Crystal structure of bis-(2-{[1,1-bis-(hy-droxy-meth-yl)-2-oxidoeth-yl]imino-meth-yl}-6-meth-oxy-phenolato)manganese(IV) 0.39-hydrate.

The title compound, [Mn(C12H15NO5)2]·0.39H2O, is a 0.39 hydrate of the isostructural complex bis-(2-{[1,1-bis-(hy-droxy-meth-yl)-2-oxidoeth-yl]imino-meth-yl}-6-meth-oxy-phenolato)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 mol-ecule. The title compound crystallizes in the tetra-gonal chiral space group P41212; the neutral [Mn(IV)(C12H15NO5)2] mol-ecule is situated on a crystallographic C 2 axis. The overall geometry about the central manganese ion is octa-hedral 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 mol-ecules are stacked in a helical fashion along the c-axis direction.

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 (H4 L) (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 [MnIV(H2 L)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 H2 L 2– containing two O− donors effectively stabilizes the MnIV oxidation state. Stabilization of MnIV 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)].

Structural commentary

The title compound (1) crystallizes in the tetra­gonal chiral space group P41212; the neutral [MnIV(C12H15NO5)2] mol­ecule is situated on a crystallographic C 2 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 MnIV—N(imine) [1.992 (5) Å], MnIV–O(phenolate) [1.939 (4) Å] and MnIV—O(alkoxo) [1.871 (4) Å] bond lengths in (1) are strictly comparable to those for several reported MnIV 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.

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.

Table 1

Selected geometric parameters (, )

Mn1O111	1.871(4)	Mn1N10	1.992(5)
Mn1O11	1.939(4)
O111Mn1O111i	94.0(3)	O111iMn1N10	88.07(19)
O111Mn1O11i	89.58(16)	O11iMn1N10	98.44(18)
O111Mn1O11	172.89(18)	O11Mn1N10	89.82(17)
O11iMn1O11	87.6(2)	N10Mn1N10i	168.6(3)
O111Mn1N10	84.14(18)

Symmetry code: (i) .

The mol­ecular structure of (1) closely resembles that of the MnII complex of the same ligand, [MnII(H3 L)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 MnII—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 MnII—O(phenolate) and MnII—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 H4 L 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 MnII complex.

Supra­molecular features

In the crystal lattice, individual [MnIV(H2 L)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 ▸.

Figure 3

Crystal packing of (1) showing the helical arrangement of MnIV(H2 L)2 mol­ecules in the c-axis direction. H atoms are not shown.

Table 2

Hydrogen-bond geometry (, )

DHA	DH	HA	D A	DHA
O112H112O11ii	0.84	2.2	2.850(7)	134
O112H112O16ii	0.84	2.1	2.802(7)	141
O113H113O112iii	0.84	2.3	2.965(12)	137

Symmetry codes: (ii) ; (iii) .

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- CoIICoIII, 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 H4 L ligand can stabilize manganese in various oxidation states. Apart from MnII (ROMROB) and MnIV [(1); IGOSII] complexes, the structure of the MnIII derivative, [Mn4(HL)2(H2 L)2(CH3OH)4](ClO4)2]·4CH3OH has also been reported (Zhu et al., 2014 ▸). Stabilization of MnIV species by similar ligands with phenolate oxygen atoms has been reported previously with details of three structures of [MnIVN2O4] complexes with tridentate Schiff base ligands similar to H4 L (Kessissoglou et al., 1987 ▸; Chandra et al., 1990 ▸; Pradeep et al., 2004 ▸).

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.

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 ()	8.0953(2), 37.568(2)
V (3)	2461.97(18)
Z	4
Radiation type	Cu K
(mm1)	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 > 2(I)] reflections	18553, 2214, 1885
R int	0.103
(sin /)max (1)	0.600
Refinement
R[F 2 > 2(F 2)], wR(F 2), S	0.052, 0.136, 1.05
No. of reflections	2214
No. of parameters	181
H-atom treatment	H-atom parameters constrained
max, min (e 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 ▸).

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989015018551/sj5481sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015018551/sj5481Isup2.hkl

Supporting information file. DOI: 10.1107/S2056989015018551/sj5481Isup3.pdf

Click here for additional data file.

Supporting information file. DOI: 10.1107/S2056989015018551/sj5481Isup4.tif

CCDC reference: 1429416

Additional supporting information: crystallographic information; 3D view; checkCIF report

[Mn(C12H15NO5)2]·0.39H2O	Dx = 1.534 Mg m−3
Mr = 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

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

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(Fo2) + (0.0691P)2 + 1.3653P] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.136	(Δ/σ)max < 0.001
S = 1.05	Δρmax = 0.54 e Å−3
2214 reflections	Δρmin = −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)

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

	x	y	z	Uiso*/Ueq	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)

	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)

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

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