[Cr₈(PhCO₂)₁₆O₄]·4CH₃CN·2H₂O: structural origin of magnetic anisotropy in a mol­ecular spin cluster

The Cr₄O₄ hetero-cubane-centered octa­chromium(III) cluster [Cr₈(PhCO₂)₁₆O₄] crystallizes from fluoro­benzene–aceto­nitrile as dodeca-μ₂-benzoato-tetra­benzoatotetra-μ₄-oxido-octa­chromium(III) acetonitrile tetra­solvate dihydrate, [Cr₈(C₇H₅O₂)₁₆O₄]·4C₂H₃N·2H₂O, (I). Crystals produced by this method are significantly more stable than the originally published dichloro­methane penta­solvate, [Cr₈(PhCO₂)₁₆O₄]·5CH₂Cl₂ [Atkinson et al. (1999). Chem. Commun. pp. 285–286], leading to a significantly higher quality structure and allowing the production of large quanti­ties of high-quality nondeuterated and deuterated material suitable for inelastic neutron scattering (INS) measurements. Compound (I) reveals a higher symmetry structure in which the cluster sits on a twofold rotation axis, and is based on an asymmetric unit containing four crystallographically independent Cr positions, two oxide ligands, eight benzoate ligands, two acetonitrile solvent mol­ecules and one disordered water mol­ecule. All the Cr atoms are six-coordinate, with an octa­hedral geometry for the inner cubane and a more highly distorted coordination environment in the outer positions. Despite the higher symmetry, the coordination geometries observed in (I) are largely similar to the dichloro­methane penta­solvate structure, indicating that crystal-packing effects have little influence on the mol­ecular structure of [Cr₈(PhCO₂)₁₆O₄]. Close structural analysis reveals that the high magnetic anisotropy observed in the INS measurements is a consequence of the distorted coordination geometry of the four outer Cr atoms.

S1. Comment

The chemistry of metal carboxylates is exceptionally structurally rich, giving rise to a wide range of clusters (e.g. Affronte et al., 2007; Engelhardt et al., 2008; Sessoli et al.., 1993; Tasiopoulos et al., 2004) and network structures (e.g. Cornia et al., 1999; Fielden et al., 2009; Moushi et al., 2006; Wang et al., 2004) as a consequence of the range of coodination modes offered by the CO₂^- group. As carboxylate bridging modes frequently give rise to strong magnetic interactions between metal centres, discrete and infinite three-dimensional metal carboxylates are intensively investigated for their magnetic properties. One such cluster is the {Cr₈} heterocubane [Cr₈O₄(O₂CPh)₁₆], which has recently been the subject of detailed inelastic neutron scattering (INS) measurements (Vaknin et al., 2010).

The {Cr₈} cubane-type cluster was originally published in 1999 (Atkinson et al., 1999) and was synthesized by heating the triangular [Cr₃O(O₂CPh)₆(H₂O)₂(OH)] precursor at 648–673 K under inert gas. Crystallization was originally achieved as [Cr₈(PhCO₂)₁₆O₄].5CH₂Cl₂ [Cambridge Structural Database (CSD; Allen, 2002) refcode HIPGIW; Reference?] from CH₂Cl₂/ⁿPrOH. While we could produce single crystals on a small scale using this technique, we were unable to produce polycrystalline material on the >5 g scale needed for INS. Furthermore, the included dichloromethane solvent is easily lost under ambient conditions, producing degraded crystals in which the cluster is apparently vulnerable to hydrolysis by atmospheric water. These issues mandated a search for an alternative crystallization method, and we identified the PhF/MeCN solvent system as a more readily scalable method that produces higher quality crystals which exhibit no hydrolysis under ambient conditions. These allowed room-temperature determination of a crystal structure of the acetonitrile–water solvate {Cr₈} cubane, [Cr₈(PhCO₂)₁₆O₄].4CH₃CN.2H₂O, (I), with the adventitious water molecules thought to result from the acetonitrile (Fisher, circa 0.3% H₂O). This structure is significantly higher in quality than the published structure of [Cr₈(PhCO₂)₁₆O₄].5CH₂Cl₂ obtained at 150 K (R1 = 0.0496 versus 0.1025, R_int = 0.052 versus 0.0832, θ_max = 26.38 versus 25.11).

Compound (I) crystallizes in the space group C2/c, and as such the cluster adopts a higher symmetry than seen in [Cr₈(PhCO₂)₁₆O₄].5CH₂Cl₂ (P2₁/c). The asymmetric unit (Fig. 1a) contains only a half rather than a complete {Cr₈} cubane cluster, e.g. four six-coordinate Cr atoms, two terminal and six bridging benzoate ligands, two oxo ligands and half of the solvent molecules (omitted from the figure for clarity). None of these atoms are located on special positions. The complete µ₄-oxo bridged {Cr₈O₄} core (Figs. 1b and 1c), with terminal and bridging benzoate ligands, is generated from the asymmetric unit by a twofold rotation axis passing through the centre of the cubane and the faces described by Cr1/Cr1ⁱ/O1/O1ⁱ and Cr2/Cr2ⁱ/O13/O13ⁱ [symmetry code: (i) 2 - x, y, 1/2 - z Please check added symop]. In the crystal structure of (I), the {Cr₈} cubane packs in rows running parallel to the crystallographic b axis. As in [Cr₈(PhCO₂)₁₆O₄].5CH₂Cl₂ (HIPGIW), there is no evidence for strong intermolecular interactions (e.g. hydrogen bonds) or other important intermolecular contacts.

Coordination bond lengths and angles for (I) are listed in Table 1, with the higher quality data obtained resulting in consistently lower standard uncertainties than seen in HIPGIW. The absence of potentially distorting intermolecular interactions in either structure means that the differences between their coordination bond lengths and angles are small, although the lower-symmetry structure has a wider range of Cr—O bond distances and O—Cr—O angles than seen in compound (I) (Table 2). As the crystals of (I) seem to be stable, these slight crystal-packing-induced differences may account for the small differences in magnetic susceptibility between (I) and [Cr₈(PhCO₂)₁₆O₄].5CH₂Cl₂ (Luban et al., 2003; Vaknin et al., 2010).

More significantly, INS measurements on compound (I) have indicated that this material must have a high zero-field splitting (ZFS), as the magnetic energy spectrum cannot be accurately described by an isotropic model (Vaknin et al., 2010). This was not apparent from the previously obtained 2–290 K magnetic susceptibility data, and prompted us to re-examine the structures of both compound (I) and [Cr₈(PhCO₂)₁₆O₄].5CH₂Cl₂ to elucidate if slight geometric differences in the CrO₆ environments could possibly account for significant differences in ZFS. In compound (I), the coordination environments of the central four Cr atoms (Cr1/Cr2 and their symmetry-generated positions Cr1ⁱ/Cr2ⁱ) show only relatively small deviations from octahedral, with Cr—O bond distances varying only ±2% from the 1.979 (2) Å average and cis O—Cr—O deviating less than ±10% from the ideal 90° (see Tables 1 and 2). In HIPGIW, these inner Cr (Cr1–Cr4) environments show a slightly higher variation of ±3% from an average Cr—O distance of 1.984 (8) Å, and a very slightly larger deviation of the angles from 90°. However, the outer Cr atoms of both structures [Cr3/Cr4/Cr3ⁱ/Cr4ⁱ in (I) and Cr5–Cr8 in HIPGIW] show significant distortion in their angles due to restrictions imposed by the κ²-chelating coordination mode of the terminal benzoate ligands (see Fig. 2). These two environments both have one very small O—Cr—O angle (ϕ in Fig. 2, circa 65°) and one that is rather wide (θ, circa 108°). For both structures, the average outer Cr—O bond distances are little different from those of the inner Cr atoms, although the variation [±3% in (I) and ±4% in HIPGIW] is slightly larger. Therefore, it seems likely that the magnetic anisotropy apparent in the INS measurements is a consequence of the highly distorted coordination bond angles of the outer Cr atoms, which are apparent in both structures.

In order to probe the effects of this distortion on the resulting ZFS, we have carried out point-charge electrostatic model (PCEM) calculations of the individual outer CrO₆ polyhedra of both structures using the computational framework CONDON (Schilder & Lueken, 2004) and the standard ligand field and spin orbit-coupling parameter sets. The resulting eigenvalues for the corresponding individual Cr atoms indeed show a clear splitting compared with a regular O_h-symmetric CrO₆ octahedron. Importantly, the differences in the eigenvalues of the resulting 28 Kramers doublets (stemming from the ⁴F ground term of Cr³⁺) for the outer CrO₆ octahedra in (I) and for those in HIPGIW are very small and amount to 0.01–2.4%. For example, the splitting between the lowest |±3/2> doublet and the first excited |±1/2> doublet results in values of 14.02 cm^-1 for Cr3 in (I) and 13.81 cm^-1 for Cr5 in HIPGIW. This confirms that compound (I), within the resolution of INS measurements, represents a magnetochemically virtually identical equivalent to HIPGIW, despite small geometric differences.

Related literature

For related literature, see: Affronte et al. (2007); Allen (2002); Atkinson et al. (1999); Cornia et al. (1999); Engelhardt et al. (2008); Fielden et al. (2009); Luban et al. (2003); Moushi et al. (2006); Schilder & Lueken (2004); Sessoli et al. (1993); Tasiopoulos et al. (2004); Vaknin et al. (2010); Wang et al. (2004).

S2. Experimental

Benzoic acid (21.74 g, 0.178 mol) and KOH (10.99 g, 0.196 mol) were dissolved in water (500 ml) with heating to 353 K, resulting in a solution with pH \sim 5.3. The pH was adjusted to ~8.0 by addition of aqueous KOH, before a solution of Cr(NO₃)₃.9H₂O (20.01 g, 0.05 mol) in water (30 ml) was added, resulting in instantaneous production of a pale-blue precipitate. After heating and stirring for a further 30 min this was recovered by filtration, washed with water (4 × 50 ml) and methanol (3 × 50 ml) and air-dried to yield the pale-blue intermediate [Cr₃O(O₂CPh)₆(H₂O)₂(OH)] (yield 15.87 g, 0.0167 mol, 100%). The amorphous precipitate was heated under a constant stream of argon at 648 K for 1 h, producing dark-green crude [Cr₈O₄(O₂CPh)₁₆] (yield 12.96 g). The crude material was dissolved in fluorobenzene (125 ml), filtered and crystallized in a PFTE flask by the addition of acetonitrile (1500 ml), yielding compound (I) as a mixture of dark-green single crystals and microcrystalline powder (yield 5.76 g, 0.0022 mol, 35%). Spectroscopic analysis: FTIR (KBr disc, ν, cm^-1): 3424 (m), 3066 (m), 3030 (w), 2933 (vw), 1965 (vw), 1921 (vw), 1821 (vw), 1611 (vs), 1572 (vs), 1543 (m), 1498 (s), 1423 (vs), 1311 (w), 1180 (m), 1159 (w), 1070 (w), 937 (vw), 876 (m), 830 (vw), 811 (vw), 716 (s), 685 (s), 634 (m), 559 (s), 516 (m).

S3. Refinement

All carbon-bound H atoms were placed in geometrically idealized positions, with C—H = 0.93 (aromatic) or 0.96 Å (methyl), and constrained to ride or ride and rotate on their parent atoms, with U_iso(H) = 1.2U_eq(C) for aromatic H atoms and U_iso(H) = 1.5U_eq(C) for idealized methyl H atoms. The H atoms on the solvent water molecule O19A/O19B could not be located and are not included in the structural model. A relatively high U_eq(max)/U_eq(min) ratio is observed for the C atoms of the chromium benzoate cluster; this is a consequence of slight disorder and has not been restrained. The solvent water molecule O19A/O19B is disordered over two positions; refinement indicates that their occupancies are equal.

Computing details

Data collection: SMART (Bruker, 2001); cell refinement: SMART (Bruker, 2001); data reduction: SAINT (Bruker, 2001); 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: publCIF (Westrip, 2010).

Figures

Fig. 1. (a) The asymmetric unit of (I), showing the numbering scheme for Cr and O atoms. For clarity, a ball-and-stick representation is used, and H atoms, solvent molecules and labels for C atoms have been omitted. (b) The complete structure of (I), with displacement ellipsoids drawn at the 30% probability level, omitting solvent molecules, H atoms and phenyl groups. (c) The {Cr8O4} core in (I), with displacement ellipsoids drawn at the 50% probability level. [Symmetry code: (i) 2 - x, y, 1/2 - z.]

Fig. 2. Ball-and-stick representation of the distorted coordination environment of one of the outer Cr positions (Cr3) of (I), showing the large and small O—Cr—O angles θ and ϕ.

dodeca-µ₂-benzoato-tetrabenzoatotetra-µ₄-oxido-octachromium(III) acetonitrile tetrasolvate dihydrate

Crystal data

[Cr8(C7H5O2)16O4]·4C2H3N·2H2O	F(000) = 5360
Mr = 2618.01	Dx = 1.424 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 23.406 (5) Å	Cell parameters from 959 reflections
b = 18.970 (4) Å	θ = 2.7–27.0°
c = 27.592 (6) Å	µ = 0.77 mm^−1
β = 94.730 (4)°	T = 293 K
V = 12210 (4) Å^3	Prism, green
Z = 4	0.20 × 0.20 × 0.10 mm

Data collection

Bruker SMART CCD area-detector diffractometer	12440 independent reflections
Radiation source: fine-focus sealed tube	8093 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.052
ϕ and ω scans	θmax = 26.4°, θmin = 1.4°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −29→28
Tmin = 0.86, Tmax = 1	k = −23→23
50439 measured reflections	l = −34→34

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)] = 0.050	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.147	H-atom parameters constrained
S = 1.06	w = 1/[σ^2(Fo^2) + (0.0686P)^2 + 15.0742P] where P = (Fo^2 + 2Fc^2)/3
12440 reflections	(Δ/σ)max = 0.041
778 parameters	Δρmax = 0.52 e Å^−3
0 restraints	Δρmin = −0.37 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.

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 (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
Cr1	1.01687 (2)	0.77893 (3)	0.199324 (18)	0.03029 (14)
Cr2	0.93862 (2)	0.66736 (3)	0.230580 (19)	0.03052 (14)
Cr3	0.88054 (2)	0.84035 (3)	0.21915 (2)	0.03442 (14)
Cr4	1.02990 (2)	0.60978 (3)	0.15071 (2)	0.03646 (15)
C1	1.13729 (16)	0.79785 (18)	0.17843 (13)	0.0380 (8)
C2	1.18155 (16)	0.7886 (2)	0.14307 (14)	0.0462 (9)
C3	1.1661 (2)	0.7647 (3)	0.09722 (16)	0.0708 (14)
H3	1.1277	0.7565	0.0875	0.085*
C4	1.2074 (3)	0.7529 (4)	0.0652 (2)	0.106 (2)
H4	1.1967	0.7364	0.0340	0.127*
C5	1.2634 (3)	0.7650 (4)	0.0789 (2)	0.109 (2)
H5	1.2910	0.7574	0.0571	0.130*
C6	1.2790 (2)	0.7880 (4)	0.1238 (2)	0.095 (2)
H6	1.3176	0.7958	0.1331	0.114*
C7	1.23851 (19)	0.8003 (3)	0.15673 (17)	0.0640 (12)
H7	1.2498	0.8165	0.1879	0.077*
C8	0.95442 (15)	0.93159 (18)	0.28384 (13)	0.0370 (8)
C9	0.96580 (16)	1.00314 (18)	0.30461 (14)	0.0428 (9)
C10	1.0071 (2)	1.0115 (2)	0.34255 (17)	0.0637 (12)
H10	1.0278	0.9725	0.3546	0.076*
C11	1.0184 (2)	1.0771 (3)	0.3631 (2)	0.0799 (15)
H11	1.0462	1.0820	0.3890	0.096*
C12	0.9888 (3)	1.1341 (3)	0.3452 (2)	0.0801 (16)
H12	0.9952	1.1779	0.3598	0.096*
C13	0.9503 (3)	1.1276 (2)	0.3064 (2)	0.0882 (18)
H13	0.9315	1.1674	0.2935	0.106*
C14	0.9384 (2)	1.0612 (2)	0.28532 (19)	0.0692 (13)
H14	0.9119	1.0570	0.2584	0.083*
C15	0.78425 (16)	0.84009 (19)	0.18501 (13)	0.0398 (8)
C16	0.72424 (16)	0.8405 (2)	0.16411 (14)	0.0454 (9)
C17	0.69565 (17)	0.7785 (2)	0.15252 (16)	0.0567 (11)
H17	0.7143	0.7355	0.1576	0.068*
C18	0.6389 (2)	0.7803 (3)	0.13324 (18)	0.0733 (14)
H18	0.6195	0.7385	0.1257	0.088*
C19	0.6118 (2)	0.8431 (4)	0.12532 (19)	0.0809 (17)
H19	0.5738	0.8438	0.1125	0.097*
C20	0.6400 (2)	0.9059 (3)	0.1360 (2)	0.0799 (16)
H20	0.6213	0.9487	0.1302	0.096*
C21	0.69601 (19)	0.9044 (2)	0.15537 (17)	0.0621 (12)
H21	0.7152	0.9465	0.1627	0.074*
C22	0.85351 (15)	0.62956 (18)	0.29728 (13)	0.0375 (8)
C23	0.79107 (16)	0.6240 (2)	0.30381 (15)	0.0449 (9)
C24	0.75195 (17)	0.6493 (3)	0.26789 (17)	0.0599 (11)
H24	0.7647	0.6696	0.2401	0.072*
C25	0.6938 (2)	0.6446 (3)	0.2731 (2)	0.0812 (16)
H25	0.6674	0.6609	0.2485	0.097*
C26	0.6753 (2)	0.6158 (3)	0.3144 (2)	0.0899 (18)
H26	0.6363	0.6136	0.3183	0.108*
C27	0.7134 (2)	0.5904 (3)	0.3500 (2)	0.0861 (17)
H27	0.7002	0.5701	0.3777	0.103*
C28	0.77209 (19)	0.5947 (3)	0.34526 (18)	0.0639 (12)
H28	0.7982	0.5779	0.3698	0.077*
C29	0.90575 (16)	0.64700 (18)	0.12744 (13)	0.0388 (8)
C30	0.86178 (17)	0.6528 (2)	0.08576 (14)	0.0473 (9)
C31	0.8077 (2)	0.6743 (3)	0.09292 (17)	0.0737 (15)
H31	0.7986	0.6862	0.1240	0.088*
C32	0.7666 (3)	0.6788 (4)	0.0546 (2)	0.111 (2)
H32	0.7299	0.6942	0.0598	0.133*
C33	0.7794 (3)	0.6605 (4)	0.0087 (2)	0.107 (2)
H33	0.7513	0.6625	−0.0171	0.128*
C34	0.8332 (3)	0.6395 (4)	0.00121 (18)	0.099 (2)
H34	0.8422	0.6282	−0.0300	0.118*
C35	0.8749 (2)	0.6348 (3)	0.03966 (17)	0.0736 (14)
H35	0.9116	0.6196	0.0344	0.088*
C36	0.96117 (17)	0.51555 (19)	0.20542 (14)	0.0430 (9)
C37	0.94165 (18)	0.44154 (19)	0.20981 (15)	0.0485 (9)
C38	0.8938 (2)	0.4258 (2)	0.23267 (17)	0.0641 (12)
H38	0.8724	0.4615	0.2455	0.077*
C39	0.8772 (3)	0.3552 (3)	0.2366 (2)	0.0885 (17)
H39	0.8446	0.3439	0.2522	0.106*
C40	0.9085 (3)	0.3036 (3)	0.2180 (2)	0.099 (2)
H40	0.8964	0.2570	0.2199	0.119*
C41	0.9569 (3)	0.3183 (3)	0.1967 (3)	0.100 (2)
H41	0.9788	0.2819	0.1852	0.120*
C42	0.9739 (2)	0.3879 (2)	0.1920 (2)	0.0725 (14)
H42	1.0069	0.3984	0.1768	0.087*
C43	1.05469 (16)	0.6122 (2)	0.06948 (14)	0.0471 (9)
C44	1.0660 (2)	0.6146 (3)	0.01782 (16)	0.0598 (12)
C45	1.0682 (3)	0.5520 (3)	−0.0081 (2)	0.099 (2)
H45	1.0630	0.5091	0.0071	0.119*
C46	1.0780 (4)	0.5543 (4)	−0.0563 (2)	0.133 (3)
H46	1.0780	0.5127	−0.0742	0.160*
C47	1.0878 (3)	0.6164 (4)	−0.0781 (2)	0.120 (3)
H47	1.0963	0.6168	−0.1105	0.144*
C48	1.0852 (3)	0.6793 (4)	−0.05333 (18)	0.0927 (19)
H48	1.0910	0.7220	−0.0688	0.111*
C49	1.0740 (2)	0.6777 (3)	−0.00514 (17)	0.0719 (14)
H49	1.0717	0.7196	0.0120	0.086*
C50	0.93220 (15)	0.82409 (18)	0.12342 (13)	0.0377 (8)
C51	0.92037 (17)	0.8377 (2)	0.07059 (14)	0.0480 (9)
C52	0.8803 (2)	0.8878 (3)	0.05438 (17)	0.0723 (14)
H52	0.8598	0.9124	0.0764	0.087*
C53	0.8713 (3)	0.9009 (4)	0.0050 (2)	0.101 (2)
H53	0.8441	0.9342	−0.0062	0.121*
C54	0.9013 (3)	0.8659 (4)	−0.0276 (2)	0.101 (2)
H54	0.8956	0.8763	−0.0605	0.121*
C55	0.9400 (3)	0.8156 (4)	−0.01175 (18)	0.0940 (19)
H55	0.9597	0.7904	−0.0340	0.113*
C56	0.9500 (2)	0.8019 (3)	0.03738 (15)	0.0669 (13)
H56	0.9770	0.7682	0.0481	0.080*
C57	0.0693 (6)	0.9270 (8)	0.0597 (6)	0.249 (7)
H57A	0.0395	0.9610	0.0520	0.374*
H57B	0.1015	0.9498	0.0769	0.374*
H57C	0.0552	0.8905	0.0796	0.374*
C58	0.0874 (7)	0.8959 (8)	0.0140 (7)	0.186 (6)
C59	0.7737 (6)	−0.0101 (5)	0.3013 (4)	0.194 (5)
H59A	0.7834	−0.0584	0.3086	0.292*
H59B	0.7860	0.0020	0.2700	0.292*
H59C	0.7330	−0.0041	0.3010	0.292*
C60	0.8016 (6)	0.0344 (8)	0.3375 (4)	0.191 (5)
N1	0.1027 (7)	0.8693 (8)	−0.0212 (5)	0.232 (6)
N2	0.8215 (6)	0.0714 (10)	0.3642 (4)	0.320 (10)
O1	0.94494 (9)	0.77335 (11)	0.23444 (8)	0.0308 (5)
O2	0.81283 (10)	0.78308 (12)	0.19001 (9)	0.0416 (6)
O3	0.91989 (11)	0.92542 (12)	0.24653 (9)	0.0426 (6)
O4	0.80947 (11)	0.89664 (13)	0.19926 (9)	0.0453 (6)
O5	0.84785 (10)	0.82774 (13)	0.28193 (9)	0.0428 (6)
O6	0.90187 (11)	0.85525 (13)	0.15241 (9)	0.0422 (6)
O7	1.01974 (10)	0.88152 (12)	0.19441 (9)	0.0406 (6)
O8	0.97333 (10)	0.78230 (12)	0.13563 (8)	0.0367 (5)
O9	1.08763 (10)	0.77542 (12)	0.16609 (8)	0.0382 (5)
O10	0.86657 (9)	0.66482 (12)	0.26108 (9)	0.0372 (5)
O11	0.93298 (10)	0.56365 (12)	0.22536 (9)	0.0385 (6)
O12	1.00629 (12)	0.52565 (13)	0.18368 (10)	0.0496 (7)
O13	1.01469 (9)	0.67374 (11)	0.20460 (8)	0.0290 (5)
O14	0.89439 (10)	0.67265 (12)	0.16753 (8)	0.0355 (5)
O15	1.11180 (11)	0.59952 (14)	0.17226 (10)	0.0474 (6)
O16	0.95178 (11)	0.61621 (14)	0.11958 (9)	0.0486 (7)
O17	1.05126 (12)	0.66902 (14)	0.09392 (9)	0.0487 (6)
O18	1.04730 (11)	0.55481 (14)	0.09109 (10)	0.0494 (7)
O19A	0.7408 (8)	0.0411 (10)	0.9580 (14)	0.27 (2)	0.48 (3)
O19B	0.7363 (8)	0.0357 (15)	1.0235 (13)	0.318 (19)	0.52 (3)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cr1	0.0286 (3)	0.0296 (3)	0.0326 (3)	−0.0007 (2)	0.0022 (2)	0.0011 (2)
Cr2	0.0267 (3)	0.0288 (3)	0.0363 (3)	−0.0007 (2)	0.0040 (2)	−0.0016 (2)
Cr3	0.0310 (3)	0.0324 (3)	0.0394 (3)	0.0037 (2)	0.0002 (2)	−0.0002 (2)
Cr4	0.0331 (3)	0.0350 (3)	0.0422 (3)	0.0000 (2)	0.0086 (2)	−0.0070 (2)
C1	0.037 (2)	0.0329 (18)	0.044 (2)	−0.0019 (15)	0.0052 (17)	0.0077 (16)
C2	0.038 (2)	0.055 (2)	0.047 (2)	−0.0044 (18)	0.0116 (17)	0.0072 (18)
C3	0.053 (3)	0.106 (4)	0.055 (3)	−0.019 (3)	0.014 (2)	−0.010 (3)
C4	0.082 (4)	0.178 (7)	0.061 (3)	−0.022 (4)	0.032 (3)	−0.027 (4)
C5	0.067 (4)	0.190 (7)	0.074 (4)	−0.014 (4)	0.038 (3)	−0.016 (4)
C6	0.046 (3)	0.156 (6)	0.085 (4)	−0.010 (3)	0.021 (3)	0.001 (4)
C7	0.046 (3)	0.092 (3)	0.055 (3)	−0.004 (2)	0.013 (2)	0.006 (2)
C8	0.0327 (19)	0.0369 (19)	0.042 (2)	−0.0010 (15)	0.0070 (16)	−0.0008 (16)
C9	0.043 (2)	0.0337 (19)	0.052 (2)	0.0015 (16)	0.0082 (18)	−0.0035 (16)
C10	0.076 (3)	0.043 (2)	0.069 (3)	0.001 (2)	−0.017 (2)	−0.005 (2)
C11	0.094 (4)	0.060 (3)	0.081 (4)	−0.011 (3)	−0.018 (3)	−0.017 (3)
C12	0.100 (4)	0.043 (3)	0.096 (4)	−0.009 (3)	0.000 (3)	−0.021 (3)
C13	0.107 (5)	0.037 (3)	0.116 (5)	0.018 (3)	−0.015 (4)	−0.006 (3)
C14	0.074 (3)	0.040 (2)	0.091 (4)	0.007 (2)	−0.013 (3)	−0.003 (2)
C15	0.040 (2)	0.041 (2)	0.0384 (19)	0.0057 (17)	0.0036 (16)	0.0004 (16)
C16	0.036 (2)	0.055 (2)	0.044 (2)	0.0060 (18)	0.0012 (17)	−0.0012 (18)
C17	0.042 (2)	0.068 (3)	0.061 (3)	0.001 (2)	0.004 (2)	−0.012 (2)
C18	0.049 (3)	0.092 (4)	0.078 (3)	−0.005 (3)	−0.002 (2)	−0.021 (3)
C19	0.039 (3)	0.131 (5)	0.071 (3)	0.016 (3)	−0.009 (2)	−0.012 (3)
C20	0.055 (3)	0.097 (4)	0.085 (4)	0.032 (3)	−0.008 (3)	0.004 (3)
C21	0.050 (3)	0.060 (3)	0.074 (3)	0.015 (2)	−0.004 (2)	0.004 (2)
C22	0.0297 (19)	0.0367 (18)	0.047 (2)	−0.0020 (15)	0.0077 (16)	−0.0092 (16)
C23	0.033 (2)	0.045 (2)	0.058 (2)	−0.0059 (16)	0.0128 (18)	−0.0095 (18)
C24	0.034 (2)	0.081 (3)	0.065 (3)	−0.002 (2)	0.004 (2)	−0.008 (2)
C25	0.036 (3)	0.116 (5)	0.091 (4)	−0.001 (3)	0.003 (3)	−0.014 (3)
C26	0.039 (3)	0.121 (5)	0.112 (5)	−0.010 (3)	0.021 (3)	−0.019 (4)
C27	0.061 (3)	0.111 (5)	0.092 (4)	−0.014 (3)	0.035 (3)	0.011 (3)
C28	0.049 (3)	0.075 (3)	0.071 (3)	−0.004 (2)	0.020 (2)	0.007 (2)
C29	0.038 (2)	0.0362 (19)	0.043 (2)	−0.0055 (16)	0.0037 (16)	−0.0038 (16)
C30	0.046 (2)	0.051 (2)	0.044 (2)	−0.0021 (18)	−0.0004 (18)	−0.0062 (17)
C31	0.060 (3)	0.105 (4)	0.054 (3)	0.023 (3)	−0.010 (2)	−0.020 (3)
C32	0.077 (4)	0.170 (7)	0.081 (4)	0.050 (4)	−0.031 (3)	−0.028 (4)
C33	0.098 (5)	0.145 (6)	0.070 (4)	0.022 (4)	−0.039 (4)	−0.008 (4)
C34	0.107 (5)	0.150 (6)	0.038 (3)	−0.006 (4)	−0.002 (3)	−0.012 (3)
C35	0.065 (3)	0.104 (4)	0.051 (3)	−0.007 (3)	0.004 (2)	−0.016 (3)
C36	0.042 (2)	0.038 (2)	0.049 (2)	−0.0030 (17)	0.0012 (18)	0.0006 (17)
C37	0.058 (3)	0.0352 (19)	0.052 (2)	−0.0044 (18)	0.0010 (19)	−0.0016 (17)
C38	0.063 (3)	0.055 (3)	0.076 (3)	−0.015 (2)	0.013 (2)	−0.004 (2)
C39	0.099 (4)	0.075 (4)	0.093 (4)	−0.037 (3)	0.018 (3)	0.000 (3)
C40	0.145 (6)	0.047 (3)	0.103 (5)	−0.039 (4)	−0.005 (4)	0.008 (3)
C41	0.134 (6)	0.034 (3)	0.132 (5)	−0.001 (3)	0.008 (5)	−0.014 (3)
C42	0.078 (4)	0.044 (2)	0.096 (4)	0.001 (2)	0.011 (3)	−0.011 (2)
C43	0.039 (2)	0.050 (2)	0.053 (2)	−0.0036 (18)	0.0083 (18)	−0.012 (2)
C44	0.059 (3)	0.073 (3)	0.050 (2)	−0.017 (2)	0.016 (2)	−0.017 (2)
C45	0.139 (6)	0.092 (4)	0.073 (4)	−0.040 (4)	0.050 (4)	−0.037 (3)
C46	0.201 (9)	0.129 (6)	0.080 (4)	−0.072 (6)	0.068 (5)	−0.051 (4)
C47	0.164 (7)	0.146 (7)	0.054 (3)	−0.055 (6)	0.034 (4)	−0.028 (4)
C48	0.108 (5)	0.122 (5)	0.050 (3)	−0.032 (4)	0.015 (3)	0.005 (3)
C49	0.074 (3)	0.086 (4)	0.057 (3)	−0.011 (3)	0.013 (2)	−0.010 (3)
C50	0.035 (2)	0.0378 (19)	0.0392 (19)	−0.0084 (16)	−0.0016 (16)	0.0014 (15)
C51	0.047 (2)	0.055 (2)	0.041 (2)	−0.0070 (19)	−0.0042 (17)	0.0056 (18)
C52	0.067 (3)	0.092 (4)	0.055 (3)	0.020 (3)	−0.007 (2)	0.015 (3)
C53	0.102 (5)	0.131 (5)	0.067 (4)	0.034 (4)	−0.016 (3)	0.033 (4)
C54	0.117 (5)	0.135 (6)	0.047 (3)	0.011 (4)	−0.013 (3)	0.017 (3)
C55	0.126 (5)	0.115 (5)	0.039 (3)	0.018 (4)	0.003 (3)	−0.001 (3)
C56	0.082 (3)	0.075 (3)	0.044 (2)	0.010 (3)	−0.001 (2)	0.001 (2)
C57	0.249 (17)	0.231 (16)	0.282 (19)	−0.051 (12)	0.101 (15)	−0.027 (14)
C58	0.170 (12)	0.170 (13)	0.216 (17)	−0.033 (10)	0.002 (12)	0.032 (12)
C59	0.302 (15)	0.096 (6)	0.178 (10)	−0.038 (8)	−0.027 (10)	−0.015 (6)
C60	0.183 (11)	0.271 (16)	0.120 (8)	−0.026 (10)	0.024 (8)	−0.037 (9)
N1	0.258 (15)	0.244 (15)	0.186 (12)	0.025 (11)	−0.022 (11)	0.032 (10)
N2	0.242 (13)	0.54 (3)	0.178 (11)	−0.069 (14)	0.024 (9)	−0.192 (14)
O1	0.0290 (12)	0.0291 (11)	0.0348 (12)	−0.0005 (9)	0.0051 (10)	−0.0022 (9)
O2	0.0358 (14)	0.0373 (13)	0.0510 (15)	0.0042 (11)	−0.0014 (11)	−0.0007 (11)
O3	0.0418 (15)	0.0352 (13)	0.0497 (15)	0.0020 (11)	−0.0020 (12)	−0.0002 (11)
O4	0.0397 (15)	0.0371 (14)	0.0580 (16)	0.0066 (11)	−0.0027 (12)	−0.0008 (12)
O5	0.0370 (14)	0.0499 (15)	0.0424 (14)	0.0108 (12)	0.0086 (11)	0.0024 (12)
O6	0.0417 (15)	0.0445 (14)	0.0402 (14)	0.0056 (11)	0.0025 (12)	0.0053 (11)
O7	0.0433 (15)	0.0322 (13)	0.0455 (14)	−0.0028 (11)	−0.0006 (11)	0.0041 (11)
O8	0.0383 (14)	0.0381 (13)	0.0333 (12)	−0.0007 (11)	0.0007 (10)	0.0015 (10)
O9	0.0321 (14)	0.0449 (14)	0.0383 (13)	−0.0017 (11)	0.0070 (10)	0.0001 (11)
O10	0.0266 (12)	0.0415 (13)	0.0442 (14)	−0.0028 (10)	0.0068 (10)	0.0001 (11)
O11	0.0367 (14)	0.0278 (12)	0.0518 (15)	−0.0025 (10)	0.0082 (11)	−0.0044 (10)
O12	0.0541 (17)	0.0367 (14)	0.0599 (17)	0.0001 (12)	0.0151 (14)	−0.0059 (12)
O13	0.0269 (12)	0.0263 (11)	0.0340 (12)	0.0005 (9)	0.0031 (9)	−0.0007 (9)
O14	0.0342 (13)	0.0359 (12)	0.0361 (13)	0.0011 (10)	0.0014 (10)	−0.0047 (10)
O15	0.0357 (15)	0.0515 (15)	0.0558 (16)	0.0049 (12)	0.0086 (12)	−0.0114 (13)
O16	0.0396 (15)	0.0543 (16)	0.0517 (16)	0.0012 (12)	0.0032 (12)	−0.0205 (13)
O17	0.0557 (17)	0.0471 (15)	0.0450 (15)	−0.0033 (13)	0.0138 (12)	−0.0076 (12)
O18	0.0484 (16)	0.0472 (16)	0.0541 (16)	−0.0022 (13)	0.0141 (13)	−0.0135 (13)
O19A	0.198 (18)	0.163 (17)	0.45 (5)	0.067 (13)	−0.01 (2)	0.10 (2)
O19B	0.182 (16)	0.36 (3)	0.42 (4)	−0.097 (16)	0.064 (18)	−0.27 (3)

Geometric parameters (Å, º)

Cr1—O7	1.952 (2)	C25—H25	0.9300
Cr1—O8	1.959 (2)	C26—C27	1.358 (8)
Cr1—O9	1.959 (2)	C26—H26	0.9300
Cr1—O1^i	1.970 (2)	C27—C28	1.393 (7)
Cr1—O13	2.002 (2)	C27—H27	0.9300
Cr1—O1	2.013 (2)	C28—H28	0.9300
Cr1—Cr1^i	2.9678 (12)	C29—O14	1.257 (4)
Cr1—Cr2	2.9729 (8)	C29—O16	1.260 (4)
Cr2—O10	1.946 (2)	C29—C30	1.483 (5)
Cr2—O14	1.952 (2)	C30—C31	1.359 (6)
Cr2—O11	1.976 (2)	C30—C35	1.375 (6)
Cr2—O13	1.977 (2)	C31—C32	1.373 (7)
Cr2—O1	2.018 (2)	C31—H31	0.9300
Cr2—O13^i	2.021 (2)	C32—C33	1.370 (9)
Cr3—O5	1.965 (2)	C32—H32	0.9300
Cr3—O6	1.968 (2)	C33—C34	1.352 (8)
Cr3—O3	1.977 (3)	C33—H33	0.9300
Cr3—O1	1.990 (2)	C34—C35	1.384 (7)
Cr3—O4	2.014 (2)	C34—H34	0.9300
Cr3—O2	2.032 (2)	C35—H35	0.9300
Cr3—C15	2.370 (4)	C36—O12	1.271 (4)
Cr4—O12	1.940 (3)	C36—O11	1.277 (4)
Cr4—O16	1.959 (3)	C36—C37	1.484 (5)
Cr4—O15	1.969 (3)	C37—C38	1.362 (6)
Cr4—O13	1.974 (2)	C37—C42	1.381 (6)
Cr4—O18	2.018 (2)	C38—C39	1.401 (7)
Cr4—O17	2.024 (3)	C38—H38	0.9300
Cr4—C43	2.362 (4)	C39—C40	1.349 (9)
C1—O5^i	1.255 (4)	C39—H39	0.9300
C1—O9	1.258 (4)	C40—C41	1.349 (9)
C1—C2	1.491 (5)	C40—H40	0.9300
C2—C3	1.363 (6)	C41—C42	1.388 (7)
C2—C7	1.373 (6)	C41—H41	0.9300
C3—C4	1.380 (7)	C42—H42	0.9300
C3—H3	0.9300	C43—O18	1.261 (5)
C4—C5	1.353 (8)	C43—O17	1.277 (4)
C4—H4	0.9300	C43—C44	1.472 (6)
C5—C6	1.335 (8)	C44—C49	1.373 (7)
C5—H5	0.9300	C44—C45	1.389 (7)
C6—C7	1.387 (7)	C45—C46	1.369 (8)
C6—H6	0.9300	C45—H45	0.9300
C7—H7	0.9300	C46—C47	1.352 (10)
C8—O7^i	1.252 (4)	C46—H46	0.9300
C8—O3	1.261 (4)	C47—C48	1.379 (9)
C8—C9	1.489 (5)	C47—H47	0.9300
C9—C14	1.361 (6)	C48—C49	1.377 (7)
C9—C10	1.375 (6)	C48—H48	0.9300
C10—C11	1.384 (6)	C49—H49	0.9300
C10—H10	0.9300	C50—O6	1.260 (4)
C11—C12	1.355 (7)	C50—O8	1.271 (4)
C11—H11	0.9300	C50—C51	1.484 (5)
C12—C13	1.347 (7)	C51—C56	1.372 (6)
C12—H12	0.9300	C51—C52	1.384 (6)
C13—C14	1.407 (6)	C52—C53	1.385 (7)
C13—H13	0.9300	C52—H52	0.9300
C14—H14	0.9300	C53—C54	1.358 (9)
C15—O4	1.271 (4)	C53—H53	0.9300
C15—O2	1.273 (4)	C54—C55	1.362 (8)
C15—C16	1.474 (5)	C54—H54	0.9300
C16—C17	1.379 (6)	C55—C56	1.381 (6)
C16—C21	1.391 (6)	C55—H55	0.9300
C17—C18	1.389 (6)	C56—H56	0.9300
C17—H17	0.9300	C57—C58	1.484 (18)
C18—C19	1.359 (7)	C57—H57A	0.9600
C18—H18	0.9300	C57—H57B	0.9600
C19—C20	1.382 (8)	C57—H57C	0.9600
C19—H19	0.9300	C58—N1	1.178 (17)
C20—C21	1.375 (6)	C59—C60	1.424 (15)
C20—H20	0.9300	C59—H59A	0.9600
C21—H21	0.9300	C59—H59B	0.9600
C22—O15^i	1.256 (4)	C59—H59C	0.9600
C22—O10	1.261 (4)	C60—N2	1.094 (14)
C22—C23	1.491 (5)	O1—Cr1^i	1.970 (2)
C23—C28	1.378 (6)	O5—C1^i	1.255 (4)
C23—C24	1.379 (6)	O7—C8^i	1.252 (4)
C24—C25	1.383 (6)	O13—Cr2^i	2.021 (2)
C24—H24	0.9300	O15—C22^i	1.256 (4)
C25—C26	1.368 (8)	O19A—O19B	1.82 (3)
O7—Cr1—O8	85.61 (10)	C20—C21—C16	120.6 (5)
O7—Cr1—O9	88.06 (10)	C20—C21—H21	119.7
O8—Cr1—O9	88.77 (10)	C16—C21—H21	119.7
O7—Cr1—O1^i	95.89 (9)	O15^i—C22—O10	125.8 (3)
O8—Cr1—O1^i	175.51 (9)	O15^i—C22—C23	118.2 (3)
O9—Cr1—O1^i	95.51 (9)	O10—C22—C23	115.9 (3)
O7—Cr1—O13	179.47 (10)	C28—C23—C24	119.8 (4)
O8—Cr1—O13	94.78 (9)	C28—C23—C22	121.0 (4)
O9—Cr1—O13	91.58 (9)	C24—C23—C22	119.2 (4)
O1^i—Cr1—O13	83.76 (9)	C23—C24—C25	120.3 (5)
O7—Cr1—O1	96.94 (10)	C23—C24—H24	119.9
O8—Cr1—O1	92.28 (9)	C25—C24—H24	119.9
O9—Cr1—O1	174.95 (9)	C26—C25—C24	119.6 (5)
O1^i—Cr1—O1	83.35 (9)	C26—C25—H25	120.2
O13—Cr1—O1	83.41 (9)	C24—C25—H25	120.2
O7—Cr1—Cr1^i	94.52 (7)	C27—C26—C25	120.8 (5)
O8—Cr1—Cr1^i	133.34 (8)	C27—C26—H26	119.6
O9—Cr1—Cr1^i	137.89 (7)	C25—C26—H26	119.6
O1^i—Cr1—Cr1^i	42.39 (6)	C26—C27—C28	120.3 (5)
O13—Cr1—Cr1^i	85.48 (6)	C26—C27—H27	119.9
O1—Cr1—Cr1^i	41.28 (6)	C28—C27—H27	119.9
O7—Cr1—Cr2	139.06 (8)	C23—C28—C27	119.3 (5)
O8—Cr1—Cr2	89.78 (7)	C23—C28—H28	120.4
O9—Cr1—Cr2	132.56 (7)	C27—C28—H28	120.4
O1^i—Cr1—Cr2	86.32 (6)	O14—C29—O16	125.2 (3)
O13—Cr1—Cr2	41.34 (6)	O14—C29—C30	118.1 (3)
O1—Cr1—Cr2	42.55 (6)	O16—C29—C30	116.7 (3)
Cr1^i—Cr1—Cr2	60.560 (17)	C31—C30—C35	119.3 (4)
O10—Cr2—O14	88.39 (10)	C31—C30—C29	120.3 (4)
O10—Cr2—O11	87.24 (10)	C35—C30—C29	120.4 (4)
O14—Cr2—O11	87.64 (10)	C30—C31—C32	120.6 (5)
O10—Cr2—O13	175.22 (9)	C30—C31—H31	119.7
O14—Cr2—O13	95.79 (9)	C32—C31—H31	119.7
O11—Cr2—O13	95.24 (9)	C33—C32—C31	120.2 (6)
O10—Cr2—O1	93.68 (9)	C33—C32—H32	119.9
O14—Cr2—O1	91.55 (9)	C31—C32—H32	119.9
O11—Cr2—O1	178.76 (10)	C34—C33—C32	119.6 (5)
O13—Cr2—O1	83.91 (8)	C34—C33—H33	120.2
O10—Cr2—O13^i	92.49 (9)	C32—C33—H33	120.2
O14—Cr2—O13^i	173.58 (9)	C33—C34—C35	120.5 (5)
O11—Cr2—O13^i	98.75 (9)	C33—C34—H34	119.7
O13—Cr2—O13^i	83.10 (9)	C35—C34—H34	119.7
O1—Cr2—O13^i	82.05 (8)	C30—C35—C34	119.8 (5)
O10—Cr2—Cr1	136.01 (7)	C30—C35—H35	120.1
O14—Cr2—Cr1	89.94 (7)	C34—C35—H35	120.1
O11—Cr2—Cr1	136.61 (7)	O12—C36—O11	125.1 (3)
O13—Cr2—Cr1	41.97 (6)	O12—C36—C37	117.0 (3)
O1—Cr2—Cr1	42.42 (6)	O11—C36—C37	117.9 (3)
O13^i—Cr2—Cr1	85.01 (6)	C38—C37—C42	119.8 (4)
O5—Cr3—O6	171.77 (10)	C38—C37—C36	121.0 (4)
O5—Cr3—O3	88.02 (11)	C42—C37—C36	119.2 (4)
O6—Cr3—O3	95.40 (11)	C37—C38—C39	119.3 (5)
O5—Cr3—O1	94.50 (9)	C37—C38—H38	120.3
O6—Cr3—O1	92.52 (10)	C39—C38—H38	120.3
O3—Cr3—O1	96.85 (10)	C40—C39—C38	120.1 (5)
O5—Cr3—O4	86.10 (11)	C40—C39—H39	119.9
O6—Cr3—O4	86.36 (11)	C38—C39—H39	119.9
O3—Cr3—O4	91.12 (10)	C39—C40—C41	121.2 (5)
O1—Cr3—O4	172.01 (10)	C39—C40—H40	119.4
O5—Cr3—O2	86.34 (11)	C41—C40—H40	119.4
O6—Cr3—O2	87.49 (10)	C40—C41—C42	119.6 (6)
O3—Cr3—O2	155.68 (10)	C40—C41—H41	120.2
O1—Cr3—O2	107.15 (9)	C42—C41—H41	120.2
O4—Cr3—O2	64.91 (10)	C37—C42—C41	120.0 (5)
O5—Cr3—C15	85.61 (11)	C37—C42—H42	120.0
O6—Cr3—C15	86.26 (11)	C41—C42—H42	120.0
O3—Cr3—C15	123.46 (11)	O18—C43—O17	117.5 (4)
O1—Cr3—C15	139.62 (11)	O18—C43—C44	121.8 (4)
O4—Cr3—C15	32.44 (11)	O17—C43—C44	120.7 (4)
O2—Cr3—C15	32.48 (11)	O18—C43—Cr4	58.68 (19)
O12—Cr4—O16	87.99 (12)	O17—C43—Cr4	58.96 (19)
O12—Cr4—O15	94.87 (12)	C44—C43—Cr4	176.1 (3)
O16—Cr4—O15	171.40 (11)	C49—C44—C45	119.6 (5)
O12—Cr4—O13	94.39 (10)	C49—C44—C43	121.0 (4)
O16—Cr4—O13	94.15 (9)	C45—C44—C43	119.4 (5)
O15—Cr4—O13	93.72 (10)	C46—C45—C44	119.4 (6)
O12—Cr4—O18	92.38 (11)	C46—C45—H45	120.3
O16—Cr4—O18	85.32 (11)	C44—C45—H45	120.3
O15—Cr4—O18	86.45 (11)	C47—C46—C45	120.5 (6)
O13—Cr4—O18	173.19 (10)	C47—C46—H46	119.7
O12—Cr4—O17	156.61 (11)	C45—C46—H46	119.7
O16—Cr4—O17	84.67 (12)	C46—C47—C48	121.1 (6)
O15—Cr4—O17	89.56 (11)	C46—C47—H47	119.4
O13—Cr4—O17	108.25 (10)	C48—C47—H47	119.4
O18—Cr4—O17	64.93 (11)	C49—C48—C47	118.6 (6)
O12—Cr4—C43	124.26 (13)	C49—C48—H48	120.7
O16—Cr4—C43	82.88 (12)	C47—C48—H48	120.7
O15—Cr4—C43	88.81 (12)	C44—C49—C48	120.6 (5)
O13—Cr4—C43	140.93 (12)	C44—C49—H49	119.7
O18—Cr4—C43	32.26 (12)	C48—C49—H49	119.7
O17—Cr4—C43	32.71 (12)	O6—C50—O8	125.4 (3)
O5^i—C1—O9	124.9 (3)	O6—C50—C51	118.2 (3)
O5^i—C1—C2	117.8 (3)	O8—C50—C51	116.4 (3)
O9—C1—C2	117.3 (3)	C56—C51—C52	119.3 (4)
C3—C2—C7	119.0 (4)	C56—C51—C50	120.5 (4)
C3—C2—C1	120.1 (4)	C52—C51—C50	120.2 (4)
C7—C2—C1	120.8 (4)	C51—C52—C53	119.1 (5)
C2—C3—C4	120.2 (5)	C51—C52—H52	120.5
C2—C3—H3	119.9	C53—C52—H52	120.5
C4—C3—H3	119.9	C54—C53—C52	121.2 (5)
C5—C4—C3	120.4 (5)	C54—C53—H53	119.4
C5—C4—H4	119.8	C52—C53—H53	119.4
C3—C4—H4	119.8	C53—C54—C55	119.9 (5)
C6—C5—C4	120.0 (5)	C53—C54—H54	120.1
C6—C5—H5	120.0	C55—C54—H54	120.1
C4—C5—H5	120.0	C54—C55—C56	120.0 (5)
C5—C6—C7	120.9 (5)	C54—C55—H55	120.0
C5—C6—H6	119.6	C56—C55—H55	120.0
C7—C6—H6	119.6	C51—C56—C55	120.6 (5)
C2—C7—C6	119.6 (5)	C51—C56—H56	119.7
C2—C7—H7	120.2	C55—C56—H56	119.7
C6—C7—H7	120.2	C58—C57—H57A	109.5
O7^i—C8—O3	124.9 (3)	C58—C57—H57B	109.5
O7^i—C8—C9	116.3 (3)	H57A—C57—H57B	109.5
O3—C8—C9	118.8 (3)	C58—C57—H57C	109.5
C14—C9—C10	119.0 (4)	H57A—C57—H57C	109.5
C14—C9—C8	121.6 (4)	H57B—C57—H57C	109.5
C10—C9—C8	119.4 (3)	N1—C58—C57	177.6 (19)
C9—C10—C11	120.9 (4)	C60—C59—H59A	109.5
C9—C10—H10	119.5	C60—C59—H59B	109.5
C11—C10—H10	119.5	H59A—C59—H59B	109.5
C12—C11—C10	119.6 (5)	C60—C59—H59C	109.5
C12—C11—H11	120.2	H59A—C59—H59C	109.5
C10—C11—H11	120.2	H59B—C59—H59C	109.5
C13—C12—C11	120.3 (4)	N2—C60—C59	176 (2)
C13—C12—H12	119.8	Cr1^i—O1—Cr3	116.12 (10)
C11—C12—H12	119.8	Cr1^i—O1—Cr1	96.33 (9)
C12—C13—C14	120.5 (5)	Cr3—O1—Cr1	120.87 (11)
C12—C13—H13	119.7	Cr1^i—O1—Cr2	97.37 (9)
C14—C13—H13	119.7	Cr3—O1—Cr2	125.03 (11)
C9—C14—C13	119.5 (5)	Cr1—O1—Cr2	95.03 (9)
C9—C14—H14	120.3	C15—O2—Cr3	88.5 (2)
C13—C14—H14	120.3	C8—O3—Cr3	129.4 (2)
O4—C15—O2	117.2 (3)	C15—O4—Cr3	89.4 (2)
O4—C15—C16	121.3 (3)	C1^i—O5—Cr3	136.3 (2)
O2—C15—C16	121.5 (3)	C50—O6—Cr3	136.6 (2)
O4—C15—Cr3	58.20 (18)	C8^i—O7—Cr1	137.8 (2)
O2—C15—Cr3	58.99 (18)	C50—O8—Cr1	125.8 (2)
C16—C15—Cr3	179.4 (3)	C1—O9—Cr1	131.3 (2)
C17—C16—C21	119.3 (4)	C22—O10—Cr2	129.1 (2)
C17—C16—C15	121.0 (4)	C36—O11—Cr2	135.1 (2)
C21—C16—C15	119.8 (4)	C36—O12—Cr4	128.7 (2)
C16—C17—C18	119.8 (4)	Cr4—O13—Cr2	117.33 (10)
C16—C17—H17	120.1	Cr4—O13—Cr1	123.42 (11)
C18—C17—H17	120.1	Cr2—O13—Cr1	96.69 (9)
C19—C18—C17	120.2 (5)	Cr4—O13—Cr2^i	120.78 (10)
C19—C18—H18	119.9	Cr2—O13—Cr2^i	96.48 (9)
C17—C18—H18	119.9	Cr1—O13—Cr2^i	96.25 (9)
C18—C19—C20	120.9 (5)	C29—O14—Cr2	129.0 (2)
C18—C19—H19	119.6	C22^i—O15—Cr4	135.8 (2)
C20—C19—H19	119.6	C29—O16—Cr4	137.2 (2)
C21—C20—C19	119.2 (5)	C43—O17—Cr4	88.3 (2)
C21—C20—H20	120.4	C43—O18—Cr4	89.1 (2)
C19—C20—H20	120.4

Symmetry code: (i) −x+2, y, −z+1/2.