The structure described by NaHf3(NCl)3 crystallizes in the monoclinic C2/m space group. Na(1) is bonded to two equivalent Cl(2) and four equivalent Cl(1) atoms to form NaCl6 octahedra that share corners with two equivalent Hf(1)N4Cl3 trigonal pyramids, corners with four equivalent Hf(2)N4Cl3 trigonal pyramids, edges with three equivalent Na(1)Cl6 octahedra, edges with two equivalent Hf(1)N4Cl3 trigonal pyramids, and edges with four equivalent Hf(2)N4Cl3 trigonal pyramids. There are two inequivalent Hf sites. In the first Hf site, Hf(1) is bonded to two equivalent N(1), two equivalent N(2), one Cl(2), and two equivalent Cl(1) atoms to form distorted HfN4Cl3 trigonal pyramids that share corners with two equivalent Na(1)Cl6 octahedra, edges with two equivalent Na(1)Cl6 octahedra,  an edgeedge with one Hf(1)N4Cl3 trigonal pyramid, and edges with eight equivalent Hf(2)N4Cl3 trigonal pyramids. The corner-sharing octahedral tilt angles are 3°. In the second Hf site, Hf(2) is bonded to one N(1), three equivalent N(2), one Cl(2), and two equivalent Cl(1) atoms to form distorted HfN4Cl3 trigonal pyramids that share corners with two equivalent Na(1)Cl6 octahedra, edges with two equivalent Na(1)Cl6 octahedra, edges with four equivalent Hf(1)N4Cl3 trigonal pyramids, and edges with five equivalent Hf(2)N4Cl3 trigonal pyramids. The corner-sharing octahedral tilt angles are 3°. There are two inequivalent N sites. In the first N site, N(1) is bonded to two equivalent Hf(1) and two equivalent Hf(2) atoms to form NHf4 trigonal pyramids that share corners with two equivalent Cl(2)Na2Hf3 square pyramids, corners with four equivalent Cl(1)Na2Hf3 square pyramids, corners with six equivalent N(2)Hf4 trigonal pyramids,  an edgeedge with one Cl(2)Na2Hf3 square pyramid, edges with two equivalent Cl(1)Na2Hf3 square pyramids,  an edgeedge with one N(1)Hf4 trigonal pyramid, and edges with two equivalent N(2)Hf4 trigonal pyramids. In the second N site, N(2) is bonded to one Hf(1) and three equivalent Hf(2) atoms to form NHf4 trigonal pyramids that share corners with two equivalent Cl(2)Na2Hf3 square pyramids, corners with four equivalent Cl(1)Na2Hf3 square pyramids, corners with three equivalent N(1)Hf4 trigonal pyramids, corners with three equivalent N(2)Hf4 trigonal pyramids,  an edgeedge with one Cl(2)Na2Hf3 square pyramid, edges with two equivalent Cl(1)Na2Hf3 square pyramids,  an edgeedge with one N(1)Hf4 trigonal pyramid, and edges with two equivalent N(2)Hf4 trigonal pyramids. There are two inequivalent Cl sites. In the first Cl site, Cl(1) is bonded to two equivalent Na(1), one Hf(1), and two equivalent Hf(2) atoms to form distorted ClNa2Hf3 square pyramids that share corners with three equivalent Cl(1)Na2Hf3 square pyramids, corners with three equivalent Cl(2)Na2Hf3 square pyramids, corners with two equivalent N(1)Hf4 trigonal pyramids, corners with four equivalent N(2)Hf4 trigonal pyramids, edges with two equivalent Cl(2)Na2Hf3 square pyramids, edges with three equivalent Cl(1)Na2Hf3 square pyramids,  an edgeedge with one N(1)Hf4 trigonal pyramid, and edges with two equivalent N(2)Hf4 trigonal pyramids. In the second Cl site, Cl(2) is bonded to two equivalent Na(1), one Hf(1), and two equivalent Hf(2) atoms to form distorted ClNa2Hf3 square pyramids that share corners with six equivalent Cl(1)Na2Hf3 square pyramids, corners with two equivalent N(1)Hf4 trigonal pyramids, corners with four equivalent N(2)Hf4 trigonal pyramids,  an edgeedge with one Cl(2)Na2Hf3 square pyramid, edges with four equivalent Cl(1)Na2Hf3 square pyramids,  an edgeedge with one N(1)Hf4 trigonal pyramid, and edges with two equivalent N(2)Hf4 trigonal pyramids. is represented by the CIF file [CIF]
data_NaHf3(NCl)3
_symmetry_space_group_name_H-M   'P 1'
_cell_length_a   6.328
_cell_length_b   6.328
_cell_length_c   10.402
_cell_angle_alpha   84.176
_cell_angle_beta   84.176
_cell_angle_gamma   120.011
_symmetry_Int_Tables_number   1
_cell_volume   353.216
_cell_formula_units_Z   2
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
  Na  Na0  1  0.667  0.333  0.000  1.0
  Na  Na1  1  0.333  0.667  0.000  1.0
  Hf  Hf2  1  0.206  0.206  0.384  1.0
  Hf  Hf3  1  0.538  0.872  0.383  1.0
  Hf  Hf4  1  0.872  0.538  0.383  1.0
  Hf  Hf5  1  0.128  0.462  0.617  1.0
  Hf  Hf6  1  0.462  0.128  0.617  1.0
  Hf  Hf7  1  0.794  0.794  0.616  1.0
  N  N8  1  0.136  0.136  0.591  1.0
  N  N9  1  0.470  0.803  0.590  1.0
  N  N10  1  0.803  0.470  0.590  1.0
  N  N11  1  0.197  0.530  0.410  1.0
  N  N12  1  0.530  0.197  0.410  1.0
  N  N13  1  0.864  0.864  0.409  1.0
  Cl  Cl14  1  0.061  0.724  0.818  1.0
  Cl  Cl15  1  0.397  0.397  0.818  1.0
  Cl  Cl16  1  0.724  0.061  0.818  1.0
  Cl  Cl17  1  0.276  0.939  0.182  1.0
  Cl  Cl18  1  0.603  0.603  0.182  1.0
  Cl  Cl19  1  0.939  0.276  0.182  1.0
[/CIF]
.
The structure described by NaHf3(NCl)3 crystallizes in the monoclinic C2/m space group. Na(1) is bonded to two equivalent Cl(2) and four equivalent Cl(1) atoms to form NaCl6 octahedra that share corners with two equivalent Hf(1)N4Cl3 trigonal pyramids, corners with four equivalent Hf(2)N4Cl3 trigonal pyramids, edges with three equivalent Na(1)Cl6 octahedra, edges with two equivalent Hf(1)N4Cl3 trigonal pyramids, and edges with four equivalent Hf(2)N4Cl3 trigonal pyramids. There are two inequivalent Hf sites. In the first Hf site, Hf(1) is bonded to two equivalent N(1), two equivalent N(2), one Cl(2), and two equivalent Cl(1) atoms to form distorted HfN4Cl3 trigonal pyramids that share corners with two equivalent Na(1)Cl6 octahedra, edges with two equivalent Na(1)Cl6 octahedra,  an edgeedge with one Hf(1)N4Cl3 trigonal pyramid, and edges with eight equivalent Hf(2)N4Cl3 trigonal pyramids. The corner-sharing octahedral tilt angles are 3°. In the second Hf site, Hf(2) is bonded to one N(1), three equivalent N(2), one Cl(2), and two equivalent Cl(1) atoms to form distorted HfN4Cl3 trigonal pyramids that share corners with two equivalent Na(1)Cl6 octahedra, edges with two equivalent Na(1)Cl6 octahedra, edges with four equivalent Hf(1)N4Cl3 trigonal pyramids, and edges with five equivalent Hf(2)N4Cl3 trigonal pyramids. The corner-sharing octahedral tilt angles are 3°. There are two inequivalent N sites. In the first N site, N(1) is bonded to two equivalent Hf(1) and two equivalent Hf(2) atoms to form NHf4 trigonal pyramids that share corners with two equivalent Cl(2)Na2Hf3 square pyramids, corners with four equivalent Cl(1)Na2Hf3 square pyramids, corners with six equivalent N(2)Hf4 trigonal pyramids,  an edgeedge with one Cl(2)Na2Hf3 square pyramid, edges with two equivalent Cl(1)Na2Hf3 square pyramids,  an edgeedge with one N(1)Hf4 trigonal pyramid, and edges with two equivalent N(2)Hf4 trigonal pyramids. In the second N site, N(2) is bonded to one Hf(1) and three equivalent Hf(2) atoms to form NHf4 trigonal pyramids that share corners with two equivalent Cl(2)Na2Hf3 square pyramids, corners with four equivalent Cl(1)Na2Hf3 square pyramids, corners with three equivalent N(1)Hf4 trigonal pyramids, corners with three equivalent N(2)Hf4 trigonal pyramids,  an edgeedge with one Cl(2)Na2Hf3 square pyramid, edges with two equivalent Cl(1)Na2Hf3 square pyramids,  an edgeedge with one N(1)Hf4 trigonal pyramid, and edges with two equivalent N(2)Hf4 trigonal pyramids. There are two inequivalent Cl sites. In the first Cl site, Cl(1) is bonded to two equivalent Na(1), one Hf(1), and two equivalent Hf(2) atoms to form distorted ClNa2Hf3 square pyramids that share corners with three equivalent Cl(1)Na2Hf3 square pyramids, corners with three equivalent Cl(2)Na2Hf3 square pyramids, corners with two equivalent N(1)Hf4 trigonal pyramids, corners with four equivalent N(2)Hf4 trigonal pyramids, edges with two equivalent Cl(2)Na2Hf3 square pyramids, edges with three equivalent Cl(1)Na2Hf3 square pyramids,  an edgeedge with one N(1)Hf4 trigonal pyramid, and edges with two equivalent N(2)Hf4 trigonal pyramids. In the second Cl site, Cl(2) is bonded to two equivalent Na(1), one Hf(1), and two equivalent Hf(2) atoms to form distorted ClNa2Hf3 square pyramids that share corners with six equivalent Cl(1)Na2Hf3 square pyramids, corners with two equivalent N(1)Hf4 trigonal pyramids, corners with four equivalent N(2)Hf4 trigonal pyramids,  an edgeedge with one Cl(2)Na2Hf3 square pyramid, edges with four equivalent Cl(1)Na2Hf3 square pyramids,  an edgeedge with one N(1)Hf4 trigonal pyramid, and edges with two equivalent N(2)Hf4 trigonal pyramids. is represented by the CIF file [CIF]
data_NaHf3(NCl)3
_symmetry_space_group_name_H-M   'P 1'
_cell_length_a   6.328
_cell_length_b   6.328
_cell_length_c   10.402
_cell_angle_alpha   84.176
_cell_angle_beta   84.176
_cell_angle_gamma   120.011
_symmetry_Int_Tables_number   1
_cell_volume   353.216
_cell_formula_units_Z   2
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
  Na  Na0  1  0.667  0.333  0.000  1.0
  Na  Na1  1  0.333  0.667  0.000  1.0
  Hf  Hf2  1  0.206  0.206  0.384  1.0
  Hf  Hf3  1  0.538  0.872  0.383  1.0
  Hf  Hf4  1  0.872  0.538  0.383  1.0
  Hf  Hf5  1  0.128  0.462  0.617  1.0
  Hf  Hf6  1  0.462  0.128  0.617  1.0
  Hf  Hf7  1  0.794  0.794  0.616  1.0
  N  N8  1  0.136  0.136  0.591  1.0
  N  N9  1  0.470  0.803  0.590  1.0
  N  N10  1  0.803  0.470  0.590  1.0
  N  N11  1  0.197  0.530  0.410  1.0
  N  N12  1  0.530  0.197  0.410  1.0
  N  N13  1  0.864  0.864  0.409  1.0
  Cl  Cl14  1  0.061  0.724  0.818  1.0
  Cl  Cl15  1  0.397  0.397  0.818  1.0
  Cl  Cl16  1  0.724  0.061  0.818  1.0
  Cl  Cl17  1  0.276  0.939  0.182  1.0
  Cl  Cl18  1  0.603  0.603  0.182  1.0
  Cl  Cl19  1  0.939  0.276  0.182  1.0
[/CIF]
.