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Tetralithium hypodiphosphate hexahydrate, Li
4P
2O
6·6H
2O, forms a highly symmetrical crystal structure, where hypodiphosphate anions have
(
D3d) symmetry. Analysis of the charge distribution (experimental and theoretically calculated) shows that the charges of the P atoms are lower than in phosphates and phosphonates, whereas the O charges are similar. Values of both ρ
c and ∇
2ρ
c suggest that the P—P bond is a weak covalent one, while the P—O one is polarized covalent, with topological parameters similar to those of P—O bonds in phosphates or phosphonates. Theoretical calculations show that the hypodiphosphate anion is relatively insensitive to its coordination environment; this is brought about by the vicinity of cationic P atoms. The localization and delocalization indices have been computed and discussed.
Supporting information
Data collection: CrysAlis CCD, Oxford Diffraction Ltd.,
Version 1.171.33.55 (release 05-01-2010 CrysAlis171 .NET)
(compiled Jan 5 2010,16:28:46); cell refinement: CrysAlis RED, Oxford Diffraction Ltd.,
Version 1.171.33.55 (release 05-01-2010 CrysAlis171 .NET)
(compiled Jan 5 2010,16:28:46); data reduction: CrysAlis RED, Oxford Diffraction Ltd.,
Version 1.171.33.55 (release 05-01-2010 CrysAlis171 .NET)
(compiled Jan 5 2010,16:28:46); program(s) used to refine structure: Volkov et al., (2006); molecular graphics: Volkov et al., (2006); software used to prepare material for publication: Volkov et al., (2006).
Crystal data top
H12Li4O12P2 | Mo Kα radiation, λ = 0.7107 Å |
Mr = 293.80 | Cell parameters from 41589 reflections |
Cubic, Ia3 | θ = 3.2–72.5° |
a = 12.700 (3) Å | µ = 0.48 mm−1 |
V = 2048.4 (8) Å3 | T = 85 K |
Z = 8.0 | Parallelepiped, colourless |
F(000) = 1200 | 0.35 × 0.22 × 0.21 mm |
Dx = 1.905 Mg m−3 | |
Data collection top
Xcalibur, Onyx diffractometer | 3497 independent reflections |
Radiation source: Enhance (Mo) X-ray Source | 3178 reflections with > 3σ(I) |
Graphite monochromator | Rint = 0.039 |
Detector resolution: 8.1956 pixels mm-1 | θmax = 72.5°, θmin = 3.2° |
ω and π scans | h = −33→34 |
Absorption correction: analytical CrysAlis RED, Oxford Diffraction Ltd.,
Version 1.171.33.66 (release 28-04-2010 CrysAlis171 .NET)
(compiled Apr 28 2010,14:27:37)
Analytical numeric absorption correction using a multifaceted crystal
model based on expressions derived by R.C. Clark & J.S. Reid.
(Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887-897) | k = −34→32 |
Tmin = 0.885, Tmax = 0.919 | l = −27→31 |
103877 measured reflections | |
Refinement top
Refinement on F | 0 restraints |
Least-squares matrix: full | w1 = [Fo*sqrt(w2) + sqrt(Fo2w22 + sqrt(w22))]2
where
w2 = q/[s2(Fo2) + (0.00 P)2 + 2.50 P + 0.00 + 0.00 sin(th)]
where P = (0.3333 Fo2 + 0.6667 Fc2)
q = 1.0 |
R[F2 > 2σ(F2)] = 0.014 | (Δ/σ)max = 0.00001 |
wR(F2) = 0.013 | Δρmax = 0.32 e Å−3 |
S = 1.72 | Δρmin = −0.17 e Å−3 |
2884 reflections | Extinction correction: Becker-Coppens type 1 Gaussian isotropic, Becker, P.J. & Coppens, P. (1974) Acta Cryst., A30, 129-153. |
95 parameters | Extinction coefficient: 0.418 (18) |
Crystal data top
H12Li4O12P2 | Z = 8.0 |
Mr = 293.80 | Mo Kα radiation |
Cubic, Ia3 | µ = 0.48 mm−1 |
a = 12.700 (3) Å | T = 85 K |
V = 2048.4 (8) Å3 | 0.35 × 0.22 × 0.21 mm |
Data collection top
Xcalibur, Onyx diffractometer | 3497 independent reflections |
Absorption correction: analytical CrysAlis RED, Oxford Diffraction Ltd.,
Version 1.171.33.66 (release 28-04-2010 CrysAlis171 .NET)
(compiled Apr 28 2010,14:27:37)
Analytical numeric absorption correction using a multifaceted crystal
model based on expressions derived by R.C. Clark & J.S. Reid.
(Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887-897) | 3178 reflections with > 3σ(I) |
Tmin = 0.885, Tmax = 0.919 | Rint = 0.039 |
103877 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.014 | 95 parameters |
wR(F2) = 0.013 | 0 restraints |
S = 1.72 | Δρmax = 0.32 e Å−3 |
2884 reflections | Δρmin = −0.17 e Å−3 |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
P | 0.200353 (3) | 0.200353 (3) | 0.200353 (3) | 0.004 | |
O | 0.174504 (9) | 0.264039 (8) | 0.101346 (8) | 0.006 | |
O(W) | 0.431732 (11) | 0.149707 (10) | 0.051172 (10) | 0.008 | |
LI(1) | 0.25 | 0.34863 (4) | 0 | 0.01 | |
LI(2) | 0.5 | 0 | 0 | 0.011 | |
H(1) | 0.405447 | 0.19426 | −0.00944 | 0.026 (2) | |
H(2) | 0.366639 | 0.123312 | 0.091399 | 0.024 (2) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
P | 0.003899 (19) | 0.003899 (19) | 0.003899 (19) | −0.000086 (6) | −0.000086 (6) | −0.000086 (6) |
O | 0.00747 (3) | 0.00639 (3) | 0.00513 (3) | 0.00026 (2) | −0.00052 (2) | 0.001072 (19) |
O(W) | 0.00742 (4) | 0.00807 (4) | 0.00721 (4) | 0.00006 (2) | −0.00002 (2) | 0.00034 (3) |
LI(1) | 0.01037 (17) | 0.00940 (17) | 0.00885 (16) | 0 | 0.00072 (13) | 0 |
LI(2) | 0.01128 (13) | 0.01128 (13) | 0.01128 (13) | 0.00010 (15) | −0.00010 (15) | 0.00010 (15) |
Geometric parameters (Å, º) top
P—Pi | 2.1842 (1) | O(W)—H(1) | 1.0120 (1) |
P—O | 1.5307 (1) | O(W)—H(2) | 1.0280 (1) |
| | | |
Pi—P—O | 107.039 (5) | Oii—P—Oiii | 111.790 (4) |
O—P—Oii | 111.790 (4) | H(1)—O(W)—H(2) | 107.162 (12) |
O—P—Oiii | 111.790 (4) | | |
Symmetry codes: (i) −x+1/2, −y+1/2, −z+1/2; (ii) z, x, y; (iii) y, z, x. |
Experimental details
Crystal data |
Chemical formula | H12Li4O12P2 |
Mr | 293.80 |
Crystal system, space group | Cubic, Ia3 |
Temperature (K) | 85 |
a (Å) | 12.700 (3) |
V (Å3) | 2048.4 (8) |
Z | 8.0 |
Radiation type | Mo Kα |
µ (mm−1) | 0.48 |
Crystal size (mm) | 0.35 × 0.22 × 0.21 |
|
Data collection |
Diffractometer | Xcalibur, Onyx diffractometer |
Absorption correction | Analytical CrysAlis RED, Oxford Diffraction Ltd.,
Version 1.171.33.66 (release 28-04-2010 CrysAlis171 .NET)
(compiled Apr 28 2010,14:27:37)
Analytical numeric absorption correction using a multifaceted crystal
model based on expressions derived by R.C. Clark & J.S. Reid.
(Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887-897) |
Tmin, Tmax | 0.885, 0.919 |
No. of measured, independent and observed [ > 3σ(I)] reflections | 103877, 3497, 3178 |
Rint | 0.039 |
(sin θ/λ)max (Å−1) | 1.342 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.014, 0.013, 1.72 |
No. of reflections | 2884 |
No. of parameters | 95 |
Δρmax, Δρmin (e Å−3) | 0.32, −0.17 |
Selected geometric parameters (Å, º) topP—Pi | 2.1842 (1) | O(W)—H(1) | 1.0120 (1) |
P—O | 1.5307 (1) | O(W)—H(2) | 1.0280 (1) |
| | | |
Pi—P—O | 107.039 (5) | Oii—P—Oiii | 111.790 (4) |
O—P—Oii | 111.790 (4) | H(1)—O(W)—H(2) | 107.162 (12) |
O—P—Oiii | 111.790 (4) | | |
Symmetry codes: (i) −x+1/2, −y+1/2, −z+1/2; (ii) z, x, y; (iii) y, z, x. |
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