{2,5-Bis[3-(tert-butyl­aminoxyl)­phenyl]-1,1-dimethyl-3,4-diphenyl­silole-κO}bis­(1,1,1,5,5,5-hexa­fluoro­pentane-2,4-dionato)­manganese(II)

In the structure of the first bis-adduct of 2,5-bis­[3-(tert-butyl­aminoxyl)­phenyl]-1,1-dimethyl-3,4-diphenyl­silole with bis­(hexa­fluoro­acetyl­acetonato)­manganese(II), [Mn(C₅HF₆O₂)₂(C₃₈H₄₂N₂O₂Si)₂], the Mn atom lies on a crystallographic inversion centre and is bound to two chelating hexafluoro­acetylacetonate ligands and two monodentate nitroxide groups in a distorted octa­hedral configuration. The silole ligands present a propeller-like arrangement of the benzene rings around the Si-containing five-membered ring. The dihedral angles between the complexed nitroxides and the benzene rings to which they are bound are smaller than those found in the free ligand.

S1. Comment

The design and construction of molecule-based magnetic materials possessing a well defined structural dimensionality along with interesting magnetic properties has been a challenging proposition over the past 20 years (Miller & Epstein, 2000; Veciana & Iwamura, 2000). In this field of research, one of the most successful approaches towards molecule-based magnetic materials involves the coordination of stable organic radicals to high-spin metal ions, such as manganese in the form Mn(hfac)₂ (hfac is hexafluoroacteylacetonate). Following this approach, numerous examples of molecule-based materials possessing a large variety of dimensionalities and architectures (Mathevet & Luneau, 2001) have been reported, on account of the large number of combinations available through variations of the nitroxide radical nature and the organic spacers to which the radical unit(s) is (are) bound.

We have already reported the synthesis, structure and detailed magnetic properties of the first example of silacyclopentadiene (or silole) substituted by two phenyl-tert-butyl nitroxide radicals, (I) (Roques et al., 2003). Our goal was to take advantage of the photo-excited triplet state that was evidenced in the silole spacer to generate a reversible light-induced modification of the magnetic behaviour of this molecule (Roques et al., 2004). With the idea of further pursuing these investigations, we report here the synthesis and structure of the first manganese bis-adduct of (I), the title complex, (II). It is worth noting that (II) is only the second example of a tert-butyl nitroxide-based mononuclear manganese complex (Rajca et al., 2001). This discrete unit is a promising model for the exploration of photo-induced magnetic states in low-dimensional metal–organic magnetic materials.

Complex (II) is obtained as dark-red diamond-like blocks by reacting silole (I) with Mn(hfac)₂ (see Experimental). Structure examination reveals a linear bis-adduct structure, (I)–Mn(Hfac)₂–(I) (Fig. 1). The Mn²⁺ ion coincides with an inversion centre and is bound to two chelating hfac ligands and two monodentate nitroxides in a distorted octahedral configuration, as previously reported in the literature (Iwamura et al., 1998; Inoue et al., 2000) for extended one- and two-dimensional structures. The distortions from regular octahedral geometry about Mn are rather small, with no bond angle deviating by more than 6° from its ideal value. The largest distortions involve the pincer angles of ca 84° for the chelating hfac ligands. The Mn—O bond distances lie in the range 2.119 (2)–2.176 (2) Å. These are typical values for Mn²⁺ complexes of hfac and nitroxide ligands (Shibata et al., 1985; Dickman et al., 1986).

Coordination of the nitroxide ligands to the metal centre affords pronounced changes in its structure. As usually observed in tetraarysiloles, the molecule of (II) displays a propeller-like arrangement of the four benzene rings (Yamagushi et al., 2000). However, the C2 symmetry axis that passes through the central Si atom in the structure of (I) is lost (Roques et al., 2003). The dihedral angles between the five-membered silole ring and the phenyl rings bearing the nitroxide radicals are 45.92 (9) and 35.61 (9)°, the latter being considerably smaller than the value of 49° encountered in the parent molecule. Another difference is observed in the dihedral angles made by the nitroxide groups and the phenyl rings to which they are bonded. While in the parent silole the dihedral angles are similar to that found here for the free nitroxide [16.1 (4)°], the complexed nitroxides in (II) are only twisted by angles of 7.3 (4)°. These structural modifications are ascribed to the presence of the bulky hfac ligands in the coordination sphere of the metal centre.

In conclusion, compound (II) is the first bis-adduct of 1,1-dimethyl-2,5-bis-(3-N-tert-butyl-N-phenylaminoxyl) -3,4-diphenylsilolacyclopentadiene with bis(hexafluoroacetylacetonato)manganese(II) to have been synthesized and structurally characterized. Experiments are currently underway in our laboratory to use this bis-adduct as a building block to construct magnetic chains. Our efforts are also directed at studies of the photo-excited magnetic states of this metal–organic radical species.

S2. Experimental

A sample of Mn(hfac)₂·H₂O (12 mmol) was suspended in n-heptane (30 ml) and the mixture was refluxed for 24 h to remove water by azeotropic distillation. To the cooled solution was added bis-nitroxide silole, (I) (12 mmol) in freshly distilled dichloromethane (10 ml). After stirring for 10 min, the resulting deep-brown solution was concentrated to ca 5 ml under reduced pressure. The dark microcrystalline powder formed during the concentration step was removed by filtration, and the resulting filtrate was allowed to evaporate to dryness to yield dark-red diamond-like crystals of (II) after 4 d.

S3. Refinement

All H atoms were positioned geometrically (C—H = 0.96 Å for the H atoms of methyl groups and C—H = 0.93 Å for the other H atoms) and allowed to ride on their parent atoms [U_iso(H) = 1.2U_eq(C)].

Computing details

Data collection: KappaCCD Server Software (Nonius, 1997); cell refinement: DENZO-SMN (Otwinowski & Minor, 1997); data reduction: DENZO-SMN; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 ( Farrugia, 1997) and Mercury (Macrae et al., 2006); software used to prepare material for publication: SHELXL97.

Figures

Fig. 1. The structure of complex (II), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown a small spheres of arbitrary radi. For clarity, only selected atoms have been numbered; unlabelled atoms are related to labelled atoms by the symmetry operator (?) [Please complete].

{2,5-Bis[3-(tert-butylaminoxyl)phenyl]-1,1-dimethyl-3,4- diphenylsilole-\kO}bis(1,1,1,5,5,5-hexafluoropentane-2,4- dionato)manganese(II)

Crystal data

[Mn(C5HF6O2)2(C38H42N2O2Si)2]	F(000) = 1710
Mr = 1642.7	Dx = 1.351 Mg m^−3
MonoclinicP21/n	Mo Kα radiation, λ = 0.71069 Å
Hall symbol: -P2yn	Cell parameters from 247 reflections
a = 14.784 (2) Å	θ = 3.6–19.3°
b = 13.402 (3) Å	µ = 0.28 mm^−1
c = 21.084 (4) Å	T = 293 K
β = 104.88 (1)°	Diamond, dark red
V = 4037.4 (13) Å^3	0.30 × 0.10 × 0.10 mm
Z = 2

Data collection

Nonius KappaCCD area-detector diffractometer	8261 independent reflections
Radiation source: fine-focus sealed tube	4786 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.071
φ scans, and ω scans with κ offsets	θmax = 26.4°, θmin = 2.5°
Absorption correction: numerical (Gaussian; Reference?)	h = −18→18
Tmin = 0.921, Tmax = 0.973	k = −16→16
30037 measured reflections	l = −26→26

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)] = 0.056	H-atom parameters constrained
wR(F^2) = 0.153	w = 1/[σ^2(Fo^2) + (0.0686P)^2 + 0.9718P] where P = (Fo^2 + 2Fc^2)/3
S = 1.05	(Δ/σ)max < 0.001
8261 reflections	Δρmax = 0.47 e Å^−3
512 parameters	Δρmin = −0.36 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: 0.00020 (5)

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
Si1	−0.45510 (6)	0.44304 (6)	−0.18728 (4)	0.0426 (3)
Mn1	0.0000	0.0000	0.0000	0.0455 (2)
C1	−0.4113 (3)	0.9156 (3)	−0.2106 (2)	0.0744 (12)
H1A	−0.4028	0.8460	−0.2001	0.112*
H1B	−0.3522	0.9494	−0.1968	0.112*
H1C	−0.4359	0.9234	−0.2571	0.112*
C2	−0.4436 (3)	0.9510 (3)	−0.10043 (17)	0.0776 (12)
H2A	−0.4358	0.8818	−0.0885	0.116*
H2B	−0.4878	0.9809	−0.0798	0.116*
H2C	−0.3845	0.9846	−0.0861	0.116*
C3	−0.4797 (3)	0.9602 (3)	−0.17514 (16)	0.0536 (9)
C4	−0.4922 (3)	1.0704 (3)	−0.1929 (2)	0.0780 (12)
H4A	−0.5147	1.0772	−0.2397	0.117*
H4B	−0.4332	1.1041	−0.1783	0.117*
H4C	−0.5365	1.0994	−0.1721	0.117*
C5	−0.5907 (2)	0.8062 (2)	−0.20013 (14)	0.0443 (8)
C6	−0.5260 (2)	0.7354 (2)	−0.16774 (14)	0.0434 (8)
H6	−0.4673	0.7563	−0.1434	0.052*
C7	−0.5475 (2)	0.6335 (2)	−0.17119 (14)	0.0418 (7)
C8	−0.6354 (2)	0.6051 (3)	−0.20778 (16)	0.0543 (9)
H8	−0.6513	0.5379	−0.2112	0.065*
C9	−0.7002 (2)	0.6756 (3)	−0.23946 (18)	0.0625 (10)
H9	−0.7592	0.6550	−0.2634	0.075*
C10	−0.6785 (2)	0.7744 (3)	−0.23594 (16)	0.0553 (9)
H10	−0.7225	0.8208	−0.2575	0.066*
C11	−0.4782 (2)	0.5557 (2)	−0.14138 (14)	0.0412 (7)
C12	−0.4116 (2)	0.5588 (2)	−0.08367 (14)	0.0391 (7)
C13	−0.4007 (2)	0.6425 (2)	−0.03485 (14)	0.0389 (7)
C14	−0.3199 (2)	0.6990 (3)	−0.01920 (17)	0.0533 (9)
H14	−0.2727	0.6860	−0.0398	0.064*
C15	−0.3083 (3)	0.7748 (3)	0.02671 (19)	0.0644 (10)
H15	−0.2534	0.8119	0.0367	0.077*
C16	−0.3770 (3)	0.7954 (3)	0.05745 (17)	0.0635 (10)
H16	−0.3688	0.8461	0.0885	0.076*
C17	−0.4586 (3)	0.7406 (3)	0.04212 (16)	0.0587 (10)
H17	−0.5059	0.7545	0.0626	0.070*
C18	−0.4700 (2)	0.6651 (2)	−0.00375 (15)	0.0476 (8)
H18	−0.5254	0.6286	−0.0140	0.057*
C19	−0.3445 (2)	0.4719 (2)	−0.06930 (13)	0.0385 (7)
C20	−0.2660 (2)	0.4706 (2)	−0.00819 (14)	0.0406 (7)
C21	−0.1747 (2)	0.4597 (2)	−0.01351 (16)	0.0499 (8)
H21	−0.1636	0.4538	−0.0548	0.060*
C22	−0.1000 (3)	0.4576 (3)	0.04192 (19)	0.0606 (10)
H22	−0.0393	0.4499	0.0377	0.073*
C23	−0.1159 (3)	0.4669 (3)	0.10251 (19)	0.0659 (11)
H23	−0.0658	0.4650	0.1397	0.079*
C24	−0.2053 (3)	0.4792 (3)	0.10919 (17)	0.0601 (10)
H24	−0.2156	0.4865	0.1506	0.072*
C25	−0.2798 (2)	0.4806 (2)	0.05392 (15)	0.0479 (8)
H25	−0.3403	0.4884	0.0586	0.057*
C26	−0.3575 (2)	0.4011 (2)	−0.11663 (13)	0.0393 (7)
C27	−0.3066 (2)	0.3053 (2)	−0.11483 (14)	0.0404 (7)
C28	−0.2896 (2)	0.2684 (3)	−0.17228 (15)	0.0520 (9)
H28	−0.3084	0.3052	−0.2108	0.062*
C29	−0.2452 (3)	0.1780 (3)	−0.17317 (16)	0.0566 (9)
H29	−0.2346	0.1551	−0.2123	0.068*
C30	−0.2163 (2)	0.1211 (2)	−0.11736 (15)	0.0495 (8)
H30	−0.1874	0.0598	−0.1187	0.059*
C31	−0.2312 (2)	0.1569 (2)	−0.05837 (14)	0.0388 (7)
C32	−0.2774 (2)	0.2473 (2)	−0.05815 (14)	0.0396 (7)
H32	−0.2891	0.2697	−0.0193	0.047*
C33	−0.5502 (3)	0.3503 (3)	−0.21171 (17)	0.0618 (10)
H33A	−0.5698	0.3294	−0.1737	0.093*
H33B	−0.5281	0.2935	−0.2311	0.093*
H33C	−0.6023	0.3797	−0.2430	0.093*
C34	−0.4150 (3)	0.4860 (3)	−0.25946 (16)	0.0680 (11)
H34A	−0.3656	0.5339	−0.2455	0.102*
H34B	−0.4663	0.5163	−0.2909	0.102*
H34C	−0.3923	0.4300	−0.2792	0.102*
C35	−0.2215 (2)	0.1132 (2)	0.06378 (14)	0.0434 (8)
C36	−0.1800 (3)	0.0266 (3)	0.10883 (17)	0.0653 (11)
H36A	−0.1131	0.0269	0.1164	0.098*
H36B	−0.2046	−0.0352	0.0885	0.098*
H36C	−0.1961	0.0337	0.1499	0.098*
C37	−0.1769 (3)	0.2097 (3)	0.09531 (16)	0.0613 (10)
H37A	−0.2026	0.2652	0.0678	0.092*
H37B	−0.1105	0.2070	0.1005	0.092*
H37C	−0.1894	0.2177	0.1375	0.092*
C38	−0.3275 (2)	0.1110 (3)	0.05266 (18)	0.0687 (11)
H38A	−0.3549	0.1651	0.0243	0.103*
H38B	−0.3430	0.1178	0.0940	0.103*
H38C	−0.3515	0.0488	0.0327	0.103*
C39	0.1164 (3)	0.2618 (3)	0.12078 (18)	0.0583 (9)
C40	0.0707 (2)	0.2033 (3)	0.05869 (15)	0.0462 (8)
C41	0.0616 (2)	0.2490 (3)	−0.00143 (15)	0.0524 (9)
H41	0.0803	0.3152	−0.0021	0.063*
C42	0.0259 (2)	0.2006 (3)	−0.06103 (15)	0.0472 (8)
C43	0.0175 (3)	0.2624 (3)	−0.12286 (18)	0.0646 (11)
N1	−0.5731 (2)	0.9102 (2)	−0.19744 (13)	0.0540 (7)
N2	−0.19844 (18)	0.09798 (19)	−0.00128 (11)	0.0419 (6)
O1	−0.00141 (16)	0.11300 (16)	−0.07053 (10)	0.0492 (6)
O2	0.04573 (17)	0.11726 (17)	0.06983 (10)	0.0537 (6)
O3	−0.14813 (16)	0.02053 (16)	−0.00652 (11)	0.0515 (6)
O4	−0.6448 (2)	0.9671 (2)	−0.21445 (16)	0.0914 (9)
F1	−0.0364 (2)	0.3430 (2)	−0.12307 (13)	0.1130 (10)
F2	−0.0198 (3)	0.2152 (2)	−0.17631 (11)	0.1265 (13)
F3	0.0969 (2)	0.3003 (2)	−0.12595 (13)	0.1144 (10)
F4	0.06274 (18)	0.2634 (2)	0.16243 (11)	0.0928 (8)
F5	0.1355 (2)	0.35543 (19)	0.11055 (11)	0.1016 (9)
F6	0.19491 (18)	0.2201 (2)	0.15251 (12)	0.1019 (9)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Si1	0.0560 (6)	0.0325 (5)	0.0339 (5)	0.0016 (4)	0.0018 (4)	0.0006 (3)
Mn1	0.0542 (5)	0.0356 (4)	0.0458 (4)	0.0058 (3)	0.0114 (3)	0.0066 (3)
C1	0.090 (3)	0.056 (3)	0.083 (3)	−0.005 (2)	0.033 (2)	−0.006 (2)
C2	0.089 (3)	0.077 (3)	0.059 (2)	−0.013 (2)	0.003 (2)	−0.009 (2)
C3	0.063 (2)	0.044 (2)	0.051 (2)	−0.0019 (17)	0.0092 (17)	−0.0022 (15)
C4	0.095 (3)	0.044 (2)	0.094 (3)	0.001 (2)	0.023 (3)	0.000 (2)
C5	0.053 (2)	0.0408 (19)	0.0375 (17)	0.0071 (16)	0.0096 (15)	−0.0018 (14)
C6	0.0440 (19)	0.0399 (19)	0.0422 (17)	0.0000 (15)	0.0035 (14)	−0.0013 (14)
C7	0.0463 (19)	0.0410 (19)	0.0356 (16)	0.0020 (15)	0.0063 (14)	−0.0020 (13)
C8	0.048 (2)	0.043 (2)	0.065 (2)	−0.0004 (17)	0.0024 (17)	−0.0037 (17)
C9	0.039 (2)	0.061 (3)	0.077 (3)	−0.0009 (18)	−0.0049 (18)	−0.0070 (19)
C10	0.048 (2)	0.057 (2)	0.056 (2)	0.0136 (18)	0.0035 (17)	−0.0005 (17)
C11	0.0444 (18)	0.0327 (17)	0.0441 (18)	−0.0028 (14)	0.0069 (15)	−0.0003 (13)
C12	0.0441 (18)	0.0317 (17)	0.0398 (17)	−0.0043 (14)	0.0078 (14)	0.0003 (13)
C13	0.0392 (18)	0.0380 (18)	0.0360 (16)	0.0020 (14)	0.0035 (13)	−0.0015 (13)
C14	0.050 (2)	0.046 (2)	0.066 (2)	−0.0026 (17)	0.0169 (17)	−0.0139 (17)
C15	0.055 (2)	0.055 (2)	0.077 (3)	−0.0081 (19)	0.0043 (19)	−0.0225 (19)
C16	0.070 (3)	0.060 (2)	0.054 (2)	0.005 (2)	0.0042 (19)	−0.0214 (18)
C17	0.062 (2)	0.068 (3)	0.048 (2)	0.013 (2)	0.0167 (18)	−0.0040 (18)
C18	0.0434 (19)	0.050 (2)	0.0478 (19)	−0.0015 (16)	0.0094 (15)	−0.0035 (16)
C19	0.0437 (18)	0.0364 (17)	0.0340 (16)	−0.0027 (14)	0.0076 (13)	0.0026 (13)
C20	0.047 (2)	0.0320 (17)	0.0395 (18)	−0.0021 (14)	0.0052 (14)	−0.0004 (13)
C21	0.053 (2)	0.043 (2)	0.050 (2)	−0.0063 (16)	0.0079 (17)	0.0010 (15)
C22	0.049 (2)	0.051 (2)	0.073 (3)	−0.0050 (17)	−0.0011 (19)	0.0063 (18)
C23	0.069 (3)	0.056 (2)	0.054 (2)	−0.013 (2)	−0.0165 (19)	0.0040 (17)
C24	0.077 (3)	0.054 (2)	0.043 (2)	−0.011 (2)	0.0043 (19)	−0.0031 (16)
C25	0.055 (2)	0.0426 (19)	0.0433 (19)	−0.0052 (16)	0.0072 (16)	−0.0038 (14)
C26	0.0468 (19)	0.0331 (17)	0.0361 (16)	0.0008 (14)	0.0074 (13)	0.0035 (13)
C27	0.0428 (18)	0.0367 (18)	0.0380 (17)	0.0011 (14)	0.0037 (13)	−0.0011 (13)
C28	0.065 (2)	0.056 (2)	0.0309 (17)	0.0107 (18)	0.0042 (15)	0.0034 (15)
C29	0.072 (2)	0.061 (2)	0.0349 (18)	0.020 (2)	0.0102 (16)	−0.0052 (16)
C30	0.053 (2)	0.046 (2)	0.0450 (19)	0.0145 (16)	0.0058 (15)	−0.0069 (15)
C31	0.0386 (17)	0.0361 (17)	0.0384 (17)	0.0044 (14)	0.0036 (13)	0.0005 (13)
C32	0.0476 (19)	0.0365 (18)	0.0340 (16)	0.0021 (14)	0.0095 (14)	−0.0014 (13)
C33	0.070 (3)	0.044 (2)	0.058 (2)	−0.0037 (18)	−0.0071 (18)	−0.0013 (16)
C34	0.103 (3)	0.055 (2)	0.049 (2)	0.013 (2)	0.024 (2)	0.0133 (17)
C35	0.0495 (19)	0.0418 (19)	0.0364 (17)	0.0034 (15)	0.0064 (14)	0.0030 (14)
C36	0.091 (3)	0.050 (2)	0.051 (2)	0.005 (2)	0.010 (2)	0.0060 (16)
C37	0.078 (3)	0.050 (2)	0.052 (2)	−0.0052 (19)	0.0085 (18)	−0.0100 (17)
C38	0.055 (2)	0.093 (3)	0.060 (2)	−0.001 (2)	0.0186 (18)	0.008 (2)
C39	0.064 (3)	0.055 (2)	0.052 (2)	−0.006 (2)	0.0103 (19)	0.0010 (17)
C40	0.0460 (19)	0.045 (2)	0.048 (2)	0.0004 (16)	0.0129 (15)	−0.0018 (16)
C41	0.065 (2)	0.040 (2)	0.050 (2)	−0.0085 (17)	0.0119 (17)	0.0022 (15)
C42	0.048 (2)	0.043 (2)	0.050 (2)	−0.0006 (16)	0.0121 (15)	0.0097 (15)
C43	0.087 (3)	0.052 (2)	0.053 (2)	−0.017 (2)	0.016 (2)	0.0065 (19)
N1	0.0626 (19)	0.0415 (17)	0.0518 (16)	0.0108 (15)	0.0039 (14)	0.0049 (13)
N2	0.0457 (15)	0.0358 (15)	0.0416 (15)	0.0070 (12)	0.0064 (12)	−0.0004 (11)
O1	0.0634 (15)	0.0375 (13)	0.0449 (12)	0.0013 (11)	0.0108 (10)	0.0082 (10)
O2	0.0725 (16)	0.0433 (14)	0.0452 (12)	−0.0012 (12)	0.0152 (11)	0.0027 (10)
O3	0.0535 (14)	0.0412 (13)	0.0601 (14)	0.0122 (11)	0.0153 (11)	0.0043 (10)
O4	0.078 (2)	0.0549 (18)	0.125 (2)	0.0213 (16)	−0.0046 (18)	0.0105 (17)
F1	0.157 (3)	0.086 (2)	0.0884 (18)	0.0321 (19)	0.0181 (17)	0.0383 (15)
F2	0.240 (4)	0.0801 (19)	0.0462 (14)	−0.058 (2)	0.0132 (17)	0.0083 (12)
F3	0.133 (2)	0.130 (2)	0.0874 (18)	−0.040 (2)	0.0406 (17)	0.0323 (16)
F4	0.1058 (19)	0.113 (2)	0.0668 (15)	−0.0257 (16)	0.0346 (14)	−0.0327 (13)
F5	0.160 (3)	0.0691 (17)	0.0681 (15)	−0.0434 (17)	0.0149 (15)	−0.0111 (12)
F6	0.0771 (17)	0.125 (2)	0.0818 (16)	0.0084 (16)	−0.0184 (13)	−0.0137 (15)

Geometric parameters (Å, º)

Si1—C33	1.849 (4)	C22—H22	0.9300
Si1—C34	1.861 (3)	C23—C24	1.374 (5)
Si1—C11	1.872 (3)	C23—H23	0.9300
Si1—C26	1.874 (3)	C24—C25	1.383 (5)
Mn1—O1	2.119 (2)	C24—H24	0.9300
Mn1—O2	2.141 (2)	C25—H25	0.9300
Mn1—O3	2.176 (2)	C26—C27	1.484 (4)
C1—C3	1.524 (5)	C27—C28	1.390 (4)
C1—H1A	0.9600	C27—C32	1.398 (4)
C1—H1B	0.9600	C28—C29	1.380 (5)
C1—H1C	0.9600	C28—H28	0.9300
C2—C3	1.533 (5)	C29—C30	1.375 (5)
C2—H2A	0.9600	C29—H29	0.9300
C2—H2B	0.9600	C30—C31	1.402 (4)
C2—H2C	0.9600	C30—H30	0.9300
C3—N1	1.499 (4)	C31—C32	1.390 (4)
C3—C4	1.523 (5)	C31—N2	1.417 (4)
C4—H4A	0.9600	C32—H32	0.9300
C4—H4B	0.9600	C33—H33A	0.9600
C4—H4C	0.9600	C33—H33B	0.9600
C5—C10	1.391 (4)	C33—H33C	0.9600
C5—C6	1.395 (4)	C34—H34A	0.9600
C5—N1	1.415 (4)	C34—H34B	0.9600
C6—C7	1.400 (4)	C34—H34C	0.9600
C6—H6	0.9300	C35—N2	1.510 (4)
C7—C8	1.384 (4)	C35—C38	1.524 (5)
C7—C11	1.484 (4)	C35—C36	1.525 (4)
C8—C9	1.389 (5)	C35—C37	1.525 (5)
C8—H8	0.9300	C36—H36A	0.9600
C9—C10	1.360 (5)	C36—H36B	0.9600
C9—H9	0.9300	C36—H36C	0.9600
C10—H10	0.9300	C37—H37A	0.9600
C11—C12	1.355 (4)	C37—H37B	0.9600
C12—C13	1.504 (4)	C37—H37C	0.9600
C12—C19	1.509 (4)	C38—H38A	0.9600
C13—C14	1.380 (4)	C38—H38B	0.9600
C13—C18	1.385 (4)	C38—H38C	0.9600
C14—C15	1.383 (5)	C39—F6	1.307 (4)
C14—H14	0.9300	C39—F5	1.316 (4)
C15—C16	1.366 (5)	C39—F4	1.326 (4)
C15—H15	0.9300	C39—C40	1.527 (5)
C16—C17	1.378 (5)	C40—O2	1.251 (4)
C16—H16	0.9300	C40—C41	1.383 (4)
C17—C18	1.381 (5)	C41—C42	1.392 (4)
C17—H17	0.9300	C41—H41	0.9300
C18—H18	0.9300	C42—O1	1.241 (4)
C19—C26	1.354 (4)	C42—C43	1.522 (5)
C19—C20	1.496 (4)	C43—F2	1.287 (4)
C20—C25	1.383 (4)	C43—F3	1.296 (5)
C20—C21	1.390 (4)	C43—F1	1.342 (5)
C21—C22	1.387 (5)	N1—O4	1.281 (4)
C21—H21	0.9300	N2—O3	1.298 (3)
C22—C23	1.363 (5)
C33—Si1—C34	111.08 (18)	C23—C24—C25	119.6 (3)
C33—Si1—C11	117.41 (16)	C23—C24—H24	120.2
C34—Si1—C11	108.17 (16)	C25—C24—H24	120.2
C33—Si1—C26	113.27 (15)	C20—C25—C24	121.1 (3)
C34—Si1—C26	113.62 (16)	C20—C25—H25	119.4
C11—Si1—C26	92.08 (13)	C24—C25—H25	119.4
O1—Mn1—O2	84.40 (8)	C19—C26—C27	127.7 (3)
O1—Mn1—O2^i	95.60 (8)	C19—C26—Si1	108.1 (2)
O1—Mn1—O3	92.11 (8)	C27—C26—Si1	124.2 (2)
O2—Mn1—O3	94.91 (9)	C28—C27—C32	117.5 (3)
O1—Mn1—O3^i	87.89 (8)	C28—C27—C26	119.3 (3)
O2—Mn1—O3^i	85.09 (9)	C32—C27—C26	123.1 (3)
C3—C1—H1A	109.5	C29—C28—C27	121.2 (3)
C3—C1—H1B	109.5	C29—C28—H28	119.4
H1A—C1—H1B	109.5	C27—C28—H28	119.4
C3—C1—H1C	109.5	C30—C29—C28	121.3 (3)
H1A—C1—H1C	109.5	C30—C29—H29	119.4
H1B—C1—H1C	109.5	C28—C29—H29	119.4
C3—C2—H2A	109.5	C29—C30—C31	119.0 (3)
C3—C2—H2B	109.5	C29—C30—H30	120.5
H2A—C2—H2B	109.5	C31—C30—H30	120.5
C3—C2—H2C	109.5	C32—C31—C30	119.4 (3)
H2A—C2—H2C	109.5	C32—C31—N2	122.9 (3)
H2B—C2—H2C	109.5	C30—C31—N2	117.7 (3)
N1—C3—C4	108.2 (3)	C31—C32—C27	121.7 (3)
N1—C3—C1	110.1 (3)	C31—C32—H32	119.1
C4—C3—C1	108.3 (3)	C27—C32—H32	119.1
N1—C3—C2	109.6 (3)	Si1—C33—H33A	109.5
C4—C3—C2	108.6 (3)	Si1—C33—H33B	109.5
C1—C3—C2	111.9 (3)	H33A—C33—H33B	109.5
C3—C4—H4A	109.5	Si1—C33—H33C	109.5
C3—C4—H4B	109.5	H33A—C33—H33C	109.5
H4A—C4—H4B	109.5	H33B—C33—H33C	109.5
C3—C4—H4C	109.5	Si1—C34—H34A	109.5
H4A—C4—H4C	109.5	Si1—C34—H34B	109.5
H4B—C4—H4C	109.5	H34A—C34—H34B	109.5
C10—C5—C6	119.0 (3)	Si1—C34—H34C	109.5
C10—C5—N1	117.4 (3)	H34A—C34—H34C	109.5
C6—C5—N1	123.6 (3)	H34B—C34—H34C	109.5
C5—C6—C7	121.3 (3)	N2—C35—C38	108.7 (2)
C5—C6—H6	119.3	N2—C35—C36	108.3 (3)
C7—C6—H6	119.3	C38—C35—C36	108.4 (3)
C8—C7—C6	117.8 (3)	N2—C35—C37	109.7 (3)
C8—C7—C11	119.4 (3)	C38—C35—C37	113.3 (3)
C6—C7—C11	122.7 (3)	C36—C35—C37	108.3 (3)
C7—C8—C9	121.0 (3)	C35—C36—H36A	109.5
C7—C8—H8	119.5	C35—C36—H36B	109.5
C9—C8—H8	119.5	H36A—C36—H36B	109.5
C10—C9—C8	120.8 (3)	C35—C36—H36C	109.5
C10—C9—H9	119.6	H36A—C36—H36C	109.5
C8—C9—H9	119.6	H36B—C36—H36C	109.5
C9—C10—C5	120.2 (3)	C35—C37—H37A	109.5
C9—C10—H10	119.9	C35—C37—H37B	109.5
C5—C10—H10	119.9	H37A—C37—H37C	109.5
C12—C11—C7	128.5 (3)	C35—C37—H37C	109.5
C12—C11—Si1	107.6 (2)	H37A—C37—H37C	109.5
C7—C11—Si1	123.1 (2)	H37B—C37—H37C	109.5
C11—C12—C13	124.2 (3)	C35—C38—H38A	109.5
C11—C12—C19	116.5 (3)	C35—C38—H38B	109.5
C13—C12—C19	119.3 (2)	H38A—C38—H38B	109.5
C14—C13—C18	117.8 (3)	C35—C38—H38C	109.5
C14—C13—C12	120.5 (3)	H38A—C38—H38C	109.5
C18—C13—C12	121.6 (3)	H38A—C38—H38C	109.5
C13—C14—C15	121.0 (3)	F6—C39—F5	107.0 (3)
C13—C14—H14	119.5	F6—C39—F4	105.7 (3)
C15—C14—H14	119.5	F5—C39—F4	106.5 (3)
C16—C15—C14	120.5 (4)	F6—C39—C40	111.0 (3)
C16—C15—H15	119.8	F5—C39—C40	114.6 (3)
C14—C15—H15	119.8	F4—C39—C40	111.5 (3)
C15—C16—C17	119.6 (3)	O2—C40—C41	128.1 (3)
C15—C16—H16	120.2	O2—C40—C39	113.6 (3)
C17—C16—H16	120.2	C41—C40—C39	118.4 (3)
C16—C17—C18	119.8 (3)	C40—C41—C42	123.1 (3)
C16—C17—H17	120.1	C40—C41—H41	118.5
C18—C17—H17	120.1	C42—C41—H41	118.5
C17—C18—C13	121.3 (3)	O1—C42—C41	128.2 (3)
C17—C18—H18	119.4	O1—C42—C43	115.1 (3)
C13—C18—H18	119.4	C41—C42—C43	116.6 (3)
C26—C19—C20	124.0 (3)	F2—C43—F3	109.8 (4)
C26—C19—C12	115.5 (3)	F2—C43—F1	105.8 (4)
C20—C19—C12	120.4 (2)	F3—C43—F1	103.3 (3)
C25—C20—C21	118.0 (3)	F2—C43—C42	113.9 (3)
C25—C20—C19	123.0 (3)	F3—C43—C42	112.4 (3)
C21—C20—C19	119.1 (3)	F1—C43—C42	111.0 (3)
C22—C21—C20	120.9 (3)	O4—N1—C5	116.4 (3)
C22—C21—H21	119.5	O4—N1—C3	116.8 (3)
C20—C21—H21	119.5	C5—N1—C3	126.7 (3)
C23—C22—C21	119.7 (4)	O3—N2—C31	116.9 (2)
C23—C22—H22	120.1	O3—N2—C35	117.0 (2)
C21—C22—H22	120.1	C31—N2—C35	126.0 (2)
C22—C23—C24	120.6 (3)	C42—O1—Mn1	128.2 (2)
C22—C23—H23	119.7	C40—O2—Mn1	127.14 (19)
C24—C23—H23	119.7	N2—O3—Mn1	133.24 (19)

Symmetry code: (i) −x, −y, −z.