Crystal structure of tetra-kis-(μ3-2-{[1,1-bis-(hy-droxy-meth-yl)-2-oxidoeth-yl]imino-meth-yl}-6-meth-oxy-phenolato)tetra-kis-[aqua-copper(II)]: a redetermination at 200 K.

The crystal structure of the tetra-nuclear title compound, [Cu4(C12H15NO5)4(H2O)4], has been previously reported by Back, Oliveira, Canabarro & Iglesias [Z. Anorg. Allg. Chem. (2015), 641, 941-947], based on room-temperature data. In the previously published structure, no standard uncertainties are recorded for the deprotonated hy-droxy-methyl group and water mol-ecule O atoms coordinating to the metal atom indicating that they were not refined; furthermore, the H atoms of some OH groups and water mol-ecules have not been positioned accurately. Since the current structure was determined at a lower temperature, all atoms, including the H atoms of these hy-droxy groups and the water mol-ecule, have been determined more accurately resulting in improved standard uncertainties in the bond lengths and angles. Diffraction data were collected at 200 K, rather than the more usual 100 K, due to apparent disordering at lower temperatures. In addition, it is now possible to report intra- and inter-molecular O-H⋯O inter-actions. In the title complex molecule, which has crystallographic -4 symmetry, the Cu(II) ions are coordinated by the tridentate Schiff base ligands and water mol-ecules, forming a tetra-nuclear Cu4O4 cubane-like core. The Cu(II) ion adopts a CuNO5 elongated octa-hedral environment. The coordination environment of Cu(II) at 200 K displays a small contraction of the Cu-N/O bonds, compared with the room-temperature structure. In the crystal lattice, the neutral clusters are linked by inter-molecular O-H⋯O hydrogen bonds into a one-dimensional hydrogen-bonding network propagating along the b axis.

Chemical context

During the last few years, we have been exploring the chemistry of transition metal complexes of Schiff base ligands with the aim of preparing heterometallic polynuclear compounds with diverse potential advantages. In these studies, we continued to apply the direct synthesis of coordination compounds based on spontaneous self-assembly, in which one of the metals is introduced as a powder (zerovalent state) and oxidized during the synthesis (typically by di­oxy­gen from the air) (Pryma et al., 2003 ▸; Nesterova et al., 2008 ▸; Nesterov et al., 2012 ▸). The main advantage of this approach is the generation of building blocks in situ, in one reaction vessel, thus eliminating separate steps in building-block construction. Reactions of a metal powder and another metal salt in air with a solution containing a pre-formed Schiff base ligand have yielded a number of novel Co/Fe and Cu/Fe compounds (Chygorin et al., 2015 ▸; Nesterova et al., 2013 ▸).

The title compound was prepared in studies of the coordination behavior of the versatile multidentate Schiff base ligand 2-{[(2-hy­droxy-3-meth­oxy­phen­yl)methyl­ene]amino}-2-(hy­droxy­meth­yl)-1,3-propane­diol (H4L) (Odabaşoğlu et al., 2003 ▸) which results from the condensation between o-vanillin and tris­(hy­droxy­meth­yl)amino­methane. In the syntheses, the condensation reaction was utilized without isolation of the resulting Schiff base. In an attempt to prepare a heterometallic assembly we reacted Cu powder and Zn(CH3COO)2 with a methanol solution of the Schiff base in a 1:1:2 molar ratio. However, the isolated green microcrystalline product was identified crystallographically to be the tetra­nuclear CuII Schiff base complex Cu4(H2L)4(H2O)4 (1) of a hetero-cubane type.

The crystal structure of (1) has been reported previously at room temperature by Back et al. (2015 ▸) (refcode IGOSUU). In that report of the structure, no standard uncertainties are recorded for the oxygen atoms of the deprotonated hy­droxy­methyl group, O2, and the water mol­ecule coordin­ating to the metal atom, O6, indicating that they were not refined. The hydrogen atoms of some OH groups and water mol­ecules have also not been positioned accurately. It is clear from the checkCIF output that at least one of the water mol­ecule hydrogen atoms, H6B, and one OH hydrogen atom, H4, are incorrectly positioned. Since the present structure was determined at a lower temperature, all atoms, including these hydrogen atoms, have been determined more accurately, resulting in improved standard uncertainties in the bond lengths and angles.

Structural commentary

The neutral [Cu4(C12H15NO5)4(H2O)4] mol­ecule of (1) has crystallographic inversion symmetry. The CuII ions are coordinated by the tridentate Schiff base ligands and water mol­ecules, forming a tetra­nuclear Cu4O4 cubane-like configuration. The ligand acts in a chelating–bridging mode via phenoxo-, alkoxo-O and imine-N atoms. The two hy­droxy­methyl groups remain protonated. The coordination about the CuII atom is distorted octa­hedral as a result of a significant Jahn–Teller distortion, the two axial distances Cu1—O2 2.738 (5) Å (to the water mol­ecule) and the bridging bond, Cu1—O11 2.547 (4) Å, being significantly longer than the remainder which lie in the range 1.912 (4)–1.968 (3) Å (Fig. 1 ▸, Table 1 ▸). The trans angles at the metal atom lie in the range 159.30 (12)–171.70 (15)°, while the cis ones vary from 73.02 (12) to 116.70 (16)°. The Cu⋯Cu distances within the Cu4O4 core are 3.1724 (8) and 3.4474 (8) Å.

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. H atoms are not shown.

Table 1

Selected bond lengths ()

Cu1O1	1.912(4)	Cu1O2	2.738(5)
Cu1O11	1.941(4)	Cu1O11i	1.968(3)
Cu1N10	1.953(5)	Cu1O11ii	2.547(4)

Symmetry codes: (i) ; (ii) .

There are intra­molecular O2—H2AO⋯O13 hydrogen bonds between a hydrogen atom of the water mol­ecule and the oxygen atom of one hy­droxy­methyl group. A further intra­molecular hydrogen bond involves the other hy­droxy­methyl group (O12). Bifurcated inter­molecular hydrogen bonds are also present, involving the remaining hydrogen atom of water mol­ecule and the phenolic and methoxyl oxygen atoms. These hydrogen-bond contacts are of weak-to-moderate strength [2.736 (12)–2.892 (7) Å], Table 2 ▸.

Table 2

Hydrogen-bond geometry (, )

DHA	DH	HA	D A	DHA
O12H12O12ii	0.84	2.37	2.736(12)	107
O13H13O2iii	0.84	1.91	2.700(6)	156
O2H2AOO1iv	0.93(5)	1.92(4)	2.791(6)	155(8)
O2H2AOO6iv	0.93(5)	2.23(7)	2.853(7)	124(6)
O2H2BOO13	0.96(5)	1.95(3)	2.892(7)	165(6)

Symmetry codes: (ii) ; (iii) ; (iv) .

The title compound appears to be a new solvatomorph of the blue copper(II) complex with the same ligand, [Cu4(C12H15NO5)4(H2O)]·3.75CH3OH·2H2O (refcode SUGKUC; Tabassum & Usman, 2015 ▸). Monoclinic SUGKUC crystallizes in the P21/n space group and has no crystallographically imposed symmetry. It is also a cubane-type complex but with some of the coordinating water mol­ecules replaced by other solvents. The bond lengths and angles of (1) are comparable to those in the NiII analogue (refcode ZEHGUQ; Guo et al., 2008 ▸) and a CuII complex with a similar ligand (refcode AFIMUY; Dong et al., 2007 ▸). The ligand of the latter does not have the meth­oxy group and the copper atom is five-coordinate, the structure lacking the coordinating water mol­ecule of (1).

Supra­molecular features

Inter­actions between [Cu4(H2 L)4(H2O)4] mol­ecules in the crystal lattice are weak, the closest Cu⋯Cu inter-cluster separation exceeds 8.43 Å. The hydrogen on the hy­droxy­methyl group (O13) is involved in an inter­molecular hydrogen bond to the water mol­ecule on the cluster related by a crystallographic twofold axis (Table 2 ▸), forming a hydrogen-bonded polymer propagating along the b axis (Fig. 2 ▸). No π–π stacking is observed.

Figure 2

Part of the crystal structure with intra- and inter­molecular hydrogen bonds shown as blue dashed lines. C—H hydrogens have been omitted for clarity.

Database survey

In the solid state, the H4 L ligand adopts the keto–amine tautomeric form, with the formal ar­yl–OH H atom relocated to the N atom, and the NH group and phenolic O atom forming a strong intra­molecular N—H⋯O hydrogen bond (Odabaşoğlu et al., 2003 ▸). Crystal structures of about 30 metal complexes of this ligand are found in the Cambridge Database (CSD Version 5.36 with one update; Groom & Allen, 2014 ▸). These comprise five homometallic mononuclear Mn, Ni and Mo complexes, polynuclear Co2, V2, Cu4, Mn4, Ni4, Ln9 and Ln10 assemblies and heterometallic 1s–3d and 3d–4f clusters of 4–20 nuclearity. The ligand mol­ecules exist in either doubly or triply deprotonated forms and adopt a chelating-bridging mode, forming five- and six-membered rings. Obviously, the H4 L ligand favours formation of polynuclear paramagnetic clusters due to the presence of the tripodal alcohol functionality. At the same time, the lack of heterometallic structures with two kinds of 3d metal supported by H4 L is also evident. This perhaps explains the failure of the preparation of a Cu/Zn compound in the present study.

Synthesis and crystallization

2-Hy­droxy-3-meth­oxy-benzaldehyde (0.30 g, 2 mmol), tris(hy­droxy­meth­yl)amino­methane (0.24 g, 2 mmol), NEt3 (0.3 ml, 2 mmol) were added to methanol (20 ml) and stirred magnetically for 30 min. Next copper powder (0.06 g, 1 mmol) and Zn(CH3COO)2 (0.19 g, 1 mmol) were added to the yellow solution and the mixture was heated to 323 K under stirring until total dissolution of the copper powder was observed (1 h). The resulting green solution was filtered and allowed to stand at room temperature. Dark-green rhombic prisms of the title compound were formed in several days. They were collected by filter-suction, washed with dry PrOH and finally dried in vacuo (yield: 59% based on copper).

The IR spectrum of (1) in the range 4000–400 cm−1 shows all the characteristic Schiff base ligand frequencies: ν(OH), ν(CH) and ν(C=N) at 3400, 3066–2840, and 1604 cm−1, respectively. A strong peak at 1628 cm−1 that is due to the bending of H2O mol­ecule provides evidence of the presence of water in (1).

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 3 ▸. Diffraction data were collected at 200 K, rather than the more usual 100 K, due to apparent disordering at lower temperatures. Water mol­ecule hydrogen atoms were refined with geometries restrained to ideal values; the OH hydrogen atoms H12 and H13 were refined using a riding model. 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). Anisotropic displacement parameters were employed for the non-hydrogen atoms.

Table 3

Experimental details

Crystal data
Chemical formula	[Cu4(C12H15NO5)4(H2O)4]
M r	1339.22
Crystal system, space group	Tetragonal, I41/a
Temperature (K)	200
a, c ()	18.7108(3), 15.3800(3)
V (3)	5384.4(2)
Z	4
Radiation type	Mo K
(mm1)	1.65
Crystal size (mm)	0.39 0.23 0.17
Data collection
Diffractometer	Oxford Diffraction Xcalibur
Absorption correction	Analytical (CrysAlis CCD and CrysAlis RED; Agilent, 2013 ▸)
T min, T max	0.687, 0.843
No. of measured, independent and observed [I > 2(I)] reflections	25330, 3247, 2942
R int	0.044
(sin /)max (1)	0.660
Refinement
R[F 2 > 2(F 2)], wR(F 2), S	0.076, 0.195, 1.12
No. of reflections	3247
No. of parameters	188
No. of restraints	4
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
max, min (e 3)	1.58, 0.98

Computer programs: CrysAlis CCD (Agilent, 2013 ▸), SIR92 (Altomare et al., 1994 ▸), SHELXL2014 (Sheldrick, 2015 ▸), DIAMOND (Brandenburg, 1999 ▸) and WinGX (Farrugia, 2012 ▸).

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989015017314/sj5474sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015017314/sj5474Isup2.hkl

Supporting information file. DOI: 10.1107/S2056989015017314/sj5474Isup3.pdf

CCDC reference: 1424781

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

[Cu4(C12H15NO5)4(H2O)4]	Dx = 1.652 Mg m−3
Mr = 1339.22	Mo Kα radiation, λ = 0.71073 Å
Tetragonal, I41/a	Cell parameters from 7964 reflections
Hall symbol: -I 4ad	θ = 2.8–28.9°
a = 18.7108 (3) Å	µ = 1.65 mm−1
c = 15.3800 (3) Å	T = 200 K
V = 5384.4 (2) Å3	Prism, dark green
Z = 4	0.39 × 0.23 × 0.17 mm
F(000) = 2768

Oxford Diffraction Xcalibur diffractometer	3247 independent reflections
Radiation source: Enhance (Mo) X-ray Source	2942 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.044
Detector resolution: 16.0009 pixels mm-1	θmax = 28.0°, θmin = 2.8°
ω scans	h = −23→24
Absorption correction: analytical (CrysAlis CCD and CrysAlis RED; Agilent, 2013)	k = −23→24
Tmin = 0.687, Tmax = 0.843	l = −19→20
25330 measured reflections

Refinement on F2	4 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F2 > 2σ(F2)] = 0.076	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.195	w = 1/[σ2(Fo2) + (0.0811P)2 + 52.6317P] where P = (Fo2 + 2Fc2)/3
S = 1.12	(Δ/σ)max < 0.001
3247 reflections	Δρmax = 1.58 e Å−3
188 parameters	Δρmin = −0.98 e Å−3

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. Diffraction data were collected at 200 K, rather than the more usual 100 K, due to apparent disordering at lower temperatures. Water molecule hydrogen atoms were refined with geometries restrained to ideal values.

	x	y	z	Uiso*/Ueq
Cu1	0.47922 (3)	0.66025 (3)	0.69100 (4)	0.0279 (2)
C1	0.5392 (3)	0.5347 (3)	0.7698 (3)	0.0355 (11)
O1	0.5448 (2)	0.58332 (19)	0.7095 (2)	0.0350 (8)
C2	0.4880 (3)	0.5355 (3)	0.8386 (4)	0.0384 (12)
C3	0.4858 (4)	0.4778 (4)	0.8971 (4)	0.0533 (16)
H3	0.4506	0.4777	0.9416	0.064*
C4	0.5322 (5)	0.4225 (4)	0.8922 (5)	0.063 (2)
H4	0.5285	0.3839	0.9322	0.076*
C5	0.5845 (5)	0.4218 (3)	0.8297 (5)	0.062 (2)
H5	0.6179	0.3836	0.8277	0.075*
C6	0.5887 (4)	0.4770 (3)	0.7690 (4)	0.0531 (16)
O6	0.6377 (4)	0.4824 (3)	0.7043 (4)	0.0781 (18)
C61	0.6974 (6)	0.4339 (5)	0.7031 (7)	0.094 (3)
H61A	0.7184	0.4311	0.7614	0.14*
H61B	0.7334	0.4512	0.6619	0.14*
H61C	0.681	0.3863	0.6852	0.14*
C10	0.4376 (3)	0.5937 (4)	0.8514 (4)	0.0453 (14)
H10	0.4063	0.5904	0.8999	0.054*
N10	0.4318 (2)	0.6488 (3)	0.8033 (3)	0.0416 (11)
C101	0.3781 (4)	0.7071 (4)	0.8247 (4)	0.0492 (15)
C11	0.3629 (3)	0.7439 (3)	0.7393 (4)	0.0384 (12)
H11A	0.3232	0.7186	0.7099	0.046*
H11B	0.3468	0.7933	0.7513	0.046*
O11	0.42189 (18)	0.7465 (2)	0.6827 (2)	0.0322 (7)
C12	0.4105 (5)	0.7622 (4)	0.8871 (5)	0.065 (2)
H12A	0.4533	0.7841	0.8601	0.078*
H12B	0.3753	0.8006	0.8984	0.078*
O12	0.4299 (3)	0.7293 (3)	0.9664 (3)	0.0827 (18)
H12	0.4473	0.76	1.0001	0.124*
C13	0.3123 (4)	0.6764 (4)	0.8649 (4)	0.0551 (17)
H13A	0.3232	0.6592	0.9243	0.066*
H13B	0.2751	0.7139	0.8694	0.066*
O13	0.2862 (3)	0.6191 (3)	0.8141 (4)	0.0724 (16)
H13	0.2492	0.6023	0.8374	0.109*
O2	0.3560 (3)	0.5887 (2)	0.6505 (3)	0.0497 (10)
H2AO	0.341 (4)	0.618 (4)	0.605 (3)	0.075*
H2BO	0.326 (4)	0.601 (4)	0.699 (3)	0.075*

	U11	U22	U33	U12	U13	U23
Cu1	0.0264 (3)	0.0308 (3)	0.0265 (3)	−0.0006 (2)	−0.0008 (2)	0.0045 (2)
C1	0.044 (3)	0.030 (2)	0.033 (3)	−0.003 (2)	−0.013 (2)	0.0002 (19)
O1	0.0390 (19)	0.0342 (18)	0.0317 (17)	0.0055 (15)	0.0023 (15)	0.0060 (14)
C2	0.039 (3)	0.042 (3)	0.034 (3)	−0.010 (2)	−0.008 (2)	0.008 (2)
C3	0.062 (4)	0.051 (4)	0.046 (3)	−0.017 (3)	−0.009 (3)	0.019 (3)
C4	0.094 (6)	0.042 (3)	0.053 (4)	−0.008 (4)	−0.012 (4)	0.015 (3)
C5	0.101 (6)	0.033 (3)	0.052 (4)	0.015 (3)	−0.012 (4)	0.000 (3)
C6	0.082 (5)	0.033 (3)	0.044 (3)	0.014 (3)	−0.004 (3)	−0.004 (2)
O6	0.105 (4)	0.057 (3)	0.073 (3)	0.044 (3)	0.023 (3)	0.012 (3)
C61	0.101 (7)	0.074 (6)	0.106 (8)	0.046 (5)	0.016 (6)	0.006 (5)
C10	0.033 (3)	0.067 (4)	0.036 (3)	0.000 (3)	0.002 (2)	0.019 (3)
N10	0.033 (2)	0.054 (3)	0.038 (2)	0.011 (2)	0.0041 (19)	0.013 (2)
C101	0.055 (4)	0.054 (4)	0.039 (3)	0.020 (3)	0.009 (3)	0.002 (3)
C11	0.039 (3)	0.040 (3)	0.037 (3)	0.006 (2)	0.009 (2)	−0.005 (2)
O11	0.0298 (17)	0.0392 (19)	0.0274 (17)	0.0051 (14)	−0.0015 (13)	0.0032 (14)
C12	0.095 (6)	0.057 (4)	0.042 (4)	0.026 (4)	0.006 (4)	−0.004 (3)
O12	0.126 (5)	0.081 (4)	0.041 (3)	0.019 (4)	−0.006 (3)	−0.003 (3)
C13	0.060 (4)	0.058 (4)	0.047 (3)	0.015 (3)	0.025 (3)	0.003 (3)
O13	0.049 (3)	0.083 (4)	0.085 (4)	0.002 (3)	0.027 (3)	−0.004 (3)
O2	0.060 (3)	0.037 (2)	0.053 (3)	−0.0002 (19)	0.005 (2)	−0.0109 (19)

Cu1—O1	1.912 (4)	C61—H61C	0.98
Cu1—O11	1.941 (4)	C10—N10	1.273 (7)
Cu1—N10	1.953 (5)	C10—H10	0.95
Cu1—O2	2.738 (5)	N10—C101	1.519 (7)
Cu1—O11i	1.968 (3)	C101—C13	1.494 (9)
Cu1—O11ii	2.547 (4)	C101—C11	1.510 (8)
C1—O1	1.303 (6)	C101—C12	1.533 (11)
C1—C6	1.422 (8)	C11—O11	1.407 (6)
C1—C2	1.427 (8)	C11—H11A	0.99
C2—C3	1.406 (8)	C11—H11B	0.99
C2—C10	1.455 (9)	O11—Cu1iii	1.968 (3)
C3—C4	1.353 (11)	C12—O12	1.414 (9)
C3—H3	0.95	C12—H12A	0.99
C4—C5	1.373 (11)	C12—H12B	0.99
C4—H4	0.95	O12—H12	0.84
C5—C6	1.394 (9)	C13—O13	1.413 (9)
C5—H5	0.95	C13—H13A	0.99
C6—O6	1.356 (9)	C13—H13B	0.99
O6—C61	1.439 (9)	O13—H13	0.84
C61—H61A	0.98	O2—H2AO	0.93 (5)
C61—H61B	0.98	O2—H2BO	0.96 (5)
O1—Cu1—O11	171.70 (15)	H61A—C61—H61B	109.5
O1—Cu1—N10	94.41 (17)	O6—C61—H61C	109.5
O11—Cu1—N10	84.16 (17)	H61A—C61—H61C	109.5
N10—Cu1—O2	76.41 (16)	H61B—C61—H61C	109.5
O11—Cu1—O2	85.77 (14)	N10—C10—C2	125.6 (5)
O1—Cu1—O2	101.89 (14)	N10—C10—H10	117.2
O1—Cu1—O11i	94.54 (15)	C2—C10—H10	117.2
O11—Cu1—O11i	88.41 (16)	C10—N10—C101	120.8 (5)
N10—Cu1—O11i	166.34 (18)	C10—N10—Cu1	124.3 (4)
O2—Cu1—O11ii	159.30 (12)	C101—N10—Cu1	114.4 (3)
O1—Cu1—O11i	94.54 (15)	C13—C101—C11	112.3 (6)
O11—Cu1—O11i	88.44 (16)	C13—C101—N10	111.0 (5)
O1—Cu1—O11ii	93.29 (13)	C11—C101—N10	105.3 (4)
N10—Cu1—O11ii	116.70 (16)	C13—C101—C12	109.1 (6)
O11—Cu1—O11ii	80.15 (13)	C11—C101—C12	108.2 (6)
O11i—Cu1—O11ii	73.02 (12)	N10—C101—C12	110.9 (5)
O2—Cu1—O11i	91.64 (15)	O11—C11—C101	113.9 (5)
O2—Cu1—O11ii	159.32 (12)	O11—C11—H11A	108.8
O1—C1—C6	118.1 (5)	C101—C11—H11A	108.8
O1—C1—C2	125.1 (5)	O11—C11—H11B	108.8
C6—C1—C2	116.8 (5)	C101—C11—H11B	108.8
C1—O1—Cu1	125.5 (3)	H11A—C11—H11B	107.7
C3—C2—C1	119.2 (6)	C11—O11—Cu1	111.4 (3)
C3—C2—C10	118.0 (6)	C11—O11—Cu1iii	121.3 (3)
C1—C2—C10	122.9 (5)	Cu1—O11—Cu1iii	108.47 (17)
C4—C3—C2	122.2 (7)	O12—C12—C101	110.4 (6)
C4—C3—H3	118.9	O12—C12—H12A	109.6
C2—C3—H3	118.9	C101—C12—H12A	109.6
C3—C4—C5	120.2 (6)	O12—C12—H12B	109.6
C3—C4—H4	119.9	C101—C12—H12B	109.6
C5—C4—H4	119.9	H12A—C12—H12B	108.1
C4—C5—C6	120.2 (7)	C12—O12—H12	109.5
C4—C5—H5	119.9	O13—C13—C101	110.4 (5)
C6—C5—H5	119.9	O13—C13—H13A	109.6
O6—C6—C5	125.7 (6)	C101—C13—H13A	109.6
O6—C6—C1	113.0 (5)	O13—C13—H13B	109.6
C5—C6—C1	121.3 (7)	C101—C13—H13B	109.6
C6—O6—C61	119.2 (6)	H13A—C13—H13B	108.1
O6—C61—H61A	109.5	C13—O13—H13	109.5
O6—C61—H61B	109.5	H2AO—O2—H2BO	105 (3)

D—H···A	D—H	H···A	D···A	D—H···A
O12—H12···O12ii	0.84	2.37	2.736 (12)	107
O13—H13···O2iv	0.84	1.91	2.700 (6)	156
O2—H2AO···O1iii	0.93 (5)	1.92 (4)	2.791 (6)	155 (8)
O2—H2AO···O6iii	0.93 (5)	2.23 (7)	2.853 (7)	124 (6)
O2—H2BO···O13	0.96 (5)	1.95 (3)	2.892 (7)	165 (6)