Crystal structure of bis­(2-{[1,1-bis­(hy­droxy­meth­yl)-2-oxidoeth­yl]imino­meth­yl}-6-meth­oxy­phenolato)manganese(IV) 0.39-hydrate

Buvaylo, E.A.; Vassilyeva, O.Y.; Skelton, B.W.

doi:10.1107/S2056989015018551

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ISSN: 2056-9890

Volume 71| Part 11| November 2015| Pages 1307-1310

https://doi.org/10.1107/S2056989015018551

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Crystal structure of bis(2-{[1,1-bis(hydroxymethyl)-2-oxidoethyl]iminomethyl}-6-methoxyphenolato)manganese(IV) 0.39-hydrate

Elena A. Buvaylo,^a Olga Yu. Vassilyeva ^a ^* and Brian W. Skelton ^b

^aDepartment of Chemistry, Taras Shevchenko National University of Kyiv, 64/13 Volodymyrska Street, Kyiv 01601, Ukraine, and ^bCentre for Microscopy, Characterisation and Analysis, M313, University of Western Australia, Perth, WA 6009, Australia
^*Correspondence e-mail: vassilyeva@univ.kiev.ua

Edited by J. Simpson, University of Otago, New Zealand (Received 1 October 2015; accepted 4 October 2015; online 10 October 2015)

The title compound, [Mn(C₁₂H₁₅NO₅)₂]·0.39H₂O, is a 0.39 hydrate of the isostructural complex bis(2-{[1,1-bis(hydroxymethyl)-2-oxidoethyl]iminomethyl}-6-methoxyphenolato)manganese(IV) that has previously been reported by Back, Oliveira, Canabarro & Iglesias [Z. Anorg. Allg. Chem. (2015), 641, 941–947], based on room-temperature data. The current structure that was determined at 100 K reveals a lengthening of the c cell parameter compared with the published one due to the incorporation of the partial occupancy water molecule. The title compound crystallizes in the tetragonal chiral space group P4₁2₁2; the neutral [Mn^IV(C₁₂H₁₅NO₅)₂] molecule is situated on a crystallographic C₂ axis. The overall geometry about the central manganese ion is octahedral with an N₂O₄ core; each ligand acts as a meridional ONO donor. The coordination environment of Mn^IV at 100 K displays a difference in one of the two Mn–O bond lengths, compared with the room-temperature structure. In the crystal, the neutral molecules are stacked in a helical fashion along the c-axis direction.

Keywords: crystal structure; monomeric octahedral Mn^IV complex; Schiff base ligand; o-vanillin; tris(hydroxymethyl)aminomethane.

CCDC reference: 1429416

1. Chemical context

The title compound is a hydrate of the isostructural complex bis(2-{[1,1-bis(hydroxymethyl)-2-oxidoethyl]iminomethyl}-6-methoxyphenolato)manganese(IV) (refcode IGOSII; Back et al., 2015 ). It was isolated as an unexpected product in an attempt to prepare a heterometallic Mn/Zn compound with the multidentate Schiff base ligand 2-{[(2-hydroxy-3-methoxyphenyl)methylene]amino}-2-(hydroxymethyl)-1,3-propanediol (H₄L) (Odabaşoğlu et al., 2003 ). Zn powder and MnCl₂·4H₂O were reacted with the Schiff base formed in situ from the condensation between o-vanillin and tris(hydroxymethyl)aminomethane in methanol in a 1:1:2 molar ratio. Metal powders have been successfully applied in direct synthesis of coordination compounds to yield a number of novel monometallic (Babich & Kokozay, 1997 ; Babich et al., 1996 ; Kovbasyuk et al., 1997 ) and heterometallic complexes (Nikitina et al., 2008 ; Nesterov et al., 2011 ) of various nuclearities and dimensionalities. However, the isolated black microcrystalline product of the reaction studied appeared to be the mononuclear Schiff base complex [Mn^IV(H₂L)₂]·0.39H₂O (1). Oxidation of the manganese(II) atom directly to the manganese(IV) species proceeds easily in open air even in the presence of zerovalent Zn, indicating that the tridentate ligand H₂L^2– containing two O⁻ donors effectively stabilizes the Mn^IV oxidation state. Stabilization of Mn^IV species by similar ligands with phenolate oxygen atoms has been reported previously (Kessissoglou et al., 1987 ; Pradeep et al., 2004 ).

Remarkably, the current structure that was determined at 100 K reveals shortening of the a cell parameter compared with the published one [8.0953 (2) (1), 8.1620 (2) Å (IGOSII)] as expected in the case of low-temperature determination, but lengthening of the c cell parameter [37.568 (2) (1), 37.4557 (11) Å (IGOSII)] due to the incorporation of the partial occupancy water molecule. Also, (1) shows somewhat longer Mn—O bond lengths to the deprotonated hydroxymethyl group [1.871 (4) Å] compared to the corresponding distance in IGOSII [1.849 (2) Å], while the Mn—N bonds stay the same [1.992 (5) (1), 1.991 (3) Å (IGOSII)].

2. Structural commentary

The title compound (1) crystallizes in the tetragonal chiral space group P4₁2₁2; the neutral [Mn^IV(C₁₂H₁₅NO₅)₂] molecule is situated on a crystallographic C₂ axis, hence the asymmetric unit comprises one half of the metal complex and the O atom of a water molecule with occupancy 0.195 (15) (Fig. 1). The overall geometry about the central metal ion is distorted octahedral with an N₂O₄ core; each ligand acts as a meridional ONO donor. The Mn^IV—N(imine) [1.992 (5) Å], Mn^IV–O(phenolate) [1.939 (4) Å] and Mn^IV—O(alkoxo) [1.871 (4) Å] bond lengths in (1) are strictly comparable to those for several reported Mn^IV complexes containing similar ligation (Kessissoglou et al., 1987; Pradeep et al., 2004). The MnO₄ equatorial fragment is approximately square planar, the maximum deviation from the mean plane being about 0.11 Å. The ranges of cis and trans angles at the metal atom are 84.14 (18)–98.44 (18) and 168.6 (3)–172.89 (18)°, respectively (Table 1). The Mn—N distance is longer than the average Mn—O distance by approximately 0.1 Å. This is significantly larger than the difference in covalent radii of N and O. Thus, the primary distortion of the MnN₂O₄ octahedron is axial elongation along the MnN₂ axis.

Table 1
Selected geometric parameters (Å, °)

Mn1—O111	1.871 (4)	Mn1—N10	1.992 (5)
Mn1—O11	1.939 (4)

O111—Mn1—O111ⁱ	94.0 (3)	O111ⁱ—Mn1—N10	88.07 (19)
O111—Mn1—O11ⁱ	89.58 (16)	O11ⁱ—Mn1—N10	98.44 (18)
O111—Mn1—O11	172.89 (18)	O11—Mn1—N10	89.82 (17)
O11ⁱ—Mn1—O11	87.6 (2)	N10—Mn1—N10ⁱ	168.6 (3)
O111—Mn1—N10	84.14 (18)
Symmetry code: (i) y, x, -z+1.

Figure 1
The molecular structure of the title complex, showing the atom-numbering scheme. Non-H atoms are shown with displacement ellipsoids at the 50% probability level. Labelled atoms are related to unlabelled atoms by the symmetry operation y, x, −z + 1.

The molecular structure of (1) closely resembles that of the Mn^II complex of the same ligand, [Mn^II(H₃L)₂]·2CH₃OH·0.5H₂O (refcode ROMROB; Zhang et al., 2009 ) (Fig. 2). The latter crystallizes in the monoclinic space group P2₁/n and has no crystallographically imposed symmetry. There is a marked increase in the ROMROB Mn^II—O(H) bond length (mean 2.134 Å) when (1) is compared to ROMROB which has two additional protons to compensate for the two additional electrons. In ROMROB, the Mn^II—O(phenolate) and Mn^II—N(imine) bonds are also elongated (mean lengths 2.011 and 2.027 Å, respectively). (1) thus provides a rare structural example of variations in the metal coordination sphere to accommodate change in the metal oxidation state. The flexibility of the lattice, formed using the partly deprotonated H₄L ligand, permits distortion of the structure in the solid state to allow for changes in the charge and spin state of the Mn atom without disrupting the integrity of the crystal structure.

Figure 2
Scheme showing the structure of the closely related ROMROB Mn^II complex.

3. Supramolecular features

In the crystal lattice, individual [Mn^IV(H₂L)₂] molecules are stacked in a helical fashion along the c axis, as shown in Fig. 3, with the minimum Mn⋯Mn distances inside a column being 10.28 Å. Molecules that are translated by one unit cell in the a-axis direction [Mn⋯Mn distance equals the a-axial length, 8.0953 (2) Å] are intertwined by intermolecular hydrogen bonds between the hydroxyl groups and phenolic and methoxy oxygen atoms. There is also a possible hydrogen-bonding interaction between one hydroxyl group (O113) and the solvent water molecule (O1) considering the O113⋯O1 distance of 2.17 (2) but as the H atoms on O1 could not be located this contact could not be confirmed. Details of the hydrogen bonding are given in Table 2.

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O112—H112⋯O11ⁱⁱ	0.84	2.2	2.850 (7)	134
O112—H112⋯O16ⁱⁱ	0.84	2.1	2.802 (7)	141
O113—H113⋯O112ⁱⁱⁱ	0.84	2.3	2.965 (12)	137
Symmetry codes: (ii) x+1, y, z; (iii) y, x-1, -z+1.

Figure 3
Crystal packing of (1) showing the helical arrangement of Mn^IV(H₂L)₂ molecules in the c-axis direction. H atoms are not shown.

4. Database survey

A search of the Cambridge Structural Database (CSD Version 5.36 with one update; Groom & Allen, 2014 ) for metal complexes of this ligand reveals the crystal structures of above 30 compounds, mostly comprising polynuclear homo- Co^IICo^III, V₂, Cu₄, Mn₄, Ni₄, Ln₉ and Ln₁₀ and heterometallic 1s–3d and 3d–4f assemblies of 4–20 nuclearity. Mononuclear complexes of this ligand are limited to five Mn, Ni and Mo structures. The ligand molecules exist in either doubly or triply deprotonated forms, adopt a chelating-bridging mode and form five- and six-membered rings. The H₄L ligand can stabilize manganese in various oxidation states. Apart from Mn^II (ROMROB) and Mn^IV [(1); IGOSII] complexes, the structure of the Mn^III derivative, [Mn₄(HL)₂(H₂L)₂(CH₃OH)₄](ClO₄)₂]·4CH₃OH has also been reported (Zhu et al., 2014 ). Stabilization of Mn^IV species by similar ligands with phenolate oxygen atoms has been reported previously with details of three structures of [Mn^IVN₂O₄] complexes with tridentate Schiff base ligands similar to H₄L (Kessissoglou et al., 1987; Chandra et al., 1990 ; Pradeep et al., 2004).

5. Synthesis and crystallization

2-Hydroxy-3-methoxy-benzaldehyde (0.30 g, 2 mmol) and tris(hydroxymethyl)aminomethane (0.24 g, 2 mmol), were added to methanol (20 ml) and stirred magnetically for 30 min. Next zinc powder (0.07 g, 1 mmol) and MnCl₂·4H₂O (0.20 g, 1 mmol) were added to the yellow solution and the mixture was heated to 323 K under stirring until total dissolution of the zinc powder was observed (1 h). The resulting brown solution was filtered and allowed to stand at room temperature. Black microcrystals of the title compound were formed in several days. They were collected by filter-suction, washed with dry PrⁱOH and finally dried in vacuo (yield: 43%).

The IR spectrum of powdered (1) in the range 4000–400 cm⁻¹ shows all the characteristic Schiff base vibration bands: ν(OH), ν(CH) and ν(C=N) at 3400, 3000–2840, and 1602 cm⁻¹, respectively (see Supplementary data). A strong peak at 1618 cm⁻¹ is due to the bending of the H₂O molecule, providing evidence of the presence of water in (1). The major feature of the X-band solid-state EPR spectrum of (1) at 77 K is a strong and broad signal at g ∼4 and a weak but resolved response at g ∼2 (see Supplementary data). This corresponds to strong axial distortion with small zero-field splitting, 2D >> hυ (hυ 0.31 cm⁻¹ at the X-band frequency) in agreement with structural findings. The ⁵⁵Mn hyperfine structure is not resolved.

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 3. The solvent was modelled as a water molecule with the site occupancy refined to 0.195 (15). Associated hydrogen atoms were not located. The OH hydrogen atoms H112 and H113 were refined using a riding model with U_iso(H) = 1.5U_eq(O). All hydrogen atoms bound to carbon were included in calculated positions and refined using a riding model with isotropic displacement parameters based on those of the parent atom [C—H = 0.95 Å, U_iso(H) = 1.2U_eq(C) for CH and CH₂, 1.5U_eq(C) for CH₃].

Table 3
Experimental details

Crystal data
Chemical formula	[Mn(C₁₂H₁₅NO₅)₂]·0.39H₂O
M_r	568.46
Crystal system, space group	Tetragonal, P4₁2₁2
Temperature (K)	100
a, c (Å)	8.0953 (2), 37.568 (2)
V (Å³)	2461.97 (18)
Z	4
Radiation type	Cu Kα
μ (mm⁻¹)	4.92
Crystal size (mm)	0.09 × 0.08 × 0.01

Data collection
Diffractometer	Oxford Diffraction Gemini
Absorption correction	Analytical [CrysAlis PRO (Agilent, 2014 ) using an expression derived by Clark & Reid (1995 )]
T_min, T_max	0.695, 0.946
No. of measured, independent and observed [I > 2σ(I)] reflections	18553, 2214, 1885
R_int	0.103
(sin θ/λ)_max (Å⁻¹)	0.600

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.052, 0.136, 1.05
No. of reflections	2214
No. of parameters	181
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.54, −0.34
Absolute structure	Flack x determined using 584 quotients [(I⁺)−(I⁻)]/[(I⁺)+(I⁻)] (Parsons et al., 2013 ).
Absolute structure parameter	−0.007 (6)
Computer programs: CrysAlis PRO (Agilent, 2014), SIR92 (Altomare et al., 1993 ), SHELXL2014 (Sheldrick, 2015 ), DIAMOND (Brandenburg, 1999 ) and WinGX (Farrugia, 2012 ).

Supporting information

CCDC reference: 1429416

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S2056989015018551/sj5481sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989015018551/sj5481Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2056989015018551/sj5481Isup3.pdf

Supporting information file. DOI: https://doi.org/10.1107/S2056989015018551/sj5481Isup4.tif

checkCIF report

Computing details top

Data collection: CrysAlis PRO (Agilent, 2014); cell refinement: CrysAlis PRO (Agilent, 2014); data reduction: CrysAlis PRO (Agilent, 2014); program(s) used to solve structure: SIR92 (Altomare et al., 1993); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: DIAMOND (Brandenburg, 1999); software used to prepare material for publication: WinGX (Farrugia, 2012).

Bis(2-{[1,1-bis(hydroxymethyl)-2-oxidoethyl]iminomethyl}-6-methoxyphenolato)manganese(IV) 0.39 hydrate top

Crystal data top

[Mn(C₁₂H₁₅NO₅)₂]·0.39H₂O	D_x = 1.534 Mg m⁻³
M_r = 568.46	Cu Kα radiation, λ = 1.54178 Å
Tetragonal, P4₁2₁2	Cell parameters from 2851 reflections
Hall symbol: P 4abw 2nw	θ = 3.5–67.6°
a = 8.0953 (2) Å	µ = 4.92 mm⁻¹
c = 37.568 (2) Å	T = 100 K
V = 2461.97 (18) Å³	Plate, black
Z = 4	0.09 × 0.08 × 0.01 mm
F(000) = 1188

Data collection top

Oxford Diffraction Gemini diffractometer	2214 independent reflections
Graphite monochromator	1885 reflections with I > 2σ(I)
Detector resolution: 10.4738 pixels mm^-1	R_int = 0.103
ω scans	θ_max = 67.7°, θ_min = 4.7°
Absorption correction: analytical [CrysAlis Pro (Agilent, 2014) using an expression derived by Clark & Reid (1995)]	h = −9→9
T_min = 0.695, T_max = 0.946	k = −6→9
18553 measured reflections	l = −42→44

Refinement top

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.052	w = 1/[σ²(F_o²) + (0.0691P)² + 1.3653P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.136	(Δ/σ)_max < 0.001
S = 1.05	Δρ_max = 0.54 e Å⁻³
2214 reflections	Δρ_min = −0.34 e Å⁻³
181 parameters	Absolute structure: Flack x determined using 584 quotients [(I⁺)-(I^-)]/[(I⁺)+(I^-)] (Parsons et al., 2013).
0 restraints	Absolute structure parameter: −0.007 (6)

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Refinement. The solvent was modelled as a water molecule with a site occupancy refined to 0.195 (15). Associated hydrogen atoms were not located.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
Mn1	0.68511 (10)	0.68511 (10)	0.5	0.0286 (3)
C11	0.6187 (6)	0.4968 (6)	0.56423 (15)	0.0308 (12)
O11	0.5567 (4)	0.5690 (5)	0.53567 (9)	0.0333 (8)
C12	0.7784 (6)	0.4298 (7)	0.56576 (14)	0.0330 (13)
C13	0.8302 (7)	0.3446 (7)	0.59647 (14)	0.0365 (13)
H13	0.9372	0.2963	0.5969	0.044*
C14	0.7305 (7)	0.3297 (7)	0.62568 (16)	0.0385 (13)
H14	0.7677	0.2721	0.6462	0.046*
C15	0.5729 (7)	0.4005 (7)	0.62492 (15)	0.0394 (13)
H15	0.5037	0.393	0.6453	0.047*
C16	0.5167 (7)	0.4815 (7)	0.59479 (14)	0.0329 (11)
O16	0.3648 (5)	0.5520 (5)	0.59131 (11)	0.0414 (10)
C161	0.2522 (8)	0.5349 (8)	0.62010 (18)	0.0443 (15)
H16A	0.2355	0.4174	0.6253	0.066*
H16B	0.1462	0.5854	0.6137	0.066*
H16C	0.2971	0.5901	0.6412	0.066*
C10	0.8942 (7)	0.4456 (7)	0.53655 (15)	0.0364 (13)
H10	0.9951	0.3863	0.5385	0.044*
N10	0.8733 (5)	0.5316 (6)	0.50849 (12)	0.0349 (11)
C101	1.0070 (8)	0.5533 (9)	0.48146 (17)	0.0502 (17)
C111	0.9865 (8)	0.7342 (9)	0.46941 (19)	0.0508 (17)
H11A	1.0338	0.8087	0.4876	0.061*
H11B	1.0475	0.7518	0.4469	0.061*
O111	0.8214 (5)	0.7719 (5)	0.46438 (11)	0.0444 (10)
C112	1.1779 (9)	0.5228 (11)	0.4957 (2)	0.072 (2)
H11C	1.1897	0.4044	0.5018	0.087*
H11D	1.26	0.5492	0.477	0.087*
O112	1.2110 (7)	0.6187 (10)	0.52604 (19)	0.096 (2)
H112	1.2848	0.5727	0.5382	0.143*
C113	0.9654 (11)	0.4419 (9)	0.44961 (19)	0.065 (2)
H11E	0.8528	0.4678	0.441	0.078*
H11F	1.044	0.464	0.43	0.078*
O113	0.9740 (11)	0.2689 (7)	0.45943 (17)	0.105 (3)
H113	0.9002	0.2478	0.4745	0.157*
O1	0.787 (3)	0.090 (3)	0.4441 (6)	0.048 (9)	0.195 (15)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Mn1	0.0282 (4)	0.0282 (4)	0.0293 (6)	−0.0008 (5)	−0.0022 (4)	0.0022 (4)
C11	0.031 (3)	0.025 (3)	0.036 (3)	−0.002 (2)	−0.005 (2)	0.000 (2)
O11	0.026 (2)	0.039 (2)	0.034 (2)	−0.0011 (15)	−0.0036 (16)	0.0023 (17)
C12	0.034 (3)	0.030 (3)	0.035 (3)	−0.005 (2)	−0.003 (2)	0.002 (2)
C13	0.031 (3)	0.037 (3)	0.042 (3)	−0.001 (2)	−0.006 (2)	0.003 (2)
C14	0.043 (3)	0.035 (3)	0.037 (3)	−0.005 (3)	−0.007 (2)	0.008 (2)
C15	0.046 (3)	0.035 (3)	0.037 (3)	−0.008 (3)	0.002 (3)	0.001 (2)
C16	0.032 (3)	0.029 (3)	0.037 (3)	−0.005 (2)	0.001 (2)	0.003 (2)
O16	0.032 (2)	0.052 (2)	0.041 (2)	0.0051 (17)	0.0082 (17)	0.0053 (19)
C161	0.038 (3)	0.043 (4)	0.052 (4)	0.002 (3)	0.011 (3)	0.007 (3)
C10	0.026 (3)	0.041 (3)	0.042 (3)	0.002 (2)	−0.002 (2)	0.000 (3)
N10	0.028 (2)	0.045 (3)	0.032 (2)	−0.002 (2)	−0.0006 (18)	0.007 (2)
C101	0.036 (3)	0.067 (5)	0.047 (4)	0.008 (3)	0.007 (3)	0.012 (3)
C111	0.045 (4)	0.060 (4)	0.047 (4)	−0.008 (3)	0.004 (3)	0.016 (3)
O111	0.043 (2)	0.048 (2)	0.041 (2)	−0.010 (2)	−0.0092 (19)	0.0110 (18)
C112	0.039 (4)	0.098 (6)	0.080 (6)	0.006 (4)	0.019 (4)	0.035 (5)
O112	0.049 (3)	0.142 (6)	0.096 (5)	−0.025 (4)	−0.025 (3)	0.055 (4)
C113	0.085 (6)	0.056 (4)	0.055 (4)	0.015 (4)	0.024 (4)	0.012 (4)
O113	0.184 (8)	0.053 (3)	0.077 (4)	0.048 (4)	0.067 (5)	0.025 (3)
O1	0.055 (16)	0.037 (13)	0.052 (15)	0.017 (11)	0.016 (11)	0.008 (10)

Geometric parameters (Å, º) top

Mn1—O111	1.871 (4)	C161—H16B	0.98
Mn1—O111ⁱ	1.871 (4)	C161—H16C	0.98
Mn1—O11ⁱ	1.939 (4)	C10—N10	1.275 (7)
Mn1—O11	1.939 (4)	C10—H10	0.95
Mn1—N10	1.992 (5)	N10—C101	1.495 (7)
Mn1—N10ⁱ	1.992 (5)	C101—C112	1.504 (10)
C11—O11	1.321 (6)	C101—C113	1.536 (10)
C11—C12	1.403 (8)	C101—C111	1.542 (10)
C11—C16	1.420 (8)	C111—O111	1.384 (8)
C12—C13	1.408 (7)	C111—H11A	0.99
C12—C10	1.449 (8)	C111—H11B	0.99
C13—C14	1.368 (8)	C112—O112	1.405 (11)
C13—H13	0.95	C112—H11C	0.99
C14—C15	1.399 (9)	C112—H11D	0.99
C14—H14	0.95	O112—H112	0.84
C15—C16	1.384 (8)	C113—O113	1.450 (9)
C15—H15	0.95	C113—H11E	0.99
C16—O16	1.362 (7)	C113—H11F	0.99
O16—C161	1.421 (7)	O113—H113	0.84
C161—H16A	0.98

O111—Mn1—O111ⁱ	94.0 (3)	H16A—C161—H16B	109.5
O111—Mn1—O11ⁱ	89.58 (16)	O16—C161—H16C	109.5
O111ⁱ—Mn1—O11ⁱ	172.89 (19)	H16A—C161—H16C	109.5
O111—Mn1—O11	172.89 (18)	H16B—C161—H16C	109.5
O111ⁱ—Mn1—O11	89.58 (16)	N10—C10—C12	126.0 (5)
O11ⁱ—Mn1—O11	87.6 (2)	N10—C10—H10	117
O111—Mn1—N10	84.14 (18)	C12—C10—H10	117
O111ⁱ—Mn1—N10	88.07 (19)	C10—N10—C101	122.0 (5)
O11ⁱ—Mn1—N10	98.44 (18)	C10—N10—Mn1	125.1 (4)
O11—Mn1—N10	89.82 (17)	C101—N10—Mn1	111.8 (4)
O111—Mn1—N10ⁱ	88.07 (19)	N10—C101—C112	113.9 (5)
O111ⁱ—Mn1—N10ⁱ	84.14 (18)	N10—C101—C113	107.5 (6)
O11ⁱ—Mn1—N10ⁱ	89.82 (17)	C112—C101—C113	112.5 (7)
O11—Mn1—N10ⁱ	98.44 (18)	N10—C101—C111	103.5 (5)
N10—Mn1—N10ⁱ	168.6 (3)	C112—C101—C111	111.1 (6)
O11—C11—C12	123.7 (5)	C113—C101—C111	107.8 (5)
O11—C11—C16	118.3 (5)	O111—C111—C101	110.7 (5)
C12—C11—C16	118.0 (5)	O111—C111—H11A	109.5
C11—O11—Mn1	124.9 (3)	C101—C111—H11A	109.5
C11—C12—C13	119.8 (5)	O111—C111—H11B	109.5
C11—C12—C10	122.1 (5)	C101—C111—H11B	109.5
C13—C12—C10	118.1 (5)	H11A—C111—H11B	108.1
C14—C13—C12	121.6 (5)	C111—O111—Mn1	112.9 (4)
C14—C13—H13	119.2	O112—C112—C101	111.9 (7)
C12—C13—H13	119.2	O112—C112—H11C	109.2
C13—C14—C15	119.0 (5)	C101—C112—H11C	109.2
C13—C14—H14	120.5	O112—C112—H11D	109.2
C15—C14—H14	120.5	C101—C112—H11D	109.2
C16—C15—C14	120.7 (5)	H11C—C112—H11D	107.9
C16—C15—H15	119.7	C112—O112—H112	109.5
C14—C15—H15	119.7	O113—C113—C101	111.0 (6)
O16—C16—C15	125.0 (5)	O113—C113—H11E	109.4
O16—C16—C11	114.3 (5)	C101—C113—H11E	109.4
C15—C16—C11	120.7 (5)	O113—C113—H11F	109.4
C16—O16—C161	117.7 (5)	C101—C113—H11F	109.4
O16—C161—H16A	109.5	H11E—C113—H11F	108
O16—C161—H16B	109.5	C113—O113—H113	109.5

Symmetry code: (i) y, x, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O112—H112···O11ⁱⁱ	0.84	2.2	2.850 (7)	134
O112—H112···O16ⁱⁱ	0.84	2.1	2.802 (7)	141
O113—H113···O112ⁱⁱⁱ	0.84	2.3	2.965 (12)	137

Symmetry codes: (ii) x+1, y, z; (iii) y, x−1, −z+1.

Acknowledgements

The authors acknowledge the facilities, scientific and technical assistance of the Australian Microscopy & Microanalysis Research Facility at the Centre for Microscopy, Characterization & Analysis, the University of Western Australia, a facility funded by the University, State and Commonwealth Governments.

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