LiBC3: a new borocarbide based on graphene and heterographene networks

Milashius, V.; Pavlyuk, V.; Kluziak, K.; Dmytriv, G.; Ehrenberg, H.

doi:10.1107/S2053229617015182

LiBC₃: a new borocarbide based on graphene and heterographene networks

V. Milashius, V. Pavlyuk, K. Kluziak, G. Dmytriv and H. Ehrenberg

Li–B–C alloys have attracted much interest because of their potential use in lithium-ion batteries and superconducting materials. The formation of the new compound LiBC₃ [lithium boron tricarbide; own structure type, space group P $\overline{6}$ m2, a = 2.5408 (3) Å and c = 7.5989 (9) Å] has been revealed and belongs to the graphite-like structure family. The crystal structure of LiBC₃ presents hexagonal graphene carbon networks, lithium layers and heterographene B/C networks, alternating sequentially along the c axis. According to electronic structure calculations using the tight-binding linear muffin-tin orbital-atomic spheres approximations (TB–LMTO–ASA) method, strong covalent B—C and C—C interactions are established. The coordination polyhedra for the B and C atoms are trigonal prisms and for the Li atoms are hexagonal prisms.

Keywords: electronic structure; crystal structure; lithium intermetallic; computational chemistry; lithium-ion batteries; ternary Li–B–C system; graphene and heterographene networks.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S2053229617015182/yo3041sup1.cif Contains datablocks I, New_Global_Publ_Block
	Structure factor file (CIF format) https://doi.org/10.1107/S2053229617015182/yo3041Isup2.hkl Contains datablock I

CCDC reference: 1580572

Computing details top

Data collection: CrysAlis CCD (Oxford Diffraction, 2008); cell refinement: CrysAlis CCD (Oxford Diffraction, 2008); data reduction: CrysAlis RED (Oxford Diffraction, 2008); program(s) used to solve structure: SHELXS2014 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: DIAMOND (Brandenburg, 2006); software used to prepare material for publication: SHELXL2014 (Sheldrick, 2015).

Lithium boron tricarbide top

Crystal data top

Li_0.96BC₃	D_x = 2.091 Mg m⁻³ D_m = 2.13 (3) Mg m⁻³ D_m measured by volumetric
M_r = 53.50	Mo Kα radiation, λ = 0.71073 Å
Hexagonal, P6m2	Cell parameters from 77 reflections
a = 2.5408 (3) Å	θ = 2.7–29.6°
c = 7.5989 (9) Å	µ = 0.10 mm⁻¹
V = 42.48 (1) Å³	T = 293 K
Z = 1	Plate, metallic grey
F(000) = 25.9	0.08 × 0.06 × 0.01 mm

Data collection top

Oxford Diffraction Xcalibur3 CCD diffractometer	73 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.110
ω scans	θ_max = 29.7°, θ_min = 2.7°
Absorption correction: analytical (CrysAlis RED; Oxford Diffraction, 2008)	h = −3→3
T_min = 0.993, T_max = 0.998	k = −3→3
1554 measured reflections	l = −10→10
77 independent reflections

Refinement top

Refinement on F²	11 parameters
Least-squares matrix: full	0 restraints
R[F² > 2σ(F²)] = 0.032	w = 1/[σ²(F_o²) + (0.0528P)² + 0.0041P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.098	(Δ/σ)_max < 0.001
S = 1.23	Δρ_max = 0.15 e Å⁻³
77 reflections	Δρ_min = −0.15 e Å⁻³

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. Refined as a 2-component inversion twin.

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
C1	0.0000	0.0000	0.0000	0.0383 (19)
C2	0.3333	0.6667	0.5000	0.0350 (12)
C3	0.3333	0.6667	0.0000	0.0295 (11)
B1	0.0000	0.0000	0.5000	0.066 (4)
Li1	0.6667	0.3333	0.2500	0.083 (10)*	0.49 (6)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.037 (3)	0.037 (3)	0.041 (3)	0.0185 (13)	0.000	0.000
C2	0.0349 (18)	0.0349 (18)	0.035 (2)	0.0174 (9)	0.000	0.000
C3	0.0282 (15)	0.0282 (15)	0.032 (2)	0.0141 (7)	0.000	0.000
B1	0.066 (5)	0.066 (5)	0.068 (7)	0.033 (3)	0.000	0.000

Geometric parameters (Å, º) top

C1—C3ⁱ	1.4669 (2)	C3—Li1^vi	2.4002 (2)
C1—C3	1.4669 (2)	C3—Li1^xii	2.4002 (2)
C1—C3ⁱⁱ	1.4669 (2)	C3—Li1^iv	2.4002 (2)
C1—Li1ⁱⁱⁱ	2.4002 (2)	C3—Li1^v	2.4002 (2)
C1—Li1	2.4002 (2)	C3—Li1	2.4002 (2)
C1—Li1^iv	2.4002 (2)	B1—C2ⁱ	1.4669 (2)
C1—Li1^v	2.4002 (2)	B1—C2ⁱⁱ	1.4669 (2)
C1—Li1^vi	2.4002 (2)	B1—Li1^x	2.4002 (2)
C1—Li1ⁱⁱ	2.4002 (2)	B1—Li1ⁱⁱ	2.4002 (2)
C2—B1^vii	1.4669 (2)	B1—Li1^iv	2.4002 (2)
C2—B1^viii	1.4669 (2)	B1—Li1^xi	2.4002 (2)
C2—B1	1.4669 (2)	B1—Li1	2.4002 (2)
C2—Li1^ix	2.4002 (2)	B1—Li1^xiii	2.4002 (2)
C2—Li1^iv	2.4002 (2)	Li1—C3ⁱ	2.4002 (2)
C2—Li1^vii	2.4002 (2)	Li1—C2^xiv	2.4002 (2)
C2—Li1^x	2.4002 (2)	Li1—B1^viii	2.4002 (2)
C2—Li1^xi	2.4002 (2)	Li1—B1^xiv	2.4002 (2)
C2—Li1	2.4002 (2)	Li1—C1^xiv	2.4002 (2)
C3—C1^vii	1.4669 (2)	Li1—C3^xiv	2.4002 (2)
C3—C1^viii	1.4669 (2)	Li1—C2ⁱ	2.4002 (2)
C3—Li1^vii	2.4002 (2)	Li1—C1^viii	2.4002 (2)

C3ⁱ—C1—C3	120.0	Li1^xii—C3—Li1	144.413 (4)
C3ⁱ—C1—C3ⁱⁱ	120.0	Li1^iv—C3—Li1	63.916 (8)
C3—C1—C3ⁱⁱ	120.0	Li1^v—C3—Li1	104.651 (9)
C3ⁱ—C1—Li1ⁱⁱⁱ	72.206 (2)	C2ⁱ—B1—C2	120.0
C3—C1—Li1ⁱⁱⁱ	127.675 (5)	C2ⁱ—B1—C2ⁱⁱ	120.0
C3ⁱⁱ—C1—Li1ⁱⁱⁱ	72.206 (2)	C2—B1—C2ⁱⁱ	120.0
C3ⁱ—C1—Li1	72.206 (2)	C2ⁱ—B1—Li1^x	72.206 (2)
C3—C1—Li1	72.206 (2)	C2—B1—Li1^x	72.206 (2)
C3ⁱⁱ—C1—Li1	127.675 (5)	C2ⁱⁱ—B1—Li1^x	127.675 (5)
Li1ⁱⁱⁱ—C1—Li1	144.413 (4)	C2ⁱ—B1—Li1ⁱⁱ	72.206 (2)
C3ⁱ—C1—Li1^iv	127.675 (5)	C2—B1—Li1ⁱⁱ	127.675 (5)
C3—C1—Li1^iv	72.206 (2)	C2ⁱⁱ—B1—Li1ⁱⁱ	72.206 (2)
C3ⁱⁱ—C1—Li1^iv	72.206 (2)	Li1^x—B1—Li1ⁱⁱ	144.413 (4)
Li1ⁱⁱⁱ—C1—Li1^iv	144.413 (4)	C2ⁱ—B1—Li1^iv	127.675 (5)
Li1—C1—Li1^iv	63.916 (8)	C2—B1—Li1^iv	72.206 (2)
C3ⁱ—C1—Li1^v	72.206 (2)	C2ⁱⁱ—B1—Li1^iv	72.206 (2)
C3—C1—Li1^v	72.206 (2)	Li1^x—B1—Li1^iv	144.413 (4)
C3ⁱⁱ—C1—Li1^v	127.675 (5)	Li1ⁱⁱ—B1—Li1^iv	63.916 (7)
Li1ⁱⁱⁱ—C1—Li1^v	63.916 (7)	C2ⁱ—B1—Li1^xi	127.675 (5)
Li1—C1—Li1^v	104.651 (9)	C2—B1—Li1^xi	72.206 (2)
Li1^iv—C1—Li1^v	144.413 (4)	C2ⁱⁱ—B1—Li1^xi	72.206 (2)
C3ⁱ—C1—Li1^vi	127.675 (5)	Li1^x—B1—Li1^xi	63.916 (8)
C3—C1—Li1^vi	72.206 (2)	Li1ⁱⁱ—B1—Li1^xi	144.413 (4)
C3ⁱⁱ—C1—Li1^vi	72.206 (2)	Li1^iv—B1—Li1^xi	104.651 (9)
Li1ⁱⁱⁱ—C1—Li1^vi	63.916 (7)	C2ⁱ—B1—Li1	72.206 (2)
Li1—C1—Li1^vi	144.413 (4)	C2—B1—Li1	72.206 (2)
Li1^iv—C1—Li1^vi	104.651 (9)	C2ⁱⁱ—B1—Li1	127.675 (5)
Li1^v—C1—Li1^vi	63.916 (8)	Li1^x—B1—Li1	104.651 (9)
C3ⁱ—C1—Li1ⁱⁱ	72.206 (2)	Li1ⁱⁱ—B1—Li1	63.916 (7)
C3—C1—Li1ⁱⁱ	127.675 (5)	Li1^iv—B1—Li1	63.916 (8)
C3ⁱⁱ—C1—Li1ⁱⁱ	72.206 (2)	Li1^xi—B1—Li1	144.413 (4)
Li1ⁱⁱⁱ—C1—Li1ⁱⁱ	104.651 (9)	C2ⁱ—B1—Li1^xiii	72.206 (2)
Li1—C1—Li1ⁱⁱ	63.916 (7)	C2—B1—Li1^xiii	127.675 (5)
Li1^iv—C1—Li1ⁱⁱ	63.916 (7)	C2ⁱⁱ—B1—Li1^xiii	72.206 (2)
Li1^v—C1—Li1ⁱⁱ	144.413 (4)	Li1^x—B1—Li1^xiii	63.916 (8)
Li1^vi—C1—Li1ⁱⁱ	144.413 (4)	Li1ⁱⁱ—B1—Li1^xiii	104.651 (9)
B1^vii—C2—B1^viii	120.0	Li1^iv—B1—Li1^xiii	144.413 (4)
B1^vii—C2—B1	120.0	Li1^xi—B1—Li1^xiii	63.916 (8)
B1^viii—C2—B1	120.0	Li1—B1—Li1^xiii	144.413 (4)
B1^vii—C2—Li1^ix	72.206 (2)	C3ⁱ—Li1—C2^xiv	144.413 (4)
B1^viii—C2—Li1^ix	72.206 (2)	C3ⁱ—Li1—B1^viii	180.0
B1—C2—Li1^ix	127.675 (5)	C2^xiv—Li1—B1^viii	35.587 (4)
B1^vii—C2—Li1^iv	72.206 (2)	C3ⁱ—Li1—C1	35.587 (4)
B1^viii—C2—Li1^iv	127.675 (5)	C2^xiv—Li1—C1	180.0
B1—C2—Li1^iv	72.206 (2)	B1^viii—Li1—C1	144.413 (4)
Li1^ix—C2—Li1^iv	144.413 (4)	C3ⁱ—Li1—B1^xiv	116.084 (7)
B1^vii—C2—Li1^vii	72.206 (2)	C2^xiv—Li1—B1^xiv	35.587 (4)
B1^viii—C2—Li1^vii	72.206 (2)	B1^viii—Li1—B1^xiv	63.916 (7)
B1—C2—Li1^vii	127.675 (5)	C1—Li1—B1^xiv	144.413 (4)
Li1^ix—C2—Li1^vii	104.651 (9)	C3ⁱ—Li1—C1^xiv	35.587 (4)
Li1^iv—C2—Li1^vii	63.916 (7)	C2^xiv—Li1—C1^xiv	116.084 (8)
B1^vii—C2—Li1^x	127.675 (5)	B1^viii—Li1—C1^xiv	144.413 (4)
B1^viii—C2—Li1^x	72.206 (2)	C1—Li1—C1^xiv	63.916 (8)
B1—C2—Li1^x	72.206 (2)	B1^xiv—Li1—C1^xiv	104.651 (9)
Li1^ix—C2—Li1^x	63.916 (8)	C3ⁱ—Li1—C3^xiv	63.916 (7)
Li1^iv—C2—Li1^x	144.413 (4)	C2^xiv—Li1—C3^xiv	104.651 (9)
Li1^vii—C2—Li1^x	144.413 (4)	B1^viii—Li1—C3^xiv	116.084 (7)
B1^vii—C2—Li1^xi	72.206 (2)	C1—Li1—C3^xiv	75.349 (9)
B1^viii—C2—Li1^xi	127.675 (5)	B1^xiv—Li1—C3^xiv	116.084 (8)
B1—C2—Li1^xi	72.206 (2)	C1^xiv—Li1—C3^xiv	35.587 (4)
Li1^ix—C2—Li1^xi	63.916 (8)	C3ⁱ—Li1—C2ⁱ	104.651 (9)
Li1^iv—C2—Li1^xi	104.651 (9)	C2^xiv—Li1—C2ⁱ	63.916 (7)
Li1^vii—C2—Li1^xi	144.413 (4)	B1^viii—Li1—C2ⁱ	75.349 (9)
Li1^x—C2—Li1^xi	63.916 (8)	C1—Li1—C2ⁱ	116.084 (7)
B1^vii—C2—Li1	127.675 (5)	B1^xiv—Li1—C2ⁱ	35.587 (4)
B1^viii—C2—Li1	72.206 (2)	C1^xiv—Li1—C2ⁱ	116.084 (8)
B1—C2—Li1	72.206 (2)	C3^xiv—Li1—C2ⁱ	144.413 (4)
Li1^ix—C2—Li1	144.413 (4)	C3ⁱ—Li1—C1^viii	75.349 (9)
Li1^iv—C2—Li1	63.916 (8)	C2^xiv—Li1—C1^viii	116.084 (7)
Li1^vii—C2—Li1	63.916 (7)	B1^viii—Li1—C1^viii	104.651 (9)
Li1^x—C2—Li1	104.651 (9)	C1—Li1—C1^viii	63.916 (7)
Li1^xi—C2—Li1	144.413 (4)	B1^xiv—Li1—C1^viii	144.413 (4)
C1^vii—C3—C1^viii	120.0	C1^xiv—Li1—C1^viii	63.916 (8)
C1^vii—C3—C1	120.0	C3^xiv—Li1—C1^viii	35.587 (4)
C1^viii—C3—C1	120.0	C2ⁱ—Li1—C1^viii	180.0
C1^vii—C3—Li1^vii	72.206 (2)	C3ⁱ—Li1—B1	116.084 (7)
C1^viii—C3—Li1^vii	72.206 (2)	C2^xiv—Li1—B1	75.349 (9)
C1—C3—Li1^vii	127.675 (5)	B1^viii—Li1—B1	63.916 (7)
C1^vii—C3—Li1^vi	72.206 (2)	C1—Li1—B1	104.651 (9)
C1^viii—C3—Li1^vi	127.675 (5)	B1^xiv—Li1—B1	63.916 (8)
C1—C3—Li1^vi	72.206 (2)	C1^xiv—Li1—B1	144.413 (4)
Li1^vii—C3—Li1^vi	144.413 (4)	C3^xiv—Li1—B1	180.0
C1^vii—C3—Li1^xii	72.206 (2)	C2ⁱ—Li1—B1	35.587 (4)
C1^viii—C3—Li1^xii	72.206 (2)	C1^viii—Li1—B1	144.413 (4)
C1—C3—Li1^xii	127.675 (5)	C3ⁱ—Li1—C3	63.916 (8)
Li1^vii—C3—Li1^xii	104.651 (9)	C2^xiv—Li1—C3	144.413 (4)
Li1^vi—C3—Li1^xii	63.916 (8)	B1^viii—Li1—C3	116.084 (8)
C1^vii—C3—Li1^iv	72.206 (2)	C1—Li1—C3	35.587 (4)
C1^viii—C3—Li1^iv	127.675 (5)	B1^xiv—Li1—C3	180.0
C1—C3—Li1^iv	72.206 (2)	C1^xiv—Li1—C3	75.349 (9)
Li1^vii—C3—Li1^iv	63.916 (7)	C3^xiv—Li1—C3	63.916 (8)
Li1^vi—C3—Li1^iv	104.651 (9)	C2ⁱ—Li1—C3	144.413 (4)
Li1^xii—C3—Li1^iv	144.413 (4)	C1^viii—Li1—C3	35.587 (4)
C1^vii—C3—Li1^v	127.675 (5)	B1—Li1—C3	116.084 (8)
C1^viii—C3—Li1^v	72.206 (2)	C3ⁱ—Li1—C2	144.413 (4)
C1—C3—Li1^v	72.206 (2)	C2^xiv—Li1—C2	63.916 (8)
Li1^vii—C3—Li1^v	144.413 (4)	B1^viii—Li1—C2	35.587 (4)
Li1^vi—C3—Li1^v	63.916 (8)	C1—Li1—C2	116.084 (8)
Li1^xii—C3—Li1^v	63.916 (8)	B1^xiv—Li1—C2	75.349 (9)
Li1^iv—C3—Li1^v	144.413 (4)	C1^xiv—Li1—C2	180.0
C1^vii—C3—Li1	127.675 (5)	C3^xiv—Li1—C2	144.413 (4)
C1^viii—C3—Li1	72.206 (2)	C2ⁱ—Li1—C2	63.916 (8)
C1—C3—Li1	72.206 (2)	C1^viii—Li1—C2	116.084 (8)
Li1^vii—C3—Li1	63.916 (8)	B1—Li1—C2	35.587 (4)
Li1^vi—C3—Li1	144.413 (4)	C3—Li1—C2	104.651 (9)

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

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