The crystal structure described by Li4TiV5O12 crystallizes in the monoclinic C2/m space group. Li(1) is bonded to two equivalent O(1) and two equivalent O(2) atoms to form distorted LiO4 trigonal pyramids that share corners with two equivalent Ti(1)O6 octahedra, corners with two equivalent V(1)O6 octahedra, corners with two equivalent V(2)O6 octahedra, corners with two equivalent V(3)O6 octahedra,  an edgeedge with one V(2)O6 octahedra,  an edgeedge with one V(3)O6 octahedra, and edges with two equivalent Li(1)O4 trigonal pyramids. The corner-sharing octahedral tilt angles range from 21-71°. Ti(1) is bonded to two equivalent O(4) and four equivalent O(1) atoms to form TiO6 octahedra that share corners with eight equivalent Li(1)O4 trigonal pyramids and edges with six equivalent V(3)O6 octahedra. There are three inequivalent V sites. In the first V site, V(1) is bonded to two equivalent O(3) and four equivalent O(2) atoms to form VO6 octahedra that share corners with eight equivalent Li(1)O4 trigonal pyramids and edges with six equivalent V(2)O6 octahedra. In the second V site, V(2) is bonded to two equivalent O(3) and four equivalent O(2) atoms to form VO6 octahedra that share corners with four equivalent Li(1)O4 trigonal pyramids, edges with three equivalent V(1)O6 octahedra, edges with three equivalent V(2)O6 octahedra, and edges with two equivalent Li(1)O4 trigonal pyramids. In the third V site, V(3) is bonded to two equivalent O(4) and four equivalent O(1) atoms to form VO6 octahedra that share corners with four equivalent Li(1)O4 trigonal pyramids, edges with three equivalent Ti(1)O6 octahedra, edges with three equivalent V(3)O6 octahedra, and edges with two equivalent Li(1)O4 trigonal pyramids. There are four inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Li(1), one Ti(1), and two equivalent V(3) atoms to form OLi2TiV2 trigonal bipyramids that share corners with two equivalent O(2)Li2V3 trigonal bipyramids, corners with three equivalent O(1)Li2TiV2 trigonal bipyramids,  an edgeedge with one O(2)Li2V3 trigonal bipyramid, and edges with four equivalent O(1)Li2TiV2 trigonal bipyramids. In the second O site, O(2) is bonded to two equivalent Li(1), one V(1), and two equivalent V(2) atoms to form OLi2V3 trigonal bipyramids that share corners with two equivalent O(1)Li2TiV2 trigonal bipyramids, corners with three equivalent O(2)Li2V3 trigonal bipyramids,  an edgeedge with one O(1)Li2TiV2 trigonal bipyramid, and edges with four equivalent O(2)Li2V3 trigonal bipyramids. In the third O site, O(3) is bonded in a distorted T-shaped geometry to one V(1) and two equivalent V(2) atoms. In the fourth O site, O(4) is bonded in a distorted T-shaped geometry to one Ti(1) and two equivalent V(3) atoms. is represented by the Crystallographic Information File (CIF) [CIF]
data_Li4TiV5O12
_symmetry_space_group_name_H-M   'P 1'
_cell_length_a   5.149
_cell_length_b   5.149
_cell_length_c   10.248
_cell_angle_alpha   89.404
_cell_angle_beta   89.404
_cell_angle_gamma   119.225
_symmetry_Int_Tables_number   1
_cell_volume   237.086
_cell_formula_units_Z   1
loop_
 _symmetry_equiv_pos_site_id
 _symmetry_equiv_pos_as_xyz
  1  'x, y, z'
loop_
 _atom_site_type_symbol
 _atom_site_label
 _atom_site_symmetry_multiplicity
 _atom_site_fract_x
 _atom_site_fract_y
 _atom_site_fract_z
 _atom_site_occupancy
  Li  Li0  1  0.860  0.354  0.250  1.0
  Li  Li1  1  0.646  0.140  0.750  1.0
  Li  Li2  1  0.354  0.860  0.250  1.0
  Li  Li3  1  0.140  0.646  0.750  1.0
  Ti  Ti4  1  0.000  0.000  0.000  1.0
  V  V5  1  0.500  0.500  0.500  1.0
  V  V6  1  0.843  0.157  0.500  1.0
  V  V7  1  0.662  0.338  0.000  1.0
  V  V8  1  0.338  0.662  0.000  1.0
  V  V9  1  0.157  0.843  0.500  1.0
  O  O10  1  0.989  0.326  0.893  1.0
  O  O11  1  0.674  0.011  0.107  1.0
  O  O12  1  0.838  0.491  0.606  1.0
  O  O13  1  0.509  0.162  0.394  1.0
  O  O14  1  0.832  0.832  0.396  1.0
  O  O15  1  0.681  0.681  0.899  1.0
  O  O16  1  0.319  0.319  0.101  1.0
  O  O17  1  0.168  0.168  0.604  1.0
  O  O18  1  0.491  0.838  0.606  1.0
  O  O19  1  0.162  0.509  0.394  1.0
  O  O20  1  0.326  0.989  0.893  1.0
  O  O21  1  0.011  0.674  0.107  1.0
[/CIF]
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The crystal structure described by Li4TiV5O12 crystallizes in the monoclinic C2/m space group. Li(1) is bonded to two equivalent O(1) and two equivalent O(2) atoms to form distorted LiO4 trigonal pyramids that share corners with two equivalent Ti(1)O6 octahedra, corners with two equivalent V(1)O6 octahedra, corners with two equivalent V(2)O6 octahedra, corners with two equivalent V(3)O6 octahedra,  an edgeedge with one V(2)O6 octahedra,  an edgeedge with one V(3)O6 octahedra, and edges with two equivalent Li(1)O4 trigonal pyramids. The corner-sharing octahedral tilt angles range from 21-71°. Ti(1) is bonded to two equivalent O(4) and four equivalent O(1) atoms to form TiO6 octahedra that share corners with eight equivalent Li(1)O4 trigonal pyramids and edges with six equivalent V(3)O6 octahedra. There are three inequivalent V sites. In the first V site, V(1) is bonded to two equivalent O(3) and four equivalent O(2) atoms to form VO6 octahedra that share corners with eight equivalent Li(1)O4 trigonal pyramids and edges with six equivalent V(2)O6 octahedra. In the second V site, V(2) is bonded to two equivalent O(3) and four equivalent O(2) atoms to form VO6 octahedra that share corners with four equivalent Li(1)O4 trigonal pyramids, edges with three equivalent V(1)O6 octahedra, edges with three equivalent V(2)O6 octahedra, and edges with two equivalent Li(1)O4 trigonal pyramids. In the third V site, V(3) is bonded to two equivalent O(4) and four equivalent O(1) atoms to form VO6 octahedra that share corners with four equivalent Li(1)O4 trigonal pyramids, edges with three equivalent Ti(1)O6 octahedra, edges with three equivalent V(3)O6 octahedra, and edges with two equivalent Li(1)O4 trigonal pyramids. There are four inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Li(1), one Ti(1), and two equivalent V(3) atoms to form OLi2TiV2 trigonal bipyramids that share corners with two equivalent O(2)Li2V3 trigonal bipyramids, corners with three equivalent O(1)Li2TiV2 trigonal bipyramids,  an edgeedge with one O(2)Li2V3 trigonal bipyramid, and edges with four equivalent O(1)Li2TiV2 trigonal bipyramids. In the second O site, O(2) is bonded to two equivalent Li(1), one V(1), and two equivalent V(2) atoms to form OLi2V3 trigonal bipyramids that share corners with two equivalent O(1)Li2TiV2 trigonal bipyramids, corners with three equivalent O(2)Li2V3 trigonal bipyramids,  an edgeedge with one O(1)Li2TiV2 trigonal bipyramid, and edges with four equivalent O(2)Li2V3 trigonal bipyramids. In the third O site, O(3) is bonded in a distorted T-shaped geometry to one V(1) and two equivalent V(2) atoms. In the fourth O site, O(4) is bonded in a distorted T-shaped geometry to one Ti(1) and two equivalent V(3) atoms. is represented by the Crystallographic Information File (CIF) [CIF]
data_Li4TiV5O12
_symmetry_space_group_name_H-M   'P 1'
_cell_length_a   5.149
_cell_length_b   5.149
_cell_length_c   10.248
_cell_angle_alpha   89.404
_cell_angle_beta   89.404
_cell_angle_gamma   119.225
_symmetry_Int_Tables_number   1
_cell_volume   237.086
_cell_formula_units_Z   1
loop_
 _symmetry_equiv_pos_site_id
 _symmetry_equiv_pos_as_xyz
  1  'x, y, z'
loop_
 _atom_site_type_symbol
 _atom_site_label
 _atom_site_symmetry_multiplicity
 _atom_site_fract_x
 _atom_site_fract_y
 _atom_site_fract_z
 _atom_site_occupancy
  Li  Li0  1  0.860  0.354  0.250  1.0
  Li  Li1  1  0.646  0.140  0.750  1.0
  Li  Li2  1  0.354  0.860  0.250  1.0
  Li  Li3  1  0.140  0.646  0.750  1.0
  Ti  Ti4  1  0.000  0.000  0.000  1.0
  V  V5  1  0.500  0.500  0.500  1.0
  V  V6  1  0.843  0.157  0.500  1.0
  V  V7  1  0.662  0.338  0.000  1.0
  V  V8  1  0.338  0.662  0.000  1.0
  V  V9  1  0.157  0.843  0.500  1.0
  O  O10  1  0.989  0.326  0.893  1.0
  O  O11  1  0.674  0.011  0.107  1.0
  O  O12  1  0.838  0.491  0.606  1.0
  O  O13  1  0.509  0.162  0.394  1.0
  O  O14  1  0.832  0.832  0.396  1.0
  O  O15  1  0.681  0.681  0.899  1.0
  O  O16  1  0.319  0.319  0.101  1.0
  O  O17  1  0.168  0.168  0.604  1.0
  O  O18  1  0.491  0.838  0.606  1.0
  O  O19  1  0.162  0.509  0.394  1.0
  O  O20  1  0.326  0.989  0.893  1.0
  O  O21  1  0.011  0.674  0.107  1.0
[/CIF]
.