Role of the Li+ node in the Li-BH4 substructure of double-cation tetrahydroborates

Schouwink, P.; Smrčok, Ľ.; Černý, R.

doi:10.1107/S2052520614017351

Role of the Li⁺ node in the Li-BH₄ substructure of double-cation tetrahydroborates

The phase diagram LiBH₄-ABH₄ (A = Rb,Cs) has been screened and revealed ten new compounds Li_iA_j(BH₄)_i+j (A = Rb, Cs), with i, j ranging between 1 and 3, representing eight new structure types amongst homoleptic borohydrides. An approach based on synchrotron X-ray powder diffraction to solve crystal structures and solid-state first principles calculations to refine atomic positions allows characterizing multi-phase ball-milled samples. The Li-BH₄ substructure adopts various topologies as a function of the compound's Li content, ranging from one-dimensional isolated chains to three-dimensional networks. It is revealed that the Li⁺ ion has potential as a surprisingly versatile cation participating in framework building with the tetrahydroborate anion BH₄ as a linker, if the framework is stabilized by large electropositive counter-cations. This utility can be of interest when designing novel hydridic frameworks based on alkaline metals and will be of use when exploring the structural and coordination chemistry of light-metal systems otherwise subject to eutectic melting.

Keywords: phase diagram; homoleptic borohydrides; solid-state calculations.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S2052520614017351/dk5027sup1.cif Contains datablocks hLi2CsRietveld, hLi2RbRietveld, mLi2CsRietveld, mLi2Cs3Rietveld, mLi3CsRietveld, mLiCs2Rietveld, mLiRbRietveld, oLi3Cs2Rietveld, oLiCsRietveld, oLiRbRietveld, hLi2CsDFT, hLi2RbDFT, mLi2CsDFT, mLi2Cs3DFT, mLi3CsDFT, mLiCs2DFT, mLiRbDFT, oLi3Cs2DFT, oLiCsDFT, oLiRbDFT
	Rietveld powder data file (CIF format) https://doi.org/10.1107/S2052520614017351/dk5027hLi2CsRietveldsup2.rtv Contains datablock LiCs21_m42_384K
	Rietveld powder data file (CIF format) https://doi.org/10.1107/S2052520614017351/dk5027hLi2RbRietveldsup3.rtv Contains datablock LiRb21_m1_300K
	Rietveld powder data file (CIF format) https://doi.org/10.1107/S2052520614017351/dk5027mLi2CsRietveldsup4.rtv Contains datablock LiCs21_m1_293K
	Rietveld powder data file (CIF format) https://doi.org/10.1107/S2052520614017351/dk5027mLi2Cs3Rietveldsup5.rtv Contains datablock LiCs11_m1_293K
	Rietveld powder data file (CIF format) https://doi.org/10.1107/S2052520614017351/dk5027mLi3CsRietveldsup6.rtv Contains datablock LiCs31_s1_293K
	Rietveld powder data file (CIF format) https://doi.org/10.1107/S2052520614017351/dk5027mLiCs2Rietveldsup7.rtv Contains datablock LiCs11_m35_368K
	Rietveld powder data file (CIF format) https://doi.org/10.1107/S2052520614017351/dk5027mLiRbRietveldsup8.rtv Contains datablock LiRb11_ss23_296K
	Rietveld powder data file (CIF format) https://doi.org/10.1107/S2052520614017351/dk5027oLi3Cs2Rietveldsup9.rtv Contains datablock LiCs21_m42_384K
	Rietveld powder data file (CIF format) https://doi.org/10.1107/S2052520614017351/dk5027oLiCsRietveldsup10.rtv Contains datablock LiCs11_m35_368K
	Rietveld powder data file (CIF format) https://doi.org/10.1107/S2052520614017351/dk5027oLiRbRietveldsup11.rtv Contains datablock LiRb11_ss75_411K
	Portable Document Format (PDF) file https://doi.org/10.1107/S2052520614017351/dk5027sup12.pdf Experimental tables, sample description and supplementary figures such as in-situ diffracttion data and local environments of Li atoms

CCDC references: 1016588; 1016589; 1016590; 1016591; 1016592; 1016593; 1016594; 1016595; 1016596; 1016597; 1016598; 1016599; 1016600; 1016601; 1016602; 1016603; 1016604; 1016605; 1016606; 1016607

Computing details top

(hLi2CsRietveld) top

Crystal data top

B₃CsH₁₂Li₂	V = 616.8 (1) Å³
M_r = 191.32	Z = 3
Hexagonal, P6₂22	Synchrotron radiation, λ = 0.826887 Å
Hall symbol: P 62 2c (0 0 1)	T = 384 K
a = 7.6634 (4) Å	white
c = 12.1279 (7) Å	cylinder, ? × ? × ? mm

Data collection top

Two-axis goniometer diffractometer	Data collection mode: transmission
Specimen mounting: capillary	Scan method: Stationary detector

Refinement top

R_p = 0.045	Profile function: TCHZ
R_wp = 0.036	101 parameters
R_exp = 0.011	Only H-atom coordinates refined
R_Bragg = 0.043
χ² = 10.890	Background function: Chebychev polynomial
7029 data points

Crystal data top

B₃CsH₁₂Li₂	V = 616.8 (1) Å³
M_r = 191.32	Z = 3
Hexagonal, P6₂22	Synchrotron radiation, λ = 0.826887 Å
a = 7.6634 (4) Å	T = 384 K
c = 12.1279 (7) Å	cylinder, ? × ? × ? mm

Data collection top

Two-axis goniometer diffractometer	Data collection mode: transmission
Specimen mounting: capillary	Scan method: Stationary detector

Refinement top

R_p = 0.045	χ² = 10.890
R_wp = 0.036	7029 data points
R_exp = 0.011	101 parameters
R_Bragg = 0.043	Only H-atom coordinates refined

Special details top

Refinement. BH4 groups refined like rigid body

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	B_iso*/B_eq
Cs	0.5	0.5	0.333333	6.00 (8)
Li	0.8614 (19)	1.723 (4)	0	6.0 (8)
B1	0	0	0.5	5.7 (5)
H11	−0.0363 (9)	0.099 (2)	0.5542 (13)	5.7 (5)
B2	0.5	0	0.3076 (9)	5.7 (5)
H22	0.602 (8)	0.134 (4)	0.2534 (16)	5.7 (5)
H21	0.596 (8)	−0.041 (11)	0.3618 (16)	5.7 (5)

(hLi2RbRietveld) top

Crystal data top

B₃H₁₂Li₂Rb	V = 560.4 (3) Å³
M_r = 143.88	Z = 3
Hexagonal, P6₂22	Synchrotron radiation, λ = 0.826887 Å
Hall symbol: P 62 2c (0 0 1)	T = 300 K
a = 7.474 (2) Å	white
c = 11.585 (3) Å	cylinder, ? × ? × ? mm

Data collection top

Two-axis goniometer diffractometer	Data collection mode: transmission
Specimen mounting: capillary	Scan method: Stationary detector

Refinement top

R_p = 0.018	Profile function: TCHZ
R_wp = 0.023	68 parameters
R_exp = 0.010	Only H-atom coordinates refined
R_Bragg = 0.015
χ² = 4.709	Background function: Chebychev polynomial
7029 data points

Crystal data top

B₃H₁₂Li₂Rb	V = 560.4 (3) Å³
M_r = 143.88	Z = 3
Hexagonal, P6₂22	Synchrotron radiation, λ = 0.826887 Å
a = 7.474 (2) Å	T = 300 K
c = 11.585 (3) Å	cylinder, ? × ? × ? mm

Data collection top

Two-axis goniometer diffractometer	Data collection mode: transmission
Specimen mounting: capillary	Scan method: Stationary detector

Refinement top

R_p = 0.018	χ² = 4.709
R_wp = 0.023	7029 data points
R_exp = 0.010	68 parameters
R_Bragg = 0.015	Only H-atom coordinates refined

Special details top

Refinement. BH4 groups refined like rigid body

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	B_iso*/B_eq
Rb	0.5	0.5	0.333333	4.00 (5)
Li	0.8559 (7)	1.7118 (13)	0	4.0 (3)
B1	0	0	0.5	3.19 (13)
H11	−0.0368 (3)	0.1005 (9)	0.5557 (5)	3.19 (13)
B2	0.5	0	0.2943 (3)	3.19 (13)
H21	0.6366 (16)	0.102 (3)	0.2386 (6)	3.19 (13)
H22	0.539 (4)	−0.099 (3)	0.3501 (6)	3.19 (13)

(mLi2CsRietveld) top

Crystal data top

B₃CsH₁₂Li₂	β = 89.97 (1)°
M_r = 191.32	V = 775.4 (3) Å³
Monoclinic, Cc	Z = 4
Hall symbol: C -2yc	Synchrotron radiation, λ = 0.826887 Å
a = 7.574 (2) Å	T = 293 K
b = 7.948 (2) Å	white
c = 12.880 (3) Å	cylinder, ? × ? × ? mm

Data collection top

Two-axis goniometer diffractometer	Data collection mode: transmission
Specimen mounting: capillary	Scan method: Stationary detector

Refinement top

R_p = 0.057	Profile function: TCHZ
R_wp = 0.065	37 parameters
R_exp = 0.011	Only H-atom coordinates refined
R_Bragg = 0.072
χ² = 34.340	Background function: Chebychev polynomial
7029 data points

Crystal data top

B₃CsH₁₂Li₂	β = 89.97 (1)°
M_r = 191.32	V = 775.4 (3) Å³
Monoclinic, Cc	Z = 4
a = 7.574 (2) Å	Synchrotron radiation, λ = 0.826887 Å
b = 7.948 (2) Å	T = 293 K
c = 12.880 (3) Å	cylinder, ? × ? × ? mm

Data collection top

Two-axis goniometer diffractometer	Data collection mode: transmission
Specimen mounting: capillary	Scan method: Stationary detector

Refinement top

R_p = 0.057	χ² = 34.340
R_wp = 0.065	7029 data points
R_exp = 0.011	37 parameters
R_Bragg = 0.072	Only H-atom coordinates refined

Special details top

Refinement. BH4 groups refined like rigid body

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	B_iso*/B_eq
Cs	0.5	0.3418 (3)	0.8321	3.84 (8)
Li1	0.062 (16)	0.657 (17)	0.135 (9)	4 (3)
Li2	0.07 (2)	0.246 (15)	−0.013 (9)	4 (3)
B1	0.811 (9)	0.600 (7)	0.042 (5)	3.9 (18)
H11	0.88 (5)	0.58 (8)	−0.038 (12)	3.9 (18)
H12	0.88 (8)	0.52 (8)	0.108 (14)	3.9 (18)
H13	0.66 (5)	0.56 (15)	0.036 (17)	3.9 (18)
H14	0.82 (17)	0.745 (17)	0.062 (17)	3.9 (18)
B2	0.360 (8)	0.694 (8)	0.114 (4)	3.9 (18)
H21	0.27 (3)	0.75 (3)	0.178 (15)	3.9 (18)
H22	0.508 (18)	0.71 (3)	0.141 (18)	3.9 (18)
H23	0.34 (3)	0.77 (3)	0.035 (14)	3.9 (18)
H24	0.33 (3)	0.550 (17)	0.10 (2)	3.9 (18)
B3	0.561 (8)	0.794 (4)	0.811 (8)	3.9 (18)
H31	0.52 (5)	0.70 (3)	0.747 (16)	3.9 (18)
H32	0.44 (2)	0.82 (6)	0.866 (17)	3.9 (18)
H33	0.61 (7)	0.92 (2)	0.771 (18)	3.9 (18)
H34	0.68 (4)	0.74 (6)	0.861 (17)	3.9 (18)

(mLi2Cs3Rietveld) top

Crystal data top

B₅Cs₃H₂₀Li₂	β = 104.470 (3)°
M_r = 486.81	V = 1535.3 (2) Å³
Monoclinic, P2₁/c	Z = 4
Hall symbol: -P 2ybc	Synchrotron radiation, λ = 0.826887 Å
a = 14.444 (1) Å	T = 293 K
b = 7.4218 (6) Å	white
c = 14.7907 (10) Å	cylinder, ? × ? × ? mm

Data collection top

Two-axis goniometer diffractometer	Data collection mode: transmission
Specimen mounting: capillary	Scan method: Stationary detector

Refinement top

R_p = 0.105	Profile function: TCHZ
R_wp = 0.108	96 parameters
R_exp = 0.011	Only H-atom coordinates refined
R_Bragg = 0.078
χ² = 86.118	Background function: Chebychev polynomial
7029 data points

Crystal data top

B₅Cs₃H₂₀Li₂	β = 104.470 (3)°
M_r = 486.81	V = 1535.3 (2) Å³
Monoclinic, P2₁/c	Z = 4
a = 14.444 (1) Å	Synchrotron radiation, λ = 0.826887 Å
b = 7.4218 (6) Å	T = 293 K
c = 14.7907 (10) Å	cylinder, ? × ? × ? mm

Data collection top

Two-axis goniometer diffractometer	Data collection mode: transmission
Specimen mounting: capillary	Scan method: Stationary detector

Refinement top

R_p = 0.105	χ² = 86.118
R_wp = 0.108	7029 data points
R_exp = 0.011	96 parameters
R_Bragg = 0.078	Only H-atom coordinates refined

Special details top

Refinement. BH4 groups refined like rigid body

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	B_iso*/B_eq
Cs1	0.2691 (12)	0.747 (4)	0.6341 (15)	2.5 (4)
Cs2	0.0016 (13)	0.784 (3)	0.8502 (15)	2.5 (4)
Cs3	0.5020 (12)	0.248 (4)	0.0988 (15)	2.5 (4)
Li1	0.79 (3)	0.75 (8)	1.02 (3)	2 (9)
Li2	0.68 (3)	0.83 (6)	0.20 (4)	2 (9)
B1	0.759 (16)	0.68 (3)	0.350 (17)	0 (5)
H11	0.69 (2)	0.63 (3)	0.354 (17)	0 (5)
H12	0.815 (19)	0.64 (3)	0.41 (2)	0 (5)
H13	0.757 (16)	0.84 (4)	0.346 (17)	0 (5)
H14	0.778 (16)	0.63 (3)	0.29 (2)	0 (5)
B2	0.504 (19)	0.85 (3)	0.156 (16)	0 (5)
H21	0.51 (7)	0.73 (8)	0.11 (5)	0 (5)
H22	0.52 (7)	0.98 (7)	0.12 (6)	0 (5)
H23	0.56 (5)	0.84 (12)	0.22 (4)	0 (5)
H24	0.43 (4)	0.85 (12)	0.17 (7)	0 (5)
B3	0.73 (2)	0.55 (3)	0.13 (2)	0 (5)
H31	0.71 (2)	0.49 (3)	0.05 (3)	0 (5)
H32	0.66 (2)	0.54 (3)	0.16 (2)	0 (5)
H33	0.75 (2)	0.70 (4)	0.12 (2)	0 (5)
H34	0.79 (2)	0.47 (3)	0.17 (3)	0 (5)
B4	0.75 (2)	0.03 (3)	0.095 (17)	0 (5)
H41	0.75 (14)	0.17 (5)	0.11 (8)	0 (5)
H42	0.77 (7)	0.02 (15)	0.03 (4)	0 (5)
H43	0.68 (8)	0.0 (2)	0.09 (8)	0 (5)
H44	0.81 (9)	0.0 (2)	0.15 (5)	0 (5)
B5	0.041 (12)	0.26 (4)	0.874 (13)	0 (5)
H51	−0.04 (2)	0.27 (4)	0.837 (15)	0 (5)
H52	0.066 (13)	0.38 (5)	0.915 (15)	0 (5)
H53	0.084 (15)	0.24 (4)	0.821 (17)	0 (5)
H54	0.052 (12)	0.14 (5)	0.923 (16)	0 (5)

(mLi3CsRietveld) top

Crystal data top

B₄CsH₁₆Li₃	β = 123.767 (2)°
M_r = 213.10	V = 998.1 (1) Å³
Monoclinic, P2₁/c	Z = 4
Hall symbol: -P 2ybc	Synchrotron radiation, λ = 0.82103 Å
a = 8.1992 (3) Å	T = 293 K
b = 12.3044 (5) Å	white
c = 11.9009 (5) Å	cylinder, ? × ? × ? mm

Data collection top

Two-axis goniometer diffractometer	Data collection mode: transmission
Specimen mounting: capillary	Scan method: Stationary detector

Refinement top

R_p = 0.025	Profile function: TCHZ
R_wp = 0.018	112 parameters
R_exp = 0.001	Only H-atom coordinates refined
R_Bragg = 0.019
χ² = 478.734	Background function: Chebychev polynomial
4855 data points

Crystal data top

B₄CsH₁₆Li₃	β = 123.767 (2)°
M_r = 213.10	V = 998.1 (1) Å³
Monoclinic, P2₁/c	Z = 4
a = 8.1992 (3) Å	Synchrotron radiation, λ = 0.82103 Å
b = 12.3044 (5) Å	T = 293 K
c = 11.9009 (5) Å	cylinder, ? × ? × ? mm

Data collection top

Two-axis goniometer diffractometer	Data collection mode: transmission
Specimen mounting: capillary	Scan method: Stationary detector

Refinement top

R_p = 0.025	χ² = 478.734
R_wp = 0.018	4855 data points
R_exp = 0.001	112 parameters
R_Bragg = 0.019	Only H-atom coordinates refined

Special details top

Refinement. BH4 groups refined like rigid body

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	B_iso*/B_eq
Cs1	0.1766 (3)	0.17545 (14)	0.1542 (2)	3.71 (6)
Li1	0.297 (5)	0.927 (3)	0.485 (3)	2.0 (4)
Li2	0.718 (4)	0.333 (3)	0.276 (3)	2.0 (4)
Li3	0.691 (6)	1.010 (3)	0.185 (4)	2.0 (4)
B1	0.992 (4)	0.403 (2)	0.261 (3)	3.2 (3)
H11	0.976 (16)	0.475 (6)	0.196 (9)	3.2 (3)
H12	1.136 (10)	0.361 (9)	0.299 (12)	3.2 (3)
H13	0.867 (13)	0.344 (7)	0.200 (8)	3.2 (3)
H14	0.991 (17)	0.433 (9)	0.350 (8)	3.2 (3)
B2	0.654 (4)	0.0902 (19)	0.955 (3)	3.2 (3)
H21	0.713 (14)	0.023 (6)	0.922 (10)	3.2 (3)
H22	0.599 (15)	0.159 (6)	0.880 (8)	3.2 (3)
H23	0.774 (11)	0.120 (8)	1.058 (5)	3.2 (3)
H24	0.529 (11)	0.057 (8)	0.959 (10)	3.2 (3)
B3	0.568 (4)	0.6284 (19)	0.956 (3)	3.2 (3)
H31	0.51 (11)	0.67 (4)	1.01 (5)	3.2 (3)
H32	0.54 (12)	0.68 (3)	0.87 (5)	3.2 (3)
H33	0.49 (19)	0.55 (6)	0.92 (7)	3.2 (3)
H34	0.73 (4)	0.61 (12)	1.03 (2)	3.2 (3)
B4	0.226 (4)	0.8667 (16)	0.677 (3)	3.2 (3)
H41	0.241 (17)	0.935 (6)	0.621 (8)	3.2 (3)
H42	0.373 (7)	0.850 (11)	0.774 (7)	3.2 (3)
H43	0.17 (2)	0.791 (5)	0.612 (9)	3.2 (3)
H44	0.116 (14)	0.890 (12)	0.702 (11)	3.2 (3)

(mLiCs2Rietveld) top

Crystal data top

B₃Cs₂H₁₂Li	β = 92.693 (1)°
M_r = 317.28	V = 1985.0 (5) Å³
Monoclinic, C2/c	Z = 8
Hall symbol: -C 2yc	Synchrotron radiation, λ = 0.826887 Å
a = 7.6021 (11) Å	T = 368 K
b = 15.160 (2) Å	white
c = 17.243 (2) Å	cylinder, ? × ? × ? mm

Data collection top

Two-axis goniometer diffractometer	Data collection mode: transmission
Specimen mounting: capillary	Scan method: Stationary detector

Refinement top

R_p = 0.032	Profile function: TCHZ
R_wp = 0.042	138 parameters
R_exp = 0.011	Only H-atom coordinates refined
R_Bragg = 0.024
χ² = 16.646	Background function: Chebychev polynomial
7029 data points

Crystal data top

B₃Cs₂H₁₂Li	β = 92.693 (1)°
M_r = 317.28	V = 1985.0 (5) Å³
Monoclinic, C2/c	Z = 8
a = 7.6021 (11) Å	Synchrotron radiation, λ = 0.826887 Å
b = 15.160 (2) Å	T = 368 K
c = 17.243 (2) Å	cylinder, ? × ? × ? mm

Data collection top

Two-axis goniometer diffractometer	Data collection mode: transmission
Specimen mounting: capillary	Scan method: Stationary detector

Refinement top

R_p = 0.032	χ² = 16.646
R_wp = 0.042	7029 data points
R_exp = 0.011	138 parameters
R_Bragg = 0.024	Only H-atom coordinates refined

Special details top

Refinement. BH4 groups refined like rigid body

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	B_iso*/B_eq
Cs1	0.7504 (4)	0.10608 (19)	0.57053 (18)	4.48 (15)
Cs2	0.7297 (4)	0.7002 (2)	0.34562 (15)	4.48 (15)
Li1	0.726 (8)	0.533 (5)	0.644 (4)	2 (2)
B1	0.5	0.482 (3)	0.25	1.1 (10)
H11	0.380 (9)	0.527 (3)	0.229 (9)	1.1 (10)
H12	0.46 (2)	0.437 (3)	0.302 (4)	1.1 (10)
B2	0.769 (4)	0.896 (2)	0.4716 (18)	1.1 (10)
H21	0.74 (2)	0.832 (8)	0.507 (8)	1.1 (10)
H22	0.639 (12)	0.924 (12)	0.441 (9)	1.1 (10)
H23	0.87 (2)	0.878 (14)	0.424 (7)	1.1 (10)
H24	0.83 (3)	0.949 (8)	0.514 (8)	1.1 (10)
B3	0.704 (5)	0.157 (2)	0.3672 (18)	1.1 (10)
H31	0.66 (19)	0.20 (6)	0.422 (5)	1.1 (10)
H32	0.64 (18)	0.19 (7)	0.311 (5)	1.1 (10)
H33	0.7 (4)	0.08 (6)	0.370 (8)	1.1 (10)
H34	0.859 (9)	0.2 (2)	0.366 (8)	1.1 (10)
B4	0.5	0.931 (3)	0.25	1.1 (10)
H41	0.385 (11)	0.976 (4)	0.271 (9)	1.1 (10)
H42	0.55 (2)	0.886 (4)	0.302 (4)	1.1 (10)

(mLiRbRietveld) top

Crystal data top

B₂H₈LiRb	β = 97.776 (1)°
M_r = 122.09	V = 1855.5 (3) Å³
Monoclinic, C2/m	Z = 14
Hall symbol: -C 2y	Synchrotron radiation, λ = 0.82257 Å
a = 23.5931 (4) Å	T = 296 K
b = 4.6178 (7) Å	white
c = 17.1893 (3) Å	cylinder, ? × ? × ? mm

Data collection top

Two-axis goniometer diffractometer	Data collection mode: transmission
Specimen mounting: capillary	Scan method: Stationary detector

Refinement top

R_p = 0.022	Profile function: TCHZ
R_wp = 0.035	103 parameters
R_exp = 0.001	Only H-atom coordinates refined
R_Bragg = 0.017
χ² = 727.381	Background function: Chebychev polynomial
4054 data points

Crystal data top

B₂H₈LiRb	β = 97.776 (1)°
M_r = 122.09	V = 1855.5 (3) Å³
Monoclinic, C2/m	Z = 14
a = 23.5931 (4) Å	Synchrotron radiation, λ = 0.82257 Å
b = 4.6178 (7) Å	T = 296 K
c = 17.1893 (3) Å	cylinder, ? × ? × ? mm

Data collection top

Two-axis goniometer diffractometer	Data collection mode: transmission
Specimen mounting: capillary	Scan method: Stationary detector

Refinement top

R_p = 0.022	χ² = 727.381
R_wp = 0.035	4054 data points
R_exp = 0.001	103 parameters
R_Bragg = 0.017	Only H-atom coordinates refined

Special details top

Refinement. BH4 groups refined like rigid body

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	B_iso*/B_eq
Rb1	0	0	0.5	2.22 (10)
Rb2	0.2862 (2)	0	0.3584 (3)	2.22 (10)
Rb3	0.0684 (3)	0	0.2099 (3)	2.22 (10)
Rb4	0.35229 (19)	0.5	0.0686 (2)	2.22 (10)
Li1	0	0.5	0	0.2 (6)
Li2	0.435 (2)	0	0.264 (3)	0.2 (6)
Li3	0.203 (2)	0.5	0.144 (3)	0.2 (6)
Li4	0.163 (2)	0.5	0.429 (3)	0.2 (6)
B1	0.2495 (11)	0	0.1477 (15)	0.2 (4)
H11	0.214 (6)	0	0.185 (9)	0.2 (4)
H12	0.231 (7)	0	0.084 (4)	0.2 (4)
H13	0.2769 (16)	−0.199 (4)	0.161 (6)	0.2 (4)
B2	0.1673 (10)	0	0.4844 (14)	0.2 (4)
H21	0.140 (6)	0	0.425 (4)	0.2 (4)
H22	0.214 (2)	0	0.477 (9)	0.2 (4)
H23	0.157 (4)	−0.199 (4)	0.518 (3)	0.2 (4)
B3	0.4706 (13)	0	0.1492 (15)	0.2 (4)
H31	0.460 (8)	0	0.083 (2)	0.2 (4)
H32	0.5186 (18)	0	0.166 (10)	0.2 (4)
H33	0.452 (4)	−0.199 (4)	0.174 (5)	0.2 (4)
B4	0.0314 (9)	0.5	0.3878 (14)	0.2 (4)
H41	0.001 (6)	0.5	0.434 (8)	0.2 (4)
H42	0.006 (6)	0.5	0.327 (5)	0.2 (4)
H43	0.0594 (11)	0.301 (4)	0.395 (6)	0.2 (4)
B5	0.4014 (12)	0.5	0.3164 (14)	0.2 (4)
H51	0.365 (5)	0.5	0.266 (7)	0.2 (4)
H52	0.444 (4)	0.5	0.292 (9)	0.2 (4)
H53	0.399 (4)	0.301 (4)	0.354 (2)	0.2 (4)
B6	0.1910 (10)	0.5	0.2985 (14)	0.2 (4)
H61	0.145 (3)	0.5	0.269 (10)	0.2 (4)
H62	0.221 (6)	0.5	0.252 (8)	0.2 (4)
H63	0.199 (4)	0.301 (4)	0.3366 (19)	0.2 (4)
B7	0.1107 (11)	0.5	0.083 (2)	0.2 (4)
H71	0.067 (4)	0.5	0.104 (11)	0.2 (4)
H72	0.105 (9)	0.5	0.017 (2)	0.2 (4)
H73	0.135 (3)	0.301 (4)	0.106 (6)	0.2 (4)

(oLi3Cs2Rietveld) top

Crystal data top

B₅Cs₂H₂₀Li₃	V = 5620.1 (6) Å³
M_r = 360.85	Z = 16
Orthorhombic, Fddd	Synchrotron radiation, λ = 0.826887 Å
Hall symbol: -F 2uv 2vw	T = 384 K
a = 13.5838 (8) Å	white
b = 17.3001 (11) Å	cylinder, ? × ? × ? mm
c = 23.9151 (15) Å

Data collection top

Two-axis goniometer diffractometer	Data collection mode: transmission
Specimen mounting: capillary	Scan method: Stationary detector

Refinement top

R_p = 0.045	Profile function: TCHZ
R_wp = 0.036	101 parameters
R_exp = 0.011	Only H-atom coordinates refined
R_Bragg = 0.048
χ² = 10.890	Background function: Chebychev polynomial
7029 data points

Crystal data top

B₅Cs₂H₂₀Li₃	V = 5620.1 (6) Å³
M_r = 360.85	Z = 16
Orthorhombic, Fddd	Synchrotron radiation, λ = 0.826887 Å
a = 13.5838 (8) Å	T = 384 K
b = 17.3001 (11) Å	cylinder, ? × ? × ? mm
c = 23.9151 (15) Å

Data collection top

Two-axis goniometer diffractometer	Data collection mode: transmission
Specimen mounting: capillary	Scan method: Stationary detector

Refinement top

R_p = 0.045	χ² = 10.890
R_wp = 0.036	7029 data points
R_exp = 0.011	101 parameters
R_Bragg = 0.048	Only H-atom coordinates refined

Special details top

Refinement. BH4 groups refined like rigid body

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	B_iso*/B_eq
Cs1	0.375	0.375	0.72791 (13)	6.00 (14)
Cs2	0.625	0.625	0.50563 (16)	6.00 (14)
Li1	0.125	0.824 (5)	0.125	6.0 (19)
Li2	0.125	0.266 (5)	0.125	6.0 (19)
Li3	0.407 (7)	0.125	0.125	6.0 (19)
B1	0.006 (3)	0.625	0.625	6.0 (10)
H11	−0.042 (3)	0.613 (15)	0.663 (3)	6.0 (10)
H13	0.055 (3)	0.573 (4)	0.617 (11)	6.0 (10)
B2	0.628 (4)	0.9093 (16)	0.7209 (11)	6.0 (10)
H21	0.594 (12)	0.859 (7)	0.697 (7)	6.0 (10)
H22	0.579 (12)	0.962 (7)	0.717 (7)	6.0 (10)
H23	0.704 (8)	0.923 (10)	0.703 (8)	6.0 (10)
H24	0.635 (16)	0.893 (10)	0.767 (2)	6.0 (10)
B3	0.783 (2)	0.997 (2)	0.1371 (16)	6.0 (10)
H31	0.710 (7)	1.00 (2)	0.160 (7)	6.0 (10)
H32	0.775 (16)	1.024 (12)	0.094 (4)	6.0 (10)
H33	0.81 (4)	0.934 (8)	0.132 (9)	6.0 (10)
H34	0.84 (2)	1.03 (2)	0.162 (6)	6.0 (10)

(oLiCsRietveld) top

Crystal data top

B₂CsH₈Li	V = 593.2 (2) Å³
M_r = 169.53	Z = 4
Orthorhombic, Cmc2₁	Synchrotron radiation, λ = 0.82711 Å
Hall symbol: C 2c -2	T = 368 K
a = 4.6817 (7) Å	white
b = 15.950 (3) Å	cylinder, ? × ? × ? mm
c = 7.9438 (13) Å

Data collection top

Two-axis goniometer diffractometer	Data collection mode: transmission
Specimen mounting: capillary	Scan method: Stationary detector

Refinement top

R_p = 0.033	Profile function: TCHZ
R_wp = 0.045	138 parameters
R_exp = 0.011	Only H-atom coordinates refined
R_Bragg = 0.072
χ² = 16.646	Background function: Chebychev polynomial
7029 data points

Crystal data top

B₂CsH₈Li	V = 593.2 (2) Å³
M_r = 169.53	Z = 4
Orthorhombic, Cmc2₁	Synchrotron radiation, λ = 0.82711 Å
a = 4.6817 (7) Å	T = 368 K
b = 15.950 (3) Å	cylinder, ? × ? × ? mm
c = 7.9438 (13) Å

Data collection top

Two-axis goniometer diffractometer	Data collection mode: transmission
Specimen mounting: capillary	Scan method: Stationary detector

Refinement top

R_p = 0.033	χ² = 16.646
R_wp = 0.045	7029 data points
R_exp = 0.011	138 parameters
R_Bragg = 0.072	Only H-atom coordinates refined

Special details top

Refinement. BH4 groups refined like rigid body

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	B_iso*/B_eq
Cs	0	0.3630 (4)	0.27 (6)	4.9 (5)
Li	0	0.132 (11)	0.25	6 (5)
B1	0	0.315 (3)	0.82 (7)	6 (3)
H11	−0.206 (9)	0.316 (3)	0.91 (7)	6 (3)
H13	0	0.373 (4)	0.73 (7)	6 (3)
H14	0	0.253 (4)	0.74 (7)	6 (3)
B2	0	0.032 (6)	−0.03 (6)	6 (3)
H21	−0.206 (9)	0.064 (6)	0.02 (6)	6 (3)
H23	0	0.040 (6)	−0.18 (6)	6 (3)
H24	0	−0.040 (7)	0.00 (6)	6 (3)

(oLiRbRietveld) top

Crystal data top

B₂H₈LiRb	V = 561.69 (13) Å³
M_r = 122.09	Z = 4
Orthorhombic, Cmc2₁	Synchrotron radiation, λ = 0.82257 Å
Hall symbol: C 2c -2	T = 411 K
a = 4.5711 (10) Å	white
b = 15.4847 (10) Å	cylinder, ? × ? × ? mm
c = 7.9355 (6) Å

Data collection top

Two-axis goniometer diffractometer	Data collection mode: transmission
Specimen mounting: capillary	Scan method: Stationary detector

Refinement top

R_p = 0.031	Profile function: TCHZ
R_wp = 0.072	48 parameters
R_exp = 0.001	Only H-atom coordinates refined
R_Bragg = 0.086
χ² = 2498.000	Background function: Chebychev polynomial
4054 data points

Crystal data top

B₂H₈LiRb	V = 561.69 (13) Å³
M_r = 122.09	Z = 4
Orthorhombic, Cmc2₁	Synchrotron radiation, λ = 0.82257 Å
a = 4.5711 (10) Å	T = 411 K
b = 15.4847 (10) Å	cylinder, ? × ? × ? mm
c = 7.9355 (6) Å

Data collection top

Two-axis goniometer diffractometer	Data collection mode: transmission
Specimen mounting: capillary	Scan method: Stationary detector

Refinement top

R_p = 0.031	χ² = 2498.000
R_wp = 0.072	4054 data points
R_exp = 0.001	48 parameters
R_Bragg = 0.086	Only H-atom coordinates refined

Special details top

Refinement. BH4 groups refined like rigid body

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	B_iso*/B_eq
Rb	0	0.3684 (2)	0.27 (2)	4.0 (2)
Li	0	0.10471	0.25	4.0 (19)
B1	0	0.3124 (12)	0.69 (2)	0.2 (9)
H11	−0.202 (6)	0.3141 (12)	0.78 (2)	0.2 (9)
H13	0	0.370 (2)	0.61 (2)	0.2 (9)
H14	0	0.251 (2)	0.62 (2)	0.2 (9)
B2	0	0.010 (3)	0.01 (3)	0.2 (9)
H21	−0.202 (6)	0.042 (3)	0.07 (3)	0.2 (9)
H23	0	0.018 (3)	−0.13 (3)	0.2 (9)
H24	0	−0.061 (4)	0.05 (3)	0.2 (9)

(hLi2CsDFT) top

Crystal data top

B₃CsH₁₂Li₂	V = 616.8 (1) Å³
M_r = 191.32	Z = 3
Hexagonal, P6₂22	? radiation, λ = ? Å
Hall symbol: P 62 2c (0 0 1)	T = 384 K
a = 7.6634 (4) Å	× × mm
c = 12.1279 (7) Å

Data collection top

h = ?→?	l = ?→?
k = ?→?

Refinement top

Crystal data top

B₃CsH₁₂Li₂	V = 616.8 (1) Å³
M_r = 191.32	Z = 3
Hexagonal, P6₂22	? radiation, λ = ? Å
a = 7.6634 (4) Å	T = 384 K
c = 12.1279 (7) Å	× × mm

Data collection top

Refinement top

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
H11	0.1076	0.1460	0.2243	0.05000*
B1	0.0000	0.0000	0.1667	0.05000*
H21	0.3773	0.5151	0.0872	0.05000*
H22	0.4176	0.3524	−0.0311	0.05000*
B2	0.5000	0.5000	0.0292	0.05000*
Cs1	0.5000	0.0000	0.0000	0.05000*
Li1	0.1408	0.2817	0.0000	0.05000*

(hLi2RbDFT) top

Crystal data top

B₃H₁₂Li₂Rb	V = 560.4 (3) Å³
M_r = 143.88	Z = 3
Hexagonal, P6₂22	? radiation, λ = ? Å
Hall symbol: P 62 2c (0 0 1)	T = 300 K
a = 7.474 (2) Å	× × mm
c = 11.585 (3) Å

Data collection top

h = ?→?	l = ?→?
k = ?→?

Refinement top

Crystal data top

B₃H₁₂Li₂Rb	V = 560.4 (3) Å³
M_r = 143.88	Z = 3
Hexagonal, P6₂22	? radiation, λ = ? Å
a = 7.474 (2) Å	T = 300 K
c = 11.585 (3) Å	× × mm

Data collection top

Refinement top

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
H11	0.0380	0.1491	0.2694	0.05000*
B1	0.0000	0.0000	0.3333	0.05000*
H21	0.3477	0.4140	0.1043	0.05000*
H22	0.4829	0.6218	0.2294	0.05000*
B2	0.5000	0.5000	0.1675	0.05000*
Li1	0.2763	0.1382	0.1667	0.05000*
Rb1	0.0000	0.5000	0.1667	0.05000*

(mLi2CsDFT) top

Crystal data top

B₃CsH₁₂Li₂	β = 89.97 (1)°
M_r = 191.32	V = 775.4 (3) Å³
Monoclinic, Cc	Z = 4
Hall symbol: C -2yc	? radiation, λ = ? Å
a = 7.574 (2) Å	T = 293 K
b = 7.948 (2) Å	× × mm
c = 12.880 (3) Å

Data collection top

h = ?→?	l = ?→?
k = ?→?

Refinement top

Crystal data top

B₃CsH₁₂Li₂	β = 89.97 (1)°
M_r = 191.32	V = 775.4 (3) Å³
Monoclinic, Cc	Z = 4
a = 7.574 (2) Å	? radiation, λ = ? Å
b = 7.948 (2) Å	T = 293 K
c = 12.880 (3) Å	× × mm

Data collection top

Refinement top

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Li1	0.5582	0.1451	0.3537	0.05000*
Li2	0.5809	0.2751	0.0007	0.05000*
Cs1	0.0855	0.2071	0.1665	0.05000*
H11	0.3111	0.2273	0.4306	0.05000*
H12	0.3232	0.0264	0.3386	0.05000*
H14	0.4465	0.0276	0.4757	0.05000*
H13	0.1858	0.0111	0.4694	0.05000*
B1	0.3146	0.0726	0.4292	0.05000*
H21	0.2587	0.4978	0.3925	0.05000*
H22	0.3724	0.5734	0.5234	0.05000*
H23	0.4392	0.6771	0.3855	0.05000*
H24	0.2110	0.7297	0.4505	0.05000*
B2	0.3197	0.6188	0.4381	0.05000*
H31	0.4985	0.2957	0.2399	0.05000*
H32	0.4897	0.1445	0.1169	0.05000*
H33	0.6738	0.1045	0.2225	0.05000*
H34	0.6907	0.3091	0.1363	0.05000*
B3	0.5873	0.2134	0.1789	0.05000*

(mLi2Cs3DFT) top

Crystal data top

B₅Cs₃H₂₀Li₂	β = 104.470 (3)°
M_r = 486.81	V = 1535.3 (2) Å³
Monoclinic, P2₁/c	Z = 4
Hall symbol: -P 2ybc	? radiation, λ = ? Å
a = 14.444 (1) Å	T = 293 K
b = 7.4218 (6) Å	× × mm
c = 14.7907 (10) Å

Data collection top

h = ?→?	l = ?→?
k = ?→?

Refinement top

Crystal data top

B₅Cs₃H₂₀Li₂	β = 104.470 (3)°
M_r = 486.81	V = 1535.3 (2) Å³
Monoclinic, P2₁/c	Z = 4
a = 14.444 (1) Å	? radiation, λ = ? Å
b = 7.4218 (6) Å	T = 293 K
c = 14.7907 (10) Å	× × mm

Data collection top

Refinement top

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Cs1	0.2530	0.7816	0.1317	0.05000*
Cs2	0.0014	0.2458	0.1480	0.05000*
Cs3	0.4948	0.2305	0.0999	0.05000*
Li1	0.1818	0.2297	0.4545	0.05000*
Li2	0.3150	0.2527	0.3095	0.05000*
H11	0.2805	0.2049	0.0810	0.05000*
H12	0.1861	0.3927	0.0972	0.05000*
H13	0.3173	0.3853	0.1830	0.05000*
H14	0.2212	0.1907	0.1875	0.05000*
B1	0.2513	0.2940	0.1372	0.05000*
H21	0.5455	0.1351	0.4087	0.05000*
H22	0.4468	0.3279	0.3827	0.05000*
H23	0.4378	0.1210	0.2931	0.05000*
H24	0.5384	0.3100	0.3036	0.05000*
B2	0.4923	0.2225	0.3470	0.05000*
H31	0.2132	0.9705	0.4333	0.05000*
H32	0.3004	0.9954	0.3484	0.05000*
H33	0.1819	1.1473	0.3271	0.05000*
H34	0.1710	0.8859	0.3004	0.05000*
B3	0.2166	0.9992	0.3523	0.05000*
H41	0.3416	0.5712	0.4737	0.05000*
H42	0.2033	0.5008	0.4345	0.05000*
H43	0.3067	0.3200	0.4372	0.05000*
H44	0.2800	0.5128	0.3391	0.05000*
B4	0.2828	0.4776	0.4207	0.05000*
H51	−0.0496	0.1605	0.3408	0.05000*
H52	0.0512	0.1516	0.4606	0.05000*
H53	0.0561	0.3414	0.3649	0.05000*
H54	−0.0429	0.3541	0.4374	0.05000*
B5	0.0035	0.2520	0.4008	0.05000*

(mLi3CsDFT) top

Crystal data top

B₄CsH₁₆Li₃	β = 123.767 (2)°
M_r = 213.10	V = 998.1 (1) Å³
Monoclinic, P2₁/c	Z = 4
Hall symbol: -P 2ybc	? radiation, λ = ? Å
a = 8.1992 (3) Å	T = 293 K
b = 12.3044 (5) Å	× × mm
c = 11.9009 (5) Å

Data collection top

h = ?→?	l = ?→?
k = ?→?

Refinement top

Crystal data top

B₄CsH₁₆Li₃	β = 123.767 (2)°
M_r = 213.10	V = 998.1 (1) Å³
Monoclinic, P2₁/c	Z = 4
a = 8.1992 (3) Å	? radiation, λ = ? Å
b = 12.3044 (5) Å	T = 293 K
c = 11.9009 (5) Å	× × mm

Data collection top

Refinement top

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Cs1	0.6748	0.3281	0.1541	0.05000*
Li1	0.2162	0.0571	0.0161	0.05000*
Li2	0.2117	0.1756	0.2635	0.05000*
Li3	0.1937	0.4908	0.1585	0.05000*
H11	0.4638	0.0099	0.2071	0.05000*
H12	0.6553	0.1317	0.3065	0.05000*
H13	0.3758	0.1660	0.1732	0.05000*
H14	0.4606	0.0933	0.3491	0.05000*
B1	0.4884	0.0998	0.2585	0.05000*
H21	0.2477	0.0665	0.4019	0.05000*
H22	−0.0175	0.1116	0.3573	0.05000*
H23	0.2146	0.1177	0.5468	0.05000*
H24	0.1098	−0.0281	0.4566	0.05000*
B2	0.1374	0.0671	0.4406	0.05000*
H31	0.9912	0.1516	−0.0391	0.05000*
H32	0.9631	0.2098	0.1038	0.05000*
H33	1.0530	0.0554	0.1168	0.05000*
H34	0.7750	0.1002	−0.0219	0.05000*
B3	0.9464	0.1282	0.0399	0.05000*
H41	0.1529	0.4420	0.3066	0.05000*
H42	0.1598	0.2875	0.3521	0.05000*
H43	0.3973	0.3793	0.4669	0.05000*
H44	0.3224	0.3389	0.2827	0.05000*
B4	0.2587	0.3616	0.3514	0.05000*

(mLiCs2DFT) top

Crystal data top

B₃Cs₂H₁₂Li	β = 92.693 (1)°
M_r = 317.28	V = 1985.0 (5) Å³
Monoclinic, C2/c	Z = 8
Hall symbol: -C 2yc	? radiation, λ = ? Å
a = 7.6021 (11) Å	T = 368 K
b = 15.160 (2) Å	× × mm
c = 17.243 (2) Å

Data collection top

h = ?→?	l = ?→?
k = ?→?

Refinement top

Crystal data top

B₃Cs₂H₁₂Li	β = 92.693 (1)°
M_r = 317.28	V = 1985.0 (5) Å³
Monoclinic, C2/c	Z = 8
a = 7.6021 (11) Å	? radiation, λ = ? Å
b = 15.160 (2) Å	T = 368 K
c = 17.243 (2) Å	× × mm

Data collection top

Refinement top

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Cs1	0.2444	0.3917	0.0689	0.05000*
Cs2	0.7563	0.2004	0.1495	0.05000*
Li1	0.2422	0.4902	0.3285	0.05000*
H11	0.1299	0.0530	0.2563	0.05000*
H21	0.0065	−0.0409	0.1928	0.05000*
B1	0.0000	0.0062	0.2500	0.05000*
H21	0.8418	0.3462	0.0296	0.05000*
H22	0.8366	0.4727	0.0612	0.05000*
H23	0.6582	0.3879	0.1002	0.05000*
H24	0.6448	0.4247	−0.0107	0.05000*
B2	0.7453	0.4078	0.0448	0.05000*
H31	0.3883	0.2007	0.0768	0.05000*
H32	0.3188	0.2333	0.1828	0.05000*
H33	0.3742	0.1081	0.1579	0.05000*
H34	0.1516	0.1644	0.1118	0.05000*
B3	0.3060	0.1763	0.1324	0.05000*
H41	0.1135	0.4720	0.2238	0.05000*
H42	−0.0622	0.3785	0.1978	0.05000*
B4	0.0000	0.4250	0.2500	0.05000*

(mLiRbDFT) top

Crystal data top

B₂H₈LiRb	β = 97.776 (1)°
M_r = 122.09	V = 1855.5 (3) Å³
Monoclinic, C2/m	Z = 14
Hall symbol: -C 2y	? radiation, λ = ? Å
a = 23.5931 (4) Å	T = 296 K
b = 4.6178 (7) Å	× × mm
c = 17.1893 (3) Å

Data collection top

h = ?→?	l = ?→?
k = ?→?

Refinement top

Crystal data top

B₂H₈LiRb	β = 97.776 (1)°
M_r = 122.09	V = 1855.5 (3) Å³
Monoclinic, C2/m	Z = 14
a = 23.5931 (4) Å	? radiation, λ = ? Å
b = 4.6178 (7) Å	T = 296 K
c = 17.1893 (3) Å	× × mm

Data collection top

Refinement top

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Li1	0.0000	0.0000	0.0000	0.05000*
Li2	0.2051	0.0000	0.1491	0.05000*
Li3	0.1447	0.0000	0.4161	0.05000*
Li4	0.4501	0.5000	0.2738	0.05000*
Rb1	0.0000	0.5000	0.5000	0.05000*
Rb2	0.2960	0.5000	0.3462	0.05000*
Rb3	0.3558	0.0000	0.0807	0.05000*
Rb4	0.0802	0.5000	0.2125	0.05000*
H11	0.2372	0.0000	0.2698	0.05000*
H13	0.1822	0.2126	0.3279	0.05000*
H12	0.1534	0.0000	0.2295	0.05000*
B1	0.1889	0.0000	0.2881	0.05000*
H21	0.2063	0.5000	0.5478	0.05000*
H22	0.1796	0.5000	0.4339	0.05000*
H23	0.1363	0.2869	0.5023	0.05000*
B2	0.1643	0.5000	0.4981	0.05000*
H33	0.4758	0.2803	0.0967	0.05000*
H32	0.4209	0.5000	0.1534	0.05000*
H31	0.5049	0.5000	0.1938	0.05000*
B3	0.4692	0.5000	0.1350	0.05000*
H41	0.0677	0.0000	0.0830	0.05000*
H42	0.1120	0.0000	−0.0083	0.05000*
H43	0.1397	0.2192	0.0884	0.05000*
B4	0.1151	0.0000	0.0625	0.05000*
H53	0.0128	0.2198	0.3427	0.05000*
H51	0.0524	0.0000	0.4341	0.05000*
H52	0.0828	0.0000	0.3304	0.05000*
B5	0.0399	0.0000	0.3627	0.05000*
H63	0.2490	0.2839	0.0922	0.05000*
H62	0.2249	0.5000	0.1831	0.05000*
H61	0.3073	0.5000	0.1661	0.05000*
B6	0.2578	0.5000	0.1340	0.05000*
H73	0.4063	0.2136	0.3313	0.05000*
H72	0.4313	0.0000	0.2397	0.05000*
H71	0.3486	0.0000	0.2560	0.05000*
B7	0.3978	0.0000	0.2884	0.05000*

(oLi3Cs2DFT) top

Crystal data top

B₅Cs₂H₂₀Li₃	c = 23.9151 (15) Å
M_r = 360.85	V = 5620.1 (6) Å³
Orthorhombic, Fddd	Z = 16
Hall symbol: -F 2uv 2vw	? radiation, λ = ? Å
a = 13.5838 (8) Å	T = 384 K
b = 17.3001 (11) Å	× × mm

Data collection top

h = ?→?	l = ?→?
k = ?→?

Refinement top

Crystal data top

B₅Cs₂H₂₀Li₃	V = 5620.1 (6) Å³
M_r = 360.85	Z = 16
Orthorhombic, Fddd	? radiation, λ = ? Å
a = 13.5838 (8) Å	T = 384 K
b = 17.3001 (11) Å	× × mm
c = 23.9151 (15) Å

Data collection top

Refinement top

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Cs1	0.1250	0.1250	0.2711	0.05000*
Cs2	0.3750	0.3750	0.2421	0.05000*
Li1	0.1250	0.4181	0.1250	0.05000*
Li2	0.1250	0.0134	0.1250	0.05000*
Li3	0.4114	0.1250	0.1250	0.05000*
H11	−0.0467	0.0818	0.1542	0.05000*
H12	0.0509	0.0867	0.0929	0.05000*
B1	0.0021	0.1250	0.1250	0.05000*
H21	0.0979	0.3878	0.0430	0.05000*
H22	0.0632	0.2771	0.0555	0.05000*
H23	0.1934	0.3189	0.0821	0.05000*
H24	0.1686	0.3059	0.0007	0.05000*
B2	0.1306	0.3222	0.0450	0.05000*
H31	0.5734	0.0137	0.0879	0.05000*
H32	0.4893	0.0458	0.1518	0.05000*
H33	0.4750	−0.0598	0.1209	0.05000*
H34	0.4313	0.0290	0.0745	0.05000*
B3	0.4922	0.0075	0.1085	0.05000*

(oLiCsDFT) top

Crystal data top

B₂CsH₈Li	c = 7.9438 (13) Å
M_r = 169.53	V = 593.2 (2) Å³
Orthorhombic, Cmc2₁	Z = 4
Hall symbol: C 2c -2	? radiation, λ = ? Å
a = 4.6817 (7) Å	T = 368 K
b = 15.950 (3) Å	× × mm

Data collection top

h = ?→?	l = ?→?
k = ?→?

Refinement top

Crystal data top

B₂CsH₈Li	V = 593.2 (2) Å³
M_r = 169.53	Z = 4
Orthorhombic, Cmc2₁	? radiation, λ = ? Å
a = 4.6817 (7) Å	T = 368 K
b = 15.950 (3) Å	× × mm
c = 7.9438 (13) Å

Data collection top

Refinement top

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
H1	0.2126	0.1904	0.3720	0.05000*
H9	0.0000	0.1113	0.2216	0.05000*
H13	0.0000	0.2339	0.1698	0.05000*
B1	0.0000	0.1816	0.2825	0.05000*
H17	0.2843	−0.0330	0.5683	0.05000*
H25	0.5000	−0.0233	0.3544	0.05000*
H29	0.5000	0.0717	0.5207	0.05000*
B5	0.5000	−0.0046	0.5039	0.05000*
Cs1	0.0000	0.1374	0.7550	0.05000*
Li1	0.5000	0.0930	0.2714	0.05000*

(oLiRbDFT) top

Crystal data top

B₂H₈LiRb	c = 7.9355 (6) Å
M_r = 122.09	V = 561.7 (1) Å³
Orthorhombic, Cmc2₁	Z = 4
Hall symbol: C 2c -2	? radiation, λ = ? Å
a = 4.5711 (10) Å	T = 411 K
b = 15.4847 (10) Å	× × mm

Data collection top

h = ?→?	l = ?→?
k = ?→?

Refinement top

Crystal data top

B₂H₈LiRb	V = 561.7 (1) Å³
M_r = 122.09	Z = 4
Orthorhombic, Cmc2₁	? radiation, λ = ? Å
a = 4.5711 (10) Å	T = 411 K
b = 15.4847 (10) Å	× × mm
c = 7.9355 (6) Å

Data collection top

Refinement top

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Rb1	0.0000	0.1321	0.7071	0.05000*
Li1	0.5000	0.0992	0.2388	0.05000*
H11	0.2174	0.1966	0.3449	0.05000*
H12	0.0000	0.1258	0.1738	0.05000*
H13	0.0000	0.2537	0.1550	0.05000*
B1	0.0000	0.1931	0.2536	0.05000*
H21	0.2788	−0.0333	0.5354	0.05000*
H22	0.5000	−0.0231	0.3209	0.05000*
H23	0.5000	0.0746	0.4881	0.05000*
B2	0.5000	−0.0041	0.4709	0.05000*

Experimental details

	(hLi2CsRietveld)	(hLi2RbRietveld)	(mLi2CsRietveld)	(mLi2Cs3Rietveld)
Crystal data
Chemical formula	B₃CsH₁₂Li₂	B₃H₁₂Li₂Rb	B₃CsH₁₂Li₂	B₅Cs₃H₂₀Li₂
M_r	191.32	143.88	191.32	486.81
Crystal system, space group	Hexagonal, P6₂22	Hexagonal, P6₂22	Monoclinic, Cc	Monoclinic, P2₁/c
Temperature (K)	384	300	293	293
a, b, c (Å)	7.6634 (4), 7.6634 (4), 12.1279 (7)	7.474 (2), 7.474 (2), 11.585 (3)	7.574 (2), 7.948 (2), 12.880 (3)	14.444 (1), 7.4218 (6), 14.7907 (10)
α, β, γ (°)	90, 90, 120	90, 90, 120	90, 89.97 (1), 90	90, 104.470 (3), 90
V (Å³)	616.8 (1)	560.4 (3)	775.4 (3)	1535.3 (2)
Z	3	3	4	4
Radiation type	Synchrotron, λ = 0.826887 Å	Synchrotron, λ = 0.826887 Å	Synchrotron, λ = 0.826887 Å	Synchrotron, λ = 0.826887 Å
µ (mm⁻¹)	?	?	?	?
Specimen shape, size (mm)	Cylinder, ? × ? × ?	Cylinder, ? × ? × ?	Cylinder, ? × ? × ?	Cylinder, ? × ? × ?

Data collection
Diffractometer	Two-axis goniometer diffractometer	Two-axis goniometer diffractometer	Two-axis goniometer diffractometer	Two-axis goniometer diffractometer
Specimen mounting	Capillary	Capillary	Capillary	Capillary
Data collection mode	Transmission	Transmission	Transmission	Transmission
Data collection method	Stationary detector	Stationary detector	Stationary detector	Stationary detector
Absorption correction	–	–	–	–
No. of measured, independent and observed reflections	–	–	–	–
R_int	–	–	–	–
θ values (°)	2θ_fixed = ?	2θ_fixed = ?	2θ_fixed = ?	2θ_fixed = ?

Refinement
R factors and goodness of fit	R_p = 0.045, R_wp = 0.036, R_exp = 0.011, R_Bragg = 0.043, χ² = 10.890	R_p = 0.018, R_wp = 0.023, R_exp = 0.010, R_Bragg = 0.015, χ² = 4.709	R_p = 0.057, R_wp = 0.065, R_exp = 0.011, R_Bragg = 0.072, χ² = 34.340	R_p = 0.105, R_wp = 0.108, R_exp = 0.011, R_Bragg = 0.078, χ² = 86.118
No. of reflections/data points	7029	7029	7029	7029
No. of parameters	101	68	37	96
No. of restraints	?	?	?	?
H-atom treatment	Only H-atom coordinates refined	Only H-atom coordinates refined	Only H-atom coordinates refined	Only H-atom coordinates refined
Δρ_max, Δρ_min (e Å⁻³)	–	–	–	–

	(mLi3CsRietveld)	(mLiCs2Rietveld)	(mLiRbRietveld)	(oLi3Cs2Rietveld)
Crystal data
Chemical formula	B₄CsH₁₆Li₃	B₃Cs₂H₁₂Li	B₂H₈LiRb	B₅Cs₂H₂₀Li₃
M_r	213.10	317.28	122.09	360.85
Crystal system, space group	Monoclinic, P2₁/c	Monoclinic, C2/c	Monoclinic, C2/m	Orthorhombic, Fddd
Temperature (K)	293	368	296	384
a, b, c (Å)	8.1992 (3), 12.3044 (5), 11.9009 (5)	7.6021 (11), 15.160 (2), 17.243 (2)	23.5931 (4), 4.6178 (7), 17.1893 (3)	13.5838 (8), 17.3001 (11), 23.9151 (15)
α, β, γ (°)	90, 123.767 (2), 90	90, 92.693 (1), 90	90, 97.776 (1), 90	90, 90, 90
V (Å³)	998.1 (1)	1985.0 (5)	1855.5 (3)	5620.1 (6)
Z	4	8	14	16
Radiation type	Synchrotron, λ = 0.82103 Å	Synchrotron, λ = 0.826887 Å	Synchrotron, λ = 0.82257 Å	Synchrotron, λ = 0.826887 Å
µ (mm⁻¹)	?	?	?	?
Specimen shape, size (mm)	Cylinder, ? × ? × ?	Cylinder, ? × ? × ?	Cylinder, ? × ? × ?	Cylinder, ? × ? × ?

Data collection
Diffractometer	Two-axis goniometer diffractometer	Two-axis goniometer diffractometer	Two-axis goniometer diffractometer	Two-axis goniometer diffractometer
Specimen mounting	Capillary	Capillary	Capillary	Capillary
Data collection mode	Transmission	Transmission	Transmission	Transmission
Data collection method	Stationary detector	Stationary detector	Stationary detector	Stationary detector
Absorption correction	–	–	–	–
No. of measured, independent and observed reflections	–	–	–	–
R_int	–	–	–	–
θ values (°)	2θ_fixed = ?	2θ_fixed = ?	2θ_fixed = ?	2θ_fixed = ?

Refinement
R factors and goodness of fit	R_p = 0.025, R_wp = 0.018, R_exp = 0.001, R_Bragg = 0.019, χ² = 478.734	R_p = 0.032, R_wp = 0.042, R_exp = 0.011, R_Bragg = 0.024, χ² = 16.646	R_p = 0.022, R_wp = 0.035, R_exp = 0.001, R_Bragg = 0.017, χ² = 727.381	R_p = 0.045, R_wp = 0.036, R_exp = 0.011, R_Bragg = 0.048, χ² = 10.890
No. of reflections/data points	4855	7029	4054	7029
No. of parameters	112	138	103	101
No. of restraints	?	?	?	?
H-atom treatment	Only H-atom coordinates refined	Only H-atom coordinates refined	Only H-atom coordinates refined	Only H-atom coordinates refined
Δρ_max, Δρ_min (e Å⁻³)	–	–	–	–

	(oLiCsRietveld)	(oLiRbRietveld)	(hLi2CsDFT)	(hLi2RbDFT)
Crystal data
Chemical formula	B₂CsH₈Li	B₂H₈LiRb	B₃CsH₁₂Li₂	B₃H₁₂Li₂Rb
M_r	169.53	122.09	191.32	143.88
Crystal system, space group	Orthorhombic, Cmc2₁	Orthorhombic, Cmc2₁	Hexagonal, P6₂22	Hexagonal, P6₂22
Temperature (K)	368	411	384	300
a, b, c (Å)	4.6817 (7), 15.950 (3), 7.9438 (13)	4.5711 (10), 15.4847 (10), 7.9355 (6)	7.6634 (4), 7.6634 (4), 12.1279 (7)	7.474 (2), 7.474 (2), 11.585 (3)
α, β, γ (°)	90, 90, 90	90, 90, 90	90, 90, 120	90, 90, 120
V (Å³)	593.2 (2)	561.69 (13)	616.8 (1)	560.4 (3)
Z	4	4	3	3
Radiation type	Synchrotron, λ = 0.82711 Å	Synchrotron, λ = 0.82257 Å	?, λ = ? Å	?, λ = ? Å
µ (mm⁻¹)	?	?	?	?
Specimen shape, size (mm)	Cylinder, ? × ? × ?	Cylinder, ? × ? × ?	× ×	× ×

Data collection
Diffractometer	Two-axis goniometer diffractometer	Two-axis goniometer diffractometer	?	?
Specimen mounting	Capillary	Capillary	–	–
Data collection mode	Transmission	Transmission	–	–
Data collection method	Stationary detector	Stationary detector	?	?
Absorption correction	–	–	?	?
No. of measured, independent and observed reflections	–	–	?, ?, ?	?, ?, ?
R_int	–	–	?	?
θ values (°)	2θ_fixed = ?	2θ_fixed = ?	θ_max = ?	θ_max = ?

Refinement
R factors and goodness of fit	R_p = 0.033, R_wp = 0.045, R_exp = 0.011, R_Bragg = 0.072, χ² = 16.646	R_p = 0.031, R_wp = 0.072, R_exp = 0.001, R_Bragg = 0.086, χ² = 2498.000	R[F² > 2σ(F²)] = ?, wR(F²) = ?, S = ?	R[F² > 2σ(F²)] = ?, wR(F²) = ?, S = ?
No. of reflections/data points	7029	4054	?	?
No. of parameters	138	48	?	?
No. of restraints	?	?	?	?
H-atom treatment	Only H-atom coordinates refined	Only H-atom coordinates refined	?	?
Δρ_max, Δρ_min (e Å⁻³)	–	–	?, ?	?, ?

	(mLi2CsDFT)	(mLi2Cs3DFT)	(mLi3CsDFT)	(mLiCs2DFT)
Crystal data
Chemical formula	B₃CsH₁₂Li₂	B₅Cs₃H₂₀Li₂	B₄CsH₁₆Li₃	B₃Cs₂H₁₂Li
M_r	191.32	486.81	213.10	317.28
Crystal system, space group	Monoclinic, Cc	Monoclinic, P2₁/c	Monoclinic, P2₁/c	Monoclinic, C2/c
Temperature (K)	293	293	293	368
a, b, c (Å)	7.574 (2), 7.948 (2), 12.880 (3)	14.444 (1), 7.4218 (6), 14.7907 (10)	8.1992 (3), 12.3044 (5), 11.9009 (5)	7.6021 (11), 15.160 (2), 17.243 (2)
α, β, γ (°)	90, 89.97 (1), 90	90, 104.470 (3), 90	90, 123.767 (2), 90	90, 92.693 (1), 90
V (Å³)	775.4 (3)	1535.3 (2)	998.1 (1)	1985.0 (5)
Z	4	4	4	8
Radiation type	?, λ = ? Å	?, λ = ? Å	?, λ = ? Å	?, λ = ? Å
µ (mm⁻¹)	?	?	?	?
Specimen shape, size (mm)	× ×	× ×	× ×	× ×

Data collection
Diffractometer	?	?	?	?
Specimen mounting	–	–	–	–
Data collection mode	–	–	–	–
Data collection method	?	?	?	?
Absorption correction	?	?	?	?
No. of measured, independent and observed reflections	?, ?, ?	?, ?, ?	?, ?, ?	?, ?, ?
R_int	?	?	?	?
θ values (°)	θ_max = ?	θ_max = ?	θ_max = ?	θ_max = ?

Refinement
R factors and goodness of fit	R[F² > 2σ(F²)] = ?, wR(F²) = ?, S = ?	R[F² > 2σ(F²)] = ?, wR(F²) = ?, S = ?	R[F² > 2σ(F²)] = ?, wR(F²) = ?, S = ?	R[F² > 2σ(F²)] = ?, wR(F²) = ?, S = ?
No. of reflections/data points	?	?	?	?
No. of parameters	?	?	?	?
No. of restraints	?	?	?	?
H-atom treatment	?	?	?	?
Δρ_max, Δρ_min (e Å⁻³)	?, ?	?, ?	?, ?	?, ?

	(mLiRbDFT)	(oLi3Cs2DFT)	(oLiCsDFT)	(oLiRbDFT)
Crystal data
Chemical formula	B₂H₈LiRb	B₅Cs₂H₂₀Li₃	B₂CsH₈Li	B₂H₈LiRb
M_r	122.09	360.85	169.53	122.09
Crystal system, space group	Monoclinic, C2/m	Orthorhombic, Fddd	Orthorhombic, Cmc2₁	Orthorhombic, Cmc2₁
Temperature (K)	296	384	368	411
a, b, c (Å)	23.5931 (4), 4.6178 (7), 17.1893 (3)	13.5838 (8), 17.3001 (11), 23.9151 (15)	4.6817 (7), 15.950 (3), 7.9438 (13)	4.5711 (10), 15.4847 (10), 7.9355 (6)
α, β, γ (°)	90, 97.776 (1), 90	90, 90, 90	90, 90, 90	90, 90, 90
V (Å³)	1855.5 (3)	5620.1 (6)	593.2 (2)	561.7 (1)
Z	14	16	4	4
Radiation type	?, λ = ? Å	?, λ = ? Å	?, λ = ? Å	?, λ = ? Å
µ (mm⁻¹)	?	?	?	?
Specimen shape, size (mm)	× ×	× ×	× ×	× ×

Data collection
Diffractometer	?	?	?	?
Specimen mounting	–	–	–	–
Data collection mode	–	–	–	–
Data collection method	?	?	?	?
Absorption correction	?	?	?	?
No. of measured, independent and observed reflections	?, ?, ?	?, ?, ?	?, ?, ?	?, ?, ?
R_int	?	?	?	?
θ values (°)	θ_max = ?	θ_max = ?	θ_max = ?	θ_max = ?

Refinement
R factors and goodness of fit	R[F² > 2σ(F²)] = ?, wR(F²) = ?, S = ?	R[F² > 2σ(F²)] = ?, wR(F²) = ?, S = ?	R[F² > 2σ(F²)] = ?, wR(F²) = ?, S = ?	R[F² > 2σ(F²)] = ?, wR(F²) = ?, S = ?
No. of reflections/data points	?	?	?	?
No. of parameters	?	?	?	?
No. of restraints	?	?	?	?
H-atom treatment	?	?	?	?
Δρ_max, Δρ_min (e Å⁻³)	?, ?	?, ?	?, ?	?, ?

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Text
		Plain Text

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Text
		Plain Text