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Refinement of the title compound, Li B(OH)4, with CCD data at 120 K has led to a sevenfold increase in precision over the previously reported structure based on film data. The H atoms have been located and refined. Both Li and B are tetrahedrally coordinated. B-O distances are in the range 1.4644 (14)-1.4989 (13) Å, while Li-O distances are in the range 1.931 (2)-2.022 (2) Å.
Supporting information
Key indicators
- Single-crystal X-ray study
- T = 120 K
- Mean (O-B) = 0.001 Å
- R factor = 0.029
- wR factor = 0.069
- Data-to-parameter ratio = 12.8
checkCIF results
No syntax errors found
ADDSYM reports no extra symmetry
A 1.0 M solution of LiBH(C2H5)3 in tetrahydrofuran (0.8 ml, 0.8 mmol) was added dropwise to a rapidly stirring 1 ml me thanol solution
containing RhCl2 (et,ph-P4) (0.5 g, 0.784 mmol) and allowed to react for 24 h. A 1 ml sample of this dark-red solution was allowed to remain undisturbed
in an NMR tube for approximately 30 days, which allowed slow solvent
evaporation and the formation of colorless crystals of lithium
tetrahydroxoborate.
H atoms were located from difference maps, and were individually refined. O—H
distances were in the range 0.793 (18)–0.845 (18) Å, and Uiso values
for H atoms are in the range 0.027 (4)–0.038 (5) Å2.
Data collection: COLLECT (Nonius, 1999); cell refinement: HKL SCALEPACK (Otwinowski & Minor 1997); data reduction: HKL DENZO and SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: Direct_methods (SIR97; Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).
Lithium tetrahydroxoborate
top
Crystal data top
Li+·BO4H4− | Dx = 1.836 Mg m−3 |
Mr = 85.78 | Mo Kα radiation, λ = 0.71073 Å |
Orthorhombic, Pbca | Cell parameters from 1047 reflections |
a = 7.9362 (3) Å | θ = 2.5–30.0° |
b = 8.5220 (3) Å | µ = 0.18 mm−1 |
c = 9.1762 (4) Å | T = 120 K |
V = 620.61 (4) Å3 | Octahedron, colorless |
Z = 8 | 0.20 × 0.18 × 0.17 mm |
F(000) = 352 | |
Data collection top
KappaCCD (with Oxford Cryostream) diffractometer | 787 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.021 |
Graphite monochromator | θmax = 30.0°, θmin = 2.5° |
ω scans with κ offsets | h = −11→11 |
6073 measured reflections | k = −11→12 |
907 independent reflections | l = −12→12 |
Refinement top
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.029 | Hydrogen site location: difference Fourier map |
wR(F2) = 0.069 | All H-atom parameters refined |
S = 1.11 | w = 1/[σ2(Fo2) + (0.0204P)2 + 0.3132P] where P = (Fo2 + 2Fc2)/3 |
907 reflections | (Δ/σ)max < 0.001 |
71 parameters | Δρmax = 0.28 e Å−3 |
0 restraints | Δρmin = −0.30 e Å−3 |
Crystal data top
Li+·BO4H4− | V = 620.61 (4) Å3 |
Mr = 85.78 | Z = 8 |
Orthorhombic, Pbca | Mo Kα radiation |
a = 7.9362 (3) Å | µ = 0.18 mm−1 |
b = 8.5220 (3) Å | T = 120 K |
c = 9.1762 (4) Å | 0.20 × 0.18 × 0.17 mm |
Data collection top
KappaCCD (with Oxford Cryostream) diffractometer | 787 reflections with I > 2σ(I) |
6073 measured reflections | Rint = 0.021 |
907 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.029 | 0 restraints |
wR(F2) = 0.069 | All H-atom parameters refined |
S = 1.11 | Δρmax = 0.28 e Å−3 |
907 reflections | Δρmin = −0.30 e Å−3 |
71 parameters | |
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 | x | y | z | Uiso*/Ueq | |
Li1 | 0.1319 (2) | 0.3741 (2) | 0.3016 (2) | 0.0127 (4) | |
B1 | 0.32892 (15) | 0.33617 (13) | 0.59296 (13) | 0.0089 (2) | |
O1 | 0.16392 (10) | 0.29123 (9) | 0.65473 (9) | 0.00989 (18) | |
O2 | 0.29301 (10) | 0.41668 (9) | 0.45417 (8) | 0.01158 (19) | |
O3 | 0.42395 (10) | 0.44191 (8) | 0.68819 (8) | 0.00999 (18) | |
O4 | 0.43403 (10) | 0.19150 (9) | 0.57379 (9) | 0.01098 (18) | |
H1 | 0.097 (2) | 0.2814 (19) | 0.5891 (19) | 0.028 (4)* | |
H2 | 0.381 (2) | 0.455 (2) | 0.418 (2) | 0.038 (5)* | |
H3 | 0.492 (2) | 0.3964 (18) | 0.735 (2) | 0.027 (4)* | |
H4 | 0.373 (2) | 0.117 (2) | 0.5432 (18) | 0.027 (4)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Li1 | 0.0142 (9) | 0.0133 (9) | 0.0105 (8) | −0.0010 (7) | −0.0006 (7) | −0.0005 (7) |
B1 | 0.0090 (5) | 0.0092 (5) | 0.0084 (5) | −0.0002 (4) | 0.0003 (4) | 0.0005 (4) |
O1 | 0.0083 (4) | 0.0121 (4) | 0.0093 (4) | −0.0004 (3) | 0.0004 (3) | 0.0009 (3) |
O2 | 0.0102 (4) | 0.0148 (4) | 0.0098 (4) | −0.0032 (3) | −0.0011 (3) | 0.0030 (3) |
O3 | 0.0109 (4) | 0.0092 (4) | 0.0099 (4) | 0.0008 (3) | −0.0032 (3) | −0.0001 (3) |
O4 | 0.0094 (4) | 0.0101 (4) | 0.0135 (4) | 0.0005 (3) | −0.0007 (3) | −0.0019 (3) |
Geometric parameters (Å, º) top
Li1—O1i | 1.966 (2) | B1—O3 | 1.4644 (14) |
Li1—O2 | 1.931 (2) | B1—O4 | 1.4989 (13) |
Li1—O3ii | 1.933 (2) | O1—H1 | 0.807 (18) |
Li1—O4iii | 2.022 (2) | O2—H2 | 0.837 (19) |
B1—O1 | 1.4774 (13) | O3—H3 | 0.793 (18) |
B1—O2 | 1.4745 (14) | O4—H4 | 0.845 (18) |
| | | |
O2—Li1—O3ii | 112.95 (10) | B1—O1—Li1iv | 124.28 (8) |
O2—Li1—O1i | 123.10 (10) | B1—O1—H1 | 108.8 (12) |
O3ii—Li1—O1i | 104.01 (9) | Li1iv—O1—H1 | 110.6 (12) |
O2—Li1—O4iii | 98.98 (9) | B1—O2—Li1 | 131.84 (9) |
O3ii—Li1—O4iii | 110.53 (10) | B1—O2—H2 | 111.3 (13) |
O1i—Li1—O4iii | 106.85 (9) | Li1—O2—H2 | 109.6 (13) |
O3—B1—O2 | 109.18 (8) | B1—O3—Li1v | 134.60 (9) |
O3—B1—O1 | 112.77 (9) | B1—O3—H3 | 112.1 (12) |
O2—B1—O1 | 106.30 (8) | Li1v—O3—H3 | 104.9 (12) |
O3—B1—O4 | 106.83 (8) | B1—O4—Li1vi | 126.40 (8) |
O2—B1—O4 | 112.89 (9) | B1—O4—H4 | 109.9 (11) |
O1—B1—O4 | 108.97 (8) | Li1vi—O4—H4 | 115.0 (11) |
Symmetry codes: (i) x, −y+1/2, z−1/2; (ii) −x+1/2, −y+1, z−1/2; (iii) x−1/2, −y+1/2, −z+1; (iv) x, −y+1/2, z+1/2; (v) −x+1/2, −y+1, z+1/2; (vi) x+1/2, −y+1/2, −z+1. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···O4iii | 0.807 (18) | 1.990 (18) | 2.7835 (11) | 167.4 (16) |
O2—H2···O3vii | 0.837 (19) | 2.03 (2) | 2.8643 (11) | 173.4 (18) |
O3—H3···O1viii | 0.793 (18) | 1.919 (19) | 2.7117 (11) | 177.4 (18) |
O4—H4···O2ix | 0.845 (18) | 2.308 (18) | 3.1522 (11) | 178.6 (16) |
Symmetry codes: (iii) x−1/2, −y+1/2, −z+1; (vii) −x+1, −y+1, −z+1; (viii) x+1/2, y, −z+3/2; (ix) −x+1/2, y−1/2, z. |
Experimental details
Crystal data |
Chemical formula | Li+·BO4H4− |
Mr | 85.78 |
Crystal system, space group | Orthorhombic, Pbca |
Temperature (K) | 120 |
a, b, c (Å) | 7.9362 (3), 8.5220 (3), 9.1762 (4) |
V (Å3) | 620.61 (4) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 0.18 |
Crystal size (mm) | 0.20 × 0.18 × 0.17 |
|
Data collection |
Diffractometer | KappaCCD (with Oxford Cryostream) diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 6073, 907, 787 |
Rint | 0.021 |
(sin θ/λ)max (Å−1) | 0.703 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.029, 0.069, 1.11 |
No. of reflections | 907 |
No. of parameters | 71 |
H-atom treatment | All H-atom parameters refined |
Δρmax, Δρmin (e Å−3) | 0.28, −0.30 |
Selected geometric parameters (Å, º) topLi1—O1i | 1.966 (2) | B1—O1 | 1.4774 (13) |
Li1—O2 | 1.931 (2) | B1—O2 | 1.4745 (14) |
Li1—O3ii | 1.933 (2) | B1—O3 | 1.4644 (14) |
Li1—O4iii | 2.022 (2) | B1—O4 | 1.4989 (13) |
| | | |
O2—Li1—O3ii | 112.95 (10) | O3—B1—O2 | 109.18 (8) |
O2—Li1—O1i | 123.10 (10) | O3—B1—O1 | 112.77 (9) |
O3ii—Li1—O1i | 104.01 (9) | O2—B1—O1 | 106.30 (8) |
O2—Li1—O4iii | 98.98 (9) | O3—B1—O4 | 106.83 (8) |
O3ii—Li1—O4iii | 110.53 (10) | O2—B1—O4 | 112.89 (9) |
O1i—Li1—O4iii | 106.85 (9) | O1—B1—O4 | 108.97 (8) |
Symmetry codes: (i) x, −y+1/2, z−1/2; (ii) −x+1/2, −y+1, z−1/2; (iii) x−1/2, −y+1/2, −z+1. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···O4iii | 0.807 (18) | 1.990 (18) | 2.7835 (11) | 167.4 (16) |
O2—H2···O3iv | 0.837 (19) | 2.03 (2) | 2.8643 (11) | 173.4 (18) |
O3—H3···O1v | 0.793 (18) | 1.919 (19) | 2.7117 (11) | 177.4 (18) |
O4—H4···O2vi | 0.845 (18) | 2.308 (18) | 3.1522 (11) | 178.6 (16) |
Symmetry codes: (iii) x−1/2, −y+1/2, −z+1; (iv) −x+1, −y+1, −z+1; (v) x+1/2, y, −z+3/2; (vi) −x+1/2, y−1/2, z. |
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While attempting to prepare RhH2(et,ph-P4) from RhCl2(et,ph-P4) (where et,ph-P4 is (Et2PCH2CH2)(Ph)PCH2P(Ph)CH2CH2PEt2) using `super hydride' LiBH(C2H5)3, we encountered crystals of the title compound as a byproduct, and determined its structure to ascertain its identity. The room-temperature structure was previously reported, based on intensities from Weissenberg films, by Höhne (1964, 1966) and coworkers (Kutschabsky & Höhne, 1965; Kutschabsky & Reck, 1966). Our results confirm the published structure, with an approximate sevenfold increase in precision. Höhne's assigned H-atom positions, assigned from difference maps, lie 0.17–0.38 Å from our refined H-atom positions. Höhne's range of B—O distances, 1.472 (8) to 1.498 (8) Å, and range of Li—O distances, 1.929 (16) to 2.015 (16) Å, are in good agreement with our results (see Abstract). Although all four hydrogen bonds are nearly linear, some short intermolecular contacts exist between H atoms of hydrogen-bonded OH groups. The shortest of these is 2.06 (2) Å [H1···H3(x - 1/2, y, 3/2 - z)]. Short intramolecular O–H···O interactions also exist within the B(OH)4- ion. All four OH hydrogen atoms are approximately eclipsed (B–O–H···O torsion angles <30°) with an adjacent OH, and O···H distances are in the range 2.23 (2)–2.51 (2) Å. The O–H···O angles in these contacts are in the range 73 (2)–85 (2)°.