For lithium halides, LiX (X = Cl, Br and I), hydrates with a water content of 1, 2, 3 and 5 moles of water per formula unit are known as phases in aqueous solid–liquid equilibria. The crystal structures of the monohydrates of LiCl and LiBr are known, but no crystal structures have been reported so far for the higher hydrates, apart from LiI·3H2O. In this study, the crystal structures of the di- and trihydrates of lithium chloride, lithium bromide and lithium iodide, and the pentahydrates of lithium chloride and lithium bromide have been determined. In each hydrate, the lithium cation is coordinated octahedrally. The dihydrates crystallize in the NaCl·2H2O or NaI·2H2O type structure. Surprisingly, in the tri- and pentahydrates of LiCl and LiBr, one water molecule per Li+ ion remains uncoordinated. For LiI·3H2O, the LiClO4·3H2O structure type was confirmed and the H-atom positions have been fixed. The hydrogen-bond networks in the various structures are discussed in detail. Contrary to the monohydrates, the structures of the higher hydrates show no disorder.
Supporting information
CCDC references: 1817951; 1817950; 1817949; 1817948; 1817947; 1817946; 1817945; 1817944
Data collection: APEX2 (Bruker, 2005) for LiCl.2H2O, LiBr.2H2O; X-AREA (Stoe & Cie, 2015) for LiI.2H2O, LiCl.3H2O, LiBr.3H2O, LiI.3H2O, LiCl.5H2O, LiBr.5H2O. Cell refinement: APEX2 (Bruker, 2005) for LiCl.2H2O, LiBr.2H2O; X-AREA (Stoe & Cie, 2015) for LiI.2H2O, LiCl.3H2O, LiBr.3H2O, LiI.3H2O, LiCl.5H2O, LiBr.5H2O. Data reduction: APEX2 (Bruker, 2005) for LiCl.2H2O, LiBr.2H2O; X-RED (Stoe & Cie, 2015) for LiI.2H2O, LiCl.3H2O, LiBr.3H2O, LiI.3H2O, LiCl.5H2O, LiBr.5H2O. For all structures, program(s) used to solve structure: SHELXS97 (Sheldrick, 2008). Program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015) for LiCl.2H2O, LiBr.2H2O, LiCl.3H2O, LiBr.3H2O, LiCl.5H2O, LiBr.5H2O; SHELXL2016 (Sheldrick, 2015) for LiI.2H2O, LiI.3H2O. For all structures, molecular graphics: DIAMOND (Brandenburg, 2017); software used to prepare material for publication: publCIF (Westrip, 2010).
Lithium chloride dihydrate (LiCl.2H2O)
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Crystal data top
LiCl·2H2O | F(000) = 160.0 |
Mr = 78.42 | Dx = 1.646 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 6.0838 (8) Å | Cell parameters from 873 reflections |
b = 9.3592 (13) Å | θ = 5–55° |
c = 6.0632 (9) Å | µ = 0.95 mm−1 |
β = 113.543 (3)° | T = 200 K |
V = 316.50 (8) Å3 | Needle, colourless |
Z = 4 | 0.3 × 0.2 × 0.1 mm |
Data collection top
Bruker X8 Kappa APEXII diffractometer | 717 independent reflections |
Radiation source: fine-focus sealed tube | 698 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.021 |
ω and φ scans | θmax = 31.2°, θmin = 3.7° |
Absorption correction: numerical (APEX2; Bruker, 2005) | h = −7→7 |
Tmin = 0.629, Tmax = 0.746 | k = −11→10 |
2451 measured reflections | l = −7→7 |
Refinement top
Refinement on F2 | Hydrogen site location: difference Fourier map |
Least-squares matrix: full | All H-atom parameters refined |
R[F2 > 2σ(F2)] = 0.015 | w = 1/[σ2(Fo2) + (0.0175P)2 + 0.0458P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.037 | (Δ/σ)max = 0.001 |
S = 1.09 | Δρmax = 0.21 e Å−3 |
831 reflections | Δρmin = −0.21 e Å−3 |
54 parameters | Extinction correction: SHELXL2014 (Sheldrick, 2015), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
0 restraints | Extinction coefficient: 0.111 (6) |
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Li1 | 1.0106 (2) | 0.66255 (15) | 0.4573 (2) | 0.0174 (3) | |
Cl1 | 1.28796 (3) | 0.62688 (2) | 0.21793 (3) | 0.01219 (8) | |
O1 | 0.78908 (10) | 0.48924 (6) | 0.29212 (10) | 0.01243 (13) | |
O2 | 0.81043 (10) | 0.80558 (6) | 0.18884 (10) | 0.01305 (12) | |
H1A | 0.7742 (19) | 0.4627 (14) | 0.166 (2) | 0.029 (3)* | |
H1B | 0.662 (2) | 0.5112 (14) | 0.285 (2) | 0.032 (3)* | |
H2A | 0.7986 (19) | 0.8841 (13) | 0.2306 (19) | 0.022 (3)* | |
H2B | 0.683 (2) | 0.7842 (14) | 0.111 (3) | 0.040 (4)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Li1 | 0.0192 (6) | 0.0153 (6) | 0.0172 (6) | −0.0003 (5) | 0.0066 (5) | 0.0018 (5) |
Cl1 | 0.01299 (11) | 0.01208 (12) | 0.01222 (11) | 0.00179 (5) | 0.00579 (7) | 0.00058 (5) |
O1 | 0.0121 (3) | 0.0140 (3) | 0.0119 (3) | 0.00082 (19) | 0.00547 (19) | −0.0019 (2) |
O2 | 0.0124 (2) | 0.0104 (3) | 0.0150 (3) | 0.00003 (19) | 0.0040 (2) | −0.0009 (2) |
Geometric parameters (Å, º) top
Li1—O1i | 2.0815 (15) | Li1—Cl1ii | 2.6643 (14) |
Li1—O2 | 2.0835 (15) | Cl1—Li1iii | 2.6643 (14) |
Li1—O1 | 2.0910 (15) | O2—Li1iii | 2.2157 (16) |
Li1—O2ii | 2.2158 (15) | O1—Li1i | 2.0815 (15) |
Li1—Cl1 | 2.6497 (15) | | |
| | | |
O1i—Li1—O2 | 176.26 (8) | O2ii—Li1—Cl1 | 174.54 (7) |
O1i—Li1—O1 | 84.12 (6) | O1i—Li1—Cl1ii | 91.40 (5) |
O2—Li1—O1 | 93.46 (6) | O2—Li1—Cl1ii | 91.27 (5) |
O1i—Li1—O2ii | 86.51 (6) | O1—Li1—Cl1ii | 172.86 (7) |
O2—Li1—O2ii | 96.36 (6) | O2ii—Li1—Cl1ii | 84.42 (5) |
O1—Li1—O2ii | 89.75 (6) | Cl1—Li1—Cl1ii | 91.56 (4) |
O1i—Li1—Cl1 | 89.92 (5) | Li1—Cl1—Li1iii | 80.84 (4) |
O2—Li1—Cl1 | 87.39 (5) | Li1—O2—Li1iii | 106.48 (6) |
O1—Li1—Cl1 | 93.99 (6) | Li1i—O1—Li1 | 95.88 (6) |
Symmetry codes: (i) −x+2, −y+1, −z+1; (ii) x, −y+3/2, z+1/2; (iii) x, −y+3/2, z−1/2. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1B···Cl1iv | 0.784 (13) | 2.404 (13) | 3.1719 (7) | 166.7 (12) |
O1—H1A···Cl1v | 0.774 (13) | 2.358 (13) | 3.1315 (7) | 176.8 (12) |
O2—H2B···Cl1vi | 0.756 (14) | 2.752 (14) | 3.3772 (6) | 141.6 (12) |
O2—H2A···Cl1vii | 0.790 (12) | 2.381 (12) | 3.1608 (7) | 169.5 (10) |
Symmetry codes: (iv) x−1, y, z; (v) −x+2, −y+1, −z; (vi) x−1, −y+3/2, z−1/2; (vii) −x+2, y+1/2, −z+1/2. |
Lithium bromide dihydrate (LiBr.2H2O)
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Crystal data top
LiBr·2H2O | Z = 2 |
Mr = 122.88 | F(000) = 116 |
Triclinic, P1 | Dx = 2.306 Mg m−3 |
a = 5.3001 (11) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 6.3970 (19) Å | Cell parameters from 454 reflections |
c = 6.4060 (15) Å | θ = 5–55° |
α = 63.694 (10)° | µ = 11.38 mm−1 |
β = 82.044 (7)° | T = 200 K |
γ = 65.567 (5)° | Needle, colourless |
V = 177.00 (8) Å3 | 0.2 × 0.12 × 0.03 mm |
Data collection top
Bruker X8 Kappa APEXII diffractometer | 810 independent reflections |
Radiation source: fine-focus sealed tube | 762 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.037 |
ω and φ scans | θmax = 29.4°, θmin = 3.6° |
Absorption correction: numerical (APEX2; Bruker, 2005) | h = −3→7 |
Tmin = 0.211, Tmax = 0.746 | k = −6→8 |
1251 measured reflections | l = −8→8 |
Refinement top
Refinement on F2 | Hydrogen site location: difference Fourier map |
Least-squares matrix: full | All H-atom parameters refined |
R[F2 > 2σ(F2)] = 0.036 | w = 1/[σ2(Fo2) + 3.2148P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.097 | (Δ/σ)max < 0.001 |
S = 1.01 | Δρmax = 2.23 e Å−3 |
810 reflections | Δρmin = −1.11 e Å−3 |
54 parameters | Extinction correction: SHELXL2016 (Sheldrick, 2015), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
6 restraints | Extinction coefficient: 0.245 (19) |
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Br1 | 0.25544 (11) | 0.12204 (10) | 0.23322 (10) | 0.0076 (3) | |
Li1 | 0.309 (2) | 0.378 (2) | 0.483 (2) | 0.014 (2) | |
O1 | −0.0142 (9) | 0.7182 (8) | 0.2951 (8) | 0.0089 (8) | |
O2 | 0.6131 (9) | 0.4807 (9) | 0.2914 (8) | 0.0105 (9) | |
H1B | −0.02 (2) | 0.840 (11) | 0.312 (14) | 0.03 (3)* | |
H2A | 0.779 (7) | 0.388 (15) | 0.300 (15) | 0.03 (3)* | |
H2B | 0.588 (19) | 0.601 (14) | 0.162 (10) | 0.05 (3)* | |
H1A | −0.03 (3) | 0.770 (16) | 0.153 (5) | 0.04 (3)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Br1 | 0.0064 (4) | 0.0086 (4) | 0.0070 (4) | −0.0021 (2) | 0.0014 (2) | −0.0037 (2) |
Li1 | 0.010 (5) | 0.016 (5) | 0.015 (5) | −0.004 (4) | 0.002 (4) | −0.006 (4) |
O1 | 0.008 (2) | 0.0087 (19) | 0.010 (2) | −0.0032 (16) | 0.0018 (16) | −0.0043 (16) |
O2 | 0.006 (2) | 0.012 (2) | 0.011 (2) | −0.0004 (16) | 0.0029 (16) | −0.0050 (18) |
Geometric parameters (Å, º) top
Br1—Li1 | 2.851 (12) | Li1—O1 | 2.070 (12) |
Br1—Li1i | 2.960 (11) | Li1—O2iii | 2.174 (13) |
Li1—O2 | 2.037 (12) | Li1—Li1ii | 3.02 (2) |
Li1—O1ii | 2.061 (12) | Li1—Li1iii | 3.11 (2) |
| | | |
Li1—Br1—Li1i | 95.7 (3) | O2—Li1—Li1ii | 137.8 (7) |
O2—Li1—O1ii | 173.3 (7) | O1ii—Li1—Li1ii | 43.2 (3) |
O2—Li1—O1 | 95.2 (5) | O1—Li1—Li1ii | 43.0 (3) |
O1ii—Li1—O1 | 86.2 (5) | O2iii—Li1—Li1ii | 91.0 (5) |
O2—Li1—O2iii | 84.9 (5) | Br1—Li1—Li1ii | 93.4 (5) |
O1ii—Li1—O2iii | 88.5 (5) | Br1i—Li1—Li1ii | 133.4 (6) |
O1—Li1—O2iii | 93.0 (5) | O2—Li1—Li1iii | 44.2 (3) |
O2—Li1—Br1 | 96.3 (4) | O1ii—Li1—Li1iii | 129.2 (7) |
O1ii—Li1—Br1 | 90.1 (4) | O1—Li1—Li1iii | 95.5 (6) |
O1—Li1—Br1 | 94.9 (4) | O2iii—Li1—Li1iii | 40.8 (3) |
O2iii—Li1—Br1 | 171.8 (5) | Br1—Li1—Li1iii | 139.8 (6) |
O2—Li1—Br1i | 88.4 (4) | Br1i—Li1—Li1iii | 87.4 (5) |
O1ii—Li1—Br1i | 90.2 (4) | Li1ii—Li1—Li1iii | 119.9 (7) |
O1—Li1—Br1i | 176.4 (6) | Li1ii—O1—Li1 | 93.8 (5) |
O2iii—Li1—Br1i | 87.7 (4) | Li1—O2—Li1iii | 95.1 (5) |
Br1—Li1—Br1i | 84.3 (3) | | |
Symmetry codes: (i) −x+1, −y, −z+1; (ii) −x, −y+1, −z+1; (iii) −x+1, −y+1, −z+1. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1A···Br1iv | 0.82 (2) | 2.57 (5) | 3.345 (5) | 157 (10) |
O2—H2B···Br1v | 0.82 (2) | 2.63 (5) | 3.389 (5) | 155 (8) |
O2—H2A···Br1vi | 0.83 (2) | 2.50 (3) | 3.307 (4) | 167 (9) |
O1—H1B···Br1vii | 0.83 (2) | 2.60 (6) | 3.296 (5) | 143 (9) |
Symmetry codes: (iv) −x, −y+1, −z; (v) −x+1, −y+1, −z; (vi) x+1, y, z; (vii) x, y+1, z. |
Lithium iodide dihydrate (LiI.2H2O)
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Crystal data top
LiI·2H2O | Z = 2 |
Mr = 169.87 | F(000) = 152 |
Triclinic, P1 | Dx = 2.672 Mg m−3 |
a = 5.454 (3) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 6.842 (2) Å | Cell parameters from 243 reflections |
c = 6.970 (2) Å | θ = 3.8–25.2° |
α = 61.90 (11)° | µ = 7.39 mm−1 |
β = 80.72 (12)° | T = 200 K |
γ = 67.02 (13)° | Needle, colorless |
V = 211.1 (7) Å3 | 0.4 × 0.2 × 0.1 mm |
Data collection top
Stoe IPDS 2T diffractometer | 957 independent reflections |
Radiation source: sealed X-ray tube, 12 x 0.4 mm long-fine focus | 922 reflections with I > 2σ(I) |
Plane graphite monochromator | Rint = 0.105 |
Detector resolution: 6.67 pixels mm-1 | θmax = 27.5°, θmin = 3.3° |
rotation method scans | h = −7→7 |
Absorption correction: integration (Coppens, 1970) | k = −9→9 |
Tmin = 0.157, Tmax = 0.443 | l = −9→9 |
2530 measured reflections | |
Refinement top
Refinement on F2 | 6 restraints |
Least-squares matrix: full | Hydrogen site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.077 | All H-atom parameters refined |
wR(F2) = 0.217 | w = 1/[σ2(Fo2) + (0.1479P)2 + 4.9695P] where P = (Fo2 + 2Fc2)/3 |
S = 1.17 | (Δ/σ)max < 0.001 |
957 reflections | Δρmax = 5.12 e Å−3 |
53 parameters | Δρmin = −3.41 e Å−3 |
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
I1 | 0.25309 (15) | 0.13252 (13) | 0.22338 (12) | 0.0267 (4) | |
Li1 | 0.297 (6) | 0.406 (6) | 0.480 (5) | 0.040 (6) | |
O1 | −0.015 (2) | 0.7067 (18) | 0.3080 (17) | 0.028 (2) | |
O2 | 0.606 (2) | 0.4825 (19) | 0.3072 (18) | 0.028 (2) | |
H1A | −0.02 (3) | 0.71 (3) | 0.188 (12) | 0.02 (4)* | |
H1B | 0.06 (4) | 0.80 (3) | 0.29 (3) | 0.06 (8)* | |
H2A | 0.57 (10) | 0.61 (2) | 0.19 (3) | 0.2 (3)* | |
H2B | 0.71 (2) | 0.38 (2) | 0.27 (3) | 0.03 (5)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
I1 | 0.0310 (6) | 0.0159 (6) | 0.0242 (6) | −0.0008 (4) | −0.0024 (4) | −0.0071 (4) |
Li1 | 0.044 (15) | 0.058 (19) | 0.038 (14) | −0.028 (14) | 0.015 (12) | −0.034 (14) |
O1 | 0.032 (5) | 0.022 (5) | 0.028 (5) | −0.006 (4) | −0.001 (4) | −0.012 (4) |
O2 | 0.029 (5) | 0.020 (5) | 0.031 (5) | −0.004 (4) | 0.005 (4) | −0.012 (4) |
Geometric parameters (Å, º) top
I1—Li1 | 3.22 (3) | Li1—O2ii | 2.17 (3) |
Li1—O2 | 2.00 (3) | Li1—Li1i | 3.00 (6) |
Li1—O1 | 2.04 (4) | Li1—Li1ii | 3.07 (5) |
Li1—O1i | 2.07 (3) | | |
| | | |
O2—Li1—O1 | 101.1 (15) | O1i—Li1—Li1ii | 131.1 (16) |
O2—Li1—O1i | 172 (2) | O2ii—Li1—Li1ii | 40.4 (7) |
O1—Li1—O1i | 86.0 (12) | Li1i—Li1—Li1ii | 128 (2) |
O2—Li1—O2ii | 85.2 (11) | O2—Li1—I1 | 93.0 (10) |
O1—Li1—O2ii | 98.9 (13) | O1—Li1—I1 | 93.5 (10) |
O1i—Li1—O2ii | 91.0 (11) | O1i—Li1—I1 | 89.3 (9) |
O2—Li1—Li1i | 144 (2) | O2ii—Li1—I1 | 167.6 (16) |
O1—Li1—Li1i | 43.3 (10) | Li1i—Li1—I1 | 91.9 (11) |
O1i—Li1—Li1i | 42.7 (8) | Li1ii—Li1—I1 | 136.4 (14) |
O2ii—Li1—Li1i | 96.7 (13) | Li1—O1—Li1i | 94.0 (12) |
O2—Li1—Li1ii | 44.8 (8) | Li1—O2—Li1ii | 94.8 (11) |
O1—Li1—Li1ii | 103.6 (17) | | |
Symmetry codes: (i) −x, −y+1, −z+1; (ii) −x+1, −y+1, −z+1. |
Lithium chloride trihydrate (LiCl.3H2O)
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Crystal data top
LiCl·3H2O | Dx = 1.542 Mg m−3 |
Mr = 96.44 | Mo Kα radiation, λ = 0.71073 Å |
Orthorhombic, Cmcm | Cell parameters from 9694 reflections |
a = 7.1626 (11) Å | θ = 2.0–30.9° |
b = 10.351 (2) Å | µ = 0.75 mm−1 |
c = 5.6038 (8) Å | T = 150 K |
V = 415.48 (12) Å3 | Needle, colourless |
Z = 4 | 0.4 × 0.25 × 0.1 mm |
F(000) = 200 | |
Data collection top
Stoe IPDS 2T diffractometer | 365 independent reflections |
Radiation source: sealed X-ray tube, 12 x 0.4 mm long-fine focus | 350 reflections with I > 2σ(I) |
Detector resolution: 6.67 pixels mm-1 | Rint = 0.041 |
rotation method scans | θmax = 30.5°, θmin = 3.5° |
Absorption correction: integration (Coppens, 1970) | h = −10→9 |
Tmin = 0.787, Tmax = 0.932 | k = −14→14 |
365 measured reflections | l = −8→7 |
Refinement top
Refinement on F2 | Hydrogen site location: difference Fourier map |
Least-squares matrix: full | All H-atom parameters refined |
R[F2 > 2σ(F2)] = 0.013 | w = 1/[σ2(Fo2) + (0.028P)2 + 0.022P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.033 | (Δ/σ)max = 0.001 |
S = 1.02 | Δρmax = 0.16 e Å−3 |
365 reflections | Δρmin = −0.20 e Å−3 |
29 parameters | Extinction correction: SHELXL2016 (Sheldrick, 2015), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
0 restraints | Extinction coefficient: 0.318 (12) |
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Cl1 | 0.500000 | 0.27714 (2) | 0.750000 | 0.01204 (12) | |
Li1 | 0.500000 | 0.500000 | 1.000000 | 0.0158 (3) | |
O1 | 0.69697 (7) | 0.55202 (4) | 0.750000 | 0.01047 (13) | |
O2 | 0.000000 | 0.37887 (7) | 0.750000 | 0.01506 (16) | |
H1B | 0.7506 (19) | 0.6194 (11) | 0.750000 | 0.027 (3)* | |
H1A | 0.7786 (16) | 0.5022 (11) | 0.750000 | 0.020 (2)* | |
H2 | 0.000000 | 0.3347 (12) | 0.647 (2) | 0.038 (3)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Cl1 | 0.01365 (14) | 0.00741 (14) | 0.01507 (14) | 0.000 | 0.000 | 0.000 |
Li1 | 0.0128 (6) | 0.0228 (7) | 0.0118 (7) | 0.000 | 0.000 | 0.0039 (6) |
O1 | 0.0095 (2) | 0.0098 (2) | 0.0121 (2) | −0.00148 (18) | 0.000 | 0.000 |
O2 | 0.0151 (3) | 0.0158 (3) | 0.0142 (3) | 0.000 | 0.000 | 0.000 |
Geometric parameters (Å, º) top
Cl1—Li1 | 2.6990 (5) | Li1—O1iii | 2.0599 (4) |
Cl1—Li1i | 2.6990 (5) | Li1—O1iv | 2.0599 (4) |
Li1—O1 | 2.0599 (4) | Li1—Li1v | 2.8019 (4) |
Li1—O1ii | 2.0599 (4) | Li1—Li1i | 2.8019 (4) |
| | | |
Li1—Cl1—Li1i | 62.540 (14) | Cl1—Li1—Cl1iv | 180.0 |
O1—Li1—O1ii | 86.46 (2) | O1—Li1—Li1v | 132.853 (11) |
O1—Li1—O1iii | 93.54 (2) | O1ii—Li1—Li1v | 132.853 (11) |
O1ii—Li1—O1iii | 180.0 | O1iii—Li1—Li1v | 47.147 (11) |
O1—Li1—O1iv | 180.0 | O1iv—Li1—Li1v | 47.147 (11) |
O1ii—Li1—O1iv | 93.54 (2) | Cl1—Li1—Li1v | 121.270 (7) |
O1iii—Li1—O1iv | 86.46 (2) | Cl1iv—Li1—Li1v | 58.730 (7) |
O1—Li1—Cl1 | 82.555 (14) | O1—Li1—Li1i | 47.147 (11) |
O1ii—Li1—Cl1 | 82.555 (14) | O1ii—Li1—Li1i | 47.147 (11) |
O1iii—Li1—Cl1 | 97.445 (14) | O1iii—Li1—Li1i | 132.853 (11) |
O1iv—Li1—Cl1 | 97.445 (15) | O1iv—Li1—Li1i | 132.853 (11) |
O1—Li1—Cl1iv | 97.445 (14) | Cl1—Li1—Li1i | 58.730 (7) |
O1ii—Li1—Cl1iv | 97.445 (14) | Cl1iv—Li1—Li1i | 121.270 (7) |
O1iii—Li1—Cl1iv | 82.555 (14) | Li1v—Li1—Li1i | 180.0 |
O1iv—Li1—Cl1iv | 82.555 (14) | Li1i—O1—Li1 | 85.71 (2) |
Symmetry codes: (i) −x+1, −y+1, z−1/2; (ii) −x+1, y, z; (iii) x, −y+1, −z+2; (iv) −x+1, −y+1, −z+2; (v) −x+1, −y+1, z+1/2. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2···Cl1vi | 0.74 (1) | 2.51 (1) | 3.2340 (5) | 169 (1) |
O1—H1A···O2vii | 0.78 (1) | 2.04 (1) | 2.8149 (8) | 177 (1) |
O1—H1B···Cl1viii | 0.80 (1) | 2.42 (1) | 3.1845 (7) | 161 (1) |
Symmetry codes: (vi) −x+1/2, −y+1/2, −z+1; (vii) x+1, y, z; (viii) x+1/2, y+1/2, z. |
Lithium bromide trihydrate (LiBr.3H2O)
top
Crystal data top
LiBr·3H2O | Dx = 2.039 Mg m−3 |
Mr = 140.90 | Mo Kα radiation, λ = 0.71073 Å |
Orthorhombic, Cmcm | Cell parameters from 4551 reflections |
a = 7.2785 (17) Å | θ = 3.4–29.6° |
b = 11.088 (3) Å | µ = 8.81 mm−1 |
c = 5.687 (2) Å | T = 150 K |
V = 459.0 (2) Å3 | Needle, colourless |
Z = 4 | 0.3 × 0.2 × 0.1 mm |
F(000) = 272 | |
Data collection top
Stoe IPDS 2T diffractometer | 359 independent reflections |
Radiation source: sealed X-ray tube, 12 x 0.4 mm long-fine focus | 347 reflections with I > 2σ(I) |
Detector resolution: 6.67 pixels mm-1 | Rint = 0.078 |
rotation method scans | θmax = 29.1°, θmin = 3.4° |
Absorption correction: integration (Coppens, 1970) | h = −9→9 |
Tmin = 0.159, Tmax = 0.567 | k = −15→12 |
359 measured reflections | l = −7→7 |
Refinement top
Refinement on F2 | Hydrogen site location: difference Fourier map |
Least-squares matrix: full | All H-atom parameters refined |
R[F2 > 2σ(F2)] = 0.028 | w = 1/[σ2(Fo2) + (0.0631P)2 + 0.7506P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.073 | (Δ/σ)max = 0.001 |
S = 1.02 | Δρmax = 0.68 e Å−3 |
359 reflections | Δρmin = −0.76 e Å−3 |
29 parameters | Extinction correction: SHELXL2016 (Sheldrick, 2015), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
3 restraints | Extinction coefficient: 0.066 (6) |
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Br1 | 0.000000 | 0.72768 (3) | 0.750000 | 0.0175 (3) | |
O1 | 0.1923 (3) | 0.4535 (2) | 0.750000 | 0.0160 (5) | |
O2 | 0.500000 | 0.6072 (3) | 0.750000 | 0.0209 (7) | |
Li1 | 0.000000 | 0.500000 | 1.000000 | 0.0217 (16) | |
H2 | 0.500000 | 0.648 (5) | 0.868 (7) | 0.039 (15)* | |
H1B | 0.236 (11) | 0.385 (3) | 0.750000 | 0.07 (3)* | |
H1A | 0.289 (4) | 0.489 (4) | 0.750000 | 0.019 (12)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Br1 | 0.0168 (3) | 0.0148 (4) | 0.0210 (4) | 0.000 | 0.000 | 0.000 |
O1 | 0.0120 (10) | 0.0182 (10) | 0.0177 (10) | 0.0010 (9) | 0.000 | 0.000 |
O2 | 0.0169 (16) | 0.0241 (16) | 0.0218 (16) | 0.000 | 0.000 | 0.000 |
Li1 | 0.015 (3) | 0.034 (4) | 0.017 (4) | 0.000 | 0.000 | −0.005 (3) |
Geometric parameters (Å, º) top
Br1—Li1i | 2.8973 (7) | O1—Li1 | 2.0609 (19) |
Br1—Li1 | 2.8973 (7) | Li1—Li1ii | 2.8434 (10) |
O1—Li1i | 2.0609 (19) | Li1—Li1i | 2.8434 (10) |
| | | |
Li1i—Br1—Li1 | 58.77 (2) | O1—Li1—Li1i | 46.38 (5) |
Li1i—O1—Li1 | 87.24 (10) | Li1ii—Li1—Li1i | 180.0 |
O1iii—Li1—O1iv | 180.0 | O1iii—Li1—Br1v | 96.92 (6) |
O1iii—Li1—O1v | 94.42 (11) | O1iv—Li1—Br1v | 83.08 (6) |
O1iv—Li1—O1v | 85.58 (11) | O1v—Li1—Br1v | 83.08 (6) |
O1iii—Li1—O1 | 85.58 (11) | O1—Li1—Br1v | 96.92 (6) |
O1iv—Li1—O1 | 94.42 (11) | Li1ii—Li1—Br1v | 60.613 (11) |
O1v—Li1—O1 | 180.0 | Li1i—Li1—Br1v | 119.387 (11) |
O1iii—Li1—Li1ii | 133.62 (5) | O1iii—Li1—Br1 | 83.08 (6) |
O1iv—Li1—Li1ii | 46.38 (5) | O1iv—Li1—Br1 | 96.92 (6) |
O1v—Li1—Li1ii | 46.38 (5) | O1v—Li1—Br1 | 96.92 (6) |
O1—Li1—Li1ii | 133.62 (5) | O1—Li1—Br1 | 83.08 (6) |
O1iii—Li1—Li1i | 46.38 (5) | Li1ii—Li1—Br1 | 119.386 (11) |
O1iv—Li1—Li1i | 133.62 (5) | Li1i—Li1—Br1 | 60.614 (11) |
O1v—Li1—Li1i | 133.62 (5) | Br1v—Li1—Br1 | 180.0 |
Symmetry codes: (i) −x, −y+1, z−1/2; (ii) −x, −y+1, z+1/2; (iii) −x, y, z; (iv) x, −y+1, −z+2; (v) −x, −y+1, −z+2. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1A···O2 | 0.80 (2) | 2.02 (2) | 2.814 (3) | 169 (5) |
O1—H1B···Br1vi | 0.82 (2) | 2.60 (4) | 3.359 (3) | 155 (8) |
O2—H2···Br1vii | 0.81 (2) | 2.57 (2) | 3.382 (2) | 178 (6) |
Symmetry codes: (vi) x+1/2, y−1/2, z; (vii) −x+1/2, −y+3/2, −z+2. |
Lithium iodide trihydrate (LiI.3H2O)
top
Crystal data top
LiI·3H2O | Dx = 2.371 Mg m−3 |
Mr = 187.89 | Mo Kα radiation, λ = 0.71073 Å |
Hexagonal, P63/mmc | Cell parameters from 369 reflections |
a = 7.4610 (18) Å | θ = 4.8–29.4° |
c = 5.459 (3) Å | µ = 5.96 mm−1 |
V = 263.17 (18) Å3 | T = 250 K |
Z = 2 | Plate, colorless |
F(000) = 172 | 0.4 × 0.15 × 0.1 mm |
Data collection top
Stoe IPDS 2T diffractometer | 137 independent reflections |
Radiation source: sealed X-ray tube, 12 x 0.4 mm long-fine focus | 131 reflections with I > 2σ(I) |
Plane graphite monochromator | Rint = 0.063 |
Detector resolution: 6.67 pixels mm-1 | θmax = 27.5°, θmin = 3.2° |
rotation method scans | h = −10→10 |
Absorption correction: integration (Coppens, 1970) | k = −10→10 |
Tmin = 0.383, Tmax = 0.476 | l = −7→7 |
2706 measured reflections | |
Refinement top
Refinement on F2 | 0 restraints |
Least-squares matrix: full | Hydrogen site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.015 | All H-atom parameters refined |
wR(F2) = 0.038 | w = 1/[σ2(Fo2) + (0.0236P)2 + 0.2177P] where P = (Fo2 + 2Fc2)/3 |
S = 1.07 | (Δ/σ)max < 0.001 |
137 reflections | Δρmax = 0.25 e Å−3 |
12 parameters | Δρmin = −0.68 e Å−3 |
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
I1 | 0.666667 | 0.333333 | 0.250000 | 0.0423 (2) | |
Li1 | 0.000000 | 0.000000 | 0.000000 | 0.037 (2) | |
O1 | 0.1238 (3) | 0.2477 (5) | 0.250000 | 0.0476 (8) | |
H1 | 0.088 (9) | 0.332 (7) | 0.250000 | 0.09 (2)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
I1 | 0.0357 (2) | 0.0357 (2) | 0.0555 (3) | 0.01787 (11) | 0.000 | 0.000 |
Li1 | 0.041 (3) | 0.041 (3) | 0.027 (5) | 0.0205 (17) | 0.000 | 0.000 |
O1 | 0.0649 (18) | 0.0284 (15) | 0.0374 (14) | 0.0142 (8) | 0.000 | 0.000 |
Geometric parameters (Å, º) top
Li1—O1 | 2.103 (3) | Li1—O1iv | 2.103 (3) |
Li1—O1i | 2.103 (3) | Li1—O1v | 2.103 (3) |
Li1—O1ii | 2.103 (3) | Li1—Li1vi | 2.7295 (13) |
Li1—O1iii | 2.103 (3) | Li1—Li1vii | 2.7295 (13) |
| | | |
O1—Li1—O1i | 180.0 | O1—Li1—Li1vi | 49.54 (6) |
O1—Li1—O1ii | 97.56 (9) | O1i—Li1—Li1vi | 130.46 (6) |
O1i—Li1—O1ii | 82.44 (9) | O1ii—Li1—Li1vi | 130.46 (6) |
O1—Li1—O1iii | 82.44 (9) | O1iii—Li1—Li1vi | 49.54 (6) |
O1i—Li1—O1iii | 97.56 (9) | O1iv—Li1—Li1vi | 130.46 (6) |
O1ii—Li1—O1iii | 180.00 (16) | O1v—Li1—Li1vi | 49.54 (6) |
O1—Li1—O1iv | 97.56 (9) | O1—Li1—Li1vii | 130.46 (6) |
O1i—Li1—O1iv | 82.44 (9) | O1i—Li1—Li1vii | 49.54 (6) |
O1ii—Li1—O1iv | 82.44 (9) | O1ii—Li1—Li1vii | 49.54 (6) |
O1iii—Li1—O1iv | 97.56 (9) | O1iii—Li1—Li1vii | 130.46 (6) |
O1—Li1—O1v | 82.44 (9) | O1iv—Li1—Li1vii | 49.54 (6) |
O1i—Li1—O1v | 97.56 (9) | O1v—Li1—Li1vii | 130.46 (6) |
O1ii—Li1—O1v | 97.56 (9) | Li1vi—Li1—Li1vii | 180.0 |
O1iii—Li1—O1v | 82.44 (9) | Li1—O1—Li1vi | 80.92 (12) |
O1iv—Li1—O1v | 180.0 (3) | | |
Symmetry codes: (i) −x, −y, −z; (ii) −x, −x+y, z−1/2; (iii) x, x−y, −z+1/2; (iv) y, x, z−1/2; (v) −y, −x, −z+1/2; (vi) −x, −y, z+1/2; (vii) −x, −y, z−1/2. |
Lithium chloride pentahydrate (LiCl.5H2O)
top
Crystal data top
LiCl·5H2O | Z = 4 |
Mr = 132.47 | F(000) = 280 |
Triclinic, P1 | Dx = 1.419 Mg m−3 |
a = 6.247 (2) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 9.232 (4) Å | Cell parameters from 7772 reflections |
c = 11.677 (5) Å | θ = 10.8–29.6° |
α = 88.34 (3)° | µ = 0.55 mm−1 |
β = 77.53 (3)° | T = 140 K |
γ = 70.77 (3)° | Needle, colourless |
V = 620.2 (4) Å3 | 0.5 × 0.4 × 0.15 mm |
Data collection top
Stoe IPDS 2T diffractometer | 3284 independent reflections |
Radiation source: sealed X-ray tube, 12 x 0.4 mm long-fine focus | 3103 reflections with I > 2σ(I) |
Detector resolution: 6.67 pixels mm-1 | Rint = 0.051 |
rotation method scans | θmax = 29.2°, θmin = 2.9° |
Absorption correction: integration (Coppens, 1970) | h = −8→8 |
Tmin = 0.726, Tmax = 0.936 | k = −12→12 |
3284 measured reflections | l = −15→15 |
Refinement top
Refinement on F2 | 30 restraints |
Least-squares matrix: full | Hydrogen site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.059 | All H-atom parameters refined |
wR(F2) = 0.163 | w = 1/[σ2(Fo2) + (0.090P)2 + 1.845P] where P = (Fo2 + 2Fc2)/3 |
S = 1.01 | (Δ/σ)max < 0.001 |
3283 reflections | Δρmax = 1.43 e Å−3 |
207 parameters | Δρmin = −0.48 e Å−3 |
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Cl1 | 0.78691 (10) | 0.79885 (7) | 0.66275 (5) | 0.01835 (17) | |
Cl2 | 0.80551 (10) | 0.23008 (7) | 0.11356 (5) | 0.01806 (17) | |
O10 | 0.2808 (4) | 0.8698 (2) | 0.60670 (17) | 0.0231 (4) | |
O9 | 0.7219 (4) | 0.6734 (2) | 0.93029 (17) | 0.0215 (4) | |
O6 | 0.6819 (3) | 0.4875 (2) | 0.62282 (16) | 0.0187 (4) | |
O2 | 0.3120 (3) | 0.1007 (2) | 0.84764 (18) | 0.0199 (4) | |
O4 | 0.6054 (3) | 0.1762 (2) | 0.63678 (15) | 0.0156 (3) | |
O3 | 0.2319 (3) | 0.4922 (2) | 0.62378 (17) | 0.0190 (4) | |
O5 | 0.4167 (3) | 0.3941 (2) | 0.83745 (15) | 0.0162 (4) | |
O1 | 0.0973 (3) | 0.1915 (2) | 0.62585 (16) | 0.0167 (4) | |
O8 | 0.9264 (3) | 0.3735 (2) | 0.83957 (15) | 0.0166 (4) | |
O7 | 0.7662 (3) | 0.0882 (2) | 0.86541 (18) | 0.0215 (4) | |
Li1 | 0.2590 (8) | 0.2886 (5) | 0.7282 (4) | 0.0211 (9) | |
Li2 | 0.7594 (8) | 0.2896 (5) | 0.7317 (4) | 0.0198 (9) | |
H6B | 0.700 (5) | 0.566 (2) | 0.642 (3) | 0.028 (10)* | |
H3B | 0.125 (5) | 0.572 (3) | 0.648 (3) | 0.031 (10)* | |
H3A | 0.246 (9) | 0.486 (5) | 0.5524 (11) | 0.09 (2)* | |
H2B | 0.439 (3) | 0.086 (3) | 0.863 (3) | 0.013 (7)* | |
H1A | 0.097 (9) | 0.220 (5) | 0.5586 (17) | 0.053 (14)* | |
H4A | 0.632 (8) | 0.176 (4) | 0.5651 (9) | 0.040 (12)* | |
H1B | 0.143 (9) | 0.0974 (12) | 0.622 (4) | 0.060 (16)* | |
H7B | 0.776 (7) | 0.124 (4) | 0.927 (2) | 0.042 (12)* | |
H4B | 0.639 (8) | 0.0866 (18) | 0.656 (3) | 0.042 (12)* | |
H2A | 0.295 (6) | 0.017 (2) | 0.844 (4) | 0.044 (12)* | |
H9A | 0.615 (5) | 0.728 (4) | 0.900 (4) | 0.050 (14)* | |
H9B | 0.820 (6) | 0.717 (5) | 0.919 (5) | 0.08 (2)* | |
H10A | 0.185 (5) | 0.831 (5) | 0.643 (3) | 0.041 (12)* | |
H10B | 0.392 (5) | 0.841 (5) | 0.639 (3) | 0.047 (13)* | |
H6A | 0.543 (2) | 0.504 (4) | 0.630 (4) | 0.029 (10)* | |
H7A | 0.861 (6) | 0.001 (2) | 0.855 (3) | 0.043 (12)* | |
H5A | 0.374 (8) | 0.4881 (12) | 0.840 (4) | 0.048 (13)* | |
H8A | 0.876 (9) | 0.4644 (16) | 0.861 (4) | 0.069 (17)* | |
H5B | 0.393 (9) | 0.367 (4) | 0.9052 (16) | 0.054 (14)* | |
H8B | 0.948 (10) | 0.323 (4) | 0.897 (3) | 0.066 (17)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Cl1 | 0.0215 (3) | 0.0159 (3) | 0.0155 (3) | −0.0040 (2) | −0.0032 (2) | 0.0020 (2) |
Cl2 | 0.0202 (3) | 0.0165 (3) | 0.0165 (3) | −0.0053 (2) | −0.0034 (2) | 0.0026 (2) |
O10 | 0.0301 (10) | 0.0206 (9) | 0.0158 (8) | −0.0068 (8) | −0.0017 (7) | 0.0012 (7) |
O9 | 0.0259 (10) | 0.0218 (9) | 0.0152 (8) | −0.0062 (8) | −0.0040 (7) | 0.0025 (7) |
O6 | 0.0197 (9) | 0.0185 (9) | 0.0186 (9) | −0.0076 (7) | −0.0040 (7) | 0.0030 (7) |
O2 | 0.0191 (9) | 0.0154 (8) | 0.0249 (9) | −0.0055 (7) | −0.0046 (7) | 0.0015 (7) |
O4 | 0.0193 (8) | 0.0131 (8) | 0.0117 (8) | −0.0033 (6) | −0.0014 (6) | 0.0002 (6) |
O3 | 0.0180 (8) | 0.0177 (9) | 0.0178 (9) | −0.0024 (7) | −0.0027 (7) | 0.0029 (7) |
O5 | 0.0194 (8) | 0.0142 (8) | 0.0120 (8) | −0.0037 (6) | −0.0001 (6) | 0.0003 (6) |
O1 | 0.0192 (8) | 0.0153 (8) | 0.0137 (8) | −0.0038 (6) | −0.0026 (6) | 0.0002 (6) |
O8 | 0.0192 (8) | 0.0157 (8) | 0.0135 (8) | −0.0044 (7) | −0.0029 (6) | 0.0012 (6) |
O7 | 0.0221 (9) | 0.0173 (9) | 0.0229 (9) | −0.0015 (7) | −0.0075 (7) | −0.0025 (7) |
Li1 | 0.020 (2) | 0.023 (2) | 0.019 (2) | −0.0066 (17) | −0.0024 (16) | −0.0020 (17) |
Li2 | 0.019 (2) | 0.020 (2) | 0.018 (2) | −0.0047 (16) | −0.0017 (16) | −0.0035 (16) |
Geometric parameters (Å, º) top
O6—Li2 | 2.176 (5) | O1—Li1 | 2.105 (5) |
O2—Li1 | 2.178 (5) | O1—Li2i | 2.117 (5) |
O4—Li2 | 2.107 (5) | O8—Li2 | 2.105 (5) |
O4—Li1 | 2.118 (5) | O8—Li1ii | 2.107 (5) |
O3—Li1 | 2.190 (5) | O7—Li2 | 2.389 (5) |
O5—Li2 | 2.146 (5) | Li1—Li2i | 3.109 (7) |
O5—Li1 | 2.190 (5) | Li1—Li2 | 3.138 (7) |
| | | |
Li2—O4—Li1 | 95.93 (19) | O3—Li1—Li2 | 85.39 (18) |
Li2—O5—Li1 | 92.72 (19) | Li2i—Li1—Li2 | 178.5 (2) |
Li1—O1—Li2i | 94.87 (19) | O8—Li2—O4 | 171.7 (3) |
Li2—O8—Li1ii | 95.13 (19) | O8—Li2—O1ii | 84.76 (18) |
O1—Li1—O8i | 85.01 (19) | O4—Li2—O1ii | 94.32 (19) |
O1—Li1—O4 | 96.9 (2) | O8—Li2—O5 | 94.89 (19) |
O8i—Li1—O4 | 170.7 (3) | O4—Li2—O5 | 86.20 (18) |
O1—Li1—O2 | 94.2 (2) | O1ii—Li2—O5 | 178.7 (3) |
O8i—Li1—O2 | 84.09 (19) | O8—Li2—O6 | 97.1 (2) |
O4—Li1—O2 | 86.72 (19) | O4—Li2—O6 | 91.14 (19) |
O1—Li1—O5 | 178.2 (3) | O1ii—Li2—O6 | 92.15 (19) |
O8i—Li1—O5 | 93.30 (19) | O5—Li2—O6 | 86.64 (18) |
O4—Li1—O5 | 84.83 (18) | O8—Li2—O7 | 86.84 (18) |
O2—Li1—O5 | 86.12 (19) | O4—Li2—O7 | 85.14 (18) |
O1—Li1—O3 | 94.4 (2) | O1ii—Li2—O7 | 98.36 (19) |
O8i—Li1—O3 | 96.8 (2) | O5—Li2—O7 | 82.88 (17) |
O4—Li1—O3 | 92.09 (19) | O6—Li2—O7 | 169.1 (2) |
O2—Li1—O3 | 171.4 (3) | O8—Li2—Li1ii | 42.46 (13) |
O5—Li1—O3 | 85.29 (18) | O4—Li2—Li1ii | 136.6 (2) |
O1—Li1—Li2i | 42.72 (13) | O1ii—Li2—Li1ii | 42.42 (13) |
O8i—Li1—Li2i | 42.41 (13) | O5—Li2—Li1ii | 137.1 (2) |
O4—Li1—Li2i | 139.4 (2) | O6—Li2—Li1ii | 93.82 (19) |
O2—Li1—Li2i | 91.25 (19) | O7—Li2—Li1ii | 95.94 (18) |
O5—Li1—Li2i | 135.6 (2) | O8—Li2—Li1 | 138.9 (2) |
O3—Li1—Li2i | 95.17 (19) | O4—Li2—Li1 | 42.17 (13) |
O1—Li1—Li2 | 138.6 (2) | O1ii—Li2—Li1 | 136.2 (2) |
O8i—Li1—Li2 | 136.2 (2) | O5—Li2—Li1 | 44.19 (13) |
O4—Li1—Li2 | 41.90 (13) | O6—Li2—Li1 | 85.57 (18) |
O2—Li1—Li2 | 88.05 (18) | O7—Li2—Li1 | 84.78 (17) |
O5—Li1—Li2 | 43.09 (13) | Li1ii—Li2—Li1 | 178.5 (2) |
Symmetry codes: (i) x−1, y, z; (ii) x+1, y, z. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O8—H8B···Cl2iii | 0.82 (1) | 2.71 (3) | 3.454 (2) | 153 (5) |
O5—H5B···O9iv | 0.82 (1) | 1.97 (1) | 2.782 (3) | 170 (5) |
O8—H8A···O9 | 0.82 (1) | 1.96 (1) | 2.771 (3) | 171 (5) |
O5—H5A···Cl2v | 0.82 (1) | 2.49 (1) | 3.300 (2) | 168 (4) |
O7—H7A···Cl2vi | 0.82 (1) | 2.53 (2) | 3.304 (2) | 159 (3) |
O6—H6A···O3 | 0.82 (1) | 2.00 (1) | 2.795 (3) | 165 (3) |
O10—H10B···Cl1 | 0.83 (1) | 2.44 (2) | 3.218 (3) | 157 (3) |
O10—H10A···Cl1i | 0.83 (1) | 2.56 (2) | 3.288 (3) | 147 (3) |
O9—H9B···Cl2vii | 0.83 (1) | 2.49 (2) | 3.290 (2) | 163 (4) |
O9—H9A···Cl2v | 0.83 (1) | 2.57 (3) | 3.268 (3) | 143 (4) |
O2—H2A···Cl2viii | 0.82 (1) | 2.57 (2) | 3.364 (2) | 166 (5) |
O4—H4B···Cl1ix | 0.82 (1) | 2.51 (1) | 3.317 (2) | 166 (3) |
O7—H7B···Cl2iii | 0.82 (1) | 2.48 (1) | 3.303 (2) | 179 (4) |
O1—H1B···O10ix | 0.82 (1) | 1.99 (1) | 2.805 (3) | 175 (5) |
O4—H4A···O10v | 0.82 (1) | 1.98 (1) | 2.787 (3) | 168 (4) |
O1—H1A···Cl1v | 0.82 (1) | 2.52 (2) | 3.296 (2) | 157 (4) |
O2—H2B···O7 | 0.82 (1) | 2.06 (1) | 2.854 (3) | 164 (3) |
O3—H3A···O6v | 0.82 (1) | 2.02 (2) | 2.825 (3) | 166 (6) |
O3—H3B···Cl1i | 0.82 (1) | 2.42 (2) | 3.208 (2) | 163 (3) |
O6—H6B···Cl1 | 0.81 (1) | 2.42 (1) | 3.219 (2) | 170 (4) |
Symmetry codes: (i) x−1, y, z; (iii) x, y, z+1; (iv) −x+1, −y+1, −z+2; (v) −x+1, −y+1, −z+1; (vi) −x+2, −y, −z+1; (vii) −x+2, −y+1, −z+1; (viii) −x+1, −y, −z+1; (ix) x, y−1, z. |
Lithium bromide pentahydrate (LiBr.5H2O)
top
Crystal data top
LiBr·5H2O | Z = 4 |
Mr = 176.93 | F(000) = 352 |
Triclinic, P1 | Dx = 1.769 Mg m−3 |
a = 6.353 (2) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 9.453 (4) Å | Cell parameters from 2523 reflections |
c = 11.954 (5) Å | θ = 2.4–29.6° |
α = 89.15 (3)° | µ = 6.12 mm−1 |
β = 77.53 (3)° | T = 140 K |
γ = 71.69 (3)° | Needle, colourless |
V = 664.4 (4) Å3 | 0.3 × 0.22 × 0.05 mm |
Data collection top
Stoe IPDS 2T diffractometer | 3544 independent reflections |
Radiation source: sealed X-ray tube, 12 x 0.4 mm long-fine focus | 2942 reflections with I > 2σ(I) |
Detector resolution: 6.67 pixels mm-1 | Rint = 0.122 |
rotation method scans | θmax = 29.2°, θmin = 2.8° |
Absorption correction: integration (Coppens, 1970) | h = −8→8 |
Tmin = 0.210, Tmax = 0.719 | k = −12→12 |
3544 measured reflections | l = −16→16 |
Refinement top
Refinement on F2 | 30 restraints |
Least-squares matrix: full | Hydrogen site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.025 | All H-atom parameters refined |
wR(F2) = 0.071 | w = 1/[σ2(Fo2) + (0.0465P)2 + 0.528P] where P = (Fo2 + 2Fc2)/3 |
S = 1.00 | (Δ/σ)max = 0.001 |
3544 reflections | Δρmax = 1.05 e Å−3 |
207 parameters | Δρmin = −0.87 e Å−3 |
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Br1 | 0.78481 (4) | 0.79818 (3) | 0.66544 (2) | 0.01628 (7) | |
Br2 | 0.80949 (4) | 0.22569 (3) | 0.11052 (2) | 0.01645 (7) | |
O10 | 0.2744 (4) | 0.8763 (2) | 0.60259 (18) | 0.0214 (4) | |
O9 | 0.7185 (3) | 0.6641 (2) | 0.93852 (17) | 0.0200 (4) | |
O6 | 0.6827 (3) | 0.4783 (2) | 0.61986 (18) | 0.0199 (4) | |
O2 | 0.3050 (3) | 0.1121 (2) | 0.84164 (18) | 0.0205 (4) | |
O4 | 0.5967 (3) | 0.1797 (2) | 0.63535 (16) | 0.0154 (3) | |
O3 | 0.2358 (3) | 0.4850 (2) | 0.62145 (18) | 0.0197 (4) | |
O5 | 0.4148 (3) | 0.3942 (2) | 0.83207 (16) | 0.0159 (3) | |
O1 | 0.0896 (3) | 0.1919 (2) | 0.62827 (16) | 0.0166 (3) | |
O8 | 0.9231 (3) | 0.3759 (2) | 0.83424 (16) | 0.0171 (3) | |
O7 | 0.7573 (3) | 0.0965 (2) | 0.85603 (18) | 0.0211 (4) | |
Li1 | 0.2543 (8) | 0.2910 (5) | 0.7244 (4) | 0.0193 (9) | |
Li2 | 0.7544 (8) | 0.2887 (5) | 0.7299 (4) | 0.0205 (9) | |
H6B | 0.700 (7) | 0.553 (3) | 0.644 (4) | 0.048 (13)* | |
H3B | 0.132 (6) | 0.561 (3) | 0.650 (3) | 0.044 (12)* | |
H3A | 0.260 (9) | 0.493 (5) | 0.5513 (16) | 0.077 (19)* | |
H2B | 0.429 (4) | 0.095 (4) | 0.857 (4) | 0.039 (12)* | |
H1A | 0.102 (7) | 0.219 (3) | 0.561 (2) | 0.032 (10)* | |
H4A | 0.626 (9) | 0.177 (5) | 0.5649 (16) | 0.058 (15)* | |
H1B | 0.144 (6) | 0.0995 (19) | 0.621 (3) | 0.021 (9)* | |
H7B | 0.776 (7) | 0.125 (4) | 0.917 (2) | 0.042 (12)* | |
H4B | 0.627 (7) | 0.093 (2) | 0.654 (3) | 0.030 (10)* | |
H2A | 0.270 (6) | 0.037 (3) | 0.845 (4) | 0.047 (13)* | |
H9A | 0.614 (6) | 0.704 (5) | 0.907 (4) | 0.053 (14)* | |
H9B | 0.807 (6) | 0.713 (5) | 0.926 (4) | 0.051 (14)* | |
H10A | 0.177 (5) | 0.839 (5) | 0.633 (4) | 0.043 (13)* | |
H10B | 0.368 (6) | 0.860 (6) | 0.642 (4) | 0.060 (16)* | |
H6A | 0.549 (4) | 0.492 (5) | 0.623 (5) | 0.059 (16)* | |
H7A | 0.837 (6) | 0.009 (2) | 0.843 (3) | 0.033 (11)* | |
H5A | 0.365 (6) | 0.487 (2) | 0.840 (3) | 0.032 (10)* | |
H8A | 0.869 (7) | 0.463 (2) | 0.861 (3) | 0.035 (11)* | |
H5B | 0.394 (7) | 0.366 (4) | 0.899 (2) | 0.032 (10)* | |
H8B | 0.950 (7) | 0.323 (3) | 0.887 (3) | 0.041 (12)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Br1 | 0.01580 (12) | 0.01556 (12) | 0.01686 (13) | −0.00396 (9) | −0.00397 (9) | 0.00205 (9) |
Br2 | 0.01625 (12) | 0.01626 (12) | 0.01735 (13) | −0.00522 (9) | −0.00496 (9) | 0.00353 (9) |
O10 | 0.0221 (9) | 0.0234 (10) | 0.0200 (10) | −0.0083 (8) | −0.0059 (8) | 0.0035 (7) |
O9 | 0.0209 (9) | 0.0218 (9) | 0.0187 (9) | −0.0078 (8) | −0.0059 (7) | 0.0034 (7) |
O6 | 0.0194 (9) | 0.0207 (9) | 0.0226 (10) | −0.0096 (7) | −0.0064 (8) | 0.0034 (7) |
O2 | 0.0201 (9) | 0.0182 (9) | 0.0264 (10) | −0.0093 (7) | −0.0071 (8) | 0.0059 (8) |
O4 | 0.0172 (8) | 0.0143 (8) | 0.0142 (9) | −0.0047 (6) | −0.0031 (7) | 0.0013 (6) |
O3 | 0.0162 (9) | 0.0197 (9) | 0.0207 (10) | −0.0024 (7) | −0.0042 (7) | 0.0040 (7) |
O5 | 0.0175 (8) | 0.0140 (8) | 0.0143 (8) | −0.0036 (6) | −0.0021 (7) | 0.0013 (6) |
O1 | 0.0173 (8) | 0.0167 (8) | 0.0142 (9) | −0.0034 (7) | −0.0029 (7) | −0.0003 (7) |
O8 | 0.0177 (9) | 0.0164 (8) | 0.0162 (9) | −0.0039 (7) | −0.0042 (7) | 0.0009 (7) |
O7 | 0.0218 (9) | 0.0180 (9) | 0.0221 (10) | −0.0016 (7) | −0.0088 (8) | −0.0022 (7) |
Li1 | 0.016 (2) | 0.022 (2) | 0.021 (2) | −0.0061 (17) | −0.0045 (17) | 0.0001 (17) |
Li2 | 0.017 (2) | 0.023 (2) | 0.022 (2) | −0.0062 (17) | −0.0066 (17) | −0.0029 (18) |
Geometric parameters (Å, º) top
O6—Li2 | 2.197 (5) | O1—Li1 | 2.112 (5) |
O2—Li1 | 2.170 (5) | O1—Li2i | 2.131 (5) |
O4—Li2 | 2.124 (5) | O8—Li2 | 2.132 (5) |
O4—Li1 | 2.137 (5) | O8—Li1ii | 2.138 (5) |
O3—Li1 | 2.179 (5) | O7—Li2 | 2.342 (6) |
O5—Li2 | 2.165 (5) | Li1—Li2i | 3.169 (6) |
O5—Li1 | 2.208 (5) | Li1—Li2 | 3.185 (6) |
| | | |
Li2—O4—Li1 | 96.7 (2) | O5—Li1—Li2 | 42.72 (13) |
Li2—O5—Li1 | 93.48 (19) | Li2i—Li1—Li2 | 177.5 (3) |
Li1—O1—Li2i | 96.67 (19) | O4—Li2—O1ii | 95.6 (2) |
Li2—O8—Li1ii | 95.8 (2) | O4—Li2—O8 | 173.7 (3) |
O1—Li1—O4 | 98.0 (2) | O1ii—Li2—O8 | 83.46 (18) |
O1—Li1—O8i | 83.77 (18) | O4—Li2—O5 | 85.47 (18) |
O4—Li1—O8i | 170.5 (3) | O1ii—Li2—O5 | 178.1 (3) |
O1—Li1—O2 | 93.6 (2) | O8—Li2—O5 | 95.6 (2) |
O4—Li1—O2 | 86.09 (19) | O4—Li2—O6 | 89.21 (19) |
O8i—Li1—O2 | 84.52 (19) | O1ii—Li2—O6 | 92.2 (2) |
O1—Li1—O3 | 95.7 (2) | O8—Li2—O6 | 97.1 (2) |
O4—Li1—O3 | 91.8 (2) | O5—Li2—O6 | 86.24 (19) |
O8i—Li1—O3 | 97.3 (2) | O4—Li2—O7 | 85.49 (18) |
O2—Li1—O3 | 170.7 (3) | O1ii—Li2—O7 | 97.5 (2) |
O1—Li1—O5 | 177.4 (3) | O8—Li2—O7 | 88.45 (19) |
O4—Li1—O5 | 84.09 (17) | O5—Li2—O7 | 84.13 (19) |
O8i—Li1—O5 | 93.9 (2) | O6—Li2—O7 | 169.3 (2) |
O2—Li1—O5 | 84.88 (18) | O4—Li2—Li1ii | 137.0 (2) |
O3—Li1—O5 | 85.84 (18) | O1ii—Li2—Li1ii | 41.44 (13) |
O1—Li1—Li2i | 41.90 (13) | O8—Li2—Li1ii | 42.16 (13) |
O4—Li1—Li2i | 139.6 (2) | O5—Li2—Li1ii | 137.5 (2) |
O8i—Li1—Li2i | 42.01 (13) | O6—Li2—Li1ii | 93.56 (19) |
O2—Li1—Li2i | 91.40 (19) | O7—Li2—Li1ii | 96.63 (18) |
O3—Li1—Li2i | 96.09 (19) | O4—Li2—Li1 | 41.80 (13) |
O5—Li1—Li2i | 135.9 (2) | O1ii—Li2—Li1 | 137.1 (2) |
O1—Li1—Li2 | 139.4 (2) | O8—Li2—Li1 | 139.4 (2) |
O4—Li1—Li2 | 41.49 (13) | O5—Li2—Li1 | 43.79 (13) |
O8i—Li1—Li2 | 136.4 (2) | O6—Li2—Li1 | 84.36 (17) |
O2—Li1—Li2 | 86.45 (18) | O7—Li2—Li1 | 85.52 (17) |
O3—Li1—Li2 | 85.93 (18) | Li1ii—Li2—Li1 | 177.5 (3) |
Symmetry codes: (i) x−1, y, z; (ii) x+1, y, z. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O8—H8B···Br2iii | 0.82 (2) | 2.86 (3) | 3.594 (2) | 151 (4) |
O5—H5B···O9iv | 0.83 (2) | 1.97 (2) | 2.790 (3) | 168 (4) |
O8—H8A···O9 | 0.83 (2) | 1.98 (2) | 2.800 (3) | 174 (4) |
O5—H5A···Br2v | 0.83 (2) | 2.62 (2) | 3.442 (2) | 173 (3) |
O7—H7A···Br2vi | 0.82 (2) | 2.77 (3) | 3.491 (2) | 149 (3) |
O6—H6A···O3 | 0.81 (2) | 2.02 (2) | 2.816 (3) | 169 (4) |
O10—H10B···Br1 | 0.82 (2) | 2.60 (3) | 3.340 (2) | 151 (4) |
O10—H10A···Br1i | 0.82 (2) | 2.58 (2) | 3.347 (2) | 155 (4) |
O9—H9B···Br2vii | 0.82 (2) | 2.63 (2) | 3.407 (2) | 159 (4) |
O9—H9A···Br2v | 0.82 (2) | 2.62 (2) | 3.364 (2) | 152 (4) |
O2—H2A···Br2viii | 0.81 (2) | 2.71 (2) | 3.504 (2) | 170 (4) |
O4—H4B···Br1ix | 0.82 (2) | 2.66 (2) | 3.465 (2) | 167 (3) |
O7—H7B···Br2iii | 0.83 (2) | 2.59 (2) | 3.414 (2) | 176 (4) |
O1—H1B···O10ix | 0.83 (2) | 2.01 (2) | 2.836 (3) | 179 (3) |
O4—H4A···O10v | 0.82 (2) | 1.99 (2) | 2.794 (3) | 168 (4) |
O1—H1A···Br1v | 0.83 (2) | 2.64 (2) | 3.435 (2) | 160 (3) |
O2—H2B···O7 | 0.81 (2) | 2.09 (2) | 2.873 (3) | 162 (4) |
O3—H3A···O6v | 0.83 (2) | 2.03 (2) | 2.854 (3) | 178 (5) |
O3—H3B···Br1i | 0.83 (2) | 2.58 (2) | 3.364 (2) | 159 (4) |
O6—H6B···Br1 | 0.81 (2) | 2.57 (2) | 3.361 (2) | 165 (5) |
Symmetry codes: (i) x−1, y, z; (iii) x, y, z+1; (iv) −x+1, −y+1, −z+2; (v) −x+1, −y+1, −z+1; (vi) −x+2, −y, −z+1; (vii) −x+2, −y+1, −z+1; (viii) −x+1, −y, −z+1; (ix) x, y−1, z. |