Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270105005524/fa1119sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270105005524/fa1119Isup2.hkl |
CCDC reference: 269022
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.
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 Uiso(H) values of 1.2 times Ueq of their carrier atoms.
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).
[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) Å3 | Block, colourless |
Z = 8 | 0.65 × 0.54 × 0.50 mm |
F(000) = 1632 |
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 on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.027 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.066 | w = 1/[σ2(Fo2) + (0.0368P)2 + 0.8467P] where P = (Fo2 + 2Fc2)/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 |
[Na2(C4H12BO4)2(CH4O)2] | Z = 8 |
Mr = 379.96 | Mo Kα radiation |
Tetragonal, I4 | µ = 0.13 mm−1 |
a = 22.0496 (19) Å | T = 98 K |
c = 8.8155 (15) Å | 0.65 × 0.54 × 0.50 mm |
V = 4286.0 (9) Å3 |
Bruker SMART CCD area-detector diffractometer | 2330 independent reflections |
Absorption correction: multi-scan (Blessing, 1995) | 2070 reflections with I > 2σ(I) |
Tmin = 0.787, Tmax = 0.936 | Rint = 0.020 |
6990 measured reflections |
R[F2 > 2σ(F2)] = 0.027 | 0 restraints |
wR(F2) = 0.066 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.04 | Δρmax = 0.11 e Å−3 |
2330 reflections | Δρmin = −0.13 e Å−3 |
238 parameters | Absolute structure: Flack (1983) parameter indeterminate (racemic twin) |
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. |
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* |
U11 | U22 | U33 | U12 | U13 | U23 | |
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) |
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—B2i | 1.465 (3) | C8—H8D | 0.9800 |
O10—C10 | 1.409 (3) | C8—H8E | 0.9800 |
O10—B2i | 1.471 (3) | C8—H8F | 0.9800 |
B2—O9ii | 1.465 (3) | C9—H9A | 0.9800 |
B2—O10ii | 1.471 (3) | C9—H9B | 0.9800 |
B2—Na1ii | 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—B2i | 117.31 (17) | O7—C7—H7A | 109.5 |
C9—O9—Na1 | 125.22 (13) | O7—C7—H7B | 109.5 |
B2i—O9—Na1 | 110.13 (14) | H7A—C7—H7B | 109.5 |
C10—O10—B2i | 114.21 (18) | O7—C7—H7C | 109.5 |
C10—O10—Na2 | 103.03 (14) | H7A—C7—H7C | 109.5 |
B2i—O10—Na2 | 137.64 (14) | H7B—C7—H7C | 109.5 |
C10—O10—Na1 | 141.90 (19) | O8—C8—H8A | 109.5 |
B2i—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—O9ii | 114.34 (19) | O8—C8—H8F | 109.5 |
O5—B2—O6 | 100.85 (16) | H8D—C8—H8F | 109.5 |
O9ii—B2—O6 | 113.6 (2) | H8E—C8—H8F | 109.5 |
O5—B2—O10ii | 113.4 (2) | O9—C9—H9A | 109.5 |
O9ii—B2—O10ii | 101.16 (16) | O9—C9—H9B | 109.5 |
O6—B2—O10ii | 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—B2i | 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—O9ii | −54.8 (3) |
O10—Na2—O4—Na1 | 54.58 (5) | Na2—O5—B2—O9ii | 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—O10ii | 60.4 (3) |
O4—Na2—O5—C5 | 96.7 (3) | Na2—O5—B2—O10ii | −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—Na1ii | −8.7 (2) |
O10—Na2—O5—B2 | 78.17 (16) | Na2—O5—B2—Na1ii | 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—O9ii | 53.6 (3) |
O10—Na2—O6—C6 | 50.1 (3) | Na2—O6—B2—O9ii | −130.89 (15) |
O4—Na2—O6—C6 | −38.0 (3) | C6—O6—B2—O10ii | −61.7 (3) |
O5—Na2—O6—B2 | 5.91 (13) | Na2—O6—B2—O10ii | 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—Na1ii | 18.6 (4) |
O4—Na2—O6—B2 | 148.58 (13) | Na2—O6—B2—Na1ii | −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—B2i | 154.92 (13) | O5—Na2—B2—O9ii | −85.1 (2) |
O2—Na1—O9—B2i | 93.61 (14) | O6—Na2—B2—O9ii | 84.5 (3) |
O4—Na1—O9—B2i | −32.51 (16) | O3—Na2—B2—O9ii | −70.8 (3) |
O3—Na1—O9—B2i | −105.84 (14) | O10—Na2—B2—O9ii | 152.8 (2) |
O5—Na2—O10—C10 | −78.3 (2) | O4—Na2—B2—O9ii | 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—B2i | 73.2 (2) | O4—Na2—B2—O6 | −44.31 (17) |
O6—Na2—O10—B2i | 135.4 (2) | O5—Na2—B2—O10ii | 94.4 (2) |
O3—Na2—O10—B2i | −40.3 (2) | O6—Na2—B2—O10ii | −95.9 (2) |
O4—Na2—O10—B2i | −113.0 (2) | O3—Na2—B2—O10ii | 108.75 (18) |
O5—Na2—O10—Na1 | 140.99 (8) | O10—Na2—B2—O10ii | −27.7 (2) |
O6—Na2—O10—Na1 | −156.78 (6) | O4—Na2—B2—O10ii | −140.21 (16) |
O3—Na2—O10—Na1 | 27.51 (6) | O5—Na2—B2—Na1ii | −8.4 (2) |
O4—Na2—O10—Na1 | −45.16 (5) | O6—Na2—B2—Na1ii | 161.2 (4) |
O9—Na1—O10—C10 | 146.3 (3) | O3—Na2—B2—Na1ii | 5.9 (3) |
O1—Na1—O10—C10 | 136.1 (2) | O10—Na2—B2—Na1ii | −130.5 (2) |
O2—Na1—O10—C10 | 50.2 (3) | O4—Na2—B2—Na1ii | 116.9 (3) |
O4—Na1—O10—C10 | −43.7 (2) | B2i—O10—C10—Na2 | −159.3 (2) |
O3—Na1—O10—C10 | −118.3 (2) | Na1—O10—C10—Na2 | 81.5 (2) |
O9—Na1—O10—B2i | 19.21 (12) | O5—Na2—C10—O10 | 120.77 (17) |
O1—Na1—O10—B2i | 9.0 (2) | O6—Na2—C10—O10 | 164.38 (19) |
O2—Na1—O10—B2i | −76.98 (14) | O3—Na2—C10—O10 | −14.4 (2) |
O4—Na1—O10—B2i | −170.87 (13) | O4—Na2—C10—O10 | −81.44 (18) |
Symmetry codes: (i) y, −x+1, −z+1; (ii) −y+1, x, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
O3—H3O···O8iii | 0.79 (2) | 1.86 (2) | 2.648 (2) | 178 (2) |
O4—H4O···O7iii | 0.78 (2) | 1.84 (2) | 2.596 (2) | 162 (3) |
Symmetry code: (iii) y−1/2, −x+3/2, −z+3/2. |
Experimental details
Crystal data | |
Chemical formula | [Na2(C4H12BO4)2(CH4O)2] |
Mr | 379.96 |
Crystal system, space group | Tetragonal, I4 |
Temperature (K) | 98 |
a, c (Å) | 22.0496 (19), 8.8155 (15) |
V (Å3) | 4286.0 (9) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 0.13 |
Crystal size (mm) | 0.65 × 0.54 × 0.50 |
Data collection | |
Diffractometer | Bruker SMART CCD area-detector diffractometer |
Absorption correction | Multi-scan (Blessing, 1995) |
Tmin, Tmax | 0.787, 0.936 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 6990, 2330, 2070 |
Rint | 0.020 |
(sin θ/λ)max (Å−1) | 0.624 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.027, 0.066, 1.04 |
No. of reflections | 2330 |
No. of parameters | 238 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.11, −0.13 |
Absolute structure | Flack (1983) parameter indeterminate (racemic twin) |
Computer programs: SMART (Bruker, 2001), SMART, SAINT (Bruker, 2001) and SADABS (Sheldrick, 1996), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), PLATON (Spek, 2003).
Na1—O9 | 2.2777 (18) | Na2—O4 | 2.4088 (18) |
Na1—O3 | 2.3893 (16) | O1—B1 | 1.453 (3) |
Na2—O5 | 2.3009 (16) | O7—B1 | 1.479 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
O3—H3O···O8i | 0.79 (2) | 1.86 (2) | 2.648 (2) | 178 (2) |
O4—H4O···O7i | 0.78 (2) | 1.84 (2) | 2.596 (2) | 162 (3) |
Symmetry code: (i) y−1/2, −x+3/2, −z+3/2. |
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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(µ2-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.