (11)	C24—H24B	0.9800
Fe1—Cl5	2.2168 (5)	C24—H24C	0.9800
Fe1—Cl6	2.2214 (5)	C25—H25A	0.9800
Fe1—Cl4	2.2256 (5)	C25—H25B	0.9800
Fe2—O3	1.8243 (11)	C25—H25C	0.9800
Fe2—N8	2.1280 (14)	N26—C30	1.331 (2)
Fe2—N17	2.1395 (14)	N26—N27	1.3579 (19)
Fe2—N26	2.1592 (14)	N27—C28	1.348 (2)
Fe2—N35	2.1407 (14)	N27—H27	0.8800
Fe2—Cl7	2.3968 (4)	C28—C29	1.384 (3)
N8—C12	1.333 (2)	C28—C31	1.510 (2)
N8—N9	1.361 (2)	C29—C30	1.397 (3)
N9—C10	1.350 (2)	C29—H29	0.9500
N9—H9	0.8800	C30—H30	0.9500
C10—C11	1.377 (3)	C31—C33	1.533 (3)
C10—C13	1.513 (3)	C31—C32	1.536 (3)
C11—C12	1.396 (3)	C31—C34	1.536 (3)
C11—H11	0.9500	C32—H32A	0.9800
C12—H12	0.9500	C32—H32B	0.9800
C13—C14	1.526 (3)	C32—H32C	0.9800
C13—C15	1.535 (3)	C33—H33A	0.9800
C13—C16	1.538 (3)	C33—H33B	0.9800
C14—H14A	0.9800	C33—H33C	0.9800
C14—H14B	0.9800	C34—H34A	0.9800
C14—H14C	0.9800	C34—H34B	0.9800
C15—H15A	0.9800	C34—H34C	0.9800
C15—H15B	0.9800	N35—C39	1.333 (2)
C15—H15C	0.9800	N35—N36	1.3539 (19)
C16—H16A	0.9800	N36—C37	1.347 (2)
C16—H16B	0.9800	N36—H36	0.8800
C16—H16C	0.9800	C37—C38	1.377 (2)
N17—C21	1.331 (2)	C37—C40	1.510 (2)
N17—N18	1.3577 (19)	C38—C39	1.395 (3)
N18—C19	1.346 (2)	C38—H38	0.9500
N18—H18	0.8800	C39—H39	0.9500
C19—C20	1.380 (3)	C40—C43	1.527 (3)
C19—C22	1.515 (3)	C40—C41	1.528 (3)
C20—C21	1.393 (2)	C40—C42	1.539 (3)
C20—H20	0.9500	C41—H41A	0.9800
C21—H21	0.9500	C41—H41B	0.9800
C22—C25	1.507 (3)	C41—H41C	0.9800
C22—C24	1.512 (3)	C42—H42A	0.9800
C22—C23	1.552 (3)	C42—H42B	0.9800
C23—H23A	0.9800	C42—H42C	0.9800
C23—H23B	0.9800	C43—H43A	0.9800
C23—H23C	0.9800	C43—H43B	0.9800
C24—H24A	0.9800	C43—H43C	0.9800
O3—Fe1—Cl5	107.90 (4)	C22—C24—H24B	109.5
O3—Fe1—Cl6	107.98 (4)	H24A—C24—H24B	109.5
Cl5—Fe1—Cl6	112.14 (2)	C22—C24—H24C	109.5
O3—Fe1—Cl4	106.59 (4)	H24A—C24—H24C	109.5
Cl5—Fe1—Cl4	109.15 (2)	H24B—C24—H24C	109.5
Cl6—Fe1—Cl4	112.80 (2)	C22—C25—H25A	109.5
O3—Fe2—N8	89.50 (6)	C22—C25—H25B	109.5
O3—Fe2—N17	90.43 (5)	H25A—C25—H25B	109.5
N8—Fe2—N17	88.92 (6)	C22—C25—H25C	109.5
O3—Fe2—N35	92.12 (5)	H25A—C25—H25C	109.5
N8—Fe2—N35	177.14 (6)	H25B—C25—H25C	109.5
N17—Fe2—N35	93.43 (5)	C30—N26—N27	104.78 (14)
O3—Fe2—N26	93.61 (5)	C30—N26—Fe2	130.69 (12)
N8—Fe2—N26	93.52 (6)	N27—N26—Fe2	120.34 (10)
N17—Fe2—N26	175.29 (5)	C28—N27—N26	112.60 (14)
N35—Fe2—N26	84.02 (5)	C28—N27—H27	123.7
O3—Fe2—Cl7	177.77 (4)	N26—N27—H27	123.7
N8—Fe2—Cl7	89.81 (4)	N27—C28—C29	105.87 (15)
N17—Fe2—Cl7	87.44 (4)	N27—C28—C31	122.34 (16)
N35—Fe2—Cl7	88.66 (4)	C29—C28—C31	131.79 (16)
N26—Fe2—Cl7	88.54 (4)	C28—C29—C30	105.67 (15)
Fe1—O3—Fe2	168.50 (8)	C28—C29—H29	127.2
C12—N8—N9	105.06 (15)	C30—C29—H29	127.2
C12—N8—Fe2	133.48 (13)	N26—C30—C29	111.08 (16)
N9—N8—Fe2	120.92 (11)	N26—C30—H30	124.5
C10—N9—N8	112.29 (15)	C29—C30—H30	124.5
C10—N9—H9	123.9	C28—C31—C33	109.75 (15)
N8—N9—H9	123.9	C28—C31—C32	108.84 (16)
N9—C10—C11	105.76 (17)	C33—C31—C32	109.38 (17)
N9—C10—C13	122.54 (18)	C28—C31—C34	109.27 (15)
C11—C10—C13	131.69 (18)	C33—C31—C34	109.48 (17)
C10—C11—C12	106.42 (17)	C32—C31—C34	110.11 (17)
C10—C11—H11	126.8	C31—C32—H32A	109.5
C12—C11—H11	126.8	C31—C32—H32B	109.5
N8—C12—C11	110.47 (18)	H32A—C32—H32B	109.5
N8—C12—H12	124.8	C31—C32—H32C	109.5
C11—C12—H12	124.8	H32A—C32—H32C	109.5
C10—C13—C14	109.07 (19)	H32B—C32—H32C	109.5
C10—C13—C15	110.39 (16)	C31—C33—H33A	109.5
C14—C13—C15	109.40 (18)	C31—C33—H33B	109.5
C10—C13—C16	109.36 (17)	H33A—C33—H33B	109.5
C14—C13—C16	109.5 (2)	C31—C33—H33C	109.5
C15—C13—C16	109.1 (2)	H33A—C33—H33C	109.5
C13—C14—H14A	109.5	H33B—C33—H33C	109.5
C13—C14—H14B	109.5	C31—C34—H34A	109.5
H14A—C14—H14B	109.5	C31—C34—H34B	109.5
C13—C14—H14C	109.5	H34A—C34—H34B	109.5
H14A—C14—H14C	109.5	C31—C34—H34C	109.5
H14B—C14—H14C	109.5	H34A—C34—H34C	109.5
C13—C15—H15A	109.5	H34B—C34—H34C	109.5
C13—C15—H15B	109.5	C39—N35—N36	104.80 (14)
H15A—C15—H15B	109.5	C39—N35—Fe2	131.21 (12)
C13—C15—H15C	109.5	N36—N35—Fe2	121.81 (11)
H15A—C15—H15C	109.5	C37—N36—N35	112.56 (14)
H15B—C15—H15C	109.5	C37—N36—H36	123.7
C13—C16—H16A	109.5	N35—N36—H36	123.7
C13—C16—H16B	109.5	N36—C37—C38	105.94 (15)
H16A—C16—H16B	109.5	N36—C37—C40	123.14 (15)
C13—C16—H16C	109.5	C38—C37—C40	130.87 (16)
H16A—C16—H16C	109.5	C37—C38—C39	105.86 (16)
H16B—C16—H16C	109.5	C37—C38—H38	127.1
C21—N17—N18	104.77 (14)	C39—C38—H38	127.1
C21—N17—Fe2	134.52 (12)	N35—C39—C38	110.84 (16)
N18—N17—Fe2	119.29 (10)	N35—C39—H39	124.6
C19—N18—N17	112.49 (14)	C38—C39—H39	124.6
C19—N18—H18	123.8	C37—C40—C43	108.89 (15)
N17—N18—H18	123.8	C37—C40—C41	110.30 (15)
N18—C19—C20	105.90 (15)	C43—C40—C41	111.18 (17)
N18—C19—C22	121.75 (16)	C37—C40—C42	108.83 (16)
C20—C19—C22	132.32 (17)	C43—C40—C42	108.97 (18)
C19—C20—C21	105.85 (16)	C41—C40—C42	108.63 (16)
C19—C20—H20	127.1	C40—C41—H41A	109.5
C21—C20—H20	127.1	C40—C41—H41B	109.5
N17—C21—C20	110.98 (16)	H41A—C41—H41B	109.5
N17—C21—H21	124.5	C40—C41—H41C	109.5
C20—C21—H21	124.5	H41A—C41—H41C	109.5
C25—C22—C24	111.8 (2)	H41B—C41—H41C	109.5
C25—C22—C19	109.94 (18)	C40—C42—H42A	109.5
C24—C22—C19	110.43 (17)	C40—C42—H42B	109.5
C25—C22—C23	107.0 (2)	H42A—C42—H42B	109.5
C24—C22—C23	108.3 (2)	C40—C42—H42C	109.5
C19—C22—C23	109.27 (17)	H42A—C42—H42C	109.5
C22—C23—H23A	109.5	H42B—C42—H42C	109.5
C22—C23—H23B	109.5	C40—C43—H43A	109.5
H23A—C23—H23B	109.5	C40—C43—H43B	109.5
C22—C23—H23C	109.5	H43A—C43—H43B	109.5
H23A—C23—H23C	109.5	C40—C43—H43C	109.5
H23B—C23—H23C	109.5	H43A—C43—H43C	109.5
C22—C24—H24A	109.5	H43B—C43—H43C	109.5

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N9—H9···O3	0.88	2.45	2.8885 (19)	112
N9—H9···Cl4	0.88	2.76	3.6265 (16)	170
N18—H18···O3	0.88	2.46	2.9122 (18)	113
N18—H18···Cl5	0.88	3.03	3.7117 (16)	135
N27—H27···Cl6	0.88	2.54	3.3945 (15)	165
N36—H36···Cl7	0.88	2.59	3.1392 (15)	122