Poly[di-μ₂-methano­lato-di-μ₂-tetra­methoxy­borato-disodium(I)]

In the polymeric title compound, [Na₂(C₄H₁₂BO₄)₂(CH₄O)₂]_n, the two independent sodium cations are bound by five O atoms. All the O atoms of one tetra­methoxy­borate anion bind cations, forming a tetra­meric cluster around a tetra­gonal inversion centre [Na—O = 2.2777 (18)–2.3907 (16) Å]. Two methanol O atoms bridge the two Na atoms [Na—O = 2.3590 (15)–2.4088 (18) Å] and provide the hydrogen-bonding H atoms. The second tetra­methoxy­borate anion provides two O atoms to one Na atom [mean Na—O = 2.31 (2) Å] and two O atoms as donors for crosslinking hydrogen bonds to adjacent tetra­mers, which complete the three-dimensional packing. The crystal was a treated as a racemic twin.

S1. Comment

This study is part of a programme aimed at investigating boron diolates and alkoxides, particularly those containing sodium cations (Gainsford & Kemmitt, 2004, 2005). Although borates form a range of diolate complexes (Bachelier & Verchere, 1995; Springsteen & Wang, 2002), structural data are sparse. Tetramethoxyborate salts with organic cations, such as piperidinium tetramethoxyborate [Cambridge Structural Database (CSD; Allen, 2002) refcode BAZFAJ (Alcock et al., 1982)] and others [CSD refcodes RAVPAF (Clegg et al., 1997) and NEMYOT (Kuhn et al., 2001)], have been reported. There are some defined mixed-metal complexes [e.g. HOSXES; neodymium(III)-sodium; Gajadhar-Plummer et al., 1999] but only one reported sodium salt of this borate, which also contains bound water (TMXBNA; Heller & Horbat, 1977). The NMR spectrum in d₈-THF showed the presence of both methoxide and methanol groups, spurring our investigation, and we were also interested to confirm the absence of water.

The basic polymeric fragment of the title compound (I), with asymmetric unit formula [Na₂(C₄H₁₂BO₄)₂(CH₃OH)₂]₄ (Fig. 1), crystallized in a racemically twinned crystal. No enantiomeric resolution was expected from the synthesis nor able to be established by anomalous dispersion effects.

The use of the word `bound' here indicates atoms that are within either covalent or ionic attractive distances of each other. Both sodium cations are five-coordinate in a highly distorted square-pyramidal arrangement; the basal atoms deviate from the square plane by 0.1020 (6)–0.1792 (8) Å, with the Na atoms 0.80 (Na1) and 0.57 Å (Na2) above and towards the pyramidal O atoms (O9 and O10, respectively). Both distorted trigonal-bipyramidal [EDUNUM (Onada et al., 2002) and GOLSIJ (Hauptmann et al., 1999)] and square-pyramidal (OGEBEH; Fukin et al., 2002) environments around oxygen-bridged sodium cations have been observed previously.

Each Na atom is bound by two shared methanol O-atom bridges (O3 and O4; [Na—O = 2.3590 (15)–2.4088 (18) Å] and two O atoms from adjacent tetramethoxyborate groups [O5 and O6, and O1 and O2, respectively; 2.2994 (14)–2.3159 (15) Å] making up the square basal planes. A wider range of Na—O(methanol) distances was observed in TMXBNA (2.358–2.611 Å), with similar Na—O(tetramethoxyborate) distances of 2.282 and 2.386 Å. The fifth coordination position in (I) is provided to each Na atom by two O atoms from one fourfold roto-inversion symmetry-related tetramethoxyborate group (atoms O9 and O10, respectively). This arrangement results in the tetrameric unit with fourfold inversion symmetry shown in Fig. 1. Rather than bind to sodium cations, the two remaining tetramethoxyborate O atoms (O7 and O8) on atom B1 provide the acceptor sites for two strong hydrogen bonds that link adjacent clusters into a complete three-dimensional network (Table 2 and Fig. 2). This structural binding has some similarity to the TMXBNA structure, in which one of the two tetramethoxyborate groups is bound through two O atoms to one of the sodium atoms; however, in that case, the second (charged) tetramethoxyborate group is only retained in the lattice by hydrogen bonds to the water and bound methanol molecules.

Our interest in these structures concerns the lengthening or otherwise of the B—O bonds in relation to this and other appended alkyl groups. In (I), the longest B—O—C bonds involve the non-bridging `free' O atoms O8 and O7, bound to B1 with mean B—O and O—C distances of 1.474 (7) and 1.418 (3) Å compared with averages of 1.464 (6) and 1.409 (2) Å for the other six bond sets. These differences are statistically insignificant although they suggest that intermolecular hydrogen bonding may influence the covalent binding at the B atom. Although cell packing interactions (Table 2) can be important, steric requirements may play the dominant role. Indeed, the Na—O(methanol) bridging distances (2.359–2.409 Å) are shorter than those found in catena-[hexakis(µ<sub>2</sub>-methanolato)disodium ditelluride] (Thiele et al., 1996) 2.432 Å and a bis(trimethanolsodium) salt (Brnicevic et al., 1991) 2.45 (3) Å. Examination of previous structures of organic salts (with `free' O atoms; BAZFAJ, NEMYOT and RAVPAF) shows that these have a wide range of B—O and C—O distances, while in the comparable sodium salt (TMXBNA) the ranges are 1.461–1.482 and 1.426–1.440 Å, respectively. Ranges in other metal salts [HOSXES and the lithium complex KAJPOA (Al-Juaid et al., 1989)] are similar, with slightly lower minimum values (1.440–1.481 and 1.418–1.443 Å). We conclude that no definitive conclusions can be made about variations in bond strengths on the basis of current studies.

The B—O—C angles range from 114.21 (18) to 117.37 (15)°, again consistent with previous observations (114.4–120.5°) in the above-mentioned studies. Finally, it is noted that in the `closest relative' structure (TMXBNA) the two Na atoms are 5- and 6-coordinate, the latter coordination involving bridging water and methanol molecules only. The one-dimensional (short) chains in TMXBNA involve a tetramethoxyborate `capped' 4-Na⁺ unit built with O-atom bridges; however, these O atoms are provided by the three water and two methanol molecules, rather than by the tetramethoxyborate molecules.

S2. Experimental

The title compound was prepared by refluxing a methanol (75 ml) solution of sodium metaborate (0.1 mol, 13.8 g) for 4 h, running the condensate through a bed of molecular sieves to remove water. The crude product was obtained on removal of the solvent. X-ray quality crystals were obtained by recrystallizing the product from a methanol/toluene mixture.

S3. Refinement

Friedel pairs were merged after a full data set refinement gave a Flack (1983) parameter of 0.6 (2). The H atoms on methyl C atoms C3,C4,C5,C6,C8 and C9 were modelled as disordered over two sites rotated by 60°; the major two site occupancies were 0.73 (3), 0.78 (3), 0.79 (3), 0.52 (3), 0.78 (3) and 0.90 (3), respectively. All methyl H atoms, except those on atom C10, were constrained to their expected geometries (C—H = 0.98 Å). The hydroxy (H3O and H4O) H atoms and H atoms on atom C10 were freely refined. All H atoms were refined with U_iso(H) values of 1.2 times U_eq of their carrier atoms.

Computing details

Data collection: SMART (Bruker, 2001); cell refinement: SMART; data reduction: SAINT (Bruker, 2001) and SADABS (Sheldrick, 1996); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003).

Figures

Fig. 1. A PLATON (Spek, 2003) view of the polymeric unit of (I), with 50% probabilility displacement ellipsoids. Labels of asymmetric unit atoms, all Na atoms, and atoms O9C and O10C are shown. Atoms labelled with the suffixes A, B and C are at symmetry positions (y, 1 − x, 1 − z), (1 − x, 1 − y, −z) and (1 − y, x, 1 − z).

Fig. 2. A PLATON view (Spek, 2003) of (I), showing two representatives of the hydrogen bonds that link the polymeric units (shown in Fig. 1) into a three-dimensional network. All H atoms, except H3O and H4O, have been excluded for clarity. Atoms O7A and O8A are at the symmetry position (y − 1/2, 3/2 − x, 3/2 − z). (In the online version of the journal Na atoms are shown in green, O in red, B in yellow, C in black and H in white.)

Poly[disodium(I)-di-µ₂-methanolato-di-µ₂-tetramethoxyborato]

Crystal data

[Na2(C4H12BO4)2(CH4O)2]	Dx = 1.178 Mg m^−3
Mr = 379.96	Mo Kα radiation, λ = 0.71073 Å
Tetragonal, I4	Cell parameters from 4302 reflections
Hall symbol: I -4	θ = 2.5–26.3°
a = 22.0496 (19) Å	µ = 0.13 mm^−1
c = 8.8155 (15) Å	T = 98 K
V = 4286.0 (9) Å^3	Block, colourless
Z = 8	0.65 × 0.54 × 0.50 mm
F(000) = 1632

Data collection

Bruker SMART CCD area-detector diffractometer	2330 independent reflections
Radiation source: fine-focus sealed tube	2070 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.020
Detector resolution: 8.192 pixels mm^-1	θmax = 26.3°, θmin = 2.5°
ϕ and ω scans	h = −27→27
Absorption correction: multi-scan (Blessing, 1995)	k = −4→27
Tmin = 0.787, Tmax = 0.936	l = −6→10
6990 measured reflections

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)] = 0.027	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.066	w = 1/[σ^2(Fo^2) + (0.0368P)^2 + 0.8467P] where P = (Fo^2 + 2Fc^2)/3
S = 1.04	(Δ/σ)max = 0.001
2330 reflections	Δρmax = 0.11 e Å^−3
238 parameters	Δρmin = −0.13 e Å^−3
0 restraints	Absolute structure: Flack (1983) parameter indeterminate (racemic twin)
Primary atom site location: structure-invariant direct methods

Special details

Experimental. Crystal decay was monitored by repeating the initial 10 frames at the end of the data collection and analyzing duplicate reflections. The standard 0.8 mm diameter collimator was used.

The large ratio of maximum/minimum transmision calculated by the analytical procedure of SADABS (1996) is thought to relate to the alignment of the major and minor twin domains in the crystal coupled with sinusoidal variations in beam intensity.

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	Occ. (<1)
Na1	0.56793 (3)	0.77141 (3)	0.62989 (10)	0.02235 (19)
Na2	0.45362 (3)	0.68642 (3)	0.58714 (10)	0.02525 (19)
O1	0.60899 (6)	0.86570 (6)	0.58666 (18)	0.0254 (3)
O2	0.64129 (6)	0.81184 (6)	0.79049 (18)	0.0249 (3)
O3	0.47290 (6)	0.78641 (6)	0.50516 (18)	0.0223 (3)
H3O	0.4578 (10)	0.8120 (11)	0.555 (3)	0.027*
O4	0.49341 (7)	0.73866 (6)	0.80550 (19)	0.0271 (3)
H4O	0.4651 (11)	0.7590 (11)	0.821 (3)	0.032*
O5	0.36838 (6)	0.66410 (6)	0.44731 (19)	0.0304 (4)
O6	0.39101 (6)	0.60603 (6)	0.65094 (19)	0.0313 (4)
O7	0.71095 (6)	0.88711 (6)	0.68295 (18)	0.0270 (3)
O8	0.63015 (6)	0.92175 (6)	0.82079 (18)	0.0254 (3)
O9	0.60607 (7)	0.71476 (6)	0.43605 (19)	0.0318 (4)
O10	0.55441 (7)	0.64661 (7)	0.5789 (2)	0.0380 (4)
B1	0.64737 (10)	0.87160 (10)	0.7198 (3)	0.0240 (5)
B2	0.34938 (11)	0.60771 (11)	0.5209 (3)	0.0285 (5)
C1	0.60466 (10)	0.91633 (9)	0.4893 (3)	0.0323 (5)
H1A	0.5786	0.9471	0.5359	0.039*
H1B	0.5872	0.9037	0.3921	0.039*
H1C	0.6452	0.9333	0.4724	0.039*
C2	0.67155 (10)	0.80314 (10)	0.9298 (3)	0.0314 (5)
H2A	0.7116	0.8224	0.9255	0.038*
H2B	0.6763	0.7596	0.9488	0.038*
H2C	0.6477	0.8214	1.0118	0.038*
C3	0.47077 (12)	0.80381 (11)	0.3508 (3)	0.0379 (6)
H3A	0.4929	0.7741	0.2894	0.045*	0.73 (3)
H3B	0.4895	0.8438	0.3389	0.045*	0.73 (3)
H3C	0.4284	0.8056	0.3172	0.045*	0.73 (3)
H3D	0.4477	0.8416	0.3410	0.045*	0.27 (3)
H3E	0.4510	0.7718	0.2915	0.045*	0.27 (3)
H3F	0.5121	0.8101	0.3132	0.045*	0.27 (3)
C4	0.51337 (12)	0.71785 (14)	0.9487 (3)	0.0458 (7)
H4A	0.5484	0.6911	0.9352	0.055*	0.78 (3)
H4B	0.4805	0.6954	0.9984	0.055*	0.78 (3)
H4C	0.5250	0.7526	1.0116	0.055*	0.78 (3)
H4D	0.4875	0.7350	1.0283	0.055*	0.22 (3)
H4E	0.5554	0.7307	0.9651	0.055*	0.22 (3)
H4F	0.5110	0.6735	0.9519	0.055*	0.22 (3)
C5	0.33569 (11)	0.68273 (11)	0.3179 (3)	0.0391 (6)
H5A	0.3526	0.7209	0.2797	0.047*	0.79 (3)
H5B	0.2930	0.6888	0.3450	0.047*	0.79 (3)
H5C	0.3387	0.6515	0.2392	0.047*	0.79 (3)
H5D	0.3036	0.6532	0.2962	0.047*	0.21 (3)
H5E	0.3632	0.6853	0.2309	0.047*	0.21 (3)
H5F	0.3175	0.7226	0.3367	0.047*	0.21 (3)
C6	0.38375 (12)	0.55848 (11)	0.7560 (3)	0.0420 (6)
H6A	0.4140	0.5625	0.8367	0.050*	0.48 (3)
H6B	0.3892	0.5195	0.7043	0.050*	0.48 (3)
H6C	0.3430	0.5603	0.8000	0.050*	0.48 (3)
H6D	0.3501	0.5324	0.7239	0.050*	0.52 (3)
H6E	0.3749	0.5754	0.8564	0.050*	0.52 (3)
H6F	0.4212	0.5345	0.7607	0.050*	0.52 (3)
C7	0.74092 (10)	0.84758 (10)	0.5809 (3)	0.0352 (5)
H7A	0.7398	0.8061	0.6209	0.042*
H7B	0.7832	0.8605	0.5689	0.042*
H7C	0.7205	0.8488	0.4822	0.042*
C8	0.56980 (9)	0.91984 (10)	0.8767 (3)	0.0303 (5)
H8A	0.5627	0.9548	0.9429	0.036*	0.78 (3)
H8B	0.5637	0.8824	0.9345	0.036*	0.78 (3)
H8C	0.5413	0.9210	0.7914	0.036*	0.78 (3)
H8D	0.5491	0.8840	0.8363	0.036*	0.22 (3)
H8E	0.5481	0.9565	0.8447	0.036*	0.22 (3)
H8F	0.5705	0.9178	0.9878	0.036*	0.22 (3)
C9	0.64930 (12)	0.73478 (11)	0.3300 (3)	0.0424 (6)
H9A	0.6901	0.7258	0.3678	0.051*	0.90 (3)
H9B	0.6450	0.7786	0.3152	0.051*	0.90 (3)
H9C	0.6429	0.7139	0.2332	0.051*	0.90 (3)
H9D	0.6286	0.7531	0.2430	0.051*	0.10 (3)
H9E	0.6737	0.7003	0.2957	0.051*	0.10 (3)
H9F	0.6758	0.7650	0.3776	0.051*	0.10 (3)
C10	0.54892 (13)	0.59093 (14)	0.6561 (4)	0.0499 (7)
H10A	0.5813 (14)	0.5826 (13)	0.728 (4)	0.060*
H10B	0.5165 (14)	0.5933 (13)	0.721 (4)	0.060*
H10C	0.5472 (13)	0.5575 (14)	0.583 (4)	0.060*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Na1	0.0205 (4)	0.0206 (4)	0.0259 (5)	−0.0025 (3)	−0.0003 (3)	−0.0017 (3)
Na2	0.0229 (4)	0.0224 (4)	0.0305 (5)	−0.0044 (3)	−0.0057 (4)	0.0035 (4)
O1	0.0304 (7)	0.0205 (6)	0.0252 (9)	−0.0062 (5)	−0.0033 (7)	0.0018 (6)
O2	0.0264 (7)	0.0236 (7)	0.0248 (9)	−0.0023 (5)	−0.0042 (7)	0.0013 (6)
O3	0.0272 (7)	0.0195 (7)	0.0204 (8)	0.0044 (5)	0.0008 (6)	−0.0009 (6)
O4	0.0267 (7)	0.0319 (8)	0.0225 (9)	0.0091 (6)	0.0020 (7)	0.0031 (7)
O5	0.0325 (8)	0.0302 (7)	0.0284 (10)	−0.0126 (6)	−0.0112 (7)	0.0065 (7)
O6	0.0329 (8)	0.0305 (7)	0.0305 (10)	−0.0107 (6)	−0.0057 (7)	0.0100 (7)
O7	0.0221 (7)	0.0258 (7)	0.0332 (10)	−0.0038 (5)	0.0053 (7)	−0.0052 (7)
O8	0.0182 (6)	0.0265 (7)	0.0314 (9)	−0.0036 (5)	0.0031 (6)	−0.0070 (6)
O9	0.0359 (8)	0.0301 (7)	0.0294 (9)	0.0106 (6)	0.0038 (7)	−0.0009 (7)
O10	0.0344 (8)	0.0424 (9)	0.0371 (10)	0.0179 (7)	0.0069 (8)	0.0136 (8)
B1	0.0218 (10)	0.0234 (10)	0.0267 (14)	−0.0057 (8)	0.0008 (10)	−0.0011 (10)
B2	0.0311 (12)	0.0275 (11)	0.0268 (15)	−0.0121 (9)	−0.0027 (11)	0.0018 (11)
C1	0.0400 (12)	0.0274 (10)	0.0296 (14)	−0.0058 (9)	−0.0041 (11)	0.0049 (10)
C2	0.0324 (11)	0.0338 (11)	0.0281 (14)	−0.0005 (8)	−0.0057 (10)	0.0046 (10)
C3	0.0518 (14)	0.0374 (12)	0.0244 (14)	−0.0018 (10)	−0.0002 (12)	0.0029 (11)
C4	0.0426 (14)	0.0653 (17)	0.0294 (16)	0.0147 (12)	−0.0007 (12)	0.0144 (13)
C5	0.0391 (12)	0.0434 (13)	0.0349 (15)	−0.0134 (10)	−0.0137 (12)	0.0115 (12)
C6	0.0512 (14)	0.0370 (12)	0.0379 (17)	−0.0078 (10)	0.0035 (12)	0.0130 (12)
C7	0.0306 (11)	0.0355 (11)	0.0396 (15)	0.0010 (9)	0.0106 (11)	−0.0051 (11)
C8	0.0208 (9)	0.0338 (11)	0.0364 (14)	−0.0009 (8)	0.0029 (10)	−0.0044 (11)
C9	0.0493 (14)	0.0430 (13)	0.0350 (16)	0.0036 (11)	0.0089 (13)	0.0011 (12)
C10	0.0403 (14)	0.0583 (17)	0.051 (2)	0.0121 (12)	0.0075 (14)	0.0255 (15)

Geometric parameters (Å, º)

Na1—O9	2.2777 (18)	C3—H3B	0.9800
Na1—O1	2.2994 (14)	C3—H3C	0.9800
Na1—O2	2.3272 (15)	C3—H3D	0.9800
Na1—O4	2.3701 (17)	C3—H3E	0.9800
Na1—O3	2.3893 (16)	C3—H3F	0.9800
Na1—H3O	2.67 (2)	C4—H4A	0.9800
Na2—O5	2.3009 (16)	C4—H4B	0.9800
Na2—O6	2.3159 (15)	C4—H4C	0.9800
Na2—O3	2.3590 (15)	C4—H4D	0.9800
Na2—O10	2.3907 (16)	C4—H4E	0.9800
Na2—O4	2.4088 (18)	C4—H4F	0.9800
Na2—H4O	2.62 (3)	C5—H5A	0.9800
O1—C1	1.411 (3)	C5—H5B	0.9800
O1—B1	1.453 (3)	C5—H5C	0.9800
O2—C2	1.410 (3)	C5—H5D	0.9800
O2—B1	1.464 (3)	C5—H5E	0.9800
O3—C3	1.414 (3)	C5—H5F	0.9800
O3—H3O	0.79 (2)	C6—H6A	0.9800
O4—C4	1.413 (3)	C6—H6B	0.9800
O4—H4O	0.78 (2)	C6—H6C	0.9800
O5—C5	1.411 (3)	C6—H6D	0.9800
O5—B2	1.464 (3)	C6—H6E	0.9800
O6—C6	1.408 (3)	C6—H6F	0.9800
O6—B2	1.469 (3)	C7—H7A	0.9800
O7—C7	1.416 (3)	C7—H7B	0.9800
O7—B1	1.479 (2)	C7—H7C	0.9800
O8—C8	1.420 (2)	C8—H8A	0.9800
O8—B1	1.469 (3)	C8—H8B	0.9800
O9—C9	1.406 (3)	C8—H8C	0.9800
O9—B2^i	1.465 (3)	C8—H8D	0.9800
O10—C10	1.409 (3)	C8—H8E	0.9800
O10—B2^i	1.471 (3)	C8—H8F	0.9800
B2—O9^ii	1.465 (3)	C9—H9A	0.9800
B2—O10^ii	1.471 (3)	C9—H9B	0.9800
B2—Na1^ii	3.103 (2)	C9—H9C	0.9800
C1—H1A	0.9800	C9—H9D	0.9800
C1—H1B	0.9800	C9—H9E	0.9800
C1—H1C	0.9800	C9—H9F	0.9800
C2—H2A	0.9800	C10—H10A	0.97 (3)
C2—H2B	0.9800	C10—H10B	0.92 (3)
C2—H2C	0.9800	C10—H10C	0.98 (3)
C3—H3A	0.9800
O9—Na1—O1	103.07 (6)	O3—C3—H3C	109.5
O9—Na1—O2	114.19 (6)	H3A—C3—H3C	109.5
O1—Na1—O2	58.72 (5)	H3B—C3—H3C	109.5
O9—Na1—O4	125.37 (6)	O3—C3—H3D	109.5
O1—Na1—O4	131.05 (6)	O3—C3—H3E	109.5
O2—Na1—O4	101.61 (6)	H3D—C3—H3E	109.5
O9—Na1—O3	93.12 (6)	O3—C3—H3F	109.5
O1—Na1—O3	98.27 (6)	H3D—C3—H3F	109.5
O2—Na1—O3	146.78 (6)	H3E—C3—H3F	109.5
O4—Na1—O3	74.63 (6)	O4—C4—H4A	109.5
O5—Na2—O6	58.63 (6)	O4—C4—H4B	109.5
O5—Na2—O3	100.54 (6)	H4A—C4—H4B	109.5
O6—Na2—O3	153.79 (6)	O4—C4—H4C	109.5
O5—Na2—O10	131.65 (7)	H4A—C4—H4C	109.5
O6—Na2—O10	106.29 (6)	H4B—C4—H4C	109.5
O3—Na2—O10	99.57 (6)	O4—C4—H4D	109.5
O5—Na2—O4	145.89 (7)	H4A—C4—H4D	141.1
O6—Na2—O4	112.90 (7)	O4—C4—H4E	109.5
O3—Na2—O4	74.47 (6)	H4D—C4—H4E	109.5
O10—Na2—O4	82.02 (6)	O4—C4—H4F	109.5
C1—O1—B1	117.37 (15)	H4D—C4—H4F	109.5
C1—O1—Na1	142.12 (13)	H4E—C4—H4F	109.5
B1—O1—Na1	100.16 (11)	O5—C5—H5A	109.5
C2—O2—B1	116.72 (16)	O5—C5—H5B	109.5
C2—O2—Na1	143.74 (12)	H5A—C5—H5B	109.5
B1—O2—Na1	98.60 (12)	O5—C5—H5C	109.5
C3—O3—Na2	122.84 (13)	H5A—C5—H5C	109.5
C3—O3—Na1	120.62 (14)	H5B—C5—H5C	109.5
Na2—O3—Na1	83.55 (5)	O5—C5—H5D	109.5
C3—O3—H3O	109.3 (18)	O5—C5—H5E	109.5
Na2—O3—H3O	114.8 (17)	H5D—C5—H5E	109.5
Na1—O3—H3O	102.2 (17)	O5—C5—H5F	109.5
C4—O4—Na1	117.80 (14)	H5D—C5—H5F	109.5
C4—O4—Na2	132.21 (16)	H5E—C5—H5F	109.5
Na1—O4—Na2	82.89 (6)	O6—C6—H6A	109.5
C4—O4—H4O	107 (2)	O6—C6—H6B	109.5
Na1—O4—H4O	119.4 (19)	H6A—C6—H6B	109.5
Na2—O4—H4O	96.8 (19)	O6—C6—H6C	109.5
C5—O5—B2	117.35 (16)	H6A—C6—H6C	109.5
C5—O5—Na2	142.04 (13)	H6B—C6—H6C	109.5
B2—O5—Na2	100.26 (12)	O6—C6—H6D	109.5
C6—O6—B2	117.44 (16)	O6—C6—H6E	109.5
C6—O6—Na2	142.88 (14)	H6D—C6—H6E	109.5
B2—O6—Na2	99.42 (12)	O6—C6—H6F	109.5
C7—O7—B1	116.07 (16)	H6D—C6—H6F	109.5
C8—O8—B1	115.48 (14)	H6E—C6—H6F	109.5
C9—O9—B2^i	117.31 (17)	O7—C7—H7A	109.5
C9—O9—Na1	125.22 (13)	O7—C7—H7B	109.5
B2^i—O9—Na1	110.13 (14)	H7A—C7—H7B	109.5
C10—O10—B2^i	114.21 (18)	O7—C7—H7C	109.5
C10—O10—Na2	103.03 (14)	H7A—C7—H7C	109.5
B2^i—O10—Na2	137.64 (14)	H7B—C7—H7C	109.5
C10—O10—Na1	141.90 (19)	O8—C8—H8A	109.5
B2^i—O10—Na1	87.24 (12)	O8—C8—H8B	109.5
Na2—O10—Na1	74.55 (5)	H8A—C8—H8B	109.5
O1—B1—O2	102.12 (15)	O8—C8—H8C	109.5
O1—B1—O8	113.98 (17)	H8A—C8—H8C	109.5
O2—B1—O8	113.33 (19)	H8B—C8—H8C	109.5
O1—B1—O7	113.28 (19)	O8—C8—H8D	109.5
O2—B1—O7	112.85 (17)	O8—C8—H8E	109.5
O8—B1—O7	101.77 (14)	H8D—C8—H8E	109.5
O5—B2—O9^ii	114.34 (19)	O8—C8—H8F	109.5
O5—B2—O6	100.85 (16)	H8D—C8—H8F	109.5
O9^ii—B2—O6	113.6 (2)	H8E—C8—H8F	109.5
O5—B2—O10^ii	113.4 (2)	O9—C9—H9A	109.5
O9^ii—B2—O10^ii	101.16 (16)	O9—C9—H9B	109.5
O6—B2—O10^ii	114.15 (19)	H9A—C9—H9B	109.5
O1—C1—H1A	109.5	O9—C9—H9C	109.5
O1—C1—H1B	109.5	H9A—C9—H9C	109.5
H1A—C1—H1B	109.5	H9B—C9—H9C	109.5
O1—C1—H1C	109.5	O9—C9—H9D	109.5
H1A—C1—H1C	109.5	O9—C9—H9E	109.5
H1B—C1—H1C	109.5	H9D—C9—H9E	109.5
O2—C2—H2A	109.5	O9—C9—H9F	109.5
O2—C2—H2B	109.5	H9D—C9—H9F	109.5
H2A—C2—H2B	109.5	H9E—C9—H9F	109.5
O2—C2—H2C	109.5	O10—C10—H10A	114.7 (18)
H2A—C2—H2C	109.5	O10—C10—H10B	108.5 (19)
H2B—C2—H2C	109.5	H10A—C10—H10B	100 (3)
O3—C3—H3A	109.5	O10—C10—H10C	109.8 (19)
O3—C3—H3B	109.5	H10A—C10—H10C	109 (2)
H3A—C3—H3B	109.5	H10B—C10—H10C	115 (3)
O9—Na1—O1—C1	72.9 (2)	O3—Na1—O10—B2^i	114.60 (13)
O2—Na1—O1—C1	−176.5 (2)	O9—Na1—O10—Na2	−122.12 (8)
O4—Na1—O1—C1	−99.0 (2)	O1—Na1—O10—Na2	−132.34 (13)
O3—Na1—O1—C1	−22.3 (2)	O2—Na1—O10—Na2	141.68 (6)
O9—Na1—O1—B1	−114.68 (12)	O4—Na1—O10—Na2	47.80 (5)
O2—Na1—O1—B1	−4.12 (11)	O3—Na1—O10—Na2	−26.74 (6)
O4—Na1—O1—B1	73.36 (14)	C1—O1—B1—O2	−179.51 (17)
O3—Na1—O1—B1	150.14 (12)	Na1—O1—B1—O2	5.73 (16)
O9—Na1—O2—C2	−97.8 (2)	C1—O1—B1—O8	57.9 (2)
O1—Na1—O2—C2	171.2 (2)	Na1—O1—B1—O8	−116.87 (15)
O4—Na1—O2—C2	39.9 (2)	C1—O1—B1—O7	−57.9 (2)
O3—Na1—O2—C2	119.5 (2)	Na1—O1—B1—O7	127.38 (14)
O9—Na1—O2—B1	95.05 (12)	C1—O1—B1—Na1	174.8 (2)
O1—Na1—O2—B1	4.07 (11)	C2—O2—B1—O1	−177.15 (16)
O4—Na1—O2—B1	−127.20 (12)	Na1—O2—B1—O1	−5.63 (15)
O3—Na1—O2—B1	−47.59 (17)	C2—O2—B1—O8	−54.1 (2)
O5—Na2—O3—C3	−45.04 (17)	Na1—O2—B1—O8	117.41 (14)
O6—Na2—O3—C3	−79.9 (2)	C2—O2—B1—O7	60.9 (2)
O10—Na2—O3—C3	90.77 (17)	Na1—O2—B1—O7	−127.58 (16)
O4—Na2—O3—C3	169.64 (17)	C2—O2—B1—Na1	−171.51 (18)
O5—Na2—O3—Na1	−167.53 (6)	C8—O8—B1—O1	57.5 (2)
O6—Na2—O3—Na1	157.62 (15)	C8—O8—B1—O2	−58.7 (2)
O10—Na2—O3—Na1	−31.72 (7)	C8—O8—B1—O7	179.84 (18)
O4—Na2—O3—Na1	47.15 (5)	C8—O8—B1—Na1	−0.1 (3)
O9—Na1—O3—C3	−46.79 (15)	C7—O7—B1—O1	−55.2 (2)
O1—Na1—O3—C3	56.91 (15)	C7—O7—B1—O2	60.2 (3)
O2—Na1—O3—C3	99.55 (18)	C7—O7—B1—O8	−178.04 (18)
O4—Na1—O3—C3	−172.68 (15)	C7—O7—B1—Na1	1.8 (3)
O9—Na1—O3—Na2	77.78 (6)	O9—Na1—B1—O1	74.56 (13)
O1—Na1—O3—Na2	−178.53 (6)	O2—Na1—B1—O1	172.9 (2)
O2—Na1—O3—Na2	−135.89 (10)	O4—Na1—B1—O1	−125.17 (12)
O4—Na1—O3—Na2	−48.12 (5)	O3—Na1—B1—O1	−35.97 (14)
O9—Na1—O4—C4	98.53 (18)	O9—Na1—B1—O2	−98.31 (12)
O1—Na1—O4—C4	−91.09 (18)	O1—Na1—B1—O2	−172.9 (2)
O2—Na1—O4—C4	−32.69 (18)	O4—Na1—B1—O2	61.97 (13)
O3—Na1—O4—C4	−178.71 (17)	O3—Na1—B1—O2	151.16 (11)
O9—Na1—O4—Na2	−35.87 (8)	O9—Na1—B1—O8	168.21 (16)
O1—Na1—O4—Na2	134.51 (7)	O1—Na1—B1—O8	93.7 (2)
O2—Na1—O4—Na2	−167.09 (5)	O2—Na1—B1—O8	−93.5 (2)
O3—Na1—O4—Na2	46.90 (5)	O4—Na1—B1—O8	−31.5 (2)
O5—Na2—O4—C4	104.95 (19)	O3—Na1—B1—O8	57.7 (2)
O6—Na2—O4—C4	37.52 (19)	O9—Na1—B1—O7	−11.6 (2)
O3—Na2—O4—C4	−169.17 (19)	O1—Na1—B1—O7	−86.2 (2)
O10—Na2—O4—C4	−66.85 (18)	O2—Na1—B1—O7	86.7 (2)
O5—Na2—O4—Na1	−133.62 (10)	O4—Na1—B1—O7	148.63 (19)
O6—Na2—O4—Na1	158.95 (6)	O3—Na1—B1—O7	−122.17 (19)
O3—Na2—O4—Na1	−47.74 (5)	C5—O5—B2—O9^ii	−54.8 (3)
O10—Na2—O4—Na1	54.58 (5)	Na2—O5—B2—O9^ii	130.45 (17)
O6—Na2—O5—C5	−178.3 (3)	C5—O5—B2—O6	−177.13 (18)
O3—Na2—O5—C5	18.9 (3)	Na2—O5—B2—O6	8.17 (17)
O10—Na2—O5—C5	−94.2 (3)	C5—O5—B2—O10^ii	60.4 (3)
O4—Na2—O5—C5	96.7 (3)	Na2—O5—B2—O10^ii	−114.29 (16)
O6—Na2—O5—B2	−5.95 (13)	C5—O5—B2—Na2	174.7 (2)
O3—Na2—O5—B2	−168.76 (13)	C5—O5—B2—Na1^ii	−8.7 (2)
O10—Na2—O5—B2	78.17 (16)	Na2—O5—B2—Na1^ii	176.63 (8)
O4—Na2—O5—B2	−90.94 (17)	C6—O6—B2—O5	176.36 (18)
O5—Na2—O6—C6	179.4 (3)	Na2—O6—B2—O5	−8.09 (17)
O3—Na2—O6—C6	−139.5 (3)	C6—O6—B2—O9^ii	53.6 (3)
O10—Na2—O6—C6	50.1 (3)	Na2—O6—B2—O9^ii	−130.89 (15)
O4—Na2—O6—C6	−38.0 (3)	C6—O6—B2—O10^ii	−61.7 (3)
O5—Na2—O6—B2	5.91 (13)	Na2—O6—B2—O10^ii	113.81 (16)
O3—Na2—O6—B2	47.1 (2)	C6—O6—B2—Na2	−175.5 (2)
O10—Na2—O6—B2	−123.34 (14)	C6—O6—B2—Na1^ii	18.6 (4)
O4—Na2—O6—B2	148.58 (13)	Na2—O6—B2—Na1^ii	−165.8 (3)
O1—Na1—O9—C9	5.95 (19)	O6—Na2—B2—O5	169.7 (2)
O2—Na1—O9—C9	−55.36 (19)	O3—Na2—B2—O5	14.32 (17)
O4—Na1—O9—C9	178.52 (16)	O10—Na2—B2—O5	−122.13 (14)
O3—Na1—O9—C9	105.19 (17)	O4—Na2—B2—O5	125.36 (14)
O1—Na1—O9—B2^i	154.92 (13)	O5—Na2—B2—O9^ii	−85.1 (2)
O2—Na1—O9—B2^i	93.61 (14)	O6—Na2—B2—O9^ii	84.5 (3)
O4—Na1—O9—B2^i	−32.51 (16)	O3—Na2—B2—O9^ii	−70.8 (3)
O3—Na1—O9—B2^i	−105.84 (14)	O10—Na2—B2—O9^ii	152.8 (2)
O5—Na2—O10—C10	−78.3 (2)	O4—Na2—B2—O9^ii	40.2 (3)
O6—Na2—O10—C10	−16.1 (2)	O5—Na2—B2—O6	−169.7 (2)
O3—Na2—O10—C10	168.23 (19)	O3—Na2—B2—O6	−155.34 (12)
O4—Na2—O10—C10	95.56 (19)	O10—Na2—B2—O6	68.21 (15)
O5—Na2—O10—B2^i	73.2 (2)	O4—Na2—B2—O6	−44.31 (17)
O6—Na2—O10—B2^i	135.4 (2)	O5—Na2—B2—O10^ii	94.4 (2)
O3—Na2—O10—B2^i	−40.3 (2)	O6—Na2—B2—O10^ii	−95.9 (2)
O4—Na2—O10—B2^i	−113.0 (2)	O3—Na2—B2—O10^ii	108.75 (18)
O5—Na2—O10—Na1	140.99 (8)	O10—Na2—B2—O10^ii	−27.7 (2)
O6—Na2—O10—Na1	−156.78 (6)	O4—Na2—B2—O10^ii	−140.21 (16)
O3—Na2—O10—Na1	27.51 (6)	O5—Na2—B2—Na1^ii	−8.4 (2)
O4—Na2—O10—Na1	−45.16 (5)	O6—Na2—B2—Na1^ii	161.2 (4)
O9—Na1—O10—C10	146.3 (3)	O3—Na2—B2—Na1^ii	5.9 (3)
O1—Na1—O10—C10	136.1 (2)	O10—Na2—B2—Na1^ii	−130.5 (2)
O2—Na1—O10—C10	50.2 (3)	O4—Na2—B2—Na1^ii	116.9 (3)
O4—Na1—O10—C10	−43.7 (2)	B2^i—O10—C10—Na2	−159.3 (2)
O3—Na1—O10—C10	−118.3 (2)	Na1—O10—C10—Na2	81.5 (2)
O9—Na1—O10—B2^i	19.21 (12)	O5—Na2—C10—O10	120.77 (17)
O1—Na1—O10—B2^i	9.0 (2)	O6—Na2—C10—O10	164.38 (19)
O2—Na1—O10—B2^i	−76.98 (14)	O3—Na2—C10—O10	−14.4 (2)
O4—Na1—O10—B2^i	−170.87 (13)	O4—Na2—C10—O10	−81.44 (18)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3O···O8^iii	0.79 (2)	1.86 (2)	2.648 (2)	178 (2)
O4—H4O···O7^iii	0.78 (2)	1.84 (2)	2.596 (2)	162 (3)

Symmetry code: (iii) y−1/2, −x+3/2, −z+3/2.