Acta Cryst. (2007). E63, m1923 [ doi:10.1107/S1600536807023562 ]
The Br and Li ions of the title compound, bromido(1,4,7,10-tetraoxacyclododecane-![[kappa]](http://journals.iucr.org/logos/entities/kappa_rmgif.gif)
4O)lithium(I), [LiBr(C8H16O4)], are located on special positions of site symmetry 4mm. The crown ether ring is disordered over two positions with one C atom located on a mirror plane.
Crystallization by slow diffusion of hexane to a tetrahydrofuran (10 ml) solution of 1,4-phenylene-bridged Li scorpionate Li2[C6H4(Bpz3)2] (0.09 mmol) in the presence of LiBr and 12-crown-4 (32 mg; 0.2 mmol) gave colourless X-ray quality crystals of LiBr.12-crown-4.
H atoms were refined with fixed individual displacement parameters [Uiso(H) = 1.2Ueq(C)] using a riding model with C—H = 0.99 Å. One C and the O atom are disordered over two sites with occupation factors of 0.5 each.
Data collection: X-AREA (Stoe & Cie, 2001); cell refinement: X-AREA; data reduction: X-AREA; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP in SHELXTL-Plus (Sheldrick, 1991); software used to prepare material for publication: SHELXL97.
![[Figure 1]](./at2293fig1thm.gif)
| Fig. 1. Perspective view of the title compound with the atom numbering scheme; displacement ellipsoids are at the 50% probability level; H atoms are drawn as small spheres of arbitrary radii. Only one site of the disordered atoms is shown. Symmetry operators for generating equivalent atoms: (A) 1/2 − y, x, z; (B) 1/2 − x, y, z; (C) y, 1/2 − x, z. |
![[Figure 2]](./at2293fig2thm.gif)
| Fig. 2. Perspective view of the title compound showing the disorder of the crown ether ring. H atoms omitted for clarity. Colour codes: C: black, Br: brown, Li: magenta, O: red. |
| [LiBr(C8H16O4)] | Z = 2 |
| Mr = 263.06 | F000 = 268 |
| Tetragonal, P4/nmm | Dx = 1.567 Mg m−3 |
| Hall symbol: -P 4a 2a | Mo Kα radiation λ = 0.71073 Å |
| a = 8.4895 (10) Å | Cell parameters from 2066 reflections |
| b = 8.4895 (10) Å | θ = 3.6–24.9º |
| c = 7.7355 (9) Å | µ = 3.67 mm−1 |
| α = 90º | T = 173 (2) K |
| β = 90º | Block, colourless |
| γ = 90º | 0.29 × 0.21 × 0.17 mm |
| V = 557.51 (11) Å3 |
| Stoe IPDSII two-circle diffractometer | 330 independent reflections |
| Radiation source: fine-focus sealed tube | 316 reflections with I > 2σ(I) |
| Monochromator: graphite | Rint = 0.051 |
| T = 173(2) K | θmax = 25.5º |
| ω scans | θmin = 3.4º |
| Absorption correction: multi-scan (MULABS; Spek, 2003; Blessing, 1995) | h = −10→9 |
| Tmin = 0.416, Tmax = 0.574 | k = −10→9 |
| 2624 measured reflections | l = −9→7 |
| Refinement on F2 | H-atom parameters constrained |
| Least-squares matrix: full | w = 1/[σ2(Fo2) + (0.0565P)2 + 4.7442P] where P = (Fo2 + 2Fc2)/3 |
| R[F2 > 2σ(F2)] = 0.057 | (Δ/σ)max < 0.001 |
| wR(F2) = 0.159 | Δρmax = 1.25 e Å−3 |
| S = 1.29 | Δρmin = −0.83 e Å−3 |
| 330 reflections | Extinction correction: none |
| 31 parameters | |
| Primary atom site location: structure-invariant direct methods | |
| Secondary atom site location: difference Fourier map | |
| Hydrogen site location: inferred from neighbouring sites |
| [LiBr(C8H16O4)] | γ = 90º |
| Mr = 263.06 | V = 557.51 (11) Å3 |
| Tetragonal, P4/nmm | Z = 2 |
| a = 8.4895 (10) Å | Mo Kα |
| b = 8.4895 (10) Å | µ = 3.67 mm−1 |
| c = 7.7355 (9) Å | T = 173 (2) K |
| α = 90º | 0.29 × 0.21 × 0.17 mm |
| β = 90º |
| Stoe IPDSII two-circle diffractometer | 330 independent reflections |
| Absorption correction: multi-scan (MULABS; Spek, 2003; Blessing, 1995) | 316 reflections with I > 2σ(I) |
| Tmin = 0.416, Tmax = 0.574 | Rint = 0.051 |
| 2624 measured reflections |
| R[F2 > 2σ(F2)] = 0.057 | Δρmax = 1.25 e Å−3 |
| wR(F2) = 0.159 | Δρmin = −0.83 e Å−3 |
| S = 1.29 | Absolute structure: ? |
| 330 reflections | Flack parameter: ? |
| 31 parameters | Rogers parameter: ? |
| H-atom parameters constrained |
Experimental. ; |
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 > 2sigma(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 | Occ. (<1) | |
| Br1 | 0.2500 | 0.2500 | 0.2282 (2) | 0.0251 (6) | |
| Li1 | 0.2500 | 0.2500 | 0.544 (4) | 0.029 (6) | |
| O1 | 0.2093 (10) | 0.0249 (13) | 0.6619 (10) | 0.040 (3) | 0.50 |
| C1 | 0.3586 (16) | −0.0390 (16) | 0.7244 (18) | 0.038 (3) | 0.50 |
| H1A | 0.4217 | −0.0809 | 0.6272 | 0.046* | 0.50 |
| H1B | 0.3391 | −0.1257 | 0.8073 | 0.046* | 0.50 |
| C2 | 0.4316 (9) | 0.0684 (9) | 0.7956 (14) | 0.091 (6) | |
| H2A | 0.3661 | 0.1115 | 0.8901 | 0.109* | 0.25 |
| H2B | 0.5297 | 0.0259 | 0.8472 | 0.109* | 0.25 |
| H2C | 0.4544 | −0.0638 | 0.8153 | 0.109* | 0.25 |
| H2D | 0.4671 | 0.2250 | 0.8457 | 0.109* | 0.25 |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Br1 | 0.0250 (7) | 0.0250 (7) | 0.0252 (9) | 0.000 | 0.000 | 0.000 |
| Li1 | 0.020 (8) | 0.020 (8) | 0.045 (17) | 0.000 | 0.000 | 0.000 |
| O1 | 0.039 (9) | 0.051 (5) | 0.029 (4) | 0.008 (4) | −0.004 (4) | −0.004 (4) |
| C1 | 0.044 (8) | 0.033 (7) | 0.037 (7) | 0.015 (6) | −0.004 (6) | 0.005 (6) |
| C2 | 0.117 (11) | 0.117 (11) | 0.037 (6) | 0.100 (12) | −0.006 (3) | 0.006 (3) |
| Br1—Li1 | 2.44 (3) | Li1—O1vii | 2.145 (17) |
| Li1—O1i | 2.145 (17) | O1—C1 | 1.460 (15) |
| Li1—O1ii | 2.145 (17) | O1—C2v | 1.624 (11) |
| Li1—O1iii | 2.145 (17) | C1—H1A | 0.9900 |
| Li1—O1 | 2.145 (17) | C1—H1B | 0.9900 |
| Li1—O1iv | 2.145 (17) | C2—C1ii | 1.232 (14) |
| Li1—O1v | 2.145 (17) | C2—H2A | 0.9890 |
| Li1—O1vi | 2.145 (17) | C2—H2B | 0.9909 |
| O1ii—Li1—O1 | 96.1 (9) | O1—C1—H1A | 110.6 |
| O1iii—Li1—O1 | 79.6 (6) | C2—C1—H1B | 110.2 |
| O1ii—Li1—O1iv | 129.8 (15) | O1—C1—H1B | 110.2 |
| O1—Li1—Br1 | 115.1 (7) | H1A—C1—H1B | 108.3 |
| C1—O1—C2v | 120.8 (8) | C1—C2—O1iii | 112.0 (10) |
| C1—O1—Li1 | 109.4 (7) | H2A—C2—H2B | 108.0 |
| O1i—C1—C2 | 96.5 (14) | H2C—C2—H2D | 108.0 |
| C2—C1—O1 | 108.1 (11) | C1ii—C2—H2C | 115.3 |
| C2—C1—H1A | 109.4 | O1i—C2—H2D | 123.0 |
| Br1—Li1—O1—C1 | 102.9 (7) | C2v—O1—C1—C2 | −72.9 (14) |
| Br1—Li1—O1—C2v | −128.8 (5) | O1—C1—C2—O1iii | −62.7 (13) |
| Symmetry codes: (i) −x+1/2, y, z; (ii) −y+1/2, −x+1/2, z; (iii) −y+1/2, x, z; (iv) y, x, z; (v) y, −x+1/2, z; (vi) −x+1/2, −y+1/2, z; (vii) x, −y+1/2, z. |
Blessing, R. H. (1995). Acta Cryst. A51, 33–38.
Gingl, F., Hiller, W., Strähle, J., Borgholte, H. & Dehnicke, K. (1991). Z. Anorg. Allg. Chem. 606, 91–96.
Sheldrick, G. M. (1991). SHELXTL-Plus. Release 4.1. Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA.
Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany.
Spek, A. L. (2003). J. Appl. Cryst. 36, 7–13.
Stoe & Cie (2001). X-AREA. Stoe & Cie, Darmstadt, Germany.
Generally, LiBr is nearly insoluble in organic solvents. However, coordination of Li cation with organic ligands such as 12-crown-4 increases the solubility of LiBr therein. Therefore, we were able to obtain single crystals of the complex LiBr.12-crown-4 in a hexane–tetraydrofuran solution.
The Br and Li ions of the title compound are located on a special position of site symmetry 4 mm. The crown ether ring is disordered over two positions with one C atom located on a mirror plane.