The compound described by Na6CaHf3Si2(PO6)4 crystallizes in the triclinic P1 space group. There are six inequivalent Na sites. In the first Na site, Na(1) is bonded in a distorted hexagonal planar geometry to one O(1), one O(11), one O(21), one O(23), one O(3), and one O(9) atom. In the second Na site, Na(2) is bonded in a distorted hexagonal planar geometry to one O(10), one O(12), one O(2), one O(22), one O(24), and one O(4) atom. In the third Na site, Na(3) is bonded in a 8-coordinate geometry to one O(1), one O(13), one O(14), one O(19), one O(2), one O(20), one O(21), and one O(22) atom. In the fourth Na site, Na(4) is bonded in a 4-coordinate geometry to one O(17), one O(23), one O(24), one O(3), and one O(4) atom. In the fifth Na site, Na(5) is bonded in a 6-coordinate geometry to one O(11), one O(12), one O(14), one O(23), one O(4), and one O(5) atom. In the sixth Na site, Na(6) is bonded in a 5-coordinate geometry to one O(10), one O(16), one O(21), one O(6), and one O(9) atom. Ca(1) is bonded to one O(12), one O(14), one O(17), one O(24), one O(4), and one O(6) atom to form distorted CaO6 octahedra that share  a cornercorner with one Si(1)O4 tetrahedra,  a cornercorner with one Si(2)O4 tetrahedra,  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra, and  a cornercorner with one P(4)O4 tetrahedra. There are three inequivalent Hf sites. In the first Hf site, Hf(1) is bonded to one O(1), one O(15), one O(20), one O(21), one O(7), and one O(9) atom to form HfO6 octahedra that share  a cornercorner with one Si(1)O4 tetrahedra,  a cornercorner with one Si(2)O4 tetrahedra,  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra, and  a cornercorner with one P(4)O4 tetrahedra. In the second Hf site, Hf(2) is bonded to one O(10), one O(16), one O(19), one O(2), one O(22), and one O(8) atom to form HfO6 octahedra that share  a cornercorner with one Si(1)O4 tetrahedra,  a cornercorner with one Si(2)O4 tetrahedra,  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra, and  a cornercorner with one P(4)O4 tetrahedra. In the third Hf site, Hf(3) is bonded to one O(11), one O(13), one O(18), one O(23), one O(3), and one O(5) atom to form HfO6 octahedra that share  a cornercorner with one Si(1)O4 tetrahedra,  a cornercorner with one Si(2)O4 tetrahedra,  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra, and  a cornercorner with one P(4)O4 tetrahedra. There are two inequivalent Si sites. In the first Si site, Si(1) is bonded to one O(1), one O(10), one O(14), and one O(18) atom to form SiO4 tetrahedra that share  a cornercorner with one Ca(1)O6 octahedra,  a cornercorner with one Hf(1)O6 octahedra,  a cornercorner with one Hf(2)O6 octahedra, and  a cornercorner with one Hf(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 22-41°. In the second Si site, Si(2) is bonded to one O(12), one O(16), one O(20), and one O(3) atom to form SiO4 tetrahedra that share  a cornercorner with one Ca(1)O6 octahedra,  a cornercorner with one Hf(1)O6 octahedra,  a cornercorner with one Hf(2)O6 octahedra, and  a cornercorner with one Hf(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 20-45°. There are four inequivalent P sites. In the first P site, P(1) is bonded to one O(21), one O(22), one O(5), and one O(6) atom to form PO4 tetrahedra that share  a cornercorner with one Ca(1)O6 octahedra,  a cornercorner with one Hf(1)O6 octahedra,  a cornercorner with one Hf(2)O6 octahedra, and  a cornercorner with one Hf(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 30-35°. In the second P site, P(2) is bonded to one O(23), one O(24), one O(7), and one O(8) atom to form PO4 tetrahedra that share  a cornercorner with one Ca(1)O6 octahedra,  a cornercorner with one Hf(1)O6 octahedra,  a cornercorner with one Hf(2)O6 octahedra, and  a cornercorner with one Hf(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 18-45°. In the third P site, P(3) is bonded to one O(13), one O(17), one O(2), and one O(9) atom to form PO4 tetrahedra that share  a cornercorner with one Ca(1)O6 octahedra,  a cornercorner with one Hf(1)O6 octahedra,  a cornercorner with one Hf(2)O6 octahedra, and  a cornercorner with one Hf(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 11-43°. In the fourth P site, P(4) is bonded to one O(11), one O(15), one O(19), and one O(4) atom to form PO4 tetrahedra that share  a cornercorner with one Ca(1)O6 octahedra,  a cornercorner with one Hf(1)O6 octahedra,  a cornercorner with one Hf(2)O6 octahedra, and  a cornercorner with one Hf(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 18-44°. There are twenty-four inequivalent O sites. In the first O site, O(1) is bonded in a 4-coordinate geometry to one Na(1), one Na(3), one Hf(1), and one Si(1) atom. In the second O site, O(2) is bonded in a 4-coordinate geometry to one Na(2), one Na(3), one Hf(2), and one P(3) atom. In the third O site, O(3) is bonded in a distorted rectangular see-saw-like geometry to one Na(1), one Na(4), one Hf(3), and one Si(2) atom. In the fourth O site, O(4) is bonded in a 5-coordinate geometry to one Na(2), one Na(4), one Na(5), one Ca(1), and one P(4) atom. In the fifth O site, O(5) is bonded in a distorted bent 150 degrees geometry to one Na(5), one Hf(3), and one P(1) atom. In the sixth O site, O(6) is bonded in a distorted T-shaped geometry to one Na(6), one Ca(1), and one P(1) atom. In the seventh O site, O(7) is bonded in a bent 150 degrees geometry to one Hf(1) and one P(2) atom. In the eighth O site, O(8) is bonded in a distorted bent 150 degrees geometry to one Hf(2) and one P(2) atom. In the ninth O site, O(9) is bonded in a 4-coordinate geometry to one Na(1), one Na(6), one Hf(1), and one P(3) atom. In the tenth O site, O(10) is bonded in a distorted trigonal pyramidal geometry to one Na(2), one Na(6), one Hf(2), and one Si(1) atom. In the eleventh O site, O(11) is bonded in a distorted rectangular see-saw-like geometry to one Na(1), one Na(5), one Hf(3), and one P(4) atom. In the twelfth O site, O(12) is bonded in a distorted rectangular see-saw-like geometry to one Na(2), one Na(5), one Ca(1), and one Si(2) atom. In the thirteenth O site, O(13) is bonded in a distorted linear geometry to one Na(3), one Hf(3), and one P(3) atom. In the fourteenth O site, O(14) is bonded in a 4-coordinate geometry to one Na(3), one Na(5), one Ca(1), and one Si(1) atom. In the fifteenth O site, O(15) is bonded in a bent 150 degrees geometry to one Hf(1) and one P(4) atom. In the sixteenth O site, O(16) is bonded in a 3-coordinate geometry to one Na(6), one Hf(2), and one Si(2) atom. In the seventeenth O site, O(17) is bonded in a 3-coordinate geometry to one Na(4), one Ca(1), and one P(3) atom. In the eighteenth O site, O(18) is bonded in a distorted bent 150 degrees geometry to one Hf(3) and one Si(1) atom. In the nineteenth O site, O(19) is bonded in a 3-coordinate geometry to one Na(3), one Hf(2), and one P(4) atom. In the twentieth O site, O(20) is bonded in a distorted bent 150 degrees geometry to one Na(3), one Hf(1), and one Si(2) atom. In the twenty-first O site, O(21) is bonded in a 5-coordinate geometry to one Na(1), one Na(3), one Na(6), one Hf(1), and one P(1) atom. In the twenty-second O site, O(22) is bonded in a distorted rectangular see-saw-like geometry to one Na(2), one Na(3), one Hf(2), and one P(1) atom. In the twenty-third O site, O(23) is bonded in a 5-coordinate geometry to one Na(1), one Na(4), one Na(5), one Hf(3), and one P(2) atom. In the twenty-fourth O site, O(24) is bonded in a distorted rectangular see-saw-like geometry to one Na(2), one Na(4), one Ca(1), and one P(2) atom. is represented by the CIF file [CIF]
data_Na6CaHf3Si2(PO6)4
_symmetry_space_group_name_H-M   'P 1'
_cell_length_a   9.137
_cell_length_b   9.177
_cell_length_c   9.182
_cell_angle_alpha   90.559
_cell_angle_beta   119.525
_cell_angle_gamma   119.739
_symmetry_Int_Tables_number   1
_cell_volume   547.759
_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
  Ca  Ca0  1  0.283  0.142  0.940  1.0
  Hf  Hf1  1  0.297  0.655  0.445  1.0
  Hf  Hf2  1  0.713  0.853  0.062  1.0
  Hf  Hf3  1  0.705  0.348  0.555  1.0
  Na  Na4  1  0.996  0.502  0.999  1.0
  Na  Na5  1  0.006  0.009  0.512  1.0
  Na  Na6  1  0.838  0.256  0.233  1.0
  Na  Na7  1  0.152  0.760  0.764  1.0
  Na  Na8  1  0.509  0.384  0.786  1.0
  Na  Na9  1  0.460  0.564  0.199  1.0
  O  O10  1  0.010  0.593  0.271  1.0
  O  O11  1  0.676  0.956  0.247  1.0
  O  O12  1  0.009  0.447  0.742  1.0
  O  O13  1  0.342  0.048  0.740  1.0
  O  O14  1  0.405  0.289  0.431  1.0
  O  O15  1  0.207  0.234  0.099  1.0
  O  O16  1  0.575  0.682  0.574  1.0
  O  O17  1  0.787  0.789  0.907  1.0
  O  O18  1  0.379  0.771  0.272  1.0
  O  O19  1  0.801  0.734  0.243  1.0
  O  O20  1  0.667  0.232  0.750  1.0
  O  O21  1  0.191  0.282  0.737  1.0
  O  O22  1  0.603  0.117  0.392  1.0
  O  O23  1  0.608  0.384  0.073  1.0
  O  O24  1  0.430  0.898  0.601  1.0
  O  O25  1  0.418  0.636  0.928  1.0
  O  O26  1  0.349  0.943  0.060  1.0
  O  O27  1  0.789  0.504  0.421  1.0
  O  O28  1  0.646  0.026  0.933  1.0
  O  O29  1  0.198  0.526  0.581  1.0
  O  O30  1  0.190  0.414  0.280  1.0
  O  O31  1  0.015  0.091  0.245  1.0
  O  O32  1  0.780  0.561  0.745  1.0
  O  O33  1  0.960  0.873  0.737  1.0
  P  P34  1  0.205  0.252  0.262  1.0
  P  P35  1  0.780  0.733  0.740  1.0
  P  P36  1  0.496  0.945  0.240  1.0
  P  P37  1  0.520  0.051  0.757  1.0
  Si  Si38  1  0.803  0.555  0.250  1.0
  Si  Si39  1  0.200  0.461  0.747  1.0
[/CIF]
.
The compound described by Na6CaHf3Si2(PO6)4 crystallizes in the triclinic P1 space group. There are six inequivalent Na sites. In the first Na site, Na(1) is bonded in a distorted hexagonal planar geometry to one O(1), one O(11), one O(21), one O(23), one O(3), and one O(9) atom. In the second Na site, Na(2) is bonded in a distorted hexagonal planar geometry to one O(10), one O(12), one O(2), one O(22), one O(24), and one O(4) atom. In the third Na site, Na(3) is bonded in a 8-coordinate geometry to one O(1), one O(13), one O(14), one O(19), one O(2), one O(20), one O(21), and one O(22) atom. In the fourth Na site, Na(4) is bonded in a 4-coordinate geometry to one O(17), one O(23), one O(24), one O(3), and one O(4) atom. In the fifth Na site, Na(5) is bonded in a 6-coordinate geometry to one O(11), one O(12), one O(14), one O(23), one O(4), and one O(5) atom. In the sixth Na site, Na(6) is bonded in a 5-coordinate geometry to one O(10), one O(16), one O(21), one O(6), and one O(9) atom. Ca(1) is bonded to one O(12), one O(14), one O(17), one O(24), one O(4), and one O(6) atom to form distorted CaO6 octahedra that share  a cornercorner with one Si(1)O4 tetrahedra,  a cornercorner with one Si(2)O4 tetrahedra,  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra, and  a cornercorner with one P(4)O4 tetrahedra. There are three inequivalent Hf sites. In the first Hf site, Hf(1) is bonded to one O(1), one O(15), one O(20), one O(21), one O(7), and one O(9) atom to form HfO6 octahedra that share  a cornercorner with one Si(1)O4 tetrahedra,  a cornercorner with one Si(2)O4 tetrahedra,  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra, and  a cornercorner with one P(4)O4 tetrahedra. In the second Hf site, Hf(2) is bonded to one O(10), one O(16), one O(19), one O(2), one O(22), and one O(8) atom to form HfO6 octahedra that share  a cornercorner with one Si(1)O4 tetrahedra,  a cornercorner with one Si(2)O4 tetrahedra,  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra, and  a cornercorner with one P(4)O4 tetrahedra. In the third Hf site, Hf(3) is bonded to one O(11), one O(13), one O(18), one O(23), one O(3), and one O(5) atom to form HfO6 octahedra that share  a cornercorner with one Si(1)O4 tetrahedra,  a cornercorner with one Si(2)O4 tetrahedra,  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra, and  a cornercorner with one P(4)O4 tetrahedra. There are two inequivalent Si sites. In the first Si site, Si(1) is bonded to one O(1), one O(10), one O(14), and one O(18) atom to form SiO4 tetrahedra that share  a cornercorner with one Ca(1)O6 octahedra,  a cornercorner with one Hf(1)O6 octahedra,  a cornercorner with one Hf(2)O6 octahedra, and  a cornercorner with one Hf(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 22-41°. In the second Si site, Si(2) is bonded to one O(12), one O(16), one O(20), and one O(3) atom to form SiO4 tetrahedra that share  a cornercorner with one Ca(1)O6 octahedra,  a cornercorner with one Hf(1)O6 octahedra,  a cornercorner with one Hf(2)O6 octahedra, and  a cornercorner with one Hf(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 20-45°. There are four inequivalent P sites. In the first P site, P(1) is bonded to one O(21), one O(22), one O(5), and one O(6) atom to form PO4 tetrahedra that share  a cornercorner with one Ca(1)O6 octahedra,  a cornercorner with one Hf(1)O6 octahedra,  a cornercorner with one Hf(2)O6 octahedra, and  a cornercorner with one Hf(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 30-35°. In the second P site, P(2) is bonded to one O(23), one O(24), one O(7), and one O(8) atom to form PO4 tetrahedra that share  a cornercorner with one Ca(1)O6 octahedra,  a cornercorner with one Hf(1)O6 octahedra,  a cornercorner with one Hf(2)O6 octahedra, and  a cornercorner with one Hf(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 18-45°. In the third P site, P(3) is bonded to one O(13), one O(17), one O(2), and one O(9) atom to form PO4 tetrahedra that share  a cornercorner with one Ca(1)O6 octahedra,  a cornercorner with one Hf(1)O6 octahedra,  a cornercorner with one Hf(2)O6 octahedra, and  a cornercorner with one Hf(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 11-43°. In the fourth P site, P(4) is bonded to one O(11), one O(15), one O(19), and one O(4) atom to form PO4 tetrahedra that share  a cornercorner with one Ca(1)O6 octahedra,  a cornercorner with one Hf(1)O6 octahedra,  a cornercorner with one Hf(2)O6 octahedra, and  a cornercorner with one Hf(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 18-44°. There are twenty-four inequivalent O sites. In the first O site, O(1) is bonded in a 4-coordinate geometry to one Na(1), one Na(3), one Hf(1), and one Si(1) atom. In the second O site, O(2) is bonded in a 4-coordinate geometry to one Na(2), one Na(3), one Hf(2), and one P(3) atom. In the third O site, O(3) is bonded in a distorted rectangular see-saw-like geometry to one Na(1), one Na(4), one Hf(3), and one Si(2) atom. In the fourth O site, O(4) is bonded in a 5-coordinate geometry to one Na(2), one Na(4), one Na(5), one Ca(1), and one P(4) atom. In the fifth O site, O(5) is bonded in a distorted bent 150 degrees geometry to one Na(5), one Hf(3), and one P(1) atom. In the sixth O site, O(6) is bonded in a distorted T-shaped geometry to one Na(6), one Ca(1), and one P(1) atom. In the seventh O site, O(7) is bonded in a bent 150 degrees geometry to one Hf(1) and one P(2) atom. In the eighth O site, O(8) is bonded in a distorted bent 150 degrees geometry to one Hf(2) and one P(2) atom. In the ninth O site, O(9) is bonded in a 4-coordinate geometry to one Na(1), one Na(6), one Hf(1), and one P(3) atom. In the tenth O site, O(10) is bonded in a distorted trigonal pyramidal geometry to one Na(2), one Na(6), one Hf(2), and one Si(1) atom. In the eleventh O site, O(11) is bonded in a distorted rectangular see-saw-like geometry to one Na(1), one Na(5), one Hf(3), and one P(4) atom. In the twelfth O site, O(12) is bonded in a distorted rectangular see-saw-like geometry to one Na(2), one Na(5), one Ca(1), and one Si(2) atom. In the thirteenth O site, O(13) is bonded in a distorted linear geometry to one Na(3), one Hf(3), and one P(3) atom. In the fourteenth O site, O(14) is bonded in a 4-coordinate geometry to one Na(3), one Na(5), one Ca(1), and one Si(1) atom. In the fifteenth O site, O(15) is bonded in a bent 150 degrees geometry to one Hf(1) and one P(4) atom. In the sixteenth O site, O(16) is bonded in a 3-coordinate geometry to one Na(6), one Hf(2), and one Si(2) atom. In the seventeenth O site, O(17) is bonded in a 3-coordinate geometry to one Na(4), one Ca(1), and one P(3) atom. In the eighteenth O site, O(18) is bonded in a distorted bent 150 degrees geometry to one Hf(3) and one Si(1) atom. In the nineteenth O site, O(19) is bonded in a 3-coordinate geometry to one Na(3), one Hf(2), and one P(4) atom. In the twentieth O site, O(20) is bonded in a distorted bent 150 degrees geometry to one Na(3), one Hf(1), and one Si(2) atom. In the twenty-first O site, O(21) is bonded in a 5-coordinate geometry to one Na(1), one Na(3), one Na(6), one Hf(1), and one P(1) atom. In the twenty-second O site, O(22) is bonded in a distorted rectangular see-saw-like geometry to one Na(2), one Na(3), one Hf(2), and one P(1) atom. In the twenty-third O site, O(23) is bonded in a 5-coordinate geometry to one Na(1), one Na(4), one Na(5), one Hf(3), and one P(2) atom. In the twenty-fourth O site, O(24) is bonded in a distorted rectangular see-saw-like geometry to one Na(2), one Na(4), one Ca(1), and one P(2) atom. is represented by the CIF file [CIF]
data_Na6CaHf3Si2(PO6)4
_symmetry_space_group_name_H-M   'P 1'
_cell_length_a   9.137
_cell_length_b   9.177
_cell_length_c   9.182
_cell_angle_alpha   90.559
_cell_angle_beta   119.525
_cell_angle_gamma   119.739
_symmetry_Int_Tables_number   1
_cell_volume   547.759
_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
  Ca  Ca0  1  0.283  0.142  0.940  1.0
  Hf  Hf1  1  0.297  0.655  0.445  1.0
  Hf  Hf2  1  0.713  0.853  0.062  1.0
  Hf  Hf3  1  0.705  0.348  0.555  1.0
  Na  Na4  1  0.996  0.502  0.999  1.0
  Na  Na5  1  0.006  0.009  0.512  1.0
  Na  Na6  1  0.838  0.256  0.233  1.0
  Na  Na7  1  0.152  0.760  0.764  1.0
  Na  Na8  1  0.509  0.384  0.786  1.0
  Na  Na9  1  0.460  0.564  0.199  1.0
  O  O10  1  0.010  0.593  0.271  1.0
  O  O11  1  0.676  0.956  0.247  1.0
  O  O12  1  0.009  0.447  0.742  1.0
  O  O13  1  0.342  0.048  0.740  1.0
  O  O14  1  0.405  0.289  0.431  1.0
  O  O15  1  0.207  0.234  0.099  1.0
  O  O16  1  0.575  0.682  0.574  1.0
  O  O17  1  0.787  0.789  0.907  1.0
  O  O18  1  0.379  0.771  0.272  1.0
  O  O19  1  0.801  0.734  0.243  1.0
  O  O20  1  0.667  0.232  0.750  1.0
  O  O21  1  0.191  0.282  0.737  1.0
  O  O22  1  0.603  0.117  0.392  1.0
  O  O23  1  0.608  0.384  0.073  1.0
  O  O24  1  0.430  0.898  0.601  1.0
  O  O25  1  0.418  0.636  0.928  1.0
  O  O26  1  0.349  0.943  0.060  1.0
  O  O27  1  0.789  0.504  0.421  1.0
  O  O28  1  0.646  0.026  0.933  1.0
  O  O29  1  0.198  0.526  0.581  1.0
  O  O30  1  0.190  0.414  0.280  1.0
  O  O31  1  0.015  0.091  0.245  1.0
  O  O32  1  0.780  0.561  0.745  1.0
  O  O33  1  0.960  0.873  0.737  1.0
  P  P34  1  0.205  0.252  0.262  1.0
  P  P35  1  0.780  0.733  0.740  1.0
  P  P36  1  0.496  0.945  0.240  1.0
  P  P37  1  0.520  0.051  0.757  1.0
  Si  Si38  1  0.803  0.555  0.250  1.0
  Si  Si39  1  0.200  0.461  0.747  1.0
[/CIF]
.