Higher hydrates of lithium chloride, lithium bromide and lithium iodide

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.

Computing details

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)

Crystal data

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) Å^3	Needle, colourless
Z = 4	0.3 × 0.2 × 0.1 mm

Data collection

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

Refinement on F^2	Hydrogen site location: difference Fourier map
Least-squares matrix: full	All H-atom parameters refined
R[F^2 > 2σ(F^2)] = 0.015	w = 1/[σ^2(Fo^2) + (0.0175P)^2 + 0.0458P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 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+0.001xFc^2λ^3/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.111 (6)

Special details

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 (Ų)

	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 (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

Li1—O1^i	2.0815 (15)	Li1—Cl1^ii	2.6643 (14)
Li1—O2	2.0835 (15)	Cl1—Li1^iii	2.6643 (14)
Li1—O1	2.0910 (15)	O2—Li1^iii	2.2157 (16)
Li1—O2^ii	2.2158 (15)	O1—Li1^i	2.0815 (15)
Li1—Cl1	2.6497 (15)
O1^i—Li1—O2	176.26 (8)	O2^ii—Li1—Cl1	174.54 (7)
O1^i—Li1—O1	84.12 (6)	O1^i—Li1—Cl1^ii	91.40 (5)
O2—Li1—O1	93.46 (6)	O2—Li1—Cl1^ii	91.27 (5)
O1^i—Li1—O2^ii	86.51 (6)	O1—Li1—Cl1^ii	172.86 (7)
O2—Li1—O2^ii	96.36 (6)	O2^ii—Li1—Cl1^ii	84.42 (5)
O1—Li1—O2^ii	89.75 (6)	Cl1—Li1—Cl1^ii	91.56 (4)
O1^i—Li1—Cl1	89.92 (5)	Li1—Cl1—Li1^iii	80.84 (4)
O2—Li1—Cl1	87.39 (5)	Li1—O2—Li1^iii	106.48 (6)
O1—Li1—Cl1	93.99 (6)	Li1^i—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)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1B···Cl1^iv	0.784 (13)	2.404 (13)	3.1719 (7)	166.7 (12)
O1—H1A···Cl1^v	0.774 (13)	2.358 (13)	3.1315 (7)	176.8 (12)
O2—H2B···Cl1^vi	0.756 (14)	2.752 (14)	3.3772 (6)	141.6 (12)
O2—H2A···Cl1^vii	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)

Crystal data

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) Å^3	0.2 × 0.12 × 0.03 mm

Data collection

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

Refinement on F^2	Hydrogen site location: difference Fourier map
Least-squares matrix: full	All H-atom parameters refined
R[F^2 > 2σ(F^2)] = 0.036	w = 1/[σ^2(Fo^2) + 3.2148P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 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+0.001xFc^2λ^3/sin(2θ)]^-1/4
6 restraints	Extinction coefficient: 0.245 (19)

Special details

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 (Ų)

	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 (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

Br1—Li1	2.851 (12)	Li1—O1	2.070 (12)
Br1—Li1^i	2.960 (11)	Li1—O2^iii	2.174 (13)
Li1—O2	2.037 (12)	Li1—Li1^ii	3.02 (2)
Li1—O1^ii	2.061 (12)	Li1—Li1^iii	3.11 (2)
Li1—Br1—Li1^i	95.7 (3)	O2—Li1—Li1^ii	137.8 (7)
O2—Li1—O1^ii	173.3 (7)	O1^ii—Li1—Li1^ii	43.2 (3)
O2—Li1—O1	95.2 (5)	O1—Li1—Li1^ii	43.0 (3)
O1^ii—Li1—O1	86.2 (5)	O2^iii—Li1—Li1^ii	91.0 (5)
O2—Li1—O2^iii	84.9 (5)	Br1—Li1—Li1^ii	93.4 (5)
O1^ii—Li1—O2^iii	88.5 (5)	Br1^i—Li1—Li1^ii	133.4 (6)
O1—Li1—O2^iii	93.0 (5)	O2—Li1—Li1^iii	44.2 (3)
O2—Li1—Br1	96.3 (4)	O1^ii—Li1—Li1^iii	129.2 (7)
O1^ii—Li1—Br1	90.1 (4)	O1—Li1—Li1^iii	95.5 (6)
O1—Li1—Br1	94.9 (4)	O2^iii—Li1—Li1^iii	40.8 (3)
O2^iii—Li1—Br1	171.8 (5)	Br1—Li1—Li1^iii	139.8 (6)
O2—Li1—Br1^i	88.4 (4)	Br1^i—Li1—Li1^iii	87.4 (5)
O1^ii—Li1—Br1^i	90.2 (4)	Li1^ii—Li1—Li1^iii	119.9 (7)
O1—Li1—Br1^i	176.4 (6)	Li1^ii—O1—Li1	93.8 (5)
O2^iii—Li1—Br1^i	87.7 (4)	Li1—O2—Li1^iii	95.1 (5)
Br1—Li1—Br1^i	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)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···Br1^iv	0.82 (2)	2.57 (5)	3.345 (5)	157 (10)
O2—H2B···Br1^v	0.82 (2)	2.63 (5)	3.389 (5)	155 (8)
O2—H2A···Br1^vi	0.83 (2)	2.50 (3)	3.307 (4)	167 (9)
O1—H1B···Br1^vii	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)

Crystal data

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) Å^3	0.4 × 0.2 × 0.1 mm

Data collection

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

Refinement on F^2	6 restraints
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.077	All H-atom parameters refined
wR(F^2) = 0.217	w = 1/[σ^2(Fo^2) + (0.1479P)^2 + 4.9695P] where P = (Fo^2 + 2Fc^2)/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

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 (Ų)

	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 (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

I1—Li1	3.22 (3)	Li1—O2^ii	2.17 (3)
Li1—O2	2.00 (3)	Li1—Li1^i	3.00 (6)
Li1—O1	2.04 (4)	Li1—Li1^ii	3.07 (5)
Li1—O1^i	2.07 (3)
O2—Li1—O1	101.1 (15)	O1^i—Li1—Li1^ii	131.1 (16)
O2—Li1—O1^i	172 (2)	O2^ii—Li1—Li1^ii	40.4 (7)
O1—Li1—O1^i	86.0 (12)	Li1^i—Li1—Li1^ii	128 (2)
O2—Li1—O2^ii	85.2 (11)	O2—Li1—I1	93.0 (10)
O1—Li1—O2^ii	98.9 (13)	O1—Li1—I1	93.5 (10)
O1^i—Li1—O2^ii	91.0 (11)	O1^i—Li1—I1	89.3 (9)
O2—Li1—Li1^i	144 (2)	O2^ii—Li1—I1	167.6 (16)
O1—Li1—Li1^i	43.3 (10)	Li1^i—Li1—I1	91.9 (11)
O1^i—Li1—Li1^i	42.7 (8)	Li1^ii—Li1—I1	136.4 (14)
O2^ii—Li1—Li1^i	96.7 (13)	Li1—O1—Li1^i	94.0 (12)
O2—Li1—Li1^ii	44.8 (8)	Li1—O2—Li1^ii	94.8 (11)
O1—Li1—Li1^ii	103.6 (17)

Symmetry codes: (i) −x, −y+1, −z+1; (ii) −x+1, −y+1, −z+1.

Lithium chloride trihydrate (LiCl.3H2O)

Crystal data

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) Å^3	Needle, colourless
Z = 4	0.4 × 0.25 × 0.1 mm
F(000) = 200

Data collection

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

Refinement on F^2	Hydrogen site location: difference Fourier map
Least-squares matrix: full	All H-atom parameters refined
R[F^2 > 2σ(F^2)] = 0.013	w = 1/[σ^2(Fo^2) + (0.028P)^2 + 0.022P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 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+0.001xFc^2λ^3/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.318 (12)

Special details

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 (Ų)

	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 (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

Cl1—Li1	2.6990 (5)	Li1—O1^iii	2.0599 (4)
Cl1—Li1^i	2.6990 (5)	Li1—O1^iv	2.0599 (4)
Li1—O1	2.0599 (4)	Li1—Li1^v	2.8019 (4)
Li1—O1^ii	2.0599 (4)	Li1—Li1^i	2.8019 (4)
Li1—Cl1—Li1^i	62.540 (14)	Cl1—Li1—Cl1^iv	180.0
O1—Li1—O1^ii	86.46 (2)	O1—Li1—Li1^v	132.853 (11)
O1—Li1—O1^iii	93.54 (2)	O1^ii—Li1—Li1^v	132.853 (11)
O1^ii—Li1—O1^iii	180.0	O1^iii—Li1—Li1^v	47.147 (11)
O1—Li1—O1^iv	180.0	O1^iv—Li1—Li1^v	47.147 (11)
O1^ii—Li1—O1^iv	93.54 (2)	Cl1—Li1—Li1^v	121.270 (7)
O1^iii—Li1—O1^iv	86.46 (2)	Cl1^iv—Li1—Li1^v	58.730 (7)
O1—Li1—Cl1	82.555 (14)	O1—Li1—Li1^i	47.147 (11)
O1^ii—Li1—Cl1	82.555 (14)	O1^ii—Li1—Li1^i	47.147 (11)
O1^iii—Li1—Cl1	97.445 (14)	O1^iii—Li1—Li1^i	132.853 (11)
O1^iv—Li1—Cl1	97.445 (15)	O1^iv—Li1—Li1^i	132.853 (11)
O1—Li1—Cl1^iv	97.445 (14)	Cl1—Li1—Li1^i	58.730 (7)
O1^ii—Li1—Cl1^iv	97.445 (14)	Cl1^iv—Li1—Li1^i	121.270 (7)
O1^iii—Li1—Cl1^iv	82.555 (14)	Li1^v—Li1—Li1^i	180.0
O1^iv—Li1—Cl1^iv	82.555 (14)	Li1^i—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)

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···Cl1^vi	0.74 (1)	2.51 (1)	3.2340 (5)	169 (1)
O1—H1A···O2^vii	0.78 (1)	2.04 (1)	2.8149 (8)	177 (1)
O1—H1B···Cl1^viii	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)

Crystal data

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) Å^3	Needle, colourless
Z = 4	0.3 × 0.2 × 0.1 mm
F(000) = 272

Data collection

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

Refinement on F^2	Hydrogen site location: difference Fourier map
Least-squares matrix: full	All H-atom parameters refined
R[F^2 > 2σ(F^2)] = 0.028	w = 1/[σ^2(Fo^2) + (0.0631P)^2 + 0.7506P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 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+0.001xFc^2λ^3/sin(2θ)]^-1/4
3 restraints	Extinction coefficient: 0.066 (6)

Special details

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 (Ų)

	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 (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

Br1—Li1^i	2.8973 (7)	O1—Li1	2.0609 (19)
Br1—Li1	2.8973 (7)	Li1—Li1^ii	2.8434 (10)
O1—Li1^i	2.0609 (19)	Li1—Li1^i	2.8434 (10)
Li1^i—Br1—Li1	58.77 (2)	O1—Li1—Li1^i	46.38 (5)
Li1^i—O1—Li1	87.24 (10)	Li1^ii—Li1—Li1^i	180.0
O1^iii—Li1—O1^iv	180.0	O1^iii—Li1—Br1^v	96.92 (6)
O1^iii—Li1—O1^v	94.42 (11)	O1^iv—Li1—Br1^v	83.08 (6)
O1^iv—Li1—O1^v	85.58 (11)	O1^v—Li1—Br1^v	83.08 (6)
O1^iii—Li1—O1	85.58 (11)	O1—Li1—Br1^v	96.92 (6)
O1^iv—Li1—O1	94.42 (11)	Li1^ii—Li1—Br1^v	60.613 (11)
O1^v—Li1—O1	180.0	Li1^i—Li1—Br1^v	119.387 (11)
O1^iii—Li1—Li1^ii	133.62 (5)	O1^iii—Li1—Br1	83.08 (6)
O1^iv—Li1—Li1^ii	46.38 (5)	O1^iv—Li1—Br1	96.92 (6)
O1^v—Li1—Li1^ii	46.38 (5)	O1^v—Li1—Br1	96.92 (6)
O1—Li1—Li1^ii	133.62 (5)	O1—Li1—Br1	83.08 (6)
O1^iii—Li1—Li1^i	46.38 (5)	Li1^ii—Li1—Br1	119.386 (11)
O1^iv—Li1—Li1^i	133.62 (5)	Li1^i—Li1—Br1	60.614 (11)
O1^v—Li1—Li1^i	133.62 (5)	Br1^v—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)

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···Br1^vi	0.82 (2)	2.60 (4)	3.359 (3)	155 (8)
O2—H2···Br1^vii	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)

Crystal data

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) Å^3	T = 250 K
Z = 2	Plate, colorless
F(000) = 172	0.4 × 0.15 × 0.1 mm

Data collection

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

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.015	All H-atom parameters refined
wR(F^2) = 0.038	w = 1/[σ^2(Fo^2) + (0.0236P)^2 + 0.2177P] where P = (Fo^2 + 2Fc^2)/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

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 (Ų)

	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 (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

Li1—O1	2.103 (3)	Li1—O1^iv	2.103 (3)
Li1—O1^i	2.103 (3)	Li1—O1^v	2.103 (3)
Li1—O1^ii	2.103 (3)	Li1—Li1^vi	2.7295 (13)
Li1—O1^iii	2.103 (3)	Li1—Li1^vii	2.7295 (13)
O1—Li1—O1^i	180.0	O1—Li1—Li1^vi	49.54 (6)
O1—Li1—O1^ii	97.56 (9)	O1^i—Li1—Li1^vi	130.46 (6)
O1^i—Li1—O1^ii	82.44 (9)	O1^ii—Li1—Li1^vi	130.46 (6)
O1—Li1—O1^iii	82.44 (9)	O1^iii—Li1—Li1^vi	49.54 (6)
O1^i—Li1—O1^iii	97.56 (9)	O1^iv—Li1—Li1^vi	130.46 (6)
O1^ii—Li1—O1^iii	180.00 (16)	O1^v—Li1—Li1^vi	49.54 (6)
O1—Li1—O1^iv	97.56 (9)	O1—Li1—Li1^vii	130.46 (6)
O1^i—Li1—O1^iv	82.44 (9)	O1^i—Li1—Li1^vii	49.54 (6)
O1^ii—Li1—O1^iv	82.44 (9)	O1^ii—Li1—Li1^vii	49.54 (6)
O1^iii—Li1—O1^iv	97.56 (9)	O1^iii—Li1—Li1^vii	130.46 (6)
O1—Li1—O1^v	82.44 (9)	O1^iv—Li1—Li1^vii	49.54 (6)
O1^i—Li1—O1^v	97.56 (9)	O1^v—Li1—Li1^vii	130.46 (6)
O1^ii—Li1—O1^v	97.56 (9)	Li1^vi—Li1—Li1^vii	180.0
O1^iii—Li1—O1^v	82.44 (9)	Li1—O1—Li1^vi	80.92 (12)
O1^iv—Li1—O1^v	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)

Crystal data

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) Å^3	0.5 × 0.4 × 0.15 mm

Data collection

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

Refinement on F^2	30 restraints
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.059	All H-atom parameters refined
wR(F^2) = 0.163	w = 1/[σ^2(Fo^2) + (0.090P)^2 + 1.845P] where P = (Fo^2 + 2Fc^2)/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

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 (Ų)

	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 (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

O6—Li2	2.176 (5)	O1—Li1	2.105 (5)
O2—Li1	2.178 (5)	O1—Li2^i	2.117 (5)
O4—Li2	2.107 (5)	O8—Li2	2.105 (5)
O4—Li1	2.118 (5)	O8—Li1^ii	2.107 (5)
O3—Li1	2.190 (5)	O7—Li2	2.389 (5)
O5—Li2	2.146 (5)	Li1—Li2^i	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)	Li2^i—Li1—Li2	178.5 (2)
Li1—O1—Li2^i	94.87 (19)	O8—Li2—O4	171.7 (3)
Li2—O8—Li1^ii	95.13 (19)	O8—Li2—O1^ii	84.76 (18)
O1—Li1—O8^i	85.01 (19)	O4—Li2—O1^ii	94.32 (19)
O1—Li1—O4	96.9 (2)	O8—Li2—O5	94.89 (19)
O8^i—Li1—O4	170.7 (3)	O4—Li2—O5	86.20 (18)
O1—Li1—O2	94.2 (2)	O1^ii—Li2—O5	178.7 (3)
O8^i—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)	O1^ii—Li2—O6	92.15 (19)
O8^i—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)	O1^ii—Li2—O7	98.36 (19)
O8^i—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—Li1^ii	42.46 (13)
O5—Li1—O3	85.29 (18)	O4—Li2—Li1^ii	136.6 (2)
O1—Li1—Li2^i	42.72 (13)	O1^ii—Li2—Li1^ii	42.42 (13)
O8^i—Li1—Li2^i	42.41 (13)	O5—Li2—Li1^ii	137.1 (2)
O4—Li1—Li2^i	139.4 (2)	O6—Li2—Li1^ii	93.82 (19)
O2—Li1—Li2^i	91.25 (19)	O7—Li2—Li1^ii	95.94 (18)
O5—Li1—Li2^i	135.6 (2)	O8—Li2—Li1	138.9 (2)
O3—Li1—Li2^i	95.17 (19)	O4—Li2—Li1	42.17 (13)
O1—Li1—Li2	138.6 (2)	O1^ii—Li2—Li1	136.2 (2)
O8^i—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)	Li1^ii—Li2—Li1	178.5 (2)

Symmetry codes: (i) x−1, y, z; (ii) x+1, y, z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O8—H8B···Cl2^iii	0.82 (1)	2.71 (3)	3.454 (2)	153 (5)
O5—H5B···O9^iv	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···Cl2^v	0.82 (1)	2.49 (1)	3.300 (2)	168 (4)
O7—H7A···Cl2^vi	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···Cl1^i	0.83 (1)	2.56 (2)	3.288 (3)	147 (3)
O9—H9B···Cl2^vii	0.83 (1)	2.49 (2)	3.290 (2)	163 (4)
O9—H9A···Cl2^v	0.83 (1)	2.57 (3)	3.268 (3)	143 (4)
O2—H2A···Cl2^viii	0.82 (1)	2.57 (2)	3.364 (2)	166 (5)
O4—H4B···Cl1^ix	0.82 (1)	2.51 (1)	3.317 (2)	166 (3)
O7—H7B···Cl2^iii	0.82 (1)	2.48 (1)	3.303 (2)	179 (4)
O1—H1B···O10^ix	0.82 (1)	1.99 (1)	2.805 (3)	175 (5)
O4—H4A···O10^v	0.82 (1)	1.98 (1)	2.787 (3)	168 (4)
O1—H1A···Cl1^v	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···O6^v	0.82 (1)	2.02 (2)	2.825 (3)	166 (6)
O3—H3B···Cl1^i	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)

Crystal data

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) Å^3	0.3 × 0.22 × 0.05 mm

Data collection

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

Refinement on F^2	30 restraints
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.025	All H-atom parameters refined
wR(F^2) = 0.071	w = 1/[σ^2(Fo^2) + (0.0465P)^2 + 0.528P] where P = (Fo^2 + 2Fc^2)/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

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 (Ų)

	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 (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

O6—Li2	2.197 (5)	O1—Li1	2.112 (5)
O2—Li1	2.170 (5)	O1—Li2^i	2.131 (5)
O4—Li2	2.124 (5)	O8—Li2	2.132 (5)
O4—Li1	2.137 (5)	O8—Li1^ii	2.138 (5)
O3—Li1	2.179 (5)	O7—Li2	2.342 (6)
O5—Li2	2.165 (5)	Li1—Li2^i	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)	Li2^i—Li1—Li2	177.5 (3)
Li1—O1—Li2^i	96.67 (19)	O4—Li2—O1^ii	95.6 (2)
Li2—O8—Li1^ii	95.8 (2)	O4—Li2—O8	173.7 (3)
O1—Li1—O4	98.0 (2)	O1^ii—Li2—O8	83.46 (18)
O1—Li1—O8^i	83.77 (18)	O4—Li2—O5	85.47 (18)
O4—Li1—O8^i	170.5 (3)	O1^ii—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)
O8^i—Li1—O2	84.52 (19)	O1^ii—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)
O8^i—Li1—O3	97.3 (2)	O4—Li2—O7	85.49 (18)
O2—Li1—O3	170.7 (3)	O1^ii—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)
O8^i—Li1—O5	93.9 (2)	O6—Li2—O7	169.3 (2)
O2—Li1—O5	84.88 (18)	O4—Li2—Li1^ii	137.0 (2)
O3—Li1—O5	85.84 (18)	O1^ii—Li2—Li1^ii	41.44 (13)
O1—Li1—Li2^i	41.90 (13)	O8—Li2—Li1^ii	42.16 (13)
O4—Li1—Li2^i	139.6 (2)	O5—Li2—Li1^ii	137.5 (2)
O8^i—Li1—Li2^i	42.01 (13)	O6—Li2—Li1^ii	93.56 (19)
O2—Li1—Li2^i	91.40 (19)	O7—Li2—Li1^ii	96.63 (18)
O3—Li1—Li2^i	96.09 (19)	O4—Li2—Li1	41.80 (13)
O5—Li1—Li2^i	135.9 (2)	O1^ii—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)
O8^i—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)	Li1^ii—Li2—Li1	177.5 (3)

Symmetry codes: (i) x−1, y, z; (ii) x+1, y, z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O8—H8B···Br2^iii	0.82 (2)	2.86 (3)	3.594 (2)	151 (4)
O5—H5B···O9^iv	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···Br2^v	0.83 (2)	2.62 (2)	3.442 (2)	173 (3)
O7—H7A···Br2^vi	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···Br1^i	0.82 (2)	2.58 (2)	3.347 (2)	155 (4)
O9—H9B···Br2^vii	0.82 (2)	2.63 (2)	3.407 (2)	159 (4)
O9—H9A···Br2^v	0.82 (2)	2.62 (2)	3.364 (2)	152 (4)
O2—H2A···Br2^viii	0.81 (2)	2.71 (2)	3.504 (2)	170 (4)
O4—H4B···Br1^ix	0.82 (2)	2.66 (2)	3.465 (2)	167 (3)
O7—H7B···Br2^iii	0.83 (2)	2.59 (2)	3.414 (2)	176 (4)
O1—H1B···O10^ix	0.83 (2)	2.01 (2)	2.836 (3)	179 (3)
O4—H4A···O10^v	0.82 (2)	1.99 (2)	2.794 (3)	168 (4)
O1—H1A···Br1^v	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···O6^v	0.83 (2)	2.03 (2)	2.854 (3)	178 (5)
O3—H3B···Br1^i	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.