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In the title compound, NH4+·C6H8BO6, the trivalent boron is tetrahedrally bonded to four O atoms of the two lactate ions having a chiral carbon in each. Two of the O atoms are covalently bonded [1.4259 (13) Å] to the boron, while there is an extended B—O bonds [1.5177 (14) Å] between the boron and each of the other two O atoms. There are distortions in the tetrahedral angles around boron ranging from 104.47 (5) to 115.35 (15)°. The structure is stabilized by a network of N—H...O hydrogen bonds involving the H atoms of the ammonium cation and the O atoms of the borodilactate anion. The UV–vis transmittance window of this non-linear optical crystal is in the range 240–1250 nm.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S160053680102102X/ci6086sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S160053680102102X/ci6086Isup2.hkl
Contains datablock I

CCDC reference: 180541

Key indicators

  • Single-crystal X-ray study
  • T = 293 K
  • Mean [sigma](C-C) = 0.002 Å
  • R factor = 0.026
  • wR factor = 0.103
  • Data-to-parameter ratio = 9.7

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry

General Notes

REFLT_03 From the CIF: _diffrn_reflns_theta_max 69.72 From the CIF: _reflns_number_total 871 Count of symmetry unique reflns 538 Completeness (_total/calc) 161.90% TEST3: Check Friedels for noncentro structure Estimate of Friedel pairs measured 333 Fraction of Friedel pairs measured 0.619 Are heavy atom types Z>Si present no Please check that the estimate of the number of Friedel pairs is correct. If it is not, please give the correct count in the _publ_section_exptl_refinement section of the submitted CIF.

Comment top

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).

Experimental top

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.

Refinement top

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.

Computing details top

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).

Figures top
[Figure 1] Fig. 1. The molecular structure of (I) showing 50% probability displacement ellipsoids and the atom-numbering scheme. [Symmetry code: (i) -x, y, 1/2 - z.]
[Figure 2] Fig. 2. The molecular packing viewed down the c axis.
Ammonium 2,7-dimethyl-5-bora-1,4,6,9-tetroxaspiro[4.4]nonane-3,8-dionate top
Crystal data top
C6H12BNO6Dx = 1.428 Mg m3
Dm = 1.41 Mg m3
Dm measured by floatation method
Mr = 204.98Cu Kα radiation, λ = 1.54180 Å
Orthorhombic, C2221Cell parameters from 25 reflections
a = 9.3254 (11) Åθ = 20–30°
b = 11.9482 (15) ŵ = 1.09 mm1
c = 8.5578 (9) ÅT = 293 K
V = 953.53 (19) Å3Prismatic, white
Z = 40.15 × 0.12 × 0.09 mm
F(000) = 432
Data collection top
Enraf-Nonius CAD-4
diffractometer
870 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.021
Graphite monochromatorθmax = 69.7°, θmin = 6.0°
ω–2θ scansh = 811
Absorption correction: ψ scan
(North et al., 1968)
k = 814
Tmin = 0.854, Tmax = 0.909l = 010
988 measured reflections2 standard reflections every 120 min
871 independent reflections intensity decay: neglegible
Refinement top
Refinement on F2Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: fullAll 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 = 1.05Δρmax = 0.17 e Å3
871 reflectionsΔρmin = 0.12 e Å3
90 parametersExtinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
2 restraintsExtinction coefficient: 0.027 (3)
Primary atom site location: structure-invariant direct methodsAbsolute structure: Flack (1983)
Secondary atom site location: difference Fourier mapAbsolute structure parameter: 0.06 (19)
Crystal data top
C6H12BNO6V = 953.53 (19) Å3
Mr = 204.98Z = 4
Orthorhombic, C2221Cu Kα radiation
a = 9.3254 (11) ŵ = 1.09 mm1
b = 11.9482 (15) ÅT = 293 K
c = 8.5578 (9) Å0.15 × 0.12 × 0.09 mm
Data collection top
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 = 0.9092 standard reflections every 120 min
988 measured reflections intensity decay: neglegible
871 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.026All H-atom parameters refined
wR(F2) = 0.103Δρmax = 0.17 e Å3
S = 1.05Δρmin = 0.12 e Å3
871 reflectionsAbsolute structure: Flack (1983)
90 parametersAbsolute structure parameter: 0.06 (19)
2 restraints
Special details top

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 (Å2) top
xyzUiso*/Ueq
O10.12303 (10)0.12891 (7)0.20519 (10)0.0389 (4)
O20.05400 (11)0.26944 (8)0.37791 (13)0.0450 (4)
O30.33242 (12)0.08013 (9)0.30905 (11)0.0505 (4)
N40.4313 (2)0.00000.00000.0479 (5)
C50.17701 (14)0.21563 (10)0.44043 (14)0.0388 (4)
C60.22229 (14)0.13421 (10)0.31305 (15)0.0374 (4)
C70.1444 (2)0.15577 (16)0.59146 (15)0.0530 (4)
B10.00000.20563 (15)0.25000.0367 (5)
H50.254 (4)0.2726 (18)0.458 (2)0.067 (6)*
H710.076 (3)0.099 (2)0.580 (2)0.058 (5)*
H720.217 (3)0.1226 (16)0.629 (2)0.052 (5)*
H730.102 (3)0.208 (2)0.664 (3)0.071 (6)*
H410.381 (3)0.021 (2)0.081 (2)0.077 (7)*
H420.469 (5)0.061 (2)0.044 (4)0.133 (15)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0441 (6)0.0397 (5)0.0330 (5)0.0043 (4)0.0004 (3)0.0042 (3)
O20.0441 (5)0.0398 (6)0.0511 (6)0.0081 (4)0.0081 (4)0.0134 (4)
O30.0433 (6)0.0591 (7)0.0492 (6)0.0138 (4)0.0044 (4)0.0015 (5)
N40.0471 (10)0.0477 (10)0.0488 (9)0.0000.0000.0115 (7)
C50.0381 (6)0.0399 (6)0.0383 (7)0.0005 (5)0.0029 (5)0.0052 (5)
C60.0399 (6)0.0377 (6)0.0345 (6)0.0005 (4)0.0041 (5)0.0000 (5)
C70.0610 (9)0.0620 (10)0.0359 (7)0.0027 (8)0.0039 (6)0.0018 (6)
B10.0396 (9)0.0328 (9)0.0379 (9)0.0000.0013 (8)0.000
Geometric parameters (Å, º) top
O1—C61.3088 (16)C5—C61.5209 (17)
O1—B11.5177 (14)C5—H51.00 (3)
O2—C51.4197 (16)C7—H710.94 (3)
O2—B11.4259 (13)C7—H720.84 (3)
O3—C61.2138 (18)C7—H730.96 (3)
N4—H410.874 (17)B1—O2i1.4259 (13)
N4—H420.896 (19)B1—O1i1.5177 (14)
C5—C71.5080 (19)
C6—O1—B1109.10 (8)C5—C7—H71112.9 (13)
C5—O2—B1109.42 (9)C5—C7—H72112.8 (15)
H41—N4—H42108 (3)H71—C7—H72104 (2)
O2—C5—C7112.02 (13)C5—C7—H73109.2 (18)
O2—C5—C6104.12 (10)H71—C7—H73105 (2)
C7—C5—C6111.53 (11)H72—C7—H73113 (2)
O2—C5—H5109.4 (15)O2—B1—O2i115.35 (15)
C7—C5—H5109.6 (12)O2—B1—O1i113.33 (6)
C6—C5—H5110.1 (14)O2i—B1—O1i104.47 (5)
O3—C6—O1123.56 (12)O2—B1—O1104.47 (5)
O3—C6—C5126.56 (11)O2i—B1—O1113.33 (6)
O1—C6—C5109.88 (11)O1i—B1—O1105.69 (13)
B1—O2—C5—C7103.80 (12)C7—C5—C6—O1111.04 (14)
B1—O2—C5—C616.85 (13)C5—O2—B1—O2i142.32 (11)
B1—O1—C6—O3178.85 (12)C5—O2—B1—O1i97.32 (12)
B1—O1—C6—C50.52 (13)C5—O2—B1—O117.23 (13)
O2—C5—C6—O3170.72 (13)C6—O1—B1—O210.75 (13)
C7—C5—C6—O368.30 (19)C6—O1—B1—O2i137.12 (11)
O2—C5—C6—O19.94 (13)C6—O1—B1—O1i109.07 (9)
Symmetry code: (i) x, y, z+1/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N4—H41···O30.87 (2)2.12 (2)2.9600 (12)160 (2)
N4—H42···O2ii0.89 (3)2.14 (3)2.9494 (10)150 (4)
Symmetry code: (ii) x+1/2, y+1/2, z1/2.

Experimental details

Crystal data
Chemical formulaC6H12BNO6
Mr204.98
Crystal system, space groupOrthorhombic, C2221
Temperature (K)293
a, b, c (Å)9.3254 (11), 11.9482 (15), 8.5578 (9)
V3)953.53 (19)
Z4
Radiation typeCu Kα
µ (mm1)1.09
Crystal size (mm)0.15 × 0.12 × 0.09
Data collection
DiffractometerEnraf-Nonius CAD-4
diffractometer
Absorption correctionψ scan
(North et al., 1968)
Tmin, Tmax0.854, 0.909
No. of measured, independent and
observed [I > 2σ(I)] reflections
988, 871, 870
Rint0.021
(sin θ/λ)max1)0.608
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.026, 0.103, 1.05
No. of reflections871
No. of parameters90
No. of restraints2
H-atom treatmentAll H-atom parameters refined
Δρmax, Δρmin (e Å3)0.17, 0.12
Absolute structureFlack (1983)
Absolute structure parameter0.06 (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).

Selected geometric parameters (Å, º) top
O1—B11.5177 (14)O2—B11.4259 (13)
O2—B1—O2i115.35 (15)O2—B1—O1104.47 (5)
O2—B1—O1i113.33 (6)O1i—B1—O1105.69 (13)
Symmetry code: (i) x, y, z+1/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N4—H41···O30.87 (2)2.124 (19)2.9600 (12)160 (2)
N4—H42···O2ii0.89 (3)2.14 (3)2.9494 (10)150 (4)
Symmetry code: (ii) x+1/2, y+1/2, z1/2.
 

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