Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270104013915/av1187sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270104013915/av1187Isup2.hkl |
CCDC reference: 248146
In a typical synthesis of (I), H3BO3 (0.232 g) was dissolved in a mixed solvent containing pyridine (4.2 ml), distilled water (0.1 ml) and tetramethylammonium hydroxide (C4H13NO; 1.1 ml, 25%). The mixture, with a typical H3BO3/py/H2O/NC4H13O molar ratio of 3.7:52.0:51.4:3.0 was stirred mechanically at room temperature to a final pH of about 8 and then placed in an autoclave at 443 K for 7 d. Colorless block-like crystals, identified as (I), were obtained in 18.21% yield (based on B atoms). The powder X-ray diffraction pattern of the bulk product is in good agreement with the calculated pattern based on the single-crystal solution, indicating the phase purity of the sample. Thermogravimetric analysis (TGA) showed that there were four steps of weight loss. The initial weight loss, of about 1.5 (calculated 1.52%) from 400 to 490 K, corresponds to the removal of the water molecule. The second step, about 9 (calculated 9.1%) from 470 to 570 K, was assigned to the removal of three hydroxy groups. The third step, from 570 to 1027 K, was assigned to the partial release of C4NH12·OH, resulting the decomposition of the framework. When heated further, the volatile boron oxide phases are partly separated? from the phase. The IR spectrum (4000–400 cm−1, KBr pellets) of (I) contains the characteristic bands of the BO3 and BO4 groups, corresponding to two strong bands at about 1317 and 1087 cm−1, respectively. The wide peak between 1350 and 1500 cm−1 is assigned to the bending bands of the CH2 and streching bands of the CN groups. The stretching vibration bands of the water OH groups are observed at about 3266 cm−1 (Liu et al., 2003), and the stretching vibration of the OH groups attached to the B atom is at about 3370 cm−1 (Yu et al., 2002).
H atoms bonded to O atoms were located from difference density maps. All H atoms attached to C atoms were positioned geometrically (C—H = 0.97 Å) and were allowed to ride on their parent C atoms. The solvent water molecules are located in channels, 4.08 (2) Å from the N atoms. In Fig. 2, the water molecule and N atom almost overlap each other because of the closeness of their b and c coordinates. The small solvent molecules are probably absorbed from the solution by the structure after synthesis, a phenomenon that can be explained by the fact that the borate structure is very polar as a result of the large number of hydroxy groups in the void space of the structure, as shown in Fig. 2. Such absorption of small molecules is a familiar occurance in microporous materials. For example, Na4Ge16O28(OH)12 (van den Berg et al., 2004) absorbs small gas molecules owing to voids in its structure. The parameter of 0.25 was determined according to the Ueq value and the refinement. The presence of hydration water molecules was established experimentally by TGA and IR spectroscopy.
Data collection: SMART (Bruker, 1999); cell refinement: SMART; data reduction: SAINT and SHELXTL (Bruker, 1999); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.
C4H12N+·B5H4O10−·0.25H2O | F(000) = 616 |
Mr = 296.23 | Dx = 1.374 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 57 reflections |
a = 9.2623 (4) Å | θ = 2.4–25.1° |
b = 16.8814 (7) Å | µ = 0.12 mm−1 |
c = 9.2119 (5) Å | T = 293 K |
β = 96.281 (3)° | Block, colorless |
V = 1431.73 (12) Å3 | 0.48 × 0.40 × 0.30 mm |
Z = 4 |
Bruker SMART CCD area-detector diffractometer | 2538 independent reflections |
Radiation source: fine-focus sealed tube | 1654 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.030 |
ϕ and ω scans | θmax = 25.1°, θmin = 2.4° |
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996) | h = −11→11 |
Tmin = 0.942, Tmax = 0.963 | k = −20→16 |
4012 measured reflections | l = −10→5 |
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)] = 0.064 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.177 | w = 1/[σ2(Fo2) + (0.0671P)2 + 1.0501P] where P = (Fo2 + 2Fc2)/3 |
S = 1.12 | (Δ/σ)max = 0.005 |
2470 reflections | Δρmax = 0.28 e Å−3 |
207 parameters | Δρmin = −0.21 e Å−3 |
0 restraints | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.011 (3) |
C4H12N+·B5H4O10−·0.25H2O | V = 1431.73 (12) Å3 |
Mr = 296.23 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 9.2623 (4) Å | µ = 0.12 mm−1 |
b = 16.8814 (7) Å | T = 293 K |
c = 9.2119 (5) Å | 0.48 × 0.40 × 0.30 mm |
β = 96.281 (3)° |
Bruker SMART CCD area-detector diffractometer | 2538 independent reflections |
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996) | 1654 reflections with I > 2σ(I) |
Tmin = 0.942, Tmax = 0.963 | Rint = 0.030 |
4012 measured reflections |
R[F2 > 2σ(F2)] = 0.064 | 0 restraints |
wR(F2) = 0.177 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.12 | Δρmax = 0.28 e Å−3 |
2470 reflections | Δρmin = −0.21 e Å−3 |
207 parameters |
Experimental. Thermogravimetric analysis (TGA) was performed using a Mettler Toledo TGA/SDTA 851 e analyzer in dry N2 atmosphere from 303 to 1573 K, with a heating rate of 15 K min−1. The IR spectra (4000–400 cm−1, KBr pellets) were recorded using an ABB Bomen MB 102 spectrometer. |
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) | |
O1 | 0.8486 (2) | 0.57705 (13) | 0.1955 (2) | 0.0390 (6) | |
O2 | 1.0888 (3) | 0.53732 (16) | 0.2093 (3) | 0.0529 (7) | |
O3 | 1.0043 (2) | 0.63342 (14) | 0.0344 (3) | 0.0462 (7) | |
O4 | 0.9200 (3) | 0.72546 (18) | −0.1411 (3) | 0.0591 (8) | |
O5 | 0.7570 (2) | 0.67133 (13) | 0.0127 (2) | 0.0392 (6) | |
O6 | 0.6910 (2) | 0.68090 (13) | 0.2551 (2) | 0.0407 (6) | |
O7 | 0.5300 (3) | 0.7418 (2) | 0.4023 (4) | 0.0803 (11) | |
O8 | 0.4480 (2) | 0.63774 (16) | 0.2525 (3) | 0.0597 (8) | |
O9 | 0.3570 (2) | 0.53304 (17) | 0.1089 (3) | 0.0543 (8) | |
O10 | 0.5992 (2) | 0.57430 (12) | 0.0974 (2) | 0.0370 (6) | |
OW | 0.649 (2) | 0.8871 (12) | 0.143 (2) | 0.135 (6) | 0.25 |
B1 | 0.9795 (4) | 0.5822 (2) | 0.1457 (4) | 0.0364 (9) | |
B2 | 0.8906 (4) | 0.6768 (2) | −0.0314 (4) | 0.0378 (9) | |
B3 | 0.7253 (4) | 0.6256 (2) | 0.1413 (4) | 0.0321 (8) | |
B4 | 0.5600 (4) | 0.6874 (3) | 0.3036 (5) | 0.0468 (11) | |
B5 | 0.4718 (4) | 0.5813 (2) | 0.1516 (4) | 0.0386 (9) | |
N | 0.2069 (4) | 0.87837 (19) | 0.1203 (3) | 0.0565 (9) | |
C1 | 0.2401 (6) | 0.8739 (3) | 0.2795 (5) | 0.0878 (16) | |
H1A | 0.3415 | 0.8627 | 0.3035 | 0.132* | |
H1B | 0.1835 | 0.8324 | 0.3169 | 0.132* | |
H1C | 0.2170 | 0.9235 | 0.3223 | 0.132* | |
C2 | 0.2907 (7) | 0.9435 (3) | 0.0630 (6) | 0.107 (2) | |
H2B | 0.3927 | 0.9328 | 0.0838 | 0.160* | |
H2C | 0.2679 | 0.9923 | 0.1087 | 0.160* | |
H2D | 0.2661 | 0.9476 | −0.0406 | 0.160* | |
C3 | 0.0482 (5) | 0.8967 (3) | 0.0870 (6) | 0.0860 (15) | |
H3A | 0.0264 | 0.9453 | 0.1340 | 0.129* | |
H3B | −0.0080 | 0.8545 | 0.1224 | 0.129* | |
H3C | 0.0246 | 0.9019 | −0.0166 | 0.129* | |
C4 | 0.2369 (6) | 0.8033 (3) | 0.0465 (7) | 0.108 (2) | |
H4B | 0.3382 | 0.7906 | 0.0660 | 0.163* | |
H4C | 0.2119 | 0.8090 | −0.0569 | 0.163* | |
H4D | 0.1801 | 0.7615 | 0.0824 | 0.163* | |
H2 | 1.172 (4) | 0.539 (2) | 0.174 (4) | 0.052 (11)* | |
H4 | 0.853 (5) | 0.750 (3) | −0.178 (5) | 0.070 (15)* | |
H7 | 0.602 (6) | 0.765 (3) | 0.429 (6) | 0.11 (2)* | |
H9 | 0.371 (5) | 0.503 (3) | 0.046 (5) | 0.082 (16)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0265 (11) | 0.0462 (13) | 0.0465 (14) | 0.0025 (10) | 0.0139 (10) | 0.0095 (11) |
O2 | 0.0289 (13) | 0.0713 (18) | 0.0612 (17) | 0.0099 (12) | 0.0173 (12) | 0.0209 (14) |
O3 | 0.0281 (11) | 0.0608 (15) | 0.0525 (15) | 0.0064 (11) | 0.0179 (11) | 0.0169 (12) |
O4 | 0.0407 (15) | 0.077 (2) | 0.0635 (18) | 0.0136 (14) | 0.0227 (13) | 0.0331 (16) |
O5 | 0.0279 (11) | 0.0466 (13) | 0.0452 (13) | 0.0037 (10) | 0.0131 (10) | 0.0087 (11) |
O6 | 0.0303 (12) | 0.0449 (13) | 0.0495 (14) | −0.0062 (10) | 0.0158 (10) | −0.0124 (11) |
O7 | 0.0434 (17) | 0.099 (2) | 0.105 (3) | −0.0209 (17) | 0.0367 (17) | −0.065 (2) |
O8 | 0.0314 (13) | 0.0765 (18) | 0.0755 (18) | −0.0136 (12) | 0.0258 (12) | −0.0389 (15) |
O9 | 0.0307 (13) | 0.0680 (18) | 0.0681 (18) | −0.0135 (12) | 0.0235 (12) | −0.0296 (15) |
O10 | 0.0261 (11) | 0.0414 (13) | 0.0458 (14) | −0.0030 (9) | 0.0145 (10) | −0.0080 (10) |
OW | 0.127 (14) | 0.149 (16) | 0.121 (14) | 0.004 (13) | −0.021 (11) | −0.009 (12) |
B1 | 0.0302 (19) | 0.041 (2) | 0.039 (2) | 0.0001 (16) | 0.0106 (16) | 0.0018 (17) |
B2 | 0.034 (2) | 0.041 (2) | 0.040 (2) | 0.0022 (17) | 0.0139 (17) | 0.0012 (18) |
B3 | 0.0240 (17) | 0.0354 (18) | 0.039 (2) | −0.0011 (15) | 0.0113 (15) | −0.0023 (17) |
B4 | 0.031 (2) | 0.058 (3) | 0.054 (3) | −0.0043 (18) | 0.0168 (18) | −0.017 (2) |
B5 | 0.0280 (19) | 0.047 (2) | 0.043 (2) | −0.0017 (17) | 0.0097 (16) | −0.0083 (18) |
N | 0.065 (2) | 0.0523 (19) | 0.056 (2) | −0.0001 (16) | 0.0241 (17) | −0.0082 (16) |
C1 | 0.098 (4) | 0.105 (4) | 0.061 (3) | 0.017 (3) | 0.015 (3) | 0.012 (3) |
C2 | 0.136 (5) | 0.105 (4) | 0.088 (4) | −0.044 (4) | 0.050 (4) | −0.009 (3) |
C3 | 0.081 (3) | 0.089 (4) | 0.089 (4) | 0.024 (3) | 0.015 (3) | −0.010 (3) |
C4 | 0.093 (4) | 0.075 (3) | 0.161 (6) | 0.011 (3) | 0.033 (4) | −0.054 (4) |
O1—B1 | 1.346 (4) | O10—B5 | 1.336 (4) |
O1—B3 | 1.449 (4) | O10—B3 | 1.474 (4) |
O2—B1 | 1.346 (4) | N—C1 | 1.467 (5) |
O2—H2 | 0.87 (4) | N—C2 | 1.476 (6) |
O3—B2 | 1.368 (4) | N—C4 | 1.479 (5) |
O3—B1 | 1.379 (4) | N—C3 | 1.500 (5) |
O4—B2 | 1.354 (4) | C1—H1A | 0.9600 |
O4—H4 | 0.79 (5) | C1—H1B | 0.9600 |
O5—B2 | 1.347 (4) | C1—H1C | 0.9600 |
O5—B3 | 1.470 (4) | C2—H2B | 0.9600 |
O6—B4 | 1.342 (4) | C2—H2C | 0.9600 |
O6—B3 | 1.465 (4) | C2—H2D | 0.9600 |
O7—B4 | 1.342 (5) | C3—H3A | 0.9600 |
O7—H7 | 0.79 (6) | C3—H3B | 0.9600 |
O8—B5 | 1.366 (4) | C3—H3C | 0.9600 |
O8—B4 | 1.377 (5) | C4—H4B | 0.9600 |
O9—B5 | 1.363 (4) | C4—H4C | 0.9600 |
O9—H9 | 0.79 (5) | C4—H4D | 0.9600 |
B1—O1—B3 | 123.4 (3) | C1—N—C4 | 112.7 (4) |
B1—O2—H2 | 118 (2) | C2—N—C4 | 109.9 (4) |
B2—O3—B1 | 118.8 (3) | C1—N—C3 | 108.0 (3) |
B2—O4—H4 | 115 (3) | C2—N—C3 | 108.4 (4) |
B2—O5—B3 | 123.3 (3) | C4—N—C3 | 108.2 (4) |
B4—O6—B3 | 124.4 (3) | N—C1—H1A | 109.5 |
B4—O7—H7 | 109 (4) | N—C1—H1B | 109.5 |
B5—O8—B4 | 119.1 (3) | H1A—C1—H1B | 109.5 |
B5—O9—H9 | 114 (3) | N—C1—H1C | 109.5 |
B5—O10—B3 | 123.5 (3) | H1A—C1—H1C | 109.5 |
O2—B1—O1 | 118.5 (3) | H1B—C1—H1C | 109.5 |
O2—B1—O3 | 119.9 (3) | N—C2—H2B | 109.5 |
O1—B1—O3 | 121.6 (3) | N—C2—H2C | 109.5 |
O5—B2—O4 | 122.2 (3) | H2B—C2—H2C | 109.5 |
O5—B2—O3 | 121.2 (3) | N—C2—H2D | 109.5 |
O4—B2—O3 | 116.6 (3) | H2B—C2—H2D | 109.5 |
O1—B3—O6 | 109.7 (3) | H2C—C2—H2D | 109.5 |
O1—B3—O5 | 110.9 (2) | N—C3—H3A | 109.5 |
O6—B3—O5 | 108.7 (3) | N—C3—H3B | 109.5 |
O1—B3—O10 | 109.5 (3) | H3A—C3—H3B | 109.5 |
O6—B3—O10 | 110.1 (2) | N—C3—H3C | 109.5 |
O5—B3—O10 | 108.0 (3) | H3A—C3—H3C | 109.5 |
O6—B4—O7 | 122.9 (3) | H3B—C3—H3C | 109.5 |
O6—B4—O8 | 120.7 (3) | N—C4—H4B | 109.5 |
O7—B4—O8 | 116.3 (3) | N—C4—H4C | 109.5 |
O10—B5—O9 | 122.2 (3) | H4B—C4—H4C | 109.5 |
O10—B5—O8 | 122.1 (3) | N—C4—H4D | 109.5 |
O9—B5—O8 | 115.8 (3) | H4B—C4—H4D | 109.5 |
C1—N—C2 | 109.6 (4) | H4C—C4—H4D | 109.5 |
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2···O9i | 0.87 (4) | 1.88 (4) | 2.745 (3) | 174 (4) |
O4—H4···O6ii | 0.79 (5) | 1.94 (5) | 2.733 (4) | 173 (5) |
O7—H7···O5iii | 0.79 (6) | 1.89 (6) | 2.671 (4) | 171 (6) |
O9—H9···O10iv | 0.79 (5) | 1.90 (5) | 2.688 (3) | 176 (5) |
Symmetry codes: (i) x+1, y, z; (ii) x, −y+3/2, z−1/2; (iii) x, −y+3/2, z+1/2; (iv) −x+1, −y+1, −z. |
Experimental details
Crystal data | |
Chemical formula | C4H12N+·B5H4O10−·0.25H2O |
Mr | 296.23 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 293 |
a, b, c (Å) | 9.2623 (4), 16.8814 (7), 9.2119 (5) |
β (°) | 96.281 (3) |
V (Å3) | 1431.73 (12) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.12 |
Crystal size (mm) | 0.48 × 0.40 × 0.30 |
Data collection | |
Diffractometer | Bruker SMART CCD area-detector diffractometer |
Absorption correction | Empirical (using intensity measurements) (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.942, 0.963 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4012, 2538, 1654 |
Rint | 0.030 |
(sin θ/λ)max (Å−1) | 0.597 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.064, 0.177, 1.12 |
No. of reflections | 2470 |
No. of parameters | 207 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.28, −0.21 |
Computer programs: SMART (Bruker, 1999), SMART, SAINT and SHELXTL (Bruker, 1999), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL.
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2···O9i | 0.87 (4) | 1.88 (4) | 2.745 (3) | 174 (4) |
O4—H4···O6ii | 0.79 (5) | 1.94 (5) | 2.733 (4) | 173 (5) |
O7—H7···O5iii | 0.79 (6) | 1.89 (6) | 2.671 (4) | 171 (6) |
O9—H9···O10iv | 0.79 (5) | 1.90 (5) | 2.688 (3) | 176 (5) |
Symmetry codes: (i) x+1, y, z; (ii) x, −y+3/2, z−1/2; (iii) x, −y+3/2, z+1/2; (iv) −x+1, −y+1, −z. |
Borates have provided a rich area of research for over 50 years because of their rich crystalline structures and potential applications in mineralogy and non-linear optical materials. So far, a number of borates exhibiting one-dimensional chains, two-dimensional layers and three- dimensional open structures have been reported (Salentine et al., 1987; Touboul et al., 1999; Menchetti et al., 1982; Nowogrocki et al., 2003; Huppertz et al., 2003), most of which were usually grown by a high-temperature flux method. Recently, hydrothermal and related techniques have been widely used for the preparation of inorganic materials, including phosphates and germanates (Yang et al., 1999; Zhou et al., 2001; Plevert, 2001). Interesting borates, such as Pb6B11O18(OH)9 (Yu et al., 2002) and Zn6B12O24 (Choudhury et al., 2002), have also been obtained from hydrothermal systems. The hydrothermal technique is of perpetual interest in the construction of novel structures, because different kinds of templates, especially organic molecules, with a wide variety of shapes and sizes can be incorporated into the systems to shape diverse inorganic frameworks. Nevertheless, such research efforts have rarely been made in the borate field (Schubert et al., 2000; Weakley et al., 1985).
We report here the X-ray structure analysis of the title compound, (I) (Fig.1). Compound (I) is composed of C4H12N+ cations, B5O6(OH)4− anions and solvent water molecules. The B5O6(OH)4− anion consists of two B3O3 rings, each containing one tetrahedrally and two trigonally coordinated B atoms; two of these B3O3 rings are connected by sharing their tetrahedrally coordinated B-atom vertices. The B5O6(OH)4− clusters are further connected by strong hydrogen-bonding interactions into a three-dimensional structure. Hydrogen-bonding interactions exist between atoms O2 and O9, O4 and O6, O7 and O5, and O9 and O10, with O···O distances ranging from 2.671 (4) to 2.745 (3) Å. Interestingly, this three-dimensional structure possesses a rectangular channel along the a axis (Fig. 2), which is formed by six B5O6(OH)4− units connected via hydrogen bonds. Two C4H12N+ cations and one water molecule are located in each rectangular channel. The trigonally coordinated B atoms exhibit B—O bond lengths in the range 1.336 (4)–1.379 (4) Å, while the tetrahedrally coordinated B atoms have B—O distances of 1.449 (4)–1.474 (4) Å. The O—B—O angles lie in the ranges 115.8 (3)–122.9 (3)° and 108.0 (3)–110.9 (2)°, respectively.