Bis[μ₃-1,8-bis­(triisopropyl­silyl­amido)­naphthalene]­bis­(tetra­hydro­furan)di-μ₃-oxido-dimanganese(III)disodium

The solid-state structure of the title compound, [Na₂Mn₂(C₃₂H₅₆N₂OSi₂)₂O₂] or [1,8-C₁₀H₆(NSiⁱPr₃)₂Mn(μ₃-O)Na(THF)]₂, which lies across a crystallographic twofold axis, exhibits a central [Mn₂O₂Na₂]⁴⁺ core, with two oxide groups, each triply bridging between the two Mn^III ions and an Na⁺ ion. Additional coordination is provided to each Mn^III centre by a 1,8-C₁₀H₆(NSiⁱPr₃)₂ [1,8-bis­(triisopropyl­silyl­amido)­naph­tha­lene] ligand and to the Na⁺ centres by a tetra­hydro­furan mol­ecule. The presence of an additional Na...H—C agostic inter­action potentially contributes to the distortion around the bridging oxide group.

S1. Comment

Polynuclear transition metal complexes containing oxygen-based bridging ligands are of significant interest as models for bioinorganic systems (Vincent et al., 1989; Christou, 1989; Libby et al., 1991; Wang et al., 1991). In the case of manganese, complexes such as [Mn₄O₂(O₂CR)_xL_n]^y (x = 6 or 7; y = -1, 0, 1) have been used to model the photosynthetic water oxidation centre (WOC) within green plants and cyanobacteria. In this paper we describe the crystallographic characterization of the title compound, [1,8-C₁₀H₆(NSiⁱPr₃)₂Mn(µ₃-O)Na(THF)]₂ (THF is tetrahydrofuran), (I), which features a central [Mn₂O₂Na₂]⁴⁺ core.

The crystal structure of (I) is shown in Fig. 1, and important bond distances and angles are shown in Table 1. The complex lies across a crystallographic twofold axis and consists of a central [Mn₂O₂Na₂]⁴⁺ core, with two oxide groups, each triply bridging, between the two Mn^III ions and an Na⁺ ion. Additional coordination to each Mn^III centre is provided by a 1,8-C₁₀H₆(NSiⁱPr₃)₂ ligand and to the Na⁺ centres by a THF molecule.

The Mn^III centres in (I) are each coordinated by two amide N atoms and two bridging oxides in a tetrahedrally distorted square-planar environment where the mean tetrahedral distortion, defined as the mean of the absolute deviations of the ligand atoms from the MnN₂O₂ least-squares mean plane, is 0.51 (3) Å. The N1—Mn1—N2 angle is wider than that in 1,8-C₁₀H₆(NSiⁱPr₃)₂Li(THF)MnCl(THF), (II) [85.83 (7)°; Blake et al., 2009], presumably in part a reflection of the different coordination environments of the metal cations in these two complexes. The Mn—N distances in (I) are significantly shorter than that in (II) [2.1093 (17) Å], due to the smaller ionic radius of Mn^III compared with Mn^II (Shannon & Prewitt, 1969, 1970). In (I), the Mn^III centre lies 1.150 (3) Å out of the N1/C1/C10/C9/N2 plane of the ligand, which exhibits a significant twisting of the framework: the amide N atoms are significantly distorted from the naphthalenyl plane [N···naphthalenyl plane distances are 0.460 (5) and -0.518 (5) Å for atoms N1 and N2, respectively].

The Mn₂O₂ moiety deviates somewhat from planarity, the angle between the O1—Mn1—O1ⁱ and O1—Mn1ⁱ—O1ⁱ planes being 12.10 (4)° [symmetry code: (i) -x + 1, y, -z + 3/2]. The Mn1···Mn1ⁱ distance in (I) is longer than that found in [HC(CMeNDipp)₂Mn(µ-O)]₂, (III) [2.659 (1) Å; Dipp = 2,6-diisopropylphenyl; Chai et al., 2005], but shorter than that for the central Mn₂O₂ core in [ⁿBu₄N][Mn₄O₂(O₂CPh)₉H₂O], (IV) [2.816 (4) Å; Wang et al., 1991]. The Mn—O distances in (I) are slightly shorter than the analogous values for (IV) [1.900 (11), 1.905 (11), 1.913 (10) and 1.909 (10) Å]. Both these complexes feature µ₃-bridging oxides, between two Mn^III centres and one Na⁺ centre in the case of (I), and between three Mn^III centres in the case of (IV).

The Na—O distances in (I) (Table 1) reflect the differing coordination environments around each O atom. The Na1—O1 distance is somewhat shorter than that found in other triply-bridged complexes, e.g. [Ph₂SiO]₈[AlO₂Na]₄.5THF, which has these distances in the range 2.204 (5)–2.392 (6) Å (Veith et al., 2007). These differences are presumably a consequence of the differing coordination environments in these two complexes. The Na1—O2 distance in (I) is significantly longer than the Na1—O1 distance, but it lies within the range of other Na—THF interactions in the literature (Allen, 2002) and is very similar to analogous Na—O distances in other complexes, such as [(THF)₃Na][(N₂)Mo{N(Ad)C₆H₃-2,6-Me₂}₃] [2.254 (10) Å; Peters et al., 1999] and Na₂Ga₄(Si^tBu₃)₄.2THF [2.252 (3) Å; Wiberg et al., 2002]. The geometry around atom O1 is highly distorted trigonal pyramidal [Na1—O1—Mn1ⁱ = 156.41 (14)°], with atom O1 lying 0.286 (2) Å out of the plane defined by atoms Mn1, Mn1ⁱ and Na1.

In addition to the coordination by the triply bridging oxide and the THF molecule, the Na⁺ centre interacts significantly with atoms C9, C10 and N2 of the 1,8-bis(triisopropylsilylamido)naphthalene ligand (Table 1, Fig. 2). Finally, there is an additional agostic interaction with H14C [Na1···H14Cⁱ = 2.41 Å, Na1···C14ⁱ = 2.994 (4) Å and Na1···H14Cⁱ—C14ⁱ = 118°], which potentially contributes to the distortion around the bridging oxide.

The dimer of (I) features possible C—H···O interactions (Table 2). However, as these involve bridging O atoms, are quite long and involve unactivated methyl H atoms, they may not be significant in themselves but a result of steric crowding. One methyl H atom is also implicated in a possible intramolecular C—H···π interaction with the ring C1–C5/C10 (Table 2). There are no specific directional intermolecular interactions.

Related literature

For related literature, see: Allen (2002); Blake et al. (2009); Chai et al. (2005); Christou (1989); Libby et al. (1991); Peters et al. (1999); Shannon & Prewitt (1969, 1970); Sheldrick (2008); Veith et al. (2007); Vincent et al. (1989); Wang et al. (1991); Wiberg et al. (2002).

S2. Experimental

A solution of 1,8-C₁₀H₆(NSiⁱPr₃)₂Li(THF)MnCl(THF) (0.075 g, 0.11 mmol; Blake et al., 2009) in toluene (10 ml) was added to a stirred slurry of NaO^tBu (0.010 g, 0.11 mmol) in toluene (10 ml) and the mixture stirred at room temperature for 24 h. Removal of volatiles in vacuo gave a brown solid, which was extracted with hexanes (10 ml). The solution was filtered and concentrated to ca 5 ml, which yielded brown crystals of [1,8-C₁₀H₆(NSiⁱPr₃)₂Mn(µ₃-O)Na(THF)]₂, (I), after storage at 238 K.

S3. Refinement

The intensity of the diffraction falls off very steeply above ca 2θ = 50°, and accordingly a cut-off was applied at 2θ = 50.2°. This feature appeared consistent throughout the frame set, suggesting that no changes occurred to the crystal during data collection.

Methyl H atoms were located in circular difference Fourier syntheses and thereafter refined as part of a rigid rotating group, with C—H = 0.98 Å and U_iso(H) = 1.5U_eq(C). The remaining H atoms were placed geometrically and refined with C—H(aromatic) = 0.95 Å, C—H(methylene) = 0.99 Å and C—H(methine) = 1.00 Å, and with U_iso(H) = 1.2U_eq(C). Rigid-bond restraints (Sheldrick, 2008), with effective standard deviations of 0.01 Ų for 1,2-atom pairs and 0.001 Ų for 1,3-atom pairs, were applied to the anisotropic displacement parameters of the THF atoms (O2/C29–C32).

Computing details

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT (Bruker, 2002) and SHELXTL (Sheldrick, 2008); 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) and PLATON (Spek, 2009).

Figures

Fig. 1. A view of (I), showing the atom-numbering scheme for the reference asymmetric unit. Displacement ellipsoids are drawn at the 20% probability level and H atoms have been omitted for clarity.

Fig. 2. A view of (I), indicating the full coordination around Na1. Displacement ellipsoids are drawn at the 30% probability level. For clarity, atoms C11, C13, C16, C17 and C19 of the isopropyl groups on Si1, and atoms C20, C22, C23, C25, C26 and C28 of the isopropyl groups on Si2, have been omitted, and only those H atoms involved in agostic interactions are shown. The interactions of Na1 with atoms C9, C10, N2 and H14C are shown as dashed lines. [Symmetry code: (i) -x + 1, y, -z + 3/2.]

Bis[µ₃-1,8-bis(triisopropylsilylamido)naphthalene]bis(tetrahydrofuran)di- µ₃-oxido-dimanganese(III)disodium

Crystal data

[Na2Mn2(C32H56N2OSi2)2O2]	F(000) = 2736
Mr = 1269.80	Dx = 1.216 Mg m^−3
Orthorhombic, Pbcn	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2n 2ab	Cell parameters from 7869 reflections
a = 25.209 (2) Å	θ = 2.3–27.1°
b = 17.6946 (15) Å	µ = 0.49 mm^−1
c = 15.5541 (13) Å	T = 150 K
V = 6938.0 (10) Å^3	Plate, brown
Z = 4	0.27 × 0.27 × 0.07 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer	6173 independent reflections
Radiation source: sealed tube	5327 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.047
Detector resolution: 8.366 pixels mm^-1	θmax = 25.1°, θmin = 2.3°
ω rotation with narrow frames scans	h = −24→30
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	k = −21→20
Tmin = 0.652, Tmax = 0.746	l = −17→18
34383 measured reflections

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)] = 0.067	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.155	H-atom parameters constrained
S = 1.21	w = 1/[σ^2(Fo^2) + (0.061P)^2 + 9.211P] where P = (Fo^2 + 2Fc^2)/3
6173 reflections	(Δ/σ)max = 0.001
373 parameters	Δρmax = 0.59 e Å^−3
10 restraints	Δρmin = −0.35 e Å^−3

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

	x	y	z	Uiso*/Ueq
Mn1	0.45141 (2)	0.72512 (3)	0.78677 (3)	0.02163 (16)
Si1	0.42062 (4)	0.82489 (6)	0.97030 (7)	0.0284 (2)
Na1	0.40911 (6)	0.74511 (10)	0.59699 (10)	0.0433 (4)
O1	0.47915 (9)	0.71703 (13)	0.67526 (15)	0.0241 (5)
N1	0.42181 (11)	0.80197 (15)	0.86268 (18)	0.0244 (6)
C1	0.40060 (14)	0.8528 (2)	0.8021 (2)	0.0277 (8)
Si2	0.36400 (4)	0.59814 (6)	0.74039 (7)	0.0293 (3)
O2	0.36783 (14)	0.75504 (19)	0.4689 (2)	0.0599 (9)
N2	0.37806 (11)	0.69412 (16)	0.7531 (2)	0.0269 (7)
C2	0.41805 (17)	0.9275 (2)	0.7992 (3)	0.0372 (9)
H2	0.4489	0.9414	0.8306	0.045*
C3	0.3915 (2)	0.9825 (2)	0.7512 (3)	0.0475 (11)
H3	0.4039	1.0332	0.7520	0.057*
C4	0.3486 (2)	0.9647 (2)	0.7041 (3)	0.0466 (11)
H4	0.3303	1.0033	0.6737	0.056*
C5	0.33033 (17)	0.8886 (2)	0.6991 (2)	0.0374 (9)
C6	0.28456 (19)	0.8699 (3)	0.6520 (3)	0.0488 (12)
H6	0.2662	0.9082	0.6212	0.059*
C7	0.26663 (17)	0.7984 (3)	0.6501 (3)	0.0478 (11)
H7	0.2338	0.7876	0.6226	0.057*
C8	0.29556 (15)	0.7392 (2)	0.6882 (3)	0.0372 (9)
H8	0.2822	0.6891	0.6846	0.045*
C9	0.34357 (14)	0.7523 (2)	0.7311 (2)	0.0265 (8)
C10	0.35890 (14)	0.8301 (2)	0.7436 (2)	0.0285 (8)
C11	0.30765 (17)	0.8202 (3)	0.9726 (3)	0.0511 (12)
H11A	0.2749	0.8380	0.9997	0.077*
H11B	0.3140	0.7675	0.9887	0.077*
H11C	0.3043	0.8240	0.9099	0.077*
C12	0.35418 (16)	0.8689 (2)	1.0027 (3)	0.0375 (9)
H12	0.3532	0.8673	1.0669	0.045*
C13	0.34472 (17)	0.9513 (2)	0.9783 (3)	0.0457 (11)
H13A	0.3430	0.9559	0.9156	0.069*
H13B	0.3739	0.9825	1.0003	0.069*
H13C	0.3112	0.9686	1.0034	0.069*
C14	0.52835 (16)	0.8800 (2)	0.9599 (3)	0.0439 (11)
H14A	0.5504	0.9255	0.9635	0.066*
H14B	0.5231	0.8665	0.8994	0.066*
H14C	0.5461	0.8383	0.9897	0.066*
C15	0.47425 (16)	0.8952 (2)	1.0022 (3)	0.0366 (9)
H15	0.4623	0.9453	0.9798	0.044*
C16	0.4806 (2)	0.9052 (3)	1.0998 (3)	0.0531 (12)
H16A	0.4936	0.8579	1.1251	0.080*
H16B	0.4462	0.9181	1.1252	0.080*
H16C	0.5061	0.9458	1.1113	0.080*
C17	0.48236 (17)	0.6986 (2)	1.0332 (3)	0.0416 (10)
H17A	0.5057	0.7308	1.0678	0.062*
H17B	0.4961	0.6954	0.9744	0.062*
H17C	0.4810	0.6479	1.0585	0.062*
C18	0.42650 (16)	0.7324 (2)	1.0317 (3)	0.0366 (9)
H18	0.4042	0.6953	0.9993	0.044*
C19	0.4038 (2)	0.7337 (3)	1.1241 (3)	0.0528 (12)
H19A	0.4048	0.6825	1.1483	0.079*
H19B	0.3671	0.7517	1.1228	0.079*
H19C	0.4252	0.7675	1.1599	0.079*
C20	0.29409 (19)	0.4865 (3)	0.8192 (3)	0.0522 (12)
H20A	0.3204	0.4716	0.8623	0.078*
H20B	0.2996	0.4571	0.7665	0.078*
H20C	0.2584	0.4769	0.8415	0.078*
C21	0.30020 (16)	0.5712 (2)	0.7991 (3)	0.0390 (10)
H21	0.2701	0.5852	0.7603	0.047*
C22	0.29364 (18)	0.6179 (3)	0.8816 (3)	0.0484 (11)
H22A	0.2612	0.6023	0.9114	0.073*
H22B	0.2912	0.6717	0.8668	0.073*
H22C	0.3243	0.6097	0.9191	0.073*
C23	0.4252 (2)	0.4610 (2)	0.7654 (4)	0.0563 (13)
H23A	0.4586	0.4396	0.7868	0.084*
H23B	0.4230	0.4534	0.7030	0.084*
H23C	0.3953	0.4359	0.7934	0.084*
C24	0.42352 (16)	0.5462 (2)	0.7854 (3)	0.0376 (9)
H24	0.4552	0.5687	0.7565	0.045*
C25	0.43202 (18)	0.5582 (2)	0.8819 (3)	0.0450 (11)
H25A	0.4028	0.5350	0.9138	0.067*
H25B	0.4332	0.6125	0.8943	0.067*
H25C	0.4656	0.5349	0.8993	0.067*
C26	0.3207 (2)	0.5150 (3)	0.5934 (3)	0.0606 (14)
H26A	0.3183	0.5131	0.5305	0.091*
H26B	0.2855	0.5245	0.6176	0.091*
H26C	0.3342	0.4667	0.6150	0.091*
C27	0.35826 (17)	0.5782 (2)	0.6199 (3)	0.0407 (10)
H27	0.3429	0.6253	0.5944	0.049*
C28	0.41262 (18)	0.5685 (3)	0.5765 (3)	0.0467 (11)
H28A	0.4259	0.5173	0.5871	0.070*
H28B	0.4376	0.6054	0.6003	0.070*
H28C	0.4090	0.5767	0.5144	0.070*
C29	0.3572 (3)	0.6956 (3)	0.4095 (4)	0.0757 (17)
H29A	0.3351	0.6561	0.4371	0.091*
H29B	0.3908	0.6722	0.3901	0.091*
C30	0.3282 (3)	0.7295 (3)	0.3344 (3)	0.0718 (15)
H30A	0.3405	0.7070	0.2796	0.086*
H30B	0.2895	0.7217	0.3398	0.086*
C31	0.3417 (2)	0.8109 (3)	0.3387 (4)	0.0745 (15)
H31A	0.3137	0.8426	0.3124	0.089*
H31B	0.3761	0.8217	0.3104	0.089*
C32	0.3448 (3)	0.8224 (4)	0.4343 (5)	0.100 (2)
H32A	0.3672	0.8668	0.4480	0.120*
H32B	0.3090	0.8307	0.4586	0.120*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Mn1	0.0210 (3)	0.0221 (3)	0.0218 (3)	−0.0003 (2)	0.0002 (2)	−0.0020 (2)
Si1	0.0308 (5)	0.0298 (5)	0.0245 (5)	0.0002 (4)	0.0022 (4)	−0.0050 (4)
Na1	0.0359 (9)	0.0592 (10)	0.0348 (9)	−0.0016 (8)	−0.0039 (7)	0.0007 (8)
O1	0.0220 (12)	0.0293 (12)	0.0211 (13)	0.0007 (10)	0.0004 (10)	−0.0017 (10)
N1	0.0269 (15)	0.0223 (14)	0.0241 (16)	0.0004 (12)	0.0014 (12)	−0.0060 (12)
C1	0.0299 (19)	0.0295 (18)	0.0237 (19)	0.0028 (15)	0.0079 (15)	−0.0015 (15)
Si2	0.0282 (5)	0.0280 (5)	0.0316 (6)	−0.0072 (4)	0.0016 (4)	−0.0039 (4)
O2	0.057 (2)	0.065 (2)	0.0574 (19)	0.0079 (17)	−0.0162 (16)	−0.0167 (16)
N2	0.0205 (14)	0.0280 (15)	0.0321 (17)	−0.0023 (12)	0.0006 (13)	−0.0037 (13)
C2	0.049 (2)	0.0295 (19)	0.033 (2)	−0.0041 (18)	0.0042 (19)	−0.0016 (17)
C3	0.075 (3)	0.025 (2)	0.042 (3)	0.003 (2)	0.014 (2)	0.0032 (19)
C4	0.068 (3)	0.037 (2)	0.035 (2)	0.021 (2)	0.007 (2)	0.0090 (19)
C5	0.045 (2)	0.043 (2)	0.025 (2)	0.0132 (19)	0.0038 (18)	−0.0012 (17)
C6	0.054 (3)	0.055 (3)	0.037 (2)	0.027 (2)	−0.009 (2)	0.001 (2)
C7	0.033 (2)	0.070 (3)	0.041 (3)	0.015 (2)	−0.0073 (19)	−0.006 (2)
C8	0.030 (2)	0.049 (2)	0.033 (2)	0.0015 (18)	−0.0020 (17)	−0.0031 (19)
C9	0.0241 (18)	0.0332 (18)	0.0223 (18)	0.0052 (15)	0.0041 (14)	−0.0040 (15)
C10	0.0305 (19)	0.0298 (18)	0.0251 (19)	0.0056 (16)	0.0071 (15)	−0.0014 (15)
C11	0.036 (2)	0.066 (3)	0.051 (3)	−0.004 (2)	0.011 (2)	−0.003 (2)
C12	0.039 (2)	0.045 (2)	0.028 (2)	0.0061 (18)	0.0065 (17)	−0.0081 (18)
C13	0.038 (2)	0.051 (3)	0.048 (3)	0.012 (2)	0.005 (2)	−0.007 (2)
C14	0.037 (2)	0.037 (2)	0.058 (3)	−0.0043 (18)	0.000 (2)	−0.015 (2)
C15	0.038 (2)	0.033 (2)	0.039 (2)	−0.0009 (17)	−0.0030 (18)	−0.0084 (18)
C16	0.062 (3)	0.053 (3)	0.045 (3)	−0.004 (2)	−0.009 (2)	−0.020 (2)
C17	0.047 (3)	0.041 (2)	0.037 (2)	0.005 (2)	−0.0013 (19)	0.0031 (19)
C18	0.042 (2)	0.036 (2)	0.032 (2)	0.0010 (18)	0.0043 (18)	0.0027 (17)
C19	0.067 (3)	0.057 (3)	0.033 (2)	0.009 (2)	0.013 (2)	0.011 (2)
C20	0.051 (3)	0.052 (3)	0.054 (3)	−0.026 (2)	0.006 (2)	0.005 (2)
C21	0.031 (2)	0.046 (2)	0.040 (2)	−0.0123 (18)	0.0027 (18)	0.0040 (19)
C22	0.042 (2)	0.057 (3)	0.046 (3)	−0.002 (2)	0.014 (2)	0.002 (2)
C23	0.062 (3)	0.027 (2)	0.080 (4)	0.001 (2)	0.005 (3)	0.000 (2)
C24	0.035 (2)	0.0240 (18)	0.054 (3)	−0.0046 (16)	0.0028 (19)	0.0024 (18)
C25	0.045 (3)	0.038 (2)	0.052 (3)	−0.0003 (19)	−0.008 (2)	0.015 (2)
C26	0.069 (3)	0.066 (3)	0.047 (3)	−0.031 (3)	−0.007 (2)	−0.010 (2)
C27	0.046 (2)	0.040 (2)	0.037 (2)	−0.0123 (19)	0.0006 (19)	−0.0081 (19)
C28	0.055 (3)	0.045 (2)	0.040 (3)	−0.008 (2)	0.008 (2)	−0.011 (2)
C29	0.102 (5)	0.065 (2)	0.060 (4)	−0.010 (3)	−0.022 (3)	−0.007 (2)
C30	0.090 (4)	0.090 (4)	0.036 (2)	−0.005 (3)	−0.008 (2)	0.003 (2)
C31	0.068 (4)	0.087 (3)	0.068 (3)	0.014 (3)	0.005 (3)	0.013 (3)
C32	0.103 (5)	0.087 (3)	0.109 (5)	0.050 (4)	−0.061 (4)	−0.031 (3)

Geometric parameters (Å, º)

Mn1—O1^i	1.853 (2)	C14—H14B	0.9800
Mn1—O1	1.876 (2)	C14—H14C	0.9800
Mn1—N1	1.949 (3)	C15—C16	1.537 (6)
Mn1—N2	1.999 (3)	C15—H15	1.0000
Mn1—C1	2.608 (4)	C16—H16A	0.9800
Mn1—Mn1^i	2.7037 (10)	C16—H16B	0.9800
Mn1—Na1	3.1585 (17)	C16—H16C	0.9800
Si1—N1	1.723 (3)	C17—C18	1.530 (6)
Si1—C18	1.901 (4)	C17—H17A	0.9800
Si1—C15	1.903 (4)	C17—H17B	0.9800
Si1—C12	1.915 (4)	C17—H17C	0.9800
Na1—O1	2.201 (3)	C18—C19	1.548 (6)
Na1—O2	2.254 (4)	C18—H18	1.0000
Na1—C9	2.665 (4)	C19—H19A	0.9800
Na1—N2	2.706 (4)	C19—H19B	0.9800
Na1—C14^i	2.994 (4)	C19—H19C	0.9800
Na1—C10	3.010 (4)	C20—C21	1.539 (6)
O1—Mn1^i	1.853 (2)	C20—H20A	0.9800
N1—C1	1.408 (5)	C20—H20B	0.9800
C1—C2	1.394 (5)	C20—H20C	0.9800
C1—C10	1.447 (5)	C21—C22	1.535 (6)
Si2—N2	1.746 (3)	C21—H21	1.0000
Si2—C24	1.893 (4)	C22—H22A	0.9800
Si2—C21	1.910 (4)	C22—H22B	0.9800
Si2—C27	1.913 (4)	C22—H22C	0.9800
O2—C29	1.425 (6)	C23—C24	1.540 (5)
O2—C32	1.431 (7)	C23—H23A	0.9800
N2—C9	1.391 (5)	C23—H23B	0.9800
C2—C3	1.398 (6)	C23—H23C	0.9800
C2—H2	0.9500	C24—C25	1.530 (6)
C3—C4	1.343 (7)	C24—H24	1.0000
C3—H3	0.9500	C25—H25A	0.9800
C4—C5	1.426 (6)	C25—H25B	0.9800
C4—H4	0.9500	C25—H25C	0.9800
C5—C6	1.406 (6)	C26—C27	1.521 (6)
C5—C10	1.439 (5)	C26—H26A	0.9800
C6—C7	1.345 (7)	C26—H26B	0.9800
C6—H6	0.9500	C26—H26C	0.9800
C7—C8	1.406 (6)	C27—C28	1.537 (6)
C7—H7	0.9500	C27—H27	1.0000
C8—C9	1.402 (5)	C28—H28A	0.9800
C8—H8	0.9500	C28—H28B	0.9800
C9—C10	1.442 (5)	C28—H28C	0.9800
C11—C12	1.529 (6)	C29—C30	1.503 (7)
C11—H11A	0.9800	C29—H29A	0.9900
C11—H11B	0.9800	C29—H29B	0.9900
C11—H11C	0.9800	C30—C31	1.481 (8)
C12—C13	1.525 (6)	C30—H30A	0.9900
C12—H12	1.0000	C30—H30B	0.9900
C13—H13A	0.9800	C31—C32	1.503 (9)
C13—H13B	0.9800	C31—H31A	0.9900
C13—H13C	0.9800	C31—H31B	0.9900
C14—C15	1.538 (6)	C32—H32A	0.9900
C14—H14A	0.9800	C32—H32B	0.9900
O1^i—Mn1—O1	86.37 (11)	C12—C13—H13A	109.5
O1^i—Mn1—N1	102.86 (11)	C12—C13—H13B	109.5
O1—Mn1—N1	139.12 (11)	H13A—C13—H13B	109.5
O1^i—Mn1—N2	159.45 (11)	C12—C13—H13C	109.5
O1—Mn1—N2	94.67 (12)	H13A—C13—H13C	109.5
N1—Mn1—N2	89.78 (12)	H13B—C13—H13C	109.5
O1^i—Mn1—C1	120.12 (11)	C15—C14—H14A	109.5
O1—Mn1—C1	109.50 (11)	C15—C14—H14B	109.5
N1—Mn1—C1	32.04 (12)	H14A—C14—H14B	109.5
N2—Mn1—C1	78.89 (12)	C15—C14—H14C	109.5
O1^i—Mn1—Mn1^i	43.85 (7)	H14A—C14—H14C	109.5
O1—Mn1—Mn1^i	43.19 (7)	H14B—C14—H14C	109.5
N1—Mn1—Mn1^i	127.09 (9)	C16—C15—C14	110.5 (4)
N2—Mn1—Mn1^i	136.66 (9)	C16—C15—Si1	114.0 (3)
C1—Mn1—Mn1^i	118.93 (8)	C14—C15—Si1	113.8 (3)
O1^i—Mn1—Na1	128.71 (8)	C16—C15—H15	105.9
O1—Mn1—Na1	43.12 (8)	C14—C15—H15	105.9
N1—Mn1—Na1	111.02 (9)	Si1—C15—H15	105.9
N2—Mn1—Na1	58.22 (10)	C15—C16—H16A	109.5
C1—Mn1—Na1	79.78 (9)	C15—C16—H16B	109.5
Mn1^i—Mn1—Na1	84.86 (4)	H16A—C16—H16B	109.5
N1—Si1—C18	106.49 (16)	C15—C16—H16C	109.5
N1—Si1—C15	113.25 (17)	H16A—C16—H16C	109.5
C18—Si1—C15	112.14 (19)	H16B—C16—H16C	109.5
N1—Si1—C12	111.51 (17)	C18—C17—H17A	109.5
C18—Si1—C12	106.66 (18)	C18—C17—H17B	109.5
C15—Si1—C12	106.66 (18)	H17A—C17—H17B	109.5
O1—Na1—O2	151.22 (13)	C18—C17—H17C	109.5
O1—Na1—C9	94.31 (11)	H17A—C17—H17C	109.5
O2—Na1—C9	113.70 (14)	H17B—C17—H17C	109.5
O1—Na1—N2	70.15 (10)	C17—C18—C19	109.3 (3)
O2—Na1—N2	133.26 (13)	C17—C18—Si1	114.6 (3)
C9—Na1—N2	30.00 (10)	C19—C18—Si1	115.1 (3)
O1—Na1—C14^i	85.47 (11)	C17—C18—H18	105.6
O2—Na1—C14^i	85.41 (14)	C19—C18—H18	105.6
C9—Na1—C14^i	121.31 (13)	Si1—C18—H18	105.6
N2—Na1—C14^i	133.09 (13)	C18—C19—H19A	109.5
O1—Na1—C10	91.78 (11)	C18—C19—H19B	109.5
O2—Na1—C10	115.87 (13)	H19A—C19—H19B	109.5
C9—Na1—C10	28.62 (10)	C18—C19—H19C	109.5
N2—Na1—C10	50.60 (10)	H19A—C19—H19C	109.5
C14^i—Na1—C10	92.70 (12)	H19B—C19—H19C	109.5
O1—Na1—Mn1	35.62 (6)	C21—C20—H20A	109.5
O2—Na1—Mn1	172.06 (12)	C21—C20—H20B	109.5
C9—Na1—Mn1	58.86 (8)	H20A—C20—H20B	109.5
N2—Na1—Mn1	38.89 (7)	C21—C20—H20C	109.5
C14^i—Na1—Mn1	100.81 (10)	H20A—C20—H20C	109.5
C10—Na1—Mn1	59.33 (8)	H20B—C20—H20C	109.5
Mn1^i—O1—Mn1	92.96 (10)	C22—C21—C20	110.1 (4)
Mn1^i—O1—Na1	156.41 (14)	C22—C21—Si2	110.8 (3)
Mn1—O1—Na1	101.25 (11)	C20—C21—Si2	115.1 (3)
C1—N1—Si1	119.6 (2)	C22—C21—H21	106.8
C1—N1—Mn1	100.7 (2)	C20—C21—H21	106.8
Si1—N1—Mn1	139.41 (17)	Si2—C21—H21	106.8
C2—C1—N1	120.5 (3)	C21—C22—H22A	109.5
C2—C1—C10	118.2 (3)	C21—C22—H22B	109.5
N1—C1—C10	121.3 (3)	H22A—C22—H22B	109.5
C2—C1—Mn1	131.6 (3)	C21—C22—H22C	109.5
N1—C1—Mn1	47.27 (15)	H22A—C22—H22C	109.5
C10—C1—Mn1	93.4 (2)	H22B—C22—H22C	109.5
N2—Si2—C24	105.61 (16)	C24—C23—H23A	109.5
N2—Si2—C21	111.08 (17)	C24—C23—H23B	109.5
C24—Si2—C21	111.68 (19)	H23A—C23—H23B	109.5
N2—Si2—C27	107.79 (17)	C24—C23—H23C	109.5
C24—Si2—C27	109.5 (2)	H23A—C23—H23C	109.5
C21—Si2—C27	111.02 (18)	H23B—C23—H23C	109.5
C29—O2—C32	107.2 (4)	C25—C24—C23	109.3 (4)
C29—O2—Na1	127.0 (3)	C25—C24—Si2	114.0 (3)
C32—O2—Na1	125.7 (3)	C23—C24—Si2	115.0 (3)
C9—N2—Si2	124.5 (2)	C25—C24—H24	105.9
C9—N2—Mn1	116.1 (2)	C23—C24—H24	105.9
Si2—N2—Mn1	118.97 (16)	Si2—C24—H24	105.9
C9—N2—Na1	73.36 (19)	C24—C25—H25A	109.5
Si2—N2—Na1	106.36 (14)	C24—C25—H25B	109.5
Mn1—N2—Na1	82.88 (10)	H25A—C25—H25B	109.5
C1—C2—C3	121.8 (4)	C24—C25—H25C	109.5
C1—C2—H2	119.1	H25A—C25—H25C	109.5
C3—C2—H2	119.1	H25B—C25—H25C	109.5
C4—C3—C2	120.9 (4)	C27—C26—H26A	109.5
C4—C3—H3	119.6	C27—C26—H26B	109.5
C2—C3—H3	119.6	H26A—C26—H26B	109.5
C3—C4—C5	120.8 (4)	C27—C26—H26C	109.5
C3—C4—H4	119.6	H26A—C26—H26C	109.5
C5—C4—H4	119.6	H26B—C26—H26C	109.5
C6—C5—C4	121.0 (4)	C26—C27—C28	110.7 (4)
C6—C5—C10	119.5 (4)	C26—C27—Si2	116.6 (3)
C4—C5—C10	119.5 (4)	C28—C27—Si2	112.5 (3)
C7—C6—C5	120.6 (4)	C26—C27—H27	105.3
C7—C6—H6	119.7	C28—C27—H27	105.3
C5—C6—H6	119.7	Si2—C27—H27	105.3
C6—C7—C8	121.2 (4)	C27—C28—H28A	109.5
C6—C7—H7	119.4	C27—C28—H28B	109.5
C8—C7—H7	119.4	H28A—C28—H28B	109.5
C9—C8—C7	121.7 (4)	C27—C28—H28C	109.5
C9—C8—H8	119.2	H28A—C28—H28C	109.5
C7—C8—H8	119.2	H28B—C28—H28C	109.5
N2—C9—C8	122.3 (3)	O2—C29—C30	107.5 (5)
N2—C9—C10	120.4 (3)	O2—C29—H29A	110.2
C8—C9—C10	116.9 (3)	C30—C29—H29A	110.2
N2—C9—Na1	76.64 (19)	O2—C29—H29B	110.2
C8—C9—Na1	98.9 (2)	C30—C29—H29B	110.2
C10—C9—Na1	89.1 (2)	H29A—C29—H29B	108.5
C5—C10—C9	119.2 (3)	C31—C30—C29	104.0 (5)
C5—C10—C1	117.8 (3)	C31—C30—H30A	111.0
C9—C10—C1	123.0 (3)	C29—C30—H30A	111.0
C5—C10—Na1	101.9 (2)	C31—C30—H30B	111.0
C9—C10—Na1	62.26 (19)	C29—C30—H30B	111.0
C1—C10—Na1	108.0 (2)	H30A—C30—H30B	109.0
C12—C11—H11A	109.5	C30—C31—C32	100.9 (5)
C12—C11—H11B	109.5	C30—C31—H31A	111.6
H11A—C11—H11B	109.5	C32—C31—H31A	111.6
C12—C11—H11C	109.5	C30—C31—H31B	111.6
H11A—C11—H11C	109.5	C32—C31—H31B	111.6
H11B—C11—H11C	109.5	H31A—C31—H31B	109.4
C13—C12—C11	110.0 (4)	O2—C32—C31	106.3 (5)
C13—C12—Si1	117.4 (3)	O2—C32—H32A	110.5
C11—C12—Si1	111.2 (3)	C31—C32—H32A	110.5
C13—C12—H12	105.8	O2—C32—H32B	110.5
C11—C12—H12	105.8	C31—C32—H32B	110.5
Si1—C12—H12	105.8	H32A—C32—H32B	108.7

Symmetry code: (i) −x+1, y, −z+3/2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C17—H17B···O1^i	0.98	2.44	3.401 (5)	167
C28—H28B···O1	0.98	2.52	3.475 (5)	165
C13—H13A···Cg1	0.98	2.83	3.714 (5)	150

Symmetry code: (i) −x+1, y, −z+3/2.