Mixed lithium/ammonium perchlorate, Li
0.41(NH
4)
0.59ClO
4, has been prepared by gel diffusion using agar agar gel as the medium of growth at ambient temperature. The Cl and mixed Li/N atoms are located on the 4
a (
,
,
) and 4
b (
, 0,
) special positions, respectively, in the space group
I2
d. The structure features a twofold interpenetrated three-dimensional entanglement architecture, in which single three-dimensional networks are constructed from tetrahedral coordination based on [-(ClO
4)-(Li/NH
4)-(ClO
4)-]
diamondoid arrays. A comparison of the crystal structures of Li
0.41(NH
4)
0.59ClO
4, LiClO
4·3H
2O, LiClO
4 and NH
4ClO
4 is given.
Supporting information
Data collection: APEX2 (Bruker, 2010); cell refinement: APEX2 (Bruker, 2010); data reduction: APEX2 (Bruker, 2010); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 1999); software used to prepare material for publication: WinGX (Farrugia, 2012) and publCIF (Westrip, 2010).
Lithium/ammonium perchlorate
top
Crystal data top
Li0.41(NH4)0.59ClO4 | Dx = 1.774 Mg m−3 |
Mr = 112.92 | Mo Kα radiation, λ = 0.71073 Å |
Tetragonal, I42d | Cell parameters from 1503 reflections |
Hall symbol: I -4 2bw | θ = 3.8–33.6° |
a = 7.4946 (2) Å | µ = 0.78 mm−1 |
c = 7.5457 (2) Å | T = 293 K |
V = 423.83 (2) Å3 | Parallelepiped, colourless |
Z = 4 | 0.23 × 0.23 × 0.18 mm |
F(000) = 227 | |
Data collection top
Bruker APEXII CCD area-detector diffractometer | 488 independent reflections |
Radiation source: fine-focus sealed tube | 456 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.033 |
ω scans | θmax = 35.4°, θmin = 3.8° |
Absorption correction: multi-scan (Blessing, 1995) | h = −12→12 |
Tmin = 0.829, Tmax = 0.85 | k = −12→12 |
4093 measured reflections | l = −10→12 |
Refinement top
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.035 | All H-atom parameters refined |
wR(F2) = 0.139 | w = 1/[σ2(Fo2) + (0.0794P)2 + 0.1679P] where P = (Fo2 + 2Fc2)/3 |
S = 1.33 | (Δ/σ)max < 0.001 |
488 reflections | Δρmax = 0.88 e Å−3 |
18 parameters | Δρmin = −0.56 e Å−3 |
4 restraints | Absolute structure: Flack (1983) and Hooft et al. (2008), with 3875 Bijvoet pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.22 (17) |
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 | Occ. (<1) |
Cl1 | 0.5000 | 0.5000 | 0.5000 | 0.0218 (2) | |
O1 | 0.4152 (2) | 0.3535 (2) | 0.3858 (2) | 0.0240 (4) | |
Li1 | 0.5000 | 0.0000 | 0.2500 | 0.0197 (11) | 0.41 (3) |
N1 | 0.5000 | 0.0000 | 0.2500 | 0.0197 (11) | 0.59 (3) |
H1 | 0.605 (2) | 0.018 (11) | 0.1733 (15) | 0.030* | 0.59 (3) |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Cl1 | 0.0190 (3) | 0.0190 (3) | 0.0275 (4) | 0.000 | 0.000 | 0.000 |
O1 | 0.0199 (7) | 0.0209 (6) | 0.0309 (7) | 0.0038 (5) | −0.0062 (6) | −0.0095 (6) |
Li1 | 0.0230 (14) | 0.0230 (14) | 0.0130 (15) | 0.000 | 0.000 | 0.000 |
N1 | 0.0230 (14) | 0.0230 (14) | 0.0130 (15) | 0.000 | 0.000 | 0.000 |
Geometric parameters (Å, º) top
Cl1—O1 | 1.5339 (15) | Cl1—O1ii | 1.5339 (15) |
Cl1—O1i | 1.5339 (15) | Cl1—O1iii | 1.5339 (15) |
| | | |
O1—Cl1—O1i | 108.41 (7) | O1—Cl1—O1iii | 108.41 (7) |
O1—Cl1—O1ii | 111.61 (14) | O1i—Cl1—O1iii | 111.61 (14) |
O1i—Cl1—O1ii | 108.41 (7) | O1ii—Cl1—O1iii | 108.41 (7) |
Symmetry codes: (i) −y+1, x, −z+1; (ii) −x+1, −y+1, z; (iii) y, −x+1, −z+1. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O1iv | 0.99 (2) | 1.98 (2) | 2.9108 (15) | 157 (2) |
Symmetry code: (iv) y+1/2, −x+1/2, −z+1/2. |