Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S160053680102102X/ci6086sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S160053680102102X/ci6086Isup2.hkl |
CCDC reference: 180541
The title compound was prepared by mixing 3.93 g (0.025 M) of ammonium carbonate, 3.09 g (0.05 M) of boric acid and 9.08 g (0.1 M) of lactic acid. The components were thoroughly dissolved in 100 ml of distilled water and the mixture was evaporated to dryness by heating at 323 K for 8 h. The yield was around 50%. Single crystals were obtained by slow evaporation of the saturated aqueous solution at 293 K. Good quality single crystals of size 8 × 6 × 3 mm were obtained in a period of two months. The melting point was measured as 489–492 K. The molecular mass was obtained as 205 amu using a Finnigan Mat-8230 GC mass spectrometer. The UV–vis spectrum of the crystal recorded using a Varian Cary 5E UV-vis-NIR spectrophotometer shows a transmittance window in the range 240–1250 nm. The extended UV transparency down to 240 nm makes this crystal preferred for optoelectronic applications.
All H atoms were located from a difference map and were included in the structure-factor calculations with Uiso(H) equal to 1.1 Ueq of their respective carrier atom and their parameters were refined. There are two chiral carbons [C5 and C5i; symmetry code: (i) -x, y, 1/2 - z] in the lactate moieties. The number of Friedel pairs measured was 117 reflections. The absolute configuration of the lactate anion could not be established in the present study, because the structure contains only light atoms. However, the reported coordinates correspond to S configuration.
Data collection: CAD-4 EXPRESS (Enraf-Nonius, 1994); cell refinement: CAD-4 EXPRESS; data reduction: MolEN (Fair, 1990); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ZORTEP (Zsolnai, 1997); software used to prepare material for publication: SHELXL97, PARST (Nardelli, 1983) and PLATON (Spek, 2001).
C6H12BNO6 | Dx = 1.428 Mg m−3 Dm = 1.41 Mg m−3 Dm measured by floatation method |
Mr = 204.98 | Cu Kα radiation, λ = 1.54180 Å |
Orthorhombic, C2221 | Cell parameters from 25 reflections |
a = 9.3254 (11) Å | θ = 20–30° |
b = 11.9482 (15) Å | µ = 1.09 mm−1 |
c = 8.5578 (9) Å | T = 293 K |
V = 953.53 (19) Å3 | Prismatic, white |
Z = 4 | 0.15 × 0.12 × 0.09 mm |
F(000) = 432 |
Enraf-Nonius CAD-4 diffractometer | 870 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.021 |
Graphite monochromator | θmax = 69.7°, θmin = 6.0° |
ω–2θ scans | h = −8→11 |
Absorption correction: ψ scan (North et al., 1968) | k = −8→14 |
Tmin = 0.854, Tmax = 0.909 | l = 0→10 |
988 measured reflections | 2 standard reflections every 120 min |
871 independent reflections | intensity decay: neglegible |
Refinement on F2 | Hydrogen site location: inferred from neighbouring sites |
Least-squares matrix: full | All H-atom parameters refined |
R[F2 > 2σ(F2)] = 0.026 | w = 1/[σ2(Fo2) + (0.1P)2] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.103 | (Δ/σ)max = 0.002 |
S = 1.05 | Δρmax = 0.17 e Å−3 |
871 reflections | Δρmin = −0.12 e Å−3 |
90 parameters | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
2 restraints | Extinction coefficient: 0.027 (3) |
Primary atom site location: structure-invariant direct methods | Absolute structure: Flack (1983) |
Secondary atom site location: difference Fourier map | Absolute structure parameter: 0.06 (19) |
C6H12BNO6 | V = 953.53 (19) Å3 |
Mr = 204.98 | Z = 4 |
Orthorhombic, C2221 | Cu Kα radiation |
a = 9.3254 (11) Å | µ = 1.09 mm−1 |
b = 11.9482 (15) Å | T = 293 K |
c = 8.5578 (9) Å | 0.15 × 0.12 × 0.09 mm |
Enraf-Nonius CAD-4 diffractometer | 870 reflections with I > 2σ(I) |
Absorption correction: ψ scan (North et al., 1968) | Rint = 0.021 |
Tmin = 0.854, Tmax = 0.909 | 2 standard reflections every 120 min |
988 measured reflections | intensity decay: neglegible |
871 independent reflections |
R[F2 > 2σ(F2)] = 0.026 | All H-atom parameters refined |
wR(F2) = 0.103 | Δρmax = 0.17 e Å−3 |
S = 1.05 | Δρmin = −0.12 e Å−3 |
871 reflections | Absolute structure: Flack (1983) |
90 parameters | Absolute structure parameter: 0.06 (19) |
2 restraints |
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 | ||
O1 | 0.12303 (10) | 0.12891 (7) | 0.20519 (10) | 0.0389 (4) | |
O2 | 0.05400 (11) | 0.26944 (8) | 0.37791 (13) | 0.0450 (4) | |
O3 | 0.33242 (12) | 0.08013 (9) | 0.30905 (11) | 0.0505 (4) | |
N4 | 0.4313 (2) | 0.0000 | 0.0000 | 0.0479 (5) | |
C5 | 0.17701 (14) | 0.21563 (10) | 0.44043 (14) | 0.0388 (4) | |
C6 | 0.22229 (14) | 0.13421 (10) | 0.31305 (15) | 0.0374 (4) | |
C7 | 0.1444 (2) | 0.15577 (16) | 0.59146 (15) | 0.0530 (4) | |
B1 | 0.0000 | 0.20563 (15) | 0.2500 | 0.0367 (5) | |
H5 | 0.254 (4) | 0.2726 (18) | 0.458 (2) | 0.067 (6)* | |
H71 | 0.076 (3) | 0.099 (2) | 0.580 (2) | 0.058 (5)* | |
H72 | 0.217 (3) | 0.1226 (16) | 0.629 (2) | 0.052 (5)* | |
H73 | 0.102 (3) | 0.208 (2) | 0.664 (3) | 0.071 (6)* | |
H41 | 0.381 (3) | 0.021 (2) | 0.081 (2) | 0.077 (7)* | |
H42 | 0.469 (5) | 0.061 (2) | −0.044 (4) | 0.133 (15)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0441 (6) | 0.0397 (5) | 0.0330 (5) | 0.0043 (4) | −0.0004 (3) | −0.0042 (3) |
O2 | 0.0441 (5) | 0.0398 (6) | 0.0511 (6) | 0.0081 (4) | −0.0081 (4) | −0.0134 (4) |
O3 | 0.0433 (6) | 0.0591 (7) | 0.0492 (6) | 0.0138 (4) | 0.0044 (4) | 0.0015 (5) |
N4 | 0.0471 (10) | 0.0477 (10) | 0.0488 (9) | 0.000 | 0.000 | −0.0115 (7) |
C5 | 0.0381 (6) | 0.0399 (6) | 0.0383 (7) | 0.0005 (5) | −0.0029 (5) | −0.0052 (5) |
C6 | 0.0399 (6) | 0.0377 (6) | 0.0345 (6) | 0.0005 (4) | 0.0041 (5) | 0.0000 (5) |
C7 | 0.0610 (9) | 0.0620 (10) | 0.0359 (7) | 0.0027 (8) | 0.0039 (6) | −0.0018 (6) |
B1 | 0.0396 (9) | 0.0328 (9) | 0.0379 (9) | 0.000 | −0.0013 (8) | 0.000 |
O1—C6 | 1.3088 (16) | C5—C6 | 1.5209 (17) |
O1—B1 | 1.5177 (14) | C5—H5 | 1.00 (3) |
O2—C5 | 1.4197 (16) | C7—H71 | 0.94 (3) |
O2—B1 | 1.4259 (13) | C7—H72 | 0.84 (3) |
O3—C6 | 1.2138 (18) | C7—H73 | 0.96 (3) |
N4—H41 | 0.874 (17) | B1—O2i | 1.4259 (13) |
N4—H42 | 0.896 (19) | B1—O1i | 1.5177 (14) |
C5—C7 | 1.5080 (19) | ||
C6—O1—B1 | 109.10 (8) | C5—C7—H71 | 112.9 (13) |
C5—O2—B1 | 109.42 (9) | C5—C7—H72 | 112.8 (15) |
H41—N4—H42 | 108 (3) | H71—C7—H72 | 104 (2) |
O2—C5—C7 | 112.02 (13) | C5—C7—H73 | 109.2 (18) |
O2—C5—C6 | 104.12 (10) | H71—C7—H73 | 105 (2) |
C7—C5—C6 | 111.53 (11) | H72—C7—H73 | 113 (2) |
O2—C5—H5 | 109.4 (15) | O2—B1—O2i | 115.35 (15) |
C7—C5—H5 | 109.6 (12) | O2—B1—O1i | 113.33 (6) |
C6—C5—H5 | 110.1 (14) | O2i—B1—O1i | 104.47 (5) |
O3—C6—O1 | 123.56 (12) | O2—B1—O1 | 104.47 (5) |
O3—C6—C5 | 126.56 (11) | O2i—B1—O1 | 113.33 (6) |
O1—C6—C5 | 109.88 (11) | O1i—B1—O1 | 105.69 (13) |
B1—O2—C5—C7 | −103.80 (12) | C7—C5—C6—O1 | 111.04 (14) |
B1—O2—C5—C6 | 16.85 (13) | C5—O2—B1—O2i | −142.32 (11) |
B1—O1—C6—O3 | 178.85 (12) | C5—O2—B1—O1i | 97.32 (12) |
B1—O1—C6—C5 | −0.52 (13) | C5—O2—B1—O1 | −17.23 (13) |
O2—C5—C6—O3 | 170.72 (13) | C6—O1—B1—O2 | 10.75 (13) |
C7—C5—C6—O3 | −68.30 (19) | C6—O1—B1—O2i | 137.12 (11) |
O2—C5—C6—O1 | −9.94 (13) | C6—O1—B1—O1i | −109.07 (9) |
Symmetry code: (i) −x, y, −z+1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
N4—H41···O3 | 0.87 (2) | 2.12 (2) | 2.9600 (12) | 160 (2) |
N4—H42···O2ii | 0.89 (3) | 2.14 (3) | 2.9494 (10) | 150 (4) |
Symmetry code: (ii) −x+1/2, −y+1/2, z−1/2. |
Experimental details
Crystal data | |
Chemical formula | C6H12BNO6 |
Mr | 204.98 |
Crystal system, space group | Orthorhombic, C2221 |
Temperature (K) | 293 |
a, b, c (Å) | 9.3254 (11), 11.9482 (15), 8.5578 (9) |
V (Å3) | 953.53 (19) |
Z | 4 |
Radiation type | Cu Kα |
µ (mm−1) | 1.09 |
Crystal size (mm) | 0.15 × 0.12 × 0.09 |
Data collection | |
Diffractometer | Enraf-Nonius CAD-4 diffractometer |
Absorption correction | ψ scan (North et al., 1968) |
Tmin, Tmax | 0.854, 0.909 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 988, 871, 870 |
Rint | 0.021 |
(sin θ/λ)max (Å−1) | 0.608 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.026, 0.103, 1.05 |
No. of reflections | 871 |
No. of parameters | 90 |
No. of restraints | 2 |
H-atom treatment | All H-atom parameters refined |
Δρmax, Δρmin (e Å−3) | 0.17, −0.12 |
Absolute structure | Flack (1983) |
Absolute structure parameter | 0.06 (19) |
Computer programs: CAD-4 EXPRESS (Enraf-Nonius, 1994), CAD-4 EXPRESS, MolEN (Fair, 1990), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ZORTEP (Zsolnai, 1997), SHELXL97, PARST (Nardelli, 1983) and PLATON (Spek, 2001).
O1—B1 | 1.5177 (14) | O2—B1 | 1.4259 (13) |
O2—B1—O2i | 115.35 (15) | O2—B1—O1 | 104.47 (5) |
O2—B1—O1i | 113.33 (6) | O1i—B1—O1 | 105.69 (13) |
Symmetry code: (i) −x, y, −z+1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
N4—H41···O3 | 0.87 (2) | 2.124 (19) | 2.9600 (12) | 160 (2) |
N4—H42···O2ii | 0.89 (3) | 2.14 (3) | 2.9494 (10) | 150 (4) |
Symmetry code: (ii) −x+1/2, −y+1/2, z−1/2. |
The structure determination of the title compound, (I), was undertaken to investigate the environment around boron and the hydrogen bonds involving the ammonium cation. Non-linear Optical (NLO) materials play a vital role in the advancing laser technology and optoelectronic applications, such as optical computing, optical data storage and optical communication. Since it is reported that semiorganic NLO materials combine the large non-linearity of organics and favourable crystal growth properties of inorganic salts (Jiang & Fang, 1999; Jiang et al., 2001), we have prepared the title compound, which crystallizes in the noncentrosymmetric space group C2221 with Z = 4.
The asymmetric unit of (I) contains half a borodilactate anion and half an ammonium cation. The other halves are generated by twofold symmetry, with B1 and N4 lying on the twofold axes. Atom B1 forms two covalent bonds [1.4259 (13) Å each] with O2 and O2i and an extended coordination bond [1.5177 (14) Å] resonating between O1 and O1i [symmetry code: (i) -x, y, 1/2 - z]. The bond angles around boron, O1i–B1–O2i [104.47 (5)°], O1–B1–O1i [105.69 (13)°], O1–B1–O2i [113.33 (6)°] and O2–B1–O2i [115.35 (15)°] indicate a distorted tetrahedral environment. Similar bond lengths and deviations from the tetrahedral values of bond angles around boron have been reported in the literature (Stibrany & Brant, 2001; Hill et al., 1997). The dihedral angle between the planes of the two lactate moieties of the boro dilactate anion is 88.3°.
The structure is stabilized by a network of N—H···O hydrogen bonds involving the H atoms of the ammonium cation and two of the O atoms (O2 and O3) of the lactate moiety (Table 2). Because of the space group symmetry all the four H atoms of the ammonium ion are involved in hydrogen bonding with O3 and symmetry-related O2(-x + 1/2, -y + 1/2, z - 1/2), O2(-x + 1/2, y - 1/2, -z + 1/2) and O3(x, -y, -z).