Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807023562/at2293sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807023562/at2293Isup2.hkl |
CCDC reference: 655590
Key indicators
- Single-crystal X-ray study
- T = 173 K
- Mean (r-Li) = 0.030 Å
- Disorder in main residue
- R factor = 0.056
- wR factor = 0.159
- Data-to-parameter ratio = 10.6
checkCIF/PLATON results
No syntax errors found
Alert level A PLAT722_ALERT_1_A Angle Calc 148.00, Rep 108.00 Dev... 40.00 Deg. H2C -C2 -H2D 1.555 1.555 1.555
Alert level B PLAT301_ALERT_3_B Main Residue Disorder ......................... 36.00 Perc.
Alert level C PLAT062_ALERT_4_C Rescale T(min) & T(max) by ..................... 0.93 PLAT213_ALERT_2_C Atom C2 has ADP max/min Ratio ............. 4.00 prola PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for C1 PLAT764_ALERT_4_C Overcomplete CIF Bond List Detected (Rep/Expd) . 2.40 Ratio
Alert level G ABSTM02_ALERT_3_G When printed, the submitted absorption T values will be replaced by the scaled T values. Since the ratio of scaled T's is identical to the ratio of reported T values, the scaling does not imply a change to the absorption corrections used in the study. Ratio of Tmax expected/reported 0.933 Tmax scaled 0.536 Tmin scaled 0.388
1 ALERT level A = In general: serious problem 1 ALERT level B = Potentially serious problem 4 ALERT level C = Check and explain 1 ALERT level G = General alerts; check 1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 2 ALERT type 2 Indicator that the structure model may be wrong or deficient 2 ALERT type 3 Indicator that the structure quality may be low 2 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
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.
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.
For [Li(12-crown-4)Cl, see Gingl et al. (1991).
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.
[LiBr(C8H16O4)] | Dx = 1.567 Mg m−3 |
Mr = 263.06 | Mo Kα radiation, λ = 0.71073 Å |
Tetragonal, P4/nmm | Cell parameters from 2066 reflections |
Hall symbol: -P 4a 2a | θ = 3.6–24.9° |
a = 8.4895 (10) Å | µ = 3.67 mm−1 |
c = 7.7355 (9) Å | T = 173 K |
V = 557.51 (11) Å3 | Block, colourless |
Z = 2 | 0.29 × 0.21 × 0.17 mm |
F(000) = 268 |
Stoe IPDSII two-circle diffractometer | 330 independent reflections |
Radiation source: fine-focus sealed tube | 316 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.051 |
ω scans | θmax = 25.5°, θmin = 3.4° |
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 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.057 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.159 | H-atom parameters constrained |
S = 1.29 | w = 1/[σ2(Fo2) + (0.0565P)2 + 4.7442P] where P = (Fo2 + 2Fc2)/3 |
330 reflections | (Δ/σ)max < 0.001 |
31 parameters | Δρmax = 1.25 e Å−3 |
0 restraints | Δρmin = −0.83 e Å−3 |
[LiBr(C8H16O4)] | Z = 2 |
Mr = 263.06 | Mo Kα radiation |
Tetragonal, P4/nmm | µ = 3.67 mm−1 |
a = 8.4895 (10) Å | T = 173 K |
c = 7.7355 (9) Å | 0.29 × 0.21 × 0.17 mm |
V = 557.51 (11) Å3 |
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 | 0 restraints |
wR(F2) = 0.159 | H-atom parameters constrained |
S = 1.29 | Δρmax = 1.25 e Å−3 |
330 reflections | Δρmin = −0.83 e Å−3 |
31 parameters |
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 > 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. |
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. |
Experimental details
Crystal data | |
Chemical formula | [LiBr(C8H16O4)] |
Mr | 263.06 |
Crystal system, space group | Tetragonal, P4/nmm |
Temperature (K) | 173 |
a, c (Å) | 8.4895 (10), 7.7355 (9) |
V (Å3) | 557.51 (11) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 3.67 |
Crystal size (mm) | 0.29 × 0.21 × 0.17 |
Data collection | |
Diffractometer | Stoe IPDSII two-circle |
Absorption correction | Multi-scan (MULABS; Spek, 2003; Blessing, 1995) |
Tmin, Tmax | 0.416, 0.574 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 2624, 330, 316 |
Rint | 0.051 |
(sin θ/λ)max (Å−1) | 0.606 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.057, 0.159, 1.29 |
No. of reflections | 330 |
No. of parameters | 31 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 1.25, −0.83 |
Computer programs: X-AREA (Stoe & Cie, 2001), X-AREA, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), XP in SHELXTL-Plus (Sheldrick, 1991), SHELXL97.
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.