Crystal structure of Li3Ga(BO3)2

Smith, R.W.; Holman, D.; Villa, E.M.

doi:10.1107/S205698901700295X

research communications

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 73| Part 3| March 2017| Pages 456-458

https://doi.org/10.1107/S205698901700295X

Open

access

Crystal structure of Li₃Ga(BO₃)₂

Robert W. Smith,^a ^* Darien Holman ^a and Eric M. Villa ^b

^aDepartment of Chemistry, University of Nebraska at Omaha, 6001 Dodge Street, Omaha, Nebraska 68182, USA, and ^bDepartment of Chemistry, Creighton University, 2500 California Plaza, Omaha, Nebraska 68178, USA
^*Correspondence e-mail: robertsmith@unomaha.edu

Edited by M. Weil, Vienna University of Technology, Austria (Received 29 December 2016; accepted 21 February 2017; online 28 February 2017)

The crystal structure of trilithium gallium bis(orthoborate), Li₃Ga(BO₃)₂, is isotypic with Li₃Al(BO₃)₂ in a triclinic cell in space-group type P-1. The three Li and the unique Ga atom are coordinated by four O atoms each in tetrahedra, and the two B atoms are coordinated by three O atoms in orthoborate triangles. Chains with composition [Ga₂(BO₃)₄]⁶⁻ extend along the a axis. The Li atoms interleave these chains in tetrahedral interstices. A comparison is made between the structure model of the title compound and that of a previously reported model for a compound with the same composition [Abdullaev & Mamedov (1972 ). Zh. Strukt. Khim. 13, 943–946.]

Keywords: crystal structure; crystal diffraction; gallium; borate.

CCDC reference: 1534100

1. Chemical context

We are examining the alkali metal/gallium/borate phase diagrams, investigations of which have revealed to date, among others, the homologous series A₂Ga₂O(BO₃)₂, in which A = Na, K, Rb, and Cs (Corbel & Leblanc, 2000 ; Smith, 1995 ; Smith et al., 1997 ,2008 , respectively) and the homologous series A₃Ga(BO₃)₂, in which A = Li, Na, K, Rb, and Cs. We report herein the crystal structure of the lithium analog (Fig. 1) of the latter series, which is the only one which melts congruently, which has a unique structure among the series, and which is isotypic with Li₃Al(BO₃)₂ (He et al., 2002 ); the other analogs have yet to be crystallized in the form of single crystals, but are structurally distinct from the lithium analog and isotypic with each other based on their powder X-ray diffraction patterns.

Figure 1
A projection of the crystal structure of Li₃Ga(BO₃)₂ along the a axis. Infinite [Ga₂(BO₃)₄]⁶⁻ chains are linked together by sheets of Li atoms in tetrahedral voids. GaO₄ tetrahedra are light green, LiO₄ tetrahedra are light gray, and BO₃ triangles are blue–grey. Corner O atoms have been omitted for clarity.

A crystal structure for this compound was previously reported by Abdullaev & Mamedov (1972) in the same triclinic space-group type P $[\overline{1}]$ , and with the same gallium-borate polyhedral pattern but with important differences with the structure reported herein, to wit: slightly different cell parameters and a different reduced cell, a significantly smaller cell volume (i.e., 3% smaller), less regular bond-valence sums (BVS), greater deviations from expected interatomic distances, and irregular, five- and six-coordinate lithium-centered polyhedra. Table 1 compares interatomic distances from the structure reported by Addullaev & Mamedov (1972) and this report, with expected distances using Shannon's radii (Shannon, 1976 ); it also lists bond-valence sums for each structure. We have considered as bonds all Li—O distances under 3 Å from the 1972 report because doing so produces more reasonable BVS values, thus rendering some of the lithium atoms as being five- or six-coordinate in the previous structure report. It should be noted that the authors, however, reported all lithium atoms as tetrahedrally coordinated. The present structure model clearly differs from the 1972 structure model and hence indicates a second possible modification for this composition. Whether a polymorphic relation exists between the two phases remains unknown and needs additional proof by using complementary methods such as thermal analysis.

Table 1
Comparison of the two structures with composition Li₃Ga(BO₃)₂

Structure model	Abdullaev & Mamedov (1972)	Current work	Shannon (1976)
Reduced cell (Å, °)	4.90 (2) 6.23 (3) 7.78 (5) 72.9 (5) 90.0 (5) 90.0 (5)	4.8731 (3) 6.2429 (4) 8.0130 (5) 73.346 (6) 89.701 (5) 89.698 (5)

Range of interatomic distances (Å)
Li—O	2.28±0.41	1.965±0.054	1.97
Ga—O	2.07±0.43	1.847±0.021	1.85
B—O	1.31±0.13	1.384±0.038	1.39

Bond-valence-sum values and coordination numbers (in brackets)
Li (1, 2 & 3)	1.14 [4 + 1], 1.01 [4], 1.00 [6]	1.07 [4], 1.03 [4], 1.05 [4]
Ga (1)	2.38 [4]	2.92 [4]
B (1 & 2)	3.17 [3], 3.06 [3]	2.91 [3], 2.91 [3]

2. Structural commentary

The crystal structure of the title compound consists of lithium- and gallium-centered tetrahedra and boron-centered triangles, all of which share oxygen vertices (Fig.1). Each GaO₄ tetrahedron is linked to four BO₃ triangles and six LiO₄ tetrahedra. The gallium-centered tetrahedra and boron-centered triangles adjoin through shared vertices to form infinite chains of composition [Ga₂(BO₃)₄]⁶⁻, with the chains extending parallel to the a axis; lithium cations interleave the chains in tetrahedral interstices. Fig. 2 shows a comparison of the gallium-borate chains in both the previously reported structure (Abdullaev & Mamedov, 1972) and the structure presented here. The two exhibit the same connectivity but have sizeable differences in bond lengths, bond angles and bond-valence-sum values (see Table 1). Averaged interatomic distances for the title structure are consistent with those determined from the ionic radii reported by Shannon (1976), viz. 1.97 (5), 1.85 (2), and 1.39 (4) Å for the experimentally determined Li—O, Ga—O, and B—O distances, respectively. We also calculated the bond-valence-um values for each element using the values provided by Brese & O'Keeffe (1991 ). The results (Table 1) are in good agreement with the expected values of 1, 3, 3 and 2 for Li, Ga, B and O atoms, respectively.

Figure 2
A comparison of the infinite [Ga₂(BO₃)₄]⁶⁻ chains in the structures of Li₃Ga(BO₃)₂ with respect to the model by Abdullaev & Mamedov (1972

) (top) and the structure model presented in this manuscript. The connectivity of these two chains are the same but there are important differences in the actual bonding. In our structure model, these chains run down the c axis. Here the GaO₄ tetrahedra are light green and the BO₃ triangles are blue–grey (which are shown in light blue–grey in the 1972 structure). Corner O atoms have been omitted for clarity.

Lastly, Fig. 3 displays the anisotropic displacement parameters of the atoms within the asymmetric unit of the title structure.

Figure 3
The asymmetric unit of the title structure with atom labelling. Displacement ellipsoids are drawn at the 75% probability level.

3. Synthesis and crystallization

Powder samples were made by solid-state reactions starting with stoichiometric proportions of lithium nitrate, gallium(III) nitrate, and boric acid. We first ground the starting materials and fired them in an alumina crucible at 573 K for two h to decompose them to finely divided oxides, after which we progressively heated the samples to 973 K at 50 to 100 K and 24-hour increments, grinding the samples between each successive heat treatment. Samples were single-phase as revealed by powder X-ray diffraction.

Single crystals were grown from the melt. About 500 mg of sample were placed in a platinum dish, heated to 1033 K in a box oven, slow-cooled at 10 K h⁻¹ to about 470 K, and then air-quenched. Several small, clear, colorless crystals were physically removed from the platinum crucible and mounted on a goniometer for a preliminary scan in order to find one of suitable quality.

4. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2.

Table 2
Experimental details

Crystal data
Chemical formula	Li₃Ga(BO₃)₂
M_r	208.16
Crystal system, space group	Triclinic, P $[\overline{1}]$
Temperature (K)	293
a, b, c (Å)	4.8731 (3), 6.2429 (4), 8.0130 (5)
α, β, γ (°)	73.346 (6), 89.701 (5), 89.698 (5)
V (Å³)	233.54 (3)
Z	2
Radiation type	Mo Kα
μ (mm⁻¹)	5.84
Crystal size (mm)	0.09 × 0.03 × 0.01

Data collection
Diffractometer	Rigaku SCX mini diffractometer
Absorption correction	Multi-scan (CrysAlis PRO; Rigaku Oxford Diffraction, 2015 $[Rigaku Oxford Diffraction (2015). CrysAlis PRO. Rigaku Oxford Diffraction, Yarnton, Oxfordshire, England.]$ )
T_min, T_max	0.785, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	2936, 1397, 1265
R_int	0.029
(sin θ/λ)_max (Å⁻¹)	0.714

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.028, 0.067, 1.09
No. of reflections	1397
No. of parameters	109
Δρ_max, Δρ_min (e Å⁻³)	1.04, −0.76
Computer programs: CrysAlis PRO (Rigaku Oxford Diffraction, 2015 $[Rigaku Oxford Diffraction (2015). CrysAlis PRO. Rigaku Oxford Diffraction, Yarnton, Oxfordshire, England.]$ ), SHELXT (Sheldrick, 2015a ), SHELXL2014 (Sheldrick, 2015b ) and OLEX2 (Dolomanov et al., 2009 ).

Supporting information

CCDC reference: 1534100

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S205698901700295X/wm5356sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S205698901700295X/wm5356Isup3.hkl

Supporting information file. DOI: https://doi.org/10.1107/S205698901700295X/wm5356Isup3.cml

checkCIF report

Computing details top

Data collection: CrysAlis PRO (Rigaku Oxford Diffraction, 2015); cell refinement: CrysAlis PRO (Rigaku Oxford Diffraction, 2015); data reduction: CrysAlis PRO (Rigaku Oxford Diffraction, 2015); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

Trilithium gallium bis(orthoborate) top

Crystal data top

Li₃Ga(BO₃)₂	Z = 2
M_r = 208.16	F(000) = 196
Triclinic, P1	D_x = 2.960 Mg m⁻³
a = 4.8731 (3) Å	Mo Kα radiation, λ = 0.71073 Å
b = 6.2429 (4) Å	Cell parameters from 1687 reflections
c = 8.0130 (5) Å	θ = 2.7–32.5°
α = 73.346 (6)°	µ = 5.84 mm⁻¹
β = 89.701 (5)°	T = 293 K
γ = 89.698 (5)°	Plate, clear light colourless
V = 233.54 (3) Å³	0.09 × 0.03 × 0.01 mm

Data collection top

Rigaku SCX mini diffractometer	1397 independent reflections
Radiation source: fine-focus sealed X-ray tube, Enhance (Mo) X-ray Source	1265 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.029
ω scans	θ_max = 30.5°, θ_min = 2.7°
Absorption correction: multi-scan (CrysAlis PRO; Rigaku Oxford Diffraction, 2015)	h = −6→6
T_min = 0.785, T_max = 1.000	k = −8→8
2936 measured reflections	l = −11→11

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Primary atom site location: dual
R[F² > 2σ(F²)] = 0.028	w = 1/[σ²(F_o²) + (0.0282P)² + 0.1042P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.067	(Δ/σ)_max < 0.001
S = 1.09	Δρ_max = 1.04 e Å⁻³
1397 reflections	Δρ_min = −0.76 e Å⁻³
109 parameters

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Refinement. Crystals of Li₃Ga(BO₃)₂ were mounted on MiTeGen Microloop with non-drying immersion oil. The crystal was then optically aligned on the Rigaku SCX-Mini diffractometer using a digital camera. Initial matrix images were collected to determine the unit cell, validity and proper exposure time. Three hemispheres (where φ= 0.0, 120.0 and 240.0) of data were collected with each consisting 180 images each with 1.00° widths and a 1.00° step. The structure of Li₃Ga(BO₃)₂ was refined using SHELXT (Sheldrick, 2015) Intrinsic Phasing and SHELXL (Sheldrick, 2015). Olex2 (Dolomanov et al., 2009) was used as a graphical interface. Images of the above compound were made using CrystalMaker for Windows, version 9.2.8. The refinement proceeded without any incidents and without any need for modelling disorder or twinning or any constraints or restraints.

Refinement of the structure was based on F² against all reflections. The R-factor R is based on F²>2?(F²), but is not relevant to the choice of reflections for refinement; whereas the weighted R-factor wR and goodness of fit S are based on F². The maximum electron denisty is 1.035 and is located 1.629 Å from Li(2), 1.960 Å from Li(1) and 2.169 Å from a different Li(1), which leads to nothing reasonable. All other maximum peaks are under 0.600.

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

	x	y	z	U_iso*/U_eq
Ga1	0.65937 (6)	0.22951 (4)	0.60906 (4)	0.00968 (10)
B1	0.1691 (6)	0.0135 (5)	0.7454 (4)	0.0088 (5)
B2	0.6631 (6)	0.5014 (5)	0.2489 (4)	0.0094 (5)
O1	0.3037 (4)	0.1391 (3)	0.5958 (2)	0.0116 (4)
O2	−0.1202 (4)	−0.0028 (3)	0.7317 (2)	0.0101 (4)
O3	0.2978 (4)	−0.0830 (3)	0.8955 (2)	0.0109 (4)
O4	0.7953 (4)	0.3547 (3)	0.3900 (2)	0.0117 (4)
O5	0.3833 (4)	0.5529 (3)	0.2727 (2)	0.0100 (4)
O6	0.7921 (4)	0.5853 (3)	0.0967 (2)	0.0120 (4)
Li1	0.1828 (10)	−0.3717 (8)	1.0414 (6)	0.0154 (10)
Li2	1.1645 (10)	0.2738 (8)	0.3670 (6)	0.0143 (9)
Li3	0.6839 (10)	0.8785 (8)	−0.0399 (6)	0.0159 (10)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ga1	0.00877 (15)	0.01034 (15)	0.00789 (15)	−0.00023 (10)	0.00130 (10)	0.00064 (10)
B1	0.0103 (13)	0.0052 (11)	0.0106 (12)	0.0008 (9)	0.0021 (10)	−0.0018 (10)
B2	0.0091 (13)	0.0088 (12)	0.0095 (12)	−0.0013 (10)	0.0002 (10)	−0.0013 (10)
O1	0.0098 (9)	0.0134 (9)	0.0090 (8)	−0.0028 (7)	0.0011 (7)	0.0012 (7)
O2	0.0068 (8)	0.0105 (8)	0.0098 (8)	0.0013 (6)	0.0002 (7)	0.0020 (7)
O3	0.0107 (9)	0.0104 (8)	0.0094 (8)	−0.0007 (7)	−0.0018 (7)	0.0008 (7)
O4	0.0110 (9)	0.0138 (9)	0.0066 (8)	0.0017 (7)	0.0012 (7)	0.0030 (7)
O5	0.0088 (9)	0.0102 (8)	0.0104 (8)	0.0008 (7)	0.0013 (7)	−0.0017 (7)
O6	0.0136 (9)	0.0114 (9)	0.0088 (8)	−0.0001 (7)	0.0029 (7)	0.0005 (7)
Li1	0.019 (2)	0.013 (2)	0.013 (2)	−0.0038 (18)	0.0013 (18)	−0.0023 (18)
Li2	0.012 (2)	0.014 (2)	0.013 (2)	−0.0009 (17)	0.0008 (17)	0.0009 (17)
Li3	0.013 (2)	0.017 (2)	0.015 (2)	−0.0014 (18)	0.0000 (18)	−0.0016 (18)

Geometric parameters (Å, º) top

Ga1—O1	1.8385 (18)	B1—O2	1.421 (3)
Ga1—O2ⁱ	1.8440 (18)	B1—O3	1.339 (3)
Ga1—O4	1.8272 (18)	B2—O4	1.393 (3)
Ga1—O5ⁱⁱ	1.8759 (18)	B2—O5	1.423 (3)
B1—O1	1.393 (3)	B2—O6	1.336 (3)

O1—Ga1—O2ⁱ	111.84 (8)	Li1^xii—Li1—Li3^vii	149.2 (3)
O1—Ga1—O5ⁱⁱ	102.08 (8)	Li1^xii—Li1—Li3^ix	72.2 (2)
O1—Ga1—Li1ⁱⁱⁱ	116.15 (10)	Li2^ix—Li1—Ga1ⁱⁱⁱ	63.94 (14)
O1—Ga1—Li2^iv	124.51 (10)	Li2^ix—Li1—Li3^viii	60.89 (16)
O1—Ga1—Li2^v	35.98 (10)	Li2^ix—Li1—Li3ⁱⁱ	120.2 (2)
O1—Ga1—Li2^vi	86.55 (10)	Li3ⁱⁱ—Li1—Ga1ⁱⁱⁱ	56.40 (12)
O1—Ga1—Li2	133.42 (11)	Li3^vii—Li1—Ga1ⁱⁱⁱ	74.07 (15)
O1—Ga1—Li3^vii	86.54 (11)	Li3^viii—Li1—Ga1ⁱⁱⁱ	117.59 (17)
O2ⁱ—Ga1—O5ⁱⁱ	111.37 (8)	Li3^ix—Li1—Ga1ⁱⁱⁱ	97.77 (17)
O2ⁱ—Ga1—Li1ⁱⁱⁱ	76.62 (10)	Li3^vii—Li1—Li2^ix	117.0 (2)
O2ⁱ—Ga1—Li2^iv	115.22 (10)	Li3^ix—Li1—Li2^ix	114.0 (2)
O2ⁱ—Ga1—Li2^v	135.30 (11)	Li3ⁱⁱ—Li1—Li3^viii	156.5 (2)
O2ⁱ—Ga1—Li2^vi	37.59 (10)	Li3^vii—Li1—Li3^viii	107.55 (19)
O2ⁱ—Ga1—Li2	77.78 (10)	Li3^ix—Li1—Li3^viii	129.60 (18)
O2ⁱ—Ga1—Li3^vii	39.95 (11)	Li3^vii—Li1—Li3ⁱⁱ	49.58 (19)
O4—Ga1—O1	109.76 (8)	Li3^ix—Li1—Li3ⁱⁱ	73.05 (19)
O4—Ga1—O2ⁱ	110.94 (8)	Li3^ix—Li1—Li3^vii	116.4 (2)
O4—Ga1—O5ⁱⁱ	110.54 (8)	Ga1—Li2—Ga1^vi	105.15 (13)
O4—Ga1—Li1ⁱⁱⁱ	126.18 (10)	Ga1ⁱ—Li2—Ga1^iv	70.59 (10)
O4—Ga1—Li2	34.37 (10)	Ga1—Li2—Ga1^iv	95.24 (13)
O4—Ga1—Li2^vi	96.01 (11)	Ga1ⁱ—Li2—Ga1	104.73 (14)
O4—Ga1—Li2^v	74.92 (11)	Ga1ⁱ—Li2—Ga1^vi	81.11 (11)
O4—Ga1—Li2^iv	78.99 (10)	Ga1^vi—Li2—Ga1^iv	148.57 (16)
O4—Ga1—Li3^vii	150.82 (11)	Ga1—Li2—Li3^xiii	135.80 (19)
O5ⁱⁱ—Ga1—Li1ⁱⁱⁱ	34.75 (10)	Ga1ⁱ—Li2—Li3^xiii	110.84 (17)
O5ⁱⁱ—Ga1—Li2^iv	33.37 (10)	B1^viii—Li2—Ga1ⁱ	136.51 (18)
O5ⁱⁱ—Ga1—Li2^v	106.86 (11)	B1^viii—Li2—Ga1^vi	57.25 (11)
O5ⁱⁱ—Ga1—Li2^vi	146.78 (10)	B1^viii—Li2—Ga1^iv	152.84 (18)
O5ⁱⁱ—Ga1—Li2	116.90 (11)	B1^viii—Li2—Ga1	77.51 (13)
O5ⁱⁱ—Ga1—Li3^vii	88.33 (11)	B1^viii—Li2—B2ⁱ	135.2 (2)
Li1ⁱⁱⁱ—Ga1—Li2^iv	52.55 (11)	B1^viii—Li2—Li1^xi	97.11 (18)
Li2^v—Ga1—Li1ⁱⁱⁱ	137.36 (13)	B1^viii—Li2—Li3^xiii	58.70 (14)
Li2—Ga1—Li1ⁱⁱⁱ	110.42 (13)	B2ⁱ—Li2—Ga1	146.69 (19)
Li2^vi—Ga1—Li1ⁱⁱⁱ	112.82 (12)	B2ⁱ—Li2—Ga1^vi	100.55 (15)
Li2^v—Ga1—Li2	104.73 (14)	B2ⁱ—Li2—Ga1ⁱ	58.67 (11)
Li2—Ga1—Li2^vi	74.85 (13)	B2ⁱ—Li2—Ga1^iv	53.11 (10)
Li2^vi—Ga1—Li2^iv	148.57 (16)	B2ⁱ—Li2—Li1^xi	59.61 (14)
Li2^v—Ga1—Li2^iv	109.41 (10)	B2ⁱ—Li2—Li3^xiii	76.46 (16)
Li2^v—Ga1—Li2^vi	98.89 (11)	O1ⁱ—Li2—Ga1^vi	72.19 (15)
Li2—Ga1—Li2^iv	84.76 (13)	O1ⁱ—Li2—Ga1	75.30 (16)
Li3^vii—Ga1—Li1ⁱⁱⁱ	59.79 (12)	O1ⁱ—Li2—Ga1^iv	90.70 (18)
Li3^vii—Ga1—Li2^vi	59.91 (13)	O1ⁱ—Li2—Ga1ⁱ	34.43 (10)
Li3^vii—Ga1—Li2^v	121.95 (13)	O1ⁱ—Li2—B1^viii	112.1 (2)
Li3^vii—Ga1—Li2	117.45 (13)	O1ⁱ—Li2—B2ⁱ	93.10 (19)
Li3^vii—Ga1—Li2^iv	112.26 (13)	O1ⁱ—Li2—O2^viii	102.8 (2)
O1—B1—O2	115.8 (2)	O1ⁱ—Li2—O5ⁱ	105.5 (2)
O1—B1—Li2^viii	104.8 (2)	O1ⁱ—Li2—Li1^xi	149.9 (3)
O1—B1—Li3ⁱⁱ	113.6 (2)	O1ⁱ—Li2—Li3^xiii	124.6 (2)
O2—B1—Li2^viii	47.04 (15)	O2^viii—Li2—Ga1^vi	32.82 (9)
O2—B1—Li3ⁱⁱ	111.9 (2)	O2^viii—Li2—Ga1	102.44 (18)
O3—B1—O1	123.3 (2)	O2^viii—Li2—Ga1^iv	159.9 (2)
O3—B1—O2	120.9 (2)	O2^viii—Li2—Ga1ⁱ	113.13 (19)
O3—B1—Li2^viii	113.91 (19)	O2^viii—Li2—B1^viii	30.07 (10)
O3—B1—Li3ⁱⁱ	42.00 (16)	O2^viii—Li2—B2ⁱ	110.6 (2)
Li3ⁱⁱ—B1—Li2^viii	141.61 (18)	O2^viii—Li2—Li1^xi	99.0 (2)
O4—B2—O5	117.1 (2)	O2^viii—Li2—Li3^xiii	39.36 (13)
O4—B2—Li1^viii	106.0 (2)	O4—Li2—Ga1	33.11 (10)
O4—B2—Li2^v	88.65 (18)	O4—Li2—Ga1^vi	121.9 (2)
O4—B2—Li3	149.2 (2)	O4—Li2—Ga1ⁱ	131.9 (2)
O5—B2—Li1^viii	119.8 (2)	O4—Li2—Ga1^iv	87.97 (18)
O5—B2—Li2^v	41.16 (15)	O4—Li2—B1^viii	71.58 (17)
O5—B2—Li3	88.65 (18)	O4—Li2—B2ⁱ	136.5 (2)
O6—B2—O4	121.2 (2)	O4—Li2—O1ⁱ	107.7 (2)
O6—B2—O5	121.6 (2)	O4—Li2—O2^viii	101.6 (2)
O6—B2—Li1^viii	40.79 (15)	O4—Li2—O5ⁱ	108.5 (2)
O6—B2—Li2^v	137.1 (2)	O4—Li2—Li1^xi	87.7 (2)
O6—B2—Li3	37.74 (15)	O4—Li2—Li3^xiii	117.1 (2)
Li1^viii—B2—Li2^v	105.56 (17)	O5ⁱ—Li2—Ga1^iv	31.06 (10)
Li1^viii—B2—Li3	70.99 (16)	O5ⁱ—Li2—Ga1ⁱ	74.16 (15)
Li3—B2—Li2^v	122.03 (17)	O5ⁱ—Li2—Ga1^vi	127.9 (2)
Ga1—O1—Li2^v	109.59 (17)	O5ⁱ—Li2—Ga1	125.0 (2)
B1—O1—Ga1	120.01 (17)	O5ⁱ—Li2—B1^viii	140.4 (2)
B1—O1—Li2^v	129.9 (2)	O5ⁱ—Li2—B2ⁱ	27.93 (10)
Ga1^v—O2—Li2^viii	109.59 (15)	O5ⁱ—Li2—O2^viii	129.2 (3)
Ga1^v—O2—Li3^ix	103.87 (16)	O5ⁱ—Li2—Li1^xi	44.44 (15)
B1—O2—Ga1^v	123.74 (16)	O5ⁱ—Li2—Li3^xiii	90.06 (19)
B1—O2—Li2^viii	102.9 (2)	Li1^xi—Li2—Ga1^vi	121.89 (19)
B1—O2—Li3^ix	114.5 (2)	Li1^xi—Li2—Ga1ⁱ	116.94 (18)
Li3^ix—O2—Li2^viii	99.6 (2)	Li1^xi—Li2—Ga1	119.78 (18)
B1—O3—Li1	120.6 (2)	Li1^xi—Li2—Ga1^iv	63.51 (13)
B1—O3—Li3^vii	133.1 (2)	Li1^xi—Li2—Li3^xiii	64.81 (16)
B1—O3—Li3ⁱⁱ	110.7 (2)	Li3^xiii—Li2—Ga1^iv	120.57 (17)
Li1—O3—Li3ⁱⁱ	108.2 (2)	Li3^xiii—Li2—Ga1^vi	57.29 (12)
Li1—O3—Li3^vii	95.7 (2)	Ga1^x—Li3—Li1ⁱⁱ	63.82 (13)
Li3^vii—O3—Li3ⁱⁱ	81.0 (2)	Ga1^x—Li3—Li2^xiii	62.79 (13)
Ga1—O4—Li2	112.52 (17)	B1ⁱⁱ—Li3—Ga1^x	121.35 (18)
B2—O4—Ga1	127.86 (17)	B1ⁱⁱ—Li3—B2	69.64 (14)
B2—O4—Li2	119.6 (2)	B1ⁱⁱ—Li3—Li1ⁱⁱ	57.56 (14)
Ga1ⁱⁱ—O5—Li1^x	113.47 (16)	B1ⁱⁱ—Li3—Li1^x	106.5 (2)
Ga1ⁱⁱ—O5—Li2^v	115.56 (17)	B1ⁱⁱ—Li3—Li1^xi	80.20 (17)
B2—O5—Ga1ⁱⁱ	113.05 (16)	B1ⁱⁱ—Li3—Li2^xiii	150.9 (2)
B2—O5—Li1^x	110.1 (2)	B2—Li3—Ga1^x	168.9 (2)
B2—O5—Li2^v	110.9 (2)	B2—Li3—Li1^x	60.43 (15)
Li2^v—O5—Li1^x	92.0 (2)	B2—Li3—Li1ⁱⁱ	127.1 (2)
B2—O6—Li1^viii	112.8 (2)	B2—Li3—Li1^xi	64.26 (15)
B2—O6—Li1^xi	130.9 (2)	B2—Li3—Li2^xiii	108.51 (19)
B2—O6—Li3	117.0 (2)	O2^xi—Li3—Ga1^x	36.18 (10)
Li1^xi—O6—Li1^viii	83.6 (2)	O2^xi—Li3—B1ⁱⁱ	122.9 (2)
Li3—O6—Li1^xi	95.2 (2)	O2^xi—Li3—B2	141.0 (2)
Li3—O6—Li1^viii	112.6 (2)	O2^xi—Li3—Li1ⁱⁱ	77.94 (18)
B2^viii—Li1—Ga1ⁱⁱⁱ	150.65 (19)	O2^xi—Li3—Li1^x	130.1 (2)
B2^viii—Li1—Li2^ix	115.6 (2)	O2^xi—Li3—Li1^xi	80.86 (19)
B2^viii—Li1—Li3^ix	107.8 (2)	O2^xi—Li3—Li2^xiii	41.01 (14)
B2^viii—Li1—Li3ⁱⁱ	117.46 (19)	O2^xi—Li3—Li3^xiv	118.1 (3)
B2^viii—Li1—Li3^vii	81.65 (18)	O3ⁱⁱ—Li3—Ga1^x	97.47 (18)
B2^viii—Li1—Li3^viii	54.76 (14)	O3^x—Li3—Ga1^x	73.34 (15)
O3—Li1—Ga1ⁱⁱⁱ	90.74 (18)	O3^x—Li3—B1ⁱⁱ	116.5 (2)
O3—Li1—B2^viii	81.99 (18)	O3ⁱⁱ—Li3—B1ⁱⁱ	27.27 (10)
O3—Li1—O5^vii	110.1 (2)	O3^x—Li3—B2	101.3 (2)
O3—Li1—O6^viii	108.0 (2)	O3ⁱⁱ—Li3—B2	92.9 (2)
O3—Li1—O6^ix	117.7 (3)	O3^x—Li3—O2^xi	103.3 (2)
O3—Li1—Li1^xii	125.5 (3)	O3ⁱⁱ—Li3—O2^xi	112.5 (2)
O3—Li1—Li2^ix	153.3 (3)	O3^x—Li3—O3ⁱⁱ	99.0 (2)
O3—Li1—Li3^vii	42.42 (15)	O3ⁱⁱ—Li3—Li1^x	108.3 (2)
O3—Li1—Li3ⁱⁱ	36.20 (14)	O3ⁱⁱ—Li3—Li1^xi	103.2 (2)
O3—Li1—Li3^viii	133.3 (2)	O3^x—Li3—Li1^x	41.91 (14)
O3—Li1—Li3^ix	75.85 (19)	O3ⁱⁱ—Li3—Li1ⁱⁱ	35.65 (13)
O5^vii—Li1—Ga1ⁱⁱⁱ	31.78 (9)	O3^x—Li3—Li1ⁱⁱ	99.1 (2)
O5^vii—Li1—B2^viii	126.2 (2)	O3^x—Li3—Li1^xi	153.9 (3)
O5^vii—Li1—Li1^xii	124.5 (3)	O3ⁱⁱ—Li3—Li2^xiii	153.3 (2)
O5^vii—Li1—Li2^ix	43.60 (14)	O3^x—Li3—Li2^xiii	92.5 (2)
O5^vii—Li1—Li3^viii	86.42 (18)	O3ⁱⁱ—Li3—Li3^xiv	49.37 (18)
O5^vii—Li1—Li3^ix	126.0 (2)	O3^x—Li3—Li3^xiv	49.60 (17)
O5^vii—Li1—Li3ⁱⁱ	82.63 (18)	O6—Li3—Ga1^x	149.2 (2)
O5^vii—Li1—Li3^vii	76.30 (19)	O6—Li3—B1ⁱⁱ	82.26 (18)
O6^ix—Li1—Ga1ⁱⁱⁱ	95.39 (18)	O6—Li3—B2	25.26 (10)
O6^viii—Li1—Ga1ⁱⁱⁱ	149.8 (2)	O6—Li3—O2^xi	115.8 (3)
O6^viii—Li1—B2^viii	26.37 (10)	O6—Li3—O3ⁱⁱ	109.1 (2)
O6^ix—Li1—B2^viii	113.2 (2)	O6—Li3—O3^x	116.1 (3)
O6^viii—Li1—O5^vii	118.0 (2)	O6—Li3—Li1^x	74.64 (19)
O6^ix—Li1—O5^vii	106.5 (2)	O6—Li3—Li1^xi	42.94 (15)
O6^ix—Li1—O6^viii	96.4 (2)	O6—Li3—Li1ⁱⁱ	135.9 (2)
O6^viii—Li1—Li1^xii	48.01 (17)	O6—Li3—Li2^xiii	86.9 (2)
O6^ix—Li1—Li1^xii	48.35 (17)	O6—Li3—Li3^xiv	126.2 (3)
O6^viii—Li1—Li2^ix	92.4 (2)	Li1^x—Li3—Ga1^x	112.15 (18)
O6^ix—Li1—Li2^ix	75.35 (18)	Li1^xi—Li3—Ga1^x	116.62 (19)
O6^viii—Li1—Li3^vii	103.7 (2)	Li1^x—Li3—Li1ⁱⁱ	130.42 (19)
O6^ix—Li1—Li3ⁱⁱ	106.1 (2)	Li1^xi—Li3—Li1^x	116.4 (2)
O6^viii—Li1—Li3ⁱⁱ	143.8 (2)	Li1^xi—Li3—Li1ⁱⁱ	106.95 (18)
O6^ix—Li1—Li3^vii	155.5 (3)	Li1^x—Li3—Li2^xiii	96.3 (2)
O6^viii—Li1—Li3^ix	109.5 (2)	Li1^xi—Li3—Li2^xiii	73.57 (18)
O6^ix—Li1—Li3^ix	41.90 (15)	Li2^xiii—Li3—Li1ⁱⁱ	118.79 (19)
O6^ix—Li1—Li3^viii	96.9 (2)	Li3^xiv—Li3—Ga1^x	83.1 (2)
O6^viii—Li1—Li3^viii	33.21 (13)	Li3^xiv—Li3—B1ⁱⁱ	70.0 (2)
Li1^xii—Li1—Ga1ⁱⁱⁱ	136.1 (3)	Li3^xiv—Li3—B2	100.9 (3)
Li1^xii—Li1—B2^viii	67.7 (2)	Li3^xiv—Li3—Li1^xi	150.0 (3)
Li1^xii—Li1—Li2^ix	81.0 (2)	Li3^xiv—Li3—Li1ⁱⁱ	59.6 (2)
Li1^xii—Li1—Li3^viii	57.4 (2)	Li3^xiv—Li3—Li1^x	70.8 (2)
Li1^xii—Li1—Li3ⁱⁱ	144.5 (3)	Li3^xiv—Li3—Li2^xiii	136.2 (3)

Ga1—O4—Li2—Ga1^iv	−102.80 (13)	O6—B2—O4—Li2	0.4 (4)
Ga1—O4—Li2—Ga1^vi	66.9 (3)	O6—B2—O5—Ga1ⁱⁱ	−101.3 (3)
Ga1—O4—Li2—Ga1ⁱ	−41.4 (3)	O6—B2—O5—Li1^x	26.8 (3)
Ga1—O4—Li2—B1^viii	95.37 (14)	O6—B2—O5—Li2^v	127.1 (3)
Ga1—O4—Li2—B2ⁱ	−127.4 (3)	Li1ⁱⁱⁱ—Ga1—O1—B1	−37.0 (2)
Ga1—O4—Li2—O1ⁱ	−12.7 (3)	Li1ⁱⁱⁱ—Ga1—O1—Li2^v	135.94 (19)
Ga1—O4—Li2—O2^viii	95.0 (2)	Li1ⁱⁱⁱ—Ga1—O4—B2	−105.3 (2)
Ga1—O4—Li2—O5ⁱ	−126.46 (19)	Li1ⁱⁱⁱ—Ga1—O4—Li2	72.3 (2)
Ga1—O4—Li2—Li1^xi	−166.36 (14)	Li1^viii—B2—O4—Ga1	−140.43 (17)
Ga1—O4—Li2—Li3^xiii	133.58 (18)	Li1^viii—B2—O4—Li2	42.1 (3)
B2—O4—Li2—Ga1^iv	75.0 (2)	Li1^viii—B2—O5—Ga1ⁱⁱ	−149.04 (15)
B2—O4—Li2—Ga1^vi	−115.2 (2)	Li1^viii—B2—O5—Li1^x	−21.0 (3)
B2—O4—Li2—Ga1ⁱ	136.4 (2)	Li1^viii—B2—O5—Li2^v	79.3 (3)
B2—O4—Li2—Ga1	177.8 (3)	Li1^viii—B2—O6—Li1^xi	−101.9 (3)
B2—O4—Li2—B1^viii	−86.8 (2)	Li1^viii—B2—O6—Li3	133.1 (3)
B2—O4—Li2—B2ⁱ	50.5 (4)	Li2^vi—Ga1—O1—B1	76.7 (2)
B2—O4—Li2—O1ⁱ	165.1 (2)	Li2^v—Ga1—O1—B1	−173.0 (3)
B2—O4—Li2—O2^viii	−87.2 (3)	Li2^iv—Ga1—O1—B1	−98.1 (2)
B2—O4—Li2—O5ⁱ	51.4 (3)	Li2—Ga1—O1—B1	142.1 (2)
B2—O4—Li2—Li1^xi	11.5 (3)	Li2—Ga1—O1—Li2^v	−44.96 (17)
B2—O4—Li2—Li3^xiii	−48.6 (3)	Li2^vi—Ga1—O1—Li2^v	−110.28 (16)
O1—Ga1—O4—B2	42.2 (2)	Li2^iv—Ga1—O1—Li2^v	74.9 (2)
O1—Ga1—O4—Li2	−140.21 (19)	Li2—Ga1—O4—B2	−177.6 (3)
O1—B1—O2—Ga1^v	−38.0 (3)	Li2^iv—Ga1—O4—B2	−80.7 (2)
O1—B1—O2—Li2^viii	86.5 (3)	Li2^vi—Ga1—O4—B2	130.6 (2)
O1—B1—O2—Li3^ix	−166.5 (2)	Li2^v—Ga1—O4—B2	33.0 (2)
O1—B1—O3—Li1	−143.3 (3)	Li2^iv—Ga1—O4—Li2	96.9 (2)
O1—B1—O3—Li3ⁱⁱ	89.1 (3)	Li2^vi—Ga1—O4—Li2	−51.7 (2)
O1—B1—O3—Li3^vii	−8.1 (5)	Li2^v—Ga1—O4—Li2	−149.4 (3)
O2ⁱ—Ga1—O1—B1	48.3 (2)	Li2^viii—B1—O1—Ga1	−145.49 (15)
O2ⁱ—Ga1—O1—Li2^v	−138.71 (18)	Li2^viii—B1—O1—Li2^v	43.1 (4)
O2ⁱ—Ga1—O4—B2	166.3 (2)	Li2^viii—B1—O2—Ga1^v	−124.5 (2)
O2ⁱ—Ga1—O4—Li2	−16.1 (2)	Li2^viii—B1—O2—Li3^ix	107.0 (2)
O2—B1—O1—Ga1	165.44 (16)	Li2^viii—B1—O3—Li1	−14.5 (3)
O2—B1—O1—Li2^v	−5.9 (4)	Li2^viii—B1—O3—Li3^vii	120.7 (3)
O2—B1—O3—Li1	38.4 (4)	Li2^viii—B1—O3—Li3ⁱⁱ	−142.1 (2)
O2—B1—O3—Li3ⁱⁱ	−89.2 (3)	Li2^v—B2—O4—Ga1	−34.6 (2)
O2—B1—O3—Li3^vii	173.6 (3)	Li2^v—B2—O4—Li2	147.9 (3)
O3—B1—O1—Ga1	−13.0 (3)	Li2^v—B2—O5—Ga1ⁱⁱ	131.7 (2)
O3—B1—O1—Li2^v	175.7 (3)	Li2^v—B2—O5—Li1^x	−100.3 (3)
O3—B1—O2—Ga1^v	140.4 (2)	Li2^v—B2—O6—Li1^xi	−151.7 (3)
O3—B1—O2—Li2^viii	−95.1 (3)	Li2^v—B2—O6—Li1^viii	−49.8 (4)
O3—B1—O2—Li3^ix	12.0 (3)	Li2^v—B2—O6—Li3	83.2 (4)
O4—Ga1—O1—B1	171.88 (18)	Li3^vii—Ga1—O1—B1	16.7 (2)
O4—Ga1—O1—Li2^v	−15.1 (2)	Li3^vii—Ga1—O1—Li2^v	−170.3 (2)
O4—B2—O5—Ga1ⁱⁱ	80.4 (2)	Li3^vii—Ga1—O4—B2	162.9 (3)
O4—B2—O5—Li1^x	−151.6 (2)	Li3^vii—Ga1—O4—Li2	−19.4 (3)
O4—B2—O5—Li2^v	−51.3 (3)	Li3ⁱⁱ—B1—O1—Ga1	33.9 (2)
O4—B2—O6—Li1^viii	78.0 (3)	Li3ⁱⁱ—B1—O1—Li2^v	−137.4 (3)
O4—B2—O6—Li1^xi	−23.9 (4)	Li3ⁱⁱ—B1—O2—Ga1^v	94.3 (2)
O4—B2—O6—Li3	−149.0 (3)	Li3ⁱⁱ—B1—O2—Li2^viii	−141.2 (2)
O5ⁱⁱ—Ga1—O1—B1	−70.85 (19)	Li3ⁱⁱ—B1—O2—Li3^ix	−34.2 (3)
O5ⁱⁱ—Ga1—O1—Li2^v	102.13 (18)	Li3ⁱⁱ—B1—O3—Li1	127.6 (3)
O5ⁱⁱ—Ga1—O4—B2	−69.7 (2)	Li3ⁱⁱ—B1—O3—Li3^vii	−97.2 (3)
O5ⁱⁱ—Ga1—O4—Li2	107.94 (19)	Li3—B2—O4—Ga1	139.9 (3)
O5—B2—O4—Ga1	−3.7 (3)	Li3—B2—O4—Li2	−37.5 (5)
O5—B2—O4—Li2	178.8 (2)	Li3—B2—O5—Ga1ⁱⁱ	−81.93 (16)
O5—B2—O6—Li1^viii	−100.3 (3)	Li3—B2—O5—Li1^x	46.1 (2)
O5—B2—O6—Li1^xi	157.8 (3)	Li3—B2—O5—Li2^v	146.4 (2)
O5—B2—O6—Li3	32.7 (4)	Li3—B2—O6—Li1^viii	−133.1 (3)
O6—B2—O4—Ga1	177.91 (18)	Li3—B2—O6—Li1^xi	125.1 (4)

Symmetry codes: (i) x+1, y, z; (ii) −x+1, −y+1, −z+1; (iii) −x+1, −y, −z+2; (iv) −x+2, −y+1, −z+1; (v) x−1, y, z; (vi) −x+2, −y, −z+1; (vii) x, y−1, z+1; (viii) −x+1, −y, −z+1; (ix) x−1, y−1, z+1; (x) x, y+1, z−1; (xi) x+1, y+1, z−1; (xii) −x, −y−1, −z+2; (xiii) −x+2, −y+1, −z; (xiv) −x+1, −y+2, −z.

Comparison of the two structures with composition Li₃Ga(BO₃)₂ top

Structure model	Abdullaev & Mamedov (1972)	Current work
Reduced cell (Å, °)	4.90 (2) 6.23 (3) 7.78 (5) 72.9 (5) 90.0 (5) 90.0 (5)	4.8731 (3) 6.2429 (4) 8.0130 (5) 73.346 (6) 89.701 (5) 89.698 (5)

Range of interatomic distances (Å)			Shannon (1976)
Li—O	2.28±0.41	1.965±0.054	1.97
Ga—O	2.07±0.43	1.847±0.021	1.85
B—O	1.31±0.13	1.384±0.038	1.39

Bond-valence-sum values and coordination numbers (in brackets)
Li (1, 2 & 3)	1.14 [4+1], 1.01 [4], 1.00 [6]	1.07 [4], 1.03 [4], 1.05 [4]
Ga (1)	2.38 [4]	2.92 [4]
B (1 & 2)	3.17 [3], 3.06 [3]	2.91 [3], 2.91 [3]

Acknowledgements

EMV would like to acknowledge Creighton University for financial support.

References

Abdullaev, G. K. & Mamedov, Kh. S. (1972). Zh. Strukt. Khim. 13, 943–946. CAS Google Scholar
Brese, N. E. & O'Keeffe, M. (1991). Acta Cryst. B47, 192–197. CrossRef CAS Web of Science IUCr Journals Google Scholar
Corbel, G. & Leblanc, M. (2000). J. Solid State Chem. 154, 344–349. Web of Science CrossRef CAS Google Scholar
Dolomanov, O. V., Bourhis, L. J., Gildea, R. J., Howard, J. A. K. & Puschmann, H. (2009). J. Appl. Cryst. 42, 339–341. Web of Science CrossRef CAS IUCr Journals Google Scholar
He, M., Chen, X. L., Gramlich, V., Baerlocher, Ch., Zhou, T. & Hu, B. Q. (2002). J. Solid State Chem. 163, 369–376. CrossRef CAS Google Scholar
Rigaku Oxford Diffraction (2015). CrysAlis PRO. Rigaku Oxford Diffraction, Yarnton, Oxfordshire, England. Google Scholar
Shannon, R. D. (1976). Acta Cryst. A32, 751–767. CrossRef CAS IUCr Journals Web of Science Google Scholar
Sheldrick, G. M. (2015a). Acta Cryst. A71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2015b). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Smith, R. W. (1995). Acta Cryst. C51, 547–549. CrossRef CAS Web of Science IUCr Journals Google Scholar
Smith, R. W., Hu, C. & DeSpain, C. D. (2008). Acta Cryst. E64, i23. CrossRef IUCr Journals Google Scholar
Smith, R. W., Kennard, M. A. & Dudik, M. J. (1997). Mater. Res. Bull. 32, 649–656. CrossRef CAS Web of Science Google Scholar